Alpha-(N, N-dialkyl-NCSS) acetic acid collecting agent and preparation method and application thereof

Abstract

The invention belongs to the field of flotation, and particularly relates to an alpha-(N, N-dialkyl-NCSS) acetic acid collecting agent and a preparation method and application thereof, and the collecting agent is a compound with a formula 1 # imgabs0 # structure. Innovative research shows that the compound with the structure shown in the formula 1 can accidentally and synchronously consider the physicochemical characteristics of the non-ferrous metal oxidized ore and the sulfide ore based on combination and synergy of molecular structures, and excellent collecting capacity and effect can be obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral flotation, and in particular relates to the field of flotation collectors. Background Art

[0002] Nonferrous metal ores include sulfide minerals and oxide minerals. Sulfide minerals have strong surface hydrophobicity and good natural floatability, so they can be well recovered by flotation using a single mercapto collector. For example, more common collectors include xanthate collectors. In addition, as the grade of sulfide ores gradually decreases, the prior art also reports some flotation ideas of composite collectors. For example, a Chinese patent document with publication number CN117696260A discloses a combined collector for chalcopyrite in low-copper and high-sulfur copper-sulfide ores and its application, wherein the composite collector includes pyridinemethanol and ethyl xanthate.

[0003] Nonferrous metal oxide minerals have the characteristics of strong surface hydrophilicity, easy dissolution, and easy hydroxylation. The sulfhydryl collector often reacts with the metal ions dissolved in the ore pulp first instead of directly adhering to the oxide surface. Therefore, the flotation of oxide ore generally does not directly use the sulfhydryl collector. It is usually necessary to use a sulfiding agent such as sodium sulfide and sodium hydrosulfide for pre-sulfidation, and then use the sulfhydryl collector for recovery. However, in the sulfidation flotation method, it is usually faced with the problem that the amount of sulfiding agent is difficult to control, the sulfidation time is uncertain, and the sulfiding agent is easy to fail. And after using a large amount of sulfiding agents, the ore dressing wastewater cannot be treated and reused. For example, the Chinese patent document with publication number CN109261373A discloses a flotation method of white lead ore, wherein the ore containing white lead ore is ground to monomer dissociation, and then iodine ions are added for pretreatment, sodium sulfide is added after full action and stirred for 3 to 10 minutes, and then a long-chain collector octyl xanthate is added and stirred for 2 to 6 minutes, and then a foaming agent pine oil is added, and the foam is scraped out as a lead-containing concentrate product.

[0004] In the existing technology, most collectors are developed for single non-ferrous metal sulfide ores or oxide minerals, and cannot recover both sulfide minerals and oxide minerals. Although combined collectors can be used, the preparation scheme is complicated, the metal recovery rate is limited, and resources cannot be fully recovered. Summary of the invention

[0005] In view of the problem that existing collectors are difficult to have good universality for both sulfide ores and oxide ores, the first purpose of the present invention is to provide an α-(N,N-dialkyl-NCSS) acetic acid collector, aiming to provide a new collector that has good universality for both non-ferrous metal sulfide ores and oxide ores.

[0006] The second object of the present invention is to provide a method for preparing the α-(N,N-dialkyl-NCSS) acetic acid collector.

[0007] The third object of the present invention is to provide the application of the α-(N,N-dialkyl-NCSS) acetic acid collector.

[0008] An α-(N,N-dialkyl-NCSS) acetic acid collector is a compound having the structure of Formula 1;

[0009]

[0010] R1 and R2 are each independently an alkyl or substituted alkyl group having 1 to 10 carbon atoms; the substituted alkyl group is a group having at least one substituent selected from alkoxy groups having 1 to 4 carbon atoms, halogen, phenyl, and vinyl on the alkyl carbon chain having 1 to 4 carbon atoms;

[0011] M is H, Na, K or NH4.

[0012] The innovative research of the present invention shows that the compound of Formula 1 can unexpectedly take into account the physical and chemical characteristics of non-ferrous metal oxidized ores and sulfide ores simultaneously based on the combined synergy of the molecular structure, and excellent collecting ability and effect can be obtained.

[0013] In the present invention, R1 and R2 are each independently an alkyl group having 3 to 5 carbon atoms.

[0014] The present invention also provides a preparation method of the α-(N,N-dialkyl-NCSS) acetic acid collector, which is prepared by a substitution reaction of Formula 2 and Formula 3;

[0015]

[0016] R1, R2 and M in Formula 2 and Formula 3 are the same as those in Formula 1.

[0017] In the present invention, the molar ratio of Formula 2 to Formula 3 is 1:1 to 1.2.

[0018] Preferably, the substitution reaction further includes an MOH acid-binding agent; the MOH acid-binding agent is 2 to 4 times the molar amount of Formula 2;

[0019] Preferably, the temperature of the substitution reaction is 50 to 90 °C, further preferably 55 to 75 °C, and the substitution reaction time is 1 to 7 h, further preferably 3 to 5 h.

[0020] The present invention also provides an application of the α-(N,N-dialkyl-NCSS) acetic acid collector, which is used as a flotation collector for collecting non-ferrous metal ores.

[0021] In the present invention, the non-ferrous metal ore is an oxidized ore and / or a sulfide ore of at least one metal selected from zinc, copper, lead, nickel, molybdenum, antimony, silver, and lithium.

[0022] In the present invention, the non-ferrous metal ore includes at least one of chalcopyrite, sphalerite, galena, malachite, smithsonite, cerussite, lepidolite ore containing rubidium and cesium, and silver-lead composite ore.

[0023] In the present invention, the dosage of the collector is 10 - 500 g / t, and further can be 40 - 100 g / t.

[0024] In the present invention, the pH of flotation is 3 - 12, and further can be 6.5 - 7.5.

[0025] In the present invention, the temperature of flotation is 5 - 35 °C.

[0026] Beneficial effects

[0027] 1) The present invention provides a collector with a brand-new structure 1, which can take into account the physical and chemical characteristics of oxidized and sulfide non-ferrous metal ores based on the combined synergy of molecular structures, and can obtain excellent collecting ability and effect.

[0028] 2) The collector described in the present invention, based on the combination of structures, can effectively enhance the adsorption of the collector on the mineral surface, and the reagent has not only strong collecting ability but also good selectivity.

[0029] The collector described in the present invention can realize the simultaneous recovery of sulfide minerals and oxidized minerals of the same metal in the ore by using a single collector, and the simultaneous flotation of sulfide ore - oxidized ore can be realized without adding sulfiding agents (such as sodium sulfide, sodium hydrosulfide, etc.).

[0030] In addition, the collector described in the present invention does not need to add a foaming agent or only adds a small amount of foaming agent during the flotation process, which is beneficial to reducing the reagent cost and improving the flotation efficiency. Description of the drawings

[0031] Figure 1 1H NMR spectrum of formula 1A prepared for Example 1; 1 1H NMR spectrum;

[0032] Figure 2 13C NMR spectrum of formula 1A prepared for Example 1; 13 13C NMR spectrum;

[0033] Figure 3 Infrared spectrum of formula 1A prepared for Example 1;

[0034] Figure 4 Single mineral flotation flow chart provided for Examples 3 - 9;

[0035] Figure 5 Actual ore flotation flow chart of a certain silver-lead ore in Henan for Example 10; Detailed implementation manners

[0036] The following examples are intended to further illustrate the content of the present invention, but the scope of protection of the claims of the present invention is not limited by the specific examples.

[0037] In the following preparations, the dosage parts of the components described refer to parts by weight.

[0038] In the following cases, there is no special requirement for the temperature of the flotation process. For example, except as otherwise stated, the temperature of the flotation can be 25 ± 5 °C.

[0039] Example 1

[0040] Preparation of the collector of Formula 1A:

[0041] Add 30 parts of solvent water and 56.84 parts of 40% of Formula 2A solution to the reaction flask, mix and stir, and then slowly add Formula 3A dissolved in 40 parts of water ( Formula 3A is 1.05 - 1.1 times the molar amount of Formula 2A), heat up to the temperature in the reactor to 60 °C, keep the temperature constant for 4 hours, then cool to room temperature, add 100 parts of ethyl acetate to the reaction flask for extraction and separation to obtain a dark yellow liquid product, perform recrystallization at -4 °C to obtain a pale yellow solid, and filter to obtain the pure product of Formula 1A Perform structural characterization on the obtained Formula 1A, nuclear magnetic resonance 1 The H spectrum is as Figure 1 shown, and the nuclear magnetic resonance 13 C spectrum is as Figure 2 shown, and the infrared spectrum is shown in Figure 3 , the infrared spectrum analysis of the target product is shown in Table 1, and the nuclear magnetic resonance spectrum analysis of the target product is shown in Table 2.

[0042] Table 1 Infrared Spectrum Analysis of Formula 1A

[0043]

[0044] Table 2 Nuclear Magnetic Resonance Spectrum Analysis of Formula 1A

[0045]

[0046]

[0047] Example 2

[0048] Preparation of the collector of Formula 1A:

[0049] Add 20 parts of solvent water and 28.42 parts of 40% solution of formula 2A into the reaction flask, mix and stir, then slowly add 5.95 parts of formula 3A dissolved in 20 parts of water. Heat up to 70 °C in the reactor and react at a constant temperature for 5 hours. Then cool to room temperature, add 60 parts of ethyl acetate into the reaction flask for extraction and separation to obtain a dark yellow liquid product. Recrystallize at -4 °C to obtain a light yellow solid, and filter to obtain the pure product of formula 1A.

[0050] Example 3 - Galena Flotation

[0051] Adopt the Figure 4 shown technological process to conduct flotation on galena, where the collector is of formula 1A. At a stirring speed of 1650 r / min in the flotation machine and a pulp pH of 7.0, conduct flotation on galena with a particle size of 0.038 - 0.074 mm for 4 minutes. When the collector concentration is 2×10 -5 mol / L, the flotation recovery rate of galena is 94.02%; when the collector concentration is 4×10 -5 mol / L, the flotation recovery rate of galena is 98.14%.

[0052] Example 4 - Cerussite Flotation

[0053] Adopt the Figure 4 shown technological process to conduct flotation on cerussite, where the collector is of formula 1A. At pH = 7.0 and a stirring speed of 1650 r / min in the flotation machine, conduct flotation on cerussite with a particle size of 0.038 - 0.074 mm for 4 minutes. When the collector concentration is 1×10 -4 mol / L, the flotation recovery rate of cerussite is 80.02%; when the collector concentration is 2×10 -4 mol / L, the flotation recovery rate of cerussite is 87.32%; when the collector concentration is 3×10 -4 mol / L, the flotation recovery rate of cerussite is 96.23%.

[0054] Example 5 - Sphalerite Flotation

[0055] Adopt the Figure 4 shown technological process to conduct flotation on sphalerite, where the collector is of formula 1A. At a stirring speed of 1650 r / min in the flotation machine and a pulp pH of 7.0, conduct flotation on sphalerite with a particle size of 0.038 - 0.074 mm for 4 minutes. When the collector concentration is 1×10 -4 mol / L, the flotation recovery rate of sphalerite is 81.42%; when the collector concentration is 2×10 -4 mol / L, the flotation recovery rate of sphalerite is 84.42%.

[0056] Example 6 - Chalcopyrite Flotation

[0057] Use the process flow shown in Figure 4 to float chalcopyrite. The collector is Formula 1A. The stirring speed of the flotation machine is 1650 r / min, the pulp pH is 7.0, and chalcopyrite with a particle size of 0.038 - 0.074 mm is floated for 4 minutes. When the collector concentration is 1×10 -5 mol / L, the flotation recovery rate of chalcopyrite is 76.96%. When the collector concentration is 2×10 -5 mol / L, the flotation recovery rate of chalcopyrite is 87.78%. When the collector concentration is 3×10 -5 mol / L, the flotation recovery rate of chalcopyrite is 97.10%.

[0058] Example 7 - Malachite Flotation

[0059] Use the process flow shown in Figure 4 to float malachite. The collector is Formula 1A. The stirring speed of the flotation machine is 1650 r / min, the pulp pH is 7.0, and malachite with a particle size of 0.038 - 0.074 mm is floated for 4 minutes. When the collector concentration is 2×10 -3 mol / L, the flotation recovery rate of malachite is 68.49%. When the collector concentration is 5×10 -3 mol / L, the flotation recovery rate of malachite is 78.62%. When the collector concentration is 8×10 -3 mol / L, the flotation recovery rate of malachite is 80.71%.

[0060] Example 8 - Smithsonite Flotation

[0061] Use the process flow shown in Figure 4 to float smithsonite. The collector is Formula 1A. The stirring speed of the flotation machine is 1650 r / min, the pulp pH is 7.0, and smithsonite with a particle size of 0.038 - 0.074 mm is floated for 4 minutes. When the collector concentration is 2×10 -4 mol / L, the flotation recovery rate of smithsonite is 35.60%. When the collector concentration is 4×10 -4 mol / L, the flotation recovery rate of smithsonite is 75.63%.

[0062] Example 9 - Flotation of Lepidolite Ore Containing Rubidium and Cesium

[0063] A certain lepidolite ore containing rubidium and cesium in Jiangxi contains 2.63% Li2O, 0.82% Rb2O, and 0.16% Cs2O. Use the process flow shown in Figure 4The shown technological process is used for the flotation of lepidolite ore containing rubidium and cesium. The collector is of Formula 1A. The agitation speed of the flotation machine is 1650 r / min, the pulp pH is 7.0, and the lepidolite containing rubidium and cesium with a particle size of 0.038 - 0.074 mm is flotated for 4 minutes. When the collector concentration is 5×10 -4 mol / L, the flotation recovery rate of the lepidolite containing rubidium and cesium is 58.32%; when the collector concentration is 8×10 -4 mol / L, the flotation recovery rate of the lepidolite containing rubidium and cesium is 72.34%; when the collector concentration is 1×10 -3 mol / L, the flotation recovery rate of the lepidolite containing rubidium and cesium is 81.44%.

[0064] Example 10 - Flotation of Silver-Lead Ore

[0065] Application example 2 is applied to the flotation of a silver-lead ore in Henan:

[0066] In the embodiment of the present invention, in a silver-lead ore in Henan, the main valuable metals are lead and silver. The lead minerals are mainly lead sulfide and lead oxide minerals, the lead oxidation rate exceeds 30%, and the lead oxide is mainly cerussite. The silver grade in the original ore is about 172 g / t, the lead grade is about 1.99%, and the zinc grade is 0.40%.

[0067] The specific process is as follows: The silver-lead original ore is crushed to less than 2 mm. Each time, 500 g is weighed and ground in a small conical ball mill with 250 mL of water for 5 min 30 s. The grinding concentration is 66.7%, and the grinding fineness is about 65% passing - 0.074 mm. The ground pulp is transferred to a 1.5 L flotation cell. The flotation adopts an experimental process of one roughing. The collector of the present invention is used to recover the lead and silver minerals therein. The comparative collectors are conventional ethyl thionocarbamate (sodium diethyldithiocarbamate) and butyl thionocarbamate (sodium di-n-butyldithiocarbamate, Formula 2A). The foaming agent used is commercially available BK301. The specific technological process and flotation reagent system are shown in Figure 5 , and finally concentrate and tailings are obtained respectively. After filtration and drying, they are weighed respectively and the contents of Pb and Ag are assayed, and the metal flotation recovery rate is calculated. The flotation test results are shown in Table 3 below (the flotation pH is 7 - 7.5).

[0068] Table 3 Flotation Test Results

[0069]

[0070] From the test results, it can be seen that when the collector of Formula 1A of the present invention is compared with the traditional ethyl thionocarbamate, under the condition of the same reagent dosage (50 g / t), the Pb recovery rate and Ag recovery rate in the flotation concentrate are increased by 12.88 and 25.61 percentage points respectively, and the improvement of the metal recovery rate is very significant; when compared with butyl thionocarbamate with the same dosage, the Pb recovery rate and Ag recovery rate in the flotation concentrate are increased by 4.63 and 8.86 percentage points respectively, and the improvement of the metal recovery rate is also very significant; while when the commonly used sodium chloroacetate is used as the collector, there is no enrichment effect in flotation, and the metal grades of the raw ore, concentrate and tailings are close. The above results show that the collector of the present invention has far better collecting ability for lead sulfide, lead oxide minerals and silver minerals than the conventional ethyl thionocarbamate, butyl thionocarbamate and sodium chloroacetate.

Claims

1. An α-(N,N-dialkyl-NCSS) acetic acid collector, characterized in that, It is a compound with the structure of Formula 1; R1 and R2 are each independently an alkyl or substituted alkyl group having from C1 to C 10 ; the substituted alkyl group is a group having at least one substituent selected from alkoxy groups having from C1 to C4, halogen, phenyl, and vinyl on the alkyl carbon chain having from C1 to C4; wherein M is H, Na, K or NH4.

2. The α-(N,N-dialkyl-NCSS) acetic acid collector as described in claim 1, characterized in that, R1 and R2 are each independently an alkyl group having 3 to 5 carbon atoms.

3. A preparation method of the α-(N,N-dialkyl-NCSS) acetic acid collector according to claim 1 or 2, characterized in that, It is prepared by a substitution reaction through Formula 2 and Formula 3; R1, R2 and M in Formula 2 and Formula 3 are the same as those in Formula 1.

4. The preparation method of the α-(N,N-dialkyl-NCSS) acetic acid collector according to claim 3, characterized in that, The molar ratio of Formula 2 to Formula 3 is 1:1 to 1.2; Preferably, the substitution reaction further comprises an MOH acid-binding agent; the MOH acid-binding agent is 2 to 4 times the molar amount of Formula 2; Preferably, the temperature of the substitution reaction is 50 to 90 °C, and the substitution reaction time is 1 to 7 h.

5. Use of the α-(N,N-dialkyl-NCSS) acetic acid collector according to claim 1 or 2, characterized in that It is used as a flotation collector for flotation of non-ferrous metal ores.

6. The application of the α-(N,N-dialkyl-NCSS) acetic acid collector as described in claim 5, characterized in that, The non-ferrous metal ore is an oxide ore and / or a sulfide ore of at least one metal selected from zinc, copper, lead, nickel, molybdenum, antimony, silver, and lithium.

7. The application of the α-(N,N-dialkyl-NCSS) acetic acid collector according to claim 6, characterized in that, The non-ferrous metal ore includes at least one of chalcopyrite, sphalerite, galena, malachite, smithsonite, cerussite, rubidium- and cesium-containing lepidolite ore, and silver-lead composite ore.

8. Use of the α-(N,N-dialkyl-NCSS) acetic acid collector according to any one of claims 5 to 7, characterized in that, The dosage of the collector is 10 to 500 g / t.

9. Use of the α-(N,N-dialkyl-NCSS) acetic acid collector according to any one of claims 5 to 7, characterized in that, The pH of the flotation is 3 to 12.

10. Use of the α-(N,N-dialkyl-NCSS) acetic acid collector according to any one of claims 5 to 7, characterized in that, The temperature of the flotation is 5 to 35 °C.

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