CN111186856B - Preparation method of bismuth trifluoride - Google Patents
Preparation method of bismuth trifluoride Download PDFInfo
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- CN111186856B CN111186856B CN201811354597.4A CN201811354597A CN111186856B CN 111186856 B CN111186856 B CN 111186856B CN 201811354597 A CN201811354597 A CN 201811354597A CN 111186856 B CN111186856 B CN 111186856B
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Abstract
The invention relates toA preparation method of bismuth trifluoride, belonging to the technical field of preparation of bismuth compounds. The preparation method of the bismuth trifluoride comprises the following steps: introducing F into a first reactor containing bismuth trichloride 2 And (3) reacting the gas at the temperature of 50-200 ℃ to obtain the catalyst. The invention relates to a method for preparing bismuth trifluoride by using bismuth trichloride and F 2 The gas is used as a raw material to prepare the bismuth trifluoride, so that the energy consumption of the reaction can be reduced, and the purity of the prepared bismuth trifluoride product can be improved.
Description
Technical Field
The invention relates to a preparation method of bismuth trifluoride, belonging to the technical field of preparation of bismuth compounds.
Background
Bismuth trifluoride is a white crystal or crystalline powder, and is widely used in the fields of photocatalysis, lithium ion batteries, organic fluorination and the like due to a plurality of excellent characteristics.
(1) Photocatalysis
The bismuth trifluoride material has a more positive valence band, is beneficial to forming a cavity with high oxidation activity so as to be beneficial to the hydrolysis process, has better performance than titanium oxide, and is a novel photocatalytic material.
(2) Lithium ion battery
Bismuth trifluoride has high volume energy density (7170 Wh/L), mass energy density (969 Wh/kg) and high working voltage (3.21Vvs + ) And is a very potential lithium ion material. As a kind of goldBelongs to a fluoride anode material, biF 3 By reversible conversion reactions, high storage capacities are obtained. With more intensive studies thereon, biF 3 Will become a promising new generation of lithium ion secondary battery anode material.
(3) Organic fluorinating agent
Bismuth is a nontoxic heavy metal and has the green safety characteristics of low toxicity, low radioactivity and the like. As a fluorinating agent, the fluorinating efficiency is high, and the product is easy to stabilize and separate.
At present, most of conventional bismuth trifluoride synthesis methods are liquid phase methods and gas phase methods, wherein the liquid phase method is to obtain bismuth trifluoride by reacting hydrofluoric acid with water and metal oxide/hydroxide or bismuth nitrate, and the defects of impurity inclusion, difficulty in washing, incapability of circulating mother liquor and the like exist, so that the defects of low product purity, large three-waste generation amount, low bismuth and fluorine resource yield and the like are caused; most of the gas phase methods are reaction of fluorine gas and metal bismuth powder, the reaction temperature is high, the energy consumption is large, and the reaction rate is greatly influenced by the granularity of raw materials: the particles are too fine, and the reaction rate is not easy to control; when the particles are too coarse, the reaction takes time and is insufficient, resulting in low product purity.
Disclosure of Invention
The invention aims to provide a preparation method of bismuth trifluoride with low energy consumption and high product purity.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing bismuth trifluoride, comprising: introducing F into a first reactor containing bismuth trichloride 2 And (3) reacting the gas at the temperature of 50-200 ℃ to obtain the catalyst.
The invention relates to a method for preparing bismuth trifluoride by using bismuth trichloride and F 2 The gas is used as a raw material to prepare the bismuth trifluoride, so that the energy consumption of the reaction can be reduced, and the purity of the prepared bismuth trifluoride product can be improved.
F-containing gas is introduced into the first reactor in the reaction process 2 In gas F 2 Difficult to complete reaction, in order to increase F 2 And reducing pollution, preferably, the preparation method of bismuth trifluoride further comprises a second step of adding a catalyst into the reaction processThe gas discharged from the first reactor is introduced into a second reactor containing bismuth trichloride, and the temperature of the second reactor is controlled to be 50-200 ℃ for reaction.
Preferably, the preparation method of bismuth trifluoride comprises the steps of introducing gas discharged from a first reactor in the reaction process into a second reactor containing bismuth trichloride, and controlling the temperature of the second reactor to be 50-200 ℃ for reaction; the following steps are then repeated:
stopping introducing F-containing gas into the first reactor after the bismuth trichloride in the first reactor completely reacts 2 Gas is directly fed into the second reactor and F is contained 2 Gas, controlling the temperature to be 50-200 ℃ for reaction; after the materials in the first reactor are cooled, unloading the materials, and reloading the bismuth trichloride; introducing the gas exhausted from the second reactor into the first reactor filled with bismuth trichloride again, and controlling the temperature to be 50-200 ℃ for reaction; stopping introducing F into the second reactor after the bismuth trichloride in the second reactor completely reacts 2 Gas is directly fed into the first reactor and F is contained 2 Gas, controlling the temperature to be 50-200 ℃ for reaction; after the materials in the second reactor are cooled, unloading the materials and reloading the bismuth trichloride; and introducing the gas discharged from the first reactor into a second reactor which is refilled with bismuth trichloride, and controlling the temperature to be 50-200 ℃ for reaction. Adopts double reactors to react alternately, greatly improves F 2 The utilization ratio of (c).
In order to reduce F in the reaction process 2 And Cl in the reaction product 2 The method comprises the following steps of corroding equipment, reducing side reactions and improving the purity of products, preferably, drying bismuth trichloride at 100-150 ℃ before the bismuth trichloride is filled into a first reactor and a second reactor. The drying treatment of the bismuth trichloride can reduce the content of moisture and volatile substances in the bismuth trichloride.
Preferably, said F-containing compound 2 The gas is a mixed gas of fluorine gas and inert gas; the mass percentage of the fluorine gas in the mixed gas is 1-50%, preferably 10-30%. The inert gas in the present invention means a gas which does not participate in a chemical reaction in the production process, and is preferablyIntroducing inert gas and F into the reactor 2 Instead of pure F 2 The reason for this is that: by using a gas containing F 2 The mixed gas is beneficial to controlling the reaction rate, the fluorine gas has very active property, strong oxidizability and high reaction rate, and the reaction is too violent after the pure fluorine gas is used and is not easy to control; secondly, the corrosion strength is weakened, the type selection of industrial equipment is facilitated, and the use of mixed gas is favorable for industrial safe operation.
In order to increase the reaction rate and improve the production efficiency, it is preferable that the gauge pressure of the first reactor and the second reactor is controlled to 1 to 20KPa during the reaction.
Preferably, after the bismuth trichloride is filled in the first reactor and/or the second reactor, the corresponding reactor is vacuumized, and then gas is introduced. The bismuth trichloride is filled in the first reactor and the second reactor and then vacuumized, so that the moisture in the equipment can be further reduced, and F is reduced 2 Corrosion to equipment and reduced occurrence of side reactions.
Preferably, the introduction of F-containing gas into the first reactor and/or the second reactor is stopped 2 After the gas is generated, inert gas is introduced into the corresponding reactor to cool the materials. The material is cooled by introducing inert gas, so that the cooling rate can be increased, and unreacted F in the reactor can be cooled 2 Discharging to prevent F in the discharging process 2 The overflow of (a) has an influence on the human body and the environment.
To further increase F 2 Preferably, the gas discharged from the first reactor and not introduced into the second reactor and/or the gas discharged from the second reactor and not introduced into the first reactor is subjected to absorption treatment by using alkaline liquor.
Preferably, the alkali liquor is a sodium hydroxide solution with the concentration of not less than 100 g/L; in the absorption treatment process, the alkali liquor after the pH value is reduced to 10-11 is subjected to solid-liquid separation. The method is adopted for absorption, and byproducts of sodium hypochlorite and sodium fluoride can be prepared, so that the preparation method of bismuth trifluoride provided by the invention realizes the maximization of resource utilization, does not discharge three wastes, belongs to a clean production process, and has good economic, social and environmental benefits.
Drawings
FIG. 1 is a schematic view of an apparatus used in examples 1 to 3 of the present invention; the method comprises the following steps of 1-a first reactor, 11-a first reactor first air inlet pipeline, 111-a first reactor first air inlet valve, 12-a first reactor second air inlet pipeline, 121-a first reactor second air inlet valve, 13-a first reactor air outlet pipeline, 131-a first reactor air outlet valve, 2-a second reactor, 21-a second reactor first air inlet pipeline, 211-a second reactor first air inlet valve, 22-a second reactor second air inlet pipeline, 221-a second reactor second air inlet valve, 23-a second reactor air outlet pipeline, 231-a second reactor air outlet valve, 3-a first absorption tank and 4-a second absorption tank.
Detailed Description
The preparation method of the bismuth trifluoride provided by the invention comprises the following steps: introducing F into a first reactor containing bismuth trichloride 2 And (3) reacting the gas at the temperature of 50-200 ℃ to obtain the catalyst. The preparation method comprises the following chemical reactions: 2BiCl 3 +3F 2 →2BiF 3 +3Cl 2 ↑。
Preferably, the gas discharged from the first reactor is subjected to an absorption treatment with a basic solution.
Preferably, the gauge pressure in the first reactor is controlled to be 1 to 20KPa. More preferably, the gauge pressure in the first reactor is controlled to 5 to 15KPa.
Preferably, the preparation method of bismuth trifluoride further comprises introducing gas discharged from the first reactor in the reaction process into a second reactor containing bismuth trichloride, and controlling the temperature of the second reactor to be 50-200 ℃ for reaction.
The first reactor and the second reactor can be independently selected from a high-temperature furnace with a porous partition plate or a fluidized bed reactor. The porous partition may be provided in multiple layers in both the first reactor and the second reactor. Preferably, will contain F 2 Gas is introduced from the bottom of the first reactor and/or the second reactor to keep the materials in a suspension state. To contain F 2 Gas in the reactorContact with the materials from bottom to top, the full contact of the reaction raw materials is facilitated, the reaction is accelerated, and the production efficiency is improved.
Preferably, the preparation method of bismuth trifluoride comprises the steps of introducing gas exhausted from a first reactor in the reaction process into a second reactor containing bismuth trichloride, and controlling the temperature of the second reactor to be 50-200 ℃ for reaction; the following steps are then repeated:
stopping introducing F-containing gas into the first reactor after the bismuth trichloride in the first reactor completely reacts 2 Gas is directly introduced into the second reactor and contains F 2 Gas, controlling the temperature to be 50-200 ℃ for reaction; after the materials in the first reactor are cooled, unloading the materials, and reloading the bismuth trichloride; introducing the gas discharged from the second reactor into the first reactor which is refilled with bismuth trichloride, and controlling the temperature to be 50-200 ℃ for reaction; stopping introducing F into the second reactor after the bismuth trichloride in the second reactor completely reacts 2 Gas is directly fed into the first reactor and F is contained 2 Gas, controlling the temperature to be 50-200 ℃ for reaction; after the materials in the second reactor are cooled, unloading the materials and reloading the bismuth trichloride; and introducing the gas discharged from the first reactor into a second reactor which is refilled with bismuth trichloride, and controlling the temperature to be 50-200 ℃ for reaction.
Preferably, before the bismuth trichloride is loaded into the first reactor and the second reactor, the bismuth trichloride is dried at the temperature of 100-150 ℃. Preferably, the drying time is 2 to 3 hours.
Preferably, said F-containing compound 2 The gas is a mixed gas of fluorine gas and inert gas; the mass percentage of the fluorine gas in the mixed gas is 1-50%. Further preferably, the inert gas in the mixed gas is nitrogen; the mass fraction of the fluorine gas in the mixed gas is 10 to 30%, and for example, the mass fraction of the fluorine gas in the mixed gas can be selected from 15%, 20% and 25%.
Preferably, the gauge pressure of the first reactor and the second reactor is controlled to be 1-20 KPa during the reaction process. More preferably, the gauge pressure of the first reactor and the second reactor is controlled to be 5 to 15KPa during the reaction.
Preferably, the temperature in the first reactor and/or the second reactor is controlled to be 100 to 180 ℃ during the reaction.
Preferably, after the bismuth trichloride is filled in the first reactor and/or the second reactor, the corresponding reactor is vacuumized first, and then gas is introduced. The step of vacuumizing the corresponding reactor refers to the step of vacuumizing the corresponding reactor until the absolute pressure is 0-0.04 MPa.
Preferably, the introduction of F-containing gas into the first reactor and/or the second reactor is stopped 2 After the gas is introduced, inert gas is introduced into the corresponding reactor to cool the material. The inert gas adopted in the material cooling process is nitrogen.
Preferably, the gas which is discharged from the first reactor and is not passed into the second reactor and/or the gas which is discharged from the second reactor and is not passed into the first reactor is subjected to an absorption treatment with a basic solution. The absorption treatment is carried out in an absorption apparatus with a cooling system which controls the temperature of the lye used for absorption. The absorption equipment can be an absorption tower or an absorption tank.
The potassium hydroxide solution is adopted, so that the absorbed product is not easy to separate; calcium hydroxide and magnesium hydroxide have low solubility in water and are not suitable for use as absorption solutions; whereas sodium hydroxide has a high solubility in water. Thus, the lye is preferably a sodium hydroxide solution.
When sodium hydroxide solution is adopted for absorption, the chemical reaction mainly involved has the following equation:
F 2 +2NaOH→2NaF+H 2 O，
Cl 2 +2NaOH→NaCl+NaClO+H 2 O。
preferably, the alkali liquor is a sodium hydroxide solution with the concentration of not less than 100 g/L; in the absorption treatment process, the alkali liquor after the pH value is reduced to 10-11 is subjected to solid-liquid separation. Collecting the liquid obtained by solid-liquid separation, and washing and drying the obtained solid. The liquid obtained by solid-liquid separation is a sodium hypochlorite solution which can be used as a bleaching agent; the solid obtained by solid-liquid separation is sodium fluoride, and the sodium fluoride is washed and dried to obtain the high-purity sodium fluoride.
Further preferably, the alkali liquor is a sodium hydroxide solution with the concentration of 100-200 g/L.
Preferably, the temperature of the alkali liquor is controlled to be 20-30 ℃ in the absorption treatment process.
The technical solution of the present invention will be further described with reference to the following embodiments.
The apparatus used in the method for preparing bismuth trifluoride according to the embodiment, as shown in fig. 1, comprises a first reactor 1, a second reactor 2, and a first absorption tank 3 and a second absorption tank 4 connected in series; the bottom of the first reactor 1 is connected with a first reactor first air inlet pipeline 11 and a first reactor second air inlet pipeline 12, the first reactor first air inlet pipeline 11 is provided with a first reactor first air inlet valve 111, the first reactor second air inlet pipeline 12 is communicated with the second reactor 2 at the top of the second reactor 2, the first reactor second air inlet pipeline 12 is provided with a first reactor second air inlet valve 121, the top of the first reactor 1 is connected with a first reactor air outlet pipeline 13, and the first reactor air outlet pipeline 13 is provided with a first reactor air outlet valve 131; the bottom of the second reactor 2 is connected with a first second reactor air inlet pipeline 21 and a second reactor air inlet pipeline 22, the first second reactor air inlet pipeline 21 is provided with a first second reactor air inlet valve 211, the second reactor second air inlet pipeline 22 is communicated with the first reactor 1 at the top of the first reactor 1, the second reactor second air inlet pipeline 22 is provided with a second reactor second air inlet valve 221, the top of the second reactor 2 is provided with a second reactor air outlet pipeline 23, the second reactor air outlet pipeline 23 is provided with a second reactor air outlet valve 231, and the first reactor air outlet pipeline 13 is communicated with the second reactor air outlet pipeline 23 and then communicated with the first absorption groove 3. The first reactor and the second reactor are both fluidized bed reactors, and porous partition plates are arranged in the fluidized bed reactors.
Example 1
The preparation method of bismuth trifluoride of this example includes the following steps:
1) Drying bismuth trichloride at a constant temperature of 100 ℃ for 3 hours for later use;
then, placing the dried bismuth trichloride on a porous partition plate of a first reactor and a porous partition plate of a second reactor respectively;
2) Closing a first air inlet valve of a first reactor, a second air inlet valve of the first reactor, an air outlet valve of the first reactor, a first air inlet valve of a second reactor, a second air inlet valve of the second reactor and an air outlet valve of the second reactor, heating the first reactor and the second reactor by adopting a heating device to gradually raise the temperature of the two reactors to 100 ℃, simultaneously vacuumizing the interiors of the first reactor and the second reactor by adopting a vacuum pump until the absolute pressure is 0.04MPa, and stopping vacuumizing;
then opening a first air inlet valve of the first reactor and a second air inlet valve of the second reactor, and introducing F-containing gas through a first air inlet pipeline of the first reactor 2 When the gauge pressure in the first reactor and the second reactor reaches 15KPa, opening the gas outlet valve of the second reactor, absorbing the gas discharged from the second reactor by using 100g/L sodium hydroxide, and simultaneously adjusting the gas containing F introduced into the first reactor 2 The gauge pressure in the first reactor and the second reactor is stabilized to 15KPa by the flow of the gas, and the temperature in the first reactor and the second reactor is maintained to be 100 ℃ for reaction;
3) After the bismuth trichloride in the first reactor completely reacts, stopping heating the first reactor, switching an air source connected with a first air inlet pipe of the first reactor into nitrogen and opening an air outlet valve of the first reactor, simultaneously closing a second air inlet valve of the second reactor and opening a first air inlet valve of the second reactor, and introducing F-containing gas into the second reactor through a first air inlet pipeline of the second reactor 2 Gas, the temperature in the second reactor is maintained at 100 ℃, and the gauge pressure is maintained at 15KPa to continue the reaction;
after the materials in the first reactor are cooled, unloading and reloading the dried bismuth trichloride, closing a first air inlet valve and a first reactor air outlet valve of the first reactor, heating the first reactor by adopting a heating device to ensure that the temperature of the first reactor is raised to 100 ℃, simultaneously vacuumizing the first reactor by adopting a vacuum pump until the absolute pressure is 0.04MPa, and stopping vacuumizing; then closing the second reactor gas outlet valve, simultaneously opening the second gas inlet valve and the first reactor gas outlet valve of the first reactor, and adjusting the gas inlet valveInto a second reactor containing F 2 The flow rate of the gas ensures that the gauge pressure in the first reactor and the second reactor is stabilized to be 15KPa, and simultaneously the temperature of the first reactor and the second reactor is maintained to be 100 ℃ for reaction; absorbing the gas discharged from the first reactor by using 100g/L sodium hydroxide solution;
after the bismuth trichloride in the second reactor completely reacts, stopping heating the second reactor, switching an air source connected with a first air inlet pipeline of the second reactor into nitrogen and opening an air outlet valve of the second reactor, and simultaneously closing a second air inlet valve of the first reactor and opening a first air inlet valve of the first reactor to be introduced into the reactor containing F through the first air inlet pipeline of the first reactor 2 Gas, keeping the temperature in the first reactor at 100 ℃ and the gauge pressure at 15KPa for continuous reaction;
after the materials in the second reactor are cooled, unloading and reloading the dried bismuth trichloride, closing a first air inlet valve and a second air outlet valve of the second reactor, heating the second reactor by adopting a heating device to ensure that the temperature of the second reactor is raised to 100 ℃, simultaneously vacuumizing the second reactor by adopting a vacuum pump until the absolute pressure is 0.04MPa, and stopping vacuumizing; then closing the gas outlet valve of the first reactor, simultaneously opening the second gas inlet valve and the gas outlet valve of the second reactor, and adjusting the gas containing F introduced into the first reactor 2 The flow rate of the gas ensures that the gauge pressure in the first reactor and the second reactor is stabilized to be 15KPa, and simultaneously the temperature of the first reactor and the second reactor is maintained to be 100 ℃ for reaction; absorbing the gas discharged from the second reactor by using 100g/L sodium hydroxide solution;
if the pH value of the alkali liquor in the absorption tank reaches 10, replacing new alkali liquor, filtering the absorbed alkali liquor, collecting filtrate to obtain sodium hypochlorite solution, washing and drying the filtered solid to obtain high-purity sodium fluoride, collecting washing water, and then preparing the alkali liquor again;
4) And (5) repeating the step (3) to carry out continuous production.
The compound used in this example contains F 2 The gas consists of nitrogen and fluorine; the mass percentage of fluorine gas was 10%.
Example 2
The method for producing bismuth trifluoride of this example is different from the method for producing bismuth trifluoride of example 1 in that: drying the adopted bismuth trichloride at a constant temperature of 150 ℃ for 2.5 hours before being filled into a first reactor and a second reactor; when the first reactor and the second reactor are vacuumized by a vacuum pump, vacuumizing is carried out until the absolute pressure in the reactors is 0.02MPa; in the reaction process, the gauge pressure in the first reactor and the second reactor is maintained to be 10KPa; when a heating device is adopted to heat the first reactor and the second reactor, the temperature in the reactors is raised to 150 ℃, and the temperature of the first reactor and the second reactor is maintained to be 150 ℃ in the reaction process; adopted containing F 2 The mass percentage of fluorine gas in the gas is 20%; the alkali liquor in the absorption tank is 150g/L sodium hydroxide solution, the alkali liquor is replaced after the pH of the alkali liquor in the absorption tank reaches 10.5, and the temperature of the alkali liquor is maintained at 25 ℃ in the absorption process; nothing is said to be exactly the same as in example 1.
Example 3
The method for producing bismuth trifluoride of this example is different from the method for producing bismuth trifluoride of example 1 in that: drying the adopted bismuth trichloride at a constant temperature of 150 ℃ for 2 hours before being filled into a first reactor and a second reactor; when a vacuum pump is adopted to vacuumize the first reactor and the second reactor, the first reactor and the second reactor are both vacuumized until the absolute pressure in the reactors is 0.01MPa; in the reaction process, the gauge pressure in the first reactor and the second reactor is maintained to be 5KPa; when a heating device is adopted to heat the first reactor and the second reactor, the temperature in the reactors is increased to 180 ℃, and the temperature of the first reactor and the second reactor is maintained to be 180 ℃ in the reaction process; used containing F 2 The mass percentage of fluorine gas in the gas is 30%; the alkali liquor in the absorption tank is 200g/L sodium hydroxide solution, the alkali liquor is replaced after the pH value of the alkali liquor in the absorption tank reaches 11, and the temperature of the alkali liquor is controlled to be 30 ℃ in the absorption process; nothing is said to be exactly the same as in example 1.
Examples of the experiments
The results of examination of the bismuth trifluoride, sodium chloride and sodium hypochlorite solutions prepared in examples 1 to 3 are shown in tables 1 to 3.
TABLE 1 results of measuring bismuth trifluoride obtained in examples 1 to 3
Table 2 results of sodium fluoride detection obtained in examples 1 to 3
TABLE 3 detection results of sodium hypochlorite solutions prepared in examples 1 to 3
As can be seen from the data in tables 1-3, the bismuth trifluoride product obtained by the method for preparing bismuth trifluoride and co-producing sodium fluoride has high purity and low impurity content, and the quality of the bismuth trifluoride product is comparable to that of products of domestic manufacturers; the by-products of sodium fluoride and sodium hypochlorite meet the requirements of corresponding national standards.
Claims (10)
1. A preparation method of bismuth trifluoride is characterized by comprising the following steps: the method comprises the following steps: introducing F into a first reactor containing bismuth trichloride 2 Gas, controlling the temperature to be 50-200 ℃ for reaction to obtain; will contain F 2 Gas is introduced from the bottom of the first reactor to keep the materials in a suspended state.
2. The method for producing bismuth trifluoride according to claim 1, wherein: and introducing gas exhausted from the first reactor into a second reactor containing bismuth trichloride during the reaction process, and controlling the temperature of the second reactor to be 50-200 ℃ for reaction.
3. The method for producing bismuth trifluoride according to claim 2, wherein: the following steps are repeated:
stopping introducing F-containing gas into the first reactor after the bismuth trichloride in the first reactor completely reacts 2 Gas is directly fed into the second reactor and F is contained 2 Gas, controlling the temperature to be 50-200 ℃ for reaction;
after the materials in the first reactor are cooled, unloading the materials, and reloading the bismuth trichloride; introducing the gas discharged from the second reactor into the first reactor which is refilled with bismuth trichloride, and controlling the temperature to be 50-200 ℃ for reaction;
stopping introducing F-containing gas into the second reactor after the bismuth trichloride in the second reactor completely reacts 2 Gas is directly introduced into the first reactor and contains F 2 Gas, controlling the temperature to be 50-200 ℃ for reaction;
after the materials in the second reactor are cooled, unloading the materials and reloading the bismuth trichloride; and introducing the gas exhausted from the first reactor into a second reactor filled with bismuth trichloride again, and controlling the temperature to be 50-200 ℃ for reaction.
4. The method for producing bismuth trifluoride according to claim 2, wherein: before bismuth trichloride is loaded into a first reactor and a second reactor, drying the bismuth trichloride at the temperature of 100-150 ℃.
5. The method of producing bismuth trifluoride according to any one of claims 1 to 4, characterized in that: said group containing F 2 The gas is a mixed gas of fluorine gas and inert gas; the mass percentage of the fluorine gas in the mixed gas is 1-50%.
6. The method for producing bismuth trifluoride according to claim 2, wherein: and in the reaction process, the gauge pressure of the first reactor and the second reactor is controlled to be 1-20 KPa.
7. The method for producing bismuth trifluoride according to claim 2, wherein: after bismuth trichloride is filled in the first reactor and/or the second reactor, the corresponding reactor is vacuumized, and then gas is introduced.
8. The method of producing bismuth trifluoride according to claim 3, wherein: stopping the introduction of F-containing gas into the first reactor and/or the second reactor 2 After the gas is introduced, inert gas is introduced into the corresponding reactor to cool the material.
9. The method for producing bismuth trifluoride according to claim 3, wherein: and (3) absorbing the gas discharged from the first reactor and not introduced into the second reactor and/or the gas discharged from the second reactor and not introduced into the first reactor by using alkali liquor.
10. The method for producing bismuth trifluoride according to claim 9, wherein: the alkali liquor is a sodium hydroxide solution with the concentration of not less than 100 g/L; in the absorption treatment process, the alkali liquor after the pH value is reduced to 10-11 is subjected to solid-liquid separation.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101212050A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | Method for producing bismuth trifluoride anode material of Li secondary battery |
| CN105800685A (en) * | 2016-03-09 | 2016-07-27 | 浙江大学 | Preparation method of regular octahedral bismuth fluoride material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101212050A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | Method for producing bismuth trifluoride anode material of Li secondary battery |
| CN105800685A (en) * | 2016-03-09 | 2016-07-27 | 浙江大学 | Preparation method of regular octahedral bismuth fluoride material |
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