Oxygen-sulfur-nitrogen heterocyclic ring diketone compound, preparation method thereof and application of compound as talc inhibitor

Abstract

The invention discloses an oxygen-sulfur-nitrogen heterocyclic ring diketone compound, a preparation method thereof and application of the compound as a talc flotation inhibitor, and belongs to the technical field of mineral separation. The oxygen-sulfur-nitrogen heterocyclic ring diketone compound has a selective inhibition effect on flotation of talc, and is particularly suitable for flotation separation of metal sulfide ore (such as molybdenite and chalcopyrite) and talc.

Description

Technical Field

[0001] The present invention relates to an oxathiazinone dione compound, and also relates to a preparation method thereof and an application as a talc inhibitor, belonging to the technical field of mineral processing. Background Art

[0002] Flotation is an important means for enriching low-grade ores. Flotation inhibitors used in the flotation process can selectively regulate the hydrophilic and hydrophobic properties of minerals, and are one of the keys to realizing the flotation separation of valuable minerals and gangue. At present, the main inhibitors of talc are water glass and organic polymer polysaccharides, but they often also have a certain inhibitory effect on sulfide ores. Therefore, developing highly selective inhibitors has become a difficult point in this field.

[0003] Traditional inorganic inhibitors of talc include water glass and water-soluble metal salts, etc. However, they have a large dosage and also have an inhibitory effect on sulfide ores. Organic inhibitors of talc such as polysaccharides and lignins have poor effects on talc and limited inhibitory ability. Therefore, developing new talc inhibitors to effectively solve the above problems existing in existing talc inhibitors has become a research hotspot.

[0004] Literatures such as “Studies on the application of N, N-bis(phosphonomethyl)-sulfamic acid in the selective flotation separation of pyrite from serpentine”, ZHANG X G, et al. Minerals Engineering, 2022, 183: 107602, etc. found that the phosphonic acid group and sulfonic acid group in the synthesized agent can bind to the magnesium sites on the surface of serpentine, increasing the repulsive force between serpentine and pyrite, thereby eliminating the adverse effect of serpentine on the flotation of pyrite. However, so far, there have been no relevant reports on the synthesis of oxathiazinone dione compounds and their application as talc inhibitors. Summary of the Invention

[0005] Aiming at the technical problems existing in the prior art, the first object of the present invention is to provide an oxathiazinone dione compound, which has a selective inhibitory effect on the flotation of talc and is particularly suitable for the flotation separation of metal sulfide ores and talc.

[0006] The second object of the present invention is to provide a synthesis method of an oxathiazinone dione compound, which has the advantages of fast reaction speed, simple reaction process, mild reaction conditions, environmental protection and safety, simple post-treatment, and less waste generation, and meets large-scale production.

[0007] The third object of the present invention is to provide an application of an oxathiazinone compound, which is used as a talc inhibitor and can be used for the flotation separation of most metal minerals and talc, especially suitable for the separation of talc and molybdenite, and has the characteristics of low inhibitor concentration, wide pH adaptation range, and good inhibition effect.

[0008] The present invention provides an oxathiazinone compound, which has the following molecular structural formula:

[0009]

[0010] Among them, R is a C3-C8 hydrocarbon chain. The length of the hydrocarbon chain mainly affects the hydrophobicity of the oxathiazinone compound, thereby affecting its adsorption performance on the surface of talc. Preferably, R is a C4-C6 hydrocarbon chain.

[0011] The oxathiazinone compound of the present invention has a hydrophobic hydrocarbon chain with a ring structure, which has good compatibility with talc with a hydrophobic surface and is prone to hydrophobic attraction, so it adsorbs on the surface of talc. In particular, the adsorption force between this hydrophobic hydrocarbon chain with a ring structure and the surface of talc is much stronger than that of a conventional chain-like hydrocarbon chain, and the hydrophobic hydrocarbon chain with a ring structure has a sulfonic acid group, which is not easy to combine with bubbles. The sulfonic acid group is used to improve the hydrophilicity of the talc surface, so that the flotation of talc is inhibited. At the same time, the metal sulfide ore is repelled by the charge effect, and the flotation separation efficiency of talc and metal sulfide ore is improved.

[0012] The present invention also provides a synthesis method of an oxathiazinone compound, which is obtained by dropping a fatty dialdehyde solution into an amino sulfonic acid solution for condensation reaction.

[0013] Examples of the fatty dialdehyde of the present invention include: glutaraldehyde, malondialdehyde, succinaldehyde, adipic aldehyde, pimelic aldehyde, suberic aldehyde, decanedial.

[0014] Based on the fact that amino sulfonic acid itself has acidity and can ionize hydrogen ions, the present invention can catalyze the condensation reaction between it and glutaraldehyde to be completed quickly at room temperature.

[0015] Taking the synthesis of (Z)-5,6,7,8-tetrahydro-1,2,3-oxathiazocine-2,4-dione as an example, the reaction formula is as follows:

[0016]

[0017] As a preferred embodiment, the molar ratio of the sulfamic acid to the fatty dialdehyde is 1:(1.0 - 4.0). More preferably, the molar ratio of the sulfamic acid to the fatty dialdehyde is 1:(1.5 - 2.5). The theoretical reaction molar ratio between the sulfamic acid and the fatty dialdehyde is 1:1. Appropriately increasing the proportion of the fatty dialdehyde is beneficial to improving the conversion rate of the sulfamic acid.

[0018] As a preferred embodiment, the conditions for the condensation reaction are: the temperature is 20 - 65°C, and the time is 0.2 - 1.0 hour.

[0019] The mass percentage concentration of the sulfamic acid solution of the present invention is 20 - 50%.

[0020] The mass percentage concentration of the fatty dialdehyde solution of the present invention is 40 - 60%.

[0021] The present invention also provides an application of an oxathiazinone dione compound, which is used as a talc depressant for mineral flotation.

[0022] As a preferred embodiment, the mineral includes metal sulfide ore. As a more preferred embodiment, the metal sulfide ore includes molybdenite and / or chalcopyrite.

[0023] As a more preferred embodiment, after the metal sulfide ore is slurried, flotation reagents including an oxathiazinone dione compound and a metal sulfide ore collector are added for air flotation.

[0024] As a preferred embodiment, the pH value of the pulp is adjusted to 5.0 - 12.0. The applicable pH range of the oxathiazinone dione compound is relatively wide, and more preferably the pH value is adjusted to 6.0 - 11.0. The pH value is adjusted using hydrochloric acid or sodium hydroxide.

[0025] As a preferred embodiment, the concentration of the metal sulfide ore collector in the pulp is 5 - 150 mg / L.

[0026] Compared with the prior art, the technical solution of the present invention has the following beneficial technical effects:

[0027] The synthesis method of the oxathiazinone dione compound provided by the present invention has the advantages of fast reaction speed, high conversion rate, mild reaction conditions, environmental protection and safety, simple post-treatment, and less waste generation.

[0028] The oxathiazinone dione compound provided by the present invention can be used as a talc depressant for the efficient flotation separation of metal sulfide ore and talc, and its optimal flotation conditions are that the inhibition concentration of the oxathiazinone dione compound is relatively low, and the applicable pulp pH value range is relatively wide, having broad application prospects. Description of the Drawings

[0029] Figure 1 It is the infrared spectrum of (Z)-5,6,7,8-tetrahydro-1,2,3-oxathiazocine-4,8-dione.

[0030] Figure 2 It is the 1H NMR spectrum of (Z)-5,6,7,8-tetrahydro-1,2,3-oxathiazocine-4,8-dione.

[0031] Figure 3 It is the 13C NMR spectrum of (Z)-5,6,7,8-tetrahydro-1,2,3-oxathiazocine-4,8-dione.

[0032] Figure 4 It is the graph showing the relationship between the dosage of (Z)-5,6,7,8-tetrahydro-1,2,3-oxathiazocine-4,8-dione and its performance in inhibiting molybdenite / talc.

[0033] Figure 5 It is the graph showing the relationship between pH and the performance of (Z)-5,6,7,8-tetrahydro-1,2,3-oxathiazocine-4,8-dione in inhibiting molybdenite / talc.

[0034] Figure 6 It is the graph showing the relationship between the dosage of (Z)-5,6,7,8-tetrahydro-1,2,3-oxathiazocine-4,8-dione and its performance in inhibiting chalcopyrite / talc.

[0035] Figure 7 It is the graph showing the relationship between pH and the performance of (Z)-5,6,7,8-tetrahydro-1,2,3-oxathiazocine-4,8-dione in inhibiting chalcopyrite / talc.

[0036] Figure 8 It is the graph showing the performance of CMC in inhibiting molybdenite / talc.

[0037] Figure 9 It is the graph showing the performance of CMC in inhibiting chalcopyrite / talc. Specific Embodiments

[0038] The technical solutions of the present invention will be described in detail below through specific embodiments, but the following specific embodiments do not limit the scope of protection of the claims of the present invention.

[0039] In the following embodiments, unless otherwise specified, the reagents used are all commercially available products. The concentrations or contents in each embodiment are all mass percentages.

[0040] Example 1

[0041] The structural formula of the target inhibitor is:

[0042]

[0043] The reaction equation is:

[0044]

[0045] Synthesized by the following method:

[0046] Weigh 0.01 mol of sulfamic acid and 10 mL of water, mix and stir for 30 min, then add 0.02 mol of 50% glutaraldehyde aqueous solution dropwise; then heat up to 35 °C and react for 0.5 h; after cooling to room temperature, add ethanol to precipitate the reaction product from the mixed solution, filter to obtain a yellow solid inhibitor with a yield of 73.4%. The infrared spectrum of the obtained product is shown in Figure 1 , the 1H NMR spectrum of the obtained product is shown in Figure 2 , the 13C NMR spectrum of the obtained product is shown in Figure 3 .

[0047] Example 2

[0048] Study on the flotation performance of the inhibitor prepared in Example 1 on single minerals. Under natural pH conditions, after stirring for 2 min, add a pH adjuster (such as sodium hydroxide) for 2 min, add the inhibitor and stir for 3 min, add a collector (isobutyl sodium xanthate) at 5×10 -4 mol / L, stir for 3 min, add a frother (methyl isobutyl carbinol) at 1×10 -4 mol / L, stir for 1 min, and perform flotation for 3 min. The inhibitor concentration is 5 - 150 mg / L to obtain flotation products.

[0049] The inhibitor shown in Example 1 of the present invention has good inhibitory ability on talc and weak inhibitory ability on molybdenite; when the inhibitor concentration is 100 mg / L and pH = 8, the flotation recovery rate of the inhibitor in Example 1 for talc is 29.83%, and the flotation recovery rate for molybdenite is 71.70%. The specific situation is shown in Figures 4 - 5 .

[0050] From Figures 4 - 5 as shown, the inhibitor shown in Example 1 of the present invention maintains good inhibitory ability on talc throughout the pH value range (5 - 11); when the pH value is 8, the inhibitory ability of the inhibitor on talc and molybdenite differs greatly, and it is possible to achieve the separation of molybdenite - talc. Thus, it can be seen that the Schiff base flotation inhibitor shown in Example 1 has good selectivity.

[0051] Example 3

[0052] Study on the flotation performance of the inhibitor prepared in Example 1 for single minerals. Other flotation reagents refer to Example 2. Under natural pH conditions, after stirring for 2 min, add a pH adjuster (such as sodium hydroxide) for 2 min, add the inhibitor and stir for 3 min, add the collector and stir for 3 min, add the frother and stir for 1 min, and then perform flotation for 3 min. Select the inhibitor concentration to be 5 - 150 mg / L to obtain the flotation product. When the inhibitor concentration is 100 mg / L and pH = 8, the flotation recovery rate of the inhibitor for talc is 29.83%, and the flotation recovery rate for chalcopyrite is 81.57%. For specific details, see Figures 6 - 7 。

[0053] From Figures 6 - 7 As can be seen from the figure shown, the inhibitor shown in Example 1 of the present invention maintains good inhibitory ability for talc throughout the pH value range (5 - 11); when the pH value is 8, the inhibitory ability of the inhibitor for talc and chalcopyrite is quite different, and it is possible to achieve the separation of chalcopyrite - talc. Thus, it can be seen that the flotation inhibitor prepared in Example 1 has good selectivity.

[0054] Example 4

[0055] Study on the flotation performance of the inhibitor prepared in Example 1 for artificial mixed ore. Other flotation reagents refer to Example 2. Under natural pH conditions, after stirring for 2 min, add a pH adjuster (such as sodium hydroxide) for 2 min, add the inhibitor and stir for 3 min, add the collector and stir for 3 min, add the frother and stir for 1 min, and then perform flotation for 3 min. The inhibitor concentration is 75 mg / L or 100 mg / L to obtain the flotation product. The specific reagent conditions and their results are shown in Table 1.

[0056] The experimental results in Table 1 show that the inhibitor prepared in Example 1 of the present invention can well separate molybdenite / chalcopyrite - talc. When the inhibitor concentration is 100 mg / L and pH = 8, the flotation recovery rate of the inhibitor in Example 1 for molybdenite is 60.67%, and the flotation recovery rate for talc is 21.44%; the grade of molybdenite in the concentrate is 73.89%, and the grade of talc is 26.11%. Under the same conditions, the flotation recovery rate of the inhibitor in Example 1 for chalcopyrite is 91.84%, and the flotation recovery rate for talc is 42.95%; the grade of chalcopyrite in the concentrate is 68.14%, and the grade of talc is 31.86%. Thus, it can be seen that the inhibitory ability of the inhibitor for talc and molybdenite / chalcopyrite is quite different, and it is possible to achieve the separation of molybdenite / chalcopyrite - talc. The flotation inhibitor shown in Example 1 has good selectivity.

[0057]

[0058] Comparative Example 1

[0059] This comparative example is under the same collector and frother conditions. The collector and frother refer to Example 2. The performance of the inhibitor CMC in flotation separation of molybdenite-talc is studied. Under natural pH conditions, after stirring for 2 minutes, add the pH adjuster (such as sodium hydroxide) for 2 minutes, add the inhibitor and stir for 3 minutes, add the collector and stir for 3 minutes, add the frother and stir for 1 minute, float for 3 minutes, and the inhibitor concentration is 50-500 mg / L to obtain the flotation product. For details, see Figure 8 .

[0060] Comparative Example 2

[0061] This comparative example is under the same collector and frother conditions. The collector and frother refer to Example 2. The performance of the inhibitor CMC in flotation separation of chalcopyrite and talc is studied. Under natural pH conditions, after stirring for 2 minutes, add the pH adjuster (such as sodium hydroxide) for 2 minutes, add the inhibitor and stir for 3 minutes, add the collector and stir for 3 minutes, add the frother and stir for 1 minute, float for 3 minutes, and the inhibitor concentration is 50-500 mg / L to obtain the flotation product. For details, see Figure 9 .

[0062] Comparing Example 2 with Comparative Example 1, it can be concluded that the amount of reagent required for TOD to inhibit talc is significantly reduced, and the flotation separation effect of molybdenite-talc is significantly improved.

[0063] By comparing Example 3 with Comparative Example 2, it can be concluded that the use of TOD as a flotation depressant can achieve higher talc inhibition ability with a smaller amount of depressant, and the flotation separation effect of chalcopyrite-talc is significantly improved.

[0064] Although the present invention has been described in detail above by means of general description, specific implementation methods and tests, it is obvious to those skilled in the art that some modifications or improvements may be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. An oxathiazolyl heterocyclic dione compound, characterized in that: It has the following molecular structure: ； Among them, R is a hydrocarbon chain of C3~C8.

2. The method for synthesizing an oxathiazolyl heterocyclic dione compound according to claim 1, characterized in that: The fatty dialdehyde solution is added dropwise into the aminosulfonic acid solution to carry out condensation reaction to obtain the product.

3. The method for synthesizing an oxathiazolyl heterocyclic dione compound according to claim 2, characterized in that: The molar ratio of the aminosulfonic acid to the fatty dialdehyde is 1:(1.0-4.0).

4. The method for synthesizing an oxathiazolyl heterocyclic dione compound according to claim 3, characterized in that: The molar ratio of the aminosulfonic acid to the fatty dialdehyde is 1:(1.5-2.5).

5. A method for synthesizing an oxathiazolyl heterocyclic dione compound according to any one of claims 2 to 4, characterized in that: The conditions of the condensation reaction are: temperature of 20-65° C. and time of 0.2-1.0 hour.

6. The use of an oxathiazolyl heterocyclic dione compound according to claim 1, characterized in that: Used as talc depressant in mineral flotation.

7. The use of an oxathiazolyl heterocyclic dione compound according to claim 6, characterized in that: The minerals include metallic sulfide ores.

8. The use of an oxathiazolyl heterocyclic dione compound according to claim 7, characterized in that: The metal sulfide ore includes molybdenite and / or chalcopyrite.

9. The use of an oxathiazolyl compound according to any one of claims 6 to 8, characterized in that: After the metal sulfide ore is slurried, flotation reagents including oxysulfuric acid and nitrogen heterocyclic dione compounds and metal sulfide ore collectors are added to carry out aeration flotation.

10. The use of an oxathiazolyl heterocyclic dione compound according to claim 9, characterized in that: The pH value of the slurry is adjusted to 5.0-12.0.

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