CN115747848A - Safe production method of high-purity fluorine gas - Google Patents
Safe production method of high-purity fluorine gas Download PDFInfo
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Abstract
The invention provides a safe production method of high-purity fluorine gas, which is realized by an electrolytic cell device, wherein the electrolytic cell device comprises a closed electrolytic cell, heating elements arranged on the periphery of the electrolytic cell, a cathode bar, a diaphragm and an anode bar, wherein the cathode bar and the anode bar are separated by the diaphragm; the safety production method comprises the following steps: s11, acquiring pressure information of two sides of the diaphragm, judging whether the pressure difference of the two sides of the diaphragm is in a set range, if so, continuing to operate, otherwise, entering a step S12; and S12, controlling the inner side pressure of the diaphragm by controlling the opening and closing size of the linkage control valve, so that the pressure difference between two sides of the diaphragm is in a set range.
Description
Technical Field
The invention relates to a safe production method of high-purity fluorine gas.
Background
Fluorine gas is a simple substance of elemental fluorine, is light yellow, has very active chemical properties and strong oxidizability, and can be used as an oxidant in rocket fuels, a raw material of halogenated fluorine, a refrigerant, plasma etching and the like in industry. Wherein, the high-purity fluorine gas is an important raw material in the field of fine chemical engineering, and is widely applied to high and new fields such as electronics, laser technology, medical plastics, electronics, new materials, aerospace and the like.
However, in the prior art, the purity of the fluorine gas produced by the traditional industrial fluorine gas preparation method is low, and the purity after adsorption can not meet the application in the fine chemical industry and high-end electronic industry. In addition, in the existing preparation process, the mixing of fluorine gas and hydrogen gas is easy to generate, so that danger is generated.
Disclosure of Invention
The invention provides a safe production method of high-purity fluorine gas, which can effectively solve the problems.
The invention is realized by the following steps:
a safe production method of high-purity fluorine gas is realized by an electrolytic cell device, wherein the electrolytic cell device comprises a closed electrolytic cell, heating elements arranged around the electrolytic cell, a cathode bar, a diaphragm and an anode bar, wherein the diaphragm is used for isolating the cathode bar and the anode bar; the safety production method comprises the following steps:
s11, acquiring pressure information of two sides of the diaphragm, judging whether the pressure difference of the two sides of the diaphragm is in a set range, if so, continuing to operate, otherwise, entering a step S12;
and S12, controlling the inner side pressure of the diaphragm by controlling the opening and closing size of the linkage control valve, so that the pressure difference between two sides of the diaphragm is in a set range.
The invention has the beneficial effects that: the safety production method of the high-purity fluorine gas provided by the invention has the advantages that the concentration of the prepared fluorine gas can reach more than 90%, so that the subsequent separation and purification procedures are greatly reduced, and the application in fine chemical engineering and high-end electronic industries can be met. Furthermore, the pressure difference between the hydrogen outlet and the fluorine outlet is controlled within a preset range by controlling the opening and closing of the linkage control valve, so that the safety performance of the electrolytic cell device in the production process can be greatly improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram showing the construction of an electrolyzer unit in a highly integrated high purity fluorine gas supply system according to an embodiment of the present invention.
FIG. 2 is a flow diagram of a process for the safety production of high purity fluorine gas according to an embodiment of the present invention.
FIG. 3 is a flow chart of an efficient control method of an electrolyzer for a safe production method of a high-purity fluorine gas, provided by an embodiment of the invention.
FIG. 4 is a schematic view showing a part of the constitution of a high-purity fluorine gas supply system with high integration according to an embodiment of the present invention.
Fig. 5 is a flow chart of a method for preparing the adsorbent according to the embodiment of the present invention.
Fig. 6 is a flowchart of a safety control method of a fluorine gas purification apparatus according to an embodiment of the present invention.
Fig. 7 is a schematic diagram showing a part of the configuration of a high-purity fluorine gas supply system of high integration according to an embodiment of the present invention.
FIG. 8 is a flow chart of a method for distributing high purity nitrogen gas/fluorine gas mixing device according to an embodiment of the present invention.
Figure 9 is a modular schematic of a highly integrated high purity fluorine gas supply system provided by an embodiment of the present invention.
Detailed Description
In order to make 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 of the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive efforts based on the embodiments of the present invention, are within the scope of protection of the present invention. Thus, the following detailed description of the embodiments of the present invention, 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, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to imply that the number of technical features indicated is significant. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Referring to fig. 1, an embodiment of the present invention provides an electrolyzer apparatus 10 for the preparation of high-purity fluorine gas, the electrolyzer apparatus 10 for the preparation of high-purity fluorine gas comprising:
the electrolytic cell 11 is closed, the top of the electrolytic cell 11 is provided with a hydrogen outlet 111, a fluorine outlet 112, a feeding hole 113, and heating elements 110 arranged around the electrolytic cell 11;
the cathode bar 12, the diaphragm 13 and the anode bar 14 are arranged in the electrolytic cell 11, wherein the diaphragm 13 is used for separating the cathode bar 12 and the anode bar 14;
a first gas pressure sensor 17 disposed 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 linkage control valve 19, respectively, wherein the control unit is configured to control the opening and closing of the linkage control valve 19 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 within a predetermined range.
The structure and shape of the sealed electrolytic cell 11 are not limited as long as they have the functions of corrosion prevention and sealing. In one embodiment, the electrolytic cell 11 includes a cell body and a cover body matching with the cell body, and the cell body and the cover body are made of corrosion-resistant alloy, such as monel or passivated carbon steel alloy, and the like, which is not limited herein. The feed inlet 113 is used for feeding KHF according to the proportion 2 HF raw material. In one embodiment, the feed port 113 comprises KHF 2 Feed line 1130, HF feed line 1132, KHF 2 /HF feed line 1134. The benefits of having the feed inlet 113 in three passes are: KHF 2 the/HF feed conduit 1134 can serve as a feed conduit for the initial feedstock, i.e. KHF 2 Mixing the mixture of KHF and HF 2 /HF feed line 1134; during the electrolysis, HF raw material needs to be replenished regularly due to the rapid consumption of HF so as to maintain KHF in the system 2 The ratio/HF is within a predetermined range. Further, KHF is generated during the electrolysis process 2 Can be partially entrained by fluorine gas and can affect KHF 2 The ratio of HF to KHF, therefore, it is necessary to replenish KHF for a certain period of time 2 Raw materials. The heating element 110 may be a resistance wire or a hydrothermal heater, etc., and is not limited hereinThe heating element 110 is used for controlling the temperature of the electrolytic bath 11 to be 60-110 ℃ so as to ensure that the KHF 2 HF thawing. The hydrogen outlet 111 and the fluorine outlet 112 are isolated from each other by the diaphragm 13.
The number of the cathode bars 12 and the anode bars 14 is not limited, and the cathode bars and the anode bars can be arranged according to actual needs. The cathode bar 12 can be made of carbon steel or Monel material; the anode rod 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 interfering with each other to explode.
The first gas pressure sensor 17 is used for acquiring first pressure information of the hydrogen outlet 111. The second gas pressure sensor 18 is used for acquiring second pressure information of the fluorine gas outlet 112. The first pressure information reflects a pressure outside the diaphragm 13, and the second pressure information reflects a pressure inside the diaphragm 13; the difference between the inside and outside pressures of the diaphragm 13 determines the liquid level L between the inside and outside of the diaphragm 1 And L 2 . If the liquid level height L 1 Or L 2 If the amount is too low, the hydrogen gas and the fluorine gas will interfere with each other and explode. Therefore, the pressure difference between the hydrogen outlet 111 and the fluorine outlet 112 needs to be strictly controlled to be within a predetermined range.
In general, the pressure difference between the hydrogen outlet 111 and the fluorine outlet 112 can be controlled to be within a predetermined range by opening and closing 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 slight negative pressure by controlling the height of the exhaust port of the hydrogen outlet to be 10-50 m, so that the hydrogen can be smoothly discharged. The pressure of the fluorine gas outlet 112 can be controlled in a linked manner by the negative pressure storage tank 21 and the linked control valve 19. In general, in order to smoothly discharge the fluorine gas, the negative pressure storage tank 21 is generally evacuated by the first vacuum pump 22, and then the pressure of the fluorine gas outlet 112 is controlled to be equal to the pressure of the hydrogen gas outlet 111 by the opening and closing of the interlocking control valve 19.
In other embodiments, the electrolyzer apparatus 10 for the preparation of high purity fluorine gas further comprises: a level sensor 15, which may be disposed inside or outside the diaphragm 13, without limitation. In one embodiment, the liquid level sensor 15 is disposed outside the diaphragm 13, so that the liquid level height L outside the diaphragm 13 can be obtained 2 . The liquid level height L 2 It is not preferable that the amount of hydrogen gas is too low, which may cause a risk of hydrogen gas cross-talk to the inside of the separator 13. Preferably, the liquid level height L 2 The height of (A) is 10-20 cm; when the liquid level is too low, HF is fed through the feed port 113 to reach a set height.
As a further improvement, in other embodiments, the control unit is further configured to obtain the liquid level height L inside the diaphragm 13 through the liquid level data of the liquid level sensor 15 and the first pressure information and the second pressure information 1 . Same, said liquid level height L 1 It is not preferable that the fluorine gas is too low, and the fluorine gas is liable to cross the outer side of the separator 13 at too low a level, which may cause a problem. Preferably, the liquid level height L 1 The height of (A) is 10-20 cm; when the liquid level is too low, HF needs to be fed through the feed port 113; or the pressure of the fluorine gas outlet 112 is controlled by the opening and closing size of the linkage control valve 19 to reach a set height.
In other embodiments, the electrolyzer apparatus 10 for the preparation of high purity fluorine gas further comprises: and an acidity sensor 16 for acquiring an acidity value of the electrolyte. KHF in electrolyte directly determined by acidity value 2 The ratio of HF/hydrogen is too low or too high, which results in low electrolysis efficiency, and therefore, the acidity sensor 16 can be used to obtain the acidity value of the electrolyte, thereby controlling the amount of HF added.
Referring to fig. 2, the embodiment of the present invention further provides a method for safely producing high purity fluorine gas, comprising the following steps:
s11, acquiring pressure information of two sides of a 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 a step S12;
and S12, controlling the opening and closing of the linkage control valve 19 to control the inner side pressure of the diaphragm 13, so that the pressure difference between two sides of the diaphragm 13 is in a set range.
In step S11, the pressure of the hydrogen outlet 111, i.e. the pressure outside the diaphragm, is generally directly communicated with the atmosphere, and the pressure can be controlled to be a slight negative pressure by controlling the height of the exhaust port of the hydrogen outlet 111, which is generally controlled to be between 10 m and 50m, so that the hydrogen can be smoothly exhausted. The pressure at the fluorine gas outlet 112, i.e., the pressure inside the diaphragm, can be controlled in a generally interlocking manner by the negative pressure storage tank 21 and the interlocking control valve 19. In general, in order to smoothly discharge the fluorine gas, the negative pressure storage tank 21 is generally evacuated by the first vacuum pump 22, and then the pressure of the fluorine gas outlet 112 is controlled to be in agreement with the pressure of the hydrogen gas outlet 111 by the opening and closing of the interlocking control valve 19. Specifically, one atmosphere is about 101325Pa, while 1 meter of water is about 9803.9 Pa and 10cm of water is about 980.4 Pa. And KHF as electrolyte 2 The density of/HF is about twice that of water; therefore, if the pressure difference between both sides is 980.4pa, the liquid level difference between both sides is about 5 cm. In the actual production process, when the pressure difference between the two sides is greater than or equal to 980.4pa, namely the liquid level difference between the two sides is greater than 5cm, an alarm needs to be given and further adjustment needs to be carried out. More preferably, when the pressure difference between the two sides is larger than or equal to 490.2pa, namely the liquid level difference between the two sides is larger than 2.5cm, an alarm needs to be given and further adjustment needs to be carried out.
In step S12, since the negative pressure storage tank 21 is in a vacuum state, the pressure inside the diaphragm 13 can be controlled by the opening and closing of the interlock control valve 19, and the pressure difference between both sides of the diaphragm 13 can be set within a predetermined range.
The safety production method can further comprise the following steps:
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;
and S15, judging whether the liquid level at least one side is lower than a set value.
In step S14, since the liquid level height on one side can be obtained by the liquid level sensor 15, and the height difference on both sides can be obtained by the pressure difference information on both sides of the diaphragm 13, the liquid level height on the other side can be obtained by these two parameters. Preferably, the liquid level L on both sides 1 And L 2 And is not preferably less than 5 cm. More preferably, the liquid level L on both sides 1 And L 2 And is not preferably less than 10 cm.
In step S15, since the pressure difference between both sides is within the set range, when the liquid level at least one side is lower than the set value, it is indicated that the electrolyte needs to be replenished as HF is greatly reduced as the electrolysis proceeds.
Therefore, after step S15, the method further includes:
and S16, controlling the feed port 113 to carry out HF liquid supplementing when the liquid level height of at least one side is judged to be lower than a set value. Specifically, the amount of the supplemented HF is preferably such that the initial electrolysis conditions are satisfied.
After step S15, the method further includes:
s17, acquiring the acidity value of the electrolyte through the acidity sensor 16, judging whether the acidity value is in a set range, and otherwise, controlling the feed port 113 to perform HF liquid supplementing. In the actual electrolytic process, as the electrolysis proceeds, the HF acid is consumed and the acidity is reduced to some extent, thereby reducing the electrolytic efficiency. Therefore, it is necessary to test the acidity, and when the acidity is lower than the set value, the feed port 113 is controlled to perform the replenishment of HF.
After step S17 or S16, when the HF addition is completed, the method may further include:
s18, the acidity sensor 16 is used for obtaining the acidity value of the electrolyte, judging whether the acidity value is in a set range, and if not, controlling the feeding port 113 to carry out KHF 2 The liquid infusion. In the actual electrolysis process, KHF is generated as the electrolysis proceeds 2 Will be partially entrained by the gas and will have an increased acidity, therebyThe electrolysis efficiency is also lowered. Therefore, it is necessary to test the acidity, and when the acidity is higher than a set value, the KHF is controlled to be applied to the feed port 113 2 The liquid is replenished.
Referring to fig. 3, an embodiment of the present invention further provides an efficient control method for an electrolytic cell, including the following steps:
s21, according to KHF 2 Mixing the electrolyte with HF in a molar ratio of 1;
s22, obtaining the acidity value of the electrolyte through the acidity sensor 16 during the electrolysis, and performing HF or KHF through the feed port 113 when the acidity exceeds a set value 2 The liquid infusion.
In step S21, electrolysis is preferably carried out while controlling the HF current consumption density to 0.74 to 0.76 kg/kA. In one embodiment, the electrolysis is carried out with the HF consumption current density controlled at 0.75 kg/kilo-ampere.
In step S22, the acidity set value is 39.0 to 40.5%. More preferably, the acidity set value is between 39.5 and 40.2%. In one embodiment thereof, the acidity set point is about 40.0%. Specifically, when the acidity is too low, HF replenishment is performed through the feed port 113; when the acidity is too high, KHF is conducted through the feed port 113 2 And (4) supplementing liquid.
After step S22, the method 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 a step S24;
and S24, controlling the opening and closing size of the linkage control valve 19 to control the inner side pressure of the diaphragm 13, so that the pressure difference between two sides of the diaphragm 13 is in 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 at least one side is lower than a set value.
After step S27, the method further includes:
and S28, controlling the feed port 113 to carry out HF liquid supplementing when the liquid level height of at least one side is judged to be lower than a set value.
Referring to fig. 4, an embodiment of the invention provides a fluorine gas purification apparatus 20, which includes: a negative pressure storage tank 21 for storing the fluorine gas mixture gas from the electrolyzer device 10; a first vacuum pump 22 for evacuating the negative pressure storage tank 21; a trap tank 23 for condensing the fluorine gas mixed gas from the negative pressure storage tank 21 to remove most of the HF acid; an adsorption tank 24 for adsorbing the gas from the capture tank 23 to remove most of the impurities; a filter 25 for subjecting the gas from the canister 24 to dust removal; a fluorine gas storage tank 26 for storing the fluorine gas from the filter 25; and a second vacuum pump 27 for evacuating the fluorine gas storage tank 26.
The trap tank 23 can condense the fluorine gas mixture gas inside the trap tank 23 by liquid nitrogen or other cold source, which removes most of the HF acid and other impurities. The temperature of the trap tank 23 may be higher than the boiling point of fluorine gas, and preferably, the temperature of the trap tank 23 may be controlled to-40 to-80 ℃. At this temperature, most of the impurities, especially HF acid gas, may be condensed out. More preferably, the temperature of the trap tank 23 may be controlled to-50 to-60 ℃.
In the present invention, the first vacuum pump 22 and the second vacuum pump 27 are provided, so that fluorine gas can freely flow without extra power, and the fluorine gas can be prevented from being corroded and damaged by the use of other power equipment.
In other embodiments, at least two adsorption tanks 24 are included, so that continuous production can be realized when one adsorption tank 24 needs to be replaced with adsorbent in the actual production process.
In other embodiments, the fluorine gas purification device 20 may further comprise absorption tanks 28 respectively connected to the adsorption tanks 24 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 to 50 parts of sodium fluoride powder, 20 to 30 parts of potassium fluoride powder and 3 to 5 parts of adhesive. Preferably, the adsorbent consists of 35 to 50 parts by weight of sodium fluoride powder, 20 to 30 parts by weight of potassium fluoride powder and 3 to 5 parts by weight of adhesive, wherein the moisture content of a measured final product of the adsorbent is less than or equal to 0.2 percent, and the porosity can reach more than 50 percent.
Referring to fig. 5, an embodiment of the 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 adhesive and 3-8 parts of diluent according to mass fraction, adding into an oil bath pan at 180-200 ℃, uniformly mixing, and melting to form a mixed solution;
s32, placing the mixed solution into a spherical mold, carrying out mold pressing in a press at 180-200 ℃, and cooling at room temperature to obtain a spherical fluoride salt mixture, wherein the mold pressing pressure is 0.2-1 Mpa;
s33, putting 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 the solvent, and finally blowing the surface of the product with nitrogen to obtain the fluoride salt adsorbent with high porosity.
As a further improvement, in step S31, the binder is selected from binders capable of forming sodium fluoride powder and potassium fluoride powder with good binding performance, 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 form good binding performance for sodium fluoride powder and potassium fluoride powder. The content of the binder is not too high, and although the binding effect is good, the channel is easy to block, and high porosity is difficult to form.
The diluent is selected from materials capable of infiltrating the three materials, such as benzophenone, or other ketone compounds containing benzene rings.
For further improvement, preferably, 36 to 40 parts of sodium fluoride powder, 22 to 25 parts of potassium fluoride powder, 3 to 6 parts of adhesive and 5 to 8 parts of diluent are weighed. In one embodiment, 36 parts of sodium fluoride powder, 24 parts of potassium fluoride powder, 5 parts of adhesive and 5 parts of diluent are weighed.
As a further refinement, it is preferred that the oil bath temperature be from 185 to 195 deg.C, and in one embodiment about 190 deg.C.
Generally, to increase the filling rate, it is generally pressed to form a spherical fluoride salt mixture. As a further modification, in step S32, the mixed solution is placed in a spherical mold having a diameter of 5 to 15 mm. The pressure of the die pressing needs to be strictly controlled, if the pressure is too high, the formed spherical fluoride salt mixture is too dense, and the later-stage diluent needs a long time to finish the extraction or is difficult to completely extract; in addition, if the pressure is too low, the resulting spherical fluoride salt mixture does not have sufficient strength, and the column of the clogged adsorbent is easily crushed. Therefore, it is preferable that the pressure for molding is 0.4 to 0.6MPa. In one embodiment, the pressure of the molding is about 0.55MPa.
As a further modification, 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 actual needs and is limited to completely extract the diluent. In one example, the spherical fluoride salt mixture was 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 in the extraction process can be controlled to be 10-50ml. Preferably, the ratio of the volatile organic solvent to the spherical fluoride salt mixture can be controlled to be 20-30ml.
In step S34, the spherical fluoride salt after extraction is taken out, and then left at room temperature to naturally volatilize the solvent.
Example A-1
Taking 36 g of sodium fluoride powder, 24 g of potassium fluoride powder, 5 g of PVDF and 5 g of benzophenone, sequentially adding the materials into a 190 ℃ oil bath pot, uniformly stirring, melting for 1.5 hours to form a mixed solution, and putting the mixed solution into the oil bath pot
The spherical mold is molded in a press at 190 ℃ under 0.55Mpa pressure, the spherical mold is cooled at 25 ℃ for 20 hours to be molded, the product is placed in ethanol for extraction for 18 hours after molding, the extract is placed in the air for 36 hours after extraction is finished to volatilize the ethanol, the surface is purged by nitrogen after the ethanol is volatilized, and the water content and the porosity of the final product are respectively measured to be 0.14% and 57.6%, please refer to 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 and the porosity of the final product are measured to be 0.13 percent and 55.4 percent.
Examples A to 3
The same as example 1 except that: taking 50 g of sodium fluoride powder and 30 g of potassium fluoride powder, and measuring the moisture content of the final product to be 0.16% and the porosity to be 58.9%.
Comparative examples A to 4
Substantially the same as in example 1, except that: taking 25 g of sodium fluoride powder and 15 g of potassium fluoride powder, and measuring the moisture content of the final product to be 0.11% and the porosity to be 48.5%.
Comparative examples A to 5
The same as 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 percent, and the porosity is measured to be 59.2 percent.
Comparative examples A to 6
The same as example 1 except that: taking 25 g of sodium fluoride powder and 35 g of potassium fluoride powder, and measuring the water content of the final product to be 0.11% and the porosity to be 48.5%.
Comparative examples A to 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 percent, and the porosity is measured to be 59.2 percent.
The examples A-1 to A-3 and the comparative examples A-4 to A-7 were subjected to the following adsorption tests:
the product is placed in a stainless steel adsorption tower, the temperature is controlled at 20 ℃, 95 percent of fluorine gas is introduced, and the flow velocity of the fluorine gas is 1m/s. The fluorine gas content and the hydrogen fluoride content volume content of the outlet gas components are detected as 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 adsorption performance of the adsorbent for hydrogen fluoride is greatly changed as the ratio of sodium fluoride powder to potassium fluoride powder is changed.
To further verify the effect of the binder on the performance of the adsorbent, examples and comparative examples are further provided, as follows:
example B-1
Substantially the same as in example 1, except that: 3 g of PVDF is taken. The final product was measured to have a moisture content of 0.12% and a porosity of 58.3%.
Example B-2
The same as example 1 except that: PVDF was taken in an amount of 8 g. The final product was measured to have a moisture content of 0.15% and a porosity of 56.2%.
Comparative example B-3
The same as example 1 except that: 2 g of PVDF is taken. The final product was measured to have a moisture content of 0.12% and a porosity of 59.8%.
Example B-4
The same as example 1 except that: 10 g of PVDF was taken. The final product was measured to have a moisture content of 0.15% and a porosity of 53.1%.
The examples A-1, B-1 to 2 and comparative examples B-2 to 3 were subjected to the following adsorption test:
the product is placed in a stainless steel adsorption tower, the temperature is controlled at 20 ℃, 95 percent of fluorine gas is introduced, and the flow velocity of the fluorine gas is 1m/s. The fluorine gas content and the hydrogen fluoride content volume content of the outlet gas components are detected as 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 porosity and adsorption performance of the adsorbent for hydrogen fluoride vary greatly with PVDF. Further, in comparative example B-3, since the binder content was too low, the binding strength was weak and the powder could be easily removed.
To further verify the impact of the compression molding pressure on the performance of the adsorbent, examples and comparative examples are further provided as follows:
example C-1:
the same as example 1 except that: the pressure for the molding was about 0.2MPa. The final product was measured to have a moisture content of 0.14% and a porosity of 58.1%.
Example C-2:
the same as example 1 except that: the pressure for the molding was about 1MPa. The final product was measured to have a moisture content of 0.14% and a porosity of 55.7%.
Comparative example C-3:
the same as example 1 except that: the pressure for the molding was about 0.1MPa. The final product was measured to have a moisture content of 0.14% and a porosity of 58.4%.
Comparative example C-4:
the same as example 1 except that: the pressure of the molding was about 1.2MPa. The final product was measured to have a moisture content of 0.14% and a porosity of 53.2%.
The examples A-1, C-1 to 2 and comparative examples C-3 to 4 were subjected to the following adsorption test:
the product is placed in a stainless steel adsorption tower, the temperature is controlled at 20 ℃, 95 percent of fluorine gas is introduced, and the flow velocity of the fluorine gas is 1m/s. The fluorine gas content and the hydrogen fluoride content volume content of the outlet gas components are detected as 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 porosity and adsorption performance of the adsorbent for hydrogen fluoride vary greatly with pressure. Further, in comparative example C-3, since the pressing pressure was too small, the adhesive strength was weak and the powder could be easily removed. In addition, in comparative example C-4, since the pressure of the film pressure was too large, it was necessary to extract the product in ethanol for 36 hours or more after molding to complete the extraction.
To further verify the effect of adsorption temperature on the performance of the adsorbent, examples and comparative examples are further provided as follows:
placing the product A-1 into a stainless steel adsorption tower, controlling the temperature at 10 ℃, 15 ℃,20 ℃, 25 ℃, 30 ℃, 35 ℃ and 40 ℃, and introducing 95% fluorine gas at the flow velocity of 1m/s. The fluorine gas content and the hydrogen fluoride content of the outlet gas component are detected according to the volume content shown in the following table 4:
table 4 shows the gas contents at different temperatures in example A-1, wherein the balance was impurity gas
From the above data, it can be seen that the adsorption performance of the adsorbent for hydrogen fluoride is greatly changed with the change of the 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 measured based on about 95% fluorine gas, and in the present invention, the fluorine gas content after passing through the trap tank 23 can be about 98% to 99%, and the fluorine gas content can be made to be 99.99% or more by further processing with the adsorbent.
In the present invention, the first vacuum pump 22 and the second vacuum pump 27 are provided, so that the fluorine gas can flow freely without additional power, and the damage of other power equipment due to the corrosion of the fluorine gas can be prevented.
Referring to fig. 6, the embodiment of the invention further provides a method for safely controlling a fluorine gas purification apparatus 20, which comprises 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 vacuumizing is finished;
s42, controlling the second vacuum pump 27 to operate, evacuating the trapping tank 23, the adsorption tank 24, the filter 25, and the fluorine gas storage tank 26, and after the evacuation, closing a pipeline corresponding to the second vacuum pump 27;
and S43, opening the linkage control valve 19 to feed the negative pressure storage tank 21, and when the pressure of the negative pressure storage tank 21 reaches a set value, opening the pipelines corresponding to the trapping tank 23, the adsorption tank 24, the filter 25 and the fluorine gas storage tank 26 to purify the fluorine gas.
In steps S41 and S42, in order to make the subsequent fluorine gas have a high purity, it is necessary to reduce the degree of vacuum in the system as much as possible.
In step S43, since the adsorption tank 24 and the filter 25 have large resistance, it is necessary to provide a large pressure difference between the negative pressure storage tank 21 and the fluorine gas storage tank 26 to smoothly purify the fluorine gas. Preferably, when the pressure in the negative pressure storage tank 21 reaches 0.5 to 0.8 atm, the fluorine gas purification process is performed by opening the corresponding lines of the trap tank 23, the adsorption tank 24, the filter 25, and the fluorine gas storage tank 26. In one embodiment, when the pressure in the negative pressure storage tank 21 reaches 0.6 atm, the trapping tank 23, the adsorption tank 24, the filter 25, and the fluorine gas storage tank 26 are opened to perform fluorine gas purification.
Further, in step S43, the temperature of the capture tank 23 is controlled between-40 ℃ and-80 ℃ at the same time. Preferably, the temperature of the trapping tank 23 is controlled to be between-50 ℃ and-60 ℃.
Further, in step S43, the temperature of the canister 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 and needs to be replaced, the adsorption tank is switched to another adsorption tank 24 for adsorption. At this time, the adsorption tank 24 requiring the replacement of the adsorbent is switched to the adsorption tank 28 to evacuate the fluorine gas, thereby preventing the occurrence of a danger.
Referring to fig. 4, the embodiment of the present invention further provides a high purity nitrogen/fluorine gas mixing device 30, wherein the high purity fluorine/nitrogen mixing device 30 comprises: a nitrogen gas supply unit 31; a gas distribution tank 33 communicating with the nitrogen gas supply unit 31 and the fluorine gas storage tank 26, respectively; a third vacuum pump 32 in communication with the gas distribution tank 33 for evacuating the gas 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 pipe 331 disposed at one side of the horizontal tank 330 and communicating with the nitrogen gas supply unit 31; a fluorine gas pipe 332 disposed at the top of the horizontal tank 330 and communicating with the fluorine gas storage tank 26; a rotary transmission shaft 333 arranged transversely in the horizontal tank 330 and a motor (not shown) for driving the rotary transmission shaft to rotate; a blade 334 disposed on the rotating transmission shaft 333.
One side of the rotary drive shaft 333 is opened so that the nitrogen gas pipe 331 is inserted into the inside of the rotary drive shaft 333. Furthermore, the rotating transmission shaft 333 is provided with a plurality of air outlet holes 3332 corresponding to two sides of the blade 334, and the nitrogen is discharged from the air outlet holes 3332 and mixed with the fluorine gas. Preferably, the air outlet holes 3332 are arranged in one-to-one correspondence with the blades 334. Since the fluorine gas has strong corrosion performance, the rotating transmission shaft 333 and the blades 334 are corroded. In this case, the nitrogen gas pipe 331 extends into the rotating transmission shaft 333 and is exhausted from both sides of the blade 334 on the rotating transmission shaft 333, and the nitrogen gas can partially coat the rotating transmission shaft 333 and the blade 334, thereby preventing the surface of the rotating transmission shaft 333 from being corroded by the fluorine gas. With the rotation of the blade 334, the corrosion performance of the fluorine gas and the nitrogen gas is remarkably reduced after the fluorine gas and the nitrogen gas are sufficiently mixed on the side wall of the horizontal tank 330, and the service life of the stirring device is further remarkably prolonged. The mixing ratio of the fluorine gas and the nitrogen gas can be controlled according to actual requirements.
The number of the blades 334 is not limited, and may be 1 to 5 groups. In one embodiment, 3 sets of the blades 334 are included.
The pressure sensor 34 is used for detecting the pressure in the gas distribution tank 33 to realize gas distribution. Specifically, when the gas distribution tank 33 is vacuumized, nitrogen and fluorine gas with predetermined pressures are respectively introduced, so that accurate gas distribution of the nitrogen and fluorine gas can be realized.
Referring to fig. 8, the embodiment of the present invention further provides a method for distributing gas of a high purity nitrogen/fluorine gas mixing device 30, which includes the following steps:
s51, evacuating the gas distribution tank 33 by the third vacuum pump 32;
s52, when the pressure of the fluorine gas storage tank 26 reaches a set vacuum degree, opening a valve to charge the fluorine gas in the fluorine gas storage tank 26 into the gas distribution tank 33, and when the pressure reaches a first set pressure, finishing fluorine gas inlet;
s53, the nitrogen gas supply unit 31 is opened to fill the nitrogen gas into the gas distribution tank 33, and when the second set pressure is reached, the nitrogen gas intake is terminated.
In steps S52 and S53, the gas 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 gas distribution ratio of the fluorine gas and the nitrogen gas can be adjusted according to actual needs, and is not limited herein.
In step S53, when the second set pressure is reached, the method may further include:
and S54, driving the blades 334 on the rotating transmission shaft 333 to slowly rotate through the motor, so that the fluorine gas and the nitrogen gas are fully mixed. The rotational speed of the vane 334 may be controlled below 30 rpm/mi n to prevent it from affecting the sensed actual value of pressure. The benefits of controlling the slow rotation of the blades 334 are: the nitrogen gas can be made to uniformly cover the surface of the blade 334 to prevent further corrosion by the fluorine gas during the mixing process.
Referring to fig. 9, a highly integrated high purity fluorine gas supply system is further provided in accordance with an embodiment of the present invention, which comprises:
an electrolyzer unit 10 and a fluorine gas purification unit 20 integrally provided on a movable substrate 40; wherein the movable substrate 40 has a horizontal plane on which the electrolyzer unit 10 is placed. The highly integrated high purity fluorine gas supply system further comprises two level meters 41 disposed on the horizontal plane, and the level meters 41 are disposed on two straight lines perpendicular to each other on the horizontal plane, respectively, so as to determine whether the entire electrolyzer apparatus 10 is horizontal, thereby achieving safe production. Through the arrangement, the high-integration high-purity fluorine gas supply system can realize mobile safe fluorine preparation, and meets the industrial pure fluorine requirement. The movable base plate 40 may be a movable box type cargo container or the like.
As a further modification, 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, thereby being used to arrange fluorine-nitrogen mixtures of different concentrations.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A safe production method of high-purity fluorine gas, characterized in that the safe production method is realized by an electrolytic cell device, the electrolytic cell device comprises a closed electrolytic cell (11), a heating element (110) arranged around the electrolytic cell (11), a cathode bar (12) arranged in the electrolytic cell (11), a diaphragm (13) and an anode bar (14), wherein the diaphragm (13) is used for isolating the cathode bar (12) and the anode bar (14); the safety production method comprises the following steps:
s11, 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 a step S12;
and S12, controlling the inner side pressure of the diaphragm (13) by controlling the opening and closing size of the linkage control valve (19) so that the pressure difference between two sides of the diaphragm (13) is in a set range.
2. The process for the safety production of a high purity fluorine gas as claimed in claim 1, wherein the pressure difference across the diaphragm (13) is within 980.4 pa.
3. The process for safely producing a high purity fluorine gas as claimed in claim 1, further comprising:
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);
and S15, judging whether the liquid level at least one side is lower than a set value.
4. The process for safely producing a high purity fluorine gas as claimed in claim 3, further comprising, after the step S15:
s16, when the liquid level height of at least one side is judged to be lower than the set value, controlling the feed port (113) to carry out HF liquid supplementing.
5. The process for safely producing a high purity fluorine gas as claimed in claim 3, further comprising, after the step S15:
s17, acquiring the acidity value of the electrolyte through the acidity sensor (16), judging whether the acidity value is in a set range, and otherwise, controlling the feed port (113) to carry out HF liquid supplementing.
6. The process for safely producing a high purity fluorine gas as claimed in claim 1, wherein the pressure of the hydrogen outlet (111) is directly communicated with the atmosphere, and the slight negative pressure is obtained by controlling the height of the exhaust port of the hydrogen outlet (111) to be 10 to 50 m.
7. The safe production method of a high purity fluorine gas as claimed in claim 1, characterized in that the heating member (110) is used for controlling the temperature of the electrolytic bath (11) to 60 to 110 ℃ to make the KHF 2 HF thawing.
8. The process for safely producing a high purity fluorine gas as claimed in claim 3, wherein the level heights L on both sides 1 And L 2 Greater than or equal to 5 cm.
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| CN209066013U (en) * | 2018-07-26 | 2019-07-05 | 福建德尔科技有限公司 | Electrolytic cell adds the device of hydrogen fluoride automatically |
| CN211199423U (en) * | 2019-12-26 | 2020-08-07 | 福建省龙德新能源股份有限公司 | Electrolytic fluorine making tank |
| CN216473512U (en) * | 2021-11-18 | 2022-05-10 | 山东飞源气体有限公司 | System for adjusting electrolyte acidity of electrolytic cell without stopping SF6 electrolytic process |
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| FR2466515A1 (en) * | 1979-09-28 | 1981-04-10 | Electricite De France | Prodn. of gas by electrolysis under pressure - in installation having control maintaining pressure in electrolyser at fixed level below pressure of gas in enclosure contg. electrolyser |
| CN200992578Y (en) * | 2006-11-30 | 2007-12-19 | 国营八一四厂 | 10kA carbon steel medium-temperature fluorine production electrolytic tank |
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| WO2015052253A1 (en) * | 2013-10-11 | 2015-04-16 | Solvay Sa | Improved electrolytic cell |
| CN209066013U (en) * | 2018-07-26 | 2019-07-05 | 福建德尔科技有限公司 | Electrolytic cell adds the device of hydrogen fluoride automatically |
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