CN110980809A - Method for preparing ammonium metatungstate by utilizing tungsten-containing waste - Google Patents
Method for preparing ammonium metatungstate by utilizing tungsten-containing waste Download PDFInfo
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Abstract
The invention discloses a method for preparing ammonium metatungstate by utilizing tungsten-containing waste, which comprises the following steps: (1) mixing tungsten-containing waste with a magnesium-containing additive to obtain a mixture; (2) roasting the mixture to obtain a roasted material; (3) mixing the roasted material with an acid solution to obtain a solid-liquid mixture; (4) carrying out solid-liquid separation on the solid-liquid mixture so as to obtain a filtrate containing nickel and cobalt and a filter residue containing tungstic acid; (5) mixing the filter residue containing the tungstic acid with ammonia water to obtain an ammonium tungstate solution; (6) extracting or ion exchanging the ammonium tungstate solution to obtain an ammonium metatungstate solution; (7) and carrying out evaporative crystallization on the ammonium metatungstate solution so as to obtain the ammonium metatungstate. The method is adopted to convert tungsten resources in the tungsten-containing waste into high-value ammonium metatungstate, the recovery rate of tungsten is up to more than 95%, and the resource utilization of the tungsten-containing waste is realized.
Description
Technical Field
The invention belongs to the field of metallurgy, and particularly relates to a method for preparing ammonium metatungstate by utilizing tungsten-containing waste.
Background
The existing technology for treating tungsten waste comprises a zinc melting method, a saltpeter melting method and a roasting alkaline leaching method, wherein the zinc melting method is based on that zinc and binding phase metals (cobalt and nickel) in hard alloy can form low-melting-point alloy, so that the binding metals are separated from the hard alloy and form zinc-cobalt solid solution alloy liquid with the zinc, thereby destroying the structure of the hard alloy, enabling compact alloy to become loose hard phase framework, and enabling the zinc not to react with various refractory metal carbides, thereby achieving the purpose of recovering tungsten. However, the method is only suitable for processing hard alloy with cobalt content lower than 10%, and has high power consumption, high requirement on zinc steam recovery equipment and large zinc volatilization pollution. The method for smelting the saltpeter is to convert tungsten carbide in the tungsten waste into sodium tungstate at high temperature by using the saltpeter as an oxidant, and oxidize other impurity elements into metal oxides which are insoluble in water, thereby achieving the purpose of recovering tungsten. However, the method has long industrial process, the used raw and auxiliary materials are expensive, the production cost is high, and the discharged tail gas causes pollution to the environment; and the waste water produced in the subsequent APT production process is more, and the loss of raw and auxiliary materials is large. The roasting alkaline leaching method is characterized in that tungsten waste is converted into tungsten oxide through oxidation roasting, and the tungsten oxide is subjected to alkaline leaching reaction to generate sodium tungstate, so that the aim of tungsten recovery is fulfilled. However, in the treatment process of the method, the roasting equipment is seriously caked, the tungsten content in the slag is high, the recovery rate is low, and the treatment cost of the secondary slag is high; and APT is produced by the traditional metallurgical process subsequently, so that more waste water is produced in the production process, and the loss of raw and auxiliary materials is large.
Thus, the existing technology for treating tungsten waste is in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one object of the present invention is to provide a method for preparing ammonium metatungstate by using tungsten-containing waste, by which tungsten resources in the tungsten-containing waste are converted into high-value ammonium metatungstate, the recovery rate of tungsten is as high as more than 95%, and the resource utilization of the tungsten-containing waste is realized.
In one aspect of the invention, the invention provides a method for preparing ammonium metatungstate by using tungsten-containing waste. According to an embodiment of the invention, the method comprises:
(1) mixing tungsten-containing waste with a magnesium-containing additive to obtain a mixture;
(2) roasting the mixture to obtain a roasted material;
(3) mixing the roasted material with an acid solution to obtain a solid-liquid mixture;
(4) filtering the solid-liquid mixture to obtain a filtrate containing nickel and cobalt and a filter residue containing tungstic acid;
(5) mixing the filter residue containing the tungstic acid with ammonia water to obtain an ammonium tungstate solution;
(6) extracting or ion exchanging the ammonium tungstate solution to obtain an ammonium metatungstate solution;
(7) and carrying out evaporative crystallization on the ammonium metatungstate solution so as to obtain the ammonium metatungstate.
According to the method for preparing ammonium metatungstate by using the tungsten-containing waste, the tungsten-containing waste and a magnesium-containing additive are mixed and roasted, magnesium tungstate is generated by tungsten and tungsten carbide in the tungsten-containing waste and magnesium in the magnesium-containing additive at a high temperature, the obtained roasted material is mixed with acid liquor and then filtered, sodium tungstate solution is obtained by separation, then ammonium metatungstate solution is obtained by ion exchange after extraction, and finally ammonium metatungstate is obtained by evaporation and crystallization. Therefore, the method is adopted to convert the tungsten resources in the tungsten-containing waste materials into high-value ammonium metatungstate, the recovery rate of tungsten is up to more than 95%, and the resource utilization of the tungsten-containing waste materials is realized.
In addition, the method for preparing ammonium metatungstate by using tungsten-containing waste materials according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, in the step (1), the tungsten content of the tungsten-containing waste is 40-95% by mass, and the cobalt content is 0-20% by mass.
In some embodiments of the invention, in step (1), the magnesium-containing additive is at least one selected from basic magnesium carbonate, magnesium oxide, magnesium hydroxide, magnesium chloride and magnesium sulfate. Thereby, the tungsten recovery rate can be improved.
In some embodiments of the invention, in step (1), Mg and WO are present in the mix3The molar ratio is (1.1-4): 1. thereby, the tungsten recovery rate can be improved.
In some embodiments of the invention, in the step (2), the roasting temperature is 500-1000 ℃ for 1-24 h, preferably, the roasting temperature is 500-800 ℃ for 8-12 h. Thereby, the tungsten recovery rate can be improved.
In some embodiments of the invention, in step (3), the acid solution is at least one of hydrochloric acid, sulfuric acid and nitric acid. Thereby, the tungsten recovery rate can be improved.
In some embodiments of the invention, in step (3), H is in the solid-liquid mixture+With WO3The molar ratio is (2.5-6): 1. thereby, the tungsten recovery rate can be improved.
In some embodiments of the invention, in the step (3), the temperature of mixing the calcine and the acid solution is 60-120 ℃ and the time is 2-8 hours. Thereby, the tungsten recovery rate can be improved.
In some embodiments of the present invention, in the step (5), the initial ammonia concentration of the ammonia water is 120 to 180g/L, and the mixing temperature is 50 to 120 ℃. Thereby, the tungsten recovery rate can be improved.
In some embodiments of the present invention, in step (6), an extracting agent adopted in the extraction process is an organic extracting agent formed by mixing di (2-ethylhexyl) phosphate or tributyl phosphate and kerosene, the extracting is performed until the pH of an aqueous phase is 2-4, the aqueous phase is separated, and the aqueous phase is cooked to obtain an ammonium metatungstate solution. Thereby, the tungsten recovery rate can be improved.
In some embodiments of the invention, the ion exchange process employs H+And (3) contacting the type cation exchange resin with the ammonium tungstate solution until the pH value of the solution is 2-4, and removing the cation exchange resin in the solution to obtain an ammonium metatungstate solution. Thereby, the tungsten recovery rate can be improved.
In some embodiments of the present invention, in the step (7), the evaporative crystallization is performed under a vacuum degree of 0.01 to 0.03MPa, and the ammonium metatungstate obtained by the evaporative crystallization is 30 to 40% by volume of the ammonium tungstate solution. Thereby, the tungsten recovery rate can be improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow chart of a method for preparing ammonium metatungstate by using tungsten-containing waste according to an embodiment of the invention.
Detailed Description
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
In one aspect of the invention, a method of recovering tungsten from a tungsten-containing waste is presented. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing tungsten-containing waste with magnesium-containing additive
In the step, the tungsten-containing waste material and the magnesium-containing additive are mixed to obtain a mixture. Preferably, the magnesium-containing additive is at least one selected from basic magnesium carbonate, magnesium oxide, magnesium hydroxide, magnesium chloride and magnesium sulfate. Further, the mixing ratio of the tungsten-containing waste material and the magnesium-containing additive is such that Mg and WO are mixed in the mixture3The molar ratio is (1.1-4): 1 is true, for example (1.1, 1.2 … … 3.9.9, 4): 1. The inventors have found that if Mg and WO are used3The molar ratio is too low, and tungsten in the tungsten waste cannot be completely converted into magnesium tungstate; if the molar ratio of the two is too high, the dosage of the medicament is large, and the cost is high. Thereby adoptingThe mixing proportion can reduce the cost of the medicament while ensuring that tungsten in the tungsten waste is completely converted into magnesium tungstate. Specifically, the term "tungsten-containing waste" in the present application refers to a floor material, a dust collecting material, a grinding material, and a waste material produced in the production process of cemented carbide, and a soft waste material such as a floor material, a dust collecting material, and a waste material produced in the production process of tungsten carbide powder and tungsten powder. In a preferred embodiment of the present invention, the tungsten-containing waste material mainly comprises: the mass content of tungsten is 40-95%, the mass content of cobalt is 0-20%, and the tungsten powder also contains a small amount of other impurity elements such as Fe, Cu, Ni, C, Ta, Ti, Nb, Cr, V, K, Na, Mo and SiO2And the like. The above-mentioned contents of elements are only necessary for satisfying disclosure, and do not limit the scheme itself, and the method provided by the present invention is applicable to tungsten-containing waste materials obtained by commercially available and conventional processing methods.
S200: roasting the mixture
In the step, the mixture obtained in the step is roasted, so that tungsten and tungsten carbide in the tungsten-containing waste material react with magnesium in the magnesium-containing additive to generate magnesium tungstate, and the roasted material containing magnesium tungstate is obtained. Further, the roasting temperature is 500-1000 ℃, such as 510 ℃, 520 ℃, … … 990 ℃, 1000 ℃, and the time is 1-24 h, such as 1h, 1.1h … … 23.9.9 h, and 24 h. The inventor finds that if the roasting temperature is too low, tungsten in the tungsten waste cannot be completely converted into magnesium tungstate, and if the roasting temperature is too high, overburning is easy to occur, thus causing furnace sintering, and the energy consumption and the cost are high; meanwhile, the roasting time is too short, tungsten in the tungsten waste cannot be completely converted into magnesium tungstate, and if the roasting time is too long, the energy consumption is high and the cost is high. Therefore, the roasting condition can ensure that the tungsten in the tungsten waste is completely converted into the magnesium tungstate and simultaneously reduce the energy consumption. Preferably, the roasting temperature is 500-800 ℃, and the roasting time is 8-12 h.
S300: mixing the roasting material with acid liquor
In the step, the obtained roasting material is mixed with an acid solution, and magnesium tungstate in the roasting material reacts with the acid solution to obtain tungstic acid, namely a solid-liquid mixture containing tungstic acid and nickel cobalt. Preferably, the acid solution is selected from hydrochloric acid,At least one of sulfuric acid and nitric acid, and further, the mixing ratio of the calcine and the acid solution is such that H is contained in the obtained solid-liquid mixture+With WO3The molar ratio is (2.5-6): 1 is standard, for example (2.5, 2.6 … … 5.9.9, 6): 1. The inventors have found that if H+With WO3The molar ratio is too low to be completely converted into tungstic acid, and the decomposition rate is low; if the molar ratio of the two is too high, the dosage of the medicament is large, and the production cost is high. Therefore, the mixing proportion can improve the tungstic acid conversion rate and reduce the cost of the medicament. Preferably, the temperature for mixing the roasted material and the acid solution is 60-120 ℃, for example 60 ℃, 61 ℃, … … 119 ℃ and 120 ℃, and the time is 2-8 h, for example 2h, 2.1h … … 7.9.9 h and 8 h. The inventor finds that if the mixing temperature is too low, the tungsten content of the slag is high, the decomposition rate is low, and if the mixing temperature is too high, the energy consumption is high, and the cost is high; meanwhile, the mixing time is too short, the tungsten content in the slag is high, the decomposition rate is low, and if the mixing time is too long, the energy consumption is high and the cost is high. Therefore, the mixing condition can reduce the tungsten content in the slag and simultaneously reduce the cost.
S400: carrying out solid-liquid separation on the solid-liquid mixture
In the step, the obtained solid-liquid mixture containing the tungstic acid and the nickel cobalt is subjected to solid-liquid separation to obtain filtrate containing the cobalt and the nickel and filter residue containing the tungstic acid. Specifically, the solid-liquid separation apparatus used in the solid-liquid separation treatment is not particularly limited as long as it can separate a solid phase from a liquid phase.
S500: mixing the filter residue containing tungstic acid with ammonia water
In the step, the filter residue containing the tungstic acid is mixed with ammonia water, so that the tungstic acid reacts with the ammonia water to obtain ammonium tungstate, and an ammonium tungstate solution is obtained. Preferably, the initial ammonia concentration of the ammonia water is 120-180 g/L, such as 120g/L, 125g/L … … 175g/L and 180g/L, the mixing temperature is 50-120 ℃, such as 50 ℃, 51 ℃, … … 119 ℃ and 120 ℃, the inventor finds that if the initial ammonia concentration is too high, the dosage of the medicament is large, the cost is high, and if the initial ammonia concentration is too low, the tungsten content in the slag is high, and the decomposition rate is low; meanwhile, if the mixing temperature is too high, the energy consumption is high, the cost is high, and if the temperature is too low, the tungsten content in the slag is high, and the decomposition rate is low; in addition, if the concentration of the residual ammonia is too high, the dosage of the medicament is large, the energy consumption is high, and if the concentration of the residual ammonia is too low, the tungsten content in the slag is high, and the decomposition rate is low. Specifically, along with the reaction, strong ammonia water is added when the residual ammonia is less than 70g/L until the solution is basically clear, the ammonium tungstate solution is obtained through filtration and brine-free washing, the ammonium tungstate solution in residual trace slag can be washed cleanly through washing, and the recovery rate is improved.
S600: extracting or ion-exchanging the ammonium tungstate solution
In the step, the obtained ammonium tungstate solution is subjected to extraction or ion exchange to obtain an ammonium metatungstate solution. Specifically, an extracting agent adopted in the extraction process is an organic extracting agent formed by mixing di (2-ethylhexyl) phosphate or tributyl phosphate and kerosene, the extracting is carried out until the pH value of a water phase is 2-4, the water phase is separated, and the water phase is steamed and boiled to obtain an ammonium metatungstate solution; ion exchange process using H+And (3) contacting the type cation exchange resin with an ammonium tungstate solution until the pH value of the solution is 2-4, and removing the cation exchange resin in the solution to obtain an ammonium metatungstate solution.
S700: evaporating and crystallizing the ammonium metatungstate solution
In the step, the obtained ammonium metatungstate solution is evaporated and crystallized so as to obtain ammonium metatungstate. Preferably, the evaporative crystallization is performed under a vacuum degree of 0.01 to 0.03MPa, for example, 0.01MPa, 0.02MPa, 0.03MPa, and the volume of the ammonium metatungstate obtained by evaporative crystallization is 30 to 40% of the volume of the ammonium tungstate solution. It should be noted that conditions such as the temperature for evaporative crystallization are conventional operations in the art, and those skilled in the art can select the conditions according to actual needs, which are not described herein again.
According to the method for preparing ammonium metatungstate by using the tungsten-containing waste, the tungsten-containing waste and a magnesium-containing additive are mixed and roasted, magnesium tungstate is generated by tungsten and tungsten carbide in the tungsten-containing waste and magnesium in the magnesium-containing additive at a high temperature, the obtained roasted material is mixed with acid liquor and then filtered, sodium tungstate solution is obtained by separation, then ammonium metatungstate solution is obtained by ion exchange after extraction, and finally ammonium metatungstate is obtained by evaporation and crystallization. Therefore, the method is adopted to convert the tungsten resources in the tungsten-containing waste materials into high-value ammonium metatungstate, the recovery rate of tungsten is up to more than 95%, and the resource utilization of the tungsten-containing waste materials is realized.
The present invention will be described in detail below by way of examples. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) Taking 20g of tungsten-containing waste (the tungsten content is 40wt percent and the cobalt content is 20 percent), adding basic magnesium carbonate, and uniformly mixing to obtain Mg and WO in the mixture3Is 1.1;
(2) roasting the mixture at 500 ℃ for 1h to obtain a roasted material;
(3) mixing the roasted material with hydrochloric acid solution according to the formula H+With WO3The molar ratio of the components is 2.5, and the mixture reacts for 2 hours at the temperature of 60 ℃ to obtain a solid-liquid mixture;
(4) filtering the solid-liquid mixture, washing the filter residue for three times by heated non-saline water to obtain filtrate containing cobalt and nickel and filter residue containing tungstic acid;
(5) drying the tungstic acid, adding the tungstic acid into ammonia water, reacting at 50 ℃, supplementing concentrated ammonia water when the concentration of initial ammonia is 120g/L and the concentration of residual ammonia is less than 70g/L until the solution is basically clarified, and filtering and washing without brine to obtain an ammonium tungstate solution;
(6) extracting with organic relative ammonium tungstate solution of tributyl phosphate and kerosene (volume mixing ratio of tributyl phosphate and kerosene is 10:1) to obtain NH4+Adding into organic phase, controlling pH of liquid phase at 3, and steaming liquid phase at 98 deg.C for 5 hr to obtain ammonium metatungstate solution;
(7) and concentrating the ammonium metatungstate solution to 30% of the initial feed liquid by concentration under the vacuum degree of 0.01MPa, and collecting crystals, namely AMT (ammonium metatungstate), wherein the recovery rate of tungsten is 95.3%.
Example 2
(1) Taking 20g of tungsten-containing waste (the tungsten content is 55wt percent, the cobalt content is 15 percent), adding magnesium oxide, and uniformly mixing to obtain Mg and WO in the mixture3Is 1.5;
(2) roasting the mixture at the temperature of 600 ℃ for 4 hours to obtain a roasted material;
(3) mixing the roasted material with sulfuric acid solution according to the formula H+With WO3The molar ratio of (1) is 4, and the mixture reacts for 4 hours at the temperature of 80 ℃ to obtain a solid-liquid mixture;
(4) filtering the solid-liquid mixture, washing the filter residue for three times by heated non-saline water to obtain filtrate containing cobalt and nickel and filter residue containing tungstic acid;
(5) drying the tungstic acid, adding the tungstic acid into ammonia water, reacting at 70 ℃, supplementing concentrated ammonia water when the concentration of initial ammonia is 140g/L and the concentration of residual ammonia is less than 70g/L until the solution is basically clarified, and filtering and washing without brine to obtain an ammonium tungstate solution;
(6) extracting with organic ammonium tungstate solution containing mixture of di (2-ethylhexyl) phosphate and kerosene (volume ratio of di (2-ethylhexyl) phosphate to kerosene is 10:1), and extracting with NH4+Adding into organic phase, controlling pH of liquid phase at 3.7, and steaming liquid phase at 98 deg.C for 4.5 hr to obtain ammonium metatungstate solution;
(7) and concentrating the ammonium metatungstate solution to 40% of the initial feed liquid by concentration under the vacuum degree of 0.02MPa, and collecting crystals, namely AMT (ammonium metatungstate), wherein the recovery rate of tungsten is 95.9%.
Example 3
(1) Taking 20g of tungsten-containing waste (the tungsten content is 65wt percent and the cobalt content is 10 percent), adding magnesium hydroxide, and uniformly mixing to obtain Mg and WO in the mixture3Is 2;
(2) roasting the mixture at 800 ℃ for 8h to obtain a roasted material;
(3) mixing the roasted material with nitric acid solution according to the formula H+With WO3The molar ratio of 6, reacting for 8 hours at 120 ℃ to obtain a solid-liquid mixture;
(4) filtering the solid-liquid mixture, washing the filter residue for three times by heated non-saline water to obtain filtrate containing cobalt and nickel and filter residue containing tungstic acid;
(5) drying the tungstic acid, adding the tungstic acid into ammonia water, reacting at 120 ℃, supplementing concentrated ammonia water when the concentration of initial ammonia is 180g/L and the concentration of residual ammonia is less than 70g/L until the solution is basically clarified, and filtering and washing without brine to obtain an ammonium tungstate solution;
(6) enabling the ammonium tungstate solution to flow through 001 × 7 strong acid type cation exchange resin, controlling the pH value of the effluent solution to be 3, and cooking the solution at 100 ℃ for 6 hours to prepare an ammonium metatungstate solution;
(7) and concentrating the ammonium metatungstate solution to 36.8% of the initial feed liquid by concentration under the vacuum degree of 0.03MPa, and collecting crystals, namely AMT (ammonium metatungstate), wherein the recovery rate of tungsten is 96.1%.
Example 4
(1) Taking 20g of tungsten-containing waste (the tungsten content is 80wt percent, the cobalt content is 5 percent), adding magnesium chloride, and uniformly mixing to obtain Mg and WO in the mixture3Is 3;
(2) roasting the mixture at 1000 ℃ for 12h to obtain a roasted material;
(3) mixing the roasted material with hydrochloric acid solution according to the formula H+With WO3The molar ratio of 5, reacting for 6 hours at 100 ℃ to obtain a solid-liquid mixture;
(4) filtering the solid-liquid mixture, washing the filter residue for three times by heated non-saline water to obtain filtrate containing cobalt and nickel and filter residue containing tungstic acid;
(5) drying the tungstic acid, adding the tungstic acid into ammonia water, reacting at 100 ℃, supplementing concentrated ammonia water when the concentration of initial ammonia is 160g/L and the concentration of residual ammonia is less than 70g/L until the solution is basically clarified, and filtering and washing without brine to obtain an ammonium tungstate solution;
(6) extracting with organic relative ammonium tungstate solution of tributyl phosphate and kerosene (volume mixing ratio of tributyl phosphate and kerosene is 10:1) to obtain NH4+Adding into organic phase, controlling pH of liquid phase at 3.5, and steaming liquid phase at 96 deg.C for 4 hr to obtain ammonium metatungstate solution;
(7) and concentrating the ammonium metatungstate solution to 34.6% of the initial feed liquid by concentration under the vacuum degree of 0.02MPa, and collecting crystals, namely AMT (ammonium metatungstate), wherein the recovery rate of tungsten is 96.5%.
Example 5
(1) Taking tungsten-containing waste (tungsten content 95 wt%, cobalt content)0%) of the magnesium sulfate, adding the magnesium sulfate, and uniformly mixing to obtain Mg and WO in the mixture3Is 4;
(2) roasting the mixture for 18 hours at the temperature of 900 ℃ to obtain a roasted material;
(3) mixing the roasted material with hydrochloric acid solution according to the formula H+With WO3The molar ratio of 6, reacting for 7 hours at 80 ℃ to obtain a solid-liquid mixture;
(4) filtering the solid-liquid mixture, washing the filter residue for three times by heated non-saline water to obtain filtrate containing cobalt and nickel and filter residue containing tungstic acid;
(5) drying the tungstic acid, adding the tungstic acid into ammonia water, reacting at 90 ℃, supplementing concentrated ammonia water when the concentration of initial ammonia is 150g/L and the concentration of residual ammonia is less than 70g/L until the solution is basically clarified, and filtering and washing without brine to obtain an ammonium tungstate solution;
(6) allowing the ammonium tungstate solution to flow through 001 × 7 strong acid type cation exchange resin, controlling the pH value of the effluent solution to be 3.2, and cooking the solution at 93 ℃ for 5.5 hours to obtain an ammonium metatungstate solution;
(7) and concentrating the ammonium metatungstate solution to 35.7% of the initial feed liquid by concentration under the vacuum degree of 0.02MPa, and collecting crystals, namely AMT (ammonium metatungstate), wherein the recovery rate of tungsten is 95.8%.
Comparative example 1
The difference from example 1 is that the Mg mixture is mixed with WO3Is 0.4, the final tungsten recovery is only 65.4%.
Comparative example 2
The difference from example 2 is that the calcination temperature is 200 ℃ and the final tungsten recovery is only 48.5%.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for preparing ammonium metatungstate by utilizing tungsten-containing waste is characterized by comprising the following steps:
(1) mixing tungsten-containing waste with a magnesium-containing additive to obtain a mixture;
(2) roasting the mixture to obtain a roasted material;
(3) mixing the roasted material with an acid solution to obtain a solid-liquid mixture;
(4) carrying out solid-liquid separation on the solid-liquid mixture so as to obtain a filtrate containing nickel and cobalt and a filter residue containing tungstic acid;
(5) mixing the filter residue containing the tungstic acid with ammonia water to obtain an ammonium tungstate solution;
(6) extracting or ion exchanging the ammonium tungstate solution to obtain an ammonium metatungstate solution;
(7) and carrying out evaporative crystallization on the ammonium metatungstate solution so as to obtain the ammonium metatungstate.
2. The method according to claim 1, wherein in the step (1), the tungsten content of the tungsten-containing waste is 40-95% by mass, and the cobalt content is 0-20% by mass.
3. The method according to claim 1 or 2, wherein in step (1), the magnesium-containing additive is at least one selected from basic magnesium carbonate, magnesium oxide, magnesium hydroxide, magnesium chloride and magnesium sulfate.
4. The method according to claim 3, wherein in step (1), Mg and WO are present in the mix3The molar ratio is (1.1-4): 1.
5. the method of claim 1, wherein in the step (2), the roasting temperature is 500-1000 ℃ and the roasting time is 1-24 h, preferably, the roasting temperature is 500-800 ℃ and the roasting time is 8-12 h.
6. The method according to claim 1, wherein in step (3), the acid solution is at least one of hydrochloric acid, sulfuric acid and nitric acid;
optionally, in step (3), H is in the solid-liquid mixture+With WO3The molar ratio is (2.5-6): 1.
7. a process according to claim 6, wherein in step (3), the calcine is mixed with the acid liquor at a temperature of 60 to 120 ℃ for 2 to 8 hours.
8. The method according to claim 1, wherein in the step (5), the initial ammonia concentration of the aqueous ammonia is 120 to 180g/L, and the mixing temperature is 50 to 120 ℃.
9. The method according to claim 1, wherein in the step (6), an extracting agent adopted in the extraction process is an organic extracting agent formed by mixing di (2-ethylhexyl) phosphate or tributyl phosphate and kerosene, the extracting is carried out until the pH value of an aqueous phase is 2-4, the aqueous phase is separated, and the aqueous phase is steamed to obtain an ammonium metatungstate solution;
optionally, the ion exchange process employs H+And (3) contacting the type cation exchange resin with the ammonium tungstate solution until the pH value of the solution is 2-4, and removing the cation exchange resin in the solution to obtain an ammonium metatungstate solution.
10. The method according to claim 1, wherein in the step (7), the evaporative crystallization is performed under a vacuum degree of 0.01 to 0.03MPa, and the ammonium metatungstate obtained by the evaporative crystallization is 30 to 40% by volume of the ammonium tungstate solution.
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