Di-tert-butyl dithiophosphate compound as well as preparation method and application thereof

Abstract

The invention relates to a di-tert-butyl dithiophosphate compound as well as a preparation method and application thereof, the structural formula of the di-tert-butyl dithiophosphate compound is # imgabs0 #, M is Na < + > or NH4 < + >; through the structural design of the dithiophosphate compound, the obtained compound has an excellent flotation effect on poor, fine and hybridized lead zinc ore, flotation does not need to be conducted under the high-alkali condition, and the hidden danger that tailings pollute the environment due to the high-alkali condition is avoided.

Description

Technical Field

[0001] The invention relates to the field of mineral flotation, and more specifically to a di-tert-butyl dithiophosphate compound and a preparation method and application thereof. Background Art

[0002] my country has rich reserves of lead-zinc ore resources, most of which are sulfide lead-zinc ore. However, the ore composition of lead-zinc ore is complex and there are many co-existing components. The overall distribution pattern is that there are more poor ores and fewer rich ores. These characteristics determine that the lead-zinc beneficiation process is mainly based on flotation. Since the lead content in domestic sulfide lead-zinc ore is generally lower than the zinc content and the floatability of lead sulfide ore is higher than that of zinc sulfide ore, most beneficiation plants adopt the process of high alkali priority flotation lead and then zinc flotation, which has a good effect on easy-to-select sulfide lead-zinc ore with simple embedding relationship and good monomer dissociation degree, but for difficult-to-select sulfide lead-zinc ore with fine vein or dense impregnation structure, there are problems such as low metal recovery rate, difficult lead-zinc separation, and serious tailing. To improve the metal recovery rate and achieve effective green separation of lead and zinc, the selection and application of flotation reagents are the key, among which the selectivity and capture of lead sulfide mineral collectors are one of the important considerations. At present, for poor, fine and mixed lead-zinc mineral resources, the commonly used traditional lead sulfide ore collectors often cannot take into account both the capture and selection of lead, making it difficult to achieve efficient and clean utilization of mineral resources.

[0003] Therefore, it is necessary to develop a new environmentally friendly lead sulfide ore collector with good selectivity and excellent collection performance in a low-alkali environment, realize lead-zinc separation, improve lead separation indicators, and provide new collector design ideas, which is of reference significance for promoting technological progress in the industry. Summary of the invention

[0004] Based on the above problems existing in the prior art, the present invention provides a di-tert-butyl dithiophosphate compound, which has an excellent flotation effect on lean, fine and hybrid lead-zinc ores, and does not need to be flotated under high alkaline conditions, thus avoiding the hidden danger of environmental pollution caused by tailings caused by using high alkaline conditions.

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

[0006] A di-tert-butyl dithiophosphate compound having the following structure:

[0007] Where M is Na + or NH4 + .

[0008] The present invention also provides a method for preparing the above-mentioned di-tert-butyl dithiophosphate compound, which comprises the following steps:

[0009] Tert-butyl alcohol is added to the solvent, phosphorus pentasulfide is added while stirring, and the temperature is raised to 80-100° C. for reaction; after the reaction is completed, the temperature is lowered to below 40° C., an alkali solution is added for neutralization, and the di-tert-butyl dithiophosphate compound is obtained.

[0010] In some embodiments, the mass ratio of the solvent, tert-butyl alcohol and phosphorus pentoxide is 4-12:3-6:1-5.

[0011] In some embodiments, the solvent is water.

[0012] In some embodiments, the alkali solution is at least one of liquid alkali and liquid ammonia; specifically, the liquid alkali is sodium hydroxide solution; and the liquid ammonia is aqueous ammonia.

[0013] In some embodiments, the pH value of the solution is controlled to be 7-10 during the neutralization process of adding alkali solution; preferably, the pH value of the solution is controlled to be 8-9.

[0014] The present invention also provides the use of the above-mentioned di-tert-butyl dithiophosphate compound as a lead collector for minerals in mineral flotation.

[0015] In some embodiments, the application specifically includes the following steps: grinding the raw ore to a particle size of -0.074 mm accounting for 75%, adding an inhibitor, a collector and a frother for roughing to obtain a lead roughing concentrate and a lead roughing tailing; adding a collector to the obtained lead roughing tailing for scavenging to obtain a lead scavenging concentrate and a lead tailing; mixing the lead roughing concentrate and the lead scavenging concentrate to obtain a lead concentrate; wherein the collector is the di-tert-butyl dithiophosphate compound, and the frother is 2 # Oil, the inhibitor is sodium sulfite.

[0016] In some embodiments, during the roughing process, the amount of collector is 80-120 g / t, the amount of frother is 10-40 g / t, and the amount of inhibitor is 250-800 g / t; during the scavenging process, the amount of collector is 10-40 g / t.

[0017] In some embodiments, the application specifically includes the following steps: grinding the raw ore to a particle size of -0.074 mm accounting for 85%, adding an inhibitor, a collector and a frother to perform three roughings to obtain a lead roughing concentrate and a lead roughing tailing; wherein, the amount of the inhibitor used in the roughing first is 900-1200 g / t, the amount of the collector used is 100-150 g / t, and the amount of the frother used is 10-20 g / t; the amount of the inhibitor used in the roughing second is 250-350 g / t, and the amount of the collector used is 30-50 g / t; the dosage of the three inhibitors in the roughing is 150-250g / t, and the dosage of the collector is 15-30g / t; after the roughing is completed, the inhibitor, collector and foaming agent are added to the lead roughing tailings for scavenging. During the scavenging process, the dosage of the inhibitor is 50-150g / t, the dosage of the collector is 5-15g / t, and the dosage of the foaming agent is 10-15g / t; in the roughing and scavenging process, the inhibitor is sodium sulfite, the collector is the di-tert-butyl dithiophosphate compound, and the foaming agent is 2 # Oil.

[0018] In some embodiments, the mineral is a lead-zinc sulfide ore, in which the Pb content is 0.68%-2.05%, the Zn content is 2.88%-5.30%, and the Fe content is 6.39%-11.47%.

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

[0020] The di-tert-butyl dithiophosphate compound of the invention can carry out lead flotation under natural pH conditions without adjusting the mineral slurry to a high alkaline state, thereby eliminating the hidden danger of environmental pollution caused by tailings brought about by the high alkaline conditions, and is beneficial to environmental protection and green environmental protection; in addition, the compound of the invention has good selectivity and collection performance for low-grade lead sulfide minerals, and compared with traditional lead sulfide mineral collectors, the lead grade of the lead concentrate obtained by using the compound of the invention is increased by 0.75%-1.74%, and the recovery rate is increased by 0.57%-1.76%.

[0021] The compound of the present invention is easy to apply on site, and there is no need to change the on-site process flow. It only needs to adjust the dosage of the agent and add the stock solution according to the amount. The operation is simple and the indicators are stable. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a process flow chart of Application Example 1-2 of the present invention;

[0023] Figure 2 This is a process flow chart of Application Example 3 of the present invention. 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] The preparation method of sodium di-tert-butyl dithiophosphate comprises the following steps:

[0028] Pour tert-butanol into the reaction container, then add deionized water to form a homogeneous solution, and then add phosphorus pentasulfide dropwise while stirring. Water, tert-butanol, and phosphorus pentasulfide are added in a mass ratio of 8:4:3. The temperature is raised to 95°C for reaction for 1.5 hours, and then cooling water is introduced to cool the temperature to below 40°C. Liquid alkali (sodium hydroxide solution) is added dropwise to control the pH value of the solution to about 9 to obtain sodium di-tert-butyl dithiophosphate.

[0029] Application Example 1

[0030] This application example is the application of sodium di-tert-butyl dithiophosphate obtained in Example 1 of the present invention as a lead collector in the low-alkali flotation separation and beneficiation of a lead-zinc sulfide mine in Guangxi. The process flow is as follows: Figure 1 shown.

[0031] The ore sample is a raw ore sample of a lead-zinc sulfide mine in Guangxi, which contains 0.73% Pb, 3.04% Zn, and 6.39% Fe. The main metal minerals are galena, sphalerite, and pyrite, and the main non-metallic minerals are dolomite and barite.

[0032] like Figure 1 After the raw ore is ground to a particle size of -0.074 mm, accounting for 75%, the lead roughing agent is sodium sulfite 300 g / t, the collector is sodium di-tert-butyl dithiophosphate 100 g / t prepared in Example 1, and the foaming agent is 2 # Oil 30-40g / t, to obtain lead rougher concentrate and lead rougher tailings; add 40g / t of collector di-tert-butyl sodium dithiophosphate to the lead rougher tailings for scavenging to obtain lead scavenging concentrate and lead tailings, and combine the lead rougher concentrate and the lead scavenging concentrate to obtain lead concentrate.

[0033] Comparative Example 1

[0034] The ore samples used in this comparative example are from the same batch as those in Application Example 1. The flotation process is as follows: Figure 1 As shown in the figure, after the raw ore is ground to -0.074mm particle size accounting for 75%, the lead roughing uses 2kg / t of lime as an inhibitor, 50g / t of butyl xanthate and 50g / t of ethyl thiocyanate as the collector, and 2 # Oil 30-40g / t, to obtain lead roughing concentrate and lead roughing tailings; add collector butyric acid 20g / t + ethyl dithiocarb 20g / t to the lead roughing tailings for scavenging, to obtain lead scavenging concentrate and lead tailings, the lead roughing concentrate and the lead scavenging concentrate are combined to obtain lead concentrate.

[0035] The flotation test results obtained in Application Example 1 and Comparative Example 1 are shown in Table 1.

[0036] Table 1 Flotation test results of a lead-zinc sulfide ore in Guangxi

[0037]

[0038] As shown in Table 1, without adding lime, the use of a new lead sulfide ore collector (sodium di-tert-butyl dithiophosphate) not only improves the grade and recovery rate of Pb in the lead concentrate, but also significantly reduces the grade and recovery rate of Zn in the lead concentrate, showing that the new lead sulfide ore collector has good selectivity and capture properties for lead.

[0039] Application Example 2

[0040] This application example is the application of sodium di-tert-butyl dithiophosphate obtained in Example 1 of the present invention as a lead collector in the low-alkali flotation separation and beneficiation of a sulfide lead-zinc ore in Inner Mongolia. The process flow is as follows: Figure 1 shown.

[0041] The ore sample is a raw ore sample of a lead-zinc sulfide mine in Inner Mongolia, which contains 0.68% Pb and 2.88% Zn. The main metal minerals are galena, sphalerite, and cerussite, and the main non-metallic minerals are quartz, sericite, kaolinite, etc.

[0042] like Figure 1 After the raw ore is ground to a particle size of -0.074 mm, which accounts for 75%, the lead roughing agent is sodium sulfite 600 g / t, the collector is sodium di-tert-butyl dithiophosphate 120 g / t prepared in Example 1, and the foaming agent is 2 # Oil 10-30g / t, to obtain lead rougher concentrate and lead rougher tailings; add 30g / t of collector di-tert-butyl sodium dithiophosphate to the lead rougher tailings for scavenging to obtain lead scavenging concentrate and lead tailings, combine the lead rougher concentrate and the lead scavenging concentrate to obtain lead concentrate.

[0043] Comparative Example 2

[0044] The ore samples used in this comparative example are from the same batch as those in Application Example 2. The flotation process is as follows: Figure 1As shown, after the raw ore is ground to -0.074mm particle size accounting for 75%, the lead roughing uses inhibitors such as zinc sulfate 1kg / t + sodium sulfite 1kg / t, collectors such as xanthate 60g / t + ethylthiocyanate 60g / t, and frothers such as 2 # Oil 10-30g / t, to obtain lead roughing concentrate and lead roughing tailings; add 20g / t of collector butyric acid to the lead roughing tailings for scavenging to obtain lead scavenging concentrate and lead tailings, combine the lead roughing concentrate and the lead scavenging concentrate to obtain lead concentrate.

[0045] The flotation test results obtained in Application Example 2 and Comparative Example 2 are shown in Table 2.

[0046] Table 2 Flotation test results of a lead-zinc sulfide ore in Inner Mongolia

[0047]

[0048] As shown in Table 2, under the same low-alkali conditions, the new lead sulfide ore collector used only in combination with sodium sulfite inhibitor is better than the conventional collector butyrate + ethylthiocyanate combined with zinc sulfate and sodium sulfite inhibitor. The grade and recovery rate of Pb in lead concentrate are improved, while the grade and recovery rate of Zn are significantly reduced, which once again demonstrates the good selectivity and collection of the new lead sulfide ore collector for lead.

[0049] Application Example 3

[0050] This application example is the application of sodium di-tert-butyl dithiophosphate obtained in Example 1 of the present invention as a lead collector in the low-alkali flotation separation and beneficiation of a lead-zinc sulfide mine in Guangdong. The process flow is as follows: Figure 2 shown.

[0051] The ore sample is a raw ore sample of a lead-zinc sulfide mine in Guangdong, which contains 2.05% Pb, 5.30% Zn, and 11.47% Fe. The main metal minerals are galena, sphalerite, and pyrite. The secondary metal minerals are arsenopyrite, chalcopyrite, pyrrhotite, and chalcocite. The gangue minerals are mainly quartz, calcite, micas, dolomite, etc.

[0052] like Figure 2 After the raw ore is ground to a particle size of -0.074 mm, accounting for 85%, the lead roughing agent is 1 kg / t of sodium sulfite as an inhibitor, 120 g / t of di-tert-butyl sodium dithiophosphate prepared in Example 1 as a collector, and 2 # Oil 10-20g / t; lead roughing 2 uses sodium sulfite 300g / t, collector sodium di-tert-butyl dithiophosphate 30g / t; lead roughing 3 uses sodium sulfite 200g / t, collector sodium di-tert-butyl dithiophosphate 20g / t; lead sweeping uses sodium sulfite 100g / t, collector sodium di-tert-butyl dithiophosphate 10g / t, and foaming agent 2 #Oil 10-15g / t; no lime is added during the entire lead flotation process, and the lead rougher concentrate and the lead scavenger concentrate are finally combined to obtain lead concentrate.

[0053] Comparative Example 3

[0054] The ore samples used in this comparative example are from the same batch as those in Application Example 3. The flotation process is as follows: Figure 2 After the raw ore is ground to -0.074mm particle size, accounting for 85%, the lead roughing is carried out with 2kg / t lime as inhibitor, 60g / t butyl xanthate and 60g / t ethyl thiocyanate as collector, and 2 # Oil 10-20g / t; Lead roughing 2 uses lime 300g / t, collector 15g / t of butyl xanthate + 15g / t of ethyl thiocyanate; Lead roughing 3 uses lime 1kg / t, collector 10g / t of butyl xanthate + 10g / t of ethyl thiocyanate; Lead sweeping uses lime 300g / t, collector 10g / t of butyl xanthate, 2 # Oil 10-15g / t; finally, the lead rougher concentrate and the lead scavenger concentrate are combined to obtain lead concentrate.

[0055] The flotation test results obtained in Application Example 3 and Comparative Example 3 are shown in Table 3.

[0056] Table 3 Flotation test results of a lead-zinc sulfide ore in Guangdong

[0057]

[0058] As shown in Table 3, without adding lime, the new lead sulfide ore collector was used. While the lead recovery rate was improved, the Pb grade in the lead concentrate was greatly improved. In addition, the grade and recovery rate of Zn in the lead concentrate decreased significantly, which also showed that the new lead sulfide ore collector had good selectivity and collection ability for lead.

[0059] In summary, the di-tert-butyl dithiophosphate compound of the present invention is used as a lead sulfide ore collector in the flotation of lead-zinc ore, and can show excellent selectivity and good collection effect without adjusting the slurry to a high alkaline state, and reduces the pollution of the high alkaline slurry to the environment, which is environmentally friendly.

[0060] 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.

[0061] 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 di-tert-butyl dithiophosphate compound, characterized in that: It has the following structure: Where M is Na + or NH4 + .

2. The method for preparing the di-tert-butyl dithiophosphate compound according to claim 1, characterized in that: The following steps are involved: Tert-butyl alcohol is added to the solvent, phosphorus pentasulfide is added while stirring, and the temperature is raised to 80-100° C. for reaction; after the reaction is completed, the temperature is lowered to below 40° C., an alkali solution is added for neutralization, and the di-tert-butyl dithiophosphate compound is obtained.

3. The method for preparing the di-tert-butyl dithiophosphate compound according to claim 2, characterized in that: The mass ratio of the solvent, tert-butyl alcohol and phosphorus pentoxide is 4-12:3-6:1-5.

4. The method for preparing the di-tert-butyl dithiophosphate compound according to claim 2, characterized in that: The alkali solution is at least one of liquid alkali and liquid ammonia.

5. The method for preparing the di-tert-butyl dithiophosphate compound according to claim 2, characterized in that: During the neutralization process of adding alkali solution, the pH value of the solution is controlled at 7-10.

6. Use of the di-tert-butyl dithiophosphate compound according to claim 1 as a lead collector for minerals.

7. The use according to claim 6, characterized in that: The following steps are involved: After grinding the raw ore to a particle size of -0.074 mm accounting for 75%, adding an inhibitor, a collector and a frother for roughing to obtain a lead roughing concentrate and a lead roughing tailing; adding a collector to the obtained lead roughing tailing for scavenging to obtain a lead scavenging concentrate and a lead tailing; mixing the lead roughing concentrate and the lead scavenging concentrate to obtain a lead concentrate; wherein the collector is the di-tert-butyl dithiophosphate compound, and the frother is 2 # Oil, the inhibitor is sodium sulfite.

8. The use according to claim 7, characterized in that: In the roughing process, the amount of collector is 80-120g / t, the amount of frother is 10-40g / t, and the amount of inhibitor is 250-800g / t; in the scavenging process, the amount of collector is 10-40g / t.

9. The use according to claim 6, characterized in that: The following steps are involved: After the raw ore is ground to a particle size of -0.074 mm accounting for 85%, inhibitors, collectors and frothers are added for three roughing to obtain lead roughing concentrate and lead roughing tailings; wherein, the amount of inhibitor used in the roughing first is 900-1200g / t, the amount of collector used is 100-150g / t, and the amount of frother used is 10-20g / t; the amount of inhibitor used in the roughing second is 250-350g / t, and the amount of collector used is 30-50g / t; the amount of inhibitor used in the roughing third is The amount of the inhibitor is 150-250g / t, and the amount of the collector is 15-30g / t; after the roughing is completed, the inhibitor, the collector and the foaming agent are added to the lead roughing tailings for scavenging. During the scavenging process, the inhibitor is 50-150g / t, the collector is 5-15g / t, and the foaming agent is 10-15g / t; in the roughing and scavenging process, the inhibitor is sodium sulfite, the collector is the di-tert-butyl dithiophosphate compound, and the foaming agent is 2 # Oil.

10. The use according to claim 6, characterized in that: The mineral is lead-zinc sulfide ore, in which the Pb content is 0.68%-2.05%, the Zn content is 2.88%-5.30%, and the Fe content is 6.39%-11.47%.

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