A preparation device and preparation process of perfluorotributylamine

Abstract

The invention relates to a perfluorotributylamine preparation device and a preparation process, and belongs to the field of perfluorotributylamine preparation and fluid working system. In the process, tributylamine and hydrogen fluoride are in a mass ratio of 80-100kg:200-230kg, hydrogen fluoride is first added to an electrolytic cell, and then tributylamine is added; before reaction, air in the electrolytic cell is replaced by nitrogen, and the air is replaced by nitrogen for preliminary mixing and preparing electrolyte; then low-voltage current is passed to carry out electrolytic replacement reaction, and the reaction pressure is controlled at 0.1-1.5MPa, and the temperature is controlled at -10-30°C; by controlling the reflux distribution of circulating liquid and the single circulation path, products with high specific gravity are deposited in pipeline equipment, so as to improve reaction activity, fluorination efficiency and conversion rate; the electrolytic fluorination method is adopted, the reaction is mild and controllable, the process is simple, the efficiency is high, the impurities are few and easy to separate, and the scheme also provides a perfluorotributylamine preparation device, which is adapted to the preparation process, and a perfluorotributylamine crude product with a purity of more than 80% is obtained under the conditions of simple reaction raw materials and simple reaction device.

Description

Technical Field

[0001] The invention belongs to the technical field of perfluorotributylamine preparation and fluid working system, and specifically relates to a perfluorotributylamine preparation device and preparation process. Background Art

[0002] Perfluorotributylamine is mainly used in anti-corrosion transmission fluids of instruments and meters, dielectric insulating fluids, electronic components, device leak detection fluids, perfluorocarbon artificial plasma, etc. Perfluorotributylamine can be used as a blood substitute and is also an excellent dielectric insulating fluid. In addition, it can also be used as a heat-conducting coolant, antioxidant lubricant, chemical reaction stabilizing diluent, etc.

[0003] Perfluorotributylamine molecule is an important perfluoro tertiary amine compound. Due to its many excellent physical, chemical and physiological properties, it has been widely used in modern civilized society. Perfluorotributylamine is a colorless and transparent liquid at room temperature, with almost no amine smell. It is insoluble in water and ethanol, and its solubility in organic solvents such as butanone, ether, chloroform, dioxane, ethyl acetate, benzene and petroleum ether is also very small, but it can be miscible with chlorofluoroalkanes. Perfluorotributylamine is completely non-toxic to the human body and can dissolve and carry a large amount of oxygen and carbon dioxide. It is one of the main components of artificial plasma used in the field of modern medicine. It is also used as an anti-corrosion transmission fluid, dielectric insulation fluid, and electronic component and device leak detection fluid for instruments and meters. The production of perfluorotributylamine is of great significance to the country's scientific progress and development.

[0004] In the existing technology for preparing perfluorotributylamine, such as using fluorine gas and tributylamine to directly react, this preparation method has the following disadvantages: low reaction efficiency, complex process, difficult reaction control, high risk factor, etc., which violates the development trend of energy-saving, clean, environmentally friendly and efficient fine chemical industry. The reaction formula of this preparation is as follows: Figure 1 As shown; There is also an electrochemical combined fluorination process in the existing technology for preparing perfluorotributylamine, using low-boiling carbon compounds and high-boiling amine compounds as two raw materials to be fluorinated, dissolving the combination of the two raw materials to be fluorinated in anhydrous hydrogen fluoride, and conducting a combined electrolytic fluorination reaction to simultaneously obtain corresponding low-boiling perfluorocarbon compounds and high-boiling perfluoroamine compounds. This preparation method has the following disadvantages: complex reaction conditions, complex and diverse reaction products and tail gases, high difficulty and high cost in separation, uncontrollable reaction direction, etc., which is not conducive to industrial production; The most widely used method for preparing perfluorotributylamine is the electrolytic fluorination method, in which tributylamine and hydrogen fluoride are fed into a low-voltage direct current in an electrolytic cell to generate free fluorine atoms to directly replace the hydrogen atoms in tributylamine, but this method still has the following disadvantages: low reaction activity, low fluorination efficiency, low conversion rate, large raw material loss, etc., and the overall production capacity is limited.

[0005] Therefore, this solution proposes a perfluorotributylamine preparation device and preparation process that can solve the above problems. Summary of the invention

[0006] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is to provide a perfluorotributylamine preparation device and a preparation process, through which a crude perfluorotributylamine with a purity of more than 80% can be obtained under the conditions of simple reaction raw materials and simple reaction device.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is: a perfluorotributylamine preparation device, comprising an electrolysis component, a cooling component, a circulation component and an exhaust gas treatment component;

[0008] The electrolysis assembly comprises an electrolytic cell body, a cover body and a plurality of electrolytic plate kits, wherein the cover body is sealed and covered on the electrolytic cell body, the electrolytic cell body is provided with a liquid inlet chamber and an electrolytic reaction chamber spaced apart from each other in the upper and lower parts, the plurality of electrolytic plate kits are located in the electrolytic reaction chamber and spaced apart from each other in the left and right parts, the electrolytic plate kit comprises a plurality of groups of reaction plates sequentially arranged in the left and right parts, the reaction plates comprise an anode plate and a cathode plate, a liquid inlet channel is provided between the anode plate and the cathode plate, the liquid inlet chamber and the electrolytic reaction chamber are blocked by a partition, a plurality of liquid inlets are formed on the partition, the lower openings of the plurality of liquid inlets correspond to the upper openings of the plurality of liquid inlet channels, and the two side walls of the lower openings of the liquid inlets are provided with oppositely arranged drainage plates, and the drainage plates are used to introduce liquid into the liquid inlet channel;

[0009] The circulation assembly includes a pump body and a circulation pipeline, the pump body and the cooling assembly are located on the circulation pipeline, the liquid inlet end of the circulation pipeline is connected to the liquid outlet at the lower end of the electrolytic reaction chamber, the liquid outlet end of the circulation pipeline is connected to the inlet at the upper end of the liquid inlet chamber, the pump body includes a pump body, an exhaust pipe and an exhaust pipeline, the axis of the exhaust pipe is horizontally arranged, the inlet of the exhaust pipe is located above one side end surface and is connected to the circulation pipeline, the outlet of the exhaust pipe is located below the other side end surface and is connected to the pump body, the exhaust pipeline is vertically arranged above the exhaust pipe, and the exhaust pipeline is used to discharge gas in the liquid material;

[0010] The tail gas treatment assembly is used to collect and process the gas in the electrolytic cell body and the exhaust pipe.

[0011] Furthermore, the width of the upper opening of the liquid inlet is smaller than the width of the lower opening of the liquid inlet, the vertical cross-section of the lower opening of the liquid inlet is arc-shaped, one end of the guide plate is rotatably connected to the side wall of the lower opening of the liquid inlet, and a torsion spring is provided at the rotation point between the guide plate and the side wall of the lower opening of the liquid inlet, and the opening between the two guide plates increases as the liquid inlet amount increases.

[0012] Furthermore, the distance between the anode plate and the cathode plate is 50 mm-120 mm.

[0013] Furthermore, the bottom of the electrolytic reaction chamber is an arc-shaped bottom or a conical bottom.

[0014] Furthermore, the partition is detachably and hermetically connected to the electrolytic cell body, a limiting step arranged in a closed loop is formed on the inner peripheral surface of the electrolytic cell body, and the partition is mounted on the upper surface of the limiting step.

[0015] Furthermore, a limiting pressure block is formed on the inner circumferential surface of the cover body, and when the cover body is closed above the electrolytic cell body, the lower surface of the limiting pressure block abuts against the upper surface of the partition.

[0016] Furthermore, the cooling component includes a cooling tower, in which a plurality of baffles are arranged at intervals up and down, and the plurality of baffles are connected to the left and right sides of the inner wall of the cooling tower. The coolant path in the cooling tower is in the shape of a vertically arranged equal-amplitude oscillation curve, and the circulation pipeline in the cooling tower is arranged in a spiral manner.

[0017] The present invention provides a perfluorotributylamine process, comprising the following steps:

[0018] S1. Replace the air in the electrolytic cell with nitrogen, first add hydrogen fluoride into the electrolytic cell body, then add tributylamine, and form an electrolyte after preliminary mixing;

[0019] S2, perform low-pressure electrolysis, control the reaction pressure at 0.1MPa-1.5MPa, control the temperature at -10°C-30°C, and circulate the electrolyte;

[0020] S3, during the circulation of the electrolyte, flushing the surfaces of the anode plate and the cathode plate, and discharging the gas mixed in the electrolyte in the circulation pipeline;

[0021] S4. After the cyclic electrolysis is completed, a crude product of perfluorotributylamine with a purity of more than 80% is obtained.

[0022] Furthermore, a process for preparing perfluorotributylamine is provided, wherein a perfluorotributylamine preparation device is used for preparation;

[0023] The specific steps of step S3 are as follows: the electrolyte flows into the circulation pipeline from the bottom of the electrolytic reaction chamber, passes through the exhaust pipe, the pump body and the cooling assembly in sequence, and finally flows in from the top of the liquid inlet chamber, enters from the liquid inlet port of the partition, passes through two guide plates and is guided to the liquid inlet channels between the anode plate and the cathode plate. While reacting, the surfaces of the anode plate and the cathode plate are flushed. When the electrolyte enters the exhaust pipe, it overflows 60-70% of the height of the exhaust pipe. The gas of the electrolyte in the exhaust pipe rises to the top of the electrolyte, enters above the exhaust pipe, and is finally discharged from the exhaust pipe.

[0024] Furthermore, the mass ratio of tributylamine to hydrogen fluoride in step S1 is 80-100kg:200-230kg.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The invention provides a process for preparing perfluorotributylamine. The mass ratio of tributylamine to hydrogen fluoride is 80-100kg:200-230kg. Hydrogen fluoride is first added to an electrolytic cell, and then tributylamine is added. Before the reaction, the air in the electrolytic cell is replaced by nitrogen, and the air is replaced by nitrogen for preliminary mixing and preparing electrolyte. Then, a low-voltage current is passed to carry out an electrolytic replacement reaction, and the reaction pressure is controlled at 0.1-1.5MPa and the temperature is controlled at -10-30°C. By controlling the reflux distribution of the circulating liquid and the single circulation path, the product with a large specific gravity is placed in the pipeline equipment to improve the reaction activity, fluorination efficiency, and conversion rate. The electrolytic fluorination method has mild and controllable reaction, simple process, high efficiency, less impurities and easy separation. The present invention also provides a perfluorotributylamine preparation device for preparing perfluorotributylamine, by dividing the electrolytic cell into two chambers, one of which is a liquid inlet chamber for the circulation pipeline to inlet liquid, and the other is an electrolytic reaction chamber for the electrolytic reaction, the circulating electrolyte enters the liquid inlet chamber, and after being pressurized through the liquid inlet, enters the liquid inlet channel between the anode plate and the cathode plate from between the two guide plates below the liquid inlet, so that the electrolyte is arranged to fully carry out the electrolytic reaction, because tar and the like will be produced in the electrolysis process and adhere to the surface of the plate, affecting the electrolysis, the above-mentioned guide plate is arranged during the electrolyte circulation process, and the surface of the anode plate and the cathode plate can be flushed to prevent tar from adhering, and at the same time, the incompletely fluorinated products and the fluorine raw materials produced by the electrolysis are made to be completely fluorinated. The electrolyte will be in full contact with the anode and cathode plates to make the fluorination more thorough; since the circulating electrolyte will directly enter the electrolysis chambers of the anode and cathode plates, the high-pressure electrolyte will splash down and cause sputtering. In addition, the volume of the liquid inlet channel is small and the liquid inlet channel will always be filled with liquid during circulation. Therefore, the electrolyte will bring gas or splashed bubbles into the circulation pipeline during the flow. More bubbles in the circulation pipeline will affect the normal operation of the pump body. Therefore, an exhaust pipe is set in front of the pump body. Through the control of the pump body, the electrolyte in the exhaust pipe will only cover 70%-80% of the height of the exhaust pipe. Due to density reasons, the electrolyte in the circulation pipeline will be located in the upper layer. When entering the exhaust pipe, it will directly enter the cavity area of ​​the exhaust pipe and then be discharged from the exhaust pipe.

[0027] 2. The cooling components and circulation components in this solution use a single circulation pipeline for flow circulation and heat exchange, which can avoid the accumulation of electrolysis products.

[0028] 3. The bottom of the electrolytic reaction chamber is an arc-shaped bottom or a conical bottom, so that the products produced by electrolysis can be fully circulated.

[0029] 4. It is more reasonable to connect the drain plate to the lower opening of the liquid inlet by a rotating connection, because directly setting two drain plates so that they can be set up on both sides of the liquid inlet channel requires very precise processing technology, and the production cost of the partition will be increased. By setting a rotatably connected drain plate, the drain plate can swing to both sides due to the stamping of water pressure until it hits both sides of the liquid inlet channel when the electrolyte passes through. The production cost is low, the precision control does not need to be too high, and it can be adapted to the liquid inlet channel between each anode plate and cathode plate through manual adjustment. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is the chemical formula for the direct reaction of fluorine gas and tributylamine in the background technology of the present invention;

[0031] Figure 2 This is a schematic diagram of the principle structure of a perfluorotributylamine preparation device in the present invention;

[0032] Figure 3 It is a schematic diagram of the three-dimensional structure of the electrolytic component in the present invention;

[0033] Figure 4 It is a schematic diagram of the three-dimensional structure of the electrolytic cell body and the partition after being assembled in the present invention;

[0034] Figure 5 It is a schematic diagram of the three-dimensional structure of the electrolytic cell body in the present invention;

[0035] Figure 6 It is a schematic diagram of the three-dimensional structure of the cover body in the present invention;

[0036] Figure 7 It is a schematic diagram of the three-dimensional structure of the partition in the present invention;

[0037] Figure 8 For the present invention Figure 7 A schematic diagram of the local enlarged structure at point A in the middle;

[0038] Fig. 9 It is a schematic diagram of the three-dimensional structure of the partition in another direction of the present invention;

[0039] Fig.10 For the present invention Fig. 9 A schematic diagram of the local enlarged structure at B in the middle;

[0040] Fig.11 It is a schematic diagram of the three-dimensional structure of the electrolytic plate set in the present invention;

[0041] Fig.12 It is a cross-sectional structural schematic diagram of the present invention;

[0042] Fig.13 For the present invention Fig.12 A schematic diagram of the local enlarged structure at C in the middle;

[0043] Fig.14 For the present invention Fig.13 A schematic diagram of the local enlarged structure at D in the middle;

[0044] Fig.15 It is a schematic diagram of the three-dimensional structure of the pump body in the present invention;

[0045] Fig.16 It is a schematic diagram of the cross-sectional structure of the pump body in the present invention;

[0046] Fig.17 It is a simplified cross-sectional structural schematic diagram of the cooling assembly in the present invention.

[0047] Markings in the figure: 1, electrolytic assembly; 11, electrolytic cell body; 111, liquid inlet chamber; 112, electrolytic reaction chamber; 113, partition; 1131, liquid inlet; 1132, expansion; 1133, drainage plate; 1134, baffle; 114, limiting step; 12, cover; 121, inlet; 122, limiting pressure block; 13, electrolytic plate kit; 131, fixing column; 132, reaction plate; 1321, anode plate; 1322, cathode plate; 1323, liquid inlet channel; 133, left fixing plate; 134, right fixing Plate; 135, middle plate; 136, power supply column; 2, cooling component; 21, cooling tower; 211, baffle; 3, circulation component; 31, circulation pipeline; 311, first pipeline; 3111, first solenoid valve; 312, second pipeline; 3121, second solenoid valve; 313, third pipeline; 3131, third solenoid valve; 314, fourth pipeline; 3141, fourth solenoid valve; 32, pump body; 321, pump body; 322, exhaust pipe; 323, exhaust pipeline; 324, pump motor; 4, exhaust gas treatment component. DETAILED DESCRIPTION

[0048] In order to make the above features and advantages of the present invention more obvious and easy to understand, embodiments are given below with reference to the accompanying drawings for detailed description as follows.

[0049] like Figure 1-Figure 17 As shown, this embodiment provides a perfluorotributylamine preparation device, including an electrolysis component 1, a cooling component 2, a circulation component 3 and an exhaust gas treatment component 4.

[0050] like Figure 2-Figure 6As shown, the electrolysis assembly 1 includes an electrolytic cell body 11, a cover body 12 and five electrolytic plate sets 13. The cover body 12 is sealed and covered on the top of the electrolytic cell body 11, and an inlet 121 is arranged on the top of the cover body 12. The electrolytic cell body 11 is provided with a liquid inlet chamber 111 and an electrolytic reaction chamber 112 arranged at intervals up and down. Preferably, the bottom of the electrolytic reaction chamber 112 is an arc bottom or a conical bottom, so that the products produced by electrolysis can be fully circulated. A first density meter for measuring the nitrogen density in the reaction area is arranged in the middle of the circumference of the electrolytic cell body 11, and a second density meter for measuring the density of the electrolyte after the reaction is arranged below the electrolytic cell body 11. The side wall of the electrolytic cell body 11 is also provided with a nitrogen inlet and an electrolyte raw material inlet.

[0051] like Figure 11-Figure 14 As shown, five electrolytic plate sets 13 are located in the electrolytic reaction chamber 112 and are arranged at intervals on the left and right. Specifically, the same fixing column 131 passes through the five electrolytic plate sets 13 and the two ends are respectively connected to the two inner walls of the electrolytic reaction chamber 112 to achieve fixation. The two inner walls of the electrolytic reaction chamber 112 are formed with mounting grooves for adapting the fixing column 131. The electrolytic plate set 13 includes a plurality of groups of reaction plates 132, left fixing plates 133, right fixing plates 134 and adjacent middle plates 135 arranged in sequence on the left and right. The reaction plates 132, the left fixing plates 133, the right fixing plates 134 and the adjacent middle plates 135 are connected by bolts. , adjacent middle plates 135 are located between adjacent reaction plates 132, the left fixed plate 133 and the right fixed plate 134 are respectively located at the leftmost and rightmost sides of the entire electrolytic plate set 13, and the electrolytic plate set 13 is also pierced by two power supply poles 136, one of which is used to supply power to the anode plate 1321 in the reaction plate 132, and the other power supply pole 136 is used to supply power to the cathode plate 1322 in the reaction plate 132, and one side of the two power supply poles 136 passes through the side wall of the electrolytic cell body 11, and the number of reaction plates 132 is set according to actual needs. The above structure is implemented using the common settings in existing electrolysis devices, which will not be repeated again. The actual innovative points in this scheme are as follows: the reaction plate 132 includes an anode plate 1321, a cathode plate 1322 and an ion diaphragm, the ion diaphragm is located between the anode plate 1321 and the cathode plate 1322, a liquid inlet channel 1323 is formed between the anode plate 1321 and the cathode plate 1322, the distance between the anode plate 1321 and the cathode plate 1322 is 50mm-120mm, and in this scheme, the distance between the anode plate 1321 and the cathode plate 1322 is 100mm, and the distance between the anode plate 1321 and the cathode plate 1322 is set according to the actual situation with reference to the number of electrolytic plate kits 13 and the volume of the electrolytic reaction chamber 112.

[0052] like Figure 7-10As shown, the liquid inlet chamber 111 and the electrolytic reaction chamber 112 are separated by a partition 113. Specifically, the partition 113 is detachably sealed and connected to the electrolytic cell body 11. A closed-loop limiting step 114 is formed on the inner circumference of the electrolytic cell body 11. The partition 113 is mounted on the upper surface of the limiting step 114. A closed-loop first sealing groove is formed on the inner side of the limiting step 114. A special sealing ring is arranged in the first sealing groove for separating the liquid inlet chamber 111 and the electrolytic reaction chamber 112. At least two limiting pressure blocks 122 are formed on the inner circumferential surface of the cover body 12. In the present embodiment, the number of limiting pressure blocks 122 is two and they are stacked. When the cover body is closed above the electrolytic cell body 11, the lower surface of the limiting pressure block 122 abuts against the upper surface of the partition 113. Through the above arrangement, when the cover body 12 is closed, the limiting pressure block 122 can just press the partition 113, so that the partition 113 will not shift during operation.

[0053] like Figure 7-10 As shown, a plurality of strip-shaped liquid inlets 1131 are formed on the partition 113, and the number of the liquid inlets 1131 and the reaction plates 132 are matched, and the lower openings of the plurality of liquid inlets 1131 correspond to the upper openings of the plurality of liquid inlet channels 1323, and the two side walls of the lower openings of the liquid inlets 1131 are provided with oppositely arranged guide plates 1133, and the length of the guide plates 1133 is the same as that of the liquid inlet 1131 and is less than that of the reaction plates 132, and the guide plates 1133 are used to introduce the liquid into the liquid inlet channels 1323 Preferably, the width of the upper opening of the liquid inlet 1131 is smaller than the width of the lower opening of the liquid inlet 1131, the vertical cross-section of the lower opening of the liquid inlet 1131 is in the shape of an arc, and a flare 1132 is formed at the upper opening of the liquid inlet 1131. One end of the guide plate 1133 is rotatably connected to the side wall of the lower opening of the liquid inlet 1131, and a torsion spring is provided at the rotational position of the guide plate 1133 and the side wall of the lower opening of the liquid inlet 1131. The opening between the two guide plates 1133 increases as the amount of liquid inflow increases, such as Fig.14 As shown, the arrow direction is the opposite direction of rotation. It is more reasonable for the drain plate 1133 to be connected to the lower opening of the liquid inlet 1131 by a rotational connection, because directly setting two drain plates 1133 just to be set on both sides of the liquid inlet channel 1323 requires a very precise processing technology, and the production cost of the partition 113 will be increased. When the drain plate 1133 is rotatably connected, the drain plate 1133 can swing to both sides due to the stamping of the water pressure until it hits the two sides of the liquid inlet channel 1323 when the electrolyte passes through, the production cost is low, and the precision control does not need to be too high, and it can be adapted to the liquid inlet channel 1323 between each anode plate 1321 and cathode plate 1322 through manual adjustment.

[0054] Preferably, baffles 1134 are formed on both sides of the lower opening of the liquid inlet 1131 , and the baffles 1134 are used to block the gap between the two sides of the guide plate 1133 and the reaction plate 132 . The length of the baffles 1134 is equal to or less than the distance between the anode plate 1321 and the cathode plate 1322 .

[0055] By means of the above arrangement, when the reaction liquid is circulated, it enters from the liquid inlet chamber 111, then passes through the liquid inlet 1131 of the partition 113 to be pressurized, and then passes through the guide plate to be accurately introduced into the liquid inlet channel 1323, which not only enables the electrolyte to fully undergo an electrolysis reaction, but also can flush the surfaces of the anode plate 1321 and the cathode plate 1322 to prevent tar from adhering, thus killing two birds with one stone.

[0056] In another embodiment, the two sides of the multiple reaction plates 132 are blocked by the same insulating plate, which can ensure that the electrolyte can react further and fully in the feed channel.

[0057] The circulation assembly 3 includes a pump body 32 and a circulation pipeline 31. The pump body 32 and the cooling assembly 2 are located on the circulation pipeline 31. The liquid inlet end of the circulation pipeline 31 is connected to the liquid outlet at the lower end of the electrolytic reaction chamber 112, and the liquid outlet end of the circulation pipeline 31 is connected to the inlet at the upper end of the liquid inlet chamber 111. Specifically, the circulation pipeline 31 includes a first pipeline 311, a second pipeline 312, a third pipeline 313 and a fourth pipeline 314. The first pipeline 311 is connected to the liquid outlet at the lower end of the electrolytic reaction chamber 112 and the pump body 32. The first pipeline 311 is connected, a first solenoid valve 3111 is arranged on the first pipeline 311, the second pipeline 312 is connected with the pump body 32 and the third pipeline 313, a second solenoid valve 3121 is arranged on the second pipeline 312, the third pipeline 313 passes through the cooling assembly 2, the third pipeline 313 is arranged in a spiral manner in the pipeline of the cooling assembly 2, a third solenoid valve 3131 is arranged on the side of the third pipeline 313 close to the second pipeline 312, and the fourth pipeline 314 is connected with the upper end of the liquid inlet chamber 111 and the third pipeline 313. A fourth solenoid valve 3141 is arranged on the fourth pipeline 314 near the outlet of the cooling assembly 2, the second pipeline 312 between the second solenoid valve 3121 and the third solenoid valve 3131 can be connected to the intermediate tank through the fifth pipeline, the fifth pipeline is provided with a fifth solenoid valve, and the opening of the fifth solenoid valve on the fifth pipeline means that the entire cycle electrolysis reaction is over.

[0058] like Figure 15-16As shown, the pump body 32 includes a pump body 321, an exhaust pipe 322, an exhaust pipeline 323 and a pump motor 324. The axis of the exhaust pipe 322 is horizontally arranged, the inlet of the exhaust pipe 322 is located above the end surface of one side and is connected to the circulation pipeline 31, the outlet of the exhaust pipe 322 is located below the end surface of the other side and is connected to the pump body 321, the pump body 321 adopts the structure of a shell plus an impeller in the prior art, the pump motor 324 drives the impeller to rotate to extract the electrolyte to realize circulation, the exhaust pipeline 323 is vertically arranged above the exhaust pipe 322, the exhaust pipeline 323 is used to discharge the gas in the liquid, preferably, the other end of the exhaust pipeline 323 is connected to the exhaust gas treatment component 4, and an air pump can be set on the exhaust pipeline 323 for exhausting air, so that a negative pressure is formed in the exhaust pipeline 323 to facilitate exhaust. The above arrangement is because the circulating electrolyte will directly enter the electrolysis chambers of the anode plate 1321 and the cathode plate 1322. The high-pressure electrolyte will cause sputtering when it rushes down. In addition, the volume of the liquid inlet channel 1323 is small and the liquid inlet channel 1323 will continue to infuse liquid during circulation. Therefore, the electrolyte will bring gas or splashed bubbles into the circulation pipeline 31 during the flow. A large number of bubbles in the circulation pipeline 31 will affect the normal operation of the pump body 321. Therefore, an exhaust pipe 322 is set in front of the pump body 321. Through the control of the pump body 321, the electrolyte in the exhaust pipe 322 will only cover 70%-80% of the height of the exhaust pipe 322. Due to density reasons, the electrolyte in the circulation pipeline 31 will be located in the upper layer. When entering the exhaust pipe 322, it will directly enter the cavity area of ​​the exhaust pipe 322 and then be discharged from the exhaust pipe.

[0059] like Fig.17 As shown, the cooling assembly 2 includes a cooling tower 21, the coolant inlet of the cooling tower 21 is at the upper end of the cooling tower 21, the coolant outlet of the cooling tower 21 is at the lower end of the cooling tower 21, a plurality of baffles 211 are arranged in the cooling tower 21 at intervals up and down, the plurality of baffles 211 are connected to the left and right sides of the inner wall of the cooling tower 21, the coolant path in the cooling tower 21 is in the shape of a vertically arranged equal-amplitude oscillation curve, and the third pipeline 313 in the circulation pipeline 31 in the cooling tower 21 is arranged in a spiral manner.

[0060] The tail gas treatment component 4 is used to collect and process the gas in the electrolytic cell body 11 and the exhaust pipe 322. Specifically, the tail gas treatment component 4 is connected to the upper end of the electrolytic reaction chamber 112, and the tail gas treatment component 4 is connected to the exhaust pipe 323. The tail gas treatment component 4 adopts the tail gas treatment component 4 commonly used in the preparation process of perfluorotributylamine in the prior art, which will not be repeated here.

[0061] This embodiment also provides a process for preparing perfluorotributylamine, which adopts the above-mentioned perfluorotributylamine preparation device for preparation, and comprises the following steps:

[0062] S1, replace the air in the electrolytic cell with nitrogen, first add hydrogen fluoride into the electrolytic cell body 11, then add tributylamine, and form an electrolyte after preliminary mixing; wherein the mass ratio of tributylamine to hydrogen fluoride in step S1 is 80-100kg:200-230kg, and the mass ratio of tributylamine to hydrogen fluoride in this embodiment is 80kg-200kg, and the specific steps of S1 are as follows: first install the partition 113, cover the cover 12 and the electrolytic cell body 11, first flush nitrogen into the electrolytic cell body 11 from the nitrogen inlet until the first density meter reaches a preset value, first introduce hydrogen fluoride from the electrolyte raw material inlet, then introduce tributylamine, the electrolyte overflows 80% of the height of the reaction plate 132, and form an electrolyte after preliminary mixing.

[0063] S2, low-pressure electrolysis is performed, the reaction pressure is controlled at 0.1MPa-1.5MPa, the temperature is controlled at -10℃-30℃, and the electrolyte is circulated. The specific steps of S2 are as follows: power is supplied through the power supply column 136, and the electrolysis reaction chamber 112 begins to perform electrolysis. The pressure is controlled at 0.1MPa-1.5MPa, and the temperature is controlled at -10℃-30℃. In this scheme, the temperature is 5℃. The pressure control and temperature control are controlled by common technologies in the prior art, which will not be repeated here. After a period of reaction (15min-30min), the first solenoid valve 3111 to the fourth solenoid valve 3141 are opened, the pump body 32 starts to operate, and the entire electrolyte circulation begins.

[0064] S3, during the circulation of the electrolyte, the surfaces of the anode plate 1321 and the cathode plate 1322 are flushed, and the gas mixed in the electrolyte is discharged in the circulation pipeline 31. The specific steps of S3 are as follows: the electrolyte flows into the circulation pipeline from the bottom of the electrolytic reaction chamber 112, passes through the exhaust pipe 322, the pump body 321 and the cooling component 2 in sequence, and the cooling component 2 performs heat exchange (cooling) on ​​it, and finally flows in from the top of the liquid inlet chamber 111, enters from the strip liquid inlet 1131 on the partition 113, and is drained to the anode plate 1321 and the cathode plate 1322 through the two guide plates 1133. Between the liquid inlet channel 1323 of 22, the guide plate 1133 flips to both sides while the liquid flows through, thereby increasing the distance between the ends of the guide plates 1133. While the electrolyte is reacting, it also washes the surfaces of the anode plate 1321 and the cathode plate 1322 to prevent tar from adhering to the surfaces of the anode plate 1321 and the cathode plate 1322. When the electrolyte enters the exhaust pipe 322, it overflows 60-70% of the height of the exhaust pipe 322. The gas of the electrolyte in the exhaust pipe 322 rises to the top of the electrolyte, enters above the exhaust pipe 322, and is finally discharged from the exhaust pipe 323.

[0065] S4. After the cyclic electrolysis is completed, a crude product of perfluorotributylamine with a purity of more than 80% is obtained.

[0066] In step S1, this embodiment also provides several relatively excellent mass ratios of tributylamine and hydrogen fluoride. The mass ratio of tributylamine and hydrogen fluoride is 90kg-210kg, and the mass ratio of tributylamine and hydrogen fluoride is 100kg-230kg.

[0067] The present invention aims to overcome the shortcomings of the prior art such as low reaction activity, low fluorination efficiency, low conversion rate, and large raw material loss. In order to break this technical barrier, a perfluorotributylamine deep fluorination device with simple reaction, high reaction activity, high fluorination degree, and high conversion rate is developed to achieve efficient and high-purity industrial production of perfluorotributylamine. The electrolytic fluorination method is adopted, and hydrogen fluoride and tributylamine are electrolyzed under the action of additives to achieve the purpose of replacing hydrogen atoms with fluorine atoms. The reaction mechanism is as follows:

[0068] Electrode reaction:

[0069] At cathode: H++e ─→ H H+H ─→ H2↑

[0070] At the anode: F--e ─→ F C-H+F ─→ C-F+H.

[0071] Through the process and apparatus of this embodiment, a crude perfluorotributylamine with a purity of more than 80% can be obtained under the conditions of simple reaction raw materials and simple reaction apparatus. The process and apparatus can increase the degree of fluorination in the reaction process from the original 70% to 80%, and the reaction raw materials and reaction apparatus are relatively simple, which is more conducive to the industrial production of perfluorotributylamine.

[0072] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for illustrating the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which shall fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A perfluorotributylamine preparation device, characterized in that: It includes electrolysis components, cooling components, circulation components and tail gas treatment components; The electrolysis assembly comprises an electrolytic cell body, a cover body and a plurality of electrolytic plate kits, wherein the cover body is sealed and covered on the electrolytic cell body, the electrolytic cell body is provided with a liquid inlet chamber and an electrolytic reaction chamber spaced apart from each other in the upper and lower parts, the plurality of electrolytic plate kits are located in the electrolytic reaction chamber and spaced apart from each other in the left and right parts, the electrolytic plate kit comprises a plurality of groups of reaction plates sequentially arranged in the left and right parts, the reaction plates comprise an anode plate and a cathode plate, a liquid inlet channel is provided between the anode plate and the cathode plate, the liquid inlet chamber and the electrolytic reaction chamber are blocked by a partition, a plurality of liquid inlets are formed on the partition, the lower openings of the plurality of liquid inlets correspond to the upper openings of the plurality of liquid inlet channels, and the two side walls of the lower openings of the liquid inlets are provided with oppositely arranged drainage plates, and the drainage plates are used to introduce liquid into the liquid inlet channel; The circulation assembly includes a pump body and a circulation pipeline, the pump body and the cooling assembly are located on the circulation pipeline, the liquid inlet end of the circulation pipeline is connected to the liquid outlet at the lower end of the electrolytic reaction chamber, the liquid outlet end of the circulation pipeline is connected to the inlet at the upper end of the liquid inlet chamber, the pump body includes a pump body, an exhaust pipe and an exhaust pipeline, the axis of the exhaust pipe is horizontally arranged, the inlet of the exhaust pipe is located above one side end surface and is connected to the circulation pipeline, the outlet of the exhaust pipe is located below the other side end surface and is connected to the pump body, the exhaust pipeline is vertically arranged above the exhaust pipe, and the exhaust pipeline is used to discharge gas in the liquid material; The tail gas treatment assembly is used to collect and process the gas in the electrolytic cell body and the exhaust pipe; The width of the upper opening of the liquid inlet is smaller than the width of the lower opening of the liquid inlet. The vertical cross-section of the lower opening of the liquid inlet is arc-shaped. One end of the guide plate is rotatably connected to the side wall of the lower opening of the liquid inlet. A torsion spring is provided at the rotation point between the guide plate and the side wall of the lower opening of the liquid inlet. The opening between the two guide plates increases as the liquid inlet amount increases.

2. A perfluorotributylamine preparation device according to claim 1, characterized in that: The distance between the anode plate and the cathode plate is 50 mm-120 mm.

3. A perfluorotributylamine preparation device according to claim 1, characterized in that: The bottom of the electrolytic reaction chamber is an arc-shaped bottom or a conical bottom.

4. A perfluorotributylamine preparation device according to claim 1, characterized in that: The partition is detachably and hermetically connected to the electrolytic cell body; a limiting step arranged in a closed loop is formed on the inner peripheral surface of the electrolytic cell body; and the partition is mounted on the upper surface of the limiting step.

5. A perfluorotributylamine preparation device according to claim 4, characterized in that: A limiting pressure block is formed on the inner circumferential surface of the cover body. When the cover body is closed above the electrolytic cell body, the lower surface of the limiting pressure block abuts against the upper surface of the partition.

6. A perfluorotributylamine preparation device according to claim 1, characterized in that: The cooling assembly includes a cooling tower, in which a plurality of baffles are arranged at intervals up and down, and the plurality of baffles are connected to the left and right sides of the inner wall of the cooling tower. The coolant path in the cooling tower is in the shape of a vertically arranged equal-amplitude oscillation curve, and the circulation pipeline in the cooling tower is arranged in a spiral manner.

7. A process for preparing perfluorotributylamine, characterized in that: The following steps are involved: The preparation is carried out using a perfluorotributylamine preparation device as claimed in any one of claims 1 to 6; S1. Replace the air in the electrolytic cell with nitrogen, first add hydrogen fluoride into the electrolytic cell body, then add tributylamine, and form an electrolyte after preliminary mixing; S2, perform low-pressure electrolysis, control the reaction pressure at 0.1MPa-1.5MPa, control the temperature at -10°C-30°C, and circulate the electrolyte; S3, during the circulation of the electrolyte, flushing the surfaces of the anode plate and the cathode plate, and discharging the gas mixed in the electrolyte in the circulation pipeline; S4. After the cyclic electrolysis is completed, a crude product of perfluorotributylamine with a purity of more than 80% is obtained.

8. A process for preparing perfluorotributylamine according to claim 7, characterized in that: The specific steps of step S3 are as follows: the electrolyte flows into the circulation pipeline from the bottom of the electrolytic reaction chamber, passes through the exhaust pipe, the pump body and the cooling assembly in sequence, and finally flows in from the top of the liquid inlet chamber, enters from the liquid inlet port of the partition, passes through two guide plates and is guided to the liquid inlet channels between the anode plate and the cathode plate. While reacting, the surfaces of the anode plate and the cathode plate are flushed. When the electrolyte enters the exhaust pipe, it overflows 60-70% of the height of the exhaust pipe. The gas of the electrolyte in the exhaust pipe rises to the top of the electrolyte, enters above the exhaust pipe, and is finally discharged from the exhaust pipe.

9. A process for preparing perfluorotributylamine according to claim 7, characterized in that: The mass ratio of tributylamine to hydrogen fluoride in step S1 is 80-100kg:200-230kg.

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