阅读说明：本技术 一种烷基醚基二硫代磷酸盐捕收剂及其制备方法与应用 (Alkyl ether group dithiophosphate collecting agent and preparation method and application thereof ) 是由 钟宏 邹松 王帅 马鑫 于 2021-08-24 设计创作，主要内容包括：本发明属于矿物浮选技术领域,具体涉及一种烷基醚基二硫代磷酸盐捕收剂及其制备方法与应用。本发明首次采用醚醇类化合物与五硫化二磷进行反应获得含有醚基官能团的二硫代磷酸盐捕收剂。该捕收剂具有一定的起泡性能,能显著提高浮选效率和金属浮选回收率,是有色金属硫化矿物的优良捕收剂,且制备原料来源广泛,工艺简单,易于实现工业化。与传统捕收剂复配使用时,能够进一步提高硫化矿的浮选性能。(The invention belongs to the technical field of mineral flotation, and particularly relates to an alkyl ether group dithiophosphate collecting agent and a preparation method and application thereof. The ether alcohol compound and phosphorus pentasulfide are firstly adopted to react to obtain the dithiophosphate collecting agent containing the ether functional group. The collecting agent has certain foaming performance, can obviously improve the flotation efficiency and the metal flotation recovery rate, is an excellent collecting agent for non-ferrous metal sulfide minerals, has wide sources of preparation raw materials and simple process, and is easy to realize industrialization. When the flotation agent is compounded with the traditional collecting agent for use, the flotation performance of the sulfide ore can be further improved.)

1. An alkyl ether group dithiophosphate collecting agent is characterized in that the structural formula of the collecting agent is shown as a formula I:

in the structural formula I, R is C₁～C₄Alkyl, Me is H⁺、NH₄ ⁺、Na⁺Or K⁺。

2. The alkyl ether dithiophosphate collector of claim 1, wherein R is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl.

3. A method of preparing an alkyl ether dithiophosphate collector according to claim 1 or 2, characterized in that the method specifically comprises:

mixing the ether alcohol compound implemented as the formula II with phosphorus pentasulfide, stirring and heating to react to obtain alkyl ether dithiophosphate;

performing neutralization reaction on the alkyl ether group dithiophosphoric acid and an alkaline reagent to obtain an alkyl ether group dithiophosphate collecting agent;

R—O—CH₂—CH₂—OH

formula II

Wherein R is C₁～C₄One of the alkyl groups.

4. The method for preparing the alkyl ether group dithiophosphate collector according to claim 3, wherein the molar ratio of the ether alcohol compound to phosphorus pentasulfide is 1: 3-8.

5. The method for preparing the alkyl ether group dithiophosphate collector according to claim 3, wherein the ether alcohol compound is mixed with phosphorus pentasulfide and stirred for 3-8 hours at the reaction temperature of 50-120 ℃ in the reaction process of heating.

6. The method for preparing an alkyl ether dithiophosphate collector according to claim 3, wherein the alkyl ether dithiophosphate is neutralized with an alkaline reagent, wherein the alkaline reagent is any one of ammonia water, sodium hydroxide or potassium hydroxide; the molar ratio of the alkyl ether group dithiophosphoric acid to the alkaline reagent is 1: 0.5-1.5.

7. Use of an alkyl ether-based dithiophosphate collector according to any one of claims 1 to 2 or obtained by the preparation method according to any one of claims 4 to 6 in mineral separation collectors for copper sulphide ores, copper molybdenum sulphide ores, lead zinc sulphide ores and copper lead zinc sulphide ores.

8. Use of an alkyl ether-based dithiophosphate collector according to claim 7, characterised in that the beneficiation process specifically comprises:

grinding ores or minerals, adding the ground ores or minerals into a flotation tank, adjusting the pH value to 3-12, adding a compound flotation collector 5-100 g/t, and performing foam flotation to obtain useful metal minerals;

the compound collector comprises an alkyl ether group dithiophosphate collector and a matched collector.

9. The use of the alkyl ether group dithiophosphate collector according to claim 8, wherein the molar ratio of the alkyl ether group dithiophosphate collector to the co-collector is 10-90: 90-10;

the matched collecting agent is as follows: any one or more of ethyl xanthate, (iso) propyl xanthate, (iso) butyl xanthate, ethioamine, propylthiourethane, butylthiourethane, ethionamide, propylthiourethane, butylthiourethane, thiourethane, mercaptobenzothiazole, mercaptobenzimidazole, mercaptobenzoxazole or diisobutyldithiophosphate.

Technical Field

The invention belongs to the technical field of mineral flotation, and particularly relates to an alkyl ether group dithiophosphate collecting agent and a preparation method and application thereof.

Background

The dialkyl dithiophosphate (salt) is commonly known as "black powder", is second to xanthate, is an important collecting agent for flotation of sulfide ores, and is commonly used for flotation of nonferrous metal sulfide ores. The black magnetic has strong capacity of collecting chalcopyrite and galena, has poor capacity of collecting the chalcopyrite, has good flotation selectivity, also has certain foaming performance, can reduce or not use other regulators and foaming agents, reduces the cost of medicaments, and is used as an auxiliary collecting agent or foaming agent to improve the recovery rate of nonferrous metal sulfide ore.

In the prior art, a dithiophosphate collecting agent serving as a flotation collecting agent mainly comprises alcohol black powder and phenol black powder, wherein the alcohol black powder and the phenol black powder are ammonium butyl black powder and sodium butyl black powder, and are mainly prepared by performing catalytic reaction on butanol and phosphorus pentasulfide and then performing neutralization reaction on liquid ammonia or sodium hydroxide, and the phenol black powder is mainly cresol black powder. Along with the large-scale utilization of sulfide ore resources, ore resources become increasingly lean, fine and hybrid, a single flotation agent system is difficult to meet the maximum benefit pursuit of people for comprehensive utilization of the mineral resources, different flotation agents are reasonably mixed and compounded for use, a synergistic interaction effect is achieved, and the method is also an important way for improving the mineral separation efficiency and the comprehensive utilization of the mineral resources, for example, when the Wangwen floats Longshan gold antimony ore by mixing a butylammonium black agent and a MA-2 mixed collecting agent, the gold recovery rate can be improved by 8% -10%, and the antimony recovery rate can be improved by 3% -6%.

Therefore, the existing dithiophosphate collecting agent is single in type, and after the dithiophosphate collecting agent is used in a matching mode, the collecting effect is improved to be low, and the requirement for comprehensive utilization of mineral resources cannot be met. At present, no report about the flotation of minerals by alkyl ether-based dithiophosphate collectors exists.

Disclosure of Invention

Aiming at the technical problems in the prior art, the invention firstly provides the dithiophosphate collecting agent containing the ether functional group, and the dithiophosphate collecting agent containing the ether functional group is obtained by reacting the ether alcohol substance with phosphorus pentasulfide.

The invention provides an alkyl ether group dithiophosphate collecting agent, which has a structural formula shown as a formula I:

in the structural formula I, R is C₁～C₄Alkyl, Me is H⁺、NH₄ ⁺、Na⁺Or K⁺。

Further, R is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

The embodiment of the invention also provides a preparation method of the alkyl ether group dithiophosphate collecting agent, which specifically comprises the following steps:

mixing the ether alcohol compound implemented as the formula II with phosphorus pentasulfide, stirring and heating to react to obtain alkyl ether dithiophosphate;

performing neutralization reaction on the alkyl ether group dithiophosphoric acid and an alkaline reagent to obtain an alkyl ether group dithiophosphate collecting agent;

R—O—CH₂—CH₂—OH

formula II

Wherein R is C₁～C₄One of the alkyl groups.

Further, the molar ratio of the ether alcohol compound to the phosphorus pentasulfide is 1: 3-8.

Further, the ether alcohol compound and phosphorus pentasulfide are mixed, stirred and heated for 3-8 hours in the reaction process, wherein the reaction temperature is 50-120 ℃.

Further, in the process of neutralization reaction between the alkyl ether-based dithiophosphoric acid and an alkaline reagent, the alkaline reagent is any one of ammonia water, sodium hydroxide or potassium hydroxide; the molar ratio of the alkyl ether group dithiophosphoric acid to the alkaline reagent is 1: 0.5-1.5.

The embodiment of the invention also provides application of the alkyl ether dithiophosphate collecting agent in mineral separation collecting agents of copper sulfide ores, copper molybdenum sulfide ores, lead zinc sulfide ores and copper lead zinc sulfide ores.

Further, the beneficiation process specifically comprises:

grinding ores or minerals, adding the ground ores or minerals into a flotation tank, adjusting the pH value to 3-12, adding a compound flotation collector 5-100 g/t, and performing foam flotation to obtain useful metal minerals;

the compound collector comprises an alkyl ether group dithiophosphate collector and a matched collector.

Further, the molar ratio of the alkyl ether group dithiophosphate collecting agent to the matched collecting agent is 10-90: 90-10;

the matched collecting agent is as follows: any one or more of ethyl xanthate, (iso) propyl xanthate, (iso) butyl xanthate, ethioamine, propylthiourethane, butylthiourethane, ethionamide, propylthiourethane, butylthiourethane, thiourethane, mercaptobenzothiazole, mercaptobenzimidazole, mercaptobenzoxazole or diisobutyldithiophosphate.

The scheme of the invention has the following beneficial effects:

(1) the alkyl ether dithiophosphate collecting agent disclosed by the invention introduces an ether functional group for the first time, can obviously reduce the surface tension, has better hydrophobic property and higher surface activity, can regulate and control the foaming property of a medicament, and obtains a better foam mineralization effect. The preparation process of the collecting agent is simple and efficient, no additional solvent is required to be added, the separation and purification of the product are simple, the product can be directly used as the collecting agent after separation, and the industrialization is easy to realize; one of the raw materials is wide in ether alcohol source, and can comprehensively utilize byproducts of petrochemical industry, thereby saving resources.

(2) The alkyl ether dithiophosphate collecting agent has strong collecting capability and flotation speed on lead sulfide ore under the condition of low-alkaline ore pulp, weak collecting capability on zinc sulfide ore and iron sulfide ore, good medicament selectivity and suitability for a low-alkaline flotation process which is more beneficial to environmental protection.

(3) The alkyl ether dithiophosphate collecting agent has certain foaming performance, and the raw material ether alcohol is also a foaming agent, so that the alkyl ether dithiophosphate collecting agent can be used as the foaming agent, and the alkyl ether dithiophosphate collecting agent does not need to be additionally added when being applied to ore flotation, so that the cost of the agent can be reduced.

(4) The alkyl ether dithiophosphate collecting agent is compounded with the traditional collecting agent, is applied to flotation of copper sulfide ores or copper sulfide molybdenum ores, and has good surface activity, so that on one hand, the surface tension of molecules of the collecting agent can be reduced and the dispersity of the existing collecting agent with poor dispersity can be effectively improved, thereby exerting the intermolecular synergistic effect; on the other hand, the ether structure is beneficial to improving the foaming performance of a flotation system, forming more stable flotation foam and reducing the entrainment of gangue, thereby improving the quality of concentrate products. The collector is compounded with traditional collectors of different types and structures, so that the flotation characteristic of a single agent functional group can be exerted, the formula product design of the collector can be carried out aiming at sulfide ores of different ore occurrence property states, the synergistic flotation is realized, and the adaptability to a complex ore flotation system is strong.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is a nuclear magnetic resonance of ammonium bis (2-butoxyethyl) thiophosphate provided in an embodiment of the present invention¹H, spectrogram;

FIG. 2 is a nuclear magnetic resonance of ammonium bis (2-butoxyethyl) thiophosphate provided in an embodiment of the present invention¹³C, spectrum;

FIG. 3 is a nuclear magnetic resonance of ammonium bis (2-butoxyethyl) thiophosphate provided in accordance with an embodiment of the present invention³¹A spectrum P;

FIG. 4 is an infrared spectrum of ammonium bis (2-butoxyethyl) thiophosphate provided in accordance with an embodiment of the present invention;

FIG. 5 shows NMR spectra of ammonium bis (2-propoxyethyl) thiophosphate provided in accordance with an embodiment of the present invention¹H, spectrogram;

FIG. 6 shows NMR spectra of ammonium bis (2-propoxyethyl) thiophosphate provided in accordance with an embodiment of the present invention¹³C spectrum；

FIG. 7 shows NMR spectra of ammonium bis (2-propoxyethyl) thiophosphate provided in accordance with an embodiment of the present invention³¹A spectrum P;

FIG. 8 is an infrared spectrum of ammonium bis (2-propoxyethyl) thiophosphate provided in accordance with an embodiment of the present invention;

FIG. 9 is a flow diagram of a single mineral flotation process provided by an embodiment of the present invention;

FIG. 10 is a flow chart of the flotation process of lead-zinc ore;

FIG. 11 is a graph comparing surface tension and surfactant concentration of ammonium bis (2-butoxyethyl) thiophosphate and ammonium dibutyldithiophosphate provided in accordance with an embodiment of the present invention.

Detailed Description

In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited to the following specific embodiments.

Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.

Example 1

Preparation of ammonium bis (2-butoxyethyl) thiophosphate collector:

adding 23.64 parts of ethylene glycol n-butyl ether into a reactor, slowly adding 13.08 parts of phosphorus pentasulfide, heating to about 85 ℃, reacting for 3 hours under a stirring state, and reacting to obtain black oily liquid. 6.81 parts of 25 percent ammonia water solution is filled into a constant pressure dropping funnel, slowly dropped into a reactor, reacts violently, white precipitate is generated after the reaction is finished, and white solid, namely the ammonium bis (2-butoxyethyl) thiophosphate, is obtained by filtering and reduced pressure distillation.

Purifying the obtained ammonium bis (2-butoxyethyl) thiophosphate, and then characterizing the ammonium bis (2-butoxyethyl) thiophosphate by nuclear magnetic resonance¹H、¹³C and³¹the figure P is respectively shown in figure 1, figure 2 and figure 3, the infrared spectrogram is shown in figure 4, the nuclear magnetic resonance wave spectrum analysis of the target product is shown in table 1, and the infrared spectrum analysis of the target product is shown in table 2.

TABLE 1 nuclear magnetic resonance bopp analysis of ammonium bis (2-butoxyethyl) thiophosphate

TABLE 2 Infrared spectroscopic analysis of ammonium bis (2-butoxyethyl) thiophosphate

Example 2

Preparation of ammonium bis (2-butoxyethyl) thiophosphate collector:

118.17 parts of ethylene glycol n-butyl ether is added into a reactor, 60.4 parts of phosphorus pentasulfide is slowly added, the temperature is raised to about 90 ℃, the mixture reacts for 4 hours under the stirring state, and black oily liquid is obtained after the reaction. 34.06 parts of 25% ammonia water solution is filled into a constant pressure dropping funnel, slowly dropped into a reactor, reacted violently, white precipitate is generated after the reaction is finished, and white solid obtained by filtering and reduced pressure distillation is the ammonium bis (2-butoxyethyl) thiophosphate.

Example 3

Preparation of ammonium bis (2-propoxyethyl) thiophosphate collector:

adding 63.12 parts of ethylene glycol propyl ether into a reactor, slowly adding 33.68 parts of phosphorus pentasulfide, heating to 90 ℃, reacting for 5 hours under the stirring state, and reacting to obtain a dark green oily liquid. And (2) filling 20.44 parts of 25% ammonia water solution into a constant-pressure dropping funnel, slowly dropping the ammonia water solution into the reactor, reacting violently, generating a white precipitate after the reaction is finished, filtering, and distilling under reduced pressure to obtain a white solid, namely the di (2-propoxyethyl) ammonium thiophosphate.

Purifying the obtained ammonium di (2-propoxyethyl) thiophosphate, and then characterizing the ammonium di (2-propoxyethyl) thiophosphate by nuclear magnetic resonance¹H、¹³C and³¹the P diagram is shown in FIG. 5, FIG. 6 and FIG. 7 respectively, the infrared spectrogram is shown in FIG. 8, the nuclear magnetic resonance wave spectrum analysis of the target product is shown in Table 3, and the infrared analysis of the target product is shown in Table 4.

TABLE 3 bis (2-propoxyethyl) ammonium thiophosphate NMR Pop resolution

TABLE 4 Infrared spectroscopic analysis of ammonium bis (2-propoxyethyl) thiophosphate

Example 4

Preparation of ammonium bis (2-propoxyethyl) thiophosphate collector:

10.52 parts of ethylene glycol propyl ether is added into a reactor, 5.61 parts of phosphorus pentasulfide is slowly added, the temperature is raised to 110 ℃, the reaction is carried out for 5 hours under the stirring state, the generated waste gas is absorbed by 10 percent of NaOH solution, and the black-green oily liquid is obtained after the reaction. 3.41 parts of 25 percent ammonia water solution is filled into a constant pressure dropping funnel, slowly dropped into a reactor, reacts violently, after the reaction is finished, the solubility of the product is reduced, a certain amount of petroleum ether is added into the solution, white precipitate is generated, and the white solid obtained by filtering and reduced pressure distillation is the ammonium di (2-propoxyethyl) thiophosphate.

Application example 1

Flotation of chalcopyrite by a bis (2-butoxyethyl) ammonium thiophosphate collector:

the process flow shown in FIG. 9 is adopted to carry out the process on the chalcopyriteAnd (3) performing flotation, wherein the collecting agent is bis (2-butoxyethyl) ammonium thiophosphate, the stirring speed of a flotation machine is 1650r/min, the pH value of ore pulp is 7-8, and chalcopyrite with the granularity of 0.038-0.074 mm is subjected to flotation for 3 minutes on the premise of not adding any foaming agent. The concentration of the collecting agent and the flotation recovery rate in the process are determined, and the concentration of the collecting agent is 4 multiplied by 10^-5At mol/L, the flotation recovery rate of the chalcopyrite is 81.17%; when the concentration of the collecting agent is 5 multiplied by 10^-5The flotation recovery rate of the chalcopyrite at mol/L is 88.65 percent.

Flotation of pyrite with ammonium bis (2-butoxyethyl) thiophosphate collector:

the pyrite is floated by adopting the process flow shown in fig. 9, wherein a collecting agent is di (2-butoxyethyl) ammonium thiophosphate, the stirring speed of a flotation machine is 1650r/min, the pH value of ore pulp is 7-8, and chalcopyrite with the granularity of 0.038-0.074 mm is floated for 3 minutes on the premise of not adding any foaming agent. The concentration of the collecting agent and the flotation recovery rate in the process are determined, and when the concentration of the collecting agent is 4 multiplied by 10^-5At mol/L, the flotation recovery rate of the pyrite is only 17.94%; when the concentration of the collecting agent is 5 multiplied by 10^-5The flotation recovery rate of the pyrite at mol/L is 23.25%.

Flotation of galena with ammonium bis (2-butoxyethyl) thiophosphate collector:

carrying out flotation on the galena by adopting the process flow shown in figure 9, wherein a collecting agent is di (2-butoxyethyl) ammonium thiophosphate, the stirring speed of a flotation machine is 1650r/min, the pH value of ore pulp is 7-8, and chalcopyrite with the granularity of 0.038-0.074 mm is floated for 3 minutes on the premise of not adding any foaming agent. The concentration of the collecting agent and the flotation recovery rate in the process are determined, and when the concentration of the collecting agent is 1.5 multiplied by 10^-5When the concentration is mol/L, the flotation recovery rate of the galena is 83.41 percent; when the concentration of the collecting agent is 4 multiplied by 10^-5The flotation recovery rate of galena at mol/L is 96.50%.

Therefore, the bis (2-butoxyethyl) ammonium thiophosphate collecting agent has stronger collecting capability on chalcopyrite and galena, has weak collecting capability on the pyrite, has good selectivity, and is more beneficial to the environment-friendly low-alkali flotation process.

Application example 2

Flotation of chalcopyrite by a compound collector of di (2-butoxyethyl) ammonium thiophosphate and ethionamide:

dissolving di (2-butoxyethyl) ammonium thiophosphate and ethionamide in an aqueous solution according to the mass ratio of 3:2 to prepare a certain concentration, thus obtaining a compound collecting agent, and carrying out flotation on chalcopyrite monomineral. The chalcopyrite is floated by adopting the process flow shown in figure 9, the stirring speed of a flotation machine is 1650r/min, the pH value of ore pulp is 7-8, and the chalcopyrite with the granularity of 0.038-0.074 mm is floated for 3 minutes. The single flotation agent and the compound flotation agent are compared, the concentration and the flotation recovery rate of the collecting agent are measured, and the result is as follows: when a single ethioure ester collector is used, the concentration is 4 multiplied by 10^-5When the mol/L of the foaming agent is 5mg/L of 4-methyl-2-pentanol (MIBC), the flotation recovery rate of the chalcopyrite is 80.45 percent; when a single ammonium bis (2-butoxyethyl) thiophosphate is used in a concentration of 4X 10^-5mol/L, the flotation recovery rate of the chalcopyrite is 81.17%; when the concentration of the compound collector is 4 multiplied by 10^-5The flotation recovery rate of the chalcopyrite is up to 92.43 percent by mol/L.

Flotation of chalcopyrite by a compound collector of ammonium di (2-butoxyethyl) thiophosphate and isobutyl xanthate:

dissolving di (2-butoxyethyl) ammonium thiophosphate and isobutyl xanthate in an aqueous solution according to the mass ratio of 1:1 to prepare a certain concentration, thus obtaining a compound collector, and carrying out flotation on chalcopyrite monominerals. The chalcopyrite is floated by adopting the process flow shown in figure 9, the stirring speed of a flotation machine is 1650r/min, the pH value of ore pulp is 7-8, and the chalcopyrite with the granularity of 0.038-0.074 mm is floated for 3 minutes. The single flotation agent and the compound flotation agent are compared, the concentration and the flotation recovery rate of the collecting agent are measured, and the result is as follows: when a single isobutyl xanthate collector is used, the concentration is 5X 10^-5When the mol/L is reached and the MIBC dosage is 8mg/L, the flotation recovery rate of the chalcopyrite is 74.67 percent; when a single ammonium bis (2-butoxyethyl) thiophosphate is used at a concentration of 5X 10^-5When mol/L is reached, the flotation recovery rate of the chalcopyrite is 88.65 percent; when the concentration of the compound collector is 5 multiplied by 10^{- 5}At mol/L, flotation of chalcopyriteThe yield is up to 93.43%.

Therefore, when the bis (2-butoxyethyl) ammonium thiophosphate is mixed with other collectors to serve as the compound collector, the collecting capacity of the compound collector is far higher than that of a single collector, and a foaming agent MIBC does not need to be additionally added when the compound collector is used for carrying out flotation on minerals, so that the reagent cost can be reduced.

Application example 3

The bis (2-butoxyethyl) ammonium thiophosphate collector is applied to the flotation of certain lead zinc sulfide ores in Hunan:

in the embodiment of the invention, the lead-zinc sulfide ore in Hunan province and the main useful minerals in the raw ore are galena, marmatite, pyrite, chalcopyrite, cassiterite and the like, wherein the lead grade is 1.8-2.0%, and the zinc grade is 5.3-5.5%.

The specific process is as follows: weighing 850g of crushed raw ore (the granularity is 0.5-3 mm) each time, adding water into a small-sized ball mill for wet grinding for 8min, grinding the ore until the fineness is-0.074 mm and accounts for about 75%, transferring the ground ore pulp into a flotation tank, performing flotation operation by adopting a flow experiment of primary roughing, tertiary concentration and secondary scavenging, adopting di (2-butoxyethyl) ammonium thiophosphate as a flotation collecting agent of lead in the test, and finally respectively obtaining lead concentrate and lead tailing products, weighing the lead concentrate and the lead tailing products respectively after filtering and drying, testing the content of valuable metals, and calculating the flotation recovery rate, wherein the results of closed circuit flotation are shown in the following table 1.

TABLE 1 closed circuit flotation test results

From the results, the collecting agent obtained by the invention can finally obtain the flotation lead concentrate with the lead grade of 45.37% and the lead recovery rate of 88.83% under the closed conditions of primary roughing, tertiary concentration and secondary scavenging in lead flotation, and the zinc grade in the lead concentrate is 2.81% and the recovery rate is only 1.86%, so that the collecting agent is suitable for the preferential lead flotation process in lead-zinc sulfide ores, has weaker flotation capacity on zinc blende and shows excellent selectivity.

The method comprises the steps of carrying out surface tension measurement on bis (2-butoxyethyl) ammonium thiophosphate provided by the embodiment of the invention and a traditional collector dibutyl ammonium dithiophosphate, specifically adopting a platinum plate method on a surface tension meter with a model number of QBZY, washing the platinum plate with ethanol and distilled water in sequence before an experiment, burning the whole platinum plate with an alcohol lamp until the whole platinum plate is red, then carrying out measurement operation, and adopting an automatic operation method for surface tension measurement, wherein the result is shown in figure 11. According to the results, the surface tension of the ammonium di (2-butoxyethyl) thiophosphate and the ammonium dibutyl dithiophosphate is reduced along with the increase of the concentration of the surfactant, and the reduction range of the ammonium di (2-butoxyethyl) thiophosphate is larger than that of the ammonium dibutyl dithiophosphate in the tested concentration range, so that the novel collector has higher surface activity and is more beneficial to the formation of stable foam. In addition, with the increasing concentration, the surface tension of the ammonium bis (2-butoxyethyl) thiophosphate has an inflection point under a certain concentration, and the ammonium dibutyl dithiophosphate has no obvious change, which shows that the ammonium bis (2-butoxyethyl) thiophosphate has stronger hydrophobic property than the traditional collector.

While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.