A tungsten-molybdenum oxide ore collector and application thereof

Abstract

The application relates to a tungsten-molybdenum oxide ore collector and application thereof, and belongs to the field of ore-dressing reagents. The problems that the collector for the flotation of the molybdenum-tungsten oxide ore associated with calcium-containing gangue minerals in the prior art is poor in selectivity, the flotation process is complex, the flotation condition is difficult to control, and the collector cannot be degraded to pollute the environment are solved. A kind of tungsten-molybdenum oxide ore collector is used for the flotation of low-grade tungsten-molybdenum oxide ore, and the chemical structural formula of the collector is as follows: wherein R is an alkyl group with 12-18 carbon atoms; X + is an inorganic cation or an organic cation. The molybdenum-tungsten oxide ore is efficiently and highly-recoverably floated.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ore-dressing reagent, in particular to a tungsten-molybdenum oxide ore collector and application thereof. BACKGROUND

[0002] Tungsten and molybdenum are important strategic metal resources in China. They have excellent properties such as high melting point and high hardness, and are widely used in alloy, electronics, chemical industry, aerospace, nuclear industry and other fields. However, with the development of science and technology, the demand for tungsten and molybdenum is increasing, and the easily mined and selected primary tungsten and molybdenum resources are gradually decreasing. Complex and difficult to handle tungsten and molybdenum resources are gradually gaining attention. Tungsten-molybdenum oxide ore is a typical representative of difficult to handle tungsten and molybdenum resources. It has extremely low natural hydrophilicity and hydrophobicity, incomplete crystallization, and is mostly in fine-grained disseminated form, which makes it difficult to recover. In addition, tungsten-molybdenum oxide ore is often associated with calcareous gangue minerals such as calcite and fluorite. The main difficulties in the separation of these calcareous minerals are as follows: (1) the valuable minerals and gangue minerals have similar surface properties; (2) the dissolution and transformation among the calcareous minerals further make the surface composition of the valuable minerals and gangue minerals converge.

[0003] At present, the collectors used for tungsten-molybdenum oxide ore are basically fatty acid, sulfonic acid and hydroxamic acid collectors. Fatty acid collectors have good collection effect but poor selectivity for tungsten-molybdenum oxide ore; sulfonic acid collectors have slightly better selectivity but poor collection performance; hydroxamic acid collectors have chelation effect to improve selectivity but high reagent cost, which makes them difficult to be applied in industrial production. In addition, hydroxamic acid collectors generally do not have foaming effect, so additional foaming agent needs to be added in the production process, which undoubtedly further increases the production cost of enterprises. SUMMARY

[0004] In view of the above analysis, the embodiments of the present application aim to provide a tungsten-molybdenum oxide ore collector and application thereof, to solve at least one of the problems such as poor selectivity of the existing collector for tungsten-molybdenum oxide ore associated with calcareous gangue minerals, high cost, environmental pollution caused by the collector which cannot be degraded, toxicity of the hydrolysis product, and unsuitability for low-grade tungsten-molybdenum oxide ore flotation.

[0005] In one aspect, the embodiments of the present application provide a tungsten-molybdenum oxide ore collector for low-grade tungsten-molybdenum oxide ore flotation, and the chemical structural formula of the collector is as follows:

[0006]

[0007] wherein R is an alkyl group with 12-18 carbon atoms; X is an inorganic cation or an organic cation. +

[0008] In another aspect, the embodiments of the present application further provide a preparation method of the tungsten-molybdenum oxide ore collector, comprising the following steps: ​

[0009] S1, weigh the appropriate amount of alkyl primary alcohol, heat to 70-90°C to melt, and keep stirring;

[0010] S2, weigh the appropriate amount of maleic anhydride, slowly add to the molten alkyl primary alcohol, keep the reaction system temperature unchanged, and continue stirring for 2-3h to obtain a monomaleate carboxylic acid, keep the system temperature at 70-90°C;

[0011] S3, dissolve the appropriate amount of sulfonating agent in deionized water, heat to 70-90°C for preheating;

[0012] S4, slowly add the preheated sulfonating agent solution to the monomaleate carboxylic acid, the dropwise addition speed is adjusted to keep the reaction system temperature unchanged, and the mixture is stirred vigorously, kept at 70-90°C and reacted for 2-3h;

[0013] S5, after the reaction is completed, mix the reaction system with petroleum ether, extract multiple times, collect the transparent liquid at the bottom of the separatory funnel, and dry to obtain a tungsten-molybdenum oxide ore collector product.

[0014] Preferably, the molar ratio of the alkyl primary alcohol and maleic anhydride in S1 and S2 is 1:1.05.

[0015] Specifically, the sulfonating agent in S3 includes one of sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, ammonium sulfite, ammonium bisulfite, monoethanolamine sulfonate, diethanolamine sulfonate, or triethanolamine sulfonate.

[0016] Exemplarily, the molar ratio of the monomaleate carboxylic acid and the sulfonic acid group provided by the sulfonating agent in S3 is 1:1.05.

[0017] Preferably, a 5% urea solution by mass fraction is added to the reaction system at the initial stage of S4.

[0018] Preferably, the stirring speed in S4 is 600-800r / min.

[0019] On the other hand, the embodiment of the present application also provides an application of the tungsten-molybdenum oxide ore collector. The tungsten-molybdenum oxide ore and gangue mineral are floated by using the tungsten-molybdenum oxide collector, and the method comprises the following steps:

[0020] Step 1, grinding: crushing and grinding;

[0021] Step 2, adding flotation reagents: adding sodium carbonate and stirring for 3-5min, then adding water glass and stirring for 3-5min, and finally adding the tungsten-molybdenum oxide ore collector and stirring for 2-3min;

[0022] Step 3, filtering, drying and weighing the concentrate and tailings respectively, and calculating the yield and recovery rate.

[0023] Preferably, the mineral particle size is -74~+38 mu m after crushing and grinding in step 1.

[0024] Preferably, the amount of sodium carbonate added in step 2 is 900~1100g / t, the amount of water glass added is 3500~4000g / t, and the amount of tungsten-molybdenum oxide collector added is 90~110g / t.

[0025] Compared with the prior art, the present application can at least achieve one of the following beneficial effects:

[0026] 1. The tungsten-molybdenum oxide collector provided by the present application ensures excellent hydrophobicity by introducing a long non-polar carbon chain, so that the ore can obtain sufficient floatability after adsorption;

[0027] The molecule structure includes carboxylic acid groups and sulfonic acid groups, and the introduction of multiple polar groups enhances its water solubility, and the two polar groups can be adsorbed on the surface of the valuable mineral with double active points, thereby strengthening the adsorption capacity and chelation of the collector and the metal ions on the mineral surface, thereby improving the selectivity;

[0028] The ester group structure introduced into the molecule through esterification reaction has an oxygen atom (C=O) with only second to the oxygen atom on the sulfonic acid group and the carboxylic acid group in electronegativity and charge strength, which provides the collector of the present application with an adsorption reaction site other than the carboxylic acid group and the sulfonic acid group, thereby enhancing the adsorption of the reagent on the surface of the tungsten-molybdenum oxide and strengthening its selective flotation capacity; and easily forming a hydrogen bond with the hydrogen atom in the water molecule, thereby enhancing the hydrophilicity of the compound, so that it can be better dissolved and dispersed in the ore pulp, thereby facilitating the simplification of the flotation process;

[0029] The three electronegative points of the carboxylic acid group, the sulfonic acid group and the carbonyl oxygen atom (C=O) share and concentrate the electron density, and the electric fields superimpose on each other, forming a stronger adsorption field, which greatly improves the adsorption capacity of the tungsten-molybdenum oxide.

[0030] 2. The collector provided by the present application contains three electronegative points and has a long carbon chain surfactant structure similar to that of a fatty acid collector, and has the advantages of good selectivity, strong collecting performance and strong foaming performance compared with the prior art, greatly reducing the dosage of the flotation reagent, and being able to adapt to the flotation ore pulp environment of complex and low-grade tungsten-molybdenum oxide ore.

[0031] 3、The collector of the present application is prepared by taking alkyl primary alcohol with 12-18 carbon atoms as raw material, and compared with the collector used in the existing tungsten-molybdenum oxide ore, the synthesis cost is lower, and can be widely applied in actual large-scale production; the preparation process of the collector is simple, and does not need to add catalyst, and the reaction condition is mild; by selecting suitable reaction sequence, controlling reasonable reactant ratio and reaction temperature, preheating the sulfonating agent solution, and adopting the way of external stirring paddle to stir intensively, the synthesis is ensured to be carried out rapidly, and the side reaction is reduced.

[0032] 4、The ester group structure of the collector of the present application is easy to hydrolyze under strong alkaline conditions, and the product after hydrolysis is primary alcohol, which is mild, safe and non-toxic, and no harmful by-products are generated in the synthesis process, and is friendly to the environment, and meets the green development concept.

[0033] 5、The collector provided by the present application has more electronegative points, can be more effectively adsorbed on the surface of tungsten-molybdenum oxide ore, greatly improves the selective adsorption capacity for tungsten-molybdenum oxide ore, and the electronegative points are more inclined to form a strong adsorption effect with the metal oxide on the surface of tungsten-molybdenum oxide ore, so as to reduce the adsorption on silicate minerals, alleviate the problem of excessive water glass consumption caused by competitive adsorption, reduce the consumption of flotation water glass, and achieve the purpose of reducing cost and increasing efficiency.

[0034] 6、The collector of the present application has good separation effect on valuable minerals and gangue minerals in the range of pH=7-11, and as a double anionic surfactant, has excellent foaming performance, is helpful to stabilize the foam in the mineral processing and flotation process, and improves the flotation conditions.

[0035] In the present application, the above technical solutions can be combined with each other to realize more preferred combination solutions. Other features and advantages of the present application will be described in the subsequent specification, and some advantages will become apparent from the specification, or will be understood by implementing the present application. The purposes and other advantages of the present application can be realized and obtained from the contents specifically pointed out in the specification and the drawings. BRIEF DESCRIPTION OF DRAWINGS

[0036] The accompanying drawings are included to provide a further understanding of the present application, and are incorporated herein and constitute a part of the detailed description. The drawings illustrate embodiments of the present application and, together with the description, serve to explain the principles of the present application. In the drawings:

[0037] Figure 1 The infrared spectrum results of the synthesized compounds octadecyl succinate ester disodium sulfonate (MS-18), hexadecyl succinate ester disodium sulfonate (MS-16) and dodecyl succinate ester disodium sulfonate (MS-12) of example 1, example 2 and example 3 of the present application;

[0038] Figure 2High resolution mass spectrum result of compound MS-18 synthesized in the embodiment 1 of the present application;

[0039] Figure 3 High resolution mass spectrum result of compound MS-16 synthesized in the embodiment 2 of the present application;

[0040] Figure 4 High resolution mass spectrum result of compound MS-12 synthesized in the embodiment 3 of the present application;

[0041] Figure 5 Single mineral flotation flow chart in the application example 1 of the present application;

[0042] Fig. 6(a) is a diagram showing the influence of pH on the separation effect of synthetic collector MS-18 on scheelite, calcium molybdate and calcite in the embodiment 1 of the present application;

[0043] Fig. 6(b) is a diagram showing the influence of pH on the separation effect of synthetic collector MS-16 on scheelite, calcium molybdate and calcite in the embodiment 2 of the present application;

[0044] Fig. 7(a) is a diagram showing the influence of dosage on the separation effect of synthetic collector MS-18 on scheelite, calcium molybdate and calcite in the embodiment 1 of the present application;

[0045] Fig. 7(b) is a diagram showing the influence of dosage on the separation effect of synthetic collector MS-16 on scheelite, calcium molybdate and calcite in the embodiment 2 of the present application;

[0046] Figure 8 X-ray diffraction analysis diagram of actual ore in the application example 2 of the present application;

[0047] Figure 9 Flotation flow chart of actual ore in the application example 2 of the present application;

[0048] Figure 10 Local charge distribution of collector MS-12 prepared in the embodiment 3 of the present application Figure 1 .

[0049] Figure 11 Local charge distribution of collector MS-12 prepared in the embodiment 3 of the present application Figure 2 . DETAILED DESCRIPTION

[0050] The preferred embodiments of the present application will be described in detail below with reference to the drawings, which form a part of this application, and together with the embodiments of the present application illustrate the principles of the present application, but are not intended to limit the scope of the present application.

[0051] Tungsten-molybdenum ore generally has a high degree of oxidation, and molybdenum in the tungsten-molybdenum ore mainly exists in the form of sulfide (molybdenite) and oxide (calcium molybdate), and tungsten exists in the form of oxide (scheelite); the commonly used collectors in the flotation process of the oxide ore include fatty acids (such as oleic acid and its soaps), sulfonic acids (such as sodium dodecyl benzene sulfonate), chelating collectors (such as hydroxamic acids) and the like, these collectors form chemical bonds or chelates with metal ions on the surface of the mineral, enhance the hydrophobicity of the mineral, and need to use pH regulators, depressants such as water glass to optimize the flotation conditions and improve the selectivity, so as to realize the flotation.

[0052] The oxidized tungsten-molybdenum ore contains a large amount of fluorite, silicate and carbonate gangue minerals, the gangue minerals not only dissolve calcium ions in the ore pulp, making the mineral surface properties tend to be the same, but also dissolve silicate structures similar to the structure of the depressant water glass, which will compete for adsorption in the ore pulp, interfere with the effect of the depressant, increase the difficulty of separation, and cause poor effects of traditional collectors such as oleic acid, sodium dodecyl benzene sulfonate and hydroxamic acid.

[0053] In one specific embodiment of the present application, an oxidized tungsten-molybdenum ore collector is disclosed for the flotation of low-grade oxidized tungsten-molybdenum ore, and the chemical structural formula of the collector is:

[0054]

[0055] wherein R is an alkyl group with 12-18 carbon atoms; X + is an inorganic cation or an organic cation, including one of H + , Na + , K + , NH4 + , [C2H7NO] + , [C4H 11 NO] + or [C6H 15 NO] + .

[0056] The oxidized tungsten-molybdenum ore collector, by introducing a long nonpolar carbon chain, ensures excellent hydrophobicity of the collector, so that the ore has sufficient floatability after adsorption; the oxygen atoms in the carbonyl (C=O) and (-O-) structures have strong electronegativity, easily form hydrogen bonds with hydrogen atoms in water molecules, thereby enhancing the hydrophilicity of the compound, so that the compound can be better dissolved and dispersed in the ore pulp, and the flotation process can be simplified;

[0057] Further, the DMol3 module of the Materials Studio software is used to perform molecular dynamics simulation calculation on one of the synthesized collectors MS-12, and the local charge distribution of the molecule is as follows: Figure 10 ,Figure 11 as shown in the figure;

[0058] The results show that the two polar groups of carboxylic acid group and sulfonic acid group in the molecular structure have the strongest electronegativity, the carbonyl oxygen atom (C=O) of the ester group structure introduced into the molecule by the esterification reaction has the second strongest electronegativity and charge strength after the oxygen atom of the sulfonic acid group and the carboxylic acid group, and the electric fields of the three superimpose on each other to form a stronger adsorption field, which greatly enhances the adsorption of the reagent on the surface of the tungsten-molybdenum oxide ore and strengthens the ability of selective flotation.

[0059] In the adsorption process of the reagent and the mineral, the more negative charge indicates that the collector has stronger electrostatic attraction or coordination effect at the position, the electrostatic adsorption is more likely to occur at the position, or the chemical bond generated after adsorption is more stable.

[0060] In addition, the introduction of multiple polar groups not only enhances the water solubility, but also enables the collector to be adsorbed on the surface of the valuable mineral at multiple active sites, thereby strengthening the adsorption capacity and chelation of the collector and the metal ions on the surface of the mineral, and improving the selectivity.

[0061] Further, the preparation method of the tungsten-molybdenum oxide ore collector comprises the following steps:

[0062] S1, weigh an appropriate amount of alkyl primary alcohol, heat to 70-90℃ to melt, and keep stirring;

[0063] S2, weigh an appropriate amount of maleic anhydride, slowly add it to the molten alkyl primary alcohol, keep the temperature of the reaction system unchanged, and continuously stir for 2-3h to obtain a mono-maleate carboxylic acid, and keep the temperature of the system at 70-90℃;

[0064] S3, weigh an appropriate amount of sulfonating agent, dissolve it in deionized water, and heat to 70-90℃ for preheating;

[0065] S4, slowly add the preheated sulfonating agent solution to the mono-maleate carboxylic acid, and the dropping speed is adjusted to keep the temperature of the reaction system unchanged, and keep the stirring speed of the external mechanical stirring paddle at 600-800r / min, and keep the temperature at 70-90℃ and react for 2-3h;

[0066] S5, after the reaction is completed, mix the reaction system with petroleum ether, extract multiple times, collect the transparent liquid at the bottom of the separatory funnel, dry, and obtain the tungsten-molybdenum oxide ore collector product.

[0067] The esterification reaction of maleic anhydride and alkyl primary alcohol is carried out first, and then the sulfonation reaction of the mono-maleate carboxylic acid is carried out, without adding a catalyst, reducing the operation steps, and the esterification reaction can reduce the possible side reactions in the sulfonation reaction and improve the selectivity of the sulfonation reaction.

[0068] Specifically, the molar ratio of the alkyl primary alcohol and maleic anhydride in S1 and S2 is 1:1.05. The molar ratio of the alkyl primary alcohol and maleic anhydride is precisely controlled to ensure complete reaction of the reactants and to preferentially adduct the carbon-carbon double bond of the maleic anhydride with the alkyl primary alcohol to form a half-ester intermediate.

[0069] Preferably, the heating and melting temperature of the alkyl primary alcohol in S1 is 70℃, 75℃, 80℃, 85℃, or 90℃; and the reaction time in S2 is 2h, 2.5h, or 3h, and the system temperature is 70℃, 75℃, 80℃, 85℃, or 90℃.

[0070] Preferably, the tungsten-molybdenum oxide collector is prepared using an alkyl primary alcohol with 12-18 carbon atoms as a raw material, and has a lower synthesis cost than existing collectors used for tungsten-molybdenum oxide ores, and can be widely used in actual large-scale production.

[0071] Illustratively, the sulfonating agent in S3 includes one of sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, ammonium sulfite, ammonium bisulfite, monoethanolamine sulfonate, diethanolamine sulfonate, or triethanolamine sulfonate.

[0072] Further, the molar ratio of the mono-maleate carboxylic acid and the sulfonic acid group provided by the sulfonating agent in S3 is 1:1.05. This ensures complete sulfonation and avoids increasing side reactions.

[0073] Preferably, the preheating temperature of the sulfonating agent is 70℃, 75℃, 80℃, 85℃, or 90℃.

[0074] Illustratively, a 5% urea solution by mass is added dropwise to the reaction system at the beginning of S4; this reduces the viscosity of the reaction system and promotes the reaction.

[0075] Preferably, the mechanical stirring speed in S4 is 600r / min, 700r / min, or 800r / min, the reaction temperature is 70℃, 75℃, 80℃, 85℃, or 90℃, and the reaction time is 2h, 2.5h, or 3h.

[0076] By controlling a reasonable reaction temperature, preheating the sulfonating agent solution, and using an external stirring paddle for vigorous stirring, the synthesis is ensured to proceed quickly while reducing side reactions.

[0077] It should be noted that the ester group structure of the tungsten-molybdenum oxide collector is easily hydrolyzed under alkaline conditions, and the product after hydrolysis is a primary alcohol, which is mild, safe, and non-toxic, does not produce harmful byproducts during synthesis, is environmentally friendly, and conforms to the concept of green development.

[0078] In another aspect, the embodiment of the present application also discloses an application of the tungsten-molybdenum oxide collector, and the tungsten-molybdenum oxide and gangue mineral are floated by using the tungsten-molybdenum oxide collector, and the method comprises the following steps:

[0079] Step 1, grinding: crushing and grinding are performed;

[0080] Step 2, adding a flotation reagent: 900-1100 g / t of sodium carbonate is added and stirred for 3-5 min, then 3500-4000 g / t of water glass is added and stirred for 3-5 min, and finally 100-110 g / t of the tungsten-molybdenum oxide collector is added and stirred for 2-3 min;

[0081] Step 3, the concentrate and the tailings are respectively filtered, dried and weighed, and the yield and the recovery rate are calculated.

[0082] Exemplarily, the mineral particle size is-74+38 μm after the crushing and grinding in step 1; the surface area of the ore is increased by the crushing and grinding, which is beneficial to the contact and reaction between the reagent and the mineral in the subsequent flotation process, and the flotation efficiency is improved; the mineral particle size is controlled within a certain range, so that the mineral reaches the best flotation condition, the selectivity and the efficiency of the flotation are improved, and the mechanical entrainment phenomenon is reduced.

[0083] Preferably, in step 2, the sodium carbonate is mainly used to adjust the pH value in the flotation process, and also plays a role in dispersing the ore pulp; the tungsten-molybdenum oxide collector has good separation effect on the valuable mineral and the gangue mineral within the range of pH=7-11, and as a double anion surfactant, has excellent foaming performance, which is helpful to stabilize the foam in the mineral processing flotation process and improve the flotation condition; the longer the carbon chain length of the tungsten-molybdenum oxide collector is, the stronger the selective flotation performance for the tungsten-molybdenum oxide is. Preferably, in step 2, the adding amount of the sodium carbonate is 900 g / t, 1000 g / t or 1100 g / t, the adding amount of the water glass is 3500 g / t, 3800 g / t, 3900 g / t or 4000 g / t, and the adding amount of the tungsten-molybdenum oxide collector is 100 g / t, 105 g / t or 110 g / t.

[0084] The tungsten-molybdenum oxide collector contains three electronegative points and has a long carbon chain surfactant structure similar to the fatty acid collector, and compared with the prior art, has the advantages of good selectivity, strong collecting performance and strong foaming performance, greatly reduces the dosage of the flotation reagent, and can adapt to the flotation ore pulp environment of complex and low-grade tungsten-molybdenum oxide ore.

[0085] Notably, the tungsten-molybdenum oxide collector provided by the application has high selective flotation capacity for tungsten-molybdenum oxide ore, can partially offset the adverse effects of dissolved silicate in the flotation process, solve the problem of excessive water glass consumption caused by competitive adsorption, reduce the consumption of flotation water glass, and achieve the purpose of reducing cost and increasing efficiency.

[0086] To sum up, the collector provided by the application contains three electronegative points, has a long carbon chain surfactant structure similar to that of a fatty acid collector, and has the advantages of good selectivity, strong collecting performance and strong foaming performance compared with the prior art, greatly reduces the consumption of flotation reagents, and can adapt to the flotation slurry environment of complex and low-grade tungsten-molybdenum oxide ore; the collector is prepared from a primary alkyl alcohol with 12-18 carbon atoms, and has lower synthesis cost than the collector used for existing tungsten-molybdenum oxide ore, so it can be widely applied in actual large-scale production; the preparation process of the collector is simple, no catalyst needs to be added, and the reaction conditions are mild; the ester group structure of the collector is easy to hydrolyze under strong alkaline conditions, and the product after hydrolysis is a primary alcohol, which is mild, safe and non-toxic, and no harmful by-products are generated in the synthesis process, which is friendly to the environment and meets the green development concept.

[0087] The preparation and application of the tungsten-molybdenum oxide ore collector will be described below in combination with specific examples.

[0088] Example 1

[0089] The present embodiment provides a preparation method of a new type of tungsten-molybdenum oxide ore collector.

[0090] The method comprises the following steps:

[0091] S1, weigh 0.1 mol of n-octadecyl primary alcohol, and add it to a 500 mL three-necked flask equipped with a stirrer, a thermometer and a spherical condenser reflux tube, heat to 75 DEG C to melt it, and keep stirring to prevent solidification.

[0092] S2, weigh 0.105 mol of maleic anhydride, and slowly add it to the molten n-octadecyl primary alcohol for esterification reaction, the addition rate of anhydride is based on the temperature of the reaction system; continuously stir for 2.5 h to obtain an intermediate product of monomaleate carboxylic acid; keep the system temperature at 75 DEG C after the reaction is completed.

[0093] S3, dissolve 0.105 mol of sodium sulfite in 150 mL of deionized water, and heat it to 75 DEG C, then slowly drop the sodium sulfite solution into the monomaleate carboxylic acid for sulfonation reaction, keep mechanical stirring during the reaction process to prevent the reaction system from being affected by the rapid increase in viscosity at the initial stage of the reaction, and keep the temperature at 75 DEG C for 2.5 h.

[0094] S4, with the reaction going on, the reaction system gradually becomes transparent from white turbidity, and the solution viscosity gradually decreases, and finally a colorless transparent low viscosity target product solution is obtained; the target product solution is mixed with petroleum ether and extracted for several times, the lower transparent liquid in the separatory funnel is rotary evaporated and dried to obtain a white solid product.

[0095] The white solid product obtained is compound MS-18, and the infrared spectrum is as shown in Figure 1 The vibration absorption peaks related to carboxyl and sulfonic acid groups appear in the spectrum, which preliminarily indicates the success of the synthesis of MS-18. Figure 2 The mass spectrum result of MS-18 with ESI as ionization source is shown, and the sum of [M-2Na+H]- and [M-Na]-(M is the uncharged reaction end product MS-18 molecule) ion peaks appear in the spectrum, which indicates the success of the synthesis of MS-18. - and [M-Na] - (M is the uncharged reaction end product MS-18 molecule) ion peaks appear in the spectrum, which indicates the success of the synthesis of MS-18.

[0096] Example 2

[0097] The embodiment provides a preparation method of a new type of tungsten-molybdenum oxide ore collecting agent.

[0098] The specific process is the same as that in example 1, and the difference between the implementation method of the embodiment and that of example 1 is that the n-octadecyl alcohol in example 1 is replaced by n-hexadecyl alcohol.

[0099] The white solid product obtained is compound MS-16, and the infrared spectrum is as shown in Figure 1 The vibration absorption peaks related to carboxyl and sulfonic acid groups appear in the spectrum, which preliminarily indicates the success of the synthesis of MS-16. Figure 3 The mass spectrum result of MS-16 with ESI as ionization source is shown, and the sum of [M-2Na+H]- and [M-Na]-(M is the uncharged reaction end product MS-16 molecule) ion peaks appear in the spectrum, which indicates the success of the synthesis of MS-16.

[0100] Example 3

[0101] The embodiment provides a preparation method of a new type of tungsten-molybdenum oxide ore collecting agent.

[0102] The specific process is the same as that in example 1, and the difference between the implementation method of the embodiment and that of example 1 is that the n-octadecyl alcohol in example 1 is replaced by n-dodecyl alcohol.

[0103] The white solid product obtained is compound MS-12, and the infrared spectrum is as shown in Figure 1 The vibration absorption peaks related to carboxyl and sulfonic acid groups appear in the spectrum, which preliminarily indicates the success of the synthesis of MS-12. Figure 4The mass spectrum result of MS-12 is shown in the mass spectrum of ESI as ionization source, the addition ion peak of [M-2Na+H]- and [M-Na]-(M is the uncharged reaction end product MS-12 molecule) appears in the spectrum, which indicates the success of MS-12 synthesis.

[0104] Comparative Example 1

[0105] The embodiment provides a preparation method of a new tungsten-molybdenum oxide ore collector.

[0106] The specific process is the same as that of Example 3, and the difference between the implementation method and that of Example 3 is that the amount of maleic anhydride added in S2 is 0.12 mol.

[0107] The addition ion peak area of [M-2Na+H]- and [M-Na]-(M is the uncharged product molecule) in the mass spectrum is less than that of Example 3, indicating that the synthesis efficiency of MS-12 is reduced.

[0108] Comparative Example 2

[0109] The embodiment provides a preparation method of a new tungsten-molybdenum oxide ore collector.

[0110] The specific process is the same as that of Example 3, and the difference between the implementation method and that of Example 3 is that the amount of maleic anhydride added in S2 is 0.1 mol.

[0111] The addition ion peak area of [M-2Na+H]- and [M-Na]-(M is the uncharged product molecule) in the mass spectrum is less than that of Example 3, indicating that the synthesis efficiency of MS-12 is reduced.

[0112] Comparative Example 3

[0113] The embodiment provides a preparation method of a new tungsten-molybdenum oxide ore collector.

[0114] The specific process is the same as that of Example 3, and the difference between the implementation method and that of Example 3 is that the amount of maleic anhydride added in S2 is 0.1 mol.

[0115] The addition ion peak area of [M-2Na+H]- and [M-Na]-(M is the uncharged product molecule) in the mass spectrum is less than that of Example 3, indicating that the synthesis efficiency of MS-12 is reduced.

[0116] As can be seen from Example 3 and Comparative Examples 1-3, in the preparation process of the tungsten-molybdenum oxide collector, the reactant ratio does not meet the requirements of the embodiment, and the synthesis efficiency of the collector is reduced.

[0117] Application Example 1

[0118] The application example provides a method for single mineral flotation by using the collector prepared in Example 1 and Example 2. As shown in Figure 5

[0119] The flotation objects are single minerals of white tungsten ore, calcium molybdate and calcite with purity of 98% or above, and the single minerals are subjected to cleaning, crushing, grinding and screening, and the minerals with particle size of-74 to +38 μm are selected for flotation test.

[0120] Flotation machine: XFG type hanging groove flotation machine, the flotation tank volume is 40 mL, and the main shaft rotation speed of the flotation machine is set to 1900 r / min.

[0121] The specific flotation steps are as follows:

[0122] Step 1, accurately weigh 2.0 g of mineral sample with particle size of-74 to +38 μm in the flotation tank, add 35 mL of deionized water, and stir for 1 min;

[0123] Step 2, add 0.1 mol / L NaOH or HCl aqueous solution to adjust the pH value of the ore pulp, and stir for 2 min;

[0124] Step 3, use the collectors MS-18 and MS-16 synthesized in Example 1 and Example 2 respectively, stir for 2 min, and float for 3 min;

[0125] Step 4, filter, dry and weigh the floated foam product and the tank product respectively, and calculate the flotation recovery rate.

[0126] As shown in Figure 6(a), when MS-18 is used as a collector, under the condition that the dosage is 3.0×10 -4 mol / L, the influence of the pH value of the ore pulp on the flotation behavior of the three minerals. As shown in the figure, within the experimental pH range, the recovery rate of the white tungsten ore maintains a high level and is basically unchanged; with the increase of the pH value, the flotation recovery rate of calcium molybdate gradually increases. Overall, within a wide pH value range, the flotation recovery rate of the tungsten-molybdenum oxide ore is quite different from that of calcite, and the floatability is ranked from large to small as follows: white tungsten ore ≈ calcium molybdate > calcite. When the pH value is 7, the recovery rates of the three minerals are as follows: white tungsten ore 88.33%, calcium molybdate 73.72%, and calcite 32.58%, which can achieve the best separation effect.

[0127] As shown in Figure 6(b), when MS-16 is used as a collector, under the condition that the dosage is 1.0×10 -4 ​The influence of pulp pH on the flotation behaviors of the three minerals under the condition of 0.5 mol / L is shown in Fig. 2. As can be seen from the figure, the overall recovery rate trend is similar to that of MS-18, but due to the enhanced collecting ability of calcite, the recovery rate difference between the oxidized tungsten-molybdenum ore and calcite is reduced. Under the condition of pH = 7, the recovery rates of the three minerals are 85.34% for scheelite, 81.73% for calcium molybdate, and 37.83% for calcite, respectively, and the recovery rate difference between the oxidized tungsten-molybdenum ore and calcite can still reach about 50%, which can achieve the best separation effect.

[0128] As shown in Fig. 7(a), under the condition of pH = 7, the influence of reagent dosage on the flotation behaviors of the three minerals when MS-18 is used as a collector. As can be seen from the figure, with the increase of reagent dosage, the recovery rate of scheelite gradually increases, and the recovery rates of calcium molybdate and calcite show a basically unchanged and slowly increasing trend, respectively, but there is still a large difference in the recovery rates of the two minerals in a large range of reagent dosage. When the reagent dosage is 3.0 x 10 -4 Under the condition of 0.5 mol / L, the recovery rate difference between scheelite and calcite is about 55%, and the recovery rate difference between calcium molybdate and calcite is about 40%, which achieves good separation effect.

[0129] As shown in Fig. 7(b), under the condition of pH = 7, the influence of reagent dosage on the flotation behaviors of the three minerals when MS-16 is used as a collector. As can be seen from the figure, with the increase of reagent dosage, the recovery rates of the three minerals all increase to a certain extent, but the increase of scheelite is the largest, followed by calcium molybdate, and the recovery rates of the two minerals gradually stabilize when the recovery rate is close to 95%, while the recovery rate of calcite also increases with the increase of reagent dosage, but there is still a difference of about 40% between the recovery rate of the oxidized tungsten-molybdenum ore and that of calcite, so the flotation separation of the oxidized tungsten-molybdenum ore and calcite can be realized at a low reagent dosage.

[0130] It can be known from the single mineral flotation application research that the oxidized tungsten-molybdenum ore collector provided by the application can effectively realize the efficient and high recovery rate flotation separation of the oxidized tungsten-molybdenum ore, and the flotation separation of the oxidized tungsten-molybdenum ore and calcite can be realized in the pH range of 7-11.

[0131] Application Example 2

[0132] The application example provides a method for actual mineral flotation by using the collector prepared in Example 3, as shown in Fig. 8. Figure 9

[0133] The flotation object is a low-grade tungsten-molybdenum ore in Henan, and the X-ray diffraction pattern of the raw ore is as shown in Fig. 9. Figure 8 ​As shown in the X-ray diffraction pattern of the raw ore, the analysis result shows that the raw ore contains a large amount of fluorite, silicate and carbonate gangue minerals; the molybdenum in the raw ore mainly exists in the form of sulfide (molybdenite) and oxide (calcium molybdate), and the tungsten exists in the form of oxide (scheelite).

[0134] The flotation process of one roughing of the oxide ore is adopted, and the specific process is as follows:

[0135] Step 1, grinding: crushing and grinding to make 90% of the mass fraction of the mineral particle size in-74~+38μm;

[0136] Step 2, adding flotation reagents: adding 1000g / t sodium carbonate and stirring for 3min, then adding 4000g / t water glass and stirring for 3min, then adding 100g / t collector MS-12 and stirring for 2min, and finally aerating and floating for 4min to obtain concentrate product and tailings.

[0137] Step 3, filtering, drying and weighing the concentrate and tailings respectively, and calculating the yield, recovery rate and concentrate enrichment ratio, as shown in Table 1.

[0138] Comparative application example 1

[0139] The application example provides a method for actual mineral flotation by using sodium oleate as a collector.

[0140] The flotation object is a certain low-grade tungsten-molybdenum ore in Henan, and the X-ray diffraction pattern of the raw ore is as shown in Figure 8 The analysis result shows that the raw ore contains a large amount of fluorite, silicate and carbonate gangue minerals; the molybdenum in the raw ore mainly exists in the form of sulfide (molybdenite) and oxide (calcium molybdate), and the tungsten exists in the form of oxide (scheelite).

[0141] The flotation process of one roughing of the oxide ore is adopted, and the specific process is as follows:

[0142] Step 1, grinding: crushing and grinding to make 90% of the mass fraction of the mineral particle size in-74~+38μm;

[0143] Step 2, adding flotation reagents: adding 1000g / t sodium carbonate and stirring for 3min, then adding 4000g / t water glass and stirring for 3min, then adding 200g / t sodium oleate and stirring for 2min, and finally aerating and floating for 4min to obtain concentrate product and tailings.

[0144] Step 3, filtering, drying and weighing the concentrate and tailings respectively, and calculating the yield, recovery rate and concentrate enrichment ratio, as shown in Table 1.

[0145] Table 1 Comparison of results of different reagent flotation of actual ore

[0146]

[0147] From table 1, application example 2 and comparative application example 1, when the dosage of the collector is 200 g / t, the grade of WO3 in the concentrate is 0.604%, the enrichment ratio is 3.36, and the recovery of WO3 is 44.73% when using the traditional oxidized ore collector sodium oleate; while using the oxidized tungsten-molybdenum collector MS-12 of the application, the grade of WO3 in the concentrate can reach 0.741, the enrichment ratio can reach 4.12, and the recovery can reach 52.69% when the dosage of the collector is 100 g / t, and the flotation indexes are all better than those of sodium oleate when the dosage of the collector is only half of that of sodium oleate; this shows that the newly synthesized sodium alkyl succinate sulfonate can achieve good beneficiation indexes for this kind of low-grade, complex-impurity-containing oxidized tungsten-molybdenum ore.

[0148] In summary, the collector provided by the application contains three electronegative points, and has a long carbon chain surfactant structure similar to that of a fatty acid collector, and has the advantages of good selectivity, strong collecting performance and strong foaming performance compared with the prior art, greatly reduces the dosage of the flotation reagent, and can adapt to the flotation slurry environment of complex, low-grade oxidized tungsten-molybdenum ore; the collector of the application is prepared from a C12-18 alkyl primary alcohol, and has a lower synthesis cost than the collector used for the existing oxidized tungsten-molybdenum ore, and can be widely used in actual large-scale production; the preparation process of the collector of the application is simple, does not need to add a catalyst, and has mild reaction conditions; the ester group structure of the collector of the application is easy to hydrolyze under strong alkaline conditions, and the product after hydrolysis is a primary alcohol, which is mild, safe and non-toxic, and no harmful by-products are produced during the synthesis process, which is friendly to the environment and meets the green development concept.

[0149] The above is only a preferred specific embodiment of the application, but the protection scope of the application is not limited thereto, and any changes or replacements that can be easily thought of by those skilled in the art within the technical range disclosed by the application should be covered within the protection scope of the application.

Claims

1. A tungsten-molybdenum ore oxidizer collector characterized by, The collector has a chemical structural formula for low-grade tungsten-molybdenum oxide ore flotation. ； wherein R is an alkyl group having 12 to 18 carbon atoms; X + is an inorganic cation or an organic cation.

2. A process for the preparation of tungsten molybdenum ore oxidizer collector characterized in that, The preparation method of the tungsten-molybdenum oxide ore collector in claim 1 comprises the following steps: S1, an appropriate amount of alkyl primary alcohol is weighed and heated to 70-90 DEG C to melt, and stirring is kept; S2, an appropriate amount of maleic anhydride is slowly added to the molten alkyl primary alcohol, the temperature of the reaction system is kept unchanged, and stirring is continuously kept for 2-3 hours to obtain a mono-maleate carboxylic acid, and the temperature of the system is kept at 70-90 DEG C; S3, an appropriate amount of sulfonating agent is dissolved in deionized water and heated to 70-90 DEG C for preheating; S4, the preheated sulfonating agent solution is slowly added dropwise to the mono-maleate carboxylic acid, the dropping speed is kept unchanged to keep the temperature of the reaction system unchanged, and stirring is kept, and the system is kept at 70-90 DEG C for 2-3 hours; S5, after the reaction is completed, the reaction system is mixed with petroleum ether, extracted for multiple times, and the transparent liquid at the lower layer of the separating funnel is collected and dried to obtain the tungsten-molybdenum oxide ore collector product.

3. The preparation method according to claim 2, characterized in that, The molar ratio of the alkyl primary alcohol to the maleic anhydride in S1 and S2 is 1:1.

05.

4. The preparation method according to claim 2, characterized in that, The sulfonating agent in S3 includes one of sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, ammonium sulfite, ammonium bisulfite, monoethanolamine sulfonate, diethanolamine sulfonate or triethanolamine sulfonate.

5. The preparation method according to claim 4, characterized in that, The molar ratio of the mono-maleate carboxylic acid to the sulfonate provided by the sulfonating agent in S3 is 1:1.

05.

6. The preparation method according to claim 2, characterized in that, A 5% urea solution by mass fraction is added dropwise to the reaction system at the initial stage of S4.

7. The preparation method according to claim 6, characterized in that, The stirring speed in S4 is 600-800 r / min.

8. Use of a tungsten-molybdenum ore oxidizer characterized in that, The tungsten-molybdenum oxide ore collector in claim 1 or prepared by the preparation method in any one of claims 2-7 is used for tungsten-molybdenum oxide ore and gangue mineral flotation, which comprises the following steps: Step 1, grinding: crushing and grinding are performed; Step 2, adding flotation reagents: sodium carbonate is added and stirred for 3-5 minutes, then water glass is added and stirred for 3-5 minutes, and finally the tungsten-molybdenum oxide ore collector is added and stirred for 2-3 minutes; Step 3, the concentrate and the tailings are respectively filtered, dried and weighed, and the yield and the recovery rate are calculated.

9. Use according to claim 8, characterized in that, The mineral particle size is-74+38 μm after crushing and grinding in step 1.

10. Use according to claim 8, characterized in that, The addition amount of sodium carbonate in step 2 is 900-1100 g / t, the addition amount of water glass is 3500-4000 g / t, and the addition amount of the tungsten-molybdenum oxide ore collector is 90-110 g / t.

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