CN114622106B - Method for recycling tungsten in tungsten-containing waste by chloridizing roasting method - Google Patents
Method for recycling tungsten in tungsten-containing waste by chloridizing roasting method Download PDFInfo
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Abstract
The invention relates to a method for recycling tungsten in tungsten-containing waste by using a chloridizing roasting method, which aims to solve the problems of long process flow, complex separation method, low recovery rate, high equipment requirement, high energy consumption and the like in the existing various tungsten-containing waste recycling treatment technologies. The invention adopts the solid chlorinating agent and combines the low-temperature roasting technology, thereby avoiding the need of introducing chlorine with high price and strong toxicity in the traditional chloridizing roasting method, having lower roasting temperature and reducing energy consumption. The invention also effectively removes impurities contained in the crude sodium tungstate solution by adjusting the dosage and the types of the solid chlorinating agent and the additive, the roasting process parameters and the pH value of the alkali liquor, improves the quality of the sodium tungstate solution, and ensures that the recovery rate of tungsten exceeds 95 percent. The method has the advantages of short process flow, simple method, high separation efficiency, high tungsten recovery rate, high purity and wide application market prospect.
Description
Technical Field
The invention belongs to the field of recycling industrial solid wastes, and particularly relates to a novel technology for recycling tungsten in tungsten-containing waste by using a chloridizing roasting method.
Background
Tungsten is an important resource and is known as an "industrial tooth". Currently, the global tungsten supply is mainly composed of two parts, one part is a new tungsten concentrate supply, which accounts for about 76% of the total tungsten supply, 66% of which enters the final tungsten product, and 10% is produced as scrap in the production process. The other part is from the recycling of tungsten secondary resources, namely the recycling of solid waste residues and end consumer product wastes in the tungsten production process, such as waste hard alloy, tungsten material, alloy steel, tungsten contact materials, chemical catalysts and the like, and the part accounts for about 24 percent. Tungsten waste includes two major categories: one type is the processing residue of tungsten and tungsten alloy materials, such as sintered rod end material (crop head), tungsten carbide workshop ground garbage, grinding residue, metal scale, cutting fragments and the like. The other is worn, worn out or discarded tungsten-containing materials, such as discarded tungsten carbide cutters and spent catalysts. Tungsten waste is a secondary tungsten resource, and the recycling of the tungsten waste has extremely high economic value.
With the continuous development of tungsten industry, the consumption of metal tungsten raw materials is larger and the available resources are smaller, so that the recycling of tungsten is attracting attention of various governments, in addition, in the tungsten industry at present, an important sign for measuring the technology, scale and comprehensive competitiveness of a tungsten enterprise is whether the enterprise can recycle secondary tungsten resources in an environment-friendly way, and compared with tungsten concentrate, the tungsten recycling is high in tungsten content and easy to recycle, so that the recycling of tungsten is an attention point of the tungsten industry. The hard alloy industry is a type of industry which highly depends on resources, the resources have great influence on the development of the hard alloy industry, the recycling cost of tungsten-containing waste is lower than the tungsten ore smelting processing cost, and the recycling economy and the recycling technology become the current hot spots. Tungsten and cobalt are recycled by taking tungsten-containing waste as raw materials through a reasonable regeneration treatment process, so that energy sources can be saved, the smelting process flow is shortened, the production cost is reduced, the environmental pollution is lightened, the exploitation and utilization of primary mineral resources can be further reduced, and the method has very important positive significance from the aspects of comprehensive analysis in ecological, economic and sustainable development and the like.
At present, although a large number of scientific researchers do a large amount of work for recycling tungsten secondary resources, the recycling treatment difficulty of tungsten-containing waste still faces great difficulty because tungsten waste has complex and various components and existence states of tungsten are difficult to determine. Along with the continuous improvement of the recycling rate of tungsten secondary resources in various countries, the recycling technology of tungsten resources is also continuously increased, and the existing recycling treatment technology of tungsten-containing waste materials at home and abroad mainly comprises the following steps: zinc smelting, niter smelting, acid leaching, alkaline leaching, electrochemical, in-situ oxidation-reduction carbonization, etc., and these resource recycling techniques have certain advantages and disadvantages. The zinc melting method is based on that zinc and binding phase metals (cobalt and nickel) in the hard alloy can form low-melting-point alloy, so that the binding metal is separated from the hard alloy and forms zinc-cobalt solid solution alloy liquid with zinc, thereby destroying the structure of the hard alloy, and the compact alloy becomes a loose hard phase framework, and zinc cannot react with various refractory metal carbides, so that the aim of recovering tungsten is fulfilled. However, the method is only suitable for processing hard alloy with cobalt content lower than 10%, and has high electricity consumption, high requirement on zinc vapor recovery equipment and large zinc volatilization pollution. In addition, the zinc melting method is easy to introduce impurities, has low recovery rate and is not suitable for treating powder waste. The nitrate smelting method uses nitrate as oxidant to convert tungsten carbide in tungsten waste into sodium tungstate at high temperature, and other impurity elements are oxidized into metal oxide which is insoluble in water, so as to achieve the purpose of recovering tungsten. However, the method has long industrial flow, expensive raw and auxiliary materials, high production cost and environmental pollution caused by the discharged tail gas; and more waste water is generated in the subsequent APT production process, and the loss of raw and auxiliary materials is large. In addition, the recovery rate of the nitrate melting method is low and the cost is high. The roasting alkaline leaching method is that tungsten waste is converted into tungsten oxide through oxidation roasting, and sodium tungstate is generated through alkaline leaching reaction of the tungsten oxide, so that the purpose of recovering tungsten is achieved. However, in the treatment process of the method, the roasting equipment has serious furnace junction, the tungsten content of the slag is high, the recovery rate is low, and the secondary slag treatment cost is high; and APT is produced by the traditional metallurgical process in the subsequent process, so that more waste water is produced in the production process, and the loss of raw and auxiliary materials is large. The subsequent regeneration flow of the acid leaching method is longer, harmful gas can be generated, and the cost is higher; the electrochemical method is only suitable for treating waste hard alloy with Co content more than 8% (mass fraction), namely the treatment range is limited; the in-situ oxidation-reduction carbonization method has the problems of insufficient powder purity, substandard alloy performance and the like. It can be seen that there are still a number of problems with the prior art techniques for recovering tungsten from tungsten-containing waste materials, and further research and improvement are needed.
In addition, the regenerated tungsten industry in China starts late, and the recycling of waste tungsten is relatively low. The tungsten secondary resource recovery surface of China is relatively narrow, the tungsten secondary resource recovery surface is mainly concentrated in the aspects of hard alloy and chemical catalysts, the recycling field is mainly concentrated in the fields of alloy and sodium tungstate, and certain recovery methods cause serious secondary environmental pollution, so that the recycling of tungsten resources is important in China from the aspects of protecting environment and efficiently utilizing resources, the research on low-cost, high-quality, high-grade and high-purity tungsten recovery technology is enhanced, the comprehensive recovery rate of tungsten and valuable metal elements is improved, and the resource advantage is changed into technical advantage.
In view of the problems of the existing process technology for recovering tungsten components from tungsten-containing waste, there is an urgent need to develop a method for regenerating and treating tungsten-containing waste, which has the advantages of short process, high efficiency, cleanliness and low cost, so as to achieve the purpose of high-efficiency utilization of solid waste resources.
Disclosure of Invention
In order to solve the problems of long process flow, complex separation method, low recovery rate, high equipment requirement, high energy consumption and the like in various tungsten-containing waste regeneration treatment technologies in the prior art, the invention provides a novel method for recovering tungsten in tungsten-containing waste by using a chloridizing roasting method.
In one aspect of the invention, the invention provides a method for recycling tungsten in tungsten-containing waste by using a chloridizing roasting method, comprising the following steps:
s1: uniformly mixing tungsten-containing waste with a solid chlorinating agent and an additive to obtain a mixture;
s2: chloridizing and roasting the mixture obtained in the step S1 under the condition of introducing air or oxygen;
s3: introducing the gas phase product volatilized in the chloridizing roasting process in the step S2 into alkali liquor for collection, controlling the pH value of the alkali liquor properly, and filtering to obtain sodium tungstate solution; while the cobalt, iron and other components in the tungsten-containing waste are remained in the roasting slag.
Further, the method comprises the following step S1The tungsten waste material is powder tungsten-containing waste material such as floor material, dust collecting material, grinding material and waste material generated in the production process of the hard alloy; the tungsten-containing waste mainly comprises the following components: the tungsten content is 40-95% by mass, the cobalt content is 2-20% by mass, and the alloy also contains a small amount of other impurity elements such as Fe, cu, C, cr, siO 2 Ni, V, etc.
Further, the solid chlorinating agent in the step S1 is at least one of sodium chloride, calcium chloride, magnesium chloride, ferric chloride and aluminum chloride.
Further, the additive in the step S1 is at least one of silica and alumina.
Further, the proportion of ingredients in the process of uniformly mixing the three materials in the step S1 is that the solid chlorinating agent: additive: the mass ratio of the tungsten-containing waste is (1-6): (0.5 to 3.5): 1.
further, in the step S2, the flow rate of the air or the oxygen is 10-30 m 3 And/h, wherein the air inlet pressure is 0.5-2 MPa.
Further, in the step S2, the roasting temperature is 500-950 ℃, the heating rate is 2.5-10 ℃/min, and the heat preservation time is 0.5-6 hours.
Further, in the step S3, the alkali solution includes at least one of sodium hydroxide with a mass fraction of 5-30%, sodium carbonate with a mass fraction of 5-40%, and sodium bicarbonate with a mass fraction of 5-40%.
Further, in the step S3, the gas phase product volatilized in the chloridizing roasting process is introduced into an alkali liquor for collection, and the pH value of the alkali liquor is controlled: 9-11, filtering to obtain sodium tungstate solution.
Further, the sodium tungstate solution is subjected to evaporation crystallization to obtain a sodium tungstate product, or the sodium tungstate solution is subjected to extraction or ion exchange process to obtain an ammonium tungstate solution, and the ammonium tungstate solution is subjected to evaporation crystallization to obtain an APT product.
Further, in the chlorination roasting process of the tungsten-containing waste, cobalt, iron and other components are left in roasting slag, and the roasting slag is used for recycling valuable metals.
Furthermore, the invention also protects products obtained by the technical method for treating the tungsten-containing waste, which comprise at least one of sodium tungstate solution, sodium tungstate product and APT product.
The invention has the beneficial effects that:
the treatment method is applicable to common tungsten-containing waste materials, including floor materials, dust collecting materials, grinding materials and waste materials generated in the production process of hard alloy, and powdery tungsten-containing waste materials such as floor materials, dust collecting materials and waste materials in the production process of tungsten carbide powder and tungsten powder. In addition, the invention adopts the low-temperature roasting technology of the solid chlorinating agent, thereby avoiding the need of introducing chlorine with high price and strong toxicity in the traditional chloridizing roasting method, having lower roasting temperature and reducing energy consumption. Furthermore, the method effectively removes Cr, cu, fe, siO contained in the crude sodium tungstate solution by adjusting the dosage and the types of the solid chlorinating agent and the additive, the roasting process parameters and the pH value of the alkali liquor 2 And the quality of the sodium tungstate solution is improved due to the impurities. Tungsten recovery exceeded 95% by analysis of the resulting solution for tungsten content.
In a word, the tungsten-containing waste treatment method has the advantages of short process flow, high tungsten recovery rate and good raw material adaptability, is a resource recycling method with high production efficiency, low energy consumption and low cost, and has great popularization significance.
Drawings
The invention is further described below in conjunction with the accompanying drawings to facilitate understanding by those skilled in the art. In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be made on the accompanying drawings, which are given by way of illustration only and not limitation of the present invention.
FIG. 1 is a schematic diagram of the process flow of the chloridizing roasting method for producing sodium tungstate solution by using the tungsten-containing waste.
Detailed Description
The present invention will be further described in the following examples for the purpose of more clearly understanding the objects, technical solutions and advantageous effects of the present invention, but the scope of the present invention is not limited to the following examples, which are given by way of illustration only and are not intended to limit the scope of the present invention in any way. The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the related raw materials are all commercial conventional industrial raw materials unless specified; the processing and manufacturing methods are conventional methods unless otherwise specified. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
In order to solve the technical problems of long process flow, complex separation method, low recovery rate, high equipment requirement, high energy consumption and the like in the existing tungsten-containing waste regeneration treatment technology, the invention provides a method for recovering tungsten in tungsten-containing waste by using a chloridizing roasting method, which comprises the following steps:
s1: and uniformly mixing the tungsten-containing waste with a solid chlorinating agent and an additive to obtain a mixture.
Further, in the embodiment of the invention, the tungsten-containing waste material sources are ground plate materials, dust collecting materials, grinding materials and waste materials generated in the production process of the hard alloy, and powdery tungsten-containing waste materials such as tungsten carbide powder, ground plate materials, dust collecting materials and waste materials in the production process of the tungsten powder.
Further, in the embodiment of the present invention, the main composition of the tungsten-containing waste material is: the tungsten mass content is 40% -95%, the cobalt mass content is 2-20%, and meanwhile, the tungsten alloy also contains a small amount of other impurity elements such as Fe, cu, C, cr, siO, ni, V and the like. The above-mentioned material and element contents are only required to satisfy the disclosure, and do not limit the scheme itself, and the method provided by the present invention is applicable to tungsten waste obtained by commercial and existing processing methods. In addition, the source of tungsten scrap is not particularly limited, and it may be commercially available or produced in accordance with the existing cemented carbide production process.
Further, in an embodiment of the present invention, wherein the solid chlorinating agent is at least one of sodium chloride, calcium chloride, magnesium chloride, ferric chloride, aluminum chloride; in addition, the sources of the solid chlorinating agents such as sodium chloride, calcium chloride, magnesium chloride, ferric chloride, aluminum chloride and the like are not particularly limited, and the solid chlorinating agents can be obtained commercially or prepared by the existing method technology.
Further, in the embodiment of the present invention, in order to promote the chlorination reaction of the tungsten-containing phase in the tungsten-containing waste material with the solid chlorinating agent to sufficiently occur, at least one of silica or alumina is added as an additive, thereby improving the overall recovery rate of tungsten. The source of the additive such as silica or alumina is not particularly limited, and the additive may be commercially available or may be prepared by itself according to a conventional method.
Further, in the embodiment of the invention, the proportion of ingredients in the process of uniformly mixing the three materials is a solid chlorinating agent: additive: the mass ratio of the tungsten-containing waste is (1-6): (0.5 to 3.5): 1. the inventors found that if the addition amount of the solid chlorinating agent is too small, the addition amount of the additive is too small, and the total recovery rate of tungsten is low; if the addition amount of the solid chlorinating agent is too large, the production cost is too high and reagent waste is caused. Thus, the preferred solid chlorinating agent of the present invention: additive: the mass ratio of the tungsten-containing waste is (2-4): (1.5 to 3): 1.
s2: and (3) chloridizing and roasting the mixture obtained in the step (S1) under the condition of introducing air or oxygen.
Further, in the embodiment of the invention, the mixture is subjected to chloridizing roasting under the condition of introducing air or oxygen, and the representative chloridizing roasting reaction of the tungsten carbide which is one of main components in the tungsten-containing waste is shown as the following reaction equation:
（1）WC + 6NaCl + 3SiO 2 + 2.5O 2(g) = 3Na 2 SiO 3 + WCl 6(g) + CO 2(g) ；
（2）WC + 3CaCl 2 + 3SiO 2 + 2.5O 2(g) = 3CaSiO 3 + WCl 6(g) + CO 2(g) ；
（3）WC + 3MgCl 2 + 3SiO 2 + 2.5O 2(g) = 3MgSiO 3 + WCl 6(g) + CO 2(g) ；
（4）WC + 6NaCl + 3Al 2 O 3 + 2.5O 2(g) = 6NaAlO 2 + WCl 6(g) + CO 2(g) ；
（5）WC + 3CaCl 2 + 3Al 2 O 3 + 2.5O 2(g) = 3Ca(AlO 2 ) 2 + WCl 6(g) + CO 2(g) ；
（6）WC + 3MgCl 2 + 3Al 2 O 3 + 2.5O 2(g) = 3Mg(AlO 2 ) 2 + WCl 6(g) + CO 2(g) ；
（7）WC + 6NaCl + 3Al 2 O 3 + 6SiO 2 + 2.5O 2(g) = 6NaAlSiO 4 + WCl 6(g) + CO 2(g) ；
（8）WC + 3CaCl 2 + 3Al 2 O 3 + 3SiO 2 + 2.5O 2(g) = 3CaAl 2 SiO 6 + WCl 6(g) + CO 2(g) ；
（9）WC + 3MgCl 2 + 3Al 2 O 3 + 7.5SiO 2 + 2.5O 2(g) = 1.5Mg 2 Al 4 Si 5 O 18 + WCl 6(g) + CO 2(g) 。
further, in the embodiment of the invention, silicon dioxide or aluminum oxide is selected as an additive, so that the chlorination reaction of the tungsten-containing waste material can be promoted to generate aluminosilicate with low melting point, thereby accelerating the generation of tungsten-containing chloride and greatly improving the recovery rate of tungsten.
Further, in an embodiment of the present invention, the flow rate of the air or the oxygen is 10-30 m 3 And/h, wherein the air inlet pressure is 0.5-2 MPa; the inventor finds that if the air or oxygen flow is smaller and the air inlet pressure is too small, low-price tungsten-containing tungsten chloride which is inconvenient for alkali liquor collection is generated in the chloridizing roasting process, so that the recovery rate of tungsten is low; if the air or oxygen flow is too large, the intake pressure is too large, some impurity components are brought upThe alkali liquor is added to cause higher impurity concentration in the sodium tungstate solution, and the gas consumption is high, so that the cost is increased; therefore, in the preferred scheme of the invention, the flow rate of air or oxygen is 15-25 m 3 And/h, wherein the air inlet pressure is 0.8-1.2 MPa.
Further, in the embodiment of the invention, the roasting temperature is 500-950 ℃ and the heating rate is 2.5-10 ℃/min. The inventor finds that if the roasting temperature is too low, tungsten in tungsten waste cannot be completely and effectively converted; if the roasting temperature is too high, the roasting is easy to be performed, so that the furnace is formed, the energy consumption is high, and the cost is high; therefore, the preferred firing temperature in the present invention is 500℃to 950 ℃.
Further, in the embodiment of the present invention, the roasting time is 0.5 to 6 hours, and the inventor finds that the chlorination reaction is insufficient when the time is short, and the production benefit is affected when the time is long, so that the roasting time is preferably 1 to 4 hours in the present invention.
S3: introducing the gas phase product volatilized in the chloridizing roasting process in the step S2 into alkali liquor for collection, controlling the pH value of the alkali liquor properly, and filtering to obtain sodium tungstate solution; while the cobalt, iron and other components in the tungsten-containing waste are remained in the roasting slag.
Further, in this step, the low boiling point tungsten-containing chloride gas volatilized during the chloridizing roasting process is converted into sodium tungstate solution by chemical reaction with alkali when passing through alkali solution, as shown in the following reaction equation:
（10）WCl 6(g) +8NaOH = Na 2 WO 4 +6NaCl+4H 2 O
（11）WCl 6(g) +8NaHCO 3 = Na 2 WO 4 +6NaCl+8CO 2(g) +4H 2 O
（12）WCl 6(g) +4Na 2 CO 3 = Na 2 WO 4 +6NaCl+4CO 2(g)
further, even if chlorides such as cobalt chloride and ferric chloride are generated in the chloridizing roasting process, the chlorides remain in the roasting slag due to the high boiling point of the chlorides, so that the tungsten in the tungsten-containing waste is separated from other metals efficiently.
Further toWherein, in the steps, the alkali liquor comprises at least one of sodium hydroxide with the mass fraction of 5-30%, sodium carbonate with the mass fraction of 5-40% and sodium bicarbonate with the mass fraction of 5-40%; controlling the pH value of the alkali liquor: 9-11, the inventor finds that Cr, cu, fe, siO in the sodium tungstate solution can be effectively removed under the condition of the pH value range through a large number of experiments 2 、C O And impurities such as sodium tungstate solution purity is improved, and subsequent preparation of qualified tungsten products is facilitated.
Further, in the embodiment of the invention, the purified sodium tungstate solution can be directly evaporated, concentrated and crystallized to obtain a high-purity sodium tungstate product, or an ion exchange-evaporation crystallization process can be used for producing a high-quality ammonium paratungstate product, or the sodium tungstate solution is subjected to an extraction-evaporation crystallization process to obtain the ammonium paratungstate product. Wherein the extractant used for extraction can be at least one selected from N235, TOA, alamine-336, quaternary ammonium salt, etc., and the ion exchange resin used for ion exchange can be strong alkaline anion exchange resin such as D201×7, amberlite IRA-400, AB-17N, amberlite IRA-4200, etc., or weak alkaline anion exchange resin such as AH-80N, etc. The specific operation process of extracting or ion-exchanging the solution containing sodium tungstate to obtain ammonium tungstate solution is conventional in the art, and is not described herein.
Further, in the embodiment of the present invention, step S3 further includes evaporating and crystallizing the sodium tungstate solution to obtain a sodium tungstate product, or extracting or ion-exchanging the sodium tungstate solution to obtain an ammonium tungstate solution, and evaporating and crystallizing the ammonium tungstate solution to obtain an APT product. The method for obtaining the APT product from the ammonium tungstate solution by evaporation and crystallization is the same as that of the prior art, and it is well known to those skilled in the art, and will not be described in detail herein.
Further, in embodiments of the present invention, the APT product may also be calcined to provide at least one of Huang Wu, blue tungsten and violet tungsten. The method of calcining APT products to obtain tungsten yellow, tungsten blue, tungsten violet, etc. is the same as the prior art, and those skilled in the art will be aware of this, and will not be described here.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way. In addition, the percentages stated in the examples and comparative examples refer generally to percent by mass unless otherwise specified.
Further, the method for measuring the recovery rate of tungsten in the embodiment of the present invention is as shown in the following formula (12):
（12）
wherein W is the percentage of tungsten in the tungsten-containing waste material, and M is the mass of the tungsten-containing waste material; c is the mass concentration of tungsten element in the sodium tungstate solution, and V is the volume of the sodium tungstate solution.
Example 1
The method for producing the sodium tungstate solution by using the tungsten-containing waste material comprises the following steps:
step one: taking 30g of tungsten-containing waste, adding sodium chloride and silicon dioxide with the mass ratio of 3 times and 1 time respectively into the tungsten-containing waste, and uniformly mixing to obtain a mixture;
step two: roasting the mixture under the condition of introducing air, wherein the roasting temperature is 800 ℃ and the roasting time is 4 hours;
step three: and (3) introducing the gas phase product volatilized in the step of the dichloro roasting process into 15% sodium hydroxide alkali liquor for collection, controlling the pH value of the alkali liquor to be 10, and filtering to obtain sodium tungstate solution, wherein the recovery rate of tungsten is up to 95.6%.
Example 2
The method for producing the sodium tungstate solution by using the tungsten-containing waste material comprises the following steps:
step one: taking 30g of tungsten-containing waste, adding calcium chloride and aluminum oxide with the mass ratio of 6 times and 0.5 time respectively into the tungsten-containing waste, and uniformly mixing to obtain a mixture;
step two: roasting the mixture under the condition of introducing oxygen, wherein the roasting temperature is 700 ℃ and the roasting time is 2 hours;
step three: and (3) introducing the gas-phase product volatilized in the step of the dichloro roasting process into 40% sodium carbonate alkali liquor for collection, controlling the pH value of the alkali liquor to be 9, and filtering to obtain sodium tungstate solution, wherein the recovery rate of tungsten reaches 97.8%.
Example 3
The method for producing the sodium tungstate solution by using the tungsten-containing waste material comprises the following steps:
step one: taking 30g of tungsten-containing waste, adding magnesium chloride and silicon dioxide with the mass ratio of 1 time to 2 times respectively into the tungsten-containing waste, and uniformly mixing to obtain a mixture;
step two: roasting the mixture under the condition of introducing air, wherein the roasting temperature is 500 ℃ and the roasting time is 6 hours;
step three: and (3) introducing the gas phase product volatilized in the step of the dichloro roasting process into 10% sodium bicarbonate alkali liquor for collection, controlling the pH value of the alkali liquor to be 11, and filtering to obtain sodium tungstate solution, wherein the recovery rate of tungsten reaches 98.1%.
Example 4
The method for producing the sodium tungstate solution by using the tungsten-containing waste material comprises the following steps:
step one: taking 30g of tungsten-containing waste, adding ferric chloride and aluminum oxide with the mass ratio of 4 times and 2 times respectively into the tungsten-containing waste, and uniformly mixing to obtain a mixture;
step two: roasting the mixture under the condition of introducing oxygen, wherein the roasting temperature is 950 ℃ and the roasting time is 0.5h;
step three: and (3) introducing the gas phase product volatilized in the step of the dichloro roasting process into 5% sodium hydroxide alkali liquor for collection, controlling the pH value of the alkali liquor to be 9, and filtering to obtain sodium tungstate solution, wherein the recovery rate of tungsten is 96.3%.
Example 5
The method for producing the sodium tungstate solution by using the tungsten-containing waste material comprises the following steps:
step one: taking 30g of tungsten-containing waste, adding 3 times of aluminum chloride and 3.5 times of silicon dioxide into the tungsten-containing waste, and uniformly mixing to obtain a mixture;
step two: roasting the mixture under the condition of introducing air, wherein the roasting temperature is 500 ℃ and the roasting time is 4 hours;
step three: and (3) introducing the gas phase product volatilized in the step of the dichloro roasting process into 30% sodium hydroxide alkali liquor for collection, controlling the pH value of the alkali liquor to be 10, and filtering to obtain sodium tungstate solution, wherein the recovery rate of tungsten reaches 97.7%.
Example 6
The method for producing the sodium tungstate solution by using the tungsten-containing waste material comprises the following steps:
step one: taking 30g of tungsten-containing waste, adding sodium chloride, aluminum chloride and silicon dioxide with the mass ratio of 2 times to 1 time respectively into the tungsten-containing waste, and uniformly mixing to obtain a mixture;
step two: roasting the mixture under the condition of introducing air, wherein the roasting temperature is 800 ℃ and the roasting time is 4 hours;
step three: and (3) introducing the gas phase product volatilized in the step of the dichloro roasting process into 15% sodium hydroxide alkali liquor for collection, controlling the pH value of the alkali liquor to be 10, and filtering to obtain sodium tungstate solution, wherein the recovery rate of tungsten is 96.9%.
Comparative example 1
Other conditions are unchanged, the roasting temperature and the roasting time in the embodiment 1 are respectively changed to 400 ℃ and 0.4h, and the recovery rate of the final tungsten is only 35.7%, namely, the roasting temperature is reduced, the roasting time is shortened, and the recovery rate of the tungsten is obviously reduced.
Comparative example 2
Other conditions are unchanged, only the adding amount of sodium chloride in the embodiment 1 is changed into 0.5 times of the mass ratio of the tungsten-containing waste material and the adding amount of silicon dioxide is changed into 4 times of the mass ratio of the tungsten-containing waste material, and the recovery rate of the final tungsten is only 42.2 percent, namely the adding amounts of the solid chlorinating agent and the additive are required to be reasonably matched so as to be beneficial to the full implementation of the chlorination reaction.
Comparative example 3
Other conditions are unchanged, the roasting temperature and the pH value of the alkali liquor in the embodiment 2 are changed to 1000 ℃ and 8 respectively, and the recovery rate of the final tungsten is only 76.9%, namely, the higher roasting temperature and the weak alkaline alkali liquor are not beneficial to the recovery of tungsten in the chlorination roasting process of the tungsten-containing waste.
Comparative example 4
Other conditions were unchanged, only in example 1, no silica additive was added, and the final tungsten recovery was only 45.6%, i.e., only solid chlorinating agent was added, and no additive was added, and the tungsten recovery was significantly reduced.
The sodium tungstate solutions obtained in the examples and comparative examples were measured as shown in table 1 below:
TABLE 1
Therefore, the tungsten-containing waste treatment method disclosed by the invention has the advantages of short process flow, high tungsten recovery rate and good raw material adaptability, is a resource recycling method with high production efficiency, low energy consumption and low cost, and has great popularization significance.
The above embodiments are only illustrative of and explain the present invention and should not be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Claims (5)
1. A method for recycling tungsten in tungsten-containing waste by using a chloridizing roasting method is characterized by comprising the following steps:
s1: uniformly mixing tungsten-containing waste with a solid chlorinating agent and an additive to obtain a mixture; the solid chlorinating agent in the step S1 adopts at least one of sodium chloride, calcium chloride, magnesium chloride, ferric chloride and aluminum chloride; the additive in the step S1 adopts at least one of silicon dioxide and aluminum oxide; the proportion of ingredients in the process of uniformly mixing the three materials in the step S1 is that a solid chlorinating agent: additive: the mass ratio of the tungsten-containing waste material is (1-6): (0.5-3.5): 1, a step of;
s2: chloridizing and roasting the mixture obtained in the step S1 under the condition of introducing air or oxygen; the flow rate of the air or the oxygen in the step S2 is 10-30 m 3 And/h, the air inlet pressure is 0.5-2 MPa; the roasting temperature in the step S2 is 500-950 ℃, the heating rate is 2.5-10 ℃/min, and the heat preservation time is 0.5-6 hours;
s3: and (3) introducing the gas-phase product volatilized in the chloridizing roasting process in the step (S2) into alkali liquor for collection, controlling the pH value of the alkali liquor, and filtering to obtain sodium tungstate solution.
2. The method according to claim 1, characterized in thatThe method is characterized in that the tungsten-containing waste material in the step S1 is derived from floor materials, dust collecting materials, grinding materials and waste materials generated in the production process of hard alloy, or from floor materials, dust collecting materials and waste materials in the production process of tungsten carbide powder and tungsten powder; the tungsten-containing waste comprises the following components: the mass content of tungsten is 40-95%, the mass content of cobalt is 2-20%, and the other is Fe, cu, C, cr, siO 2 Ni and/or V impurity elements.
3. The method according to any one of claims 1-2, wherein the lye in step S3 comprises at least one of 5-30% by mass sodium hydroxide, 5-40% by mass sodium carbonate, 5-40% by mass sodium bicarbonate.
4. The method according to any one of claims 1-2, wherein in step S3, the gas phase product volatilized during the chloridizing roasting process is introduced into an alkaline solution for collection, the pH value of the alkaline solution is controlled to be 9-11, and the sodium tungstate solution is obtained by filtration.
5. The method according to any one of claims 1-2, wherein step S3 further comprises subjecting the sodium tungstate solution to an evaporative crystallization to obtain a sodium tungstate product, or subjecting the sodium tungstate solution to an extraction or ion exchange process to obtain an ammonium tungstate solution, and subjecting the ammonium tungstate solution to an evaporative crystallization to obtain an APT product.
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| WO2020103642A1 (en) * | 2018-11-23 | 2020-05-28 | 华南理工大学 | Device and method for treating heavy metal hazardous waste by means of vacuum chlorination roasting |
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| AU480304B2 (en) * | 1973-11-20 | 1975-05-22 | Union Carbide Corporation | Recovery of tungsten from low grade tungsten ores |
| JP2018062691A (en) * | 2016-10-13 | 2018-04-19 | Ｊｘ金属株式会社 | Method for collecting tungsten concentrate from cobalt-tungsten raw material |
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