Method for efficiently recycling tartaric acid and tungsten through green conversion of scheelite tartaric acid decomposition residues

Abstract

The invention belongs to the field of green smelting of tungsten and comprehensive utilization of secondary resources, and particularly relates to a method for efficiently recovering tartaric acid and tungsten by green conversion of scheelite tartaric acid decomposition slag, which comprises the following steps: preparing the scheelite tartaric acid decomposition slag into slurry, adding sulfuric acid for normal-temperature green conversion, and converting calcium tartrate into calcium sulfate, meanwhile, tartaric acid is released, secondary dissolution is conducted on the released tartaric acid and residual tungsten in decomposition residues, then filtering and washing are conducted, solid-liquid separation is achieved, the obtained solid is calcium sulfate and can be used for preparing building materials, filtered thick materials are subjected to resin adsorption to recover tungsten, and an obtained sodium tungstate solution is returned to the main tungsten smelting process. The resin adsorption raffinate is subjected to secondary preparation and is used as a leaching agent of scheelite, and recycling of tartaric acid is achieved. According to the method, green conversion of the scheelite tartaric acid decomposition residues is achieved, meanwhile, tartaric acid and tungsten are efficiently recycled, and a novel green resource utilization method is provided for the scheelite tartaric acid decomposition residues.

Description

Technical Field

[0001] The invention belongs to the field of green smelting of tungsten and comprehensive utilization of secondary resources, and specifically relates to a method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten. Background Art

[0002] As a pillar material of the modern industrial system, tungsten plays an irreplaceable role in key areas such as electronic component manufacturing, precision chemical synthesis, and medical equipment production. my country's scheelite reserves account for 68.70% of the total tungsten mineral resources, but due to its inherent characteristics such as low ore grade, complex mineral composition, and insufficient effective utilization, it is classified as a typical difficult-to-process tungsten mineral, which seriously restricts the technological upgrading and sustainable development of the tungsten smelting industry.

[0003] Although the high-temperature alkaline pressure cooking process, which is currently the most widely used in industry, can achieve the leaching and extraction of tungsten elements, its inherent defects are prominently manifested as follows: the high temperature and high pressure operating conditions lead to accelerated equipment corrosion rate and increased energy consumption intensity, and the alkaline leaching slag produced is difficult to achieve resource recycling. In order to break through the bottleneck of traditional processes, the new tartaric acid room temperature decomposition technology successfully achieved the room temperature dissociation of tungsten-calcium chemical bonds in scheelite by introducing tartaric acid into an acidic medium. However, this process faces two technical obstacles in its industrial promotion: first, tartaric acid combines with calcium ions in the reaction process to form a stable calcium tartrate solid phase, resulting in unexpected consumption of effective reaction reagents; second, 0.3% to 1.0% WO still remains in the final decomposition slag. 3 Not effectively extracted.

[0004] If the tartaric acid decomposition residue of scheelite is directly landfilled, it will not only lead to the waste of tungsten-containing resources and organic reagents, but also there are potential ecological risks such as the slow decomposition of calcium tartrate in the natural environment, which may cause changes in the physical and chemical properties of the soil. However, the existing decomposition residue recovery technology system has significant technical shortcomings: the strong acid leaching method aggravates equipment loss due to the need to use high-concentration corrosive acid; the high-temperature roasting method causes irreversible damage to the molecular structure of tartaric acid while achieving tungsten recovery, blocking its recycling path; the biological leaching technology is limited by the poor environmental adaptability of microorganisms and has not yet broken through the technical and economic bottleneck of industrial application.

[0005] Solving the technical problem of green recycling of tartaric acid decomposition slag of scheelite will directly improve the overall economy and environmental friendliness of the tartaric acid decomposition process. Therefore, building an efficient and low-carbon decomposition slag resource utilization technology system has become an urgent need to promote the clean transformation of the tungsten metallurgical industry. Summary of the invention

[0006] In order to solve the problems of green transformation of tartaric acid decomposition slag of scheelite and efficient recovery and utilization of tartaric acid and tungsten in the slag, the present invention provides a method for green transformation of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten.

[0007] The embodiment of the present invention provides a method for green conversion of tartaric acid decomposition residue of scheelite and efficient recovery of tartaric acid and tungsten, comprising the following steps: S1. Prepare slurry: put the tartaric acid decomposition residue of scheelite into a reactor, add tap water and stir to prepare slurry; S2, room temperature green conversion: gradually add sulfuric acid to the slurry obtained in step S1 and stir, the conversion temperature is 20°C to 35°C, after the conversion is completed, the conversion slurry is obtained, and the next step is entered; S3, filtration and washing: after step S2 is completed, the conversion pulp is filtered, the obtained conversion concentrate is collected for standby use, and the conversion slag is washed twice again. The residual liquid of the first washing is collected and used for the next slurry preparation, and the residual liquid of the second washing is collected, part of which is used as the first washing water of the next filtration step, and part is collected for treatment; S4, resin adsorption recovery of tungsten: The conversion concentrate obtained in step S3 is dynamically adsorbed by a simulated exchange column, and the residual liquid containing tartaric acid after adsorption is collected and sent to the next step, and the tungstate solution obtained by desorption of the loaded resin is collected and returned to the main tungsten smelting process; S5. Secondary preparation and recycling: the tartaric acid adsorption residual liquid obtained in step S4 is placed in a dissolver and stirred, and then a sample is taken to analyze the concentration of tartaric acid and calculate the amount of solid tartaric acid to be added, and a secondary dissolution preparation is performed, and the prepared tartaric acid solution is returned to the decomposition link of the scheelite.

[0008] As preferred embodiments of the present invention, in step S1, the liquid-to-solid ratio of tap water to tartaric acid decomposition slag of scheelite is 4:1 mL / g to 10:1 mL / g.

[0009] As preferred embodiments of the present invention, in step S2, the conversion time is 3 h to 6 h, and the stirring speed is 60 r / min to 120 r / min.

[0010] As preferred in some embodiments of the present invention, in step S2, when the concentration of sulfate in the supernatant of the slurry is ≥0.5 mol / L, the conversion is completed and the addition of sulfuric acid is stopped.

[0011] As preferred embodiments of the present invention, in step S3, the amount of tap water used for the first washing is 4 to 10 times the weight of the original tartaric acid decomposition residue of the scheelite, and the amount of tap water used for the second washing is 4 to 10 times the weight of the original tartaric acid decomposition residue of the scheelite.

[0012] As a preference of some embodiments of the present invention, in step S4, the adsorption column is filled with D318 resin, and the ratio of the diameter of the simulation column to the height of the resin layer is 1:6 to 1:12.

[0013] As a preferred embodiment of some embodiments of the present invention, in step S4, when WO in the adsorption residual solution is 3 When the concentration is ≥0.01g / L, stop adsorption.

[0014] As preferred embodiments of the present invention, in step S4, the desorbent is NaOH solution or dilute ammonia solution, the concentration of which is controlled to be 80 g / L to 100 g / L, and sodium tungstate solution or ammonium tungstate solution is obtained by desorption.

[0015] As preferred in some embodiments of the present invention, in step S5, stirring is performed for 10 min to 30 min, and the stirring speed is controlled to be 60 r / min to 120 r / min.

[0016] As preferred in some embodiments of the present invention, in step S5, the concentration of tartaric acid prepared by secondary dissolution is controlled to be 120 g / L to 180 g / L.

[0017] Compared with the prior art, the present invention has the following beneficial effects: 1. Green environmental protection and efficient resource circulation: Through the room temperature sulfuric acid conversion reaction, the calcium tartrate in the tartaric acid decomposition residue of scheelite is converted into calcium sulfate (a harmless byproduct that can be directly used in the production of building materials), while tartaric acid is released and residual tungsten is dissolved for a second time, achieving efficient recovery of tartaric acid and tungsten. The whole process does not involve high temperature, high pressure or harmful reagents, which significantly reduces waste emissions and reduces environmental burden.

[0018] 2. Economic efficiency and resource recycling: The staged washing residual liquid recycling technology is adopted to use the washing water and adsorption residual liquid for slurry preparation, filtration and scheelite decomposition, respectively, to achieve the recycling of tartaric acid and greatly reduce the consumption of fresh reagents; the resin adsorption method is used to accurately recover tungsten, and after desorption, sodium tungstate or ammonium tungstate solution that can be returned to the main smelting process is directly obtained, reducing production costs and improving the comprehensive utilization rate of resources.

[0019] 3. Process simplification and industrial adaptability: Based on room temperature reaction conditions and conventional equipment, the operation process is simple and energy consumption is low, avoiding complex high-energy consumption processes. The secondary dissolution efficiency of tungsten in the conversion slag is high, and the conversion rate of calcium tartrate is close to complete, which not only solves the conversion and disposal problem of tartaric acid decomposition slag of scheelite, but also completes the recovery of tartaric acid and residual tungsten in the decomposition slag, realizing the efficient resource utilization of tartaric acid decomposition slag of scheelite, and the technology is stable and easy to promote on a large scale, providing an efficient and sustainable solution for the green smelting of scheelite. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the specific implementation of the present invention or the technical solution in the prior art, the drawings required for describing the specific implementation or the prior art will be briefly introduced below. Obviously, the drawings described below are only one implementation of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0021] Figure 1 This is a schematic diagram of the process flow of an embodiment of the present application; Figure 2 This is an EDS analysis result diagram of tartaric acid decomposition slag of scheelite in the embodiment of the present application; Figure 3 This is the EDS analysis result of the conversion slag of Example 1 of the present application; Figure 4 This is the EDS analysis result of the conversion slag of Example 2 of the present application; Figure 5 This is the EDS analysis result of the conversion slag in Example 3 of the present application. DETAILED DESCRIPTION

[0022] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the technical scheme in the specific implementation mode of the present invention is clearly and completely described below to further illustrate the present invention. Obviously, the specific implementation mode described is only a part of the implementation mode of the present invention, rather than all styles.

[0023] The embodiment of the present application solves the problems of waste in landfill and difficulty in recycling of tartaric acid decomposition slag of scheelite in the prior art by providing a method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten. By constructing a coordinated recovery system of slurry preparation-normal temperature conversion-filtration separation-resin adsorption-recycling, the tartaric acid decomposition slag of scheelite is converted at room temperature to achieve a phase transition of calcium tartrate to calcium sulfate and release of bound tartaric acid, and a tungstate solution for reuse in the main process can be obtained through desorption.

[0024] The technical solution in the embodiment of the present application is to solve the above-mentioned recycling difficulties, and the overall idea is as follows: like Figure 1 As shown, the decomposed slag is first prepared into slurry and then introduced into sulfuric acid for room temperature conversion. The core reaction is: C 4 H 4 CaO 6(s) +2H 2 O (aq) +H 2 SO 4(aq) →CaSO 4 ·2H 2 O (s) +C4 H 6 O 6(aq) , achieving the physical transformation of calcium tartrate to calcium sulfate and releasing bound tartaric acid. At the same time, the residual calcium tungstate (CaWO 4 ) reacts with free tartaric acid to form a secondary reaction: CaWO 4(s) +2C 4 H 6 O 6(aq) +4H 2 O=C 4 H 4 CaO 6 ·4H 2 O (S) +H 2 WO 4 (C 4 H 6 O 6 ), the newly generated calcium tartrate can further react with sulfuric acid to achieve deep leaching of tungsten. The solid-liquid separation is achieved through graded filtration and washing. After the conversion liquid is selectively adsorbed by D318 resin, it is desorbed to obtain a tungstate solution that can be directly reused in the main process. The adsorption residual liquid is rich in tartaric acid and returns to the initial decomposition process after concentration control, forming a complete material circulation system.

[0025] In order to better understand the above technical solution, the above technical solution is described in detail below with specific implementation methods.

[0026] Source of raw materials: tartaric acid decomposition residue of scheelite, which is mixed with multiple batches of washing residues produced by tartaric acid decomposition of scheelite at room temperature. After low-temperature drying and ball milling, the residue is prepared into dry powder samples for standby use. The sampling is tested by weight method. 3 The content is 0.91%. The decomposition slag was characterized by EDS, and the results are shown in Figure 2 .Depend on Figure 2 It can be seen that the distribution contents of O, C, Ca, W, Cl, S and Na elements in the decomposition slag are 59.83%, 22.38%, 16.74%, 0.97%, 0.07%, 0% and 0%, respectively.

[0027] Example 1: This example is a method for green conversion of tartaric acid decomposition residue of scheelite and efficient recovery of tartaric acid and tungsten, and the specific steps are as follows: S1. Prepare slurry: weigh 200g of the tartaric acid decomposition residue of scheelite, put it in a 2000ml glass beaker, add tap water at a liquid-solid ratio of 5:1mL / g, and stir to prepare slurry; S2, room temperature green conversion: sulfuric acid is gradually added to the slurry obtained in step S1, the conversion time is controlled to 6h, the stirring speed is 60r / min, the conversion temperature is room temperature (25°C, using a water bath to maintain temperature balance), when the sulfuric acid is added to the end point of the conversion process, the concentration of sulfate in the supernatant of the conversion slurry is 0.67mol / L, and the conversion slurry obtained after the conversion is completed enters the next step; S3, Filtration and washing: After step S2 is completed, the room temperature green conversion slurry is filtered and washed. First, the conversion slurry is filtered. After the filtration is completed, the obtained conversion concentrate is collected for use (after testing, the volume of the conversion concentrate is 945ml, WO 3 The concentration of tartaric acid was 1.85g / L and the concentration of tartaric acid was 113.90g / L). The conversion slag was washed twice. For the first washing, the amount of tap water was 5 times the weight of the original tartaric acid decomposition slag of the scheelite. The residual liquid of the first washing was collected and used for the next slurry preparation. For the second washing, the amount of tap water was 5 times the weight of the original tartaric acid decomposition slag of the scheelite. The residual liquid of the second washing was collected, part of which was used as the first washing water for the next filtration step, and part was collected for treatment. The final conversion slag was dried at 105℃ for 6h, and then weighed to 166.20g. The WO 3 The conversion slag was characterized by EDS. Figure 3 .Depend on Figure 3 It can be seen that the distribution contents of O, Ca, S, C, W, Cl, and Na in the conversion slag are 49.08%, 29.09%, 21.66%, 0.11%, 0.04%, and 0.02%, respectively. Compared with the distribution of elements in the tartaric acid decomposition slag of scheelite, the distribution content of C element is reduced from 22.38% to 0.11%, and the distribution content of W element is reduced from 0.97% to 0.04%. 3 The secondary dissolution rate is 95.43%, and the conversion rate of calcium tartaric acid is 99.59% calculated based on the C in the slag before and after conversion (calculation formula: WO 3 Secondary dissolution rate = (1- (0.05% × 166.20 ÷ 0.91% ÷ 200)) × 100%; conversion rate of tartaric acid = (1- (0.11% × 166.20 ÷ 22.38% ÷ 200)) × 100%); S4, resin adsorption recovery of tungsten: The conversion concentrate obtained in step S3 is subjected to dynamic adsorption using a simulated exchange column (the specification of the exchange column is φ2cm×70cm), the adsorption column is filled with D318 resin, the ratio of the diameter of the simulated column to the height of the resin layer is 1:6, the volume of the adsorption residual liquid is 936ml when the adsorption is completed, and the adsorption is stopped. The adsorption residual liquid containing tartaric acid is collected and entered into the next step. The loaded resin is desorbed, and the desorbent is a dilute ammonia solution with a concentration controlled at 100g / L. The ammonium tungstate solution obtained by desorption (tested, WO 3The concentration is 92.36g / L) and is collected and returned to the main tungsten smelting process; S5, secondary preparation and recycling: The adsorption residual liquid containing tartaric acid obtained in step S3 is placed in a dissolver and stirred for 30 minutes at a stirring speed of 120 r / min. 3 The amount of solid tartaric acid to be added is calculated (in this embodiment, 49.97 g of solid tartaric acid is required to be added based on the concentration of 165.0 g / L), and then a secondary dissolution preparation is performed. After the preparation, the final tartaric acid concentration is 164.12 g / L. The prepared tartaric acid solution is returned to the decomposition stage of the scheelite.

[0028] Example 2: This example is a method for green conversion of tartaric acid decomposition residue of scheelite and efficient recovery of tartaric acid and tungsten, and the specific steps are as follows: S1. Prepare slurry: weigh 200g of the tartaric acid decomposition residue of scheelite, put it in a 2000ml glass beaker, add tap water at a liquid-solid ratio of 6:1mL / g, and stir to prepare slurry; S2, room temperature green conversion: sulfuric acid is gradually added to the slurry obtained in step S1, the conversion time is controlled to 6h, the stirring speed is 80r / min, the conversion temperature is room temperature (25°C, using a water bath to maintain temperature balance), when sulfuric acid is added to the end of the conversion process, the concentration of sulfate in the supernatant of the conversion slurry is 0.58mol / L, and after the conversion is completed, the conversion slurry is obtained and enters the next step; S3, Filtration and washing: After step S2 is completed, the room temperature green conversion slurry is filtered and washed. First, the conversion slurry is filtered. After the filtration is completed, the obtained conversion concentrate is collected for use (after testing, the volume of the conversion concentrate is 1145ml, WO 3 The concentration of tartaric acid was 1.56g / L and the concentration of tartaric acid was 94.12g / L), and then washed twice. In the first washing, the amount of tap water was 6 times the weight of the original tartaric acid decomposition residue of the scheelite. The residual liquid of the first washing was collected and used for the next preparation of slurry. The amount of tap water was 6 times the weight of the original tartaric acid decomposition residue of the scheelite. The residual liquid of the second washing was collected, part of which was used as the first washing water of the next filtration step, and part of which was collected for treatment. The final conversion slag was dried at 105℃ for 6h, and then weighed to 167.30g. The WO 3 The conversion slag was characterized by EDS. Figure 4 .Depend on Figure 4It can be seen that the distribution contents of O, Ca, S, C, W, Cl, and Na in the conversion slag are 49.49%, 29.27%, 21.08%, 0.16%, 0%, 0%, and 0%, respectively. Compared with the distribution of elements in the tartaric acid decomposition slag of scheelite, the distribution content of C element is reduced from 22.38% to 0.16%, and the distribution content of W element is reduced from 0.97% to 0.01%. 3 The secondary dissolution rate is 99.08%, and the conversion rate of calcium tartaric acid is 99.40% according to the C in the slag before and after conversion (calculation formula: WO 3 Secondary dissolution rate = (1- (0.01% × 167.30 ÷ 0.91% ÷ 200)) × 100%; conversion rate of tartaric acid = (1- (0.16% × 167.30 ÷ 22.38% ÷ 200)) × 100%); S4, resin adsorption to recover tungsten, the conversion concentrate obtained in step S3 is dynamically adsorbed by a simulated exchange column (the exchange column specification is φ2cm×70cm), the adsorption column is filled with D318 resin, the ratio of the simulated column diameter to the resin layer height is 1:6, and the adsorption residual liquid volume is 1147ml when the adsorption is completed. The tartaric acid adsorption residual liquid is collected and entered the next step. The loaded resin is desorbed, and the desorbent is NaOH solution, the concentration is controlled to 80g / L, and the sodium tungstate solution (tested, WO 3 The concentration is 85.45g / L) and is collected and returned to the main tungsten smelting process; S5, secondary preparation and recycling: The tartaric acid adsorption residual liquid obtained in step S4 is placed in a dissolver and stirred for 25 minutes at a stirring speed of 100 r / min. 3 The amount of solid tartaric acid to be added is calculated (in this embodiment, 46.48 g of solid tartaric acid is required to be added based on the concentration of 135.0 g / L), and then a secondary dissolution preparation is performed. After the preparation is completed, the final tartaric acid concentration is 135.31 g / L. The prepared tartaric acid solution is returned to the decomposition stage of the scheelite.

[0029] Example 3: This example is a method for green conversion of tartaric acid decomposition residue of scheelite and efficient recovery of tartaric acid and tungsten, and the specific steps are as follows: S1. Prepare slurry: weigh 200g of the tartaric acid decomposition residue of scheelite, put it in a 2000ml glass beaker, add tap water at a liquid-solid ratio of 4:1mL / g, and stir to prepare slurry; S2, room temperature green conversion: sulfuric acid is gradually added to the slurry obtained in step S1, the conversion time is controlled to 5h, the stirring speed is 100r / min, the conversion temperature is room temperature (25°C, using a water bath to maintain temperature balance), when the sulfuric acid is added to the end point of the conversion process, the concentration of sulfate in the supernatant of the conversion slurry is 0.75mol / L, and after the conversion is completed, the conversion slurry is obtained and enters the next step; S3, Filtration and washing: After step S2 is completed, the room temperature green conversion slurry is filtered and washed. First, the conversion slurry is filtered. After the filtration is completed, the obtained conversion concentrate is collected for use (after testing, the volume of the conversion concentrate is 755ml, WO 3 The concentration of tap water was 2.36g / L, and the concentration of tartaric acid was 142.74g / L), and then washed twice. In the first washing, the amount of tap water was 4 times the weight of the original tartaric acid decomposition residue of the scheelite. The residual liquid of the first washing was collected and used for the next slurry preparation. In the second washing, the amount of tap water was 4 times the weight of the original tartaric acid decomposition residue of the scheelite. The residual liquid of the second washing was collected, part of which was used as the first washing water of the next filtration step, and part was collected for treatment. The final conversion slag was dried at 105℃ for 6h, and then weighed to 168.46g. The WO 3 The conversion slag was characterized by EDS. Figure 5 .Depend on Figure 5 It can be seen that the distribution contents of O, Ca, S, C, W, Cl, and Na in the conversion slag are 48.67%, 29.49%, 21.30%, 0.54%, 0%, 0%, and 0%, respectively. Compared with the distribution of elements in the decomposition slag, the distribution content of C element decreases from 22.38% to 0.54%, and the distribution content of W element decreases from 0.97% to 0.03%. 3 The secondary dissolution rate is 97.22%, and the conversion rate of calcium tartaric acid is 97.97% based on the C in the slag before and after conversion (calculation formula: WO 3 Secondary dissolution rate = (1- (0.03% × 168.46 ÷ 0.91% ÷ 200)) × 100%; conversion rate of tartaric acid = (1- (0.54% × 168.46 ÷ 22.38% ÷ 200)) × 100%); S4, resin adsorption recovery of tungsten: The conversion concentrate obtained in step S3 is dynamically adsorbed by a simulated exchange column (the exchange column specification is φ2cm×70cm), the adsorption column is filled with D318 resin, the ratio of the simulated column diameter to the resin layer height is 1:6, and the adsorption residual liquid volume is 746ml when the adsorption is completed. The tartaric acid adsorption residual liquid is collected and entered the next step. The loaded resin is desorbed, and the desorbent is NaOH solution, the concentration is controlled to be 100g / L, and the sodium tungstate solution obtained by desorption (tested, WO 3The concentration is 96.71g / L) and is collected and returned to the main tungsten smelting process; S5, secondary preparation and recycling: The tartaric acid adsorption residual liquid obtained in step S4 is placed in a dissolver and stirred for 20 minutes at a stirring speed of 80 r / min. 3 The amount of solid tartaric acid to be added is calculated (in this embodiment, 4.21 g of solid tartaric acid is required to be added based on the concentration of 145.0 g / L), and then a secondary dissolution preparation is performed. After the preparation, the final tartaric acid concentration is 144.89 g / L. The prepared tartaric acid solution is returned to the decomposition stage of the scheelite.

[0030] The above describes the main technical features and basic principles of the present invention and the related advantages. It is obvious to those skilled in the art that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the concept or basic features of the present invention. Therefore, no matter from which point of view, the above specific embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the attached claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims are included in the present invention.

[0031] In addition, it should be understood that although the present specification is described according to various implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation method may also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for green conversion of tartaric acid decomposition residue of scheelite and efficient recovery of tartaric acid and tungsten, characterized in that: The steps include: S1. Prepare slurry: put the tartaric acid decomposition residue of scheelite into a reactor, add tap water and stir to prepare slurry; S2, room temperature green conversion: gradually add sulfuric acid to the slurry obtained in step S1 and stir, the conversion temperature is 20°C to 35°C, after the conversion is completed, the conversion slurry is obtained, and the next step is entered; S3, filtration and washing: after step S2 is completed, the conversion pulp is filtered, the obtained conversion concentrate is collected for standby use, and the conversion slag is washed twice again. The residual liquid of the first washing is collected and used for the next slurry preparation, and the residual liquid of the second washing is collected, part of which is used as the first washing water of the next filtration step, and part is collected for treatment; S4, resin adsorption recovery of tungsten: The conversion concentrate obtained in step S3 is dynamically adsorbed by a simulated exchange column, and the residual liquid containing tartaric acid after adsorption is collected and sent to the next step, and the tungstate solution obtained by desorption of the loaded resin is collected and returned to the main tungsten smelting process; S5. Secondary preparation and recycling: the tartaric acid adsorption residual liquid obtained in step S4 is placed in a dissolver and stirred, and then a sample is taken to analyze the concentration of tartaric acid and calculate the amount of solid tartaric acid to be added, and a secondary dissolution preparation is performed, and the prepared tartaric acid solution is returned to the decomposition link of the scheelite.

2. The method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten according to claim 1 is characterized in that: In step S1, the liquid-to-solid ratio of tap water to tartaric acid decomposition slag of scheelite is 4:1 mL / g to 10:1 mL / g.

3. The method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten according to claim 1 is characterized in that: In step S2, the conversion time is 3 h to 6 h, and the stirring speed is 60 r / min to 120 r / min.

4. The method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten according to claim 1 is characterized in that: In step S2, when the concentration of sulfate in the supernatant of the slurry is ≥0.5 mol / L, the conversion is completed and the addition of sulfuric acid is stopped.

5. The method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten according to claim 1 is characterized in that: In step S3, the amount of tap water used for the first washing is 4 to 10 times the weight of the original tartaric acid decomposition residue of scheelite, and the amount of tap water used for the second washing is 4 to 10 times the weight of the original tartaric acid decomposition residue of scheelite.

6. The method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten according to claim 1 is characterized in that: In step S4, the adsorption column is filled with D318 resin, and the ratio of the diameter of the simulation column to the height of the resin layer is 1:6 to 1:

12.

7. The method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten according to claim 1 is characterized in that: In step S4, when WO3 in the adsorption residual solution is ≥ 0.01 g / L, the adsorption is stopped.

8. The method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten according to claim 1 is characterized in that: In step S4, the desorbent is NaOH solution or dilute ammonia solution, and the concentration is controlled to be 80 g / L to 100 g / L, and sodium tungstate solution or ammonium tungstate solution is obtained by desorption.

9. The method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten according to claim 1 is characterized in that: In step S5, stirring is performed for 10 min to 30 min, and the stirring speed is controlled to be 60 r / min to 120 r / min.

10. The method for green conversion of tartaric acid decomposition slag of scheelite and efficient recovery of tartaric acid and tungsten according to claim 1, characterized in that: In step S5, the concentration of tartaric acid prepared by secondary dissolution is controlled to be 120 g / L to 180 g / L.

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