Xanthate collecting agent and preparation method and application thereof

Abstract

The invention belongs to the technical field of mineral flotation, and particularly discloses a xanthate collecting agent and a preparation method and application thereof, and the xanthate collecting agent is obtained by taking ether alcohol, carbon disulfide and caustic alkali as raw materials to react; the xanthate collecting agent is selected from at least one of formulas I-VI. The xanthate collecting agent has the advantages of being free of peculiar smell, easy to degrade, high in yield, high in purity, efficient in mineral flotation and the like, the working environment of the xanthate collecting agent in the production and using process can be effectively improved, operation is easy and convenient, cost is low, and industrial production is easy to achieve.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation technology, and in particular to a xanthate collector, its preparation method, and its application. Background Technology

[0002] Xanthates, scientifically known as dithiocarbonates, commonly called xanthates, have the general structural formula R-OCSSM, where R is usually a C2-C8 hydrocarbon group and M is Na or K. In 1925, Keller used xanthates as a flotation collector for metallic sulfide ores, greatly promoting the development of mineral flotation technology. To this day, xanthates remain the most widely used and consumed sulfide ore collector. Industrially used xanthates typically have hydrocarbon chain lengths ranging from ethyl to octyl.

[0003] Numerous patents and publications exist regarding the synthesis and structural modification of xanthates and their derivatives. Patent CN119306643A discloses a method for reacting alkali metals with isopropanol to generate isopropoxide, which is then reacted with carbon disulfide to generate diisopropyl xanthate, and subsequently reacted with sulfur and sulfur dichloride to synthesize diisopropyl xanthate tetrasulfide, used as a rubber additive. Patent CN112409280A discloses a method for preparing 2,4,6-(N-tetramethylxanthate sodium)-4,6-(N-dihydroxymethylamino)-1,3,5-triazine by reacting hexamethylolmelamine with caustic soda and carbon disulfide. Patent CN106380436A discloses a method for preparing diisopropyl xanthate disulfide using isopropanol, solid alkali, carbon disulfide, and chlorine as raw materials. Patent CN102463104A discloses a method for preparing clay-based xanthates by reacting alkali-treated clay with carbon disulfide. Patent CN113245066A discloses a method for preparing xanthate collectors by reacting polyalkoxy xanthates with halogenated compounds. Patent CN1138031A discloses the synthesis of 1,3-dimethylbutyl xanthate from methyl isobutyl methanol with alkali and carbon disulfide. Liao Wei reported that diethylamine methanol xanthate (structural formula shown in formula a below) performed better than conventional xanthates in stibnite flotation (Liao Wei. Diethylamine methanol xanthate. Nonferrous metals (mineral processing section), 1991(6):27-28.). Han Qiaofeng et al. reported two aromatic xanthate compounds, sodium benzyl xanthate and sodium p-aminophenyl xanthate (structural formula shown in formula b below), and studied their extraction performance (Han Qiaofeng, Fan Shulong, Yang Xujie, et al. Synthesis and extraction performance study of aromatic xanthates. Jiangsu Chemical Industry, 2002, 30(3):33-34.). Patent CN105601755A discloses a method for preparing a cellulose xanthate heavy metal scavenger. Patents US3711444 and US3965137 disclose xanthates and xanthate esters with specific structures (structural formulas shown in c and d below) and their applications in polymer synthesis. Patent CN109225647A discloses a tert-butoxyethyl dithiocarbonate and its preparation method and application. The preparation method uses 2-tert-butoxyethanol, carbon disulfide, and a caustic base as raw materials to react and generate tert-butoxyethyl dithiocarbonate. Patent CN114478339B discloses a method for reacting xanthates with an organic alcohol, carbon disulfide, and a caustic base in a linear ether. Structural formulas a~d are shown below:

[0004] (Formula a); (Formula b); (Formula c); (Equation d, where X is S or O).

[0005] Currently, the irritating odors produced during the production and use of traditional alkyl xanthates pollute the environment. With the increasing environmental protection requirements of the country for mineral processing reagents, the development of efficient and environmentally friendly new collectors has become an urgent need to achieve green mineral flotation. Summary of the Invention

[0006] In view of the above-mentioned problems, the present invention provides a xanthate collector, its preparation method, and its application. The xanthate collector of the present invention has the advantages of being odorless, easily degradable, having high yield, high purity, and high efficiency in flotation of minerals. Furthermore, the preparation method of the xanthate collector of the present invention can effectively improve the working environment of the production and use process of the xanthate collector, without causing pollution, and is simple to operate, low in cost, and easy to realize industrial production.

[0007] To address the aforementioned problems, this invention provides a xanthate collector, which is obtained by reacting an ether alcohol, carbon disulfide, and a caustic soda as raw materials; the xanthate collector is selected from at least one of formulas I to VI.

[0008] ;

[0009] Formula I;

[0010] ;

[0011] Formula II;

[0012] ;

[0013] Formula III;

[0014] ;

[0015] Formula IV;

[0016] ;

[0017] Formula V;

[0018] ;

[0019] Formula VI;

[0020] In formulas I to VI, R is selected from one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec-pentyl, and neopentyl; M is Na or K.

[0021] Preferably, R is selected from one of methyl, ethyl, n-propyl, and n-butyl.

[0022] Preferably, the ether alcohol is at least one selected from propylene glycol monoether, dipropylene glycol monoether, tripropylene glycol monoether, and tetrapropylene glycol monoether.

[0023] Preferably, the propylene glycol monoethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monopentyl ether; the dipropylene glycol monoethers include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monopentyl ether; the tripropylene glycol monoethers include tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, and tripropylene glycol monopentyl ether; and the tetrapropylene glycol monoethers include tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, and tripropylene glycol monopentyl ether.

[0024] Preferably, the ether alcohol is the residue from the distillation vessel during the production of propylene glycol ethers using the propylene oxide process.

[0025] It should be noted that propylene oxide has a lower overall hazard compared to ethylene oxide. For example, propylene oxide is a liquid at room temperature, making it easier to control than gaseous ethylene oxide; its acute toxicity and carcinogenicity are significantly lower than those of ethylene oxide; at the same time, it is more chemically stable, and its storage and handling requirements are relatively less stringent. Furthermore, the propylene oxide structure in xanthates ultimately produced from propylene oxide endows them with higher gas-liquid interfacial activity and liquid-solid interfacial adsorption density compared to ethylene oxide, thus exhibiting superior selective flotation and collection capabilities for target minerals.

[0026] Preferably, the molar ratio of the ether alcohol, carbon disulfide and caustic alkali is 1:0.5-10:1-1.5.

[0027] Preferably, the reaction temperature is 5-50℃ and the time is 0.5-8h.

[0028] Based on the same inventive concept, the present invention also provides a method for preparing any of the above-mentioned xanthate collectors, comprising the following steps:

[0029] The xanthate collector is obtained by reacting ether alcohol, carbon disulfide, and caustic alkali at 5-50℃ for 0.5-8h; wherein the molar ratio of the ether alcohol, carbon disulfide, and caustic alkali is 1:0.5-10:1-1.5.

[0030] Preferably, the caustic alkali includes at least one of sodium hydroxide and potassium hydroxide; the caustic alkali is in powder, granule or flake form.

[0031] Based on the same inventive concept, the present invention also provides the application of any of the above-described xanthate collectors in mineral flotation.

[0032] Preferably, the mineral includes any one of copper sulfide ore, lead-zinc ore, pyrite, nickel sulfide ore, and copper-molybdenum ore; the amount of xanthate collector added is 10-150 g / t, and the slurry pH is 4-13.

[0033] In the preparation process of the xanthate collector of the present invention, the chemical reaction equations for obtaining the xanthate collectors of formulas I to VI from ether alcohol, carbon disulfide, and caustic alkali are as follows:

[0034] ;

[0035] ;

[0036] ;

[0037] ;

[0038] ;

[0039] ;

[0040] In the above 6 reaction equations, R is selected from one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec-pentyl, and neopentyl; M is Na or K; preferably, R is selected from one of methyl, ethyl, n-propyl, and n-butyl.

[0041] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0042] (1) The xanthate collector of the present invention has strong collecting ability and good selectivity, and the dosage is low in the actual flotation process. It is particularly suitable for a variety of sulfide mineral systems such as copper sulfide ore, nickel sulfide ore, copper-molybdenum ore, pyrite and lead-zinc ore. This type of collector can also be used in combination with commonly used collectors such as xanthate, thiocyanate, and thiocyanate to further improve the flotation index and provide a new technical path for the efficient separation of complex ores;

[0043] (2) The xanthate collector of the present invention has a much lower toxicity than traditional isobutyl xanthate. Acute oral toxicity test in mice showed that the LD50 in male mice was significantly lower than that in female mice. 50 =6810mg / kg, female LD50 50 =3160mg / kg, with significantly better safety than isobutyl xanthate (681mg / kg for males, 926mg / kg for females). In acute toxicity tests in fish, 96hLC... 50 >100mg / L, which is considered non-toxic, and far lower than isobutyl xanthate (9.61mg / L).

[0044] (3) The ether bonds in the xanthate collector of the present invention have unique bond angles and high electronegativity of oxygen atoms, which can act as hydrogen bond acceptors to form hydrogen bonds with water or alcohol molecules, thereby constructing an ordered self-assembled structure. Compared with traditional alkyl xanthates, the present invention cleverly introduces different numbers of ether bonds into the molecular structure of traditional alkyl xanthate collectors, promoting the formation of supramolecular assemblies by bridging with water molecules through hydrogen bonding, thereby effectively reducing volatile odor. The moderate hydrophilicity of ether oxygen atoms helps to regulate the hydrophilic-hydrophobic balance of the entire molecule, so that while having good water dispersibility, it can form a denser and more stable hydrophobic film on the mineral surface through the synergistic effect of multiple hydrophobic branches. This combination of "flexible ether bond connection" and "stereohydrophobic group" enhances the bubble mineralization efficiency, significantly improves flotation performance, and achieves precise control of flotation collection performance;

[0045] (4) The xanthate collector of the present invention has no irritating odor, effectively avoiding the pollution of the production and use environment caused by the irritating odor of traditional xanthate collectors. This xanthate collector can eliminate the irritating odor of xanthate from the source, and no irritating odor is generated during use, thus realizing the elimination of the irritating odor of xanthate molecules from the source, thereby improving the working environment of xanthate production and use. According to the direct olfactory method of GB / T15549-1995, its odor score is only 1.3 (1 point is no odor, 6 points is intolerable), which is far lower than that of commercially available isobutyl xanthate (5.8) and isopentyl xanthate (5.9), solving the odor problem from the source;

[0046] (5) The xanthate collector of the present invention can be rapidly degraded in the slurry solution under the action of metal ions, which is conducive to the recycling of mineral processing tailings water, conforms to the development direction of green mineral processing reagents, and has good environmental compatibility.

[0047] (6) The xanthate collector of the present invention uses propylene glycol ether, which is widely available, as the main raw material. It can also directly utilize the distillation kettle liquid generated during the industrial synthesis of propylene glycol ether using the propylene oxide method, thereby realizing the resource utilization of by-products. This method not only alleviates the corrosion problem of equipment caused by the traditional acid catalysis route, but also avoids the bottleneck of the difficulty in separating the alkaline catalyst, and significantly reduces the overall production cost;

[0048] (7) The ether alcohols (such as propylene glycol monoether, dipropylene glycol monoether, tripropylene glycol monoether, and tetrapropylene glycol monoether) used in the preparation of the xanthate collector of the present invention are heteropolar surfactants with polar and nonpolar structures, and have certain foaming and collecting properties. Even if they are not completely converted in the xanthate reaction, they remain in the final product and can still play a synergistic promoting role in the flotation process, thereby enhancing the separation effect;

[0049] (8) In the preparation process of the xanthate collector of the present invention, the proportion of various ether alcohols in the raw materials is controlled to precisely adjust the content of each component in formula I-VI in the final product, thereby achieving directional control of the flotation performance of the collector and meeting the flotation requirements of different mineral systems;

[0050] (9) The xanthate collector of the present invention has high purity and yield, low impurity content, simple process flow, good environmental compatibility, and good potential for industrial promotion. Attached Figure Description

[0051] Figure 1 The ultraviolet spectrum of potassium O-(1-methyl-2-methoxy)dithiocarbonate as described in Example 1; Figure 2 The potassium O-(1-methyl-2-methoxy)dithiocarbonate described in Example 1 1 H NMR spectrum; Figure 3 The potassium O-(1-methyl-2-methoxy)dithiocarbonate described in Example 1 13 C NMR spectrum; Figure 4 The ultraviolet spectrum of potassium O-(1-methyl-2-ethoxy)dithiocarbonate as described in Example 2; Figure 5 The infrared spectrum of potassium O-(1-methyl-2-ethoxy)dithiocarbonate as described in Example 2; Figure 6 The potassium O-(1-methyl-2-ethoxy)dithiocarbonate described in Example 2 1 H NMR spectrum; Figure 7 The potassium O-(1-methyl-2-ethoxy)dithiocarbonate described in Example 2 13 C NMR spectrum; Figure 8 The ultraviolet spectrum of potassium O-(1-methyl-2-propoxy)dithiocarbonate described in Example 3; Figure 9 The infrared spectrum of O-(1-methyl-2-propoxy)dithiocarbonate as described in Example 3; Figure 10 The potassium O-(1-methyl-2-propoxy)dithiocarbonate described in Example 3 1 H NMR spectrum; Figure 11 The potassium O-(1-methyl-2-propoxy)dithiocarbonate described in Example 3 13 C NMR spectrum; Figure 12The ultraviolet spectrum of potassium O-(1-methyl-2-butoxy)dithiocarbonate as described in Example 4; Figure 13 The O-(1-methyl-2-butoxy)dithiocarbonate as described in Example 4 1 H NMR spectrum; Figure 14 The O-(1-methyl-2-butoxy)dithiocarbonate as described in Example 4 13 C NMR spectrum; Figure 15 The ultraviolet spectrum of O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate as described in Example 5 of this invention; Figure 16 The O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate described in Example 5 of this invention 1 H NMR spectrum; Figure 17 The O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate described in Example 5 of this invention 13 C NMR spectrum; Figure 18 This is a flowchart of a single mineral flotation process; Figure 19 The flotation recoveries of chalcopyrite and pyrite were determined by different amounts of O-(1-methyl-2-butoxy) dithiocarbonate and sodium isobutyl dithiocarbonate. Figure 20 The flotation recoveries of lead ore and sphalerite were compared with different amounts of O-(1-methyl-2-ethoxy) dithiocarbonate. Figure 21 The flotation process of a copper sulfide ore is shown in the flotation flow chart of the xanthate collector prepared in Example 14 and the commercially available isobutyl dithiocarbonate in Comparative Example 2. Figure 22 The flotation flow chart shows the flotation process of a certain lead-zinc sulfide ore using O-(1-methyl-2-butoxy) dithiocarbonate prepared in Example 4 and sodium isobutyl dithiocarbonate in Comparative Example 2. Figure 23 The flotation flow chart shows the flotation process of a copper sulfide ore using O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate prepared in Example 5 and sodium isobutyl dithiocarbonate of Comparative Example 2. Figure 24 The flotation recovery rates of chalcopyrite were measured using the four collectors prepared in Examples 6-9 and the commercially available sodium isobutyl dithiocarbonate from Comparative Example 2 as collectors. Figure 25The flotation recovery rates of galena and sphalerite were compared between O-(1-methyl-2-butoxy) dithiocarbonate prepared in Example 4 and tert-butoxyethyl dithiocarbonate prepared in Comparative Example 1. Detailed Implementation

[0052] To make the present invention easier to understand, specific embodiments are described below to further illustrate the invention. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise defined, the technical terms used below have the same meaning as understood by those skilled in the art; unless otherwise specified, the raw materials and reagents involved herein can be purchased commercially or obtained by known methods.

[0053] It should be noted that the parts in the examples and comparative examples are all parts by weight.

[0054] To address the problems mentioned in the background art, this invention provides a xanthate collector, its preparation method, and its applications. The xanthate collector of this invention has advantages such as being odorless, easily degradable, having high yield, high purity, and high efficiency in mineral flotation. Furthermore, the preparation method of the xanthate collector of this invention can effectively improve the working environment during the production and use of the xanthate collector, without causing pollution, and is simple to operate, low in cost, and easy to implement for industrial production.

[0055] The following examples and comparative models further illustrate this point.

[0056] Example 1

[0057] O-(1-methyl-2-methoxy)potassium dithiocarbonate ( The preparation method of ) includes the following steps:

[0058] 9.10 parts of propylene glycol methyl ether and 38.45 parts of carbon disulfide were added to a three-necked flask. Then, 6.93 parts of granular potassium hydroxide (85 wt%) were added in three batches at 10°C with mechanical stirring. After the addition was complete, the mixture was heated to 20°C and reacted for 5 hours. 20.82 parts of a pale yellow powdery xanthate collector with a purity of 92.39% were obtained, with a yield of 94.70%.

[0059] The above product was purified by multiple recrystallization processes and then subjected to ultraviolet spectroscopy. 1 H NMR spectrum and 13 The results of the C NMR spectral characterization are as follows: Figure 1-3 As shown. By Figure 1It can be seen that the maximum absorption wavelength of the above product is at 302nm, and a small peak appears at 228nm; from Figure 2 It can be seen that the proton chemical shifts and their assignments for the above products are as follows: 400MHz 1 ¹H NMR (DMSO-d6): δ 1.13 (3H, CH₃), 3.26 (3H, CH₃), 3.32 (1H, CH₂), 3.45 (1H, CH₂), 5.56 (1H, CH); Figure 3 It can be seen that the above products 13 C10 NMR (DMSO-d6) values ​​were δ 17.37 (CH3), 58.77 (CH3), 74.62 (CH2), 75.18 (CH2), and 75.18 (CH). This indicates that the above product is O-(1-methyl-2-methoxy)dithiocarbonate ( ).

[0060] Example 2

[0061] O-(1-methyl-2-ethoxy)potassium dithiocarbonate ( The preparation method of ) includes the following steps:

[0062] 10.52 parts of propylene glycol ethyl ether and 61.53 parts of carbon disulfide were added to a three-necked flask. Then, 6.93 parts of granular potassium hydroxide (85 wt%) were added in three batches at 10°C with mechanical stirring. After the addition was complete, the mixture was heated to 20°C and reacted for 5 hours. 23.24 parts of a pale yellow powdery xanthate collector with a purity of 93.93% were obtained, representing a yield of 92.34%.

[0063] The above products were purified by multiple recrystallization processes, followed by ultraviolet and infrared spectroscopy. 1 H NMR spectrum and 13 The results of the C NMR spectral characterization are as follows: Figure 4-7 As shown. By Figure 4 It can be seen that the maximum absorption wavelength of the above product is at 302nm, and a small peak appears at 228nm; from Figure 5 It can be seen that the key characteristic peak of the above products is: 2975 cm⁻¹ -1 2933cm -1 2894cm -1 and 2862cm -1 Stretching vibration peaks attributed to CH3 and CH2; 1447 cm⁻¹ -1 1385cm -1 Attributable to CH3 deformation vibration peak; 1131 cm⁻¹ -1 Attributable to the stretching vibration peak of COC; 1051 cm⁻¹ -1 Assigned to SC=S absorption peak; 969 cm⁻¹ -1It belongs to the CS stretching vibration peak. (By...) Figure 6 It can be seen that the proton chemical shifts and their assignments for the above products are as follows: 400MHz 1 H NMR (DMSO-d6): δ 1.13 (3H, CH3), 1.15 (3H, CH3), 3.33 (1H, CH2), 3.45 (2H, CH2), 3.50 (0.8H, CH2), 5.54 (1H, CH); from Figure 7 It can be seen that the above products 13 C10 NMR (DMSO-d6) values ​​were δ 15.63 (CH3), 17.48 (CH3), 66.15 (CH2), 73.09 (CH2), 74.82 (CH), and 229.71 (C=S). This indicates that the above product is O-(1-methyl-2-ethoxy)dithiocarbonate (DMSO-d6). ).

[0064] Example 3

[0065] O-(1-methyl-2-propoxy) dithiocarbonate ( The preparation method of ) includes the following steps:

[0066] 11.94 parts of propylene glycol propyl ether and 61.53 parts of carbon disulfide were added to a three-necked flask. Then, 6.93 parts of granular potassium hydroxide (85 wt%) were added in three batches at 10°C with mechanical stirring. After the addition was complete, the mixture was heated to 20°C and reacted for 5 hours. 23.66 parts of a yellow powdery xanthate collector with a purity of 90.06% were obtained, representing a yield of 91.68%.

[0067] The above products were purified by multiple recrystallization processes, followed by ultraviolet and infrared spectroscopy. 1 H NMR spectrum and 13 The results of the C NMR spectral characterization are as follows: Figure 8-11 As shown. By Figure 8 It can be seen that the maximum absorption wavelength of the above product is at 302nm, and a small peak appears at 228nm; from Figure 9 It can be seen that the key characteristic peak of the above products is: 2973 cm⁻¹ -1 2958cm -1 and 2874cm -1 Stretching vibration peaks attributed to CH3 and CH2; 1458 cm⁻¹ -1 1383cm -1 Attributable to CH3 deformation vibration peak; 1170 cm⁻¹ -1 Attributable to the stretching vibration peak of COC; 1053 cm⁻¹ -1 Assigned to SC=S absorption peak; 944 cm⁻¹ -1 It belongs to the CS stretching vibration peak. (By...) Figure 10It can be seen that the proton chemical shifts and their assignments for the above products are as follows: 400MHz 1 H NMR (DMSO-d6): δ 1.11 (3H, CH3), 1.15 (3H, CH3), 3.33 (1.2H, CH2), 3.45 (2H, CH2), 3.50 (0.8H, CH2), 5.54 (1H, CH); by Figure 11 It can be seen that the above products 13 CNMR (DMSO-d6) values ​​are δ 17.50 (CH3), 22.93 (CH3), 72.50 (CH2), 73.20 (CH2), 74.78 (CH), and 229.71 (C=S). This indicates that the above product is O-(1-methyl-2-propoxy)dithiocarbonate ( ).

[0068] Example 4

[0069] O-(1-methyl-2-butoxy)potassium dithiocarbonate ( The preparation method of ) includes the following steps:

[0070] 6.68 parts of propylene glycol butyl ether and 30.76 parts of carbon disulfide were added to a three-necked flask. Then, 3.47 parts of granular potassium hydroxide (85 wt%) were added in three batches at 15°C with mechanical stirring. After the addition was complete, the temperature was raised to 20°C and the reaction was carried out for 5 hours. 13.60 parts of an orange-yellow powder xanthate collector with a purity of 84.83% were obtained, with a yield of 87.26%.

[0071] The above product was purified by multiple recrystallization processes and then subjected to ultraviolet spectroscopy. 1 H NMR spectrum and 13 The results of the C NMR spectral characterization are as follows: Figure 12-14 As shown. By Figure 12 It can be seen that the maximum absorption wavelength of the above product is at 302nm, and a small peak appears at 228nm; from Figure 13 It can be seen that the proton chemical shifts and their assignments for the above products are as follows: 400MHz 1 H NMR (DMSO-d6): δ 0.88 (3H, CH3), 1.15 (3H, CH3), 1.33 (1H, CH2), 1.48 (2H, CH2), 3.32 (1H, CH2), 3.40 (2H, CH2), 3.50 (0.8H, CH2), 5.54 (1H, CH); by Figure 14 It can be seen that the above products 13C10 NMR (DMSO-d6) values ​​were δ 14.25 (1C, CH3), 17.45 (2C, CH3), 19.30 (1C, CH2), 31.79 (1C, CH2), 70.60 (1C, CH), 73.25 (1C, CH2), 74.84 (1C, CH), and 229.81 (C=S). This indicates that the above product is O-(1-methyl-2-butoxy)dithiocarbonate (DMSO-d6). ).

[0072] Example 5

[0073] The preparation method of O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate includes the following steps:

[0074] 9.71 parts of dipropylene glycol butyl ether and 23.07 parts of carbon disulfide were added to a three-necked flask. Then, 3.47 parts of granular potassium hydroxide (85 wt%) were added in three batches at 10°C with mechanical stirring. After the addition was complete, the mixture was heated to 25°C and reacted for 4 hours. 15.18 parts of a yellow powdery xanthate collector with a purity of 88.10% were obtained, representing a yield of 87.81%.

[0075] The above product was purified by multiple recrystallization processes and then subjected to ultraviolet spectroscopy. 1 H NMR spectrum and 13 The results of the C NMR spectral characterization are as follows: Figure 15-17 As shown. By Figure 15 It can be seen that the maximum absorption wavelength of the above product is at 303nm, and a small peak appears at 229nm; from Figure 16 It can be seen that the proton chemical shifts and their assignments for the above products are as follows: 400MHz 1 H NMR (DMSO-d6): δ 5.62-5.42(m,1H), 3.62-3.51(m,2H), 3.43-3.33(m,4H), 1.47(ddt,J=8.8, 7.5,5.8Hz,2H), 1.37-1.27(m,2H), 1.15(dd,J=6.3,0.8Hz,3H), 1.06(dd,J =6.3,1.8Hz,3H), 0.88(td,J=7.3,0.9Hz,3H); from Figure 17 It can be seen that the above products 13The C10 NMR (DMSO-d6) values ​​are δ 229.76 (1C, C=S), 75.09 (1C, CH), 74.67 (1C, CH), 74.38 (1C, CH2), 71.62 (1C, CH2), 70.64 (1C, CH2), 31.78 (1C, CH2), 19.30 (1C, CH2), 17.75 (1C, CH3), 17.50 (1C, CH3), and 14.24 (1C, CH3). This indicates that the product is O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate.

[0076] Example 6

[0077] O-(1-[2-(2-methoxy-1-methylethoxy)-1-methylethoxy]-2-propyl)potassium dithiocarbonate The preparation method of ) includes the following steps:

[0078] 21.05 parts of tripropylene glycol methyl ether and 61.53 parts of carbon disulfide were added to a three-necked flask. Then, 6.93 parts of powdered potassium hydroxide (85 wt%) were added in three batches at 10°C with mechanical stirring. After the addition was complete, the temperature was raised to 25°C and the reaction was carried out for 6 hours. 33.92 parts of a yellow powdered xanthate collector with a purity of 80.24% were obtained, with a yield of 85.73%. The product was identified as O-(1-[2-(2-methoxy-1-methylethoxy)-1-methylethoxy]-2-propyl)dithiocarbonate (…). ).

[0079] Example 7

[0080] O-(2-ethoxypropyl) dithiocarbonate ( The preparation method of ) includes the following steps:

[0081] 5.26 parts of propylene glycol ethyl ether and 19.23 parts of carbon disulfide were added to a three-necked flask. Then, 3.47 parts of powdered potassium hydroxide (85 wt%) were added in three batches at 10°C with mechanical stirring. After the addition was complete, the temperature was raised to 25°C and the reaction was carried out for 4 hours. 11.85 parts of a light yellow powdered xanthate collector with a purity of 85.95% were obtained, with a yield of 91.27%. Analysis showed that the above product was O-(2-ethoxypropyl) dithiocarbonate (…). ).

[0082] Example 8

[0083] O-(2-(2-ethoxypropoxy)propyl)dithiocarbonate ( The preparation method of ) includes the following steps:

[0084] 16.37 parts of dipropylene glycol monoethyl ether and 61.53 parts of carbon disulfide were added to a three-necked flask. Then, 6.93 parts of powdered potassium hydroxide (85 wt%) were added in three batches at 10°C with mechanical stirring. After the addition was complete, the temperature was raised to 25°C and the reaction was carried out for 6 hours. 29.47 parts of a yellow powdered xanthate collector with a purity of 81.07% were obtained, with a yield of 86.23%. Analysis showed that the above product was O-(2-(2-ethoxypropoxy)propyl)dithiocarbonate (…). ).

[0085] Example 9

[0086] O-(2-(2-methoxypropoxy)propoxypropyl)potassium dithiocarbonate ( The preparation method of ) includes the following steps:

[0087] 10.52 parts of tripropylene glycol methyl ethyl ether and 17.30 parts of carbon disulfide were added to a three-necked flask. Then, 3.47 parts of powdered potassium hydroxide (85 wt%) were added in three batches at 5°C with mechanical stirring. After the addition was complete, the temperature was raised to 30°C and the reaction was carried out for 6 hours. 16.83 parts of a yellow powdered xanthate collector with a purity of 81.44% were obtained, with a yield of 85.25%. Analysis showed that the above product was O-(2-(2-methoxypropoxy)propoxypropyl)potassium disulfide (…). ).

[0088] Example 10: Synthesis of xanthate collector using propylene glycol monoethyl ether reaction solution as raw material

[0089] The reaction was carried out in a 1L stainless steel autoclave equipped with a stirrer. Before the reaction, the entire apparatus was purged with nitrogen. Then, 46.1 parts of anhydrous ethanol, 58.1 parts of propylene oxide, and 1.0 part of potassium hydroxide were accurately weighed and added to the autoclave. After purging with nitrogen to maintain the predetermined initial pressure, stirring was started and the mixture was rapidly heated to 80-85°C for 3.0 h. After the reaction, the mixture was cooled with cooling water. The reaction solution was transferred to a three-necked flask, and 429.2 parts of carbon disulfide and 61.4 parts of potassium hydroxide were added. The mixture was stirred at 25°C for 4 h. The carbon disulfide solvent was recovered by vacuum distillation, yielding 206.6 parts of a light yellow powdery xanthate collector, with a yield of 94.06%.

[0090] Example 11: After recovering ethanol and 90% of propylene glycol monoethyl ether from the propylene glycol monoethyl ether reaction solution, xanthate collectors were synthesized using the distillation still liquid as raw material.

[0091] The reaction was carried out in a 1L stainless steel autoclave equipped with a stirrer. Before the reaction, the entire apparatus was purged with nitrogen. Then, 36.9 parts of anhydrous ethanol, 58.1 parts of propylene oxide, and 1.2 parts of potassium hydroxide were accurately weighed and added to the autoclave. After purging with nitrogen to maintain the predetermined initial pressure, stirring was started and the mixture was rapidly heated to 75-80°C for 4.5 hours. After the reaction, the mixture was cooled with cooling water. The reaction solution was transferred to a still, and unreacted ethanol was recovered by distillation at 77-79°C. The temperature was then increased to 132-133°C for further recovery, yielding 41.2 parts of propylene glycol monoethyl ether, with a purity of 99.5%. After distillation, the distillate was transferred to a three-necked flask, and 126.5 parts of carbon disulfide and 17.1 parts of potassium hydroxide were added. The mixture was stirred at 25°C for 6 hours. The carbon disulfide solvent was recovered by vacuum distillation, yielding 82.3 parts of a yellow powdered xanthate collector, with a yield of 93.37%.

[0092] Example 12: Synthesis of xanthate collector using propylene glycol monobutyl ether reaction solution as raw material

[0093] The reaction was carried out in a 1L stainless steel autoclave equipped with a stirrer. Before the reaction, the entire apparatus was purged with nitrogen. Then, 74.1 parts of n-butanol, 116.2 parts of propylene oxide, and 2.6 parts of potassium hydroxide were accurately weighed and added to the autoclave. After purging with nitrogen to maintain the predetermined initial pressure, stirring was started and the mixture was rapidly heated to 75-80°C for 4.5 hours. After the reaction, the mixture was cooled with cooling water. The reaction solution was transferred to a three-necked flask, and 478.8 parts of carbon disulfide and 56.2 parts of potassium hydroxide were added. The mixture was stirred at 25°C for 4 hours. The carbon disulfide solvent was recovered by vacuum distillation, yielding 314.28 parts of a light yellow powdered xanthate collector, with a yield of 95.56%.

[0094] Example 13: Synthesis of xanthate collector using propylene glycol monobutyl ether reaction solution as raw material

[0095] The reaction was carried out in a 1L stainless steel autoclave equipped with a stirrer. Before the reaction, the entire apparatus was purged with nitrogen. Then, 74.1 parts of n-butanol, 58.1 parts of propylene oxide, and 1.3 parts of potassium hydroxide were accurately weighed and added to the autoclave. After purging with nitrogen to maintain the predetermined initial pressure, stirring was started and the mixture was rapidly heated to 75-80°C for 4.5 hours. After the reaction, the mixture was cooled with cooling water to obtain a propylene glycol butyl ether reaction solution. The propylene glycol butyl ether reaction solution was transferred to a three-necked flask, and 456.8 parts of carbon disulfide and 64.7 parts of potassium hydroxide were added. The mixture was stirred at 25°C for 4 hours. The carbon disulfide solvent was recovered by vacuum distillation, yielding 257.5 parts of a pale yellow powder product, with a yield of 93.85%.

[0096] The components of the above-mentioned propylene glycol butyl ether reaction solution are: n-butanol 20.62wt%, propylene glycol butyl ether 52.25wt%, dipropylene glycol butyl ether 21.18wt%, tripropylene glycol butyl ether 4.97wt%, tetrapropylene glycol butyl ether 0.79wt%, and other heavy components 0.19wt%.

[0097] Example 14: After recovering n-butanol and 90% of propylene glycol butyl ether from the reaction solution, xanthate collector was synthesized using the distillation still liquid as raw material.

[0098] The reaction was carried out in a 1L stainless steel autoclave equipped with a stirrer. Before the reaction, the entire apparatus was purged with nitrogen. Then, 60.0 parts of n-butanol, 58.1 parts of propylene oxide, and 9.4 parts of potassium hydroxide were accurately weighed and added to the autoclave. After purging with nitrogen to maintain the predetermined initial pressure, stirring was started and the mixture was rapidly heated to 75-80°C for 4.5 hours. After the reaction, the mixture was cooled with cooling water to obtain a propylene glycol monobutyl ether reaction solution. The propylene glycol monobutyl ether reaction solution was transferred to a still, and unreacted n-butanol was recovered by distillation at 117-118°C. The temperature was then increased to 170-171°C for further recovery, yielding 51.4 parts of propylene glycol monobutyl ether, with a purity of 99.5%. After distillation, the distillate was transferred to a three-necked flask, and 114.2 parts of carbon disulfide and 7.1 parts of potassium hydroxide were added. The mixture was stirred at 25°C for 4 hours. The carbon disulfide solvent was recovered by vacuum distillation, yielding 80.87 parts of a yellow powder product with a yield of 91.56%.

[0099] The components of the above-mentioned propylene glycol monobutyl ether reaction solution are: n-butanol 12.32wt%, propylene glycol butyl ether 48.27wt%, dipropylene glycol butyl ether 29.13wt%, tripropylene glycol butyl ether 8.27wt%, tetrapropylene glycol butyl ether 1.43wt%, and other heavy components 0.58wt%.

[0100] Example 15: After recovering n-butanol from the reaction solution for the synthesis of propylene glycol monobutyl ether, xanthate collector was synthesized using the distillate as a raw material.

[0101] The reaction was carried out in a 1L stainless steel autoclave equipped with a stirrer. Before the reaction, the entire apparatus was purged with nitrogen. Then, 185.3 parts of n-butanol, 58.1 parts of propylene oxide, and 18.7 parts of potassium hydroxide were accurately weighed and added to the autoclave. After purging with nitrogen to maintain the predetermined initial pressure, stirring was started and the mixture was rapidly heated to 75-80°C for 4.5 hours. After the reaction, the mixture was cooled with cooling water to obtain a propylene glycol monobutyl ether reaction solution. The propylene glycol monobutyl ether reaction solution was transferred to a still, and 110.7 parts of unreacted n-butanol were recovered by distillation. After distillation, the distillate was transferred to a three-necked flask, and 466.0 parts of carbon disulfide and 48.6 parts of potassium hydroxide were added. The mixture was stirred at 25°C for 4 hours. The carbon disulfide solvent was recovered by vacuum distillation, yielding 264.2 parts of a yellow powdered xanthate collector, with a yield of 95.14%.

[0102] The components of the above-mentioned propylene glycol monobutyl ether reaction solution are: n-butanol 51.48wt%, propylene glycol butyl ether 42.54wt%, dipropylene glycol butyl ether 5.20wt%, tripropylene glycol butyl ether 0.25wt%, and other heavy components 0.53wt%.

[0103] Example 16: After recovering methanol from the reaction solution for the synthesis of propylene glycol monomethyl ether, xanthate collectors were synthesized using the distillation residue as raw material.

[0104] The reaction was carried out in a 1L stainless steel autoclave equipped with a stirrer. Before the reaction, the entire apparatus was purged with nitrogen. Then, 32.0 parts of methanol, 58.1 parts of propylene oxide, and 5.0 parts of sodium hydroxide were accurately weighed and added to the autoclave. After purging with nitrogen to maintain the predetermined initial pressure, stirring was started and the mixture was rapidly heated to 75-80°C for 4.5 hours. After the reaction, the mixture was cooled with cooling water to obtain a propylene glycol monomethyl ether reaction solution. The obtained propylene glycol monomethyl ether reaction solution was transferred to a still and distilled at 64-65°C to recover 9.1 parts of unreacted methanol. After distillation, the distillate was transferred to a three-necked flask, and 266.5 parts of carbon disulfide and 24.2 parts of sodium hydroxide were added. The mixture was stirred at 25°C for 3 hours. The carbon disulfide solvent was recovered by vacuum distillation to obtain 170.17 parts of a light yellow powdered xanthate collector, with a yield of 97.96%.

[0105] Example 17:

[0106] A method for preparing a mixture of O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate / sodium includes the following steps:

[0107] 25.00 parts of dipropylene glycol butyl ether and 50 parts of carbon disulfide were added to a three-necked flask. A mixture of 3.29 parts of powdered potassium hydroxide and 3.29 parts of powdered sodium hydroxide was added in portions at 10°C with mechanical stirring. After the addition was complete, the temperature was raised to 25°C and the reaction proceeded for 6 hours. 78.60 parts of a yellow powdered xanthate collector with a purity of 86.19% were obtained.

[0108] Example 18:

[0109] The method for preparing O-(1-methyl-2-ethoxy)dithiocarbonate using a kneader includes the following steps:

[0110] 1200.0 parts of propylene glycol ethyl ether and 1052.7 parts of carbon disulfide were added to a 10L kneader, and the speed was set to 60 rpm. Then, a total of 746.7 parts of powdered potassium hydroxide were added in batches. After the addition was complete, the reaction was continued for 3.5 hours. 2850.4 parts of orange-yellow powdered xanthate collector with a purity of 82.81% were obtained.

[0111] Example 19:

[0112] The method for preparing O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate using a kneader includes the following steps:

[0113] 1200.0 parts of dipropylene glycol butyl ether and 576.0 parts of carbon disulfide were added to a 10L kneader, and the speed was set to 60 rpm. Then, 409.0 parts of powdered potassium hydroxide were added in three batches. After the addition was complete, the mixture was reacted at 30~35℃ for 2.5h. 2113.8 parts of orange-yellow powdered xanthate collector with a purity of 87.47% were obtained.

[0114] Example 20:

[0115] The method for preparing xanthate collectors using the distillate from Example 11 as raw material and a kneader includes the following steps:

[0116] 1412.8 parts of the distillate from Example 11 and 1028.9 parts of carbon disulfide were added to a 10L kneader, and the speed was set to 60 rpm. Then, a total of 729.75 parts of powdered potassium hydroxide were added in three batches. After the addition was complete, the mixture was reacted at 30-35°C for 4.0 h. 3042.8 parts of orange-yellow powdered xanthate collector with a purity of 81.01% were obtained.

[0117] Comparative Example 1

[0118] The difference between this comparative example and Example 4 is that 6.68 parts of propylene glycol butyl ether were replaced with 5.97 parts of 2-tert-butoxyethanol; all other steps and parameters were the same as in Example 4. A final yield of 12.55 parts of a yellow powder with a purity of 80.23% was obtained, representing a yield of 91.21%. Testing confirmed that the product was tert-butoxyethyl dithiocarbonate.

[0119] Comparative Example 2

[0120] Commercially available sodium isobutyl dithiocarbonate.

[0121] Performance testing and results analysis:

[0122] The O-(1-methyl-2-butoxy)dithiocarbonate prepared in Example 4 and the commercially available isobutyl dithiocarbonate of Comparative Example 2 were used as collectors in flotation experiments on chalcopyrite and pyrite. The specific flotation process flow is as follows: Figure 18 As shown, the pulp pH is 8, and the dosage of O-(1-methyl-2-butoxy)dithiocarbonate and sodium isobutyldithiocarbonate is 0~10×10⁻⁶. -5 mol / L, the amount of foaming agent MIBC used is 7.5×10 -4 The flotation concentration was mol / L, and the particle size of chalcopyrite and pyrite was -0.076 to +0.038 mm. The flotation test results are as follows: Figure 19 As shown. By Figure 19 It can be seen that, compared with commercially available sodium isobutyl dithiocarbonate, the O-(1-methyl-2-butoxy) dithiocarbonate prepared in Example 4 of this invention exhibits stronger collecting ability and better selectivity for chalcopyrite.

[0123] Potassium O-(1-methyl-2-ethoxy)dithiocarbonate prepared in Example 2 was used as a collector in flotation experiments on galena and sphalerite. The specific flotation process is as follows: Figure 18 As shown, the pulp pH is 8, and the amount of O-(1-methyl-2-ethoxy) dithiocarbonate used is 0~10×10⁻⁶. -5 mol / L, the amount of foaming agent MIBC used is 7.5×10 -4 The flotation results for galena and sphalerite, with a particle size of -0.076 to +0.038 mm at mol / L, are as follows: Figure 20 As shown. By Figure 20 It can be seen that the amount of O-(1-methyl-2-ethoxy)dithiocarbonate used is 2×10 -5 At mol / L, the recoveries of galena and sphalerite were 91.44% and 3.19%, respectively.

[0124] The xanthate collector prepared in Example 14 and the commercially available sodium isobutyl dithiocarbonate from Comparative Example 2 were used as collectors in a roughing experiment on a copper sulfide ore. The specific flotation process is as follows: Figure 21 As shown, in each experiment, 500g of ore powder, 300mL of water, and a certain amount of lime were added to a ball mill for grinding until the mineral particle size met the beneficiation requirements. The slurry was then transferred to a 1.5L single-cell flotation machine for flotation experiments. The flotation machine was turned on and stirred for 3 minutes, then a collector was added and stirred for another 3 minutes. A frother was then added and stirred for another 1 minute. The foam was collected as concentrate, and the product in the water tank was the tailings. After the concentrate was thoroughly dried, it was ground and samples were prepared. The copper content was analyzed, and the yield and recovery rate were calculated. The reagent formulation was as follows: grinding fineness was -200 mesh (66%), lime dosage was 400 g / t, frother was No. 2 oil (24 g / t), and collectors were the xanthate collector prepared in Example 14 and the commercially available sodium isobutyl dithiocarbonate product (85.0 wt%) in Comparative Example 2 (the dosage of the product in Example 14 was the same as that of the commercially available sodium isobutyl dithiocarbonate product in Comparative Example 2, which was 32 g / t). Other flotation test conditions and results are shown in Table 1.

[0125] Table 1:

[0126]

[0127] As shown in Table 1, the xanthate collector prepared in Example 14 of this invention has a flotation recovery rate of copper sulfide ore and a copper concentrate grade that are 6.39 and 0.33 percentage points higher than those of the commercially available sodium isobutyl dithiocarbonate collector in Comparative Example 2, respectively. This indicates that the flotation performance of the xanthate collector prepared in Example 14 is superior to that of sodium isobutyl dithiocarbonate.

[0128] The O-(1-methyl-2-butoxy)dithiocarbonate prepared in Example 4 and the commercially available isobutyl dithiocarbonate from Comparative Example 2 were used as collectors in a roughing experiment on a lead-zinc sulfide ore. The flotation flow chart is shown below. Figure 22As shown, the lead-zinc sulfide ore was taken from a mine in Yunnan Province. The main lead-bearing mineral in the ore was galena, and the main zinc-bearing mineral was sphalerite. The lead and zinc contents in the ore were 6.31% and 17.24%, respectively. The required feed particle size after ball milling of the lead-zinc sulfide ore was -74 μm, accounting for 70%. The reagent system was as follows: grinding fineness was -200 mesh, accounting for 70%; lime dosage was 400 g / t; frother was No. 2 oil, with a dosage of 24 g / t; and collectors were O-(1-methyl-2-butoxy) dithiocarbonate prepared in Example 4 and commercially available isobutyl dithiocarbonate (content was 85.0%) from Comparative Example 2 (the dosage of the product in Example 4 was the same as that of the commercially available isobutyl dithiocarbonate from Comparative Example 2, multiplied by 85.0%, both being 32 g / t). Other flotation experimental conditions and results are shown in Table 2.

[0129] Table 2:

[0130]

[0131] As shown in Table 2, the O-(1-methyl-2-butoxy)potassium dithiocarbonate collector prepared in Example 4 of this invention has a higher flotation recovery rate and lead concentrate grade for lead in sulfide lead-zinc ore than that of the sodium isobutyl dithiocarbonate collector by 2.22 and 0.63 percentage points, respectively. This indicates that the O-(1-methyl-2-butoxy)potassium dithiocarbonate prepared in Example 4 has better flotation performance than sodium isobutyl dithiocarbonate.

[0132] The O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate prepared in Example 5 and the commercially available isobutyl dithiocarbonate from Comparative Example 2 were used as collectors for flotation of a copper sulfide ore. The flotation flow chart is shown below. Figure 23 As shown in the first roughing stage, the ore sample came from a copper mine in Northeast China, containing 0.45% copper. Each feed consisted of 500g of ore. The reagent regime was as follows: grinding fineness of -200 mesh (65%), lime dosage of 2000g / t, pulp pH of approximately 11.0, frother of No. 2 oil at 32g / t, and collectors of O-[1-(2-butoxy-1-methylethoxy)-2-propyl]dithiocarbonate prepared in Example 5 and commercially available isobutyl dithiocarbonate (content 85.0%) from Comparative Example 2 (the dosage of the product in Example 5 was the same as that of the commercially available isobutyl dithiocarbonate from Comparative Example 2, multiplied by 85.0%, both being 50g / t). Other flotation experimental conditions and results are shown in Table 3.

[0133] Table 3:

[0134]

[0135] As shown in Table 3, the O-[1-(2-butoxy-1-methylethoxy)-2-propyl] dithiocarbonate collector prepared in Example 5 of this invention has a flotation recovery rate of copper sulfide ore and a copper concentrate grade that are 3.11 and 0.58 percentage points higher than those of the commercially available isobutyl dithiocarbonate collector in Comparative Example 2, respectively. This indicates that the O-[1-(2-butoxy-1-methylethoxy)-2-propyl] dithiocarbonate prepared in Example 5 has better flotation performance than the commercially available isobutyl dithiocarbonate.

[0136] The four collectors prepared in Examples 6-9 (namely, O-(1-[2-(2-methoxy-1-methylethoxy)-1-methylethoxy]-2-propyl)potassium dithiocarbonate (Formula III), O-(2-ethoxypropyl)potassium dithiocarbonate (Formula IV), O-(2-(2-ethoxypropoxy)propyl)potassium dithiocarbonate (Formula V), and O-(2-(2-methoxypropoxy)propoxypropyl)potassium dithiocarbonate (Formula VI)) and the commercially available sodium isobutyl dithiocarbonate of Comparative Example 2 were used as collectors in single-mineral flotation experiments on chalcopyrite. The specific flotation process flow is as follows: Figure 18 As shown, the slurry pH was 8, and the dosage of the four collectors prepared in Examples 6-9 of this invention and the commercially available sodium isobutyl dithiocarbonate of Comparative Example 2 was 0~10×10⁻⁶. -5 mol / L, the amount of foaming agent MIBC used is 7.5×10 -4 The mol / L concentration of chalcopyrite, with a particle size of -0.076 to +0.038 mm, yielded the following flotation results: Figure 24 As shown. By Figure 24 It can be seen that the recovery rates of chalcopyrite obtained by the four collectors prepared in Examples 6-9 of the present invention and the commercially available sodium isobutyl dithiocarbonate of Comparative Example 2 were 85.88%, 85.96%, 87.02%, 86.98%, and 85.62%, respectively; indicating that compared with the commercially available sodium isobutyl dithiocarbonate of Comparative Example 2, the four collectors prepared in Examples 6-9 of the present invention all showed stronger collecting ability for chalcopyrite.

[0137] The O-(1-methyl-2-butoxy)dithiocarbonate prepared in Example 4 and the tert-butoxyethyldithiocarbonate prepared in Comparative Example 1 were used as collectors in flotation experiments on galena and sphalerite. The specific flotation process is as follows: Figure 18 As shown, the slurry pH was 8, and the amounts of O-(1-methyl-2-butoxy)dithiocarbonate prepared in Example 4 and tert-butoxyethyldithiocarbonate prepared in Comparative Example 1 were 0~10×10⁻⁶. -5 mol / L, the amount of foaming agent MIBC used is 7.5×10 -4The flotation results for galena and sphalerite, with a particle size of -0.076 to +0.038 mm at mol / L, are as follows: Figure 25 As shown. By Figure 25 As can be seen, compared with the potassium tert-butoxyethyl dithiocarbonate prepared in Comparative Example 1, the O-(1-methyl-2-butoxy)dithiocarbonate prepared in Example 4 of this invention exhibits stronger collecting ability and better selectivity for galena. This is because O-(1-methyl-2-butoxy)dithiocarbonate has higher gas-liquid interfacial activity; at the same time, the steric hindrance effect generated by the methyl branch near the xanthate fixophilic group can achieve selective adsorption of specific minerals, thereby enhancing the selective flotation collecting effect.

[0138] The above embodiments merely illustrate several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the inventive concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A xanthate collector, characterized in that, The xanthate collector is obtained by reacting ether alcohol, carbon disulfide, and caustic alkali as raw materials; the xanthate collector is selected from at least one of formulas I to VI: ； Formula I; ； Formula II; ； Formula III; ； Formula IV; ； Formula V; ； Formula VI; In formulas I to VI, R is selected from one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec-pentyl, and neopentyl; M is Na or K.

2. The xanthate collector according to claim 1, characterized in that, The R is selected from one of methyl, ethyl, n-propyl, and n-butyl.

3. The xanthate collector according to claim 1, characterized in that, The ether alcohol is at least one of propylene glycol monoether, dipropylene glycol monoether, tripropylene glycol monoether, and tetrapropylene glycol monoether.

4. The xanthate collector according to claim 3, characterized in that, The propylene glycol monoethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monopentyl ether; the dipropylene glycol monoethers include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monopentyl ether; the tripropylene glycol monoethers include tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, and tripropylene glycol monopentyl ether; the tetrapropylene glycol monoethers include tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, and tripropylene glycol monopentyl ether.

5. The xanthate collector according to claim 1, characterized in that, The molar ratio of the ether alcohol, carbon disulfide and caustic alkali is 1:0.5-10:1-1.

5.

6. The xanthate collector according to claim 1, characterized in that, The reaction is carried out at a temperature of 5-50℃ for a time of 0.5-8 hours.

7. The method for preparing the xanthate collector according to any one of claims 1-6, characterized in that, Includes the following steps: The xanthate collector is obtained by reacting ether alcohol, carbon disulfide, and caustic alkali at 5-50℃ for 0.5-8h; wherein the molar ratio of the ether alcohol, carbon disulfide, and caustic alkali is 1:0.5-10:1-1.

5.

8. The method for preparing the xanthate collector according to claim 7, characterized in that, The caustic alkali includes at least one of sodium hydroxide and potassium hydroxide; the caustic alkali is in powder, granule or flake form.

9. The application of the xanthate collector according to any one of claims 1-6 in mineral flotation.

10. The application according to claim 9, characterized in that, The minerals include any one of copper sulfide ore, lead-zinc ore, pyrite, nickel sulfide ore, and copper-molybdenum ore; the amount of xanthate collector added is 10-150 g / t, and the slurry pH is 4-13.

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