A combined collector and its preparation method and application

Abstract

This invention belongs to the technical field of mineral flotation collectors, specifically disclosing a combined collector, its preparation method, and its application. The combined collector comprises component A and component B. Component A is propylene glycol ether dithiophosphate, with a structure shown in formulas I-VI, and component B is ethylthiocyanate and / or mercaptobenzothiazole. This invention utilizes the excellent coupling and solubilizing ability imparted by the ether oxygen group and methyl branch in the propylene glycol ether dithiophosphate molecule, enabling it to function as both a collector and an intrinsic "coupling agent" in the compound system. This significantly improves its compatibility and dispersion stability with ethylthiocyanate or mercaptobenzothiazole. The two components work synergistically through a co-adsorption mechanism of "rapid spreading—chemical anchoring—dense film formation," forming a denser and more stable composite adsorption film on the mineral surface. This combined collector is easy to formulate, has good component compatibility, and balances collecting capacity and selectivity, making it suitable for the efficient flotation of various sulfide ores, such as copper sulfide ores and lead-zinc sulfide ores.

Description

Technical Field

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

[0002] Flotation is one of the most widely used separation methods in the field of mineral beneficiation, especially suitable for the efficient separation and recovery of non-ferrous metal sulfide ores and their associated minerals. With the continuous development of mineral resources, easily beneficiated and enriched high-quality mineral resources are becoming increasingly scarce. Currently, the ores being beneficiated are gradually showing characteristics of being lean, fine-grained, and complex. Some ores also exhibit increased oxidation, severe mud formation, and increased difficulty in separating valuable minerals from gangue minerals. This resource situation places higher demands on the flotation performance, adaptability, and stability of flotation processes and reagents.

[0003] In mineral flotation, the combined use of different types of collectors to achieve complementary advantages and improve flotation efficiency has become an important development direction in this field. In existing technologies, dichlorodiphenyl ether, ethyl thiocyanate, and mercaptobenzothiazole are all commonly used collectors in sulfide ore flotation, but each has its limitations: dichlorodiphenyl ether collectors often lack selectivity in complex mineral systems; ethyl thiocyanate collectors, when used alone, still have limitations in terms of reagent stability, applicable mineral range, and compatibility with on-site process conditions; while mercaptobenzothiazole collectors have weak collecting capacity, making it difficult to balance recovery rate and concentrate grade when used alone. Therefore, researchers have attempted to combine these reagents to achieve synergistic effects.

[0004] In recent years, collectors containing ether functional groups have attracted widespread attention. Patent CN113680535B discloses an ethylene glycol ether-based dithiophosphate, which can be used as a collector for sulfide minerals, and mentions its compatibility with various traditional collectors (including ethyl thiocyanate, mercaptobenzothiazole, etc.). However, this compatibility scheme still faces many challenges: because the molecular structure of ethylene glycol ether-based dithiophosphate is based on a linear ethylene (-CH2CH2-) linkage, the compatibility and dispersion stability of the components when compounded with nitrogen- and sulfur-containing polar collectors such as ethyl thiocyanate or mercaptobenzothiazole still need further improvement. On-site preparation often requires the addition of external organic solvents or strong stirring to maintain system homogeneity. Fluctuations in the ratio, temperature, or order of addition can easily lead to uneven dispersion or even stratification, resulting in cumbersome operation and insufficient process stability. Furthermore, propylene glycol ether-based dithiocarbonate (CN121927751A) has been disclosed in the prior art, which also contains propylene glycol ether structural units. However, due to the fundamental differences between dithiocarbonate and dithiophosphate in molecular structure, fixative properties, and flotation mechanism, those skilled in the art find it difficult to obtain technical inspiration from it to apply the propylene glycol ether structure to dithiophosphate complex systems to improve their compatibility and synergistic performance. Therefore, developing a combined collector based on a dithiophosphate with a specific structure and ethyl thiocyanate or mercaptobenzothiazole, which possesses good component compatibility, stability, and synergistic flotation performance, has significant research significance and application value. Summary of the Invention

[0005] In view of the above-mentioned problems, this invention provides a combined collector, its preparation method, and its application. This invention utilizes the excellent coupling and solubilizing ability imparted by the ether oxygen group and methyl branch in the propylene glycol ether dithiophosphate molecule, enabling it to function as both a collector and an intrinsic "coupling agent" in the compound system. This significantly improves its compatibility and dispersion stability with ethyl thiocyanate or mercaptobenzothiazole. The two work synergistically through a co-adsorption mechanism of "rapid spreading—chemical anchoring—dense film formation," forming a denser and more stable composite adsorption film on the mineral surface. This combined collector is easy to formulate, has good component compatibility, and balances collecting capacity and selectivity, making it suitable for the efficient flotation of various sulfide ores, such as copper sulfide ores and lead-zinc sulfide ores.

[0006] To address the above problems, the present invention provides a combined collector comprising component A and component B; component A is an ether dithiophosphate, wherein the ether dithiophosphate is at least one of the compounds shown in formulas I to VI; and component B is an auxiliary collector, wherein the auxiliary collector is selected from at least one of ethyl thiocyanate and mercaptobenzothiazole. ; 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 H, NH4, Na, or K.

[0007] Preferably, in the combined collector, the content of component A is 5% to 80%, and the content of component B is 20% to 95%.

[0008] Preferably, R is selected from one of methyl, ethyl, n-propyl, and n-butyl.

[0009] Preferably, the ether alcohol used to prepare component A is at least one of propylene glycol monoether, dipropylene glycol monoether, tripropylene glycol monoether, and tetrapropylene glycol monoether; The propylene glycol monoether includes at least one of propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monopentyl ether; The dipropylene glycol monoether includes at least one of dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monopentyl ether; The tripropylene glycol monoether includes at least one of tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, and tripropylene glycol monopentyl ether; The tetrapropylene glycol monoether includes at least one of tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, and tetrapropylene glycol monopentyl ether.

[0010] Based on the same inventive concept, the present invention also provides a method for preparing the combined collector described in any of the above claims, comprising the following steps: S1. Mix ether alcohol with phosphorus pentasulfide and stir and heat to react to obtain ether-based dithiophosphoric acid; S2. The ether-based dithiophosphate is mixed with an alkaline solution containing ethyl thiocyanate and / or mercaptobenzothiazole to obtain the combined collector.

[0011] It should be noted that in this invention, the ether-based dithiophosphate (A component) is directly added to the alkaline solution containing component B for neutralization, rather than neutralizing the ether-based dithiophosphate separately first and then mixing it with component B. This is mainly based on the following considerations: Firstly, ether-based dithiophosphate itself is acidic and usually an oily substance. After direct contact with the alkaline solution containing component B, it can undergo an in-situ neutralization reaction in the liquid phase system, and be promptly converted into ether-based dithiophosphate with good water solubility, which is beneficial to its rapid dispersion and uniform existence in the system. Secondly, the alkali in the alkaline solution can come from excess alkali in the preparation process of ethyl thiocyanate, alkali added during the salt formation or dissolution of mercaptobenzothiazole, or additional alkali added when dissolving the powder component B. Therefore, the preparation, dissolution, or salt formation process of component B can be organically coupled with the neutralization process of component A, so that the salting of component A and the compounding of the two collecting active components are completed simultaneously. This method not only eliminates the concentration and drying steps in the traditional ethyl thiocyanate process, or the subsequent acidification and precipitation steps of mercaptobenzothiazole, but also avoids the additional steps and energy consumption caused by the separate neutralization and salt preparation of ether-based dithiophosphoric acid followed by compounding. Simultaneously, the in-situ neutralization of component A in an alkaline medium containing component B helps reduce localized uneven neutralization, oil phase agglomeration, and phase separation, improving the uniformity and stability of the resulting combined collector. Furthermore, it allows for flexible adjustment of the ratio of components A to B as needed, enhancing process applicability and industrial implementation convenience.

[0012] Preferably, in step S1, the molar ratio of the ether alcohol to phosphorus pentasulfide is 4-8:1, the reaction temperature is 50-120℃, and the reaction time is 2-8 hours. More preferably, the heating reaction temperature is 60-120℃, and the reaction time is 3-8 hours.

[0013] Preferably, in step S2, the alkaline component in the alkaline solution is selected from at least one of sodium hydroxide, potassium hydroxide, ammonia, and liquid ammonia.

[0014] Based on the same inventive concept, the present invention also provides the application of the combined collectors described in any of the above claims or the combined collectors prepared by the preparation methods described in any of the above claims in mineral flotation.

[0015] Preferably, the mineral includes any one of copper sulfide ore, lead-zinc sulfide ore, copper-molybdenum sulfide ore, and nickel sulfide ore.

[0016] Preferably, the combined collector is added at a rate of 5-300 g / t, and the slurry pH is 4-13.

[0017] The chemical reaction formulas for the preparation process of component A in the combined collector of the present invention, formulas I to VI, are as follows: ; ; ; ; ; .

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) This invention provides a combined collector comprising component A and component B, wherein component A is propylene glycol ether dithiophosphate and component B is ethyl thiocyanate and / or mercaptobenzothiazole. This invention creatively combines propylene glycol ether dithiophosphate with ethyl thiocyanate and / or mercaptobenzothiazole, achieving complementary advantages and synergistic effects in the performance of class II / III collectors. From a microscopic mechanism perspective, the synergistic effect of the combined collector of this invention is mainly reflected in the synergistic effect of the co-adsorption mechanism and the hydrophobic enhancement mechanism. The propylene glycol ether dithiophosphate molecule of this invention simultaneously contains a polar collecting group of dithiophosphate, an ether oxygen group, and a propylene glycol ether segment with a methyl branch. This structure not only maintains the dithiophosphate's activity on the metal sites (such as Cu) on the surface of sulfide minerals. + Pb 2+ The combined collector exhibits strong chemical affinity for components A and B, and imparts enhanced "coupling-solubilization-dispersion" characteristics to the molecules. When component A and component B coexist in the flotation pulp system, propylene glycol ether dithiophosphate can rapidly spread on the mineral surface and form a relatively uniform initial hydrophobic layer; ethyl thiocyanate or mercaptobenzothiazole contains N and S coordination sites, readily undergoing strong chemical adsorption with the metal active sites on the mineral surface. After co-adsorption, a composite adsorption film with both rapid spreading and fixed-point anchoring effects can be formed, significantly improving the density, continuity, and resistance to hydration interference of the adsorption film layer, thereby simultaneously improving collection efficiency and selectivity. This multi-step synergistic mechanism of "rapid spreading-chemical anchoring-dense film formation" makes the flotation performance of the combined collector far superior to that of using each component alone. (2) The propylene glycol ether dithiophosphate used in this invention differs fundamentally in molecular structure from traditional black drug collectors and ethylene glycol ether dithiophosphate. This difference enables it to exert a unique intrinsic "solventization and coupling" function in the compound system. Public information shows that propylene glycol ethers are a type of solvent structure with high aqueous phase compatibility, active dissolving ability and coupling ability. The molecular structure of traditional alcohol black drugs and phenol black drugs is mainly composed of dithiophosphate groups and alkyl or aryl hydrophobic groups. The structure lacks ether-oxygen type "bridging units" that can simultaneously interface with aqueous and organic phases. Therefore, when compounded with nitrogen- and sulfur-containing collectors such as ethyl thiocyanate or mercaptobenzothiazole, they often rely more on the addition of organic solvents, emulsifiers or strong on-site stirring to maintain short-term uniformity. Once the ratio, temperature or order of addition fluctuates, local uneven concentration, insufficient dispersion or even stratification will more easily occur. In contrast, the ethylene glycol ether segments in ethylene glycol ether dithiophosphate exhibit stronger hydrophilicity and a more linear structural characteristic, resulting in relatively weaker solvation and coupling effects. The propylene glycol ether structure employed in this invention, however, possesses a more suitable hydrophilic-hydrophobic balance: the ether oxygen groups in its propylene glycol ether structural units facilitate hydrogen bonding, ionic-dipole, or dipole-dipole interactions with aqueous phases, ionic components, or strongly polar components, while the methyl branches enhance its affinity for moderately hydrophobic organic components. This unique amphiphilic characteristic allows it to be neither as hydrophobic and narrowly compounded as traditional black powders, nor as purely hydrophilic as linear ethylene glycol ether segments. Instead, it can simultaneously accommodate both highly polar and highly hydrophobic components, forming a more homogeneous and stable compounding system. At the molecular level, propylene glycol ether dithiophosphate is not only a collector in the compound system, but also acts as an intrinsic "coupling agent", making it easier for component B to enter the same liquid phase or form a stable dispersed phase. This significantly reduces the need for on-site dissolution, emulsification and forced mixing, and fundamentally solves the bottleneck problems of poor compatibility and complicated preparation of existing compound systems. (3) Component A (propylene glycol ether dithiophosphate) in the combined collector of the present invention also has good structural tunability. Since the propylene glycol ether system can have different carbon chain lengths, homologue compositions, isomer forms and polymerization degrees, different types of propylene glycol ether raw materials can be screened and targeted synthesis can be carried out to finely control the hydrophilicity-hydrophobicity balance, steric hindrance, interfacial distribution behavior and adsorption strength on mineral surfaces of the obtained collector molecules, thereby achieving a fine balance between collecting ability and selectivity. When component A is combined with component B (ethyl thiocyanate and / or mercaptobenzothiazole), the two can further enhance their selective recognition of target minerals through a "complementary adsorption" mechanism: the N,N-diethyldithiocarbamate structure of ethyl thiocyanate has high coordination selectivity for metal ions such as lead and copper, while the heterocyclic structure of mercaptobenzothiazole can form chelate adsorption with the mineral surface through its N and S heteroatoms. Both complement the polar dithiophosphate group of propylene glycol ether dithiophosphate in terms of adsorption sites, adsorption configuration, and adsorption strength. Based on this tunability, this invention can develop a series of products more suitable for different ore systems by adjusting the propylene glycol ether chain segment structure of component A (e.g., selecting R groups with different carbon chain lengths and propylene glycol ether skeletons with different degrees of polymerization) and the ratio of component A to component B, according to different mineral properties, intercalation relationships, and interference conditions of associated minerals. This improves the applicability and process adaptability of the combined collector to complex mineral systems. (4) The combined collectors provided by this invention exhibit significantly better flotation performance than single components in practical flotation applications. Single mineral flotation tests show that, under the same dosage conditions, the combined collectors prepared in the embodiments of this invention have significantly higher recoveries of chalcopyrite and galena than when using O,O-bis(1-butoxypropyl-2-yl)dithiophosphoric acid, ethyl thiocyanate, or mercaptobenzothiazole alone. In the actual flotation of copper sulfide ore, the combined collectors prepared in Examples 2 and 3 of this invention, with a collector dosage of only 30 g / t, achieved copper concentrate grades of 8.21% and 8.82%, respectively, and copper recoveries of 89.67% and 88.22%, respectively, all significantly better than those achieved when using component A alone (copper grade 8.11%, recovery rate 85.17%), ethyl thiocyanate (copper grade 7.82%, recovery rate 84.97%), or mercaptobenzothiazole (copper grade 10.82%, recovery rate 77.59%). In the flotation of actual lead-zinc sulfide ores, the combined collector of Example 2 of this invention achieved a lead concentrate Pb recovery rate of 84.28% with a collector dosage of only 20 g / t, significantly higher than the recovery rates achieved by using component A (82.10%), ethyl thiocyanate (77.50%), or mercaptobenzothiazole (66.49%) alone. These results indicate that component A and component B achieve a synergistic effect of "1+1>2" through a "co-adsorption—complementary anchoring—dense film formation" mechanism. This significantly improves the recovery rate of the target mineral while effectively reducing gangue mineral inclusions in the concentrate and increasing the concentrate grade. (5) The preparation method of the combined collector of the present invention has a simple process route. It only requires the reaction of ether alcohol with phosphorus pentasulfide to generate ether-based dithiophosphoric acid, which is then directly mixed with an alkaline solution containing ethyl thionione and / or mercaptobenzothiazole to obtain the target combined product. This method does not require the separate preparation of component A and component B before mixing. Instead, it utilizes the neutralization reaction process of propylene glycol ether-based dithiophosphoric acid to simultaneously complete the compounding with component B, realizing the integrated preparation of "reaction-neutralization-compounding". This integrated process not only simplifies the operation steps and reduces the production cost, but more importantly, by utilizing the characteristic of propylene glycol ether-based dithiophosphoric acid to simultaneously neutralize and dissolve with component B under alkaline conditions, it can ensure that the two components are fully mixed at the molecular level, fundamentally guaranteeing the uniformity and stability of the combined collector product. In addition, the propylene glycol ether raw materials used in the present invention are widely available. They can be selected from various propylene glycol monoethers and their homologues, or the distillation residue in the process of producing propylene glycol ethers by the propylene oxide method can be directly utilized for resource utilization, which has good raw material availability and economy. The preparation method of this invention has a short process route, simple reaction steps, good matching between raw materials and product system, and is easy to control reaction and post-processing, and has good prospects for industrial application. Attached Figure Description

[0019] Picture 1The sample prepared in Example 1 of this invention O,O UV spectrum of bis(1-ethoxypropyl-2-yl)dithiophosphoric acid; Picture 2 The sample prepared in Example 1 of this invention O,O Infrared spectrum of 1-bis(1-ethoxypropyl-2-yl)dithiophosphoric acid; Picture 3 The sample prepared in Example 1 of this invention O,O Mass spectrum of bis(1-ethoxypropyl-2-yl)dithiophosphoric acid; Picture 4 The sample prepared in Example 1 of this invention O,O UV spectrum of bis(1-butoxypropyl-2-yl)dithiophosphoric acid; Picture 5 The sample prepared in Example 1 of this invention O,O Infrared spectrum of bis(1-butoxypropyl-2-yl)dithiophosphoric acid; Picture 6 The sample prepared in Example 1 of this invention O,O Mass spectrum of bis(1-butoxypropyl-2-yl)dithiophosphoric acid; Picture 7 The sample prepared in Example 4 of this invention O,O UV spectrum of bis[1-(1-butoxypropyl-2-yloxy)propyl-2-yl]dithiophosphoric acid; Picture 8 The sample prepared in Example 4 of this invention O,O Infrared spectrum of bis[1-(1-butoxypropyl-2-yloxy)propyl-2-yl]dithiophosphoric acid; Picture 9 The sample prepared in Example 4 of this invention O,O Mass spectrum of bis[1-(1-butoxypropyl-2-yloxy)propyl-2-yl]dithiophosphoric acid; Picture 10 The following are single-mineral flotation flow charts for Application Examples 1 and 2 of this invention; Picture 11 Line graphs showing the flotation recovery rates of chalcopyrite at different dosages of the combined collectors of Example 2 (Application Example 1), the combined collectors of Example 3, O,O-bis(1-ethoxypropyl-2-yl)dithiophosphoric acid (Comparative Example 1), ethyl thiocyanate (Comparative Example 2), and mercaptobenzothiazole (Comparative Example 3). Picture 12 Line graphs showing the flotation recovery rates of galena at different dosages of the combined collectors of Example 2 (Application Example 1), the combined collectors of Example 3, O,O-bis(1-ethoxypropyl-2-yl)dithiophosphoric acid (Comparative Example 1), ethyl thiocyanate (Comparative Example 2), and mercaptobenzothiazole (Comparative Example 3). Picture 13 This is a flowchart of the actual flotation process for copper sulfide ore, as described in Application Example 3 of the present invention. Picture 14 The above is a flowchart of the actual flotation process for lead-zinc sulfide ore, which is an application example 4 of this invention. Detailed Implementation

[0020] 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 prepared by known methods.

[0021] To address the technical problems mentioned in the background section, this invention provides a combined collector, its preparation method, and its application. The combined collector of this invention is characterized by ease of formulation, convenient use, good component compatibility, and superior flotation performance, meeting the application requirements of high efficiency and stability for collectors in complex mineral flotation processes.

[0022] The following examples and comparative models further illustrate this point.

[0023] Example 1 O,O The preparation method of the combined collector of sodium bis(1-ethoxypropyl-2-yl)dithiophosphate and ethyl thiocyanate includes the following steps: By weight, 31.56 parts of propylene glycol ethyl ether were added to a three-necked flask, and 16.84 parts of phosphorus pentasulfide were added in portions (the molar ratio of propylene glycol ethyl ether to phosphorus pentasulfide was approximately 4:1). After the addition was complete, the temperature was raised to 90°C, and the reaction was carried out with stirring for 4 hours. 45.42 parts of a dark green oily liquid dithiophosphate product were obtained.

[0024] The above products were purified and characterized by ultraviolet, mass spectrometry, and infrared spectroscopy. The results are as follows: Picture 1 As shown in Figure 3. From Picture 1 It can be seen that the ultraviolet spectrum of the above products in the 200-300nm range has a characteristic ultraviolet absorption peak near 225nm, which is attributed to P(=S)S. - Characteristic functional groups; composed of Picture 2 It can be seen that the main infrared characteristic peak of the above products is: 2977 cm⁻¹ -1 2934cm-1 and 2872cm -1 Stretching vibration peaks attributed to CH3 and CH2; 1447 cm⁻¹ -1 1381cm -1 The peak is attributed to the deformation vibration of CH in CH3 and CH-OP; 1118 cm⁻¹ -1 Attributable to the stretching vibration peak of COC; 1072 cm⁻¹ -1 978cm -1 Asymmetric stretching vibration peak attributable to POC; 763 cm⁻¹ -1 663cm -1 Attribution to the P=S vibration peak; by Picture 3 It can be seen that the test results showed [MH] with a mass-to-charge ratio of 301.0750. - The peak indicates that the molecular formula of the compound matches the expectation. This indicates that the above product is... O,O -Di(1-ethoxypropyl-2-yl)dithiophosphate ( ).

[0025] Take the above O,O 27.97 parts of bis(1-ethoxypropyl-2-yl)dithiophosphoric acid were placed in a beaker, 60.00 parts of water were added, followed by 30.00 parts of commercially available ethyl thiocyanate and 3.85 parts of sodium hydroxide. The mixture was stirred until homogeneous and golden-yellow in color. O,O 121.82 parts of a product containing a combination of sodium di(1-ethoxypropyl-2-yl)dithiophosphate and ethyl thiocyanate collector. The total content of the active ingredient in this product is 50.00 wt.%, of which... O,O The content of sodium di(1-ethoxypropyl-2-yl)dithiophosphate and ethyl nitrogen is 25.00 wt.%.

[0026] Example 2 O,O The preparation method of the combined collector of sodium bis(1-butoxypropyl-2-yl)dithiophosphate and ethyl thiocyanate includes the following steps: By weight, 40.06 parts of propylene glycol butyl ether were added to a three-necked flask, and 16.84 parts of phosphorus pentasulfide were added in portions (the molar ratio of propylene glycol butyl ether to phosphorus pentasulfide was approximately 4:1). After the addition was complete, the temperature was raised to 90°C, and the reaction was carried out with stirring for 4 hours. 54.08 parts of a dark green oily liquid dithiophosphate product were obtained.

[0027] The above products were purified and characterized by ultraviolet spectroscopy, mass spectrometry, and infrared spectroscopy. The results are as follows: Picture 4 As shown in Figure 6. Picture 4It can be seen that the ultraviolet spectrum of the above products in the 200-300nm range has a characteristic ultraviolet absorption peak near 225nm, which is attributed to P(=S)S. - Characteristic functional groups; composed of Picture 5 It can be seen that the main infrared characteristic peak of the above products is: 2959 cm⁻¹ -1 2934cm -1 and 2872cm -1 Stretching vibration peaks attributed to CH3 and CH2; 1457 cm⁻¹ -1 1380cm -1 The peak is attributed to the deformation vibration of CH in CH3 and CH-OP; 1118 cm⁻¹ -1 Attributable to the stretching vibration peak of COC; 1056 cm⁻¹ -1 981cm -1 Asymmetric stretching vibration peak attributable to POC; 765 cm⁻¹ -1 665cm -1 Attribution to the P=S vibration peak; by Picture 6 It can be seen that the test results showed [MH] with a mass-to-charge ratio of 357.1374. - The peak indicates that the molecular formula of the compound matches the expectation. This indicates that the above product is... O,O -Di(1-butoxypropyl-2-yl)dithiophosphoric acid ( ).

[0028] By weight, 12.94 parts of diethylamine and 55.00 parts of water were added to a three-necked flask, followed by 14.82 parts of carbon disulfide. The system was kept below 15°C in an ice bath, and then 8.93 parts of sodium hydroxide were added in batches. After the addition was complete, the mixture was reacted at 25°C for 2.5 hours to obtain 88.14 parts of a wine-red ethyl thiocyanate aqueous solution.

[0029] Take the above O,O 14.13 parts of bis(1-butoxypropyl-2-yl)dithiophosphoric acid were placed in a beaker, and then 85.00 parts of the above-mentioned ethyl thiocyanate aqueous solution product were added. The mixture was stirred until homogeneous and a golden-yellow color was obtained. O,O 99.13 parts of a product containing a combination of sodium di(1-butoxypropyl-2-yl)dithiophosphate and ethyl thiocyanate collector. The total content of the active ingredient in this product is 45.00 wt.%, of which... O, O The contents of sodium di(1-butoxypropyl-2-yl)dithiophosphate and ethyl thiocyanate are 15.00 wt.% and 30.00 wt.%, respectively.

[0030] Example 3 O,OThe preparation method of the combined collector of sodium bis(1-butoxypropyl-2-yl)dithiophosphate and mercaptobenzothiazole includes the following steps: Take the preparation obtained in Example 2 O,O 9.42 parts of bis(1-butoxypropyl-2-yl)dithiophosphate were placed in a beaker, followed by 17.68 parts of mercaptobenzothiazole and 20.00 parts of water, then 5.49 parts of sodium hydroxide. After stirring until homogeneous, 52.59 parts of a golden-yellow, homogeneous O,O-bis(1-butoxypropyl-2-yl)dithiophosphate sodium and mercaptobenzothiazole combined collector were obtained. The total content of the active ingredients in this product was 60.00 wt.%. O,O The contents of sodium di(1-butoxypropyl-2-yl)dithiophosphate and mercaptobenzothiazole were 20.00 wt.% and 40.00 wt.%, respectively.

[0031] Example 4 O,O The preparation method of the combined collector of sodium bis[1-(1-butoxypropyl-2-yloxy)propyl-2-yl]dithiophosphate and mercaptobenzothiazole includes the following steps: By weight, 58.24 parts of dipropylene glycol butyl ether were added to a three-necked flask, followed by the addition of 16.84 parts of phosphorus pentasulfide in portions (the molar ratio of dipropylene glycol butyl ether to phosphorus pentasulfide was approximately 4.04:1). After the addition was complete, the mixture was heated to 90°C and reacted with stirring for 5 hours. 72.25 parts of a dark green, oily liquid dithiophosphate product were obtained, with a yield of 92.64%.

[0032] The above products were purified and characterized by ultraviolet spectroscopy, mass spectrometry, and infrared spectroscopy. The results are as follows: Picture 7 As shown in Figure 9. Picture 7 It can be seen that the ultraviolet spectrum of the above products in the 200-300nm range has a characteristic ultraviolet absorption peak near 225nm, which is attributed to P(=S)S. - Characteristic functional groups; composed of Picture 8 It can be seen that the main infrared characteristic peaks of the above products are: 2960 cm⁻¹ -1 2934cm -1 and 2870cm -1 Stretching vibration peaks attributed to CH3 and CH2; 1457 cm⁻¹ -1 1378cm -1 The peak is attributed to the deformation vibration of CH in CH3 and CH-OP; 1114 cm⁻¹ -1 Attributable to the stretching vibration peak of COC; 1056 cm⁻¹ -1 981cm -1 Asymmetric stretching vibration peak attributable to POC; 769 cm⁻¹ -1 666cm-1 It belongs to the P=S vibration peak. (From...) Picture 9 It can be seen that the test results showed [MH] with a mass-to-charge ratio of 473.2210. - The peak indicates that the molecular formula of the compound matches the expectation. This indicates that the above product is... O,O -Di[1-(1-butoxypropyl-2-yloxy)propyl-2-yl]dithiophosphate ( ).

[0033] Take the above O,O 28.67 parts of bis[1-(1-butoxypropyl-2-yloxy)propyl-2-yl]dithiophosphoric acid were placed in a beaker, 60.00 parts of water were added, followed by 26.51 parts of commercially available mercaptobenzothiazole and 9.12 parts of sodium hydroxide. The mixture was stirred until homogeneous and light yellow. O,O - 124.30 parts of a product containing a combination of sodium di[1-(1-butoxypropyl-2-yloxy)propyl-2-yl]dithiophosphate and mercaptobenzothiazole as a collector. The total content of the active ingredients in this product is 50.00 wt.%, of which the contents of sodium di[1-butoxypropyl-2-yl]dithiophosphate and mercaptobenzothiazole are 25.00 wt.% and 25.00 wt.%, respectively.

[0034] Example 5 O,O The preparation method of the combined collector of ammonium dithiophosphate and ethyl thiocyanate, comprising the following steps: By weight, 63.15 parts of tripropylene glycol methyl ether were added to a three-necked flask, and 16.84 parts of phosphorus pentasulfide were added in portions (the molar ratio of tripropylene glycol methyl ether to phosphorus pentasulfide was approximately 4.04:1). After the addition was complete, the temperature was raised to 90°C, and the reaction was carried out with stirring for 5 hours. A dark green oily liquid dithiophosphate product was obtained. At 25°C, 10.22 parts of a 25% ammonia solution were slowly added dropwise to the three-necked flask using a constant pressure dropping funnel. After the addition was complete, stirring was continued for 0.5 hours to obtain a light green product. O,O -86.21 parts of bis[1-((1-((1-methoxypropyl-2-yl)oxy)propyl-2-yl)oxy)propyl-2-yl]dithiophosphate ammonium product.

[0035] Take the above O,O 10.00 parts of bis[1-((1-(((1-methoxypropyl-2-yl)oxy)propyl-2-yl)oxy)propyl-2-yl]dithiophosphate ammonium were placed in a beaker, and then 30.00 parts of commercially available ethyl thiocyanate and 40.00 parts of water were added. The mixture was stirred until homogeneous and golden in color to obtain a uniform solution. O,O-80.00 parts of a product containing a combination of ammonium dithiophosphate and ethyl thiocyanate as a collector. The total content of the active ingredients in this product is 50.00 wt.%. O,O The contents of bis[1-((1-((1-methoxypropyl-2-yl)oxy)propyl-2-yl)oxy)propyl-2-yl]dithiophosphate ammonium and ethyl thiocyanate are 12.50 wt.% and 37.50 wt.%, respectively.

[0036] Comparative Example 1 The preparation obtained in Example 2 O,O -Di(1-Butoxypropyl-2-yl)dithiophosphoric acid.

[0037] Comparative Example 2 Commercially available ethyl thiocyanate collector.

[0038] Comparative Example 3 Commercially available mercaptobenzothiazole collector.

[0039] Application Example 1 The combined collector prepared in Example 2, the combined collector prepared in Example 3, and the combined collector prepared in Comparative Example 1 O,O 1-Di(1-butoxypropyl-2-yl)dithiophosphoric acid, commercially available ethyl thiocyanate (Comparative Example 2), and commercially available mercaptobenzothiazole (Comparative Example 3) were used as collectors in flotation tests of chalcopyrite. The specific flotation process flow is as follows: Picture 10 As shown. The pulp pH was adjusted to 7 using 1.0 mol / L NaOH solution. The dosage of each collector was 0–30 mg / L, and the dosage of the frother MIBC was 3.6 × 10⁻⁶ mg / L. -4 mol / L, chalcopyrite particle size is 0.076~+0.038mm. The flotation test results are as follows: Picture 11 As shown. By Picture 11 It can be seen that when the collector dosage is 30 mg / L, the combined collector of Example 2, the combined collector of Example 3, and the one used in Comparative Example 1 are effective. O,O The recoveries of chalcopyrite were 88.17%, 91.84%, 84.65%, 81.42%, and 69.77% for bis(1-ethoxypropyl-2-yl)dithiophosphoric acid, ethyl thiocyanate (comparative Example 2), and mercaptobenzothiazole (comparative Example 3), respectively. These results indicate that, compared to using [the specific chalcopyrite] alone... O,O The combined collectors prepared in Examples 2 and 3 of this invention, consisting of bis(1-butoxypropyl-2-yl)dithiophosphoric acid, ethyl thiocyanate, or mercaptobenzothiazole, exhibit stronger collecting ability for chalcopyrite.

[0040] Application Example 2 The combined collector prepared in Example 2, the combined collector prepared in Example 3, and the combined collector prepared in Comparative Example 1 O,O 1-Di(1-butoxypropyl-2-yl)dithiophosphoric acid, commercially available ethyl thiocyanate (Comparative Example 2), and commercially available mercaptobenzothiazole (Comparative Example 3) were used as collectors in flotation tests on galvanite. The specific flotation process flow is as follows: Picture 10 As shown. The pulp pH was adjusted to 7 using 1.0 mol / L NaOH solution. The dosage of each collector was 0-20 mg / L, and the dosage of the frother MIBC was 3.6 × 10⁻⁶ mg / L. -4 mol / L, galena particle size is 0.076~+0.038mm. The flotation test results are as follows: Picture 12 As shown. By Picture 12 It can be seen that when the collector dosage is 20 mg / L, the galena recoveries using the combined collector of Example 2, the combined collector of Example 3, O,O-bis(1-butoxypropyl-2-yl)dithiophosphoric acid of Comparative Example 1, ethyl thiocyanate of Comparative Example 2, and mercaptobenzothiazole of Comparative Example 3 are 96.21%, 96.53%, 94.14%, 88.07%, and 80.24%, respectively. Furthermore, under the same dosage conditions, the galena recoveries obtained by the combined collectors are all higher than those obtained by the individual comparative collectors. These results indicate that the combined collectors prepared in Examples 2 and 3 of this invention exhibit stronger collecting ability for galena compared to using O,O-bis(1-butoxypropyl-2-yl)dithiophosphoric acid, ethyl thiocyanate, or mercaptobenzothiazole alone.

[0041] Application Example 3 The combined collector prepared in Example 2, the combined collector prepared in Example 3, and the combined collector prepared in Comparative Example 1 O,O 1-Di(1-butoxypropyl-2-yl)dithiophosphoric acid, commercially available ethyl thiocyanate (Comparative Example 2), and commercially available mercaptobenzothiazole (Comparative Example 3) were used as collectors in flotation tests on a copper sulfide ore. The specific flotation process flow is as follows: Picture 13 As shown, a roughing process was conducted. In each experiment, 500g of ore powder, 300mL of water, and a certain amount of lime were ground in a conical ball mill until the mineral particle size met the requirements for beneficiation. The slurry was then transferred to a 1.5L single-cell flotation machine for flotation. The flotation machine was turned on and stirred for 3 minutes, followed by the addition of a collector and stirring for another 3 minutes. Then, frother #2 oil was added and stirring continued for 1 minute. The foam was collected as concentrate, and the product in the water tank was the tailings. The concentrate and tailings were filtered, dried, ground, and then samples were prepared for copper content analysis. The yield and recovery rate were calculated. The reagent regime was as follows: grinding fineness of -200 mesh (71%), lime dosage of 600g / t, and other flotation test conditions and results are shown in Table 1.

[0042] Table 1:

[0043] As shown in Table 1, compared with Comparative Examples 1-3 used alone, the combined collectors prepared in Examples 2 and 3 of this invention achieved higher copper recovery rates. Specifically, the copper concentrate grades obtained in Examples 2 and 3 were higher than those in Comparative Examples 1 and 2, and the copper recovery rate was significantly improved while maintaining a high concentrate grade. Considering the concentrate grade, copper recovery rate, and reagent dosage, the combined collectors prepared in Examples 2 and 3 of this invention exhibited superior flotation performance for this copper sulfide ore. Furthermore, as shown in Table 1, while achieving better flotation indicators, the dosages of the combined collector and frother were lower than those in Comparative Examples 2 and 3, demonstrating better synergistic effects and economic efficiency.

[0044] Application Example 4 The combined collector prepared in Example 2, the combined collector prepared in Example 3, and the combined collector prepared in Comparative Example 1 O,O 1-Di(1-butoxypropyl-2-yl)dithiophosphoric acid, commercially available ethyl thiocyanate (Comparative Example 2), and commercially available mercaptobenzothiazole (Comparative Example 3) were used as collectors in flotation tests on a certain lead-zinc sulfide ore. The specific flotation process flow is as follows: Picture 14 As shown, a roughing process was conducted. For each experiment, 500g of ore powder, 300mL of water, and a certain amount of lime were added to a ball mill and ground until the mineral particle size met the requirements for beneficiation. The slurry was then transferred to a 1.5L single-cell flotation machine for flotation. The flotation machine was turned on and stirred for 3 minutes, ZnSO4 was added as a depressant, and stirring was continued for 3 minutes. Then, a collector was added and stirred for 3 minutes. Finally, a frother was added and stirring was continued for 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 lead and zinc contents were analyzed, and the yield and recovery were calculated. The reagent regime was as follows: grinding fineness of -200 mesh (69%), ZnSO4 dosage of 800g / t, and lime dosage of 600g / t. Other flotation test conditions and results are shown in Table 2.

[0045] Table 2:

[0046] As shown in Table 2, the combined collector prepared in Example 3 outperformed Comparative Examples 1-3 in both lead concentrate grade and lead recovery rate. The combined collector prepared in Example 2 exhibited the highest lead recovery rate, and its lead concentrate grade was higher than Comparative Examples 1 and 2, only lower than Comparative Example 3. In summary, the combined collectors prepared in Examples 2 and 3 of this invention demonstrated superior overall flotation performance compared to Comparative Examples 1-3 for this sulfide lead-zinc ore. Furthermore, when ether-based dithiophosphate is combined with mercaptobenzothiazole, the combined collector product is more conducive to improving concentrate grade; when combined with ethyl thiocyanate, the combined collector product is more conducive to improving concentrate recovery rate. The combined collector provided by this invention can be adjusted according to different mineral properties and actual flotation conditions, thereby improving mineral resource utilization.

[0047] To further elucidate the synergistic mechanism of the combined collectors of this application, the inventors, based on a comparison between the combined collectors of Examples 2-3 and the single components of Comparative Examples 1-3, and combined with surface tension testing, adsorption configuration calculations, and molecular dynamics (MD) simulations, systematically analyzed the synergistic mechanism between component A (propylene glycol ether dithiophosphate) and component B (ethyl thiocyanate / mercaptobenzothiazole). Component A contains a propylene glycol ether segment (-CH(CH3)-CH2-O- or -CH2-CH(CH3)-O-), possessing both a certain degree of hydrophobic branching structure and polar ether oxygen groups. It can undergo chemisorption on the mineral surface through the fixophilic dithiophosphate group and can also oriented at the gas-liquid interface using its interfacial activity. Component B, on the other hand, forms strong coordination bonds with the metal active sites on the mineral surface through its N and S coordinating atoms.

[0048] The surface tension test results show that: component A can significantly reduce the critical micelle concentration and surface tension of the combined collector system, improve the dispersibility of component B in the aqueous phase, and make the two form a more uniform co-dispersion system in the flotation pulp; the adsorption configuration calculation results show that: after component A forms a relatively loose initial adsorption layer on the mineral surface, component B can be embedded in the vacancies or gaps in the adsorption layer of component A, forming a composite adsorption configuration of "rapid spreading of component A + fixed anchoring of component B", thereby improving the density of the adsorption layer and the ability to resist hydration interference; (3) the molecular dynamics simulation results show that: the ether oxygen atoms of the propylene glycol ether segment in component A can form hydrogen bonds with the aqueous phase, and its methyl side chain also gives the segment a certain hydrophobic property. This amphiphilic property enables component A to effectively reduce the interfacial energy at both the solid-liquid interface and the bubble surface, promoting the migration of component B to the interface and stable co-adsorption. The above-mentioned synergistic differences in surface activity matching, adsorption configuration complementarity and interfacial co-adsorption make the flotation performance of the combined collector of this application significantly better than that of each single component.

[0049] 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 combined collector characterized in that, It includes component A and component B; component A is an ether dithiophosphate, which is at least one of the compounds shown in formulas I to VI; component B is an auxiliary collector, which is selected from at least one of ethyl thiocyanate and mercaptobenzothiazole. ； 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 H, NH4, Na, or K.

2. The combined collector reagent according to claim 1, characterized in that, In the combined collector, the content of component A is 5% to 80%, and the content of component B is 20% to 95%.

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

4. The combined collector reagent according to claim 1, characterized in that, The ether alcohol used to prepare component A is at least one of propylene glycol monoether, dipropylene glycol monoether, tripropylene glycol monoether, and tetrapropylene glycol monoether; The propylene glycol monoether includes at least one of propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monopentyl ether; The dipropylene glycol monoether includes at least one of dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monopentyl ether; The tripropylene glycol monoether includes at least one of tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, and tripropylene glycol monopentyl ether; The tetrapropylene glycol monoether includes at least one of tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, and tetrapropylene glycol monopentyl ether.

5. A process for the preparation of a combined collector as claimed in any one of claims 1 to 4, characterized in that, Includes the following steps: S1. Mix ether alcohol with phosphorus pentasulfide and stir and heat to react to obtain ether-based dithiophosphoric acid; S2. The ether-based dithiophosphate is mixed with an alkaline solution containing ethyl thiocyanate and / or mercaptobenzothiazole to obtain the combined collector.

6. The preparation method according to claim 5, characterized in that, In step S1, the molar ratio of the ether alcohol to phosphorus pentasulfide is 4-8:1, the reaction temperature is 50-120℃, and the reaction time is 2-8h.

7. The preparation method according to claim 5, characterized in that, In step S2, the alkaline component in the alkaline solution is selected from at least one of sodium hydroxide, potassium hydroxide, ammonia, and liquid ammonia.

8. The application of a combined collector as described in any one of claims 1-4 or a combined collector prepared by any one of claims 5-7 in mineral flotation.

9. The application according to claim 8, characterized in that, The minerals include any one of copper sulfide ore, lead-zinc sulfide ore, copper-molybdenum sulfide ore, and nickel sulfide ore.

10. The application according to claim 8, characterized in that, The combined collector is added at a rate of 5-300 g / t, and the slurry pH is 4-13.

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