Focused phosphoric acid p-phenylenediamine polyphosphate compound as well as preparation method and application thereof

Abstract

The invention relates to a focused phosphoric acid p-phenylenediamine polyphosphate compound as well as a preparation method and application thereof, the structural general formula of the compound is as follows: # imgabs0 #, m is equal to 1000-2000, n is equal to 1000-2000, and [M] is a metal ion or NH4 < + >; the compound provided by the invention is applied to mineral flotation, and shows excellent performance in copper-lead separation and tungsten ore beneficiation processes.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis and mineral flotation, and more specifically to a focused p-phenylenediamine phosphate polyphosphate compound and a preparation method and application thereof. Background Art

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

[0003] However, there are still some deficiencies in the current research on the application of polyphosphate in mineral processing. The research on the interaction mechanism between polyphosphate and different mineral surfaces is not in-depth enough, and the selective inhibition of polyphosphate in complex mineral systems needs to be further explored. At the same time, the research on the stability and degradation characteristics of polyphosphate in the mineral processing process needs to be strengthened, and the synergistic mechanism with other mineral processing agents is still unclear. These problems limit the further application and development of polyphosphate in mineral processing. Summary of the invention

[0004] Based on the above technical problems existing in the prior art, the present invention provides a focused phosphonic acid p-phenylenediamine polyphosphate compound, which can show excellent performance in the copper-lead separation and tungsten ore beneficiation process.

[0005] In order to achieve the above object, the technical solution of the present invention is as follows:

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

[0007]

[0008] Wherein, m = 1000-2000, n = 1000-2000, [M] is a metal ion or NH 4 + .

[0009] The present invention also provides a method for preparing the above-mentioned focused p-phenylenediamine phosphate polyphosphate compound, and the general reaction formula of the method is as follows:

[0010]

[0011] The method comprises the following steps:

[0012] Phosphoric acid, compound A, polyphosphate, catalyst, additive and solvent are mixed and reacted to obtain the focused phosphonic acid p-phenylenediamine polyphosphate compound; 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 metal ion or NH 4 + .

[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, it includes but is not limited to ferric chloride, copper sulfate, copper trifluoromethanesulfonate, aluminum chloride, palladium acetate, etc.; more preferably, it is 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 H 2 SO 4 , NaOH, HNO 3 、Na 2 CO 3 , molecular sieve, (NH 4 ) 2 HPO 4 , KH 2 PO 4 etc.; more preferably, H 2 SO 4 , NaOH, HNO 3 、Na 2 CO 3 , molecular sieve, (NH 4 ) 2 HPO 4 , KH 2 PO 4 At least one of .

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

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

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

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

[0020] The focused phosphate p-phenylenediamine polyphosphate compound provided by the present invention exhibits excellent performance in the beneficiation process of lead ore and tungsten ore; specifically, for lead ore, this type of compound can effectively inhibit the flotation of galena, especially in the range of pH 7-10; in the beneficiation of tungsten ore, it can be used as a regulator 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, reducing the interaction between these minerals and the collector, thereby achieving preferential flotation of scheelite. The new modified polyphosphate provided by the present invention is expected to improve the separation effect of copper-lead separation and tungsten ore beneficiation, and provide a new solution to solve the long-standing technical problems in the beneficiation of these minerals.

[0021] The preparation method of the present invention uses phosphoric acid, polyphosphate, p-phenylenediamine and its derivatives as reaction raw materials, and adds a catalyst and an additive to the reaction system to induce the reaction, thereby realizing a one-step synthesis of a focused phosphonic acid p-phenylenediamine polyphosphate compound. The present invention uses common and economical reagents as raw materials, and realizes efficient synthesis of the target compound by optimizing the reaction conditions.

[0022] Compared with the traditional method, the preparation method of the present invention has significant advantages in many aspects: first, the method greatly simplifies the synthesis process, condenses the multi-step reaction into a single-step operation, and greatly improves the synthesis efficiency; second, the reaction conditions are mild, and no special equipment or harsh environment is required, which enhances the practicality and scalability of the method. In addition, it performs well in terms of atom economy, substrate application range and product purity, fully reflecting the concept of green chemistry.

[0023] The method of the present invention overcomes the limitations of the prior art, such as the need to pre-prepare substrates and use special catalysts, and provides new possibilities for the industrial production of polyphosphate compounds of p-phenylenediamine phosphate. This not only helps to reduce production costs, but also opens up new ways for the application of related compounds in multiple fields. DETAILED DESCRIPTION

[0024] Many specific details are set forth in the following description to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar modifications without violating the connotation of the present invention, so the present invention is not limited to the specific implementation disclosed below.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0026] Example 1

[0027] Add 100g phosphoric acid, 100g p-phenylenediamine, 50g ammonium polyphosphate, 50mg FeCl 3 Catalyst, 50 mg (NH 4 ) 2 HPO 4 and 100 mL of dimethyl sulfoxide, react at a pressure of 0.1 MPa and 200° C. for 12 hours, then stop stirring, reduce the pressure and cool to room temperature, and finally filter and wash with deionized water to obtain the target product.

[0028] Example 2

[0029] Add 100g phosphoric acid, 100g p-phenylenediamine, 1000g sodium polyphosphate, 50mg FeCl 3 Catalyst, 50 mg Na 2 HPO 4 and 100 mL of dimethyl sulfoxide, react at a pressure of 0.1 MPa and 200° C. for 16 hours, then stop stirring, reduce the pressure and cool to room temperature, and finally filter and wash with deionized water to obtain the target product.

[0030] Example 3

[0031] Add 100g phosphoric acid, 100g p-phenylenediamine, 100g potassium polyphosphate, 50mg FeCl 3 Catalyst, 50 mg K 2 HPO 4 and 100 mL of dimethyl sulfoxide, react at a pressure of 0.1 MPa and 200° C. for 24 hours, then stop stirring, reduce the pressure and cool to room temperature, and finally filter and wash with deionized water to obtain the target product.

[0032] Example 4

[0033] Add 100g phosphoric acid, 100g p-phenylenediamine sulfonic acid, 50g ammonium polyphosphate, 50mg AlCl 3 Catalyst, 50 mg (NH 4 ) 2 HPO 4 and 100 mL of N,N-dimethylformamide, react at a pressure of 0.1 MPa and 250° C. for 10 hours, then stop stirring, reduce the pressure and cool to room temperature, and finally filter and wash with deionized water to obtain the target product.

[0034] Example 5

[0035] Add 100g phosphoric acid, 100g 2.6-diynyl-p-phenylenediamine, 50g ammonium polyphosphate, 50mg FeCl 3 Catalyst, 50 mg (NH 4 ) 2 HPO 4 and 100 mL of ethanol, react at a pressure of 0.1 MPa and 100° C. for 24 hours, then stop stirring, reduce the pressure and cool to room temperature, and finally filter and wash with deionized water to obtain the target product.

[0036] Example 6

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

[0038] 1. Mineral raw materials:

[0039] The mineral raw materials used are copper-lead mixed flotation rough concentrate, with lead content of 45.38% and copper content of 4.23%. Phase analysis shows that lead is mainly galena, with a small amount of pyrite and cerussite, copper is mainly chalcopyrite and a small amount of bornite, in addition to a small amount of pyrite and siliceous gangue minerals.

[0040] 2. Flotation reagents and operating conditions:

[0041]

[0042]

[0043] In the flotation separation operation, sodium carbonate is added to adjust the pH value to 7.5-8, and then sodium hexametaphosphate is used as a mineral dispersant to improve the dispersibility of the mineral, and then the focused phosphoric acid p-phenylenediamine polyphosphate prepared in Example 1 is added as a lead mineral inhibitor, and the aniline black medicine copper mineral collector is used to collect the copper mineral. The whole process includes one roughing, three scavenging and two concentrating, and finally the copper and lead are separated to obtain copper concentrate with a copper content of 18.28% and a lead content of 52.29%, and the copper and lead recoveries reach 90.21% and 90.17%, respectively.

[0044] Comparative Example 1

[0045] 1. Mineral raw materials:

[0046] The mineral raw material used is a coarse concentrate of copper-lead mixed flotation, which is the same batch of ore samples as the mineral in Example 6, and the lead content in the ore is 45.38% and the copper content is 4.23%. Phase analysis shows that the lead is mainly galena, with a small amount of pyrite and cerussite, and the copper is mainly chalcopyrite and a small amount of bornite, in addition to a small amount of pyrite and siliceous gangue minerals.

[0047] 2. Flotation reagents and operating conditions:

[0048]

[0049] In the flotation separation operation, sodium carbonate is added to adjust the pH value to 7.5-8, and then sodium hexametaphosphate is used as a mineral dispersant to improve the dispersibility of the mineral. Potassium dichromate is then added as a lead mineral inhibitor, and aniline black medicine is used as a collector to capture copper minerals. The entire process includes one roughing, three sweeping and two concentrating, and finally achieves copper-lead separation. Copper concentrate and lead concentrate with a copper content of 16.27% and a lead content of 50.56% are obtained, and the copper and lead recoveries are 87.50% and 88.90% respectively.

[0050] Example 7

[0051] Another application example of the paraphenylenediamine phosphate polyphosphate prepared in Example 5 of the present invention in the flotation separation of fluorite and calcite comprises the following steps:

[0052] 1. Mineral raw materials:

[0053] The mineral raw materials used are coarse concentrates of mixed flotation of fluorite and calcite, with the fluorite content of 87.59% and the calcite content of 8.57%, and a small amount of siliceous gangue minerals.

[0054] 2. Flotation reagents and operating conditions:

[0055]

[0056] In the flotation separation operation, water glass is first added, and then sodium hexametaphosphate is used as a mineral dispersant to improve the dispersibility of the mineral, and then the focused phosphoric acid 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 concentrating, and finally the flotation separation of fluorite and calcite is achieved to obtain a fluorite concentrate with a fluorite content of 96.45% and a recovery rate of 89.26%, and the calcite content in the concentrate is only 0.56%.

[0057] Comparative Example 2

[0058] 1. Mineral raw materials:

[0059] The mineral raw materials used are coarse concentrates of mixed flotation of fluorite and calcite, which are from the same batch of ore samples as those in Example 7, and the fluorite content in the ore is 87.59%, and the calcite content is 8.57%. There is also a small amount of siliceous gangue minerals.

[0060] 2. Flotation reagents and operating conditions:

[0061]

[0062] In the flotation separation operation, water glass is first added, and then sodium hexametaphosphate is used as a mineral dispersant to improve the dispersibility of the mineral, and then tannin extract is added as a fluorite mineral inhibitor, and sodium oleate is used as a collector of fluorite minerals. The entire process includes one roughing, three scavenging and four concentrating, and finally the flotation separation of fluorite and calcite is achieved to obtain a fluorite concentrate with a fluorite content of 93.50% and a recovery rate of 85.68%. The calcite content in the concentrate is 1.45%.

[0063] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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 above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A focused p-phenylenediamine phosphate polyphosphate compound, characterized in that: Its general structure is as follows: Wherein, m = 1000-2000, n = 1000-2000, [M] is a metal ion or NH4 + .

2. The method for preparing the focused phosphonic acid p-phenylenediamine phosphate compound according to claim 1, characterized in that: The following steps are involved: Phosphoric acid, compound A, polyphosphate, catalyst, additive and solvent are mixed and reacted to obtain the focused phosphonic acid p-phenylenediamine polyphosphate compound; 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 metal ion or NH4 + .

3. The method for preparing the phosphate-containing p-phenylenediamine phosphate compound according to claim 2, characterized in that: The mass ratio of the phosphoric acid, compound A and polyphosphate is 2:2:1-10.

4. The method for preparing the phosphate-containing p-phenylenediamine phosphate compound according to claim 2, characterized in that: The catalyst is at least one of a metal salt, a Lewis acid or a Lewis base.

5. The method for preparing the phosphate-containing p-phenylenediamine phosphate compound according to claim 2, characterized in that: The additive is an inorganic acid or an inorganic base.

6. The method for preparing the phosphate-containing p-phenylenediamine phosphate compound according to claim 2, characterized in that: The reaction temperature is 0-300°C.

7. The method for preparing the p-phenylenediamine phosphate compound according to claim 2, characterized in that: The pressure in the reaction system is 0.5-3 MPa.

8. The method for preparing the phosphate-containing p-phenylenediamine phosphate compound according to claim 2, characterized in that: The solvent is an organic solvent or water.

9. Use of the focused phosphonic acid p-phenylenediamine polyphosphate compound according to claim 1 or the focused phosphonic acid p-phenylenediamine polyphosphate compound obtained by the preparation method according to any one of claims 2 to 8 in mineral flotation.

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