O,o-di-(thiocarbamoylthioalkyl)-phosphorodithioate collectors and combined collectors, flotation reagents, and preparation and use thereof

Abstract

The present application relates to the field of flotation, in particular to a kind of O, O-di-(thiocarbamoyl sulfanylalkyl)-dithiophosphoric acid collector, it is compound with formula 1 structure.The present application also includes the combined collection of the collector, flotation reagent comprising it and its preparation and application.The present application research shows that using the new collector, can be based on the synergy of intramolecular structure, can unexpectedly show better collection performance.

Description

Technical Field

[0001] This invention belongs to the field of mineral flotation technology, specifically relating to a collector for sulfide minerals. Background Technology

[0002] Non-ferrous metal sulfide ores are a type of non-renewable resource, and the research and application of flotation reagents are one of the key technologies driving the development of sulfide ore resource utilization technology. Traditional sulfide ore collectors mainly include xanthates and thiocyanates. Because xanthates are readily soluble in water and have very strong collecting ability, they can form insoluble salts with heavy metal ions, making them one of the most widely used collectors in sulfide ore flotation. However, xanthates have poor selectivity, and the separation between different sulfide minerals requires high alkalinity or the addition of large amounts of depressants, which not only increases beneficiation costs but also hinders the recovery of certain associated precious metals. Thiocyanates are obtained by replacing the thiol group in xanthic acid molecules with an alkyl amino group; therefore, thiocyanates can also be considered derivatives of xanthates. Currently, the most widely used thiocyanate collector in my country is ethyl thiocyanate, code Z-200. Thiocyanates have good selectivity, but their collecting ability is relatively weak.

[0003] To address the aforementioned issues, existing technologies have reported some improvement solutions. For example, Xiang Ping et al. used a novel Y89 series xanthate collector instead of isobutyl xanthate in a flotation desulfurization test of a cassiterite polymetallic sulfide ore. The novel xanthate collector demonstrated stronger flotation capability for sulfide ores, higher desulfurization yield, and faster flotation speed, which is beneficial for increasing the throughput of flotation equipment. Yu Zhicui studied the effect of ethyl thiocyanate Z-200 in the beneficiation of copper slag. The experiment used Z-200 alone and in mixtures with other reagents to conduct flotation tests on copper slag, and determined the optimal dosage of Z-200.

[0004] Although the effectiveness of flotation reagents has been continuously improved with the deepening of research and development, there is still room for improvement. Synthesizing new sulfide mineral collectors that have both good collecting ability and selectivity is of great significance for the efficient development and utilization of non-ferrous metal sulfide mineral resources in my country. Summary of the Invention

[0005] In response to the problems existing in the prior art, this invention proposes for the first time an O,O-di-(thiocarbamoylthioalkyl)-dithiophosphate collector (also referred to as flotation collector), aiming to provide a new collector with excellent collecting ability.

[0006] The second objective of this invention is to provide a method for preparing and using the aforementioned collector.

[0007] A third objective of this invention is to provide a combined collector comprising the novel collector, and its preparation and application.

[0008] O,O-di-(thiocarbamoylthioalkyl)-dithiophosphate collector, is a compound having the structure of Formula 1;

[0009] Formula 1

[0010] In Equation 1, R1 and R2 are individually C1~C 20 Alkyl groups or C1-C6 substituted alkyl groups with substituents;

[0011] X is C1~C 20 saturated carbon chain, C2~C 20 A hybrid carbon chain containing heteroatoms; wherein the heteroatoms are O and / or N;

[0012] Substituents are permitted on the carbon atoms of the saturated or hybrid carbon chains.

[0013] The substituent is at least one selected from C1-C6 alkyl, C1-C6 alkoxy, halogen, phenyl, nitro, and trifluoromethyl.

[0014] M is H, Na, K or NH4.

[0015] This invention provides a collector with a novel structure that can synergistically enhance its harvesting ability based on the combination of intramolecular fragments and spatial structure.

[0016] In this invention, R1 and R2 are individually C2-C6 alkyl groups;

[0017] Preferably, X is an alkylene group having a carbon number of C2 to C4, or is... The oxygen-carbon chain.

[0018] The alkylene group is, for example, 1,2-ethylene, 1,3-propylene, 1,2-isopropylene, 1,4-butylene, 1,3-isobutylene, or 1,2-tert-butylene.

[0019] Preferably, R3 is a C1-C6 alkylene group;

[0020] Preferably, M is H.

[0021] The present invention also provides a method for preparing the flotation collector described above, wherein the compound of formula 2 is reacted with phosphorus pentasulfide to obtain the product;

[0022] Formula 2

[0023] In Equation 2, the selection ranges of R1, R2, and X are the same as in Equation 1.

[0024] In this invention, the ratio of the compound of formula 2 and phosphorus pentasulfide can be adjusted according to the required content of the prepared product.

[0025] In this invention, the reaction temperature is 40~120℃, more preferably 70~100℃. The reaction time is 1~9h, more preferably 4~8h.

[0026] In this invention, the reaction can be carried out by self-solvent or by adding an additional solvent. To consider cost, when adding a solvent, the amount of solvent can be controlled to be below 100 mL solvent / mol phosphorus pentasulfide.

[0027] The present invention also provides a combined collector comprising collector A and collector B, wherein collector A is a flotation collector of formula 1 as described in the present invention, and collector B is a compound of formula 2 as described in the present invention.

[0028] The combined collector described in this invention, based on the combination of collectors A and B, can exhibit superior mineral collection ability.

[0029] In this invention, the content of collector A can be adjusted as needed, for example, it can be 10~95 mol.

[0030] The present invention also provides a method for preparing the combined collector described above, wherein phosphorus pentasulfide in a lower amount than the theoretical reaction amount is reacted with the compound of formula 2 to obtain a combined collector containing the collector A and the collector B.

[0031] For example, in this invention, the molar ratio of the compound of formula 2 to phosphorus pentasulfide is 1:0.05 to 0.3, preferably 1:0.05 to 0.25, and more preferably 1:0.1 to 0.2.

[0032] The present invention also provides a flotation reagent comprising a collector, wherein the collector comprises a flotation collector of Formula 1 as described in the present invention;

[0033] Preferably, the collector is the combined collector described in this invention, or the combined collector prepared by the method described in this invention.

[0034] Preferably, it also includes at least one of a foaming agent, an inhibitor, and a pH adjuster.

[0035] In this invention, the foaming agent, inhibitor, and pH adjuster can all be components known in the industry.

[0036] The present invention also provides a flotation method for sulfide ores, wherein the flotation reagents described herein are used for flotation.

[0037] In this invention, the innovative use of a flotation agent containing the novel collector of this invention can achieve stronger collection capacity and better selectivity.

[0038] In this invention, the sulfide ore is a sulfide ore containing at least one metallic element such as lead, zinc, copper, molybdenum, nickel, antimony, and bismuth, preferably at least one of lead-zinc sulfide ore, copper sulfide ore, copper-molybdenum sulfide ore, copper-zinc sulfide ore, copper-nickel sulfide ore, antimony sulfide ore, and bismuth sulfide ore.

[0039] In this invention, the pH during the flotation process is 3-12, more preferably 6.5-9, and even more preferably 7-7.5;

[0040] Preferably, the amount of collector used is 5 g / t or more. Considering the effect and cost, it can be further 5 to 150 g / t, more preferably 10 to 100 g / t, and most preferably 35 to 65 g / t. Alternatively, the concentration of the collector in the flotation pulp is 4 mg / L, and more preferably 4 to 10 mg / L.

[0041] Beneficial effects:

[0042] The novel collector described in this invention exhibits excellent collecting ability based on intramolecular synergy of molecular fragments, and it shows superior collecting ability compared to free combined collectors containing similar groups. Attached Figure Description

[0043] Figure 1 The infrared spectrum of the collector provided in Example 1 of this invention;

[0044] Figure 2 The infrared spectrum of the collector provided in Example 2 of this invention;

[0045] Figure 3 The infrared spectrum of the collector provided in Example 3 of this invention;

[0046] Figure 4 The infrared spectrum of the collector provided in Example 4 of this invention;

[0047] Figure 5 A single mineral flotation flow chart provided in an embodiment of the present invention;

[0048] Figure 6 A flotation process diagram of a lead-zinc sulfide ore in Inner Mongolia provided for an embodiment of the present invention. Detailed Implementation

[0049] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments. However, the scope of protection of the present invention is not limited to the following specific embodiments.

[0050] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0051] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0052] In the following examples, "parts" refer to parts by weight. The specific dosage can be determined according to the scale of the experiment, for example, it can be a laboratory scale of 1~1000g, or a pilot-scale or production scale of more than 1kg.

[0053] Example 1

[0054]

[0055] 70 mL of xylene solvent was added to the reactor, and 19.33 g of phosphorus pentasulfide was slowly added and stirred until evenly dispersed in the solvent. Then, 80 g of Formula 2-A (at a molar ratio of phosphorus pentasulfide of 1:0.2) was slowly added dropwise, and the temperature was slowly raised to 90 ± 5 °C. The reaction was carried out under stirring for 5 h. After the reaction was completed, the solvent was removed by vacuum distillation, yielding a yellow oily liquid mixture, which was the target collector product. Analysis showed that the conversion rate of phosphorus pentasulfide was close to 100%. The obtained product was characterized, and the infrared spectrum is shown below. Figure 1 The infrared spectrum analysis of the product is shown in Table 1. The results show that both C=S and P=S groups appeared in the molecule, indicating that the product formed formula 1-A.

[0056]

[0057] Example 2

[0058] 50 mL of xylene solvent was added to the reactor, and 9.67 g of phosphorus pentasulfide was slowly added and stirred until evenly dispersed in the solvent. Then, 77.33 g of formula 2-A (at a molar ratio of phosphorus pentasulfide of 1:0.1) was slowly added dropwise, and the temperature was slowly raised to 80 ± 5 °C. The reaction was carried out for 6 h under stirring. After the reaction was completed, the solvent was removed by vacuum distillation, yielding a yellow oily liquid mixture, which was the target collector product. Analysis showed that the conversion rate of phosphorus pentasulfide was close to 100%. The obtained product was characterized, and the infrared spectrum is shown below. Figure 2 The infrared spectrum analysis of the target product is shown in Table 1. The results show that C=S and P=S groups appeared in the molecule at the same time, indicating that the product formed formula 1-A.

[0059]

[0060] Example 3

[0061] 77.33 parts of Formula 2-A were added to the reactor, and 4.83 parts of phosphorus pentasulfide (0.05 eqv) were added under stirring. The temperature was then slowly increased to 90±5℃, and the reaction was carried out under stirring for 4 hours. After the reaction was completed, a yellow oily liquid mixture was obtained, which was the target collector product. Analysis showed that the conversion rate of phosphorus pentasulfide was close to 100%. The obtained product was characterized, and the infrared spectrum is shown below. Figure 3 The infrared spectrum analysis of the target product is shown in Table 3. The presence of both C=S and P=S groups in the molecule indicates that the product is of formula 1-A.

[0062]

[0063] Example 4

[0064]

[0065] 47.48 parts of Formula 2-B were added to the reactor, and 3.22 parts of phosphorus pentasulfide (0.07 eqv) were added under stirring. The temperature was then slowly increased to 90±5℃, and the reaction was carried out under stirring for 5 hours. After the reaction was completed, a yellow oily liquid mixture was obtained, which was the target collector product. Analysis showed that the conversion rate of phosphorus pentasulfide was close to 100%. The obtained product was characterized, and the infrared spectrum is shown below. Figure 4 The infrared spectrum analysis of the target product is shown in Table 4. The presence of both C=S and P=S groups in the molecule indicates that the product is of formula 1-B.

[0066]

[0067] Application Example 1

[0068] Galena was floated using the collector from Example 1:

[0069] According to such Figure 5 The process flow shown involves flotation of galena as a single mineral, using the collector prepared according to the method in Example 1. The flotation machine was operated at a stirring speed of 1650 r / min, with a pulp pH of 7.0. Galena particles with a size of 0.038–0.074 mm were floated for 3 minutes. The frother, methyl isobutyl methanol (MIBC), was used at a concentration of 10 mg / L. Measurements of the collector concentration and flotation recovery rate in this process showed that when the collector concentration was 2 mg / L, the flotation recovery rate of galena was 53.90%; and when the collector concentration was 5 mg / L, the flotation recovery rate of galena was 94.39%.

[0070] Application Example 2

[0071] Chalcopyrite was floated using the collector from Example 1:

[0072] According to such Figure 5 The process flow shown is for the flotation of chalcopyrite, a single mineral, using the collector prepared according to the method in Example 1. The flotation machine is operated at a stirring speed of 1650 r / min, the pulp pH is 7.0, and chalcopyrite particles with a size of 0.038–0.074 mm are floated for 3 minutes. The frother MIBC dosage is 10 mg / L. Measurements of the collector concentration and flotation recovery rate in this process show that when the collector concentration is 2 mg / L, the flotation recovery rate of chalcopyrite is 75.32%; when the collector concentration is 5 mg / L, the flotation recovery rate of chalcopyrite is 97.58%.

[0073] Application Example 3

[0074] Galena was floated using the collector in Example 2:

[0075] According to such Figure 5 The process flow shown involves flotation of galena, a single mineral, using the collector prepared according to the method in Example 2. The flotation machine was operated at a stirring speed of 1650 r / min, with a pulp pH of 7.0. Galena particles with a size of 0.038–0.074 mm were floated for 3 minutes, and the frother MIBC dosage was 10 mg / L. Measurements of the collector concentration and flotation recovery rate in this process showed that when the collector concentration was 2 mg / L, the flotation recovery rate of galena was 53.90%; and when the collector concentration was 5 mg / L, the flotation recovery rate of galena was 93.47%.

[0076] Application Example 4

[0077] Chalcopyrite was floated using the collector from Example 2:

[0078] According to such Figure 5 The process flow shown illustrates the flotation of chalcopyrite as a single mineral. The collector used is the one prepared according to the method in Example 2. The flotation machine is operated at a stirring speed of 1650 r / min, the pulp pH is 7.0, and chalcopyrite particles with a size of 0.038–0.074 mm are floated for 3 minutes. The frother MIBC dosage is 10 mg / L. Measurements of the collector concentration and flotation recovery rate in this process show that when the collector concentration is 2 mg / L, the flotation recovery rate of chalcopyrite is 75.32%; when the collector concentration is 5 mg / L, the flotation recovery rate of chalcopyrite is 97.58%.

[0079] Compare with application example 1:

[0080] Compared to application example 1, the only difference is that it adopts... Comparative formula A, as a collector, specifically includes:

[0081] According to such Figure 5The process flow shown depicts the flotation of galena as a single mineral, using the traditional comparative collector A. The flotation machine is operated at a stirring speed of 1650 r / min, with a pulp pH of 7.0. Galena particles with a size of 0.038–0.074 mm are floated for 3 minutes, and the frother MIBC is used at a concentration of 10 mg / L. Measurements of the concentration of comparative collector A and the flotation recovery rate during this process show that when the collector concentration is 2 mg / L, the flotation recovery rate of galena is only 38.17%; when the collector concentration is 5 mg / L, the flotation recovery rate of galena is 84.03%.

[0082] Compare with application example 2:

[0083] Compared to application example 1, the only difference is that it adopts... Comparative formula B, as a collector, specifically includes:

[0084] According to such Figure 5 The process flow shown depicts the flotation of galena as a single mineral, using the traditional comparative collector B. The flotation machine is operated at a stirring speed of 1650 r / min, with a pulp pH of 7.0. Galena particles with a size of 0.038–0.074 mm are floated for 3 minutes, and the frother MIBC dosage is 10 mg / L. Measurements of the concentration of comparative collector B and the flotation recovery rate during this process show that when the collector concentration is 2 mg / L, the flotation recovery rate of galena is only 67.75%; when the collector concentration is 5 mg / L, the flotation recovery rate of galena is 86.33%.

[0085] Compare with application example 3:

[0086] Compared to Application Example 1, the only difference is that comparative formula A and comparative formula B are used as the collector, specifically:

[0087] Formulas A and B were dissolved in an aqueous solution at a molar ratio of 1:2 to prepare a compound collector C. This compound collector C was then used for flotation of galena as a single mineral. The flotation machine was operated at a stirring speed of 1650 r / min, with a pulp pH of 7.0, and galena particles with a size of 0.038–0.074 mm were floated for 3 minutes. The results showed that when the concentration of the compound collector was 2 mg / L, the flotation recovery rate of galena was only 36.79%; while when the concentration was 5 mg / L, the flotation recovery rate was 88.16%.

[0088] As can be seen from Application Example 1 and Comparative Application Examples 1-3, the novel collector described in this invention, based on the combination of groups in the molecular fragment, can achieve intramolecular synergy and unexpectedly obtain superior collecting ability.

[0089] Compare with application example 4:

[0090] Compared to application example 1, the only difference is that the collector is... Other operations and parameters are the same as in Application Example 1. Measurements of the collector concentration and flotation recovery during this process show that when the collector concentration is 2 mg / L, the flotation recovery of galena is only 3.55%; and when the collector concentration is 5 mg / L, the flotation recovery of galena is only 6.70%.

[0091] Application Example 5

[0092] Application of the collector prepared in Example 2 in the flotation of a lead-zinc mine in Inner Mongolia:

[0093] The raw ore is a lead-zinc ore from Inner Mongolia. The most valuable elements for recovery in the ore are lead and zinc, with contents of 1.61% and 1.72%, respectively. However, the oxidation rates of lead and zinc in the ore are both high, at 25.54% and 16.04%, respectively, classifying it as a mixed lead-zinc ore (for sulfide ores).

[0094] Specific process: 500g of crushed raw ore (particle size 0.5~3mm) is weighed and wet-milled with water in a small conical ball mill until the grinding concentration is approximately 66.7%. After grinding, the fineness is approximately -0.074mm, accounting for about 85%. The ground slurry is then transferred to a 1.5L flotation cell. The flotation operation uses a single roughing stage. The froth product is the rough concentrate, and the bottom product is the tailings. For detailed process flow and flotation reagent system, see [link to relevant documentation]. Figure 6 After filtration and drying, each sample was weighed and tested for lead and zinc content. The flotation recovery rate was calculated, and the test results are shown in Table 5 below.

[0095] As shown in Table 5, the sulfide ore composite collector in Example 2 of this invention, compared with the traditional comparative formula A, under the same reagent dosage, has a higher lead recovery rate in the rough concentrate, with a lead recovery rate increase of 12.40%; compared with the traditional comparative formula B, the lead recovery rate in the rough concentrate is also significantly better, with a lead recovery rate increase of 18.20%; compared with the combination of formula A and formula B, the lead recovery rate in the rough concentrate is also higher, with a lead recovery rate increase of 14.05%. This indicates that the sulfide ore composite collector of this invention has a significantly better collecting ability for lead-zinc ore than the traditional collectors comparative formula A, comparative formula B, and the combination of formula A and formula B.

[0096]

[0097] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. The application of an O,O-di-(thiocarbamoylthioalkyl)-dithiophosphate collector, characterized in that, It is used for the collection of sulfide minerals, wherein the O,O-di-(thiocarbamoylthioalkyl)-dithiophosphate collector is a compound having the structure of Formula 1. Formula 1 In Equation 1, R1 and R2 are individually C1~C 20 Alkyl groups or C1-C6 substituted alkyl groups with substituents; X is C1~C 20 saturated carbon chain, C2~C 20 A hybrid carbon chain containing heteroatoms; wherein the heteroatoms are O and / or N; Substituents are permitted on the carbon atoms of the saturated or hybrid carbon chains. The substituent is at least one selected from C1-C6 alkyl, C1-C6 alkoxy, halogen, phenyl, nitro, and trifluoromethyl. M is H, Na, K or NH4.

2. The application as described in claim 1, characterized in that, R1 and R2 are individually C2-C6 alkyl groups; X is an alkylene group having a carbon number of C2 to C4, or is... oxo-hexacarbon chain; The R3 is a C1-C6 alkylene group; The M mentioned is H.

3. A method for preparing the O,O-di-(thiocarbamoylthioalkyl)-dithiophosphate collector as described in claim 1 or 2, characterized in that, The compound of formula 2 is reacted with phosphorus pentasulfide to obtain the product; Formula 2 In Equation 2, the selection ranges of R1, R2, and X are the same as in Equation 1.

4. The preparation method according to claim 3, characterized in that, The reaction temperature is 40~120℃, and the reaction time is 1~9h.

5. A combined collector, characterized in that, It comprises collector A and collector B, wherein collector A is the O,O-di-(thiocarbamoylthioalkyl)-dithiophosphate collector described in the application of claim 1 or 2, and collector B is the compound of formula 2 described in the preparation method of claim 3.

6. The combined collector as described in claim 5, characterized in that, The content of collector A is 10~95 mol.

7. A method for preparing the combined collector according to claim 5 or 6, characterized in that, Using the preparation method described in claim 3 or 4, phosphorus pentasulfide and compound of formula 2 are reacted in amounts lower than the theoretical reaction amount to obtain a combined collector containing collector A and collector B.

8. The method for preparing the combined collector as described in claim 7, characterized in that, The molar ratio of compound 2 to phosphorus pentasulfide is 1:0.05~0.

3.

9. The method for preparing the combined collector as described in claim 8, characterized in that, The molar ratio of compound 2 to phosphorus pentasulfide is 1:0.05~0.

25.

10. A flotation reagent comprising a collector, characterized in that, The collector comprises the O,O-di-(thiocarbamoylthioalkyl)-dithiophosphate collector as described in the application of claim 1 or 2, and further comprises at least one of a foaming agent, an inhibitor, and a pH adjuster.

11. The flotation reagent as described in claim 10, characterized in that, The collector is the combined collector as described in any one of claims 5 to 6, or the combined collector prepared by any one of claims 7 to 9.

12. A flotation method for sulfide ores, characterized in that, Flotation is performed using the flotation reagents described in claim 10 or 11.

13. The flotation method for sulfide ores as described in claim 12, characterized in that, The sulfide minerals mentioned are sulfide minerals containing at least one metallic element, namely lead, zinc, copper, molybdenum, nickel, antimony, or bismuth.

14. The flotation method for sulfide ores as described in claim 13, characterized in that, Sulfide minerals are at least one of the following: lead-zinc sulfide minerals, copper sulfide minerals, copper-molybdenum sulfide minerals, copper-zinc sulfide minerals, copper-nickel sulfide minerals, antimony sulfide minerals, and bismuth sulfide minerals.

15. The flotation method for sulfide ores as described in claim 14, characterized in that, The pH during the flotation process is 3~12; The dosage of the collector is 5~150g / t.

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