CN108793192B - Preparation method and preparation system of ammonium fluoride - Google Patents
Preparation method and preparation system of ammonium fluoride Download PDFInfo
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- CN108793192B CN108793192B CN201810948368.9A CN201810948368A CN108793192B CN 108793192 B CN108793192 B CN 108793192B CN 201810948368 A CN201810948368 A CN 201810948368A CN 108793192 B CN108793192 B CN 108793192B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/162—Ammonium fluoride
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Abstract
The invention relates to a preparation method and a preparation system of ammonium fluoride, comprising a liquid ammonia tank, a hydrogen fluoride tank, an anhydrous organic solvent tank, a reaction kettle, a centrifuge, a mother liquor tank, a condensing device, a thermometer and a pH meter, wherein ammonia and hydrogen fluoride are sequentially dissolved in an organic solvent, and the hydrogen fluoride and ammonia gas react in the organic solvent to produce anhydrous ammonium fluoride; the solubility of the hydrogen fluoride and ammonia in the organic solvent is higher than the solubility of the anhydrous ammonium fluoride in the organic solvent. The anhydrous ammonium fluoride powder obtained by the preparation method has small granularity and high purity, and the organic solvent can be recycled all the time in the reaction.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a preparation method and a preparation system of ammonium fluoride.
Background
The production methods of ammonium fluoride are respectively gas phase method, sublimation method and liquid phase method. Commonly used in industry is a neutralization process among liquid phase processes: a predetermined amount of hydrofluoric acid was put into a lead or plastic container. The outside of the container is cooled by water, ammonia gas is slowly introduced under stirring until the Ph value of the reaction solution reaches about 4. And cooling and crystallizing the reaction solution, centrifugally separating, and drying by airflow to obtain the ammonium fluoride product. The reaction principle is as follows: NH (NH)3+HF→NH4F. However, the method has some defects, such as high water content and low purity of ammonium fluoride prepared by a medium-sized method, more ammonia gas and hydrogen fluoride gas discharged into air, and great environmental pollution. In addition, the ammonium fluoride produced by the method has uneven acidity and higher content of metal impurities.
Disclosure of Invention
Therefore, the preparation method of ammonium fluoride and the matched preparation system thereof are needed to be provided, wherein the preparation method is simple to operate, safe in operation process, free of pollution and low in production cost.
The inventor provides a preparation method of ammonium fluoride, ammonia and hydrogen fluoride are sequentially dissolved in an organic solvent, and the hydrogen fluoride and the ammonia react in the organic solvent to produce anhydrous ammonium fluoride;
the solubility of the hydrogen fluoride and ammonia in the organic solvent is higher than the solubility of the anhydrous ammonium fluoride in the organic solvent.
Further, the solubility of the hydrogen fluoride and ammonia in the organic solvent is 20g or more, and the solubility of the anhydrous ammonium fluoride in the organic solvent is 1g or less.
Further, the organic solvent includes methanol, ethanol, acetonitrile, dichloromethane, or a mixture thereof.
Further, the preparation method comprises the following steps:
preparing an ammonia solution: adding liquid ammonia into the organic solvent, uniformly mixing, and preparing an ammonia solution;
and (3) synthesizing ammonium fluoride: and introducing hydrogen fluoride gas into the ammonia solution, reacting the hydrogen fluoride with the ammonia solution to generate anhydrous ammonium fluoride, and separating white anhydrous ammonium fluoride powder from the reaction solution.
Further, in the step of preparing the ammonia solution, the mass ratio of the liquid ammonia to the organic solvent is 5-50: 50-95.
Further, in the step of synthesizing the ammonium fluoride, hydrogen fluoride gas is introduced until the pH value of the reaction solution is 7-8, and then the reaction is terminated.
When the mass ratio of ammonia to the organic solvent is 50:50, the pH value of the reaction termination is 8; and when the mass ratio of ammonia to the organic solvent was 5:95, the pH at which the reaction was terminated was 7.
Further, in the step of preparing the ammonia solution, the adding speed of the liquid ammonia is 10L/min-500L/min; in the step of synthesizing the ammonium fluoride, the aeration speed of the hydrogen fluoride is 10L/min-500L/min.
Further, in the step of preparing the ammonia solution, the feeding temperature is controlled to be 10-30 ℃, and the final temperature of the ammonia solution is controlled to be 0-10 ℃. In the step of synthesizing the ammonium fluoride, the reaction temperature is controlled to be 10-30 ℃, and the high-temperature reaction is avoided from being too violent.
The temperature of the ammonia solution is controlled to be gradually reduced to 0-10 ℃, the ammonia solution is configured into a high exothermic reaction, the intensity of the reaction can be reduced by controlling the temperature, and the operation safety is enhanced. Meanwhile, the temperature of the ammonia solution is finally reduced to 0-10 ℃, which is beneficial to controlling the temperature in the later ammonium fluoride synthesis step, controlling the reaction temperature and avoiding over violent reaction.
Further, the preparation method also comprises a solid-liquid separation step and a vacuum drying step, and the preparation method specifically comprises the following steps:
solid-liquid separation: carrying out solid-liquid separation on the solution containing white anhydrous ammonium fluoride powder obtained in the ammonium fluoride synthesis step to obtain a crude product of ammonium fluoride,
and (3) vacuum drying: and (4) carrying out reduced pressure vacuum drying on the ammonium fluoride crude product to obtain an ammonium fluoride finished product.
The inventor also provides a system for preparing ammonium fluoride, which comprises a liquid-free ammonia tank, a hydrogen fluoride tank, an anhydrous organic solvent tank, a reaction kettle, a centrifuge, a mother liquor tank, a condensing device, a thermometer and a pH meter;
the reaction kettle is characterized in that a stirrer is arranged at the bottom of the reaction kettle cavity, a liquid ammonia inlet, a hydrogen fluoride air inlet, an anhydrous organic solvent inlet, an air exhaust port, a first backflow port, a second backflow port, a thermometer port and a pH meter port are arranged above the reaction kettle, a reaction kettle liquid outlet is arranged below the reaction kettle, the liquid ammonia tank liquid outlet is communicated with the liquid ammonia inlet arranged on the reaction kettle through a first valve, a hydrogen fluoride air outlet of the hydrogen fluoride tank is communicated with the hydrogen fluoride air inlet arranged on the reaction kettle through a second valve, the anhydrous organic solvent tank liquid outlet is communicated with the anhydrous organic solvent inlet arranged on the reaction kettle through a third valve, the reaction kettle liquid outlet is communicated with a mother liquid tank inlet arranged on the mother liquid tank through a centrifugal machine and a fourth valve, the mother liquid tank liquid outlet arranged on the mother liquid tank is communicated with the first backflow port through a conveying pump, the thermometer is inserted into the reaction kettle through the thermometer port, and the pH meter is inserted into the reaction kettle through the pH meter port;
the condensing device comprises a condenser, a gas-liquid separator and a receiving groove, the exhaust port is communicated with a gas-liquid separator liquid inlet formed in the upper end of the gas-liquid separator through the condenser and a fifth valve, a first gas-liquid separator liquid outlet is formed in the lower end of the gas-liquid separator, a second gas-liquid separator liquid outlet is formed in the side face of the gas-liquid separator, a receiving groove liquid inlet is formed in the upper end of the receiving groove, the first gas-liquid separator liquid outlet is communicated with the receiving groove liquid inlet through a sixth valve, and the second gas-liquid separator liquid outlet is communicated with a second backflow port through a seventh valve;
the reaction kettle cavity wall is of a sandwich structure, a cooling liquid inlet and a cooling liquid outlet are respectively formed in the reaction kettle cavity wall, the cooling liquid inlet is externally connected with a refrigerant source, and an eighth valve is arranged at the cooling liquid inlet.
Different from the prior art, the technical scheme provides a preparation method and a preparation system of ammonium fluoride, ammonia and hydrofluoric acid are dissolved in an organic solvent in sequence, and the ammonia and the hydrofluoric acid react in the organic solvent to produce anhydrous ammonium fluoride; the solubility of the hydrogen fluoride and ammonia in the organic solvent is higher than the solubility of the anhydrous ammonium fluoride in the organic solvent. The anhydrous ammonium bifluoride powder obtained by the preparation method has small granularity and high purity, and the organic solvent can be recycled all the time in the reaction.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for preparing ammonium fluoride according to this embodiment.
Description of reference numerals:
1. a liquid ammonia tank;
2. a hydrogen fluoride tank;
3. an anhydrous organic solvent tank;
4. a reaction kettle;
41. a thermometer;
42. a pH meter;
43. a stirrer;
44. the wall of the reaction kettle;
441. a cooling liquid inlet;
442. a cooling liquid outlet;
5. a centrifuge;
6. a mother liquor tank;
71. a condenser;
72. a gas-liquid separator;
73. a receiving slot;
81. a first valve;
82. a second valve;
83. a third valve;
84. a fourth valve;
85. a fifth valve;
86. a sixth valve;
87. and a seventh valve.
Detailed Description
To explain technical contents, structural features, achieved objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying figure 1 of the specification in conjunction with specific embodiments.
EXAMPLE 1 preparation of ammonium fluoride
Referring to fig. 1, the inventor provides a system for preparing ammonium fluoride, which includes a liquid ammonia tank 1, a hydrogen fluoride tank 2, an anhydrous organic solvent tank 3, a reaction kettle 4, a centrifuge 5, a mother liquid tank 6, a condensing device, a thermometer 41 and a pH meter 42;
liquid ammonia tank is used for the raw materials liquid ammonia of splendid attire preparation ammonium fluoride, the hydrogen fluoride gas tank is used for the raw materials hydrogen fluoride gas of splendid attire preparation ammonium fluoride, anhydrous organic solvent tank is used for the anhydrous organic solvent of splendid attire, ammonium fluoride is by ammonia and anhydrous hydrogen fluoride reaction formation in anhydrous organic solvent, reation kettle is as the container of ammonium fluoride reaction, centrifuge's effect is to isolate the solution in the ammonium fluoride follow reation kettle that the reaction generates, thereby obtain the ammonium fluoride result, the mother liquor groove is arranged in the splendid attire to be followed the solution that centrifugal separation was gone out from centrifuge, and carry it back to continue participating in the reaction in reation kettle.
The reactor is characterized in that a stirrer 43 is arranged at the bottom of the reactor cavity and used for mixing liquid ammonia and an anhydrous organic solvent to generate ammonia solution, the stirrer can also be used for mixing the ammonia solution and the hydrogen fluoride gas in the process of introducing the hydrogen fluoride gas into the reactor, and the reactor also comprises a power mechanism, the stirrer is in transmission connection with the power mechanism, the power mechanism drives the stirrer to rotate and stir the liquid ammonia, the anhydrous organic solvent and the anhydrous hydrogen fluoride in the reactor, so that the liquid ammonia, the anhydrous organic solvent and the anhydrous hydrogen fluoride are uniformly distributed in the reactor, the reaction is uniformly carried out in the organic solvent of the reactor, the local overheating phenomenon caused by the excessive local concentration is avoided, and the reactor is helpful for reaction heat dissipation.
A liquid ammonia inlet, a hydrogen fluoride inlet, an anhydrous organic solvent inlet, an exhaust port, a first backflow port, a second backflow port, a thermometer port and a pH meter port are formed above the reaction kettle, the liquid ammonia inlet is used for inputting liquid ammonia into the reaction kettle, the hydrogen fluoride inlet is used for inputting hydrogen fluoride gas into the reaction kettle, the anhydrous organic solvent inlet is used for inputting anhydrous organic solvent into the reaction kettle, the preparation of ammonium fluoride in the reaction kettle is a heat release reaction, the gas in the reaction kettle can expand in the reaction process, the exhaust port is used for outputting the expanded gas in the reaction kettle out of the reaction kettle, the explosion condition caused by the gas building in the reaction kettle is avoided, the first reflux opening is used for inputting the solution which is contained in the mother liquid tank and is centrifugally separated by the centrifugal machine back to the reaction kettle, the second reflux opening is used for conveying the ammonia gas and the hydrogen fluoride gas separated from the gas-liquid separator back to the reaction kettle to continuously participate in the reaction. A reaction kettle liquid outlet is formed below the reaction kettle, and the reaction kettle liquid outlet is used for outputting an ammonium fluoride product and liquid in the kettle out of the reaction kettle after the reaction is finished.
The liquid ammonia tank liquid outlet is linked together through the liquid ammonia inlet of seting up on first valve 81 and pipeline and reation kettle, the hydrogen fluoride gas inlet of seting up on hydrogen fluoride gas tank gas outlet through second valve 82 and pipeline and reation kettle is linked together, the anhydrous organic solvent tank liquid outlet is linked together through the anhydrous organic solvent inlet of seting up on third valve 83 and pipeline and the reation kettle, the reation kettle liquid outlet is linked together through the mother cistern inlet of seting up on centrifuge and fourth valve 84 and the mother cistern, the mother cistern liquid outlet of seting up on the mother cistern is linked together through delivery pump and first backflow mouth.
Opening the first valve and the third valve, inputting liquid ammonia in the liquid ammonia tank into the reaction kettle, inputting anhydrous organic solvent in the anhydrous organic solvent tank into the reaction kettle, starting the stirrer, uniformly mixing the liquid ammonia and the anhydrous organic solvent, opening the second valve again, introducing hydrogen fluoride gas into the reaction kettle, finally preparing ammonium fluoride, opening the fourth valve, inputting ammonium fluoride products in the reaction kettle and residual solution in the reaction into a centrifugal machine, separating the ammonium fluoride products from the solution by the centrifugal machine, conveying the residual solution into a mother liquid tank, opening a conveying pump again, and conveying the solution in the mother liquid tank into the reaction kettle through the first backflow port.
The condensing unit includes a condenser 71 for cooling the gas discharged from the gas discharge port, which contains ammonia gas as a main component, a small amount of hydrogen fluoride gas, and a vaporized organic solvent, a gas-liquid separator 72, and a receiver 73. The gas-liquid separator is used for separating the condensed organic solvent in the condenser from gas to realize the purpose of gas-liquid separation, the organic solvent condensed into liquid is stored in the receiving tank, and the residual ammonia gas and hydrogen fluoride gas are introduced into the reaction kettle to continuously participate in the reaction.
The exhaust port is communicated with a gas-liquid separator liquid inlet formed in the upper end of the gas-liquid separator through a condenser, a fifth valve 85 and a pipeline, a first gas-liquid separator liquid outlet is formed in the lower end of the gas-liquid separator, a second gas-liquid separator liquid outlet is formed in the side face of the gas-liquid separator, a receiving groove liquid inlet is formed in the upper end of the receiving groove, the first gas-liquid separator liquid outlet is communicated with the receiving groove liquid inlet through a sixth valve 86, and the second gas-liquid separator liquid outlet is communicated with the second backflow port through a seventh valve 87.
And gas expanded by heating in the reaction kettle is input into the condenser through a pipeline, the condenser is started, the vaporous organic solvent in the condenser is condensed into liquid, the fifth valve is opened, the organic solvent condensed into liquid carries ammonia and hydrogen fluoride gas to be conveyed into the gas-liquid separator from the condenser, the gas-liquid separator separates the ammonia and the hydrogen fluoride gas from the organic solvent, the sixth valve is opened, the organic solvent in the gas-liquid separator is conveyed into the receiving tank, the seventh valve is opened, and the ammonia and the hydrogen fluoride gas in the gas-liquid separator are conveyed back into the reaction kettle through the second backflow port. In some preferred embodiments, a vent valve is connected to an inlet of the gas-liquid separator to prevent the condensation device from generating a gas hold-up phenomenon, and the gas discharged from the condensation device is mainly air and the main component of the gas is nitrogen.
The utility model discloses a cooling device, including reation kettle cavity wall 44, coolant liquid inlet 441 and coolant liquid outlet 442, the through-hole structure that constitutes between inner wall and the outer wall is the coolant liquid, and coolant liquid inlet and coolant liquid outlet are all run through into the intermediate layer by the outer wall, and the external coolant liquid source of coolant liquid inlet, coolant liquid inlet department is provided with the eighth valve, and the coolant liquid is poured into the coolant liquid into reation kettle's intermediate layer through the coolant liquid inlet to reation kettle's intermediate layer, and the coolant liquid flows in the intermediate layer from the coolant liquid inlet to flow the intermediate layer from the coolant liquid outlet, with the temperature that reduces in the reation kettle. In some preferred embodiments, the cooling liquid inlet is arranged below the reaction kettle, and the cooling liquid outlet is arranged above the reaction kettle, so that the cooling liquid can be filled in an interlayer of the reaction kettle, and the cooling effect is better;
in some preferred embodiments, when the reaction kettle needs to be overhauled, the cooling liquid outlet is externally connected with air, the air is introduced into the interlayer wall of the reaction kettle, and the coolant in the interlayer structure is evacuated for overhauling.
In certain preferred embodiments, the cooling fluid is brine, which has the beneficial effects that: brine has a lower melting point than clear water, is able to absorb more heat, and is less costly than other cooling fluids.
The thermometer is used for monitoring the reaction temperature in the reaction kettle in real time, a thermometer opening is formed in the upper portion of the reaction kettle, and the thermometer is inserted into the thermometer opening.
The pH meter is used for monitoring the pH value in the reaction kettle in real time, a pH meter port is formed above the reaction kettle, and the pH meter is inserted in the pH meter port.
In certain preferred embodiments, the cooling fluid is brine, which has the beneficial effects that: brine has a lower melting point than clear water, is able to absorb more heat, and is less costly than other cooling fluids.
When producing ammonium fluoride, a first valve at a liquid outlet of the anhydrous organic solvent tank is opened, 400 kg of methanol is added into a dry reaction kettle, then a third valve at a liquid outlet of the liquid ammonia tank is opened, 400 kg of liquid ammonia is slowly added into the reaction kettle (the adding speed is 100L/min), and the temperature is controlled to be 20-30 ℃.
The stirrer at the bottom of the reaction kettle cavity is started, the stirring speed is 85 revolutions per minute, after the stirring is carried out for 10 minutes, the eighth valve arranged at the coolant inlet is opened, the coolant enters the sandwich structure on the wall of the reaction kettle cavity to cool the reaction kettle, and the temperature of the materials in the kettle is gradually reduced to 0 ℃ in the stirring process. When the temperature is reduced to 0 ℃, a second valve at the gas outlet of the hydrogen fluoride gas tank is opened, hydrogen fluoride stored in the hydrogen fluoride gas tank is introduced into the reaction kettle at the speed of 200L/min, and ammonia and hydrogen fluoride react in the organic solvent to generate ammonium fluoride. And introducing hydrogen fluoride gas until the pH value of the liquid in the kettle is 8, and stopping introducing the hydrogen fluoride gas. Because a large amount of heat is generated in the generation of ammonium fluoride, a small amount of ammonia gas is released and collected by a condensing device.
In the process of hydrogen fluoride, a large amount of white solid ammonium fluoride is generated in the kettle, a cooling liquid is required to be led into the wall of the reaction kettle cavity to carry out timely heat exchange cooling on the reaction kettle and a solvent in the kettle, the reaction temperature is controlled to be 10-30 ℃, and excessive pressure generated due to over violent reaction in the reaction kettle is avoided.
And after stopping introducing the hydrogen fluoride, centrifuging the materials in the reaction kettle by using a centrifugal machine (the centrifugal rotating speed is 900 revolutions per minute), and performing solid-liquid separation on the materials to obtain crude ammonium fluoride with the wet weight of about 970 kilograms. And collecting the mother liquor obtained after solid-liquid separation by using a mother liquor tank, wherein the mother liquor can be added into the reaction kettle for recycling.
The solubility of hydrofluoric acid in methanol at 25 ℃ is 50g, the solubility of ammonia in methanol is 35g, and the solubility of anhydrous ammonium fluoride in methanol is less than 0.1 g.
And (3) drying the obtained crude ammonium fluoride product in vacuum at the vacuum degree of 0.08MPa and the temperature of 60 ℃ for 2 hours to obtain 865 kg of white solid ammonium fluoride finished product with the purity of 99.4 percent and the yield of 99 percent.
EXAMPLE 2 preparation of ammonium fluoride end product
Example 2 differs from example 1 in that the organic solvent used in example 2 is ethanol; the liquid ammonia was added at a rate of 500L/min.
The solubility of hydrofluoric acid in ethanol at 25 ℃ is 50g, the solubility of ammonia in ethanol is 35g, and the solubility of anhydrous ammonium fluoride in ethanol is less than 0.1 g.
The total amount of the obtained white solid ammonium bifluoride finished product is 865 kg, the purity is 99.4 percent, and the yield is 99 percent.
Example 3
Example 3 differs from example 1 in that acetonitrile was used as the organic solvent in example 3; the liquid ammonia was added at a rate of 10L/min.
The solubility of hydrofluoric acid in acetonitrile at 25 ℃ is 48g, the solubility of ammonia in acetonitrile is 35g, and the solubility of anhydrous ammonium fluoride in acetonitrile is less than 0.1 g.
866 kg of white solid ammonium fluoride finished product is finally obtained, the purity is 99.8 percent, and the yield is 99 percent.
Example 4
The difference between example 4 and example 1 is: in example 4, ethanol was used as an organic solvent, the liquid ammonia was added at a rate of 300L/min, the hydrofluoric acid gas was introduced at a rate of 500L/min, and the time of introduction was 10 hours. The total amount of the obtained white solid ammonium fluoride finished product is 865 kg, the purity is 99.5 percent, and the yield is 99 percent.
Example 5
The difference between example 5 and example 1 is: example 5 dichloromethane was used as organic solvent.
The solubility of hydrofluoric acid in dichloromethane at 25 ℃ is 48g, the solubility of ammonia in dichloromethane is 35g, and the solubility of the anhydrous ammonium fluoride in dichloromethane is less than 0.1 g.
861 kg of white solid ammonium fluoride finished products are finally obtained, the purity is 99.3%, and the yield is 99%.
Example 6
The difference between example 6 and example 1 is: in example 6, the amount of liquid ammonia added was 50 kg, the amount of methanol added was 950 kg, hydrofluoric acid gas was introduced after the temperature of the ammonia solution gradually decreased to 10 ℃ during stirring, the rate of hydrofluoric acid gas introduction was 10L/min, hydrofluoric acid was introduced until the pH of the liquid in the tank became 8, and hydrofluoric acid introduction was stopped. 86.6 kg of the finally obtained white solid ammonium fluoride finished product has the purity of 99.3 percent and the yield of 99 percent.
Example 7
The difference between example 7 and example 6 is: in example 7, acetonitrile and methanol were mixed at a mass ratio of 1:1 as an organic solvent, hydrofluoric acid gas was introduced after the temperature of the ammonia solution gradually decreased to 5 ℃ during stirring at a hydrofluoric acid gas introduction rate of 50L/min until the pH of the liquid in the tank became 8, and the hydrofluoric acid introduction was stopped. Finally obtaining the white solid ammonium fluoride finished product.
Example 8
The difference between example 8 and example 6 is: in example 8, dichloromethane, acetonitrile and methanol were mixed (mass ratio 1:1:1) as an organic solvent, hydrofluoric acid gas was introduced after the temperature of the ammonia solution gradually decreased to 10 ℃ during stirring, the flow rate of hydrofluoric acid was 150L/min, and the flow of hydrofluoric acid gas was stopped until the pH of the liquid in the tank became 8. Finally obtaining the white solid ammonium fluoride finished product.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.
Claims (8)
1. A preparation method of ammonium fluoride is characterized in that ammonia and anhydrous hydrogen fluoride are sequentially dissolved in an organic solvent, and the anhydrous hydrogen fluoride and the ammonia react in the organic solvent to produce anhydrous ammonium fluoride;
the anhydrous hydrogen fluoride and ammonia have a solubility in the organic solvent that is higher than the solubility of the anhydrous ammonium fluoride in the same organic solvent;
the solubility of the anhydrous hydrogen fluoride and ammonia in the organic solvent is more than 20g, and the solubility of the anhydrous ammonium fluoride in the organic solvent is less than 1 g;
the organic solvent comprises methanol, ethanol, acetonitrile, dichloromethane or mixtures thereof.
2. The method of claim 1, comprising the steps of:
preparing an ammonia solution: adding liquid ammonia into the organic solvent, uniformly mixing, and preparing an ammonia solution;
and (3) synthesizing ammonium fluoride: and introducing hydrogen fluoride gas into the ammonia solution, reacting the hydrogen fluoride with the ammonia solution to generate anhydrous ammonium fluoride, and separating white anhydrous ammonium fluoride powder from the reaction solution.
3. The production method according to claim 2, wherein in the ammonia solution preparation step, the mass ratio of the liquid ammonia to the organic solvent is 5-50: 50-95.
4. The method according to claim 2, wherein in the step of synthesizing ammonium fluoride, the reaction is terminated after hydrogen fluoride gas is introduced until the pH of the reaction solution is 7 to 8.
5. The method according to claim 2, wherein in the step of preparing the ammonia solution, the liquid ammonia is added at a rate of 10L/min to 500L/min; in the step of synthesizing the ammonium fluoride, the aeration speed of the hydrogen fluoride is 10L/min-500L/min.
6. The preparation method according to claim 2, wherein in the ammonia solution preparation step, the feeding temperature is controlled to be 10-30 ℃, and the final temperature of the ammonia solution is controlled to be 0-10 ℃; in the step of synthesizing the ammonium fluoride, the reaction temperature is controlled to be 10-30 ℃.
7. The preparation method according to claim 2, further comprising a solid-liquid separation step and a vacuum drying step, and the preparation method comprises the following specific steps:
solid-liquid separation: carrying out solid-liquid separation on the solution containing white anhydrous ammonium fluoride powder obtained in the ammonium fluoride synthesis step to obtain a crude product of ammonium fluoride,
and (3) vacuum drying: and (4) carrying out reduced pressure vacuum drying on the ammonium fluoride crude product to obtain an ammonium fluoride finished product.
8. A system for preparing ammonium fluoride according to any one of claims 2 to 7, comprising a liquid ammonia tank, a hydrogen fluoride tank, a water-free organic solvent tank, a reaction kettle, a centrifuge, a mother liquor tank, a condensing device, a thermometer and a pH meter;
the reactor is characterized in that a stirrer is arranged at the bottom of the reaction kettle cavity, a liquid ammonia inlet, a hydrogen fluoride air inlet, an anhydrous organic solvent inlet, an air exhaust port, a first reflux port, a second reflux port, a thermometer port and a pH meter port are arranged above the reaction kettle, a reaction kettle liquid outlet is arranged below the reaction kettle and is communicated with the liquid ammonia inlet arranged on the reaction kettle through a first valve, a hydrogen fluoride air inlet arranged on the reaction kettle is communicated with a hydrogen fluoride tank air outlet through a second valve, the anhydrous organic solvent tank liquid outlet is communicated with the liquid ammonia inlet arranged on the reaction kettle through a third valve, the reaction kettle liquid outlet is communicated with a mother liquid tank inlet arranged on the mother liquid tank through a centrifugal machine and a fourth valve, the mother liquid tank liquid outlet arranged on the mother liquid tank is communicated with the first reflux port through a delivery pump, and the thermometer is inserted into the reaction kettle through the thermometer port, the pH meter is inserted into the reaction kettle through a pH meter port;
the condensing device comprises a condenser, a gas-liquid separator and a receiving groove, the exhaust port is communicated with a gas-liquid separator liquid inlet formed in the upper end of the gas-liquid separator through the condenser and a fifth valve, a first gas-liquid separator liquid outlet is formed in the lower end of the gas-liquid separator, a second gas-liquid separator liquid outlet is formed in the side face of the gas-liquid separator, a receiving groove liquid inlet is formed in the upper end of the receiving groove, the first gas-liquid separator liquid outlet is communicated with the receiving groove liquid inlet through a sixth valve, and the second gas-liquid separator liquid outlet is communicated with a second backflow port through a seventh valve;
the reaction kettle cavity wall is of a sandwich structure, a cooling liquid inlet and a cooling liquid outlet are respectively formed in the reaction kettle cavity wall, the cooling liquid inlet is externally connected with a refrigerant source, and an eighth valve is arranged at the cooling liquid inlet.
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| CN103539157B (en) * | 2013-10-31 | 2016-06-01 | 洛阳氟钾科技股份有限公司 | The technique of fluorine resource is reclaimed from potassium feldspar decomposition residue |
| CN105197959B (en) * | 2015-09-09 | 2017-10-20 | 洛阳国兴矿业科技有限公司 | Chemically floatation handles the method that fluorine resource is reclaimed in low product bauxite technique |
| CN105253907B (en) * | 2015-09-09 | 2017-03-22 | 洛阳国兴矿业科技有限公司 | Comprehensive utilization method for processing low-grade bauxite through chemical floating method |
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