Extraction system for extracting tungsten as well as preparation method and application of extraction system

Abstract

The invention discloses an extraction system for tungsten extraction and a preparation method and application thereof.The extraction system comprises a hydrocarbon solvent, trioctylamine and an alcohol compound, the oil-water partition coefficient of the alcohol compound at the temperature of 20 DEG C is 3.0-5.0, the carbon number of a carbon chain of the alcohol compound is C9-C13, and the extraction system comprises, by mass, 77%-82% of the hydrocarbon solvent, 8%-9% of trioctylamine and the balance alcohol. And the alcohol compound accounts for 9%-15%. The preparation method comprises the following steps: mixing and stirring the hydrocarbon solvent, the trioctylamine and the alcohol compound. The extraction system provided by the invention can shorten the extraction and negative washing phase separation time, improve the product quality, effectively reduce the COD values of the sulfonated aqueous phase and the raffinate, is green and environment-friendly, and can be well applied to the field of tertiary amine acidic tungsten extraction.

Description

Technical Field

[0001] The invention belongs to the technical field of tertiary amine acidic extraction of tungsten, and relates to an extraction system for tungsten extraction, a preparation method and application thereof, and in particular to an extraction system for tungsten extraction which can simultaneously shorten the phase separation time and reduce the COD of the raffinate, a preparation method and application thereof. Background Art

[0002] my country is rich in tungsten resources and is the world's largest tungsten producer and seller. Its tungsten production and export volume ranks first in the world. Currently, more than 80% of the world's tungsten industrial consumption comes from my country. As of June 2024, from the perspective of ammonium paratungstate production enterprises, there are a total of 25 domestic enterprises producing ammonium paratungstate, of which only 4 use the tertiary amine acid tungsten extraction process; from the perspective of production output (energy), ion exchange production of ammonium paratungstate accounts for 73%, extraction method 18%, and other methods 9%. The tertiary amine acid tungsten extraction process is still at a disadvantage in the industry, whether in terms of the number of production enterprises or the output effect, resulting in less manpower, material resources and investment in scientific research. The reason is that the advantages are very prominent and the disadvantages are obvious: the advantage is that the purity, crystal form and appearance, and invisible impurities of its product ammonium paratungstate and its downstream products are better than those of ion exchange process products and their downstream products, and can be more widely used in high-end products, such as aerospace, high-end medical, precision instruments, micro-drilling and other fields. In terms of environmental protection of wastewater treatment, each ton of product produces 10 tons of wastewater, which has an absolute advantage compared with the ion exchange process that produces about 100 tons of wastewater; the disadvantage is that the process is slightly longer and the overall cost is equivalent or slightly higher.

[0003] However, with the country's emphasis on rare metal materials, environmental protection, green development, and high-quality development in recent years, the ion exchange method is no longer comparable to the tertiary amine acid tungsten extraction process. For example, the chloride ions of the analytical agent of the ion exchange method remain in the product ammonium paratungstate, which directly affects the development of downstream products towards high-end products. At present, the more unified view in the industry is that the tertiary amine acid tungsten extraction process has strong vitality whether from the perspective of high-quality product development or green environmental protection. The increasing number of companies also reflects that it is gradually recognized by the market. In the existing technology, when using a hydrocarbon solvent (such as sulfonated kerosene)-N235 (trioctylamine)-paraoctanol extraction system to extract tungsten, the following defects exist:

[0004] (1) When the hydrocarbon solvent-trioctylamine-alcohol extraction system is configured, the system does not have the extraction function, and a sulfuric acid sulfonation extraction system is required to sulfonate the polar molecule extractant trioctylamine to become an ionic compound with extraction function. At this time, the organic phase becomes sulfonated air, and the water phase (dilute sulfuric acid) becomes a sulfonated water phase (waste acid) containing COD 1000-2000mg / L because of the soluble organic matter dissolved in it, some unsaturated organic phases form soluble substances after sulfonation, and contain tiny organic droplets. The high COD sulfonated water phase is recycled into the process, and there are three main destinations: First, it is returned to the concentrated sulfuric acid preparation dilute sulfuric acid process. When the concentrated sulfuric acid is mixed with the high COD sulfonated water to form 2-3 mol / L dilute sulfuric acid, the concentrated sulfuric acid has high oxidizing and dehydrating properties, and the COD (organic matter) in the sulfonated water phase is carbonized into carbon and carbon dioxide. The carbon adheres to the inner wall of the equipment, which directly causes the scaling of the heat exchange tower of the dilute sulfuric acid preparation tower, greatly reducing the heat exchange coefficient and posing a safety hazard; the generated carbon dioxide gas causes the tower pressure to increase, posing a safety hazard. Second, it is used as dilute sulfuric acid to adjust the pH of the front-end purification station and the sulfurization acid adjustment station. Because it contains organic matter and has a certain hydrophobicity, it affects the filtering effect when filtering in these stations. Third, other destinations. After the main process is used, there is still excess sulfonated water phase, which is directly merged into the raffinate and enters the wastewater treatment station for treatment. The high COD increases the wastewater treatment pressure, and there are certain environmental risks.

[0005] (2) When the phase separation time of extraction and washing is long (the effect of the extraction system on the extraction phase separation and washing is consistent, that is, the longer the extraction phase separation, the longer the washing will be), it exceeds the extraction time designed for the extraction process equipment, and the raffinate is entrained or wrapped in the loaded organic phase, which will make it difficult to separate the raffinate from the organic phase, especially after the third phase is generated and difficult to disappear, resulting in excessive impurities such as sodium, phosphorus, arsenic, silicon, and magnesium in the loaded organic phase, which in turn affects the quality of the stripping product ammonium tungstate solution and the final product ammonium paratungstate. For example, the raffinate, which is a high sodium solution, contains 35-50g / L of sodium. Compared with the production requirement of the extraction-stripping product ammonium tungstate solution containing less than 0.05g / L of sodium, once the extraction phase separation is slightly longer, the impurity sodium will exceed the standard. Although the duration of the extraction phase separation is related to the quality of the acid conditioning solution to be treated, in the same acid conditioning solution, it is determined by the phase composition of the extraction system. Therefore, the design of the phase composition of the extraction system is crucial.

[0006] (3) Industrial-grade 2-octanol products often carry 2-octanone with the odor of rotten apples, which produces an unpleasant odor. However, due to its low price and easy availability, 2-octanol has been used for decades in the extraction of tungsten using a hydrocarbon solvent-trioctylamine-alcohol extraction system. However, there are problems such as high COD, unfriendly raffinate odor, and high environmental pressure. Existing technologies usually use oxidation technologies such as sodium hypochlorite, chlorine, and ozone to reduce COD, but these technologies have obvious disadvantages. They either introduce other odors or are too costly, which only treats the symptoms but not the root cause.

[0007] In summary, it can be seen that there is an urgent need to develop a new extraction system in order to simultaneously solve the above problems such as long phase separation time, high COD of the raffinate, and unfriendly odor. Summary of the invention

[0008] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide an extraction system for tungsten extraction which can simultaneously shorten the extraction and washing phase separation time, reduce the COD of the raffinate and is environmentally friendly, as well as a preparation method and application thereof.

[0009] In order to solve the above technical problems, the present invention adopts the following technical solutions.

[0010] An extraction system for extracting tungsten, the extraction system comprising a hydrocarbon solvent, trioctylamine and an alcohol compound, wherein the oil-water partition coefficient of the alcohol compound at 20°C is 3.0-5.0, and the carbon chain of the alcohol compound contains carbon numbers of C9-C13; by mass fraction, the hydrocarbon solvent is 77%-82%, the trioctylamine is 8%-9%, and the alcohol compound is 9%-15%.

[0011] In the above-mentioned extraction system for extracting tungsten, preferably, the oil-water partition coefficient of the alcohol compound at 20° C. is 3.0-4.8, and the carbon chain of the alcohol compound has a carbon number of C9-C11.

[0012] In the above-mentioned extraction system for extracting tungsten, preferably, the alcohol compound is an isomeric alcohol, and the isomeric alcohol includes one or more of isomeric nonanol, isomeric decanol and isomeric undecanol.

[0013] In the above extraction system for tungsten extraction, preferably, the flash point of the hydrocarbon solvent is 60°C to 80°C, and the kinematic viscosity of the hydrocarbon solvent at 40°C is 1.5 mm 2 / s~2.5mm 2 / s, and the bromine value of the hydrocarbon solvent is 5mg / 100g to 100mg / 100g.

[0014] In the above-mentioned extraction system for extracting tungsten, preferably, the hydrocarbon solvent is sulfonated kerosene.

[0015] As a general technical concept, the present invention also provides a method for preparing the above-mentioned extraction system for extracting tungsten, comprising the following steps: mixing the hydrocarbon solvent, the trioctylamine and the alcohol compound, and stirring under heating conditions of 30° C. to 70° C. to obtain an extraction system. The hydrocarbon solvent is a diluent, the trioctylamine is an extractant, and the alcohol compound is a polarity improver.

[0016] In the above-mentioned method for preparing the extraction system for tungsten extraction, preferably, the heating conditions are water bath heating or steam heating, the stirring speed is 300r / min to 500r / min, more preferably 300r / min to 400r / min, and the stirring time is 2min to 4min, more preferably 2min to 3min.

[0017] As a general technical concept, the present invention also provides an application of the above-mentioned extraction system for extracting tungsten in the field of tertiary amine acidic extraction of tungsten.

[0018] The above application preferably comprises the following steps:

[0019] S1, sulfonation: the extraction system is mixed with H2SO4 solution, and stirred under heating conditions of 40°C to 70°C to sulfonate trioctylamine, and then allowed to stand and separate phases to obtain sulfonated air phase and sulfonated water phase;

[0020] S2, extraction: sulfonated ether is mixed with acid-adjusting solution containing tungsten trioxide, stirred under heating conditions of 40℃~70℃, tungsten polyacid ions in the acid-adjusting solution are extracted, stirring is stopped, the obtained oil-water mixture is phase-separated until the third phase with a thickness of 1mm is separated, and the phase separation is completed, and the supernatant is retained to obtain the loaded organic phase, i.e. ether;

[0021] S3, washing the negative oil: mix the negative oil obtained above with water, stir and wash under heating conditions of 40℃~70℃, stop stirring, separate the obtained oil-water mixture into phases, and complete the phase separation when the third phase with a thickness of 1mm is separated, and strip the organic phase with ammonia water to obtain the stripping product, ammonium tungstate solution.

[0022] In the above application, preferably, in step S1, the concentration of the H2SO4 solution is 2 mol / L to 2.5 mol / L, the volume ratio of the extraction system to the H2SO4 solution is 5 to 10:1, the stirring speed is 300 r / min to 500 r / min, the stirring time is 2 min to 4 min, and the standing time is 2 min to 5 min.

[0023] In the above application, preferably, in step S2, the concentration of tungsten trioxide in the acid adjustment solution containing tungsten trioxide is 70g / L~110g / L, the volume ratio of the sulfonated ether to the acid adjustment solution containing tungsten trioxide is 1:0.7~1, the stirring speed is 300r / min~500r / min, the stirring extraction time is 2min~4min, the phase separation is implemented by a separating funnel, and the speed of pouring the oil-water mixture into the separating funnel is 80mL / s~100mL / s.

[0024] In the above application, preferably, in step S3, the volume ratio of the oil to the water is 5 to 9:1, the stirring speed is 300 r / min to 500 r / min, the stirring and washing time is 2 min to 4 min, the phase separation is carried out by a separating funnel, and the speed at which the oil-water mixture is poured into the separating funnel is 80 mL / s to 100 mL / s.

[0025] In the above application, preferably, in steps S1, S2, and S3, the heating condition is water bath heating or steam heating.

[0026] The terms of the present invention are explained as follows:

[0027] Oil-water partition coefficient logP: It is the logarithm of the ratio of the partition coefficients of a substance in n-octanol and water.

[0028] Sulfonated air: refers to the organic phase after the hydrocarbon solvent-trioctylamine-alcohol system is sulfonated by H2SO4 solution.

[0029] Sulfonated aqueous phase: The aqueous phase after the extraction system (empty organic phase) is sulfonated with dilute sulfuric acid and phase separated.

[0030] Acid adjustment solution: refers to the sodium tungstate solution that has been acidified with H2SO4 solution to a pH of 2-3 and impurities removed.

[0031] Loaded organic phase: The abbreviation of loaded organic phase, which refers to the organic phase that has extracted the substance to be separated.

[0032] The third phase refers to the immiscible second organic phase formed between the organic phase and the aqueous phase during the solvent extraction process.

[0033] Compared with the prior art, the advantages of the present invention are:

[0034] 1. In the extraction system for tungsten extraction of the present invention, hydrocarbon solvent is used as diluent, trioctylamine (N235) is used as extractant, and alcohol compounds with an oil-water partition coefficient of 3.0-5.0 and a carbon chain carbon number of C9-C13 are used as polarity improvers. When the extraction system is used for tungsten extraction, the following effects can be achieved simultaneously: (1) the extraction and washing phase separation time are reduced, the quality of the waste is improved, and finally the product quality is improved; (2) the COD of the raffinate can be reduced, the loss of the extraction components is reduced, and the press reagent consumption of the wastewater treatment station is reduced; (3) the amount of COD removal agent sodium hypochlorite is reduced, and its odor in the wastewater is reduced, so as to achieve green and environmentally friendly development.

[0035] 2. Tertiary amine acidic tungsten extraction process Many technologies are based on high-quality smelting raw material tungsten concentrate. Due to the tight supply of raw tungsten ore, the tungsten content of tungsten smelting raw materials on the market currently generally does not reach 30%. Therefore, it is necessary to pick up the research on tertiary amine acidic tungsten extraction technology again to adapt it to the current raw material environment.

[0036] The ore decomposition process used in combination with the tertiary amine acidic tungsten extraction process is the soda / sodium fluoride decomposition of scheelite. Scheelite with a tungsten content of less than 30% contains a large amount of organic flotation agents and raw ore impurities. The former is enriched in the extraction system, affecting the overall performance indicators of the organic phase, and the latter combines with tungsten to form heteropolyacids. The final appearance of the two is: a serious three-phase extraction occurs, and phase separation is difficult. The most fundamental reason is that the overall polarity of the extraction system has been changed.

[0037] In the extraction process, the organic phase and the aqueous phase need to be fully mixed to achieve efficient mass transfer between the two phases, so that tungsten enters the organic phase from the aqueous phase, and the sulfonate enters the aqueous phase from the organic phase. The higher the polarity of the organic phase, the easier it is for the two phases to mix evenly. However, when the polarity improver adjusts the polarity of the system too high, the extractant easily separates from the organic phase and enters the aqueous phase to form an ointment precipitate. In the extraction static phase separation process, the lower the polarity of the organic phase, the easier it is for the two phases to separate, the more thorough the phase separation, and the lower the load of the organic phase containing water (raffinate). However, when the polarity improver adjusts the polarity of the system too low, the mass transfer between the two phases is not deep during the extraction and negative washing process, and the envisioned effect cannot be achieved. It can be seen that the polarity of the extraction system is a contradiction in the extraction process and static phase separation. Therefore, it is particularly important to develop a polarity improver with moderate polarity and shorten the extraction and negative washing phase separation time.

[0038] In view of the influence of the above-mentioned flotation agent and the heteropolyacid of the mineral impurities on the polarity of the extraction system, as well as the extraction link and the static separation on the polarity of the extraction system, the existing sulfonated kerosene-trioctylamine-sec-octanol extraction system is difficult to meet the requirements. In addition, the odor of sec-octanol and sulfonated kerosene is incompatible with the current environmental protection and green development. Therefore, the present invention develops an efficient extraction and green environmental protection extraction system.

[0039] As the market mineral resources become more complex, there are many types of organic flotation agents remaining in the smelting raw material tungsten ore, such as 731, oleic acid, natural fatty acids of animals and plants, modified fatty acids and other fats, phosphonic acids, hydroxamic acid, etc., and the residual amounts vary greatly. During the smelting process, these organic flotation agents have great damage to the sulfonated kerosene-trioctylamine-sec-octanol extraction system, and are often accompanied by problems such as oil-in-water, water-in-oil, and the formation of ointment, resulting in phase composition imbalance, which ultimately affects product quality, output, cost, etc. The applicant found in the research work on the polar action mechanism in the extraction system:

[0040] (1) The improvement of the polarity of the extraction system by medium- and high-carbon saturated alcohols presents a quasi-normal distribution on the whole. That is, for medium- and high-carbon saturated alcohols with similar structures, as the carbon number of the carbon chain increases, the improvement of the polarity of the extraction system first increases, reaches a peak, and then decreases.

[0041] (2) Whether or not there is a hydrocarbon branch on the 1° carbon of the polarity improver alcohol has a great influence on the polarity of the functional group hydroxyl group. That is, the hydrocarbon branch on the 1° carbon has a steric hindrance effect, which weakens or even shields the polarity of the hydroxyl group, and the ability to deal with the above problems is very different.

[0042] (3) The smell of polarity improver alcohols plays a decisive role in causing the strong odor of the extraction system. The more carbon atoms in the alcohol, the lighter the odor; the fewer the branches, the lighter the odor; and the farther the branches are from the functional group hydroxyl group, the lighter the odor.

[0043] (4) Research on the unsaturation of the extraction system found that although sulfonated kerosene is sulfonated with sulfuric acid, there are still a certain amount of unsaturated bonds, especially the unsaturated bonds of aromatic hydrocarbons, which are difficult to be sulfonated with sulfuric acid and have a strong odor.

[0044] (5) The unsaturation of the extraction system directly affects the COD content of the sulfonated water phase and the raffinate.

[0045] In summary, the carbon chain length, unsaturation, branching spatial position, and hydroxyl activity of the hydrocarbon solvent and polarity modifier of the extraction system are closely related to their macroscopic bromine value and oil-water partition coefficient logP. Therefore, the extraction system developed in the present invention can effectively solve the above problems and present the above series of advantages. DETAILED DESCRIPTION

[0046] The present invention is further described below in conjunction with specific preferred embodiments, but the protection scope of the present invention is not limited thereby. The materials and instruments used in the following embodiments are all commercially available, and isomeric decanol, isomeric undecanol and isomeric tridecanol are all purchased from ExxonMobil Corporation of the United States.

[0047] Example 1

[0048] An extraction system for tungsten extraction of the present invention is composed of a hydrocarbon solvent, trioctylamine and an alcohol compound, wherein the oil-water partition coefficient logP of the alcohol compound at 20°C is 3.8, and the carbon chain of the alcohol compound contains C10 carbon. In this embodiment, the alcohol compound is isomeric decanol, the hydrocarbon solvent is sulfonated kerosene, the flash point of sulfonated kerosene is 60°C, and the kinematic viscosity at 40°C is 2 mm 2 / s, the bromine value is 80mg / 100g. Calculated by mass fraction, the sulfonated kerosene is 79.5%, the trioctylamine N235 is 8.5%, and the isomeric decanol is 12%.

[0049] A preparation method of an extraction system for extracting tungsten according to the present embodiment comprises the following steps: mixing sulfonated kerosene, trioctylamine and isomeric decanol, wherein the sulfonated kerosene is used as a diluent, the trioctylamine is used as an extractant, and the isomeric decanol is used as a polarity improver; mechanically stirring the mixture in a water bath at 60° C., with a stirring speed of 300 r / min and a stirring time of 2 min; and after stirring and mixing, obtaining an extraction system.

[0050] An application of the extraction system for tungsten extraction of this embodiment in the field of tertiary amine acid extraction of tungsten, this embodiment specifically treats the acid adjustment solution containing tungsten trioxide, including the following steps:

[0051] S1. Sulfonation: Mix the extraction system with 2.3 mol / L H2SO4 solution in a volume ratio of 8:1, then stir mechanically at 300 r / min for 2 min in a 60°C water bath, mix well, let stand for 5 min, separate the phases with a separatory funnel, and retain the supernatant in the separatory funnel to obtain a sulfonated phase. The sulfonated phase is an ionic sulfonated phase with extraction function. The COD of the obtained sulfonated aqueous phase is 625 mg / L.

[0052] S2, extraction: sulfonated ether is mixed with acid adjustment liquid containing tungsten trioxide, the concentration of tungsten trioxide in the acid adjustment liquid is 80g / L, the COD of the acid adjustment liquid is 6000mg / L, the pH value is 2, the volume ratio of sulfonated ether to the acid adjustment liquid containing tungsten trioxide is 1:0.8, under the condition of 60℃ water bath, mechanically stirred at a speed of 300r / min for 2min, then stopped stirring, wiped the water hanging on the wall of the water bath pot on the outer cup wall, immediately transferred to the separating funnel, started timing, the oil-water mixture was poured into the separating funnel at a speed of 80mL / s, and the timing was terminated when the solution in the separating funnel was phase-separated to the third phase thickness of 1mm, and the phase separation time was 126s. The supernatant of the separating funnel is the negative, and the lower clear liquid is the raffinate, the COD of the raffinate is 440mg / L, and the odor is light.

[0053] S3, washing of the negative: Mix the negative obtained above with pure water, the volume ratio of the negative to pure water is 6:1, under the condition of 60℃ water bath, stir mechanically at a speed of 300r / min for 2min, then stop stirring, wipe the water hanging on the wall of the water bath pot on the outer cup wall, immediately transfer to the separating funnel, start timing, pour the oil-water mixture into the separating funnel at a speed of 80mL / s, when the separating funnel solution is phase-separated to the third phase thickness of 1mm, it is the end of timing, and the phase separation time is 102s. The organic phase is stripped with ammonia water to obtain the stripping product ammonium tungstate solution.

[0054] Example 2

[0055] An extraction system for extracting tungsten of the present invention is composed of a hydrocarbon solvent, trioctylamine and an alcohol compound, wherein the oil-water partition coefficient logP of the alcohol compound at 20°C is 4.5, and the carbon chain of the alcohol compound contains C10. Specifically, in this embodiment, the alcohol compound is n-decanol, the hydrocarbon solvent is sulfonated kerosene, the flash point of sulfonated kerosene is 60°C, and the kinematic viscosity at 40°C is 2 mm 2 / s, the bromine value is 80mg / 100g. Calculated by mass fraction, the sulfonated kerosene is 79.5%, the trioctylamine N235 is 8.5%, and the n-decanol is 12%.

[0056] A preparation method of an extraction system for extracting tungsten according to the present embodiment comprises the following steps: mixing sulfonated kerosene, trioctylamine and n-decanol, wherein the sulfonated kerosene is a diluent, the trioctylamine is an extractant and the n-decanol is a polarity improver; mechanically stirring the mixture in a water bath at 60° C., the stirring speed is 300 r / min and the stirring time is 2 min; after stirring and mixing, an extraction system is obtained.

[0057] An application of the extraction system for tungsten extraction of this embodiment in the field of tertiary amine acid extraction of tungsten, this embodiment specifically treats the acid adjustment solution containing tungsten trioxide, including the following steps:

[0058] S1. Sulfonation: Mix the extraction system with 2.3 mol / L H2SO4 solution in a volume ratio of 8:1, then stir mechanically at 300 r / min for 2 min in a 60°C water bath, mix well, let stand for 5 min, separate the phases with a separatory funnel, and retain the supernatant in the separatory funnel to obtain the sulfonated phase. The COD of the sulfonated aqueous phase is 680 mg / L.

[0059] S2, extraction: sulfonated ether is mixed with acid adjustment solution containing tungsten trioxide, the concentration of tungsten trioxide in the acid adjustment solution is 80g / L, COD is 6000mg / L, pH value is 2, the volume ratio of sulfonated ether to acid adjustment solution containing tungsten trioxide is 1:0.8, under 60℃ water bath condition, mechanically stir at 300r / min speed for 2min, then stop stirring, wipe the water hanging on the wall of the water bath pot on the outer cup wall, immediately transfer to the separating funnel, start timing, the oil-water mixture is poured into the separating funnel at a speed of 80mL / s, when the separating funnel solution is phase-separated to the third phase thickness of 1mm, the timing end point, the phase separation time is 147s. The supernatant of the separating funnel is the negative, and the lower clear liquid is the raffinate, the COD of the raffinate is 445mg / L, and the odor is light.

[0060] S3, washing of the negative: Mix the negative obtained above with pure water, the volume ratio of the negative to pure water is 6:1, under the condition of 60℃ water bath, stir mechanically at a speed of 300r / min for 2min, then stop stirring, wipe the water hanging on the wall of the water bath pot on the outer cup wall, immediately transfer to the separating funnel, start timing, pour the oil-water mixture into the separating funnel at a speed of 80mL / s, when the separating funnel solution is phase-separated to the third phase thickness of 1mm, it is the end of timing, and the phase separation time is 116s. The organic phase is stripped with ammonia water to obtain the stripping product ammonium tungstate solution.

[0061] Example 3

[0062] An extraction system for extracting tungsten of the present invention is composed of a hydrocarbon solvent, trioctylamine and an alcohol compound, wherein the oil-water partition coefficient logP of the alcohol compound at 20°C is 4.8, and the carbon chain of the alcohol compound contains C13 carbons. Specifically, in this embodiment, the alcohol compound is isomeric tridecanol, the hydrocarbon solvent is sulfonated kerosene, the flash point of the sulfonated kerosene is 60°C, and the kinematic viscosity at 40°C is 2 mm 2 / s, the bromine value is 80mg / 100g. Calculated by mass fraction, the sulfonated kerosene is 79.5%, the trioctylamine N235 is 8.5%, and the isomeric tridecanol is 12%.

[0063] A preparation method of an extraction system for extracting tungsten according to the present embodiment comprises the following steps: mixing sulfonated kerosene, trioctylamine and isotridecyl alcohol, wherein the sulfonated kerosene is used as a diluent, the trioctylamine is used as an extractant, and the isotridecyl alcohol is used as a polarity improver; mechanically stirring the mixture in a water bath at 60° C., with a stirring speed of 300 r / min and a stirring time of 2 min; and after stirring and mixing, obtaining an extraction system.

[0064] An application of the extraction system for tungsten extraction of this embodiment in the field of tertiary amine acid extraction of tungsten, this embodiment specifically treats the acid adjustment solution containing tungsten trioxide, including the following steps:

[0065] S1. Sulfonation: Mix the extraction system with 2.3 mol / L H2SO4 solution in a volume ratio of 8:1, then stir mechanically at 300 r / min for 2 min in a 60°C water bath, mix well, let stand for 5 min, separate the phases with a separatory funnel, and retain the supernatant in the separatory funnel to obtain the sulfonated phase. The COD of the sulfonated aqueous phase is 620 mg / L.

[0066] S2, extraction: sulfonated ether is mixed with acid adjustment solution containing tungsten trioxide, the concentration of tungsten trioxide in the acid adjustment solution is 80g / L, COD is 6000mg / L, pH value is 2, the volume ratio of sulfonated ether to acid adjustment solution containing tungsten trioxide is 1:0.8, under 60℃ water bath condition, mechanically stir at 300r / min speed for 2min, then stop stirring, wipe the water hanging on the wall of the water bath pot on the outer cup wall, immediately transfer to the separating funnel, start timing, the oil-water mixture is poured into the separating funnel at a speed of 80mL / s, when the separating funnel solution is phase-separated to the third phase thickness of 1mm, the timing end point, the phase separation time is 147s. The supernatant of the separating funnel is the negative, and the lower clear liquid is the raffinate, the COD of the raffinate is 577mg / L, and the odor is light.

[0067] S3, washing of the negative: Mix the negative obtained above with pure water, the volume ratio of the negative to pure water is 6:1, under the condition of 60℃ water bath, stir mechanically at a speed of 300r / min for 2min, then stop stirring, wipe the water hanging on the wall of the water bath pot on the outer cup wall, immediately transfer to the separating funnel, start timing, pour the oil-water mixture into the separating funnel at a speed of 80mL / s, when the separating funnel solution is phase-separated to the third phase thickness of 1mm, it is the end of timing, and the phase separation time is 150s. The organic phase is stripped with ammonia water to obtain the stripping product ammonium tungstate solution.

[0068] Comparative Example 1

[0069] An extraction system for tungsten extraction and its application are basically the same as Example 1, except that the isomeric decanol in the extraction system is replaced by sec-octanol, and the oil-water partition coefficient logP is 2.86. When the extraction system is applied to tungsten extraction with tertiary amine acid, the COD of the obtained sulfonated water phase is 1120 mg / L, the extraction phase separation time is 157 s, the COD of the raffinate is 650 mg / L, the odor is unfriendly (severe), and the negative washing phase separation time is 156 s.

[0070] Comparative Example 2

[0071] An extraction system for tungsten extraction and its application are basically the same as Example 3, except that the isomeric tridecanol in the extraction system is replaced by n-tridecanol, and the oil-water partition coefficient logP is 5.8. When the extraction system is applied to tungsten extraction with tertiary amine acid, the COD of the obtained sulfonated water phase is 675 mg / L, the extraction phase separation time is 180 s, the COD of the raffinate is 570 mg / L, the odor is light, and the negative washing phase separation time is 170 s.

[0072] The above is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as above in the preferred embodiment, it is not used to limit the present invention. Any technician familiar with the art can make many possible changes and modifications to the technical solution of the present invention by using the methods and technical contents disclosed above without departing from the spirit and technical solution of the present invention, or modify it into an equivalent embodiment of equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention, still fall within the scope of protection of the technical solution of the present invention.

Claims

1. An extraction system for extracting tungsten, characterized in that: The extraction system comprises hydrocarbon solvent, trioctylamine and alcohol compound, wherein the oil-water partition coefficient of the alcohol compound at 20° C. is 3.0-5.0, and the carbon chain of the alcohol compound contains carbon numbers of C9-C13; in terms of mass fraction, the hydrocarbon solvent is 77%-82%, the trioctylamine is 8%-9%, and the alcohol compound is 9%-15%.

2. The extraction system for extracting tungsten according to claim 1, characterized in that: The oil-water partition coefficient of the alcohol compound at 20° C. is 3.0-4.8, and the carbon number of the carbon chain of the alcohol compound is C9-C11.

3. The extraction system for extracting tungsten according to claim 2, characterized in that: The alcohol compound is an isomeric alcohol, and the isomeric alcohol includes one or more of isomeric nonanol, isomeric decanol and isomeric undecanol.

4. The extraction system for extracting tungsten according to any one of claims 1 to 3, characterized in that: The flash point of the hydrocarbon solvent is 60°C to 80°C, and the kinematic viscosity of the hydrocarbon solvent at 40°C is 1.5 mm 2 / s~2.5mm 2 / s, and the bromine value of the hydrocarbon solvent is 5mg / 100g to 100mg / 100g.

5. The extraction system for extracting tungsten according to claim 4, characterized in that: The hydrocarbon solvent is sulfonated kerosene.

6. A method for preparing an extraction system for extracting tungsten according to any one of claims 1 to 5, characterized in that: The following steps are involved: The hydrocarbon solvent, the trioctylamine and the alcohol compound are mixed, and stirred under heating conditions of 30° C. to 70° C. to obtain an extraction system.

7. The method for preparing the extraction system for tungsten extraction according to claim 6, characterized in that: The heating condition is water bath heating or steam heating, the stirring speed is 300 r / min to 500 r / min, and the stirring time is 2 min to 4 min.

8. Use of the extraction system for extracting tungsten as claimed in any one of claims 1 to 5 in the field of tertiary amine acidic extraction of tungsten.

9. The use according to claim 8, characterized in that: The following steps are involved: S1, sulfonation: the extraction system is mixed with H2SO4 solution, and stirred under heating conditions of 40°C to 70°C to sulfonate trioctylamine, and then allowed to stand and separate phases to obtain sulfonated air phase and sulfonated water phase; S2, extraction: sulfonated ether is mixed with acid-adjusting solution containing tungsten trioxide, stirred under heating conditions of 40℃~70℃, tungsten polyacid ions in the acid-adjusting solution are extracted, stirring is stopped, the obtained oil-water mixture is phase-separated until the third phase with a thickness of 1mm is separated, and the phase separation is completed, and the supernatant is retained to obtain the loaded organic phase, i.e. ether; S3, washing the negative oil: mix the negative oil obtained above with water, stir and wash under heating conditions of 40℃~70℃, stop stirring, separate the obtained oil-water mixture into phases, and complete the phase separation when the third phase with a thickness of 1mm is separated, and strip the organic phase with ammonia water to obtain the stripping product, ammonium tungstate solution.

10. The use according to claim 9, characterized in that: In step S1, the concentration of the H2SO4 solution is 2 mol / L to 2.5 mol / L, the volume ratio of the extraction system to the H2SO4 solution is 5 to 10:1, the stirring speed is 300 r / min to 500 r / min, the stirring time is 2 min to 4 min, and the standing time is 2 min to 5 min; In step S2, the concentration of tungsten trioxide in the acid conditioning solution containing tungsten trioxide is 70g / L-110g / L, the volume ratio of the sulfonated ether to the acid conditioning solution containing tungsten trioxide is 1:0.7-1, the stirring speed is 300r / min-500r / min, the stirring extraction time is 2min-4min, the phase separation is implemented by a separating funnel, and the speed of pouring the oil-water mixture into the separating funnel is 80mL / s-100mL / s; In step S3, the volume ratio of the oil to the water is 5 to 9:1, the stirring speed is 300 r / min to 500 r / min, the stirring washing time is 2 min to 4 min, the phase separation is carried out by a separating funnel, and the speed of pouring the oil-water mixture into the separating funnel is 80 mL / s to 100 mL / s; In steps S1, S2 and S3, the heating condition is water bath heating or steam heating.