Process for the preparation and use of oxygen-containing heterocyclic aliphatic flotation reagents

Abstract

The application provides a preparation and application method of an oxygen-containing heterocyclic aliphatic flotation reagent. The application relates to the technical field of flotation reagents in mineral processing engineering. The method comprises the following steps: mixing 2-methyl-3-mercaptotetrahydrofuran, maleic anhydride and benzene, heating and reacting, then sequentially extracting with water and furan, and then placing in a high-pressure reaction kettle to react. Through a series of derivatization methods, 2-methyl-3-mercaptotetrahydrofuran is modified, functional groups are introduced, and the structure is optimized, so that an oxygen-containing heterocyclic aliphatic flotation reagent which can be used for flotation separation of antimony glance and arsenopyrite is prepared. In addition, the oxygen-containing heterocyclic aliphatic flotation reagent has the characteristics of high water solubility, strong selectivity, non-corrosiveness and strong inhibition ability to arsenopyrite, and can realize the flotation separation of antimony glance and arsenopyrite in the conventional flotation process, and can effectively solve the problem that the arsenic content in the antimony concentrate exceeds the standard due to the similar floatability of antimony glance and arsenopyrite.

Description

Technical Field

[0001] This invention relates to the field of flotation reagents in mineral processing engineering, and particularly to a method for preparing and applying an oxygen-containing heterocyclic aliphatic flotation reagent. Background Technology

[0002] Antimony is a key mineral resource in my country, and antimony-gold symbiotic deposits, as a type of complex antimony ore with high comprehensive value, present significant challenges in beneficiation. Currently, beneficiation processes for polymetallic antimony-gold sulfide ores mainly include antimony-suppressed flotation for gold and gold-suppressed flotation with a sequential priority of antimony-gold flotation, mixed antimony-gold flotation followed by mixed concentrate separation, and further separation of antimony and gold from other floatable minerals. Arsene and pyrite are the main carrier minerals for gold. The essence of antimony-gold separation is the separation of stibnite from gold-bearing arsenopyrite and pyrite. Due to the similarity of the surface properties of arsenopyrite and pyrite to stibnite, and the difficulty in controlling the flotation behavior of arsenopyrite, antimony-arsenic separation becomes difficult, resulting in high arsenic content in the antimony concentrate. This, in turn, leads to a series of problems in antimony smelting, such as high alkali consumption, long production cycles, low recovery rates, and severe environmental pollution.

[0003] Currently, various technologies and methods have been developed for the flotation separation of arsenopyrite and stibnite. These methods mainly rely on selecting appropriate collectors, frothers, and depressants, and optimizing the flotation process by adjusting parameters such as the pH and redox potential of the pulp to achieve effective separation of the two minerals. However, despite some progress, the flotation separation of arsenopyrite and stibnite still faces some challenges. On the one hand, the complexity of ore properties increases the difficulty of flotation separation. On the other hand, existing flotation reagents and processes still have certain limitations and shortcomings (such as large reagent dosages and low element selectivity), requiring further improvement and optimization. Existing arsenopyrite flotation depressants mainly include two categories: inorganic depressants and organic depressants. Inorganic depressants, such as lime and sodium sulfide, inhibit the flotation of arsenopyrite by adjusting the pH and ionic strength of the pulp. Organic depressants achieve the inhibition effect by reacting chemically with or adsorbing onto the surface of arsenopyrite, reducing its hydrophobicity. These depressants can achieve the flotation separation of arsenopyrite to a certain extent, but they often suffer from problems such as large dosages and unstable effects. Therefore, it is particularly necessary to develop new desiccant flotation inhibitors.

[0004] In view of this, it is necessary to design a method for the preparation and application of oxygen-containing heterocyclic aliphatic flotation reagents to solve the above problems. Summary of the Invention

[0005] To address the shortcomings of the existing technology, the present invention aims to provide a method for preparing and applying oxygen-containing heterocyclic aliphatic flotation reagents. By modifying the properties of the flotation reagents and introducing functional groups, efficient separation of arsenopyrite and stibnite can be achieved.

[0006] To achieve the above objectives, the present invention provides a method for preparing an oxygen-containing heterocyclic aliphatic flotation reagent, comprising the following steps:

[0007] S1. Add 2-methyl-3-mercaptofuran and maleic anhydride to benzene in a predetermined ratio, heat to a first predetermined temperature, and maintain the temperature within the range of the first predetermined temperature for a first predetermined time.

[0008] S2. Add water to the material from step S1 for extraction, and collect the aqueous phase to obtain product A;

[0009] S3. Add furan to product A and extract again, and collect the organic phase; then dry and dehydrate the organic phase to obtain product B;

[0010] S4. Add the product B into the high-pressure reactor, purge the air in the system with nitrogen, slowly purge the nitrogen in the system under negative pressure, and then slowly introduce hydrogen until the pressure in the reactor reaches 8-10 MPa, then stop introducing hydrogen.

[0011] S5. After raising the temperature inside the reactor to a second predetermined temperature, and maintaining the temperature within the range of the second predetermined temperature for a second predetermined time, an oxygen-containing heterocyclic aliphatic flotation reagent is obtained.

[0012] Further, in step S1, the predetermined ratio of 2-methyl-3-mercaptofuran to maleic anhydride is a molar ratio of 1:3 to 5; and the volume ratio of 2-methyl-3-mercaptofuran to benzene is 1:1.75 to 9.

[0013] Furthermore, in step S1, the first predetermined temperature is 30-35°C; the first predetermined time is 24-36 hours.

[0014] Furthermore, the volume ratio of benzene in step S1 to water in step S2 is 2-10:1-5.

[0015] Furthermore, in step S3, the volume ratio of furan to product A is 3 to 5:1.

[0016] Furthermore, in step S3, the reagent used for drying and dehydration includes anhydrous sodium sulfate.

[0017] Furthermore, in step S4, the high-pressure reactor is equipped with a sponge nickel mesh.

[0018] Furthermore, in step S5, the second predetermined temperature is 100-150°C; the second predetermined time is 4-8 hours.

[0019] This invention also provides a method for applying the oxygen-containing heterocyclic aliphatic flotation reagent prepared by the aforementioned method, comprising the following steps:

[0020] Sa, add the oxygen-containing heterocyclic aliphatic flotation reagent, lead nitrate, thiouric acid ester, and MIBC sequentially to the target antimony ore slurry with a concentration of 25-30%; stir for a certain period of time after each reagent is added.

[0021] After step Sb and step Sa are completed, flotation is carried out for 4-6 minutes to obtain antimony concentrate and tailings.

[0022] Further, in step Sa, the dosage of the oxygen-containing heterocyclic aliphatic flotation reagent is 200-500 g / t, the dosage of lead nitrate is 100-400 g / t, the dosage of thiouric acid ester is 50-150 g / t, and the dosage of MIBC is 20-40 g / t; the stirring time is 2-5 min.

[0023] The beneficial effects of this invention are:

[0024] 1. This invention provides a method for preparing an oxygen-containing heterocyclic aliphatic flotation reagent. The method involves mixing 2-methyl-3-mercaptofuran, maleic anhydride, and benzene, heating the mixture to allow it to react, then sequentially extracting it with water and furan. The target product is then placed in a high-pressure reactor for further reaction. Through this series of derivatization methods, functional groups are introduced to modify 2-methyl-3-mercaptofuran and optimize its structure. This results in an oxygen-containing heterocyclic aliphatic flotation reagent with one fixative group and two hydrophilic groups, suitable for the flotation separation of stibnite and arsenopyrite. Furthermore, the production process of the oxygen-containing heterocyclic aliphatic flotation reagent provided by this invention is easy to control, and no byproducts are produced during the preparation process.

[0025] 2. The present invention provides an application method for an oxygen-containing heterocyclic aliphatic flotation reagent. During the flotation process, the oxygen-containing heterocyclic aliphatic flotation reagent has the characteristics of high water solubility, strong selectivity, and non-corrosiveness, enabling efficient flotation separation of stibnite and arsenopyrite in conventional flotation processes. Furthermore, the oxygen-containing heterocyclic aliphatic flotation reagent has a strong inhibitory effect on arsenopyrite, effectively solving the problem of excessive arsenic content in antimony concentrate caused by the similar floatability of stibnite and arsenopyrite. Attached Figure Description

[0026] Figure 1 This is a schematic flowchart illustrating the application method of an oxygen-containing heterocyclic aliphatic flotation reagent provided in Example 1. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0028] It should also be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and / or processing steps closely related to the present invention are shown in the accompanying drawings, while other details that are not closely related to the present invention are omitted.

[0029] Additionally, it should be noted that the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0030] A method for preparing an oxygen-containing heterocyclic aliphatic flotation reagent includes the following steps:

[0031] S1. Add 2-methyl-3-mercaptofuran and maleic anhydride to benzene according to a predetermined ratio, heat to 30-35°C, and maintain the temperature within the range of 30-35°C for 24-36 hours.

[0032] S2. Add water to the material from step S1 for extraction, and collect the aqueous phase to obtain product A;

[0033] S3. Add furan to product A and extract again, and collect the organic phase; then dry the organic phase with anhydrous sodium sulfate to obtain product B; the volume ratio of furan to product A is 3-5:1.

[0034] S4. Add the product B into the high-pressure reactor, purge the air in the system with nitrogen, slowly purge the nitrogen in the system under negative pressure, and then slowly introduce hydrogen until the pressure in the reactor reaches 8-10 MPa, then stop introducing hydrogen.

[0035] S5. After raising the temperature inside the reactor to a second predetermined temperature, and maintaining the temperature within the range of the second predetermined temperature for a second predetermined time, an oxygen-containing heterocyclic aliphatic flotation reagent is obtained.

[0036] With this setup, functional groups are introduced through a series of derivatization methods to modify 2-methyl-3-mercaptofuran and optimize its structure, thereby preparing an oxygen-containing heterocyclic aliphatic flotation reagent that can be used for the flotation separation of stibnite and arsenopyrite.

[0037] Specifically, in some embodiments of the present invention, in step S1, the predetermined ratio of 2-methyl-3-mercaptofuran to maleic anhydride is a molar ratio of 1:3 to 5; the volume ratio of 2-methyl-3-mercaptofuran to benzene is 1:1.75 to 9; and the volume ratio of benzene in step S1 to water in step S2 is 2 to 10:1 to 5.

[0038] With this setup, too little 2-methyl-3-mercaptofuran will affect the efficiency of the synthesis; too much will increase the cost.

[0039] Specifically, in some embodiments of the present invention, in step S4, the high-pressure reactor is equipped with a sponge nickel mesh.

[0040] This setup allows nickel to act as a catalyst during the modification of 2-methyl-3-mercaptofuran by adding it to the high-pressure reactor.

[0041] Specifically, in some embodiments of the present invention, in step S5, the temperature inside the reactor is raised to a predetermined temperature of 100-150°C; the second predetermined time is 4-8 hours.

[0042] This invention provides a method for applying an oxygen-containing heterocyclic aliphatic flotation reagent, comprising the following steps:

[0043] Sa, add the oxygen-containing heterocyclic aliphatic flotation reagent, lead nitrate, thiouric acid ester, and MIBC sequentially to the target antimony ore slurry with a concentration of 25-30%; stir for a certain period of time after each reagent is added.

[0044] After step Sb and step Sa are completed, flotation is carried out for 4-6 minutes to obtain antimony concentrate and tailings.

[0045] Specifically, in some embodiments of the present invention, in step Sa, the dosage of the oxygen-containing heterocyclic aliphatic flotation reagent is 200-500 g / t, the dosage of lead nitrate is 100-400 g / t, the dosage of thiouric acid ester is 50-150 g / t, and the dosage of MIBC is 20-40 g / t; the stirring time is 2-5 min.

[0046] This setup allows the prepared oxygen-containing heterocyclic aliphatic flotation reagent to possess one fixative group and two hydrophilic groups. After the fixative group acts on the surface of arsenopyrite, the oxygen-containing heterocycle can further chelate with the arsenopyrite, enhancing the reagent's effect on the arsenopyrite. Furthermore, the presence of the two hydrophilic groups further strengthens the hydrophilicity of the arsenopyrite surface, widening the difference in surface properties between arsenopyrite and stibnite, thus effectively achieving flotation separation of arsenopyrite and stibnite. During the flotation process, the oxygen-containing heterocyclic aliphatic flotation reagent, due to its high water solubility, strong selectivity, and non-corrosiveness, can achieve flotation separation of stibnite and arsenopyrite in conventional flotation processes. Moreover, the oxygen-containing heterocyclic aliphatic flotation reagent also has a strong inhibitory effect on arsenopyrite, effectively solving the problem of excessive arsenic content in antimony concentrate caused by the similar floatability of stibnite and arsenopyrite.

[0047] The following describes the working principle of the preparation and application method of an oxygen-containing heterocyclic aliphatic flotation reagent provided by the present invention:

[0048] Example 1

[0049] This embodiment provides a method for preparing and applying an oxygen-containing heterocyclic aliphatic flotation reagent, including the following steps:

[0050] S1. Add 1 mol of 2-methyl-3-mercaptofuran and 4 mol of maleic anhydride to 200 ml of benzene, heat to 30 °C, and react for 30 h.

[0051] S2. Add 100ml of water to the material in step S1 for extraction, and collect the aqueous phase to obtain product A;

[0052] S3. Add furan to product A and extract again, and collect the organic phase; then dry the organic phase with anhydrous sodium sulfate to obtain product B; the furan content is 1500 mL;

[0053] S4. Add product B into a high-pressure reactor with a built-in nickel sponge mesh. After purging the air in the system with nitrogen, slowly purge the nitrogen from the system under negative pressure, and then slowly introduce hydrogen until the pressure gauge of the reactor shows that the internal pressure reaches 9 MPa. Then close the hydrogen valve and stop introducing hydrogen.

[0054] S5. Heat the reactor to 130℃ (±5℃), then maintain the temperature within the system within the range of 130℃ (±5℃) and react for 6 hours to obtain the oxygen-containing heterocyclic aliphatic flotation reagent.

[0055] This embodiment also provides an application method for the oxygen-containing heterocyclic aliphatic flotation reagent prepared according to the above method, such as... Figure 1 As shown, it includes the following steps:

[0056] This embodiment uses a complex antimony-gold mine with high arsenic content as the research object. The original ore contains 3.64% antimony and 1.80% arsenic. Antimony mainly exists in the form of stibnite, followed by antimony oxide, with an antimony oxidation rate of 5%. Arsenic mainly exists in the form of arsenopyrite, and other metal sulfides are mainly pyrite and pyrrhotite. The gangue minerals in the ore are mainly quartz and pyroxene silicate minerals, followed by feldspar, dolomite, etc.

[0057] Sa, the above-mentioned high-arsenic antimony gold ore and an equal mass of water are placed in a wet ball mill for grinding, and the content of the grinding product with a particle size of -0.074mm is controlled at 70%, and the solid phase concentration of the raw ore slurry is adjusted to 28%; the oxygen-containing heterocyclic aliphatic flotation reagent at a dosage of 200g / t, lead nitrate at a dosage of 200g / t, thiouric acid ester at a dosage of 100g / t, and MIBC at a dosage of 20g / t are added sequentially to the raw ore slurry with a concentration of 28%; after each reagent is added, the mixture is stirred for 3min.

[0058] After step Sb and step Sa are completed, flotation is performed for 5 minutes to obtain antimony concentrate and tailings.

[0059] Comparative Example 1

[0060] Comparative Example 1 provides a method for beneficiating complex antimony-gold ore with high arsenic content. The difference between Comparative Example 1 and Example 2 is that the flotation depressant used in step Sa is different: in Comparative Example 1, the oxygen-containing heterocyclic aliphatic flotation reagent is replaced with sodium metabisulfite. The remaining steps and parameters are the same as in Example 1 and will not be repeated here.

[0061] Comparative Example 2

[0062] Comparative Example 2 provides a method for beneficiating complex antimony-gold ore with high arsenic content. The difference between Comparative Example 2 and Example 1 lies in the flotation depressant used in step Sa: Comparative Example 2 replaces the oxygen-containing heterocyclic aliphatic flotation reagent with tannin. The remaining steps and parameters are consistent with Example 1 and will not be repeated here.

[0063] Comparative Example 3

[0064] Comparative Example 3 provides a method for beneficiating complex antimony-gold ore with high arsenic content. The difference from Example 1 lies in the flotation depressant used in step Sa: Comparative Example 3 replaces the oxygen-containing heterocyclic aliphatic flotation reagent with sodium mercaptoacetate. The remaining steps and parameters are consistent with Example 1 and will not be repeated here.

[0065] The experimental results of Examples 1 and Comparative Examples 1-3 are shown in Table 1. It can be seen that, under the same reagent dosage, the arsenic content in the antimony concentrate is the lowest, only 0.81%, when the oxygen-containing heterocyclic aliphatic flotation reagent prepared in this invention is used as the arsenopyrite depressant. In contrast, when sodium metabisulfite, tannin, and sodium thioglycolate, three conventional arsenopyrite depressants, the arsenic content in the antimony concentrate exceeds 2%. This shows that the depressant of this invention has a strong inhibitory effect on arsenopyrite and can solve the problem of excessive arsenic content in antimony concentrate due to the similar floatability of stibnite and arsenopyrite.

[0066] Table 1. Test results of Example 1 and Comparative Examples 1-3

[0067]

[0068] In summary, this invention provides a method for preparing and applying an oxygen-containing heterocyclic aliphatic flotation reagent. The method involves mixing 2-methyl-3-mercaptofuran, maleic anhydride, and benzene, heating the mixture to allow it to react, followed by extraction with water and then furan. The target product is then reacted in a high-pressure reactor. Through this series of derivatization methods, functional groups are introduced to modify 2-methyl-3-mercaptofuran and optimize its structure, thereby preparing an oxygen-containing heterocyclic aliphatic flotation reagent with one fixative group and two hydrophilic groups. The production process of the oxygen-containing heterocyclic aliphatic flotation reagent provided by this invention is easy to control, and there are no byproducts during preparation. Furthermore, because the prepared oxygen-containing heterocyclic aliphatic flotation reagent has one fixative group and two hydrophilic groups, the fixative group, after acting on the surface of arsenopyrite, allows the oxygen-containing heterocycle to further chelate with arsenopyrite, enhancing the reagent's effect on arsenopyrite. Furthermore, the presence of amphiphilic groups further enhances the hydrophilicity of the arsenopyrite surface, widening the difference in surface properties between arsenopyrite and stibnite, thus enabling effective flotation separation of the two minerals. During the flotation process, the oxygen-containing heterocyclic aliphatic flotation reagents used possess high water solubility, strong selectivity, and non-corrosiveness, enabling efficient flotation separation of stibnite and arsenopyrite in conventional flotation processes. Moreover, the oxygen-containing heterocyclic aliphatic flotation reagents also have a strong inhibitory effect on arsenopyrite, effectively solving the problem of excessive arsenic content in antimony concentrate caused by the similar floatability of stibnite and arsenopyrite.

[0069] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing an oxygen-containing heterocyclic aliphatic flotation reagent, characterized in that, Includes the following steps: S1. Add 2-methyl-3-mercaptofuran and maleic anhydride to benzene in a predetermined ratio, heat to a first predetermined temperature, and maintain the temperature within the range of the first predetermined temperature for a first predetermined time. S2. Add water to the material from step S1 for extraction, and collect the aqueous phase to obtain product A; S3. Add furan to product A and extract again, and collect the organic phase; then dry and dehydrate the organic phase to obtain product B; S4. Add the product B into the high-pressure reactor, purge the air in the system with nitrogen, slowly purge the nitrogen in the system under negative pressure, and then slowly introduce hydrogen until the pressure in the reactor reaches 8-10 MPa, then stop introducing hydrogen. S5. After raising the temperature inside the reactor to a second predetermined temperature, and maintaining the temperature within the range of the second predetermined temperature for a second predetermined time, an oxygen-containing heterocyclic aliphatic flotation reagent is obtained.

2. The method for preparing the oxygen-containing heterocyclic aliphatic flotation reagent according to claim 1, characterized in that: In step S1, the predetermined ratio of 2-methyl-3-mercaptofuran to maleic anhydride is a molar ratio of 1:3 to 5; the volume ratio of 2-methyl-3-mercaptofuran to benzene is 1:1.75 to 9.

3. The method for preparing the oxygen-containing heterocyclic aliphatic flotation reagent according to claim 1, characterized in that: In step S1, the first predetermined temperature is 30-35°C; the first predetermined time is 24-36 hours.

4. The method for preparing the oxygen-containing heterocyclic aliphatic flotation reagent according to claim 1, characterized in that: The volume ratio of benzene in step S1 to water in step S2 is 2-10:1-5.

5. The method for preparing the oxygen-containing heterocyclic aliphatic flotation reagent according to claim 1, characterized in that: In step S3, the volume ratio of furan to product A is 3 to 5:

1.

6. The method for preparing the oxygen-containing heterocyclic aliphatic flotation reagent according to claim 1, characterized in that: In step S3, the reagents used for drying and dehydration include anhydrous sodium sulfate.

7. The method for preparing the oxygen-containing heterocyclic aliphatic flotation reagent according to claim 1, characterized in that: In step S4, the high-pressure reactor is equipped with a sponge nickel mesh.

8. The method for preparing the oxygen-containing heterocyclic aliphatic flotation reagent according to claim 1, characterized in that: In step S5, the second predetermined temperature is 100-150℃; the second predetermined time is 4-8h.

9. A method for applying an oxygen-containing heterocyclic aliphatic flotation reagent prepared by the preparation method according to any one of claims 1 to 8, characterized in that, Includes the following steps: Sa, add the oxygen-containing heterocyclic aliphatic flotation reagent, lead nitrate, thiouric acid ester, and MIBC sequentially to the target antimony ore slurry with a concentration of 25-30%; stir for a certain period of time after each reagent is added. After step Sb and step Sa are completed, flotation is carried out for 4-6 minutes to obtain antimony concentrate and tailings.

10. The method of applying the oxygen-containing heterocyclic aliphatic flotation reagent according to claim 9, characterized in that: In step Sa, the dosage of the oxygen-containing heterocyclic aliphatic flotation reagent is 200-500 g / t, the dosage of lead nitrate is 100-400 g / t, the dosage of thiouric acid ester is 50-150 g / t, and the dosage of MIBC is 20-40 g / t; the stirring time is 2-5 min.

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