CN115747833B - High-integration-level high-purity fluorine gas supply system - Google Patents
High-integration-level high-purity fluorine gas supply system Download PDFInfo
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- CN115747833B CN115747833B CN202211353236.4A CN202211353236A CN115747833B CN 115747833 B CN115747833 B CN 115747833B CN 202211353236 A CN202211353236 A CN 202211353236A CN 115747833 B CN115747833 B CN 115747833B
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Abstract
The invention provides a high-integration high-purity fluorine gas supply system, which comprises: a movable substrate (40); an electrolyzer device (10) and a fluorine gas purification device (20) integrally provided on a movable substrate (40), wherein the movable substrate (40) has a horizontal plane on which the electrolyzer device (10) is provided; the high-integration-level high-purity fluorine gas supply system further comprises two level meters (41) arranged on the horizontal plane, wherein the level meters (41) are respectively arranged on two straight lines perpendicular to each other on the horizontal plane, and accordingly the high-integration-level high-purity fluorine gas supply system is used for judging whether the whole electrolytic tank device (10) is horizontal or not.
Description
Technical Field
The invention relates to a high-integration-level high-purity fluorine gas supply system.
Background
Fluorine gas is elemental fluorine, is light yellow, has very active chemical properties and very strong oxidizing property, and can be used as an oxidant in rocket fuel, a raw material of halogenated fluorine, a refrigerant, plasma etching and the like in industry. The high-purity fluorine gas is an important raw material in the field of fine chemical engineering, and is widely applied to high-new fields such as electronics, laser technology, medical plastics, electronics, new materials, aerospace and the like.
However, in the prior art, because the preparation of fluorine gas is dangerous, the fluorine gas is generally prepared, produced and purified by special equipment at a fixed place, and then packaged and sold. However, with the development of economy, the immediate demand for fluorine gas has increased significantly, and this approach has been difficult to meet.
Disclosure of Invention
The invention provides a high-integration-level high-purity fluorine gas supply system which can effectively solve the problems.
The invention is realized in the following way:
a high-integration high-purity fluorine gas supply system comprising:
a movable substrate;
an electrolytic cell device and a fluorine gas purifying device which are integrally arranged on a movable substrate, wherein the movable substrate is provided with a horizontal plane, and the electrolytic cell device is arranged on the horizontal plane;
the high-integration-level high-purity fluorine gas supply system further comprises two levels arranged on the horizontal plane, wherein the levels are respectively arranged on two straight lines which are mutually perpendicular on the horizontal plane, and therefore the electrolytic tank device is used for judging whether the whole electrolytic tank device is horizontal or not.
The beneficial effects of the invention are as follows: through the arrangement, the mobile safe fluorine production can be realized by the high-integration-level high-purity fluorine gas supply system, and the industrial pure fluorine demand is met.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of an electrolytic cell device in a high-integration high-purity fluorine gas supply system according to an embodiment of the present invention.
Fig. 2 is a flow chart of a safe production method for high-purity fluorine gas provided by the embodiment of the invention.
FIG. 3 is a flow chart of a method for controlling the electrolytic cell in a safe production method for high-purity fluorine gas according to an embodiment of the present invention.
Fig. 4 is a schematic view of a part of the structure of a high-integration high-purity fluorine gas supply system according to an embodiment of the present invention.
Fig. 5 is a flowchart of a method for preparing an adsorbent according to an embodiment of the present invention.
Fig. 6 is a flow chart of a safety control method of a fluorine gas purification device according to an embodiment of the present invention.
Fig. 7 is a schematic view of a part of the structure of a high-integration high-purity fluorine gas supply system according to an embodiment of the present invention.
Fig. 8 is a flow chart of a gas distribution method of the high-purity nitrogen/fluorine gas mixing device provided by the embodiment of the invention.
Fig. 9 is a schematic diagram of a high-integration high-purity fluorine gas supply system according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
In the description of the present invention, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
Referring to fig. 1, an embodiment of the present invention provides an electrolyzer apparatus 10 for preparing high purity fluorine gas, the electrolyzer apparatus 10 for preparing high purity fluorine gas comprising:
a closed electrolytic tank 11, wherein a hydrogen outlet 111, a fluorine outlet 112, a raw material inlet 113 and heating elements 110 arranged around the electrolytic tank 11 are arranged at the top of the electrolytic tank 11;
a cathode 12, a diaphragm 13, and an anode 14 disposed in the electrolytic cell 11, wherein the diaphragm 13 is configured to isolate the cathode 12 and the anode 14;
a first pressure sensor 17 provided at the hydrogen outlet 111;
a second air pressure sensor 18, a linkage control valve 19 and a negative pressure storage tank 21 which are sequentially arranged at the fluorine gas outlet 112;
and a control unit (not shown in the figure) electrically connected to the first air pressure sensor 17, the second air pressure sensor 18 and the coordinated control valve 19, respectively, where the control unit is configured to control the coordinated control valve 19 to open and close according to signals of the first air pressure sensor 17 and the second air pressure sensor 18, so as to control a pressure difference between the hydrogen outlet 111 and the fluorine outlet 112 to be within a predetermined range.
The structure and shape of the closed electrolytic cell 11 are not limited as long as they have a corrosion preventing and sealing function. In one embodiment, the electrolytic tank 11 includes a tank body and a cover body matched with the tank body, where the tank body and the cover body are made of corrosion-resistant alloy, such as monel or passivated carbon steel alloy, and the like, and the disclosure is not limited thereto. The raw material inlet 113 is used for feeding KHF according to the proportion 2 HF feedstock.In one embodiment, the feedstock inlet 113 includes a potassium bifluoride feed line 1130, a hydrogen fluoride feed line 1132, and a potassium bifluoride/hydrogen fluoride feed line 1134. The advantage of arranging the feed inlet 113 in three channels is: potassium bifluoride/hydrogen fluoride feed conduit 1132 may be the feed conduit for the initial feedstock, i.e., KHF is to be employed 2 After fully mixing the HF compound, feeding from the potassium fluoride/hydrogen fluoride feeding pipeline 1134; in the electrolysis process, the HF raw material needs to be regularly and periodically replenished to maintain KHF in the system due to the rapid consumption of HF 2 The ratio of F/HF is within a predetermined range. Further, KHF during electrolysis 2 Can be partially entrained by fluorine gas and also affect KHF 2 The ratio of HF thus requires a certain period of KHF supplementation 2 Raw materials. The heating element 110 may be a resistance wire or hydrothermal heating, etc., and the heating element 110 is used to control the temperature of the electrolytic bath 11 to 60-110 ℃ so that the KHF is maintained 2 HF melting. The hydrogen gas outlet 111 and the fluorine gas outlet 112 are isolated from each other by the membrane 13.
The number of the cathodes 12 and the anodes 14 is not limited, and may be arranged according to actual needs. The cathode 12 may be made of carbon steel or monel; the anode 14 may be made of carbon rod or the like. The diaphragm is used for isolating the hydrogen and the fluorine gas and preventing the hydrogen and the fluorine gas from being mutually interfered to cause explosion.
The first pressure sensor 17 is used for acquiring first pressure information of the hydrogen outlet 111. The second pressure sensor 18 is configured to obtain second pressure information of the fluorine gas outlet 112. The first pressure information reflects the pressure outside the diaphragm 13, and the second pressure information reflects the pressure inside the diaphragm 13; the pressure difference between the inner and outer sides of the diaphragm 13 determines the liquid level L of the inner and outer sides 1 And L 2 . If the liquid level is L 1 Or L 2 Too low can cause the hydrogen and fluorine gases to cross and explode. Therefore, it is necessary to strictly control the pressure difference between the hydrogen gas outlet 111 and the fluorine gas outlet 112 so as to be within a predetermined range.
In general, the pressure difference between the hydrogen gas outlet 111 and the fluorine gas outlet 112 may be controlled to be within a predetermined range by controlling the opening and closing of the linkage control valve 19. Specifically, the pressure of the hydrogen outlet 111 is generally directly communicated with the atmosphere, and the pressure of the hydrogen outlet 111 can be controlled to be a micro negative pressure by controlling the height of the exhaust port of the hydrogen outlet 111 to be between 10 and 50m, so that the hydrogen can be smoothly exhausted. Preferably, the height of the exhaust port of the hydrogen outlet 111 is between 30 and 40 meters. The pressure of the fluorine gas outlet 112 can be controlled by the negative pressure reservoir 21 and the linkage control valve 19. In general, in order to smoothly discharge the fluorine gas, the negative pressure storage tank 21 is evacuated by the first vacuum pump 22, and then the pressure of the fluorine gas outlet 112 is controlled by the opening and closing of the interlock control valve 19 so as to be in agreement with the pressure of the hydrogen gas outlet 111.
In other embodiments, the electrolyzer apparatus 10 for the production of high purity fluorine gas further comprises: the liquid level sensor 15 may be disposed inside or outside the diaphragm 13, and is not limited herein. In one embodiment, the liquid level sensor 15 is disposed outside the diaphragm 13, so that the liquid level L outside the diaphragm 13 can be obtained 2 . The liquid level L 2 Too low is not preferable, and too low causes the hydrogen to easily cross-talk to the inside of the separator 13, thereby creating a danger. Preferably, the liquid level L 2 The height of (2) is 10-20 cm; when the liquid level is too low, HF is fed through the raw material inlet 113 to reach a set level.
As a further improvement, in other embodiments, the control unit is further configured to obtain the liquid level height L inside the diaphragm 13 from the liquid level data of the liquid level sensor 15 and the first and second pressure information 1 . The same, the liquid level L 1 Too low is not preferable, and too low causes the fluorine gas to easily cross-talk to the outside of the separator 13, resulting in a risk. Preferably, the liquid level L 1 The height of (2) is 10-20 cm; when the liquid level is too lowFeeding HF through the feed inlet 113; or the pressure of the fluorine gas outlet 112 is controlled to a predetermined height by the opening and closing of the linkage control valve 19.
In other embodiments, the electrolyzer apparatus 10 for the production of high purity fluorine gas further comprises: an acidity sensor 16 for acquiring the acidity value of the electrolyte. KHF in electrolyte with acidity value directly determined 2 Too low or too high a ratio of/HF may result in low electrolysis efficiency, and thus, the acidity value of the electrolyte may be obtained by the acidity sensor 16, thereby controlling the addition amount of HF.
Referring to fig. 2, the embodiment of the invention further provides a safe production method for high-purity fluorine gas, which comprises the following steps:
s11, acquiring pressure information on two sides of the diaphragm 13, judging whether the pressure difference on two sides of the diaphragm 13 is in a set range, if so, continuing to operate, otherwise, entering step S12;
s12, controlling the opening and closing of the interlock control valve 19 controls the pressure inside the diaphragm 13 so that the pressure difference between both sides of the diaphragm 13 is within a set range.
In step S11, the pressure of the hydrogen outlet 111, that is, the pressure outside the membrane, is generally directly communicated with the atmosphere, and the pressure can be controlled to be a micro negative pressure by controlling the height of the exhaust port of the hydrogen outlet 111, and the height can be controlled to be between 10 and 50m, so that the hydrogen can be smoothly exhausted. The pressure of the fluorine gas outlet 112, that is, the pressure inside the diaphragm, can be controlled in a coordinated manner by the negative pressure reservoir 21 and the coordinated control valve 19. In general, in order to smoothly discharge the fluorine gas, the negative pressure storage tank 21 is evacuated by the first vacuum pump 22, and then the pressure of the fluorine gas outlet 112 is controlled by the opening and closing of the interlock control valve 19 so as to be in agreement with the pressure of the hydrogen gas outlet 111. Specifically, one atmosphere is about 101325Pa, and 1 meter of water is about 9803.9 Pa, and 10cm of water is about 980.4 Pa. And electrolyte KHF 2 HF has a density about twice that of water; thus, if the pressure difference between the two sides is 980.4Pa, the two sidesThe liquid level difference of (2) is about 5 cm. In the actual production process, when the pressure difference of two sides is larger than or equal to 980.4pa, namely the liquid level difference of two sides is larger than 5cm, an alarm is needed to be given and further adjustment is needed. More preferably, when the pressure difference between the two sides is equal to or greater than 490.2pa, that is, the liquid level difference between the two sides is greater than 2.5cm, an alarm is required and further adjustment is required.
In step S12, since the negative pressure reservoir 21 is in a vacuum state, the pressure inside the diaphragm 13 can be controlled by the opening and closing amount of the interlock control valve 19, and the pressure difference between both sides of the diaphragm 13 is set within a set range.
The safe production method may further include:
s13, acquiring the liquid level height of the inner side or the outer side of the diaphragm 13 through a liquid level sensor 15;
s14, acquiring the liquid level height of the other side through the liquid level height of the inner side or the outer side and the pressure information of the two sides of the diaphragm 13;
s15, judging whether the liquid level height of at least one side is lower than a set value.
In step S14, since the liquid level on one side can be obtained by the liquid level sensor 15 and the difference in level on both sides can be obtained by the information of the difference in pressure on both sides of the diaphragm 13, the liquid level on the other side can be obtained by these two parameters. Preferably, the liquid level L on both sides 1 And L 2 And not less than 5 cm. More preferably, the liquid level L on both sides 1 And L 2 And not less than 10 cm.
In step S15, since the pressure difference between both sides is within the set range, when the liquid level height of at least one side is lower than the set value, it is indicated that the replenishment of the electrolyte is required as the HF is largely reduced with the progress of electrolysis.
Therefore, after step S15, the method further includes:
and S16, when judging that the liquid level of at least one side is lower than the set value, controlling the raw material inlet 113 to carry out HF liquid supplementing. Specifically, the amount of HF to be supplemented is preferably such that the initial electrolysis conditions are satisfied.
After step S15, further comprising:
s17, acquiring the acidity value of the electrolyte through the acidity sensor 16, judging whether the acidity value is in a set range, otherwise, controlling the raw material inlet 113 to carry out the liquid supplementing of HF. In the actual electrolysis process, as the electrolysis proceeds, the HF acid is continuously consumed, and the acidity is somewhat reduced, so that the electrolysis efficiency is reduced. Therefore, it is necessary to test the acidity and control the raw material inlet 113 to perform the HF feeding when the acidity is lower than the set value.
After step S17 or S16, when the HF feeding is finished, it may further include:
s18, acquiring the acidity value of the electrolyte through the acidity sensor 16, judging whether the acidity value is in a set range, otherwise, controlling the raw material inlet 113 to perform KHF 2 Is added with the liquid for supplementing. In the actual electrolysis process, KHF is carried out as the electrolysis proceeds 2 Is partially entrained by the gas, and the acidity is increased, which reduces the electrolysis efficiency. Therefore, it is necessary to test acidity and control the raw material inlet 113 to perform KHF when acidity is higher than a set value 2 Is added with the liquid for supplementing.
Referring to fig. 3, the embodiment of the invention further provides a method for efficiently controlling an electrolytic cell, which comprises the following steps:
s21, according to KHF 2 Mixing the mixed solution with HF in a molar ratio of 1:2 to form electrolyte, adding the electrolyte into an electrolytic tank, controlling the reaction temperature to be 80-90 ℃ and the HF consumption current density to be 0.70-0.80 kg/kiloamp for electrolysis;
s22, acquiring the acidity value of the electrolyte by the acidity sensor 16 during electrolysis, and performing HF or KHF by the raw material inlet 113 when the acidity exceeds a set value 2 Is added with the liquid for supplementing.
In step S21, electrolysis is preferably performed with a HF consumption current density of 0.74 to 0.76 kg/kiloamp. In one embodiment, the electrolysis is performed with a controlled HF consumption current density of 0.75 kg/kiloamp.
In step S22, the acidity set value is 39.0 to 40.5%. More preferably, the acidity set point is 39.5 to 40.2%. In one embodiment thereof, the acidity settingThe value is about 40.0%. Specifically, when the acidity is too low, HF make-up is performed through the raw material inlet 113; when the acidity is too high, KHF is performed through the raw material inlet 113 2 And (5) supplementing liquid.
After step S22, it may further include:
s23, acquiring pressure information of two sides of the diaphragm 13, judging whether the pressure difference of the two sides of the diaphragm 13 is in a set range, if so, continuing to operate, otherwise, entering step S24;
s24, controlling the opening and closing of the linkage control valve 19 to control the inner pressure of the diaphragm 13, so that the pressure difference at two sides of the diaphragm 13 is within a set range.
In other embodiments, the method for efficiently controlling an electrolytic cell may further include:
s25, acquiring the liquid level height of the inner side or the outer side of the diaphragm 13 through the liquid level sensor 15;
s26, acquiring the liquid level height of the other side through the liquid level height of the inner side or the outer side and the pressure information of the two sides of the diaphragm 13;
s27, judging whether the liquid level height of at least one side is lower than a set value.
After step S27, further comprising:
and S28, when judging that the liquid level of at least one side is lower than the set value, controlling the raw material inlet 113 to carry out HF liquid supplementing.
Referring to fig. 4, an embodiment of the present invention provides a fluorine gas purification device 20, which includes: a negative pressure storage tank 21 for storing the fluorine gas mixture from the electrolyzer unit 10; a first vacuum pump 22 for evacuating the negative pressure reservoir 21; a trap tank 23 for condensing the fluorine gas mixture from the negative pressure storage tank 21 to remove most of hydrofluoric acid; an adsorption tank 24 for adsorbing the gas from the trapping tank 23 to remove most of impurities; a filter 25 for dust-removing the gas from the adsorption tank 24; a storage tank 26 for storing fluorine gas from the filter 25; and a second vacuum pump 27 for evacuating the storage tank 26.
The trapping tank 23 may condense the fluorine gas mixture in the trapping tank 23 by liquid nitrogen or other cold sources, and remove most of hydrofluoric acid and other impurities. The temperature of the trapping tank 23 may be higher than the boiling point of fluorine gas, and preferably, the temperature of the trapping tank 23 may be controlled to be-40 to-80 ℃. At this temperature, most of the impurities, especially HF acid gas, can be condensed. More preferably, the temperature of the trapping tank 23 may be controlled to be-50 to-60 ℃.
The first vacuum pump 22 and the second vacuum pump 27 are arranged, so that fluorine gas can flow freely without additional power, and other power equipment can be prevented from being corroded and damaged by the fluorine gas.
In other embodiments, at least two adsorption tanks 24 are included in parallel, so that continuous production can be achieved during actual production when one of the adsorption tanks 24 needs to be replaced with adsorbent.
In other embodiments, the fluorine gas purification device 20 may further include an absorption tank 28 connected to the adsorption tanks 24, respectively, for absorbing the fluorine gas in the adsorption tanks 24.
The adsorbent in the adsorption tank 24 is granular, has a plurality of micropores, and includes: 35-50 parts of sodium fluoride powder, 20-30 parts of potassium fluoride powder and 3-5 parts of binder. Preferably, the porous ceramic material consists of 35-50 parts by weight of sodium fluoride powder, 20-30 parts by weight of potassium fluoride powder and 3-5 parts by weight of binder, wherein the moisture content of the final product measured by the adsorbent is less than or equal to 0.2%, and the internal porosity can reach more than 50%.
Referring to fig. 5, an embodiment of the present invention provides a method for preparing an adsorbent, including the following steps:
s31, weighing 35-50 parts of sodium fluoride powder, 20-30 parts of potassium fluoride powder, 3-6 parts of binder and 3-8 parts of diluent according to mass fraction, adding into an oil bath pot at 180-200 ℃ for uniform mixing, and melting to form a mixed solution;
s32, placing the mixed solution into a spherical mold, molding in a press at 180-200 ℃, and cooling at room temperature to obtain a spherical fluoride salt mixture, wherein the molding pressure is 0.2-1 Mpa;
s33, placing the spherical fluoride salt mixture into a solvent to extract a diluent, wherein the solvent is a volatile organic solvent;
and S34, taking out the extracted spherical fluoride salt, volatilizing a solvent, and finally, blowing nitrogen to the surface of the product to obtain the fluoride salt adsorbent with high porosity.
As a further improvement, in step S31, the binder is selected from binders that can form sodium fluoride powder and potassium fluoride powder into good binding properties, such as polyvinylidene fluoride, styrene-butadiene rubber emulsion, carboxymethyl cellulose, and the like. In one embodiment, the binder is selected from polyvinylidene fluoride, which can provide good binding properties to sodium fluoride powder and potassium fluoride powder. The content of the binder is not too high, and although the binder is effective, it is easy to block the channels and it is difficult to form a high porosity.
The diluent is selected from materials which can infiltrate the three materials, such as diphenyl ketone, or other ketone compounds containing benzene rings.
As a further improvement, preferably, 36 to 40 parts of sodium fluoride powder, 22 to 25 parts of potassium fluoride powder, 3 to 6 parts of binder and 5 to 8 parts of diluent are weighed. In one example, 36 parts of sodium fluoride powder, 24 parts of potassium fluoride powder, 5 parts of a binder, and 5 parts of a diluent are weighed.
As a further refinement, it is preferred that the temperature of the oil bath is 185 to 195 ℃, in one embodiment the temperature of the oil bath is about 190 ℃.
In general, to increase the filling rate, it is generally pressed to form a spherical fluoride salt mixture. As a further improvement, in step S32, the mixed solution is placed in a spherical mold having a diameter of 5 to 15 mm. The pressure of the mould pressing needs to be strictly controlled, if the pressure is too high, the formed spherical fluoride salt mixture is too compact, and the later diluent needs a long time to be extracted or is difficult to completely extract; otherwise, if the pressure is too small, the resulting spherical fluoride salt mixture does not have sufficient strength and is liable to crush and clog the adsorbent column. Therefore, the molding pressure is preferably 0.4 to 0.6MPa. In one embodiment, the molding pressure is about 0.55Mpa.
As a further improvement, in step S33, the volatile organic solvent includes ethanol, diethyl ether, and a mixture thereof. The extraction time is 10-20 hours, which can be selected according to the actual inaudible need, and is limited by completely extracting the diluent. In one embodiment, the spherical fluoride salt mixture is placed in ethanol for 18 hours to completely extract the benzophenone.
As a further improvement, the ratio of the volatile organic solvent to the spherical fluoride salt mixture can be controlled to be 10-50 ml/1 mg during the extraction process. Preferably, the ratio of the volatile organic solvent to the spherical fluoride salt mixture can be controlled to be 20-30 ml/1 mg.
In step S34, the extracted spherical fluoride salt is taken out and left at room temperature to evaporate the solvent naturally.
Example A-1
36 g of sodium fluoride powder, 24 g of potassium fluoride powder, 5 g of polyvinylidene fluoride and 5 g of benzophenone are sequentially added into an oil bath pot at 190 ℃ to be stirred uniformly, and the mixture is melted for 1.5 hours to form a mixed solution, and the solution is put intoThe spherical mold of (2) is molded in a press at 190 ℃ under a pressure of 0.55Mpa, cooled at 25 ℃ for 20 hours, molded, the product is extracted in ethanol for 18 hours after molding, the extract is left in air for 36 hours to volatilize ethanol after the extraction is completed, the surface is purged with nitrogen after ethanol volatilization, and the moisture content of the final product is measured to be 0.14% and the internal porosity is 57.6%, see fig. 2.
Example A-2
Substantially the same as in example 1, except that: 30 g of sodium fluoride powder and 20 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.13%, and the internal porosity is measured to be 55.4%.
Example A-3
Substantially the same as in example 1, except that: 50 g of sodium fluoride powder and 30 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.16%, and the internal porosity is measured to be 58.9%.
Comparative example A-4
Substantially the same as in example 1, except that: 25 g of sodium fluoride powder and 15 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.11%, and the internal porosity is measured to be 48.5%.
Comparative example A-5
Substantially the same as in example 1, except that: 55 g of sodium fluoride powder and 35 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.20%, and the internal porosity is measured to be 59.2%.
Comparative example A-6
Substantially the same as in example 1, except that: 25 g of sodium fluoride powder and 35 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.11%, and the internal porosity is measured to be 48.5%.
Comparative example A-7
Substantially the same as in example 1, except that: 55 g of sodium fluoride powder and 15 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.20%, and the internal porosity is measured to be 59.2%.
The adsorptivity test was performed for examples A-1 to A-3 and comparative examples A-4 to A-7 as follows:
the product is put into a stainless steel adsorption tower, the temperature is controlled at 20 ℃, 95% fluorine gas is introduced, and the flow rate of the fluorine gas is 1m/s. The fluorine gas content and the hydrogen fluoride content of the outlet gas components were measured and the volume content thereof are shown in the following table 1:
table 1 shows the gas contents of examples A-1 to A-3 and comparative examples A-4 to A-7, wherein the balance is impurity gas
From the above data, it can be seen that the adsorbent has a large change in adsorption performance for hydrogen fluoride with a change in the ratio of sodium fluoride powder to potassium fluoride powder.
To further verify the effect of the binder on the adsorbent performance, examples and comparative examples are further provided as follows:
example B-1
Substantially the same as in example 1, except that: 3 g of polyvinylidene fluoride is taken. The final product was measured for moisture content of 0.12% and internal porosity of 58.3%.
Example B-2
Substantially the same as in example 1, except that: 8 g of polyvinylidene fluoride was taken. The final product was measured for moisture content of 0.15% and internal porosity of 56.2%.
Comparative example B-3
Substantially the same as in example 1, except that: 2 g of polyvinylidene fluoride is taken. The final product was measured for moisture content of 0.12% and internal porosity of 59.8%.
Example B-4
Substantially the same as in example 1, except that: 10 g of polyvinylidene fluoride was taken. The final product was measured for moisture content of 0.15% and internal porosity of 53.1%.
The adsorptivity test was performed for examples A-1, B-1 and 2 and comparative examples B-2 and 3 as follows:
the product is put into a stainless steel adsorption tower, the temperature is controlled at 20 ℃, 95% fluorine gas is introduced, and the flow rate of the fluorine gas is 1m/s. The fluorine gas content and the hydrogen fluoride content of the outlet gas components were measured and the volume content thereof are shown in the following table 2:
table 2 shows the gas contents of examples A-1, B-1 to 2 and comparative examples B-3 to 4, wherein the balance is impurity gas
From the above data, it can be seen that the adsorbent has a large change in the porosity and adsorption performance of hydrogen fluoride as polyvinylidene fluoride changes. Further, in comparative example B-3, since the content of the binder is too low, the binding strength is weak and the powder falling off is easy.
To further verify the effect of the molding pressure on the adsorbent performance, examples and comparative examples are further provided as follows:
example C-1:
substantially the same as in example 1, except that: the molding pressure was about 0.2MPa. The final product was measured for moisture content 0.14% and internal porosity 58.1%.
Example C-2:
substantially the same as in example 1, except that: the pressure of the molding was about 1MPa. The final product was measured for moisture content 0.14% and internal porosity 55.7%.
Comparative example C-3:
substantially the same as in example 1, except that: the molding pressure was about 0.1MPa. The final product was measured for moisture content of 0.14% and internal porosity of 58.4%.
Comparative example C-4:
substantially the same as in example 1, except that: the molding pressure was about 1.2MPa. The final product was measured for moisture content of 0.14% and internal porosity of 53.2%.
The adsorptivity test was performed for examples A-1, C-1 and 2 and comparative examples C-3 and 4 as follows:
the product is put into a stainless steel adsorption tower, the temperature is controlled at 20 ℃, 95% fluorine gas is introduced, and the flow rate of the fluorine gas is 1m/s. The fluorine gas content and the hydrogen fluoride content of the outlet gas components were measured and the volume contents are shown in the following table 3:
table 3 shows the gas contents of examples A-1, C-1 to 2 and comparative examples C-2 to 3, wherein the balance is impurity gas
From the above data, it can be seen that the adsorbent has a large change in the porosity and adsorption performance of hydrogen fluoride with the change in pressure. Further, in comparative example C-3, since the molding pressure was too small, the adhesive strength was weak and powder falling was liable to occur. In addition, in comparative example C-4, the product was extracted in ethanol for more than 36 hours after molding because of the excessive pressure of the membrane pressure.
To further verify the effect of adsorption temperature on adsorbent performance, examples and comparative examples are further provided as follows:
placing the A-1 product into a stainless steel adsorption tower, controlling the temperature at 10deg.C, 15deg.C, 20deg.C, 25deg.C, 30deg.C, 35deg.C, 40deg.C, and introducing 95% fluorine gas at a flow rate of 1m/s. The fluorine gas content and the hydrogen fluoride content of the outlet gas components were measured and the volume contents are shown in the following table 4:
table 4 shows the gas contents of example A-1 at different temperatures, with the remainder being impurity gases
From the above data, it can be seen that the adsorbent has a large change in adsorption performance for hydrogen fluoride with a change in adsorption temperature. When the temperature is lower than 10 ℃ or higher than 35 ℃, the adsorption performance to hydrogen fluoride is significantly reduced.
The test data of the adsorbent is based on about 95% fluorine gas, and in the present invention, the fluorine gas content after passing through the collection tank 23 may be about 98% to 99%, and the fluorine gas content may be about 99.99% or more by further treating the adsorbent.
The invention can make fluorine gas free flow without extra power by arranging the first vacuum pump 22 and the second vacuum pump 27, and prevent other power equipment from being damaged due to corrosion by fluorine gas.
Referring to fig. 6, the embodiment of the invention further provides a safety control method of the fluorine gas purification device 20, comprising the following steps:
s41, controlling the first vacuum pump 22 to work, vacuumizing the negative pressure storage tank 21, and closing a pipeline corresponding to the first vacuum pump 22 after the negative pressure storage tank is finished;
s42, controlling the second vacuum pump 27 to work, vacuumizing the trapping tank 23, the adsorption storage tank 24, the filter 25 and the storage tank 26, and closing the corresponding pipelines of the second vacuum pump 27 after the completion of vacuumizing;
and S43, opening the linkage control valve 19 to feed the negative pressure storage tank 21, and opening pipelines corresponding to the trapping tank 23, the adsorption storage tank 24, the filter 25 and the storage tank 26 to perform fluorine gas purification treatment when the pressure of the negative pressure storage tank 21 reaches a set value.
In steps S41 and S42, in order to make the subsequent fluorine gas have a higher purity, it is necessary to reduce the vacuum degree in the system as much as possible.
In step S43, since the adsorption tank 24 and the filter 25 have a large resistance, a large pressure difference between the negative pressure tank 21 and the storage tank 26 is required to smoothly purify the fluorine gas. Preferably, when the pressure of the negative pressure storage tank 21 reaches 0.5 to 0.8 atm, the fluorine gas purifying treatment may be performed by opening the corresponding pipelines of the trapping tank 23, the adsorption storage tank 24, the filter 25 and the storage tank 26. In one embodiment, when the pressure of the negative pressure storage tank 21 reaches 0.6 atm, the capturing tank 23, the adsorption storage tank 24, the filter 25 and the storage tank 26 are opened to perform the fluorine gas purification treatment.
Further, in step S43, the temperature of the trapping tank 23 is controlled to be between-40 ℃ and-80 ℃. Preferably, the temperature of the trapping tank 23 is controlled between-50 ℃ and-60 ℃ at the same time.
Further, in step S43, the temperature of the adsorption tank 24 is controlled to 15 to 30 ℃. Preferably, the temperature of the adsorption tank 24 is controlled to be 20 ℃.
Further, in step S43, when one of the adsorption tanks 24 is saturated for replacement, the adsorption tank is switched to the other adsorption tank 24 for adsorption. At this time, the adsorption tank 24, which needs to be replaced with an adsorbent, is switched to the adsorption tank 28 to be purged of fluorine gas, thereby preventing the occurrence of a hazard.
Referring to fig. 4, the embodiment of the present invention further provides a high purity nitrogen/fluorine mixing device 30, wherein the high purity fluorine/nitrogen mixing device 30 includes: a nitrogen gas supply unit 31; a gas distribution tank 33 which communicates with the nitrogen gas supply unit 31 and the storage tank 26, respectively; a third vacuum pump 32 communicating with the distribution tank 33 for evacuating the distribution tank 33; a pressure sensor 34 provided on the gas distribution tank 33; and a mixed gas outlet 35 provided at the bottom of the gas distribution tank 33.
Referring to fig. 7, the gas distribution tank 33 includes: a horizontal tank 330; a nitrogen gas inlet pipe 331 provided at one side of the horizontal tank 330 and communicating with the nitrogen gas supply unit 31; a fluorine gas inlet pipe 332 disposed at the top of the horizontal tank 330 and communicating with the storage tank 26; a rotary transmission shaft 333 transversely disposed in the horizontal tank 330, and a motor (not shown) for driving the rotary transmission shaft to rotate; and a rotating blade 334 provided on the rotating transmission shaft 333.
One side of the rotation driving shaft 333 is opened so that the nitrogen gas inlet pipe 331 is extended into the rotation driving shaft 333. Further, a plurality of air outlet holes 3332 are formed on the two sides of the rotary transmission shaft 333 corresponding to the rotary blades 334, and the nitrogen is discharged from the air outlet holes 3332 and mixed with the fluorine gas for distribution. Preferably, the air outlet holes 3332 are arranged in one-to-one correspondence with the blades of the rotating blades 334. Because the fluorine gas has strong corrosion performance, the rotating transmission shaft 333 and the rotating blades 334 are corroded. In this case, the nitrogen inlet pipe 331 extends into the rotary driving shaft 333, and is discharged from two sides of the rotary blade 334 on the rotary driving shaft 333, and the nitrogen can partially cover the rotary driving shaft 333 and the rotary blade 334, so as to prevent the fluorine from corroding the surface thereof. Along with the rotation of the rotating blades 334, after the fluorine gas and the nitrogen gas are fully mixed on the side wall of the horizontal tank 330, the corrosion performance is obviously reduced, and the service life of the stirring device is obviously prolonged. The mixing ratio of the fluorine gas and the nitrogen gas can be controlled according to actual requirements.
The number of the rotating blades 334 is not limited, and may be 1 to 5 groups. In one embodiment, 3 sets of the rotating blades 334 are included.
The pressure sensor 34 is used for detecting the pressure in the gas distribution tank 33 so as to realize gas distribution. Specifically, when the gas distribution tank 33 is evacuated, nitrogen and fluorine gas with predetermined pressures are respectively introduced at this time, so that accurate gas distribution of the nitrogen and the fluorine gas can be realized.
Referring to fig. 8, the embodiment of the invention further provides a gas distribution method of the high-purity nitrogen/fluorine mixing device 30, which comprises the following steps:
s51, vacuumizing the gas distribution tank 33 through the third vacuum pump 32;
s52, when the pressure of the storage tank 26 reaches the set vacuum degree, opening a valve to charge fluorine gas of the storage tank 26 into the gas distribution tank 33, and when the pressure reaches the first set pressure, ending the fluorine gas charging;
s53, the nitrogen supply unit 31 is opened to charge nitrogen into the gas distribution tank 33, and when the second set pressure is reached, the nitrogen gas charging is ended.
In steps S52 and S53, the distribution ratio of the fluorine gas and the nitrogen gas can be controlled by controlling the first set pressure and the second set pressure. The distribution ratio of fluorine and nitrogen can be adjusted according to actual needs, and is not limited herein.
In the process of reaching the second set pressure in step S53, it may further include:
and S54, the rotating blades 334 on the rotating transmission shaft 333 are driven by a motor to slowly rotate, so that fluorine and nitrogen are fully mixed. The rotational speed of the rotating blades 334 may be controlled below 30 rpm, thereby preventing it from affecting the actual value of the detected pressure. The benefits of controlling the slow rotation of the rotating blades 334 are: the nitrogen gas can be uniformly covered on the surface of the rotating blade 334 to prevent the fluorine gas from further corroding the rotating blade during the mixing process.
Referring to fig. 9, an embodiment of the present invention further provides a high-integration high-purity fluorine gas supply system, which includes:
an electrolytic cell device 10 and a fluorine gas purification device 20 integrally provided on a movable substrate 40; wherein the movable base plate 40 has a horizontal plane on which the electrolyzer apparatus 10 is disposed. The high-integration-level high-purity fluorine gas supply system further comprises two levels 41 arranged on the horizontal plane, wherein the levels 41 are respectively arranged on two straight lines which are mutually perpendicular on the horizontal plane, so that the electrolytic tank device 10 is used for judging whether the whole electrolytic tank device is horizontal or not, and safe production is realized. Through the arrangement, the high-integration-level high-purity fluorine gas supply system can realize movable safe fluorine production, and meets the industrial pure fluorine demand. The movable base plate 40 may be a movable container box or the like.
As a further improvement, in other embodiments, the high-integration high-purity fluorine gas supply system may further include a high-purity fluorine/nitrogen mixing device 30 connected to the fluorine gas purification device 20, so as to configure fluorine/nitrogen mixed gases with different concentrations.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A high-integration high-purity fluorine gas supply system, comprising: a movable substrate (40); an electrolyzer device (10) and a fluorine gas purification device (20) integrally provided on a movable substrate (40), wherein the movable substrate (40) has a horizontal plane on which the electrolyzer device (10) is provided; the high-integration-level high-purity fluorine gas supply system further comprises two level gauges (41) arranged on the horizontal plane, wherein the level gauges (41) are respectively arranged on two straight lines which are mutually perpendicular on the horizontal plane, so that the system is used for judging whether the whole electrolytic tank device (10) is horizontal or not;
the fluorine gas purification device (20) comprises: a negative pressure storage tank (21) for storing the fluorine gas mixture from the electrolyzer device (10); a first vacuum pump (22) for evacuating the negative pressure reservoir (21); a collection tank (23) for condensing the fluorine gas mixture from the negative pressure storage tank (21) to remove most of hydrofluoric acid; an adsorption tank (24) for adsorbing the gas from the trapping tank (23) to remove most of the impurities; a filter (25) for dust-removing the gas from the adsorption tank (24); a storage tank (26) for storing fluorine gas from the filter (25); and a second vacuum pump (27) for evacuating the storage tank (26);
the adsorbent in the adsorption storage tank (24) is granular and provided with a plurality of micropores, and the preparation method of the adsorbent comprises the following steps: 36 g of sodium fluoride powder, 24 g of potassium fluoride powder, 5 g of polyvinylidene fluoride and 5 g of benzophenone are sequentially added into an oil bath at 190 ℃ to be stirred uniformly, the mixture is melted for 1.5 hours and then put into a spherical die with phi 8, the mixture is molded in a press with 190 ℃ under the pressure of 0.55Mpa, the mixture is cooled at 25 ℃ for 20 hours to be molded, the product is put into ethanol to be extracted for 18 hours after the molding, the extract is placed in air for 36 hours to volatilize ethanol after the extraction is completed, nitrogen is used to purge the surface after the ethanol is volatilized, and the water content of the final product is measured to be 0.14 percent and the internal porosity is 57.6 percent.
2. The high-integration fluorine gas supply system according to claim 1, wherein the movable substrate (40) is a movable container.
3. The high-integration high-purity fluorine gas supply system according to claim 1, further comprising a high-purity fluorine/nitrogen mixing device (30) connected to the fluorine gas purification device (20).
4. The high-integration high-purity fluorine gas supply system according to claim 1, wherein the electrolyzer unit (10) comprises: a closed electrolytic tank (11), wherein a hydrogen outlet (111), a fluorine outlet (112), a raw material inlet (113) and heating elements (110) arranged around the electrolytic tank (11) are arranged at the top of the electrolytic tank (11); a cathode (12), a diaphragm (13) and an anode (14) which are arranged in the electrolytic tank (11), wherein the diaphragm (13) is used for isolating the cathode (12) and the anode (14); a first gas pressure sensor (17) provided at the hydrogen gas outlet (111); the second air pressure sensor (18), the linkage control valve (19) and the negative pressure container are sequentially arranged at the fluorine gas outlet (112); the control unit is respectively and electrically connected with the first air pressure sensor (17), the second air pressure sensor (18) and the linkage control valve (19), and is used for controlling the linkage control valve (19) to open and close according to signals of the first air pressure sensor (17) and the second air pressure sensor (18) so as to control the pressure difference between the hydrogen outlet (111) and the fluorine outlet (112) to be within a preset range.
5. The high-integration fluorine gas supply system according to claim 4, wherein the electrolyzer unit (10) comprises a potassium bifluoride feed line (1130), a hydrogen fluoride feed line (1132), and a potassium bifluoride/hydrogen fluoride feed line (1134).
6. The highly integrated high purity fluorine gas supply system according to claim 5, comprising at least two adsorption tanks (24) arranged in parallel.
7. A highly integrated high purity fluorine gas supply system according to claim 3 wherein said high purity fluorine/nitrogen mixing device (30) comprises: a nitrogen gas supply unit (31); a gas distribution tank (33) in communication with the nitrogen gas supply unit (31) and the storage tank (26), respectively; a third vacuum pump (32) in communication with the distribution tank (33) for evacuating the distribution tank (33); a pressure sensor (34) provided on the gas distribution tank (33); and a mixed gas outlet (35) arranged at the bottom of the gas distribution tank (33).
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