Tungsten-molybdenum oxide ore collecting agent and application thereof

Abstract

The invention relates to a tungsten-molybdenum oxide ore collecting agent and application thereof, belongs to the field of beneficiation reagents, and solves the problems that in the prior art, a collecting agent for flotation of tungsten-molybdenum oxide ore associated with calcium-containing gangue minerals is poor in selectivity, the flotation process is complex, flotation conditions are difficult to control, the collecting agent cannot be degraded, and the environment is polluted. A tungsten-molybdenum oxide ore collecting agent is used for flotation of low-grade tungsten-molybdenum oxide raw ore, the chemical structural formula of the collecting agent is # imgabs0 #, and R is alkyl with the C atom number of 12-18; x < + > is an inorganic cation or an organic cation. And high-efficiency and high-recovery-rate flotation of the molybdenum-tungsten oxide ore is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of ore dressing agents, and particularly to a collector for tungsten-molybdenum oxide ore and its application. Background Art

[0002] Both tungsten and molybdenum are important strategic metal resources in China. They have excellent properties such as high melting point and high hardness, and are thus widely used in fields such as alloys, electronics, chemical industry, aerospace, and nuclear industry. However, with the development of science and technology, the demand for tungsten and molybdenum is increasing day by day. The easily mined and beneficiated primary tungsten-molybdenum resources are gradually decreasing, and complex and refractory tungsten-molybdenum resources are gradually attracting attention. Tungsten-molybdenum oxide ore is a typical representative of refractory tungsten-molybdenum resources. It is naturally hydrophilic, has extremely low hydrophobicity, incomplete crystallization, and mostly occurs in fine-grained disseminated form, resulting in difficulty in its recovery. In addition, tungsten-molybdenum oxide ore is often associated with calcium-containing gangue minerals such as calcite and fluorite. The difficulties in separating these calcium-containing minerals mainly include two aspects: (1) the valuable minerals and gangue minerals have similar surface properties; (2) the dissolution and transformation between calcium-containing minerals further make the surface compositions of valuable minerals and gangue minerals converge.

[0003] Currently, the collectors used for tungsten-molybdenum oxide are basically fatty acid-based, sulfonic acid-based, and hydroxamic acid-based collectors. Fatty acid-based collectors have good collecting effects but poor selectivity for tungsten-molybdenum oxide ore; sulfonic acid-based collectors have slightly better selectivity but poor collecting performance; hydroxamic acid-based collectors have chelating effects to improve selectivity, but the reagent cost is high, making it difficult to be applied in industrial production. Moreover, hydroxamic acid-based collectors generally do not have foaming effects, so additional foaming agents need to be added during the production process, which undoubtedly further increases the production cost of enterprises. Summary of the Invention

[0004] In view of the above analysis, the embodiments of the present invention aim to provide a collector for tungsten-molybdenum oxide ore and its application, so as to solve at least one of the problems such as poor selectivity of the collector for the flotation of tungsten-molybdenum oxide ore associated with calcium-containing gangue minerals, high cost, the collector cannot be degraded and pollutes the environment, the hydrolysis products are toxic, and it is not suitable for the flotation of low-grade tungsten-molybdenum oxide raw ore.

[0005] On the one hand, the embodiments of the present invention provide a collector for tungsten-molybdenum oxide ore, which is used for the flotation of low-grade tungsten-molybdenum oxide raw ore. The chemical structural formula of the collector is:

[0006]

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

[0008] On the other hand, the embodiments of the present invention also provide a preparation method of a collector for tungsten-molybdenum oxide ore, including the following steps:

[0009] S1. Weigh an appropriate amount of alkyl primary alcohol, heat it to 70 - 90 °C until it melts, and keep stirring.

[0010] S2. Weigh an appropriate amount of maleic anhydride, slowly add it to the melted alkyl primary alcohol, keep the temperature of the reaction system unchanged, and continuously stir. React for 2 - 3 h to obtain mono - maleic acid ester carboxylic acid, and keep the system temperature at 70 - 90 °C.

[0011] S3. Weigh an appropriate amount of sulfonating agent and dissolve it in deionized water, and pre - heat it to 70 - 90 °C.

[0012] S4. Slowly drip the pre - heated sulfonating agent solution into the mono - maleic acid ester carboxylic acid. The dripping speed is based on keeping the temperature of the reaction system unchanged. Stir vigorously, keep it warm and react at 70 - 90 °C for 2 - 3 h.

[0013] S5. After the reaction is completed, mix the reaction system with petroleum ether, extract it multiple times, collect the transparent liquid in the lower layer of the separating funnel, and dry it to obtain the collector product for tungsten - molybdenum oxide ore.

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

[0015] Specifically, the sulfonating agent described 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 mono - maleic acid ester carboxylic acid to the sulfonic acid groups provided by the sulfonating agent in S3 is 1:1.05.

[0017] Preferably, a 5% urea solution is dripped into the reaction system at the initial stage of S4.

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

[0019] On the other hand, the embodiment of the present invention also provides an application of a collector for tungsten - molybdenum oxide ore. Using the collector for tungsten - molybdenum oxide ore for flotation of tungsten - molybdenum oxide ore and gangue minerals, it includes the following steps:

[0020] Step 1. Grinding: Carry out crushing and grinding.

[0021] Step 2. Adding flotation reagents: Add sodium carbonate and stir for 3 - 5 min, then add water glass and stir for 3 - 5 min, and finally add the collector for tungsten - molybdenum oxide ore and stir for 2 - 3 min.

[0022] Step 3. Filter, dry, and weigh the concentrate and tailings respectively, and calculate the yield and recovery rate.

[0023] Preferably, after crushing and grinding in step 1, the particle size of the mineral is -74 to +38 μm.

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

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

[0026] 1. The collector for tungsten-molybdenum oxide ore provided by the present invention ensures its excellent hydrophobic ability by introducing a long non-polar carbon chain, enabling the ore to obtain sufficient floatability after adsorption;

[0027] The molecular structure includes carboxylic acid groups and sulfonic acid groups. The introduction of multiple polar groups enhances its water solubility, and the two polar groups can adsorb on the surface of valuable minerals at double active sites, strengthening the adsorption ability and chelation effect of the collector with metal ions on the mineral surface, thereby improving selectivity;

[0028] The ester group structure introduced into the molecule through an esterification reaction has a carbonyl oxygen atom (C=O) with an electronegativity and charge intensity second only to the oxygen atoms on the sulfonic acid group and carboxylic acid group, providing an adsorption reaction site other than the carboxylic acid group and sulfonic acid group for the collector of the present invention, enhancing the adsorption of the reagent on the surface of tungsten-molybdenum oxide ore and strengthening its ability for selective flotation; and it is easy to form hydrogen bonds with hydrogen atoms in water molecules, thereby enhancing the hydrophilicity of the compound, so that it can be better dissolved and dispersed in the pulp, contributing to simplifying the flotation process;

[0029] The three electronegative sites of the carboxylic acid group, sulfonic acid group, and carbonyl oxygen atom (C=O) share and concentrate the electron density, and the electric fields are superimposed on each other to form a stronger adsorption field, greatly improving the adsorption ability for tungsten-molybdenum oxide ore.

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

[0031] 3. The collector of the present invention is prepared from primary alkyl alcohols with 12 to 18 carbon atoms. Compared with the collectors used for existing tungsten-molybdenum oxide ores, the synthesis cost is lower, and it can be widely applied in actual large-scale production. The preparation process of the collector of the present invention is simple, without the addition of a catalyst, and the reaction conditions are mild. By selecting the appropriate reaction sequence, controlling the reasonable proportion of reactants and reaction temperature, preheating the sulfonating agent solution in advance, and using an external stirring paddle to stir vigorously, the rapid progress of the synthesis is ensured, and side reactions are reduced simultaneously.

[0032] 4. The ester group structure of the collector of the present invention is easy to hydrolyze under strong alkaline conditions. The hydrolysis product is primary alcohols, with mild drug properties, safe and non-toxic, and no harmful by-products are generated during the synthesis process, which is environmentally friendly and conforms to the concept of green development.

[0033] 5. The collector provided by the present invention has many electronegative potential points, can be more effectively adsorbed on the surface of tungsten-molybdenum oxide ores, greatly improves the selective adsorption ability for tungsten-molybdenum oxide ores, and the electronegative potential points are more inclined to form a strong adsorption effect with the metal oxides on the surface of tungsten-molybdenum oxide ores, thereby reducing the adsorption on silicate minerals, alleviating the problem of excessive consumption of water glass caused by competitive adsorption, reducing the dosage of flotation water glass, and achieving the purpose of cost reduction and efficiency increase.

[0034] 6. The collector for tungsten-molybdenum oxide ores provided by the present invention has good separation effects on valuable minerals and gangue minerals within the range of pH = 7 to 11. And as a double-anionic surfactant, it has excellent foaming properties, which helps to stabilize the foam during the ore dressing flotation process and improve the flotation conditions.

[0035] In the present invention, the above technical solutions can also be combined with each other to achieve more preferred combination schemes. Other features and advantages of the present invention will be described in the subsequent description. And some advantages can be made obvious from the description, or understood by implementing the present invention. The purpose and other advantages of the present invention can be realized and obtained through the content specifically pointed out in the description and the drawings. Description of the Drawings

[0036] The drawings are only for the purpose of showing specific embodiments, and are not considered as a limitation to the present invention. Throughout the drawings, the same reference signs represent the same components.

[0037] Figure 1 It is the infrared spectrum results of sodium dioctadecyl sulfosuccinate (MS-18), sodium dihexadecyl sulfosuccinate (MS-16), and sodium dodecyl sulfosuccinate (MS-12), which are the compounds synthesized in Example 1, Example 2, and Example 3 of the present invention.

[0038] Figure 2High-resolution mass spectrometry results of the compound MS-18 synthesized in Example 1 of the present invention;

[0039] Figure 3 High-resolution mass spectrometry results of the compound MS-16 synthesized in Example 2 of the present invention;

[0040] Figure 4 High-resolution mass spectrometry results of the compound MS-12 synthesized in Example 3 of the present invention;

[0041] Figure 5 Single-mineral flotation flow chart in Application Example 1 of the present invention;

[0042] Figure 6(a) is a diagram showing the effect of pH on the separation effect of the synthesized collector MS-18 on scheelite, calcium molybdate, and calcite in Example 1 of the present invention;

[0043] Figure 6(b) is a diagram showing the effect of pH on the separation effect of the synthesized collector MS-16 on scheelite, calcium molybdate, and calcite in Example 2 of the present invention;

[0044] Figure 7(a) is a diagram showing the effect of dosage on the separation effect of the synthesized collector MS-18 on scheelite, calcium molybdate, and calcite in Example 1 of the present invention;

[0045] Figure 7(b) is a diagram showing the effect of dosage on the separation effect of the synthesized collector MS-16 on scheelite, calcium molybdate, and calcite in Example 2 of the present invention;

[0046] Figure 8 X-ray diffraction analysis diagram of the actual ore in Application Example 2 of the present invention;

[0047] Figure 9 Actual ore flotation flow chart in Application Example 2 of the present invention;

[0048] Figure 10 Local charge distribution of the collector MS-12 prepared in Example 3 of the present invention Figure 1 ;

[0049] Figure 11 Local charge distribution of the collector MS-12 prepared in Example 3 of the present invention Figure 2 . Detailed implementation manners

[0050] The following will specifically describe the preferred embodiments of the present invention in conjunction with the accompanying drawings. Among them, the accompanying drawings form a part of this application and are used together with the embodiments of the present invention to explain the principle of the present invention, rather than to limit the scope of the present invention.

[0051] Tungsten-molybdenum ores usually have a relatively high degree of oxidation. Molybdenum in tungsten-molybdenum raw ores mainly exists in the form of sulfide ores (molybdenite) and oxide ores (calcium molybdate), while tungsten occurs in the form of oxide ore (scheelite). Common collectors used in the flotation process of oxide ores include fatty acids (such as oleic acid and its soaps), sulfonic acids (such as sodium dodecylbenzenesulfonate), chelating collectors (such as hydroxamic acids), etc. These collectors enhance the hydrophobicity of minerals by forming chemical bonds or chelates with metal ions on the mineral surface, and pH regulators, inhibitors such as water glass, etc. are needed to optimize the flotation conditions and improve selectivity, thereby achieving flotation.

[0052] The tungsten-molybdenum oxide raw ore contains a large amount of gangue minerals such as fluorite, silicate, and carbonate. Gangue minerals in the pulp will not only dissolve cations such as calcium ions, making the surface properties of minerals tend to be the same; silicate minerals will also dissolve out silicate radicals, which are similar to the structure of the inhibitor water glass, and will cause competitive adsorption in the pulp, interfering with the effect of the inhibitor and increasing the difficulty of separation, resulting in poor effects of traditional collectors such as oleic acid, sodium dodecylbenzenesulfonate, and hydroxamic acid.

[0053] A specific embodiment of the present invention discloses a collector for tungsten-molybdenum oxide ore, which is used for the flotation of low-grade tungsten-molybdenum oxide raw ore. The chemical structural formula of the collector is:

[0054]

[0055] wherein R is an alkyl group with 12 to 18 carbon atoms; X + is an inorganic cation or an organic cation, including H + 、Na + 、K + 、NH 4 + 、[C 2 H 7 NO] + 、[C 4 H 11 NO] + or [C 6 H 15 NO] + and so on.

[0056] The collector for tungsten-molybdenum oxide ore ensures its excellent hydrophobic ability by introducing a long non-polar carbon chain, enabling the ore to obtain sufficient floatability after adsorption; the oxygen atoms in the carbonyl (C=O) and (-O-) structures it contains have strong electronegativity and are easy to form hydrogen bonds with hydrogen atoms in water molecules, thereby enhancing the hydrophilicity of the compound, and thus can be better dissolved and dispersed in the pulp, helping to simplify the flotation process;

[0057] Furthermore, the DMol3 module of Materials Studio software was used to perform molecular dynamics simulation calculations on one of the synthesized collectors MS-12, and the local charge distribution of its molecules is as Figure 10 , Figure 11 shown;

[0058] The results show that the two polar groups, the carboxylic acid group and the sulfonic acid group, in the molecular structure have the strongest electronegativity. The ester group structure introduced into the molecule through the esterification reaction has an electronegativity and charge intensity second only to the oxygen atoms on the sulfonic acid group and the carboxylic acid group, and the electric fields of the three are superimposed on each other to form a stronger adsorption field, greatly enhancing the adsorption of the reagent on the surface of tungsten molybdenum oxide ore and strengthening its ability of selective flotation;

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

[0060] In addition, the introduction of multiple polar groups not only enhances its water solubility, but also can adsorb on the surface of valuable minerals at multiple active sites, strengthening the adsorption ability and chelation effect of the collector with metal ions on the mineral surface, thereby improving selectivity.

[0061] Furthermore, the preparation method of the tungsten molybdenum oxide ore collector includes the following steps:

[0062] S1. Weigh an appropriate amount of alkyl primary alcohol, heat it to 70-90 °C to melt, and keep stirring;

[0063] S2. Weigh an appropriate amount of maleic anhydride, slowly add it to the melted alkyl primary alcohol, keep the temperature of the reaction system unchanged, and continue stirring. React for 2-3 h to obtain mono-maleate carboxylic acid, and keep the system temperature at 70-90 °C;

[0064] S3. Weigh an appropriate amount of sulfonating agent and dissolve it in deionized water, and preheat it to 70-90 °C;

[0065] S4. Slowly drip the preheated sulfonating agent solution into the mono-maleate carboxylic acid, with the dropping speed being based on keeping the temperature of the reaction system unchanged, and keep the external mechanical stirring paddle stirring vigorously at 600-800 r / min. Keep it warm and react at 70-90 °C for 2-3 h;

[0066] S5. After the reaction is completed, mix the reaction system with petroleum ether, extract it multiple times, collect the transparent liquid in the lower layer of the separating funnel, and dry it to obtain the tungsten molybdenum oxide ore collector product.

[0067] First, perform the esterification reaction of maleic anhydride and primary alkyl alcohol, and then perform the sulfonation reaction of mono-maleate carboxylic acid. No catalyst needs to be added, reducing the operation steps. Performing the esterification reaction first can reduce the side reactions that may occur in the sulfonation reaction and improve the selectivity of the sulfonation reaction.

[0068] Specifically, the molar ratio of primary alkyl alcohol to maleic anhydride in S1 and S2 is 1:1.05. Precisely control the molar ratio of primary alkyl alcohol to maleic anhydride to ensure the complete reaction of the reactants and enable the carbon-carbon double bond of maleic anhydride to preferentially undergo an addition reaction with primary alkyl alcohol to form a half-ester intermediate.

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

[0070] Preferably, the tungsten molybdenum oxide collector is prepared from primary alkyl alcohols with 12 to 18 carbon atoms. Compared with the collectors used for tungsten molybdenum oxide ores in the prior art, the synthesis cost is lower, and it can be widely used in actual large-scale production.

[0071] Exemplarily, 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] Furthermore, the molar ratio of the mono-maleate carboxylic acid to the sulfonate group provided by the sulfonating agent in S3 is 1:1.05. Ensure the complete progress of the sulfonation reaction and avoid the increase of side reactions.

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

[0074] Exemplarily, in the initial stage of S4, a 5% urea solution by mass is added dropwise to the reaction system; reduce the viscosity of the reaction system and promote the progress of the reaction.

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

[0076] Ensure the rapid progress of the synthesis and reduce side reactions by controlling a reasonable reaction temperature, preheating the sulfonating agent solution in advance, and using an external stirring paddle for vigorous stirring.

[0077] It should be noted that the ester group structure of the tungsten molybdenum oxide collector is easy to hydrolyze under alkaline conditions. The hydrolysis product is primary alcohol, which has mild drug properties, is safe and non-toxic, and no harmful by-products are generated during the synthesis process, being environmentally friendly and in line with the concept of green development.

[0078] On the other hand, a specific embodiment of the present invention also discloses an application of a tungsten molybdenum oxide ore collector. Using the described tungsten molybdenum oxide collector for flotation of tungsten molybdenum oxide ore and gangue minerals includes the following steps:

[0079] Step 1, grinding: performing crushing and grinding;

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

[0081] Step 3, filtering, drying and weighing the concentrate and tailings respectively, and calculating the yield and recovery rate.

[0082] Exemplarily, in Step 1, after crushing and grinding, the particle size of the mineral is -74 to +38 μm; increasing the surface area of the ore through crushing and grinding is beneficial to the contact and reaction between the reagent and the mineral in the subsequent flotation process, improving the flotation efficiency; controlling the particle size of the mineral within a certain range ensures the best flotation conditions for the mineral, improves the selectivity and efficiency of flotation, and reduces the phenomenon of mechanical entrainment.

[0083] Preferably, in Step 2, sodium carbonate is mainly used to adjust the pH value during the flotation process and at the same time plays a role in dispersing the pulp; the tungsten molybdenum oxide ore collector has a good separation effect on valuable minerals and gangue minerals within the range of pH = 7 - 11, and as a double-anionic surfactant, it has excellent foaming properties, which helps to stabilize the foam during the ore dressing flotation process and improve the flotation conditions; the longer the carbon chain length of the tungsten molybdenum oxide collector, the stronger the selective flotation performance for tungsten molybdenum oxide ore. Preferably, in Step 2, the addition amount of sodium carbonate is 900 g / t, 1000 g / t, 1100 g / t, the addition amount of water glass is 3500 g / t, 3800 g / t, 3900 g / t, 4000 g / t, and the addition amount of the tungsten molybdenum oxide ore collector is 100 g / t, 105 g / t, 110 g / t.

[0084] The tungsten molybdenum oxide collector contains three electronegative sites and has a long carbon chain surfactant-like structure similar to that of fatty acid collectors. Compared with the prior art, it has the advantages of good selectivity, strong collecting performance and strong foaming performance, greatly reducing the dosage of flotation reagents and being able to adapt to the flotation pulp environment of complex and low-grade tungsten molybdenum oxide raw ore.

[0085] It should be noted that the tungsten molybdenum oxide collector provided by the present invention has a high selective flotation ability for tungsten molybdenum oxide ore, can partially offset the adverse effects caused by the dissolution of silicate during the flotation process, solve the problem of excessive water glass dosage caused by competitive adsorption, reduce the water glass dosage in flotation, and achieve the purpose of cost reduction and efficiency improvement.

[0086] In summary, the collector provided by the present invention contains three electronegative sites and has a long carbon chain surfactant-like structure similar to that of fatty acid collectors. Compared with the prior art, it has the advantages of good selectivity, strong collecting performance and strong foaming performance, greatly reducing the dosage of flotation reagents, and being able to adapt to the flotation pulp environment of complex and low-grade tungsten molybdenum oxide raw ore; the collector of the present invention is prepared from alkyl primary alcohols with 12 to 18 carbon atoms, and has a lower synthesis cost compared with the collectors used for tungsten molybdenum oxide ore in the prior art, and can be widely used in actual large-scale production; the preparation process of the collector of the present invention is simple, without the addition of a catalyst, and the reaction conditions are mild; the ester group structure of the collector of the present invention is easy to hydrolyze under strong alkaline conditions, and the hydrolysis product is primary alcohol, with mild drug properties, safe and non-toxic, and no harmful by-products are generated during the synthesis process, which is environmentally friendly and conforms to the concept of green development.

[0087] The preparation and application of the tungsten molybdenum oxide ore collector of the present invention will be described below with reference to specific examples.

[0088] Example 1

[0089] This example provides a preparation method for a novel tungsten molybdenum oxide ore collector.

[0090] It includes the following steps:

[0091] S1. Weigh 0.1 mol of n-octadecyl alcohol and add it to a 500 mL three-necked flask equipped with a stirrer, a thermometer and a spherical condenser reflux tube. Heat it to 75 °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 melted n-octadecyl alcohol for an esterification reaction. The rate of adding the anhydride is based on keeping the temperature of the reaction system unchanged. Keep stirring continuously. After reacting for 2.5 h, an intermediate product, mono-maleic acid ester carboxylic acid, is obtained; after the reaction ends, keep the system temperature at 75 °C.

[0093] S3. Weigh 0.105 mol of sodium sulfite and dissolve it in 150 mL of deionized water, heat it to 75 °C, and then slowly drip the sodium sulfite solution into the mono-maleic acid ester carboxylic acid for a sulfonation reaction. Keep mechanical vigorous stirring during the reaction process to prevent the reaction from being affected due to the sharp increase in the viscosity of the reaction system at the initial stage of the reaction, and keep the temperature at 75 °C for 2.5 h.

[0094] S4. As the reaction proceeds, the reaction system gradually changes from white turbidity to transparent clarity, and the viscosity of the solution gradually decreases. Eventually, a colorless, transparent, low-viscosity target product solution is obtained. The target product solution is mixed with petroleum ether and extracted multiple times. The transparent liquid in the lower layer of the separatory funnel is collected, rotary evaporated, and dried to obtain a white solid product.

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

[0096] Example 2

[0097] This example provides a preparation method for a new collector for tungsten-molybdenum oxide ore.

[0098] The specific process is the same as that of Example 1. The difference in the implementation method from Example 1 is that the n-octadecanol in Example 1 is replaced by n-hexadecanol as the reaction raw material.

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

[0100] Example 3

[0101] This example provides a preparation method for a new collector for tungsten-molybdenum oxide ore.

[0102] The specific process is the same as that of Example 1. The difference in the implementation method from Example 1 is that the n-octadecanol in Example 1 is replaced by n-dodecanol as the reaction raw material.

[0103] The white solid product obtained is compound MS-12. The infrared spectrum is as Figure 1 shown. Vibration absorption peaks related to carboxyl and sulfonic acid groups appear in the spectrum, preliminarily indicating the success of the synthesis of MS-12. Figure 4The mass spectrometry results of MS-12 with ESI as the ionization source are shown. The sum ion peaks of [M-2Na+H]- and [M-Na]-(where M is the uncharged reaction end product molecule MS-12) appear in the spectrum, indicating the success of the synthesis of MS-12.

[0104] Comparative Example 1

[0105] This example provides a preparation method for a new collector for tungsten-molybdenum oxide ore.

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

[0107] The sum ion peak areas of [M-2Na+H]- and [M-Na]-(where M is the un-ionized product molecule (uncharged)) in the mass spectrometry diagram are smaller than those in Example 3, indicating a decrease in the synthesis efficiency of MS-12.

[0108] Comparative Example 2

[0109] This example provides a preparation method for a new collector for tungsten-molybdenum oxide ore.

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

[0111] The sum ion peak areas of [M-2Na+H]- and [M-Na]-(where M is the un-ionized product molecule (uncharged)) in the mass spectrometry diagram are smaller than those in Example 3, indicating a decrease in the synthesis efficiency of MS-12.

[0112] Comparative Example 3

[0113] This example provides a preparation method for a new collector for tungsten-molybdenum oxide ore.

[0114] The specific process is the same as that of Example 3. The difference in the implementation method from Example 3 is that the addition amount of sodium sulfite in S3 is 0.11 mol.

[0115] The sum ion peak areas of [M-2Na+H]- and [M-Na]-(where M is the un-ionized product molecule (uncharged)) in the mass spectrometry diagram are smaller than those in Example 3, indicating a decrease in the synthesis efficiency of MS-12.

[0116] It can be seen from Example 3 and Comparative Examples 1 to 3 that in the preparation process of the tungsten-molybdenum collector of the present invention, when the proportion of the reactants does not meet the requirements of the present invention, the synthesis efficiency of the collector decreases.

[0117] Application Example 1

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

[0119] The flotation targets are scheelite, calcium molybdate, and calcite single minerals with a purity of over 98%. The above single minerals are beneficiated, crushed, ground, and screened, and the part of the minerals with a particle size of -74 to +38 μm is selected for flotation tests.

[0120] Flotation machine: XFG type hanging trough flotation machine, the volume of the flotation cell is 40 mL, and the rotational speed of the main shaft of the flotation machine is set at 1900 r / min.

[0121] The specific flotation steps are as follows:

[0122] Step 1: Accurately weigh 2.0 g of mineral samples with a particle size of -74 to +38 μm into the flotation cell, add 35 mL of deionized water, and stir for 1 min;

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

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

[0125] Step 4: Filter, dry, and weigh the floating foam products and the products in the cell respectively, and calculate the flotation recovery rate.

[0126] As shown in Figure 6(a), when MS-18 is used as the collector, under the condition of a dosage of 3.0×10 -4 mol / L, the influence of pulp pH on the flotation behavior of the three minerals. It can be seen from the figure that within the experimental pH range, the recovery rate of scheelite remains at a high level and is basically unchanged; with the increase of pH, the flotation recovery rate of calcium molybdate gradually increases. Overall, within a relatively wide pH value range, there are significant differences in the flotation recovery rates of tungsten molybdenum oxide minerals and calcite, and their floatabilities are ranked from large to small as: scheelite ≈ calcium molybdate > calcite. When the pH value is 7, the recovery rates of the three minerals are respectively: scheelite 88.33%, calcium molybdate 73.72%, and calcite 32.58%, and the best separation effect can be achieved.

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

[0128] As shown in Figure 7(a), when MS-18 is used as the collector, under the condition of pH = 7, the influence of reagent dosage on the flotation behaviors of three minerals. As can be seen from the figure, with the increase of reagent dosage, the recovery of scheelite gradually increases; the recoveries of calcium molybdate and calcite show basically unchanged and slow increasing trends respectively, but there is still a large gap between the recoveries of the two minerals within a large range of reagent dosages. Under the condition of reagent dosage of 3.0×10 -4 mol / L, the recovery difference between scheelite and calcite reaches about 55%, and the recovery difference between calcium molybdate and calcite is about 40%, achieving a good separation effect.

[0129] As shown in Figure 7(b), when MS-16 is used as the collector, under the condition of pH = 7, the influence of reagent dosage on the flotation behaviors of three minerals. As can be seen from the figure, with the increase of reagent dosage, the recoveries of all three minerals increase to a certain extent. Among them, the increase amplitude of scheelite is the largest, followed by calcium molybdate. The recoveries of both gradually become stable when approaching about 95%. Although the recovery of calcite also increases with the increase of collector dosage, the recovery difference from tungsten-molybdenum oxide ore is still about 40%. Therefore, the flotation separation of tungsten-molybdenum oxide ore and calcite can be realized at a lower reagent dosage.

[0130] Through the application research of single mineral flotation, it can be known that the collector for tungsten-molybdenum oxide ore provided by the present invention can effectively realize the high-efficiency and high-recovery flotation separation of tungsten-molybdenum oxide ore, and the flotation separation of tungsten-molybdenum oxide ore and calcite can be realized within the range of pH from 7 to 11.

[0131] Application Example 2

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

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

[0134] Adopt the flotation process of roughing oxidized ore once, and the specific process is as follows:

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

[0136] Step 2, adding flotation reagents: Add 1000 g / t sodium carbonate and stir for 3 min, then add 4000 g / t water glass and stir for 3 min, then add 100 g / t collector MS-12 and stir for 2 min, and finally aerate and float for 4 min to obtain concentrate products and tailings.

[0137] Step 3, filter, dry and weigh the concentrate and tailings respectively, and calculate the yield, recovery rate and concentrate enrichment ratio, as shown in Table 1.

[0138] Comparative Application Example 1

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

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

[0141] Adopt the flotation process of roughing oxidized ore once, and the specific process is as follows:

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

[0143] Step 2, adding flotation reagents: Add 1000 g / t sodium carbonate and stir for 3 min, then add 4000 g / t water glass and stir for 3 min, then add 200 g / t sodium oleate and stir for 2 min, and finally aerate and float for 4 min to obtain concentrate products and tailings.

[0144] Step 3, filter, dry and weigh the concentrate and tailings obtained by flotation respectively, and calculate the yield, recovery rate and concentrate enrichment ratio, as shown in Table 1.

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

[0146]

[0147] As can be seen from Table 1, in Application Example 2 and Comparative Application Example 1, when the traditional oxide ore collector sodium oleate was used and the collector dosage was 200 g / t, the WO grade in the concentrate was 0.604%, the enrichment ratio was 3.36, and the WO recovery rate was 44.73%; while when the tungsten molybdenum oxide collector MS-12 of the present invention was used and the collector dosage was 100 g / t, the WO grade in the concentrate could reach 0.741, the enrichment ratio reached 4.12, and the recovery rate could reach 52.69%. Under the condition that the dosage of the reagent was only half of that of sodium oleate, all flotation indexes were better than those of sodium oleate; this indicates that the newly synthesized sodium alkyl succinate sulfonate will achieve good ore dressing indexes for this type of tungsten molybdenum oxide ore with low grade and complex gangue minerals. 3 grade was 0.604%, enrichment ratio 3.36, WO 3 recovery rate was 44.73%; while when using the tungsten molybdenum oxide collector MS-12 of the present invention, under the condition that the collector dosage was 100 g / t, the WO 3 grade could reach 0.741, the enrichment ratio reached 4.12, and the recovery rate could reach 52.69%. Under the condition that the dosage of the reagent was only half of that of sodium oleate, all flotation indexes were better than those of sodium oleate; this indicates that the newly synthesized sodium alkyl succinate sulfonate will achieve good ore dressing indexes for this type of tungsten molybdenum oxide ore with low grade and complex gangue minerals.

[0148] In summary, the collector provided by the present invention contains three electronegative sites and has a long carbon chain surfactant-like structure similar to that of fatty acid collectors. Compared with the prior art, it has the advantages of good selectivity, strong collecting performance and strong foaming performance, greatly reducing the dosage of flotation reagents, and being able to adapt to the flotation pulp environment of complex and low-grade tungsten molybdenum oxide raw ore; the collector of the present invention is prepared from alkyl primary alcohols with 12-18 carbon atoms, and has a lower synthesis cost compared with the collectors used for existing tungsten molybdenum oxide ores, and can be widely used in actual large-scale production; the preparation process of the collector of the present invention is simple, without the addition of catalysts, and the reaction conditions are mild; the ester group structure of the collector of the present invention is easy to hydrolyze under strong alkaline conditions, and the hydrolysis product is primary alcohols, with mild drug properties, safe and non-toxic, and no harmful by-products are generated during the synthesis process, being environmentally friendly and conforming to the concept of green development.

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

Claims

1. A tungsten oxide molybdenum ore collector, characterized in that: Used for flotation of low-grade tungsten oxide and molybdenum ore, the collector chemical structure is: Wherein R is an alkyl group having 12 to 18 carbon atoms; + It is an inorganic cation or an organic cation.

2. A method for preparing a tungsten oxide molybdenum ore collector, characterized in that: The method for preparing the tungsten oxide molybdenum collector according to claim 1 comprises the following steps: S1. Weigh an appropriate amount of alkyl primary alcohol, heat to 70-90°C to melt, and keep stirring; S2. Weigh an appropriate amount of maleic anhydride and slowly add it to the molten alkyl primary alcohol, keep the temperature of the reaction system unchanged, and continue stirring. React for 2 to 3 hours to obtain monomaleic acid ester carboxylic acid, and keep the system temperature at 70 to 90°C; S3, weigh an appropriate amount of sulfonating agent and dissolve it in deionized water, and heat it to 70-90°C for preheating; S4. Slowly add the preheated sulfonating agent solution dropwise to the monomaleic acid ester at a rate that keeps the temperature of the reaction system constant, stir vigorously, and keep warm at 70-90° C. for 2-3 hours; S5. After the reaction is completed, the reaction system is mixed with petroleum ether, extracted multiple times, the transparent liquid at the bottom of the separatory funnel is collected, and dried to obtain a tungsten oxide molybdenum ore collector product.

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

05.

4. The preparation method according to claim 2, characterized in that: The sulfonating agent described 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 monomaleate carboxylic acid and the sulfonate group provided by the sulfonating agent in S3 is 1:1.

05.

6. The preparation method according to claim 2, characterized in that: S4: At the beginning of the reaction, a 5% by mass urea solution is added dropwise to the reaction system.

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

8. An application of a tungsten oxide molybdenum ore collector, characterized in that: The flotation of tungsten oxide molybdenum ore and gangue minerals using the tungsten oxide molybdenum ore collector according to claim 1 or the tungsten oxide molybdenum ore collector obtained by the preparation method according to any one of claims 2 to 7 comprises the following steps: Step 1, grinding: crushing and grinding; Step 2, adding flotation reagent: add sodium carbonate and stir for 3 to 5 minutes, then add water glass and stir for 3 to 5 minutes, and finally add tungsten oxide molybdenum ore collector and stir for 2 to 3 minutes; Step 3: Filter, dry and weigh the concentrate and tailings respectively, and calculate the yield and recovery rate.

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

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

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