CN120026190B - Method for efficiently recycling tartaric acid and tungsten through green conversion of scheelite tartaric acid decomposition residues - Google Patents
Method for efficiently recycling tartaric acid and tungsten through green conversion of scheelite tartaric acid decomposition residuesInfo
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- CN120026190B CN120026190B CN202510502055.0A CN202510502055A CN120026190B CN 120026190 B CN120026190 B CN 120026190B CN 202510502055 A CN202510502055 A CN 202510502055A CN 120026190 B CN120026190 B CN 120026190B
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- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B34/36—Obtaining tungsten
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
本发明属于钨的绿色冶炼和二次资源综合利用领域，具体涉及一种白钨矿酒石酸分解渣绿色转化高效回收酒石酸和钨的方法，该方法首先将白钨矿酒石酸分解渣制成浆料，其次加入硫酸进行常温绿色转化，将酒石酸钙转化为硫酸钙，同时释放出酒石酸，释放出的酒石酸与分解渣中残留的钨进行二次溶出，再进行过滤洗涤，实现固液分离，得到的固体为硫酸钙，可用于制备建筑材料，过滤浓料进行树脂吸附回收钨，得到钨酸钠溶液返回钨冶炼主流程，树脂吸附余液经过二次配制，作为白钨矿的浸出剂，实现酒石酸的循环利用。该方法实现了白钨矿酒石分解渣的绿色转化，同时高效回收了酒石酸和钨，为白钨矿酒石酸分解渣提供了一种绿色资源化利用的新方法。
The present invention belongs to the field of green smelting and comprehensive utilization of secondary resources of tungsten, and specifically relates to a method for green conversion of tartaric acid decomposition residue of scheelite to efficiently recover tartaric acid and tungsten. The method first prepares the tartaric acid decomposition residue of scheelite into a slurry, then adds sulfuric acid for room-temperature green conversion, converting calcium tartrate into calcium sulfate while releasing tartaric acid. The released tartaric acid and the tungsten remaining in the decomposition residue undergo secondary dissolution, followed by filtration and washing to achieve solid-liquid separation. The resulting solid is calcium sulfate, which can be used to prepare building materials. The concentrated material is filtered and subjected to resin adsorption to recover tungsten, resulting in a sodium tungstate solution that is returned to the main tungsten smelting process. The residual solution from the resin adsorption is then re-prepared as a leaching agent for scheelite, thereby achieving the recycling of tartaric acid. The method achieves green conversion of tartaric acid decomposition residue of scheelite while efficiently recovering tartaric acid and tungsten, providing a new method for green resource utilization of tartaric acid decomposition residue of scheelite.
Description
Technical Field
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 recycling tartaric acid and tungsten through green conversion of scheelite tartaric acid decomposition residues.
Background
Tungsten is used as a support material of a modern industrial system and plays an irreplaceable role in key fields of electronic component manufacturing, precise chemical synthesis, medical equipment production and the like.
Although the leaching extraction of tungsten element can be realized by the most widely used high-temperature alkaline pressure cooking process in the current industry, the inherent defects are highlighted in that the equipment corrosion rate is accelerated and the energy consumption intensity is increased due to the high-temperature high-pressure operation condition, and the generated alkaline leaching slag is difficult to realize recycling. In order to break through the bottleneck of the traditional process, the new technology of normal temperature decomposition of tartaric acid successfully realizes normal temperature dissociation of tungsten-calcium bonds in scheelite by introducing tartaric acid into an acidic medium. However, the process faces double technical barriers in industrialized popularization, namely that tartaric acid and calcium ions are combined to generate a stable calcium tartrate solid phase in the reaction process, so that the effective reaction reagent is not consumed unexpectedly, and the WO 3 still remains in the final decomposed slag for 0.3% -1.0% and is not extracted effectively.
If the scheelite tartaric acid decomposition slag is directly buried, not only tungsten-containing resources and organic reagents are wasted, but also potential ecological risks such as soil physicochemical property change and the like caused by slow decomposition of calcium tartrate in natural environment exist. The existing decomposed slag recovery technology system has the obvious problems that the strong acid leaching method aggravates equipment loss due to the adoption of high-concentration corrosive acid liquor, the high-temperature roasting method causes irreversible damage to the tartaric acid molecular structure and blocks the recycling path of the tartaric acid molecular structure while realizing tungsten recovery, the biological leaching technology is limited by the problems of poor adaptability of microorganism environment and the like, and the technical and economic bottlenecks of industrial application are not broken through yet.
The technical problem of green recovery of the scheelite tartaric acid decomposition slag is solved, and the overall economy and environmental friendliness of the tartaric acid decomposition process are directly improved. Therefore, constructing a high-efficiency and low-carbon decomposing slag resource utilization technology system has become an urgent need for promoting clean transformation of the tungsten metallurgy industry.
Disclosure of Invention
The invention provides a method for efficiently recycling tartaric acid and tungsten from green conversion of scheelite tartaric acid decomposition slag, which aims to solve the problems of green conversion of scheelite tartaric acid decomposition slag and efficient recycling of tartaric acid and tungsten in slag.
The embodiment of the invention provides a method for efficiently recycling tartaric acid and tungsten by green conversion of scheelite tartaric acid decomposition slag, which comprises the following steps:
S1, preparing slurry, namely placing scheelite tartaric acid decomposition slag into a reactor, adding tap water and stirring to prepare the slurry;
s2, performing normal-temperature green conversion, namely gradually adding sulfuric acid into the slurry obtained in the step S1, stirring, obtaining converted ore pulp after conversion is completed, and performing the next step;
S3, filtering and washing, namely filtering the converted ore pulp after the step S2 is completed, collecting the obtained converted concentrated material for standby, washing converted slag twice, collecting washing residual liquid for the first time for preparing the slurry for the next time, collecting washing residual liquid for the second time, taking part of washing residual liquid as first washing water for the next filtering link, and collecting and treating part of washing residual liquid;
S4, resin adsorption for recovering tungsten, namely dynamically adsorbing the converted concentrated material obtained in the step S3 by adopting a simulated exchange column, collecting residual adsorption liquid containing tartaric acid after adsorption, entering the next link, and collecting tungstate solution obtained by carrying out desorption on resin, and returning to a tungsten smelting main process;
S5, carrying out secondary preparation and recycling, namely placing the tartaric acid-containing adsorption residual liquid obtained in the step S4 into a dissolver for stirring, sampling and analyzing the concentration of tartaric acid, calculating the amount of solid tartaric acid to be added, carrying out secondary dissolution and preparation, and returning the prepared tartaric acid solution to a decomposing link of scheelite.
As the preference of some embodiments of the invention, in the step S1, the liquid-solid ratio of tap water to scheelite tartaric acid decomposition slag is 4:1mL/g to 10:1mL/g.
As the preference of some embodiments of the invention, in the step S2, the conversion time is 3-6 h, and the stirring speed is 60-120 r/min.
As a preference for some embodiments of the invention, in step S2, the conversion is completed and the addition of sulfuric acid is stopped when the concentration of sulfate radicals in the supernatant of the slurry is not less than 0.5 mol/L.
As the preference of some embodiments of the invention, in the step S3, the consumption of the first washing tap water is 4-10 times of the weight of the original scheelite tartaric acid decomposition slag, and the consumption of the second washing tap water is 4-10 times of the weight of the original scheelite tartaric acid decomposition slag.
As a preference of some embodiments of the present invention, in step S4, D318 resin is filled in the simulated exchange column, and the ratio of the diameter of the simulated exchange column to the height of the resin layer is 1:6-1:12.
As a preference for some embodiments of the invention, in step S4, the adsorption is stopped when WO 3. Gtoreq.0.01 g/L in the adsorption raffinate.
As the preference of some embodiments of the invention, in the step S4, the desorbing agent is NaOH solution or dilute ammonia water, the concentration is controlled to be 80 g/L-100 g/L, and the sodium tungstate solution or the ammonium tungstate solution is obtained through desorption.
As the preference of some embodiments of the invention, in the step S5, stirring is carried out for 10-30 min, and the stirring speed is controlled to be 60-120 r/min.
As the preference of some embodiments of the invention, in the step S5, the concentration of tartaric acid prepared by secondary dissolution is controlled to be 120 g/L-180 g/L.
Compared with the prior art, the invention has the beneficial effects that:
1. The method is environment-friendly and resource efficient and circulates, namely calcium tartrate in scheelite tartaric acid decomposition slag is converted into calcium sulfate (harmless byproducts can be directly used for building material production) through normal-temperature sulfuric acid conversion reaction, and simultaneously tartaric acid is released and residual tungsten is secondarily dissolved out, so that the efficient recovery of the tartaric acid and the tungsten is realized. The whole process has no intervention of high temperature and high pressure or harmful reagents, obviously reduces the waste emission and reduces the environmental burden.
2. The method has the advantages of economy and resource recycling, namely, a sectional washing residual liquid recycling technology is adopted, washing water and adsorption residual liquid are respectively used for slurry preparation, filtration and scheelite decomposition links, recycling of tartaric acid is realized, consumption of fresh reagents is greatly reduced, tungsten is accurately recovered by a resin adsorption method, and sodium tungstate or ammonium tungstate solution which can be returned to a smelting main process is directly obtained after desorption, so that the production cost is reduced, and the comprehensive utilization rate of resources is improved.
3. The process simplification and industrialization suitability are based on normal temperature reaction conditions and conventional equipment, the operation flow is simple, the energy consumption is low, and the complex high-energy consumption process is avoided. The secondary dissolution efficiency of tungsten in the converted slag is high, the conversion rate of calcium tartrate is nearly complete, the problem of conversion treatment of the scheelite tartaric acid decomposed slag is solved, the recovery of tartaric acid and residual tungsten in the decomposed slag is completed, the efficient recycling of the scheelite tartaric acid decomposed slag is realized, the technology is stable and easy to popularize in a large scale, and an efficient and sustainable solution is provided for scheelite green smelting.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for the description of the embodiments or the prior art will be briefly described, and it is apparent that the drawings in the following description are only one embodiment of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view of a process flow according to an embodiment of the present application;
FIG. 2 is a graph showing the EDS analysis results of the scheelite tartaric acid decomposition slag according to the example of the present application;
FIG. 3 is the EDS analysis result of the converted slag of example 1 of the present application;
FIG. 4 shows the EDS analysis result of the converted slag of example 2 of the present application;
FIG. 5 shows the EDS analysis of the converted slag of example 3 of the present application.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the present invention easy to understand, the technical solutions in the embodiments of the present invention are clearly and completely described below to further illustrate the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all versions.
According to the embodiment of the application, the method for efficiently recycling tartaric acid and tungsten through green conversion of scheelite tartaric acid decomposition slag solves the problems of waste landfill and difficult recycling of scheelite tartaric acid decomposition slag in the prior art, and the scheelite tartaric acid decomposition slag is subjected to normal-temperature conversion by constructing a slurry preparation-normal-temperature conversion-filtration separation-resin adsorption-recycling collaborative recycling system, so that the phase conversion of calcium tartrate to calcium sulfate and the release of combined tartaric acid are realized, and a tungstate solution with a main recycling flow can be obtained through desorption.
The technical scheme in the embodiment of the application aims to solve the problem of difficult recovery, and the general idea is as follows:
As shown in fig. 1, the decomposing slag is prepared by slurry and then is introduced into sulfuric acid for normal temperature conversion, and the core reaction is ：C4H4CaO6(s)+2H2O(aq)+H2SO4(aq)→CaSO4·2H2O(s)+C4H6O6(aq), to realize the phase conversion of calcium tartrate phase to calcium sulfate and release combined tartaric acid. Meanwhile, the residual calcium tungstate (CaWO 4) and free tartaric acid undergo secondary reaction ：CaWO4(s)+2C4H6O6(aq)+4H2O=C4H4CaO6·4H2O(S)+H2WO4(C4H6O6), to obtain newly generated calcium tartrate which can further react with sulfuric acid to realize deep leaching of tungsten. The solid-liquid high-efficiency separation is realized through fractional filtration and washing, and the tungstate solution which can be directly recycled in the main flow is obtained through desorption after the conversion solution is selectively adsorbed by D318 resin. The residual adsorption liquid is rich in tartaric acid, and returns to the initial decomposition process after concentration regulation, so that a complete substance circulation system is formed.
In order to better understand the above technical solution, the following detailed description will explain the above technical solution with specific embodiments.
The raw material source is scheelite tartaric acid decomposition slag, which is formed by mixing a plurality of batches of washing slag generated in the link of decomposing scheelite by tartaric acid at normal temperature, and the slag is prepared into a dry powder sample for standby after low-temperature drying and ball milling treatment, wherein the content of WO 3 in the decomposition slag is 0.91 percent by adopting a gravimetric method for detection. EDS characterization was performed on the decomposed slag, and the results are shown in FIG. 2. As can be seen from fig. 2, the distribution content of O, C, ca, W, cl, S, na elements in the decomposed slag was 59.83%, 22.38%, 16.74%, 0.97%, 0.07%, 0%, respectively.
Embodiment 1. The method for efficiently recovering tartaric acid and tungsten by green conversion of scheelite tartaric acid decomposition slag comprises the following specific steps:
S1, preparing slurry, namely weighing 200g of scheelite tartaric acid decomposition slag, placing the slag in a 2000ml glass beaker, adding tap water according to a liquid-solid ratio of 5:1mL/g, and stirring to prepare slurry;
s2, performing normal-temperature green conversion, namely gradually adding sulfuric acid into the slurry obtained in the step S1, controlling the conversion time to be 6h, controlling the stirring speed to be 60r/min, controlling the conversion temperature to be normal temperature (25 ℃, maintaining temperature balance by using a water bath), and when the sulfuric acid is added to the end point in the conversion process, converting the concentration of sulfate radical in the supernatant of the slurry to be 0.67mol/L, converting the obtained converted ore slurry, and entering the next step;
And S3, filtering and washing, namely filtering and washing the normal-temperature green conversion ore pulp after the step S2 is completed. Firstly, filtering the converted ore pulp, collecting the obtained converted concentrated material for later use (through detection, the volume of the converted concentrated material is 945ml, the concentration of WO 3 is 1.85g/L, the concentration of tartaric acid is 113.90 g/L), washing the converted slag twice, wherein the first washing is performed, the consumption of tap water is 5 times of the weight of the original scheelite tartaric acid decomposed slag, the first washing residual liquid is collected and used for preparing the slurry next time, the second washing is performed, the consumption of tap water is 5 times of the weight of the original scheelite tartaric acid decomposed slag, the second washing residual liquid is collected, and part of the washing residual liquid is used as the first washing water of the next filtering link, and part of washing residual liquid is collected and treated. The resulting conversion was dried at 105℃for 6h, then weighed 166.20g, analyzed for WO 3 to 0.05%, and EDS characterized as shown in FIG. 3. As can be seen from FIG. 3, the distribution content of O, ca, S, C, W, cl, na element in the converted slag was 49.08%, 29.09%, 21.66%, 0.11%, 0.04%, 0.02%, and 0%, respectively, and the distribution content of C element was reduced from 22.38% to 0.11% and the distribution content of W element was reduced from 0.97% to 0.04% as compared with the distribution content of element in the scheelite tartaric acid decomposed slag. The secondary dissolution rate of WO 3 was 95.43% by slag, and the calcium tartrate conversion rate was 99.59% by C in the slag before and after conversion (calculation formula: the secondary dissolution rate of WO 3 = (1- (0.05%. Times. 166.20. Times.0.91%. Times.200)). Times.100%); the conversion rate of tartaric acid = (1- (0.11%. Times. 166.20. Times.22.38%. Times.200)). Times.100%);
S4, absorbing and recycling tungsten by resin, namely dynamically absorbing the converted concentrated material obtained in the step S3 by adopting a simulated exchange column (the specification of the exchange column is phi 2cm multiplied by 70 cm), filling D318 resin into the adsorption column, wherein the ratio of the diameter of the simulated column to the height of the resin layer is 1:6, and stopping absorbing when the volume of residual liquid is 936 ml. And collecting the residual adsorption liquid containing tartaric acid to enter the next link. Desorbing the loaded resin, wherein the desorbing agent is a dilute ammonia water solution, the concentration is controlled to be 100g/L, and the ammonium tungstate solution (detected by WO 3 with the concentration of 92.36 g/L) obtained by desorption is collected and returned to the tungsten smelting main process;
S5, carrying out secondary preparation and recycling, namely placing the adsorption residual liquid containing the tartaric acid obtained in the step S3 in a dissolver, firstly stirring for 30min, controlling the stirring speed to be 120r/min, calculating the amount of the solid tartaric acid to be added according to the concentration of the tartaric acid (detected by WO 3 to be 0.001g/L and the concentration of the tartaric acid to be 111.61 g/L) (in the embodiment, calculating the concentration of the solid tartaric acid to be added to be 49.97g according to the concentration of 165.0 g/L), carrying out secondary dissolution and preparation, and returning the prepared tartaric acid solution to a decomposing link of scheelite after the preparation is finished, wherein the final concentration of the tartaric acid is 164.12 g/L.
Example 2 this example is a method for recycling tartaric acid and tungsten from scheelite tartaric acid decomposition slag by green conversion, comprising the following steps:
S1, preparing slurry, namely weighing 200g of scheelite tartaric acid decomposition slag, placing the slag in a 2000ml glass beaker, adding tap water according to a liquid-solid ratio of 6:1mL/g, and stirring to prepare slurry;
S2, performing normal-temperature green conversion, namely gradually adding sulfuric acid into the slurry obtained in the step S1, controlling the conversion time to be 6h, controlling the stirring speed to be 80r/min, controlling the conversion temperature to be normal temperature (25 ℃, maintaining temperature balance by using a water bath), and when the sulfuric acid is added to the end point in the conversion process, converting the concentration of sulfate radical in the supernatant of the slurry to be 0.58mol/L, obtaining converted ore pulp after the conversion is completed, and entering the next step;
And S3, filtering and washing, namely filtering and washing the normal-temperature green conversion ore pulp after the step S2 is completed. Firstly, filtering the converted ore pulp, collecting the obtained converted concentrated material for later use (through detection, the volume of the converted concentrated material is 1145ml, the concentration of WO 3 is 1.56g/L, the concentration of tartaric acid is 94.12 g/L), and then washing twice, wherein the first washing is performed, the consumption of tap water is 6 times of the weight of the original scheelite tartaric acid decomposed slag, the first washing residual liquid is collected and used for preparing the slurry for the next time, the second washing is performed, the consumption of tap water is 6 times of the weight of the original scheelite tartaric acid decomposed slag, the second washing residual liquid is collected, and part of the washing residual liquid is used as the first washing water of the next filtering link, and part of washing residual liquid is collected and treated. The resulting conversion was dried at 105℃for 6h, then weighed 167.30g, analyzed for WO 3 to 0.01%, and EDS characterized as shown in FIG. 4. As can be seen from fig. 4, the distribution content of O, ca, S, C, W, cl, na element in the converted slag was 49.49%, 29.27%, 21.08%, 0.16%, 0%, and 0%, respectively, and the distribution content of C element was reduced from 22.38% to 0.16% and the distribution content of W element was reduced from 0.97% to 0.01% as compared with the distribution content of element in the scheelite tartaric acid decomposed slag. The secondary dissolution rate of WO 3 is 99.08% based on slag, and the conversion rate of calcium tartrate is 99.40% based on C in slag before and after conversion (calculation formula: the secondary dissolution rate of WO 3 = (1- (0.01%. Times. 167.30. Times.0.91%. Times.200)). Times.100%). Times.the conversion rate of tartaric acid = (1- (0.16%. Times. 167.30%. Times.22.38%. Times.200)). Times.100%);
S4, absorbing and recycling tungsten by resin, wherein the converted concentrated material obtained in the step S3 is dynamically absorbed by adopting a simulated exchange column (the specification of the exchange column is phi 2cm multiplied by 70 cm), D318 resin is filled in the absorption column, the ratio of the diameter of the simulated column to the height of the resin layer is 1:6, and the volume of the absorption residual liquid is 1147ml when the absorption is finished. And collecting the residual adsorption liquid containing tartaric acid to enter the next link. Desorbing the loaded resin, wherein the desorbing agent is NaOH solution, the concentration is controlled to be 80g/L, and the sodium tungstate solution (detected, the concentration of WO 3 is 85.45 g/L) obtained by desorption is collected and returned to the tungsten smelting main process;
S5, carrying out secondary preparation and recycling, namely placing the tartaric acid-containing adsorption residual liquid obtained in the step S4 in a dissolver, firstly stirring for 25min, controlling the stirring speed to be 100r/min, calculating the amount of solid tartaric acid to be added according to the concentration of tartaric acid (detected, WO 3 is 0.001g/L, the concentration of tartaric acid is 94.48 g/L) (in the embodiment, the concentration of solid tartaric acid to be added is calculated to be 46.48g according to the preparation of 135.0 g/L), carrying out secondary dissolution preparation, and returning the prepared tartaric acid solution to a decomposing link of scheelite after the preparation is finished, wherein the final concentration of tartaric acid is 135.31 g/L.
Embodiment 3. The method for efficiently recovering tartaric acid and tungsten by green conversion of scheelite tartaric acid decomposition slag comprises the following specific steps:
S1, preparing slurry, namely weighing 200g of scheelite tartaric acid decomposition slag, placing the slag in a 2000ml glass beaker, adding tap water according to a liquid-solid ratio of 4:1ml/g, and stirring to prepare slurry;
S2, performing normal-temperature green conversion, namely gradually adding sulfuric acid into the slurry obtained in the step S1, controlling the conversion time to be 5h, controlling the stirring speed to be 100r/min, controlling the conversion temperature to be normal temperature (25 ℃, maintaining temperature balance by using a water bath), and when the sulfuric acid is added to the end point in the conversion process, converting the concentration of sulfate radical in the supernatant of the slurry to be 0.75mol/L, obtaining converted ore pulp after the conversion is completed, and entering the next step;
And S3, filtering and washing, namely filtering and washing the normal-temperature green conversion ore pulp after the step S2 is completed. Firstly, filtering the converted ore pulp, collecting the obtained converted concentrated material for later use (through detection, the volume of the converted concentrated material is 755ml, the concentration of WO 3 is 2.36g/L, the concentration of tartaric acid is 142.74 g/L), and then washing twice, wherein the first washing is performed, the consumption of tap water is 4 times of the weight of the original scheelite tartaric acid decomposition slag, the first washing residual liquid is collected and used for preparing the slurry next time, the second washing is performed, the consumption of tap water is 4 times of the weight of the original scheelite tartaric acid decomposition slag, the second washing residual liquid is collected, and part of the washing residual liquid is used as the first washing water of the next filtering link and part of washing treatment is performed. The resulting conversion was dried at 105℃for 6h, then weighed 168.46g, analyzed for WO 3 to 0.03%, and EDS characterized as shown in FIG. 5. As can be seen from FIG. 5, the distribution content of O, ca, S, C, W, cl, na elements in the converted slag was 48.67%, 29.49%, 21.30%, 0.54%, 0%, and 0%, respectively, and the distribution content of C elements was reduced from 22.38% to 0.54% and the distribution content of W elements was reduced from 0.97% to 0.03% as compared with the distribution content of elements in the decomposed slag. The secondary dissolution rate of WO 3 was 97.22% by slag, and the calcium tartrate conversion rate was 97.97% by C in the slag before and after conversion (calculation formula: the secondary dissolution rate of WO 3 = (1- (0.03%. Times. 168.46. Times.0.91%. Times.200)). Times.100%); the conversion rate of tartaric acid = (1- (0.54%. Times. 168.46. Times.22.38%. Times.200)). Times.100%);
S4, absorbing and recycling tungsten by resin, namely dynamically absorbing the converted concentrated material obtained in the step S3 by adopting a simulated exchange column (the specification of the exchange column is phi 2cm multiplied by 70 cm), filling D318 resin into the adsorption column, wherein the ratio of the diameter of the simulated column to the height of the resin layer is 1:6, and the volume of the residual liquid after absorption is 746ml. And collecting the residual adsorption liquid containing tartaric acid to enter the next link. Desorbing the loaded resin, wherein the desorbing agent is NaOH solution, the concentration is controlled to be 100g/L, and the sodium tungstate solution (the concentration of WO 3 is 96.71g/L through detection) obtained through desorption is collected and returned to the tungsten smelting main process;
S5, carrying out secondary preparation and recycling, namely placing the tartaric acid-containing adsorption residual liquid obtained in the step S4 into a dissolver, firstly stirring for 20min, controlling the stirring speed to be 80r/min, calculating the amount of solid tartaric acid to be added according to the concentration of tartaric acid (detected, WO 3 is 0.001g/L, the concentration of tartaric acid is 139.36 g/L) (in the embodiment, the concentration of the solid tartaric acid to be added is calculated to be 145.0 g/L), carrying out secondary dissolution and preparation, and returning the prepared tartaric acid solution to a decomposing link of scheelite after the preparation is finished, wherein the concentration of the final tartaric acid is 144.89 g/L.
Having described the main technical features and fundamental principles of the present invention and related advantages, it will be apparent to those skilled in the art that the present invention is not limited to the details of the above exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The above detailed description is, therefore, to be taken in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments in terms of various embodiments, not every embodiment is described in terms of a single embodiment, but rather that the descriptions of embodiments are merely provided for clarity, and that the descriptions of embodiments in terms of various embodiments are provided for persons skilled in the art on the basis of the description.
Claims (8)
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| CN108975376A (en) * | 2018-08-29 | 2018-12-11 | 厦门钨业股份有限公司 | A kind of method and device thereof of white tungsten slag comprehensive utilization of resources |
| CN114807634A (en) * | 2022-04-28 | 2022-07-29 | 湖北绿钨资源循环有限公司 | Method for separating and recovering tungsten from tungsten-containing solution |
| CN118773456A (en) * | 2024-09-11 | 2024-10-15 | 赣南科技学院 | A method for efficiently decomposing scheelite at room temperature |
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| CN103276208B (en) * | 2013-06-05 | 2015-07-29 | 中南大学 | A kind of method of decompose tunstite |
| CN105925822A (en) * | 2016-05-20 | 2016-09-07 | 中南大学 | Method for processing scheelite concentrate through sulfuric acid to prepare tungstate solution |
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| CN108975376A (en) * | 2018-08-29 | 2018-12-11 | 厦门钨业股份有限公司 | A kind of method and device thereof of white tungsten slag comprehensive utilization of resources |
| CN114807634A (en) * | 2022-04-28 | 2022-07-29 | 湖北绿钨资源循环有限公司 | Method for separating and recovering tungsten from tungsten-containing solution |
| CN118773456A (en) * | 2024-09-11 | 2024-10-15 | 赣南科技学院 | A method for efficiently decomposing scheelite at room temperature |
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