CN110629052B - Method for recovering tungsten carbide and cobalt sulfate from tungsten carbide waste - Google Patents
Method for recovering tungsten carbide and cobalt sulfate from tungsten carbide waste Download PDFInfo
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- CN110629052B CN110629052B CN201910870659.5A CN201910870659A CN110629052B CN 110629052 B CN110629052 B CN 110629052B CN 201910870659 A CN201910870659 A CN 201910870659A CN 110629052 B CN110629052 B CN 110629052B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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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
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for recovering tungsten carbide and cobalt sulfate from tungsten carbide waste, which comprises the following steps: (1) mixing and pulping the tungsten carbide waste with concentrated sulfuric acid and water to obtain mixed slurry; (2) carrying out high-pressure oxygen leaching treatment on the mixed slurry so as to obtain an oxygen leaching solution; (3) and carrying out solid-liquid separation treatment on the oxygen immersion liquid so as to obtain a cobalt sulfate solution and tungsten carbide. The method can effectively recover tungsten and cobalt elements in the tungsten carbide waste, has high recovery rate and cobalt recovery rate of more than 97 percent, and is free from harmful gas, simple to operate, low in investment cost and suitable for industrial production compared with the traditional recovery process.
Description
Technical Field
The invention belongs to the field of tungsten carbide waste recycling, and particularly relates to a method for recycling tungsten carbide and cobalt sulfate from tungsten carbide waste.
Background
With the rapid development of the chemical industry, the leading position of resources is higher and higher, and the environmental protection pressure is heavier and heavier. Tungsten and cobalt are important non-renewable resources, and with increasing shortage of ores, the recovery of secondary resources becomes more important. The existing process mainly adopts a saltpeter smelting method, a crushing method, a chemical method and the like to recover tungsten and cobalt in the tungsten carbide waste. The method mainly adopts the mode of oxidizing and roasting the tungsten carbide waste, alkaline leaching to recover tungsten, and strong acid reduction wet leaching technology to recover cobalt in the slag after tungsten recovery, wherein the reducing agent mainly comprises sodium sulfite, sulfur dioxide, hydrogen peroxide and the like. On one hand, the addition amount of the reducing agent is large in the treatment process; on the other hand, the sodium sulfite and the sulfur dioxide can release sulfur dioxide gas in the using process, and the leaching time is long and the leaching rate is not high. In addition, the adopted method is to leach the tungsten carbide waste material under normal pressure by acid to recover cobalt therein, and the slag after recovering the cobalt is oxidized and roasted to recover tungsten therein, and the method has long leaching time and low leaching rate.
Therefore, the existing technology for recovering tungsten and cobalt from tungsten carbide scrap 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 recovering tungsten carbide and cobalt sulfate from tungsten carbide waste, by which tungsten and cobalt elements in the tungsten carbide waste can be effectively recovered, and the recovery rate is high and the cobalt recovery rate is as high as 97% or more.
In one aspect of the invention, a method of recovering tungsten carbide and cobalt sulfate from tungsten carbide scrap is provided. According to an embodiment of the invention, the method comprises:
(1) mixing and pulping the tungsten carbide waste with concentrated sulfuric acid and water to obtain mixed slurry;
(2) carrying out high-pressure oxygen leaching treatment on the mixed slurry so as to obtain an oxygen leaching solution;
(3) and carrying out solid-liquid separation treatment on the oxygen immersion liquid so as to obtain a cobalt sulfate solution and tungsten carbide.
According to the method for recovering the tungsten carbide and the cobalt sulfate from the tungsten carbide waste material, provided by the embodiment of the invention, the tungsten and cobalt elements in the tungsten carbide waste material can be effectively recovered, the recovery rate is high, and the cobalt recovery rate is up to more than 97%.
In addition, the method for recovering tungsten carbide and cobalt sulfate from tungsten carbide scraps according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, in the step (1), the tungsten carbide waste has a tungsten content of 3 to 95wt% and a cobalt content of 3 to 20 wt%. Therefore, the resource utilization of the tungsten carbide waste material can be realized.
In some embodiments of the present invention, in step (1), the tungsten carbide scrap has an oil content of not higher than 0.5wt%, a moisture content of not higher than 0.5wt%, and a particle size of not lower than 60 mesh.
In some embodiments of the present invention, in step (1), when the tungsten carbide scrap has an oil content of more than 0.5wt%, a water content of more than 0.5wt% and a particle size of less than 60 mesh, the tungsten carbide scrap is subjected to drying and crushing treatment in advance, and dust obtained by the drying treatment and the crushing treatment is recovered by a dust collecting device.
In some embodiments of the present invention, the temperature of the drying treatment is 150 to 300 ℃ for 4 to 24 hours, preferably 180 to 250 ℃ for 8 to 12 hours. Thus, the recovery rates of cobalt and tungsten can be remarkably improved.
In some embodiments of the invention, the particle size of the crushed tungsten carbide scrap is not less than 60 mesh, more preferably not less than 100 mesh, more preferably not less than 150 mesh. Thus, the recovery rates of cobalt and tungsten can be remarkably improved.
In some embodiments of the present invention, in the step (1), the addition amount of the concentrated sulfuric acid is 1.2 to 3 times of the theoretical amount. Thus, the recovery rates of cobalt and tungsten can be remarkably improved.
In some embodiments of the present invention, in step (1), the solid-to-liquid ratio in the mixed slurry is 1: (3-10), preferably 1: (4-6). Thus, the recovery rates of cobalt and tungsten can be remarkably improved.
In some embodiments of the invention, in the step (2), the rotation speed of the high pressure oxygen leaching treatment is 150 to 500r/min, the temperature is 100 to 200 ℃, the oxygen pressure is 0.5 to 2.0MPa, and the time is 1 to 12 hours. Thus, the recovery rates of cobalt and tungsten can be remarkably improved.
In some embodiments of the invention, in the step (2), the rotation speed of the high pressure oxygen leaching treatment is 300-400 r/min, the temperature is 130-160 ℃, the oxygen pressure is 1.0-1.5 MPa, and the time is 6-10 h. Thus, the recovery rates of cobalt and tungsten can be remarkably 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 diagram of a process for recovering tungsten carbide and cobalt sulfate from tungsten carbide scrap, according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, a method of recovering tungsten carbide and cobalt sulfate from tungsten carbide scrap is provided. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing and size mixing tungsten carbide waste with concentrated sulfuric acid and water
In the step, the tungsten carbide waste is mixed with concentrated sulfuric acid and water for size mixing, so that cobalt in the tungsten carbide waste reacts with the concentrated sulfuric acid to generate cobalt sulfate (Co + H)2SO4＝CoSO4+H2) And the tungsten carbide does not participate in the reaction and remains in the slag phase to obtain mixed slurry.
Specifically, in the present invention, the tungsten carbide waste refers to soft waste such as floor material, dust collecting material, grinding material, waste material, etc. generated in the production process of cemented carbide. In a preferred embodiment of the present invention, the tungsten carbide scrap mainly comprises: tungsten content of 3-95 wt%, cobalt content of 3-20 wt%, and small amount of other impurity elements such as Fe, Cu, Ni, C, Ta, Ti, Nb, Cr, V, and SiO2And the like. The contents of the above elements are only required to satisfy the disclosure, and are not construed as being sufficientThe process provided by the present invention is applicable to tungsten-containing waste materials obtained by both commercial and existing processing methods, subject to limitations on the protocol itself. In the present invention, the source of the tungsten-containing scrap is not particularly limited, and the tungsten-containing scrap may be commercially available or may be scrap produced in the conventional cemented carbide production process.
In the invention, the tungsten carbide waste material in the mixing and size mixing process with concentrated sulfuric acid and water needs to meet the requirements that the content of oil in the tungsten carbide waste material is not higher than 0.5wt%, the moisture is not higher than 0.5wt%, and the particle size is not lower than 60 meshes. When the oil content, the water content and the particle size of the initial tungsten carbide waste material do not meet the requirements of the invention, for example, when the oil content and the water content of the initial tungsten-containing waste material are both higher than 0.5wt% and the particle size is lower than 60 meshes, the method provided by the invention preferably further comprises the step of sequentially drying and crushing the initial tungsten carbide waste material, wherein the drying condition comprises the temperature of 150-300 ℃, preferably 180-250 ℃; the time is 4-24 h, preferably 8-12 h. Further, the drying may be performed in existing various drying apparatuses. The crushing treatment process is realized by adopting universal crushing equipment. And (3) screening the crushed tungsten carbide waste material by a 60-mesh screen, preferably by a 100-mesh screen, more preferably by a 150-mesh screen to obtain a crushed material with the particle size of not less than 60 meshes, preferably not less than 100 meshes, more preferably not less than 150 meshes, and then mixing the tungsten carbide waste material meeting the requirements with concentrated sulfuric acid and water to prepare a blended slurry. And dust collecting equipment is adopted for recovering dust generated in the drying process and the crushing process. The drying process equipment, the crushing process equipment and the dust collecting equipment can be various existing equipment capable of respectively realizing the functions, the structures of the equipment are not particularly limited, and people skilled in the art can know the equipment, and the details are not described herein.
In the invention, the concentrated sulfuric acid is 98% by mass, wherein the use amount of the concentrated sulfuric acid is 1.2-3 times of a theoretical value, and preferably 1.5-2.0 times of the theoretical value. The inventor finds that if the theoretical amount of concentrated sulfuric acid is too low, the cobalt content of the slag is high, the decomposition rate of cobalt is low, and if the theoretical amount of sulfuric acid is too high, the chemical agent sulfuric acid is wasted, and the decomposition cost is high. The theoretical value of the concentrated sulfuric acid is calculated according to the following formula: the molecular weight of sulfuric acid x the weight of tungsten carbide waste x (1-oil mass-water mass) x the mass of cobalt/the molecular weight of cobalt/0.98. Further, the solid-to-liquid ratio in the obtained mixed slurry is 1: (3-10), preferably 1: (4-6). The inventor finds that if the solid-liquid ratio of the mixed slurry is too high, the single batch processing capacity is large, the energy consumption is high, and the decomposition cost is high, and if the solid-liquid ratio of the mixed slurry is too low, the cobalt content of the slag is high, and the decomposition rate of the cobalt is low.
S200: subjecting the mixed slurry to high pressure oxygen leaching treatment
In the step, the obtained mixed slurry is subjected to high-pressure oxygen leaching treatment, oxygen reacts with unreacted cobalt in the tungsten carbide waste to generate cobalt oxide, the cobalt oxide is easy to react with sulfuric acid to generate cobalt sulfate, and the reaction equation is Co + O2＝CoO，CoO+H2SO4＝CoSO4+H2O) to obtain an oxygen leaching solution containing cobalt sulfate and tungsten carbide.
In the present invention, the hyperbaric oxygen leaching reaction is usually carried out under stirring, specifically, the temperature is raised to the reaction temperature, oxygen is blown in to ensure the oxygen partial pressure is not changed, and the reaction is kept at a constant temperature until the material is discharged. The conditions of the high-pressure oxygen leaching reaction comprise that the rotating speed is 150-500 r/min, and preferably 300-400 r/min; the reaction temperature is 100-200 ℃, and preferably 130-160 ℃; the oxygen pressure is 0.5-2.0 MPa, preferably 1.0-1.5 MPa; the reaction time is 1-12 h, preferably 6-10 h. The inventor finds that if the temperature is too high, the energy consumption is high, the decomposition cost is high, and if the temperature is too low, the cobalt content in the slag is high, and the decomposition rate of the cobalt is low; meanwhile, the reaction time is too long, the energy consumption is high, the decomposition cost is high, the time is too short, the cobalt content in the slag is high, and the decomposition rate of the cobalt is low; in addition, if the reaction rotating speed is too high, the equipment is loaded, the requirement on the equipment is high, the cost is high, and if the rotating speed is too low, the contact between oxygen and materials is not easy, the cobalt content in the slag is high, and the decomposition rate of the cobalt is low. Thus, the decomposition rate of cobalt in the tungsten carbide scrap can be increased while the cost is reduced under the reaction conditions. In the present invention, the pressures are gauge pressures.
S300: subjecting the oxygen extract to solid-liquid separation
In the step, the obtained oxygen immersion liquid is subjected to solid-liquid separation treatment to obtain a cobalt sulfate solution and tungsten carbide. The oxygen immersion liquid is preferably supplied from the high-pressure oxygen immersion step to the solid-liquid separation step by a material-pumping pump. Specifically, the obtained oxygen leaching solution is subjected to solid-liquid separation treatment, the obtained filter residue is washed by hot water, a washing solution is added into the filtrate to obtain a cobalt sulfate solution and a filter residue containing tungsten carbide, and the cobalt sulfate solution remained in the filter residue can be washed cleanly by washing, so that the recovery rate is improved. It should be noted that the solid-liquid separation mode is any technology capable of realizing solid-liquid separation in the prior art, for example, a plate-and-frame filter pressing, a filtration, and the like, and details are not described here.
According to the method for recovering the tungsten carbide and the cobalt sulfate from the tungsten carbide waste material, provided by the embodiment of the invention, the tungsten and cobalt elements in the tungsten carbide waste material can be effectively recovered, the recovery rate is high, and the cobalt recovery rate is up to more than 97%.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Taking 300kg of tungsten carbide waste (the mass content of tungsten is 3%, the mass content of cobalt is 20%, the mass content of oil is 5%, and the mass content of water is 3%), drying the tungsten carbide waste at the drying temperature of 150 ℃ for 24h to obtain a dried material with the oil content of 0.2 wt% and the water content of 0.1 wt%;
(2) crushing the dried material by crushing equipment, and sieving by a sieve of 150 meshes to obtain a crushed material with the particle size of not less than 150 meshes;
(3) adding water into the crushed material for size mixing, adding concentrated sulfuric acid into the size mixing liquid, wherein the adding amount of the concentrated sulfuric acid is 1.2 times of the theoretical value, then adding water for adjusting to the solid-to-liquid ratio to be 1:10, then sending the obtained size mixing liquid into a high-pressure oxygen leaching device for high-pressure oxygen leaching reaction, wherein the reaction conditions comprise the rotating speed of 500r/min, the temperature of 200 ℃, the oxygen pressure of 2.0MPa and the reaction time of 12 hours, blowing oxygen all the time in the reaction process, ensuring the oxygen partial pressure to be constant, and keeping the temperature for discharging. And then filtering the obtained reaction product, washing the filter residue with hot water, and adding the washing solution into the filtrate to obtain a cobalt sulfate solution and the filter residue containing tungsten carbide. The washing can wash the cobalt sulfate solution remained in the filter residue, thereby improving the recovery rate. The recovery of cobalt therein was 97.5%.
Example 2
(1) Taking 500kg of tungsten carbide waste (the mass content of tungsten is 95%, the mass content of cobalt is 3%, the mass content of oil is 4% and the mass content of water is 5%), drying the tungsten carbide waste at the drying temperature of 300 ℃ for 1h to obtain a dried material with the oil content of 0.3 wt% and the water content of 0.2 wt%;
(2) crushing the dried material by crushing equipment, and sieving the crushed material by a 100-mesh sieve to obtain a crushed material with the particle size of not less than 100 meshes;
(3) adding water into the crushed material for size mixing, adding concentrated sulfuric acid into the size mixing liquid, wherein the adding amount of the concentrated sulfuric acid is 3.0 times of the theoretical value, then adding water for adjusting to the solid-to-liquid ratio to be 1:3, then sending the obtained size mixing liquid into a high-pressure oxygen leaching device for high-pressure oxygen leaching reaction, wherein the reaction conditions comprise the rotating speed of 150r/min, the temperature of 160 ℃, the oxygen pressure of 1.5MPa and the reaction time of 10 hours, blowing oxygen all the time in the reaction process, ensuring the oxygen partial pressure to be constant, and keeping the temperature for discharging. And then filtering the obtained reaction product, washing the filter residue with hot water, and adding the washing solution into the filtrate to obtain a cobalt sulfate solution and the filter residue containing tungsten carbide. The washing can wash the cobalt sulfate solution remained in the filter residue, thereby improving the recovery rate. The recovery of cobalt therein was 97.1%.
Example 3
(1) Taking 400kg of tungsten carbide waste (the mass content of tungsten is 80%, the mass content of cobalt is 5%, the mass content of oil is 3%, and the mass content of water is 7%), drying the tungsten carbide waste at the drying temperature of 250 ℃ for 8h to obtain a dried material with the oil content of 0.2 wt% and the water content of 0.2 wt%;
(2) crushing the dried material by crushing equipment, and sieving by a 60-mesh sieve to obtain a crushed material with the particle size of not less than 60 meshes;
(3) adding water into the crushed material for size mixing, adding concentrated sulfuric acid into the size mixing liquid, wherein the adding amount of the concentrated sulfuric acid is 2.0 times of the theoretical value, then adding water for adjusting to the solid-to-liquid ratio to be 1:4, then sending the obtained size mixing liquid into a high-pressure oxygen leaching device for high-pressure oxygen leaching reaction, wherein the reaction conditions comprise the rotating speed of 400r/min, the temperature of 130 ℃, the oxygen pressure of 1.8MPa and the reaction time of 8 hours, blowing oxygen all the time in the reaction process, ensuring the oxygen partial pressure to be constant, and keeping the temperature for a certain time until discharging. And then filtering the obtained reaction product, washing the filter residue with hot water, and adding the washing solution into the filtrate to obtain a cobalt sulfate solution and the filter residue containing tungsten carbide. The washing can wash the cobalt sulfate solution remained in the filter residue, thereby improving the recovery rate. The recovery of cobalt therein was 97.8%.
Example 4
(1) Taking 300kg of tungsten carbide waste (the mass content of tungsten is 50%, the mass content of cobalt is 15%, the mass content of oil is 6%, and the mass content of water is 2%), drying the tungsten carbide waste at 180 ℃ for 12h to obtain a dried material with the oil content of 0.1 wt% and the water content of 0.1 wt%;
(2) crushing the dried material by crushing equipment, and sieving the crushed material by a 200-mesh sieve to obtain a crushed material with the particle size of not less than 200 meshes;
(3) adding water into the crushed material for size mixing, adding concentrated sulfuric acid into the size mixing liquid, wherein the adding amount of the concentrated sulfuric acid is 1.5 times of the theoretical value, then adding water for adjusting to the solid-to-liquid ratio to be 1:6, then sending the obtained size mixing liquid into a high-pressure oxygen leaching device for high-pressure oxygen leaching reaction, wherein the reaction conditions comprise the rotating speed of 300r/min, the temperature of 100 ℃, the oxygen pressure of 1.0MPa and the reaction time of 6 hours, blowing oxygen all the time in the reaction process, ensuring the oxygen partial pressure to be constant, and keeping the temperature for discharging. And then filtering the obtained reaction product, washing the filter residue with hot water, and adding the washing solution into the filtrate to obtain a cobalt sulfate solution and the filter residue containing tungsten carbide. The washing can wash the cobalt sulfate solution remained in the filter residue, thereby improving the recovery rate. The recovery of cobalt therein was 97.3%.
Example 5
(1) Taking 350kg of tungsten carbide waste (the mass content of tungsten is 25%, the mass content of cobalt is 10%, the mass content of oil is 3% and the mass content of water is 5%), drying the tungsten carbide waste at the drying temperature of 200 ℃ for 12h to obtain a dried material with the oil content of 0.1 wt% and the water content of 0.1 wt%;
(2) crushing the dried material by crushing equipment, and sieving the crushed material by a 200-mesh sieve to obtain a crushed material with the particle size of not less than 200 meshes;
(3) adding water into the crushed material for size mixing, adding concentrated sulfuric acid into the size mixing liquid, wherein the adding amount of the concentrated sulfuric acid is 1.8 times of the theoretical value, then adding water for adjusting to the solid-to-liquid ratio to be 1:8, then sending the obtained size mixing liquid into a high-pressure oxygen leaching device for high-pressure oxygen leaching reaction, wherein the reaction conditions comprise the rotating speed of 350r/min, the temperature of 100 ℃, the oxygen pressure of 0.5MPa and the reaction time of 12 hours, blowing oxygen all the time in the reaction process, ensuring the oxygen partial pressure to be constant, and keeping the temperature for discharging. And then filtering the obtained reaction product, washing the filter residue with hot water, and adding the washing solution into the filtrate to obtain a cobalt sulfate solution and the filter residue containing tungsten carbide. The washing can wash the cobalt sulfate solution remained in the filter residue, thereby improving the recovery rate. The recovery of cobalt therein was 97.2%.
Example 6
(1) Taking 600kg of tungsten carbide waste (the mass content of tungsten is 3%, the mass content of cobalt is 8%, the mass content of oil is 2% and the mass content of water is 8%), drying the tungsten carbide waste at the drying temperature of 220 ℃ for 8h to obtain a dried material with the oil content of 0.2 wt% and the water content of 0.1 wt%;
(2) crushing the dried material by crushing equipment, and sieving by a 325-mesh sieve to obtain a crushed material with the particle size of not less than 325 meshes;
(3) adding water into the crushed material for size mixing, adding concentrated sulfuric acid into the size mixing liquid, wherein the adding amount of the concentrated sulfuric acid is 2.5 times of the theoretical value, then adding water for adjusting to the solid-to-liquid ratio to be 1:6, then sending the obtained size mixing liquid into a high-pressure oxygen leaching device for high-pressure oxygen leaching reaction, wherein the reaction conditions comprise the rotating speed of 500r/min, the temperature of 200 ℃, the oxygen pressure of 2.0MPa and the reaction time of 1h, blowing oxygen all the time in the reaction process, ensuring the oxygen partial pressure to be constant, and keeping the temperature for a certain time until discharging. And then filtering the obtained reaction product, washing the filter residue with hot water, and adding the washing solution into the filtrate to obtain a cobalt sulfate solution and the filter residue containing tungsten carbide. The washing can wash the cobalt sulfate solution remained in the filter residue, thereby improving the recovery rate. The recovery of cobalt therein was 97.4%.
Comparative example 1
Tungsten carbide scrap was treated according to the procedure of example 1 except that the amount of concentrated sulfuric acid was changed to 1.05 times the theoretical value and the other conditions were unchanged, resulting in a cobalt recovery of 80%.
Comparative example 2
Tungsten carbide scrap was treated as in example 2 except that no oxygen was introduced in the autoclave (i.e., the reaction was carried out in the absence of oxygen) and the conditions were otherwise unchanged, resulting in a cobalt recovery of 75%.
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 (13)
1. A method for recovering tungsten carbide and cobalt sulfate from tungsten carbide waste is characterized by comprising the following steps:
(1) mixing and pulping the tungsten carbide waste with concentrated sulfuric acid and water to obtain mixed slurry; the concentrated sulfuric acid is 98% by mass;
(2) carrying out high-pressure oxygen leaching treatment on the mixed slurry so as to obtain an oxygen leaching solution; the rotating speed of the high-pressure oxygen leaching treatment is 150-500 r/min, the temperature is 100-200 ℃, the oxygen pressure is 0.5-2.0 MPa, and the time is 1-12 h;
(3) and carrying out solid-liquid separation treatment on the oxygen immersion liquid so as to obtain a cobalt sulfate solution and tungsten carbide.
2. The method according to claim 1, wherein in the step (1), the tungsten carbide waste has a tungsten content of 3 to 95wt% and a cobalt content of 3 to 20 wt%.
3. The method according to claim 1 or 2, wherein in the step (1), the tungsten carbide waste material has an oil content of not more than 0.5wt%, a water content of not more than 0.5wt%, a particle size of not less than 60 meshes, and is sieved.
4. The method according to claim 1 or 2, wherein in the step (1), when the tungsten carbide scrap has an oil content of more than 0.5wt%, a water content of more than 0.5wt%, and a particle size of less than 60 mesh, the tungsten carbide scrap is subjected to drying and crushing treatment in advance in this order, and dust obtained by the drying treatment and the crushing treatment is recovered by a dust collecting device.
5. The method according to claim 4, wherein the drying treatment is carried out at a temperature of 150 to 300 ℃ for 4 to 24 hours.
6. The method according to claim 5, wherein the drying treatment is carried out at a temperature of 180 to 250 ℃ for 8 to 12 hours.
7. The method of claim 5, wherein the crushed tungsten carbide waste material has a particle size of not less than 60 mesh and is sieved.
8. The method of claim 7, wherein the crushed tungsten carbide waste material has a particle size of not less than 100 mesh and is sieved.
9. The method of claim 7, wherein the crushed tungsten carbide waste material has a particle size of not less than 150 mesh, and is sieved.
10. The method according to claim 1, wherein in the step (1), the addition amount of the concentrated sulfuric acid is 1.2 to 3 times of the theoretical amount.
11. The method according to claim 1, wherein in the step (1), the solid-to-liquid ratio in the mixed slurry is 1:3 to 10.
12. The method according to claim 1, wherein in the step (1), the solid-to-liquid ratio in the mixed slurry is 1: 4-6.
13. The method according to claim 1, wherein in the step (2), the rotation speed of the high pressure oxygen leaching treatment is 300-400 r/min, the temperature is 130-160 ℃, the oxygen pressure is 1.0-1.5 MPa, and the time is 6-10 h.
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| CN201910870659.5A CN110629052B (en) | 2019-09-16 | 2019-09-16 | Method for recovering tungsten carbide and cobalt sulfate from tungsten carbide waste |
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| CN201910870659.5A CN110629052B (en) | 2019-09-16 | 2019-09-16 | Method for recovering tungsten carbide and cobalt sulfate from tungsten carbide waste |
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| JP2011179038A (en) * | 2010-02-26 | 2011-09-15 | Mitsubishi Materials Corp | Method for collecting tungsten from scrap of hard metal |
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| CN109628744A (en) * | 2018-12-26 | 2019-04-16 | 荆门德威格林美钨资源循环利用有限公司 | A method of recycling tungsten and cobalt from tungstenic waste hand alloy material |
| CN110156084A (en) * | 2019-06-04 | 2019-08-23 | 赣州市海龙钨钼有限公司 | A kind of process using waste hand alloy material production ammonium paratungstate |
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| JP2011179038A (en) * | 2010-02-26 | 2011-09-15 | Mitsubishi Materials Corp | Method for collecting tungsten from scrap of hard metal |
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