A focused p-phenylenediamine polyphosphate and its preparation method and application

Abstract

The present application relates to a kind of focused p-phenylenediamine polyphosphate and its preparation method and application, the structural general formula of the compound is as follows:;Wherein, m=1000-2000, n=1000-2000, [M] is metal ion or NH4 + The compound provided by the present application is applied in mineral flotation, and shows excellent performance in copper-lead separation and tungsten ore beneficiation process.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis and mineral flotation, and more particularly, to a focused p-phenylenediamine polyphosphate and a preparation method and application thereof. BACKGROUND

[0002] As an important inorganic compound, polyphosphate has a wide application prospect in the field of mineral processing. Early studies found that polyphosphate has an inhibitory effect on some minerals such as calcite, apatite and dolomite. Later studies showed that the inhibitory effect of polyphosphate on minerals is mainly achieved by complexing the metal ions on the surface of the minerals, rather than directly adsorbing on the surface of the minerals. The application of polyphosphate in mineral processing mainly includes: as an inhibitor, a slime dispersant, a mineral suspension stabilizer, a precipitant of some metal ions and a water softener, etc. Among them, the application research of polyphosphate as an inhibitor is more extensive. Studies have found that polyphosphate has a good inhibitory effect on calcium-containing minerals such as calcite and fluorite, and can be used for preferential flotation of scheelite. In addition, polyphosphate can also be used to control the accidental activation or deactivation in the process of mineral processing.

[0003] However, there are still some deficiencies in the current application research of polyphosphate in mineral processing. The research on the interaction mechanism between polyphosphate and the surface of different minerals is not deep enough, and the selective inhibitory effect of polyphosphate in complex mineral systems needs to be further explored. At the same time, the stability and degradation characteristics of polyphosphate in the process of mineral processing need to be strengthened, and the synergistic mechanism with other mineral processing agents is not clear. These problems limit the further application and development of polyphosphate in mineral processing. SUMMARY

[0004] Based on the above technical problems existing in the prior art, the present application provides a focused p-phenylenediamine polyphosphate, which can exhibit excellent performance in the process of copper-lead separation and tungsten ore dressing.

[0005] In order to achieve the above purpose, the technical scheme of the present application is as follows:

[0006] A focused p-phenylenediamine polyphosphate, the general structure formula of which is as follows:

[0007]

[0008] Wherein, m = 1000-2000, n = 1000-2000, [M] is a metal ion or NH4 + .

[0009] The present application also provides a preparation method of the above-mentioned focused p-phenylenediamine polyphosphate, and the reaction formula of the method is as follows:

[0010]

[0011] The method comprises the following steps:

[0012] The phosphoric acid, compound A, polyphosphate, catalyst, additive and solvent are mixed and then reacted to obtain the focused phosphoric acid p-phenylenediamine polyphosphate; the compound A is p-phenylenediamine or a p-phenylenediamine compound containing a substituent; the structural formula of the polyphosphate is: n = 1000-2000, [M] is a metal ion or NH4 + .

[0013] In some embodiments, [M] is an alkali metal ion, including but not limited to Na + , K + In some embodiments, the mass ratio of the phosphoric acid, compound A and polyphosphate is 2:2:1-10.

[0014] In some embodiments, the catalyst is at least one of a metal salt, a Lewis acid or a Lewis base; preferably, including but not limited to ferric chloride, copper sulfate, copper trifluoromethanesulfonate, aluminum chloride, palladium acetate and the like; more preferably, at least one of ferric chloride, copper sulfate, copper trifluoromethanesulfonate, aluminum chloride, palladium acetate.

[0015] In some embodiments, the additive is an inorganic acid or an inorganic base; preferably, including but not limited to H2SO4, NaOH, HNO3, Na2CO3, molecular sieves, (NH4)2HPO4, KH2PO4 and the like; more preferably, at least one of H2SO4, NaOH, HNO3, Na2CO3, molecular sieves, (NH4)2HPO4, KH2PO4.

[0016] In some embodiments, the solvent includes an organic solvent and water; the organic solvent includes but is not limited to at least one of dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate, methanol, ethanol, diethyl ether, acetone, acetonitrile.

[0017] In some embodiments, the reaction temperature is 0-300℃; the system pressure is controlled to be 0.05-3 MPa during the reaction; preferably, the reaction temperature is 150-250℃.

[0018] In some embodiments, the reaction time is 0-48h; preferably, 10-36h.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] The p-phenylenediamine polyphosphate provided by this invention exhibits excellent performance in the beneficiation of lead and tungsten ores. Specifically, for lead ore, this compound effectively inhibits the flotation of galena, particularly in the pH range of 7-10. In tungsten ore beneficiation, it can be used as a modifier for the preferential flotation of scheelite by selectively complexing and dissolving calcium ions on the surface of calcium-containing minerals such as calcite and fluorite, thereby reducing the interaction between these minerals and the collector and achieving preferential flotation of scheelite. The novel modified polyphosphate provided by this invention is expected to improve the separation efficiency of copper-lead and tungsten ore beneficiation, providing a new solution to long-standing technical challenges in the beneficiation of these minerals.

[0021] The preparation method of this invention uses phosphoric acid, polyphosphate, and p-phenylenediamine and its derivatives as reactants. By adding catalysts and additives to the reaction system to induce the reaction, a one-step synthesis of focused p-phenylenediamine polyphosphate is achieved. This invention uses common and economical reagents as raw materials and achieves efficient synthesis of the target compound by optimizing reaction conditions.

[0022] Compared with traditional methods, the preparation method of this invention exhibits significant advantages in several aspects: First, the method greatly simplifies the synthesis process, concentrating multi-step reactions into a single-step operation, thus greatly improving synthesis efficiency; second, the reaction conditions are mild, requiring no special equipment or harsh environments, enhancing the practicality and scalability of the method. Furthermore, it demonstrates excellent performance in terms of atom economy, substrate applicability, and product purity, fully embodying the concept of green chemistry.

[0023] The method of this invention overcomes the limitations of existing technologies, such as the need for pre-preparation of substrates and the use of special catalysts, providing new possibilities for the industrial production of p-phenylenediamine polyphosphate. This not only helps reduce production costs but also opens up new avenues for the application of related compounds in multiple fields. Detailed Implementation

[0024] Numerous specific details are set forth in the following description to provide a full understanding of the invention. However, the invention can be practiced in many other ways different from those described herein, and similar modifications can be made by those skilled in the art without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0026] Example 1

[0027] 100g of phosphoric acid, 100g of p-phenylenediamine, 50g of ammonium polyphosphate, 50mg of FeCl3 catalyst, 50mg of (NH4)2HPO4 and 100mL of dimethyl sulfoxide were added sequentially to a reaction vessel. After reacting at 0.1MPa and 200℃ for 12 hours, stirring was stopped, the pressure was reduced and the mixture was cooled to room temperature. Finally, the product was obtained by filtration and washing with deionized water.

[0028] Example 2

[0029] 100g of phosphoric acid, 100g of p-phenylenediamine, 1000g of sodium polyphosphate, 50mg of FeCl3 catalyst, 50mg of Na2HPO4 and 100mL of dimethyl sulfoxide were added sequentially to a reaction vessel. After reacting at 0.1MPa pressure and 200℃ for 16 hours, stirring was stopped, the pressure was reduced and cooled to room temperature. Finally, the product was obtained by filtration and washing with deionized water.

[0030] Example 3

[0031] 100g of phosphoric acid, 100g of p-phenylenediamine, 100g of potassium polyphosphate, 50mg of FeCl3 catalyst, 50mg of K2HPO4 and 100mL of dimethyl sulfoxide were added sequentially to a reaction vessel. After reacting at 0.1MPa pressure and 200℃ for 24 hours, stirring was stopped, the pressure was reduced and cooled to room temperature. Finally, the product was obtained by filtration and washing with deionized water.

[0032] Example 4

[0033] 100g of phosphoric acid, 100g of p-phenylenediamine sulfonic acid, 50g of ammonium polyphosphate, 50mg of AlCl3 catalyst, 50mg of (NH4)2HPO4 and 100mL of N,N-dimethylformamide were added sequentially to a reaction vessel. After reacting at 0.1MPa pressure and 250℃ for 10 hours, stirring was stopped, the pressure was reduced and cooled to room temperature. Finally, the product was obtained by filtration and washing with deionized water.

[0034] Example 5

[0035] 100g of phosphoric acid, 100g of 2,6-diynyl-p-phenylenediamine, 50g of ammonium polyphosphate, 50mg of FeCl3 catalyst, 50mg of (NH4)2HPO4 and 100mL of ethanol were added sequentially to a reaction vessel. After reacting at 0.1MPa and 100℃ for 24 hours, stirring was stopped, the pressure was reduced and the mixture was cooled to room temperature. Finally, the product was obtained by filtration and washing with deionized water.

[0036] Example 6

[0037] An application example of the focused p-phenylenediamine polyphosphate in the flotation separation of copper and lead described in Example 1 of this invention includes the following steps:

[0038] 1. Mineral raw materials:

[0039] The mineral raw material used was a copper-lead mixed flotation concentrate, with a lead content of 45.38% and a copper content of 4.23%. Phase analysis showed that the lead was mainly composed of galena, with small amounts of basalt and cerussite; the copper was mainly composed of chalcopyrite and a small amount of bornite, in addition to small amounts of pyrite and siliceous gangue minerals.

[0040] 2. Flotation reagents and operating conditions:

[0041]

[0042]

[0043] In the flotation separation process, sodium carbonate is added to adjust the pH to 7.5–8. Sodium hexametaphosphate is then used as a mineral dispersant to improve mineral dispersibility. The p-phenylenediamine polyphosphate prepared in Example 1 is then added as a lead mineral inhibitor, and aniline black copper mineral collectors are used to collect the copper minerals. The entire process includes one roughing stage, three scavenging stages, and two cleaning stages, ultimately achieving copper-lead separation and obtaining copper concentrate and lead concentrate with a copper content of 18.28% and a lead content of 52.29%, respectively. The copper and lead recoveries reached 90.21% and 90.17%, respectively.

[0044] Comparative Example 1

[0045] 1. Mineral raw materials:

[0046] The mineral raw material used was a copper-lead mixed flotation concentrate, which was from the same batch as the mineral in Example 6. The ore contained 45.38% lead and 4.23% copper. Phase analysis showed that the lead was mainly composed of galena, with small amounts of basalt and cerussite; the copper was mainly composed of chalcopyrite and a small amount of bornite, in addition to small amounts of pyrite and siliceous gangue minerals.

[0047] 2. Flotation reagents and operating conditions:

[0048]

[0049] In the flotation separation process, sodium carbonate is added to adjust the pH to 7.5–8. Sodium hexametaphosphate is then used as a mineral dispersant to improve mineral dispersibility. Potassium dichromate is added as a lead mineral depressant, and aniline black is used as a collector to collect copper minerals. The entire process includes one roughing stage, three scavenging stages, and two cleaning stages, ultimately achieving copper-lead separation. Copper concentrate and lead concentrate with a copper content of 16.27% and a lead content of 50.56% are obtained, with copper and lead recoveries reaching 87.50% and 88.90%, respectively.

[0050] Example 7

[0051] Another application example of the focused p-phenylenediamine phosphate polyphosphate prepared in Example 5 of this invention in the flotation separation of fluorite and calcite includes the following steps:

[0052] 1. Mineral raw materials:

[0053] The mineral raw materials used were a mixed flotation concentrate of fluorite and calcite, with fluorite content of 87.59% and calcite content of 8.57%. There were also a small amount of siliceous gangue minerals.

[0054] 2. Flotation reagents and operating conditions:

[0055]

[0056] In the flotation separation process, water glass is first added, followed by sodium hexametaphosphate as a mineral dispersant to improve mineral dispersibility. Then, p-phenylenediamine polyphosphate prepared in Example 5 is added as a fluorite mineral inhibitor, and sodium oleate is used as a fluorite mineral collector. The entire process includes one roughing, three scavenging, and four cleaning stages, ultimately achieving flotation separation of fluorite and calcite, obtaining a fluorite concentrate with a fluorite content of 96.45% and a recovery rate of 89.26%, while the calcite content in the concentrate is only 0.56%.

[0057] Comparative Example 2

[0058] 1. Mineral raw materials:

[0059] The mineral raw material used was a mixed flotation rough concentrate of fluorite and calcite, which was from the same batch as the mineral in Example 7. The ore contained 87.59% fluorite and 8.57% calcite. There was also a small amount of siliceous gangue minerals.

[0060] 2. Flotation reagents and operating conditions:

[0061]

[0062] In the flotation separation process, water glass is first added, followed by sodium hexametaphosphate as a mineral dispersant to improve mineral dispersibility. Tannin is then added as a fluorite mineral depressant, and sodium oleate as a fluorite mineral collector. The entire process includes one roughing stage, three scavenging stages, and four cleaning stages, ultimately achieving flotation separation of fluorite and calcite, yielding a fluorite concentrate with a fluorite content of 93.50% and a recovery rate of 85.68%, containing 1.45% calcite.

[0063] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0064] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for preparing p-phenylenediamine polyphosphate, characterized in that, Includes the following steps: Phosphoric acid, compound A, polyphosphate, catalyst, additive, and solvent are mixed and reacted to obtain the focused phosphoric acid p-phenylenediamine polyphosphate; compound A is p-phenylenediamine or a p-phenylenediamine compound containing substituents; the structural formula of the polyphosphate is: n=1000-2000, [M] is a metal ion or NH4+. + ; The mass ratio of phosphoric acid, compound A and polyphosphate is 2:2:1-10; The catalyst is at least one of ferric chloride, copper sulfate, copper trifluoromethanesulfonate, aluminum trichloride, and palladium acetate. The additive is at least one of H2SO4, NaOH, HNO3, Na2CO3, molecular sieve, (NH4)2HPO4, and KH2PO4; The reaction temperature is 150-300℃.

2. The method for preparing focused p-phenylenediamine polyphosphate according to claim 1, characterized in that, The pressure in the reaction system is 0.5-3 MPa.

3. The method for preparing focused p-phenylenediamine polyphosphate according to claim 1, characterized in that, The solvent is an organic solvent or water.

4. The focused p-phenylenediamine polyphosphate obtained by the preparation method according to any one of claims 1-3.

5. The application of the focused p-phenylenediamine phosphate polyphosphate obtained by the preparation method according to any one of claims 1-3 or the focused p-phenylenediamine phosphate polyphosphate according to claim 4 in mineral flotation.

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