CN113929820A

CN113929820A - Sulfide ore inhibitor and preparation method and use method thereof

Info

Publication number: CN113929820A
Application number: CN202111358999.3A
Authority: CN
Inventors: 李明阳; 杨诚; 张晨; 高翔鹏
Original assignee: Anhui University of Technology AHUT
Current assignee: Anhui University of Technology AHUT
Priority date: 2021-11-17
Filing date: 2021-11-17
Publication date: 2022-01-14

Abstract

The invention discloses a sulfide ore inhibitor, a preparation method and a use method thereof, belonging to the field of beneficiation. The sulfide ore inhibitor is a modified sodium alginate inhibitor AM/SA/TSC prepared by graft polymerization by taking sodium alginate SA as a grafting substrate, acrylamide AM and thiosemicarbazide TSC as grafting monomers, ammonium persulfate APS as an initiator and N, N' -methylene bisacrylamide MBAM as a cross-linking agent. Aiming at the current situation that the flotation separation effect of sulfide ore still needs to be optimized, the inhibitor modified by macromolecular organic inhibitor sodium alginate is adopted, so that the selectivity is better, the inhibition effect is stronger, the dosage is less, and the method has outstanding practical application value.

Description

Sulfide ore inhibitor and preparation method and use method thereof

Technical Field

The invention relates to the technical field of beneficiation, in particular to a sulfide ore inhibitor modified by a macromolecular organic inhibitor sodium alginate, a preparation method and a use method thereof.

Background

With the rapid development of national industry, the demand for ore is also rapidly increasing. However, with the huge ore consumption, single complex ore is increasingly reduced, ore resources gradually show the characteristics of poor quality, fineness and impurities, and the ore dressing operation is increasingly difficult. Therefore, the flotation process becomes a key ring in the mineral separation operation, the depressor is used as the most commonly used medicament in the flotation industry, and the important factor determining the quality of the flotation process is selected when the high-efficiency depressor is selected.

The main metal minerals in common sulfide ores comprise chalcopyrite, galena, sphalerite, molybdenite, pyrite and the like, which are symbiotic with each other in most cases, and gangue minerals mainly comprise quartz and sericite, and chlorite, gypsum and carbonate minerals. Most sulphide ores have similar hydrophobicity, and the inhibitor has the function of changing the hydrophobicity of the sulphide ores, so that the hydrophobicity difference between the surfaces of the ores is changed, and the flotation separation of the ores is promoted.

Through search, the application number 2010101980831 discloses a sulfide ore flotation layered silicate mineral inhibitor and a preparation method thereof, wherein the inhibitor is prepared from the following components in parts by weight: 0-20 parts of modified corn starch, 8-30 parts of sodium alginate, 1-35 parts of carboxymethyl cellulose or polyanionic cellulose or methylene dinaphthalene sulfonate and 5-55 parts of sodium hexametaphosphate. The preparation process comprises the following steps: the reagent is selected according to the type of the mineral to be inhibited, and is added into a high-speed mixing granulator according to a set proportion for granulation, and then drying is carried out, thus obtaining the specific inhibitor for the sulfide ore flotation phyllosilicate mineral. The inhibitor is mainly applied to inhibiting layered silicate minerals such as talc, serpentine, chlorite, kaolinite and the like during sulfide ore flotation, is favorable for improving the flotation concentrate grade and the metal recovery rate, and is particularly suitable for flotation of talc-containing molybdenite and nickel sulfide minerals.

Application No. 2017800754265 discloses depressant compositions and methods for depressing gangue sulfide minerals during the flotation of sulfide ores, the depressant compositions comprising a blend of one or more acrylamide/allylthiourea polymers as a first depressant and one or more carboxyalkyldithiocarbamate compounds as a second depressant, and the use of these compositions as depressants in the beneficiation of sulfide minerals of ores and/or concentrates, as well as methods for selectively separating valuable sulfide minerals from non-valuable sulfide minerals for recovery of such valuable minerals in a froth flotation process. The above applications relate to the research of different flotation inhibitors, the specific effects in practical application are different, and the development of the flotation inhibitors in the industry is continuous all the time and gradually focuses on different development directions.

Disclosure of Invention

1. Technical problem to be solved by the invention

The invention aims to provide a sulfide ore inhibitor and a preparation method and a use method thereof aiming at the current situation that the flotation separation effect of sulfide ore still needs to be optimized.

2. Technical scheme

In order to achieve the purpose, the technical scheme provided by the invention is as follows:

the invention relates to a sulfide ore inhibitor, which is a modified sodium alginate inhibitor AM/SA/TSC prepared by graft polymerization by taking sodium alginate SA as a grafting substrate, acrylamide AM and thiosemicarbazide TSC as grafting monomers, ammonium persulfate APS as an initiator and N, N' -methylene bisacrylamide MBAM as a cross-linking agent.

The synthesis method is represented by the following formula:

wherein M refers to acrylamide AM and thiosemicarbazide TSC.

Furthermore, the modified sodium alginate inhibitor comprises the following two functional group structures:

the preparation method of the sulfide ore inhibitor comprises the following steps:

s1, fully stirring and dissolving sodium alginate powder in a water bath at constant temperature to form a sodium alginate solution;

adding sodium alginate powder into a three-necked bottle, adding deionized water, and stirring for 1-3h at constant temperature of 50-60 deg.C in water bath to dissolve the sodium alginate powder sufficiently to form a pure and transparent sodium alginate solution;

s2, adding ammonium persulfate into the sodium alginate solution, uniformly stirring, then sequentially adding acrylamide, thiosemicarbazide and N, N' -methylene bisacrylamide, keeping a water bath heating environment for reaction, cooling the solution to room temperature after obvious precipitation occurs, filtering the suspension, and washing and drying the precipitate to obtain target product powder;

specifically, ammonium persulfate APS is added and stirred for 15-20min, then acrylamide AM, thiosemicarbazide TSC and N, N' -methylenebisacrylamide MBAM are sequentially added, and the mass ratio of the acrylamide AM to the thiosemicarbazide TSC to the sodium alginate SA is 2-2.5: 0.5-1: 1; the adding mass of the ammonium persulfate APS and the adding mass of the N, N' -methylene bisacrylamide MBAM are respectively 0.05-0.07% and 0.08-0.1% of that of the acrylamide AM. Heating in a water bath, keeping the temperature at 50-70 ℃ and reacting for 3-5h, wherein the precipitation amount of the target product AM/SA/TSC is increased along with the increase of the reaction time; and after obvious precipitation of the solution occurs, cooling to room temperature, filtering the suspension, washing for three times by using absolute ethyl alcohol, and drying for 2-4 hours in a vacuum drying oven at 50-60 ℃ to obtain the target product AM/SA/TSC white powder.

Furthermore, the mass ratio of the acrylamide to the thiosemicarbazide to the sodium alginate added into the solution is 2-2.5: 0.5-1: 1.

furthermore, the adding mass of the ammonium persulfate and the N, N' -methylene-bisacrylamide in the solution is respectively 0.05-0.07% and 0.08-0.1% of that of the acrylamide.

Further, in S1, adding sodium alginate powder into deionized water, and stirring for 1-3h at constant temperature of 50-60 deg.C in water bath to dissolve sodium alginate powder sufficiently to form pure and transparent sodium alginate solution.

Furthermore, in S2, the reaction is carried out for 3-5h by heating in a water bath and keeping the temperature at 50-70 ℃, and the precipitation amount increases along with the increase of the reaction time; washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 50-60 ℃ for 2-4h to obtain target product powder.

The acrylamide AM and the thiosemicarbazide TSC of the present invention are compounds having the following structures:

the amide group of acrylamide AM can form hydrogen bond with water molecule, so the water solubility of the polymer containing the amide group is generally better, and the polymer can form a hydrophilic layer on the surface of the mineral surface when being adsorbed on the mineral surface, thereby playing a role in inhibiting. Thiourea groups in the thiosemicarbazide TSC oxidize the chalcopyrite surface to produce cu (TSC) with hydrophobic properties. As the pH increases, the hydrophobicity of the chalcopyrite surface increases and passivation occurs such that the chalcopyrite surface becomes more hydrophobic. Sodium alginate SA is a natural organic macromolecular polysaccharide substance, and sodium alginate molecules contain chelating groups such as hydroxyl, carboxyl and the like, so that the sodium alginate SA can generate a chelating reaction with metal ions on the surface of a mineral, and has the potential of becoming a novel organic inhibitor.

The use method of the sulfide ore inhibitor is characterized in that the inhibitor as defined in any one of claims 1-7 is added in the sulfide ore flotation separation process, the dosage of the inhibitor is 20-50 mg/L, and the pH value is controlled to be 8-11 in the flotation separation process.

Furthermore, in the process of flotation separation of the sulphide ores, a pH regulator and an activating agent are added, and the flotation separation is carried out by using a collecting agent, wherein the types of the added collecting agent comprise isopropyl ethyl ester IPETC and isobutyl methyl xanthate KIBX, the added activating agent comprises methyl isobutyl carbinol MIBC, and the dosages of the collecting agent and the activating agent are respectively 50-100 mg/L.

Further, the sulfide ore species to which the inhibitor is applied include pyrite, chalcopyrite, galena, molybdenite and sphalerite.

3. Advantageous effects

Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:

according to the sulfide ore inhibitor, sodium alginate is used as a grafting substrate, acrylamide and thiosemicarbazide are used as grafting monomers, ammonium persulfate is used as an initiator, N, N' -methylene bisacrylamide is used as a cross-linking agent, and the modified sodium alginate inhibitor is prepared through graft polymerization; active amide groups and anionic carboxyl groups carried on a high molecular chain can perform various physical and chemical reactions with the surface of the ore, so that the ore has high molecular chain characteristics and excellent surface activity, and can be widely applied to separation and beneficiation processes of multi-metal sulfide ore combinations such as pyrite, blende, galena and the like, so as to improve separation indexes.

Detailed Description

For a further understanding of the present invention, reference will now be made in detail to the following examples.

Example 1

The sulfide ore inhibitor is a modified sodium alginate inhibitor AM/SA/TSC prepared by graft polymerization by using sodium alginate SA as a grafting substrate, acrylamide AM and thiosemicarbazide TSC as grafting monomers, ammonium persulfate APS as an initiator and N, N' -methylenebisacrylamide MBAM as a cross-linking agent.

The preparation method of the sulfide ore inhibitor of the embodiment comprises the following steps:

s1, weighing 5g of sodium alginate SA powder, adding into a three-necked bottle, adding 150ml of deionized water, and stirring for 1h under the condition of constant temperature of water bath and 50 ℃ to fully dissolve the SA powder to form a pure and transparent SA solution;

s2, adding ammonium persulfate APS into the sodium alginate SA solution, uniformly stirring for 15min, and then sequentially adding acrylamide AM, thiosemicarbazide TSC and N, N' -methylene bisacrylamide MBAM, wherein the mass ratio of the acrylamide AM to the thiosemicarbazide TSC to the sodium alginate SA is 2: 0.5: 1, adding ammonium persulfate APS and N, N' -methylene bisacrylamide MBAM by mass respectively accounting for 0.05 percent and 0.08 percent of the acrylamide AM; the reaction is carried out for 3h under the condition of keeping the temperature at 50 ℃ by heating in a water bath. The precipitation amount of the target product AM/SA/TSC increases along with the increase of the reaction time, the solution is cooled to room temperature after obvious precipitation, the suspension is filtered, washed with absolute ethyl alcohol for three times and dried in a vacuum drying oven at 50 ℃ for 3 hours, and white powder of the target product AM/SA/TSC is obtained.

The usage method of the sulfide ore inhibitor of the embodiment includes that a certain amount of chalcopyrite and galena are taken and crushed to the particle size range of 323-plus 200 meshes, the chalcopyrite and the galena are placed into an ultrasonic bath to be cleaned once, and the chalcopyrite and the galena are placed into an oven to be dried, cooled to room temperature and stored for later use. And (3) mixing the dried chalcopyrite and galena in a mass ratio of 3: 2 is placed in the flotation tank and stirred for 2min while adding the pH regulator sodium hydroxide and the activator MIBC so that the pH in the flotation tank is maintained at 8. And continuously stirring for 2min, adding the modified sodium alginate inhibitor AM/SA/TSC prepared above, and stirring for 2 min. Adding a collecting agent PIETC, inflating and stirring for 2min, scraping and soaking for 4min, and performing flotation separation. When the dosage of the modified sodium alginate inhibitor AM/SA/TSC is 20.0mg/L, and the concentration of the collecting agent PIETC and the activating agent MIBC is 50mg/L, the recovery rate of the plumbite can reach 80%, and the recovery rate of the chalcopyrite is only 8.5%.

Example 2

The sulfide ore inhibitor of this example is substantially the same as example 1, except that the specific process for preparation is as follows:

s1, weighing 7.5g of sodium alginate SA powder, adding into a three-necked bottle, adding 150ml of deionized water, and stirring for 2 hours under the conditions of constant temperature of water bath and 55 ℃ to fully dissolve the SA powder to form a pure and transparent SA solution;

s2, adding ammonium persulfate APS into the sodium alginate SA solution, uniformly stirring for 16min, and then sequentially adding acrylamide AM, thiosemicarbazide TSC and N, N' -methylenebisacrylamide MBAM, wherein the mass ratio of the acrylamide AM to the thiosemicarbazide TSC to the sodium alginate SA is 2.5: 0.75: 1, the adding mass of ammonium persulfate APS and N, N' -methylene bisacrylamide MBAM respectively accounts for 0.07 percent and 0.09 percent of that of acrylamide AM; heating in water bath to keep the temperature at 60 ℃ and reacting for 5 h. The precipitation amount of the target product AM/SA/TSC increases along with the increase of the reaction time, the solution is cooled to room temperature after obvious precipitation, the suspension is filtered, washed with absolute ethyl alcohol for three times and dried in a vacuum drying oven at 55 ℃ for 2 hours, and white powder of the target product AM/SA/TSC is obtained.

The usage method of the sulfide ore inhibitor in the embodiment includes that a certain amount of chalcopyrite and sphalerite are taken and crushed to the particle size range of 323-minus 200 meshes, the chalcopyrite and the sphalerite are placed into an ultrasonic bath to be cleaned once, and the chalcopyrite and the sphalerite are placed into an oven to be dried, cooled to room temperature and stored for later use. And (3) mixing the dried chalcopyrite and the sphalerite in a mass ratio of 1: 1 is placed in a flotation tank, and the pH regulator sodium hydroxide and the activator MIBC are added during 2min of stirring, so that the pH in the flotation tank is maintained at 11. And continuously stirring for 2min, adding the modified sodium alginate inhibitor AM/SA/TSC prepared above, and stirring for 2 min. Adding collecting agent of isobutyl methyl yellow KIBX, stirring with gas for 2min, scraping and soaking for 4min, and performing flotation separation. When the dosage of the modified sodium alginate inhibitor AM/SA/TSC is 30.0mg/L, and the concentration of the collector isobutyl methyl xanthate KIBX and the activator MIBC is 60mg/L, the recovery rate of zinc blende can reach 80%, and the recovery rate of chalcopyrite is only 10%.

Example 3

s1, weighing 10g of sodium alginate SA powder, adding into a three-necked bottle, adding 150ml of deionized water, and stirring for 3 hours at the constant temperature of 60 ℃ in a water bath to fully dissolve the SA powder to form a pure and transparent SA solution;

s2, adding ammonium persulfate APS into the sodium alginate SA solution, uniformly stirring for 20min, and then sequentially adding acrylamide AM, thiosemicarbazide TSC and N, N' -methylenebisacrylamide MBAM, wherein the mass ratio of the acrylamide AM to the thiosemicarbazide TSC to the sodium alginate SA is 2.2: 1: 1, the adding mass of ammonium persulfate APS and N, N' -methylene bisacrylamide MBAM respectively accounts for 0.06 percent and 0.1 percent of that of acrylamide AM; the reaction is carried out for 4h under the condition of keeping the temperature at 70 ℃ by heating in a water bath. The precipitation amount of the target product AM/SA/TSC increases along with the increase of the reaction time, the solution is cooled to room temperature after obvious precipitation, the suspension is filtered, washed with absolute ethyl alcohol for three times and dried in a vacuum drying oven at 60 ℃ for 4 hours, and white powder of the target product AM/SA/TSC is obtained.

The usage method of the sulfide ore inhibitor of the embodiment includes that a certain amount of chalcopyrite and molybdenite are taken and crushed to the particle size range of 323-minus 200 meshes, the chalcopyrite and the molybdenite are placed into an ultrasonic bath to be cleaned once, and the chalcopyrite and the molybdenite are placed into an oven to be dried, cooled to room temperature and stored for later use. And (3) mixing the dried chalcopyrite and the molybdenite in a mass ratio of 4: 3, putting the mixture into a flotation tank, and adding a pH regulator sodium hydroxide and an activating agent MIBC during stirring for 2min so as to keep the pH value in the flotation tank at 10.5. And continuously stirring for 2min, adding the modified sodium alginate inhibitor AM/SA/TSC prepared above, and stirring for 2 min. Adding a collecting agent PIETC and an activating agent MIBC, inflating and stirring for 2min, scraping and soaking for 4min, and performing flotation separation. When the dosage of the modified sodium alginate inhibitor AM/SA/TSC is 50.0mg/L, and the concentration of the collector PIETC and the activator MIBC is 100mg/L, the recovery rate of molybdenite can reach 79%, and the recovery rate of chalcopyrite is only 20%.

In conclusion, the sulfide ore inhibitor AM/SA/TS prepared by the invention is easy to physically and chemically adsorb the surface of ore by virtue of a plurality of polar groups and hydrophilic groups in the flotation separation of sulfide ore, realizes the hydrophobicity difference of the surface of ore, and can be used for the flotation separation of sulfide ore such as copper-lead separation, copper-sulfur separation, copper-molybdenum separation, lead-zinc separation and the like.

The present invention and its embodiments have been described above schematically, but the description is not limited to the embodiments of the present invention, and the present invention is not limited to these embodiments. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.

Claims

1. A sulfide ore suppressor characterized by: the inhibitor is a modified sodium alginate inhibitor prepared by graft polymerization by using sodium alginate as a grafting substrate, acrylamide and thiosemicarbazide as grafting monomers, ammonium persulfate as an initiator and N, N' -methylene bisacrylamide as a cross-linking agent.

2. The sulfide ore suppressor according to claim 1, wherein: the inhibitor comprises the following two functional group structures:

3. a preparation method of a sulfide ore inhibitor is characterized by comprising the following steps: the method comprises the following steps:

s2, adding ammonium persulfate into the sodium alginate solution, stirring uniformly, then sequentially adding acrylamide, thiosemicarbazide and N, N' -methylene bisacrylamide, keeping a water bath heating environment for reaction, cooling the solution to room temperature after obvious precipitation occurs, filtering the suspension, and washing and drying the precipitate to obtain the target product powder.

4. The method for preparing a sulfide ore inhibitor according to claim 3, wherein: the mass ratio of acrylamide, thiosemicarbazide and sodium alginate added into the solution is 2-2.5: 0.5-1: 1.

5. the method for preparing a sulfide ore inhibitor according to claim 3, wherein: the adding mass of the ammonium persulfate and the N, N' -methylene-bisacrylamide in the solution is respectively 0.05-0.07% and 0.08-0.1% of that of the acrylamide.

6. The method for preparing a sulfide ore inhibitor according to claim 3, wherein: and S1, adding sodium alginate powder into deionized water, and stirring for 1-3h at constant temperature of 50-60 ℃ in a water bath to fully dissolve the sodium alginate powder to form a pure and transparent sodium alginate solution.

7. The method for preparing a sulfide ore inhibitor according to claim 3, wherein: in S2, heating in water bath to keep the temperature at 50-70 ℃ for reaction for 3-5h, wherein the precipitation amount increases along with the increase of the reaction time; washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 50-60 ℃ for 2-4h to obtain target product powder.

8. A method for using a sulfide ore inhibitor, which is characterized by comprising the following steps: the inhibitor according to any one of claims 1 to 7 is added in the flotation separation process of the sulphide ores, the dosage of the inhibitor is 20-50 mg/L, and the pH value is controlled to be 8-11 in the flotation separation process.

9. The use method of a sulfide ore inhibitor according to claim 8, wherein: in the process of flotation separation of sulfide ores, a pH regulator and an activating agent are added, flotation separation is carried out by using the collecting agent, the types of the added collecting agent comprise isopropyl ethyl ester and isobutyl methyl xanthate, the added activating agent comprises methyl isobutyl carbinol, and the using amounts of the collecting agent and the activating agent are respectively 50-100 mg/L.

10. The use method of a sulfide ore inhibitor according to claim 8, wherein: the sulphide ore species used include pyrite, chalcopyrite, galena, molybdenite and sphalerite.