Column reactor and preparation method for bis(fluorosulfonyl)imide triethylamine salt

Abstract

The present application relates to the technical field of chemical devices, and in particular to a column reactor and a preparation method for bis(fluorosulfonyl)imide triethylamine salt. The column reactor comprises: a reactor main body which is provided with a gas outlet and a liquid outlet; a liquid inlet pipe arranged at the upper part of the reactor main body; a plurality of spaced column plates arranged in the reactor main body, at least one column plate being further away from the gas outlet than the liquid inlet pipe; a first gas inlet pipe arranged between any two adjacent column plates; a second gas inlet pipe arranged between any two adjacent column plates and further away from the liquid inlet pipe than the first gas inlet pipe; and a third gas inlet pipe arranged between any two adjacent column plates or mounted on the side, away from the liquid inlet pipe, of the column plate furthest away from the liquid inlet pipe, and further away from the liquid inlet pipe than the second gas inlet pipe, wherein at least one stirring mechanism is provided on at least one column plate. The at least one stirring mechanism is provided on the column plate, so that accurate temperature control is not required for the column reactor, thereby effectively improving the reaction yield.

Description

A tower reactor and a method for preparing bis(fluorosulfonyl)imide triethylamine salt Technical Field

[0001] The present application relates to the technical field of chemical equipment, and in particular to a tower reactor and a method for preparing triethylamine salt of bis(fluorosulfonyl)imide. Background Art

[0002] As a key component of lithium battery electrolytes, lithium salts significantly influence the electrochemical properties of the electrolyte. Compared to LiPF6, lithium bis(fluorosulfonyl)imide (LiFSI) offers higher electrochemical and thermal stability, better compatibility with lithium metal and graphite electrodes, and is environmentally friendly. It also boasts excellent low-temperature performance and safety, making it a promising new lithium battery electrolyte salt for industrialization.

[0003] According to patent CN102378755A, it is easier to derive lithium bis(fluorosulfonyl)imide by first preparing the triethylamine salt of bis(fluorosulfonyl)imide than other methods.

[0004] CN114506829A describes a method for preparing triethylamine salt of bis(fluorosulfonyl)imide. According to the description, the method requires evacuating the reactor to -0.09 MPa in a sealed system.

[0005] CN116281895A describes another method for preparing triethylamine salt of bis(fluorosulfonyl)imide. However, this method places more stringent requirements on the reaction equipment and requires precise control of the reaction temperature at each stage.

[0006] In summary, the preparation methods of bis(fluorosulfonyl)imide triethylamine salt in the prior art all have certain difficulties in large-scale production.

[0007] Summary of the Invention

[0008] In view of the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a tower reactor capable of large-scale industrial production of bisfluorosulfonyl imide and a method for preparing triethylamine salt of bisfluorosulfonyl imide using the tower reactor.

[0009] To achieve the above-mentioned and other related purposes, the present application provides, in one aspect, a tower reactor, comprising: a reactor body having a gas outlet and a liquid outlet;

[0010] a liquid inlet pipe, provided at the upper portion of the reactor body, for introducing liquid into the reactor body;

[0011] a plurality of spaced-apart trays disposed within the reactor body, wherein at least one tray is further away from the gas outlet than the liquid inlet pipe;

[0012] a first air inlet pipe, provided between any two adjacent trays, for introducing gas into the reactor body;

[0013] a second air inlet pipe, provided between any two adjacent trays and further away from the liquid inlet pipe than the first air inlet pipe;

[0014] a third air inlet pipe, disposed between any two adjacent trays, or disposed on a side of the tray farthest from the liquid inlet pipe, further away from the liquid inlet pipe than the second air inlet pipe;

[0015] Wherein, at least one stirring mechanism is provided on at least one tower plate.

[0016] In some embodiments of the present invention, a gas outlet is provided on the top of the reactor body.

[0017] In some embodiments of the present invention, a gas outlet is provided on the side of the reactor body, and the height of the gas outlet is higher than the liquid level of the reactor body.

[0018] In some embodiments of the present invention, a liquid outlet is provided at the bottom of the reactor body.

[0019] In some embodiments of the present invention, a liquid outlet is provided on the side of the reactor body.

[0020] In some embodiments of the present invention, a portion of the liquid inlet pipe is disposed inside the reactor body, and a portion thereof is disposed outside the reactor body.

[0021] In some embodiments of the present invention, a spray head is provided at one end of the liquid inlet pipe in the reactor body.

[0022] In some embodiments of the present invention, the trays are arranged in a staggered manner.

[0023] In some embodiments of the present invention, in each of the tower plates, the tower plates include odd-numbered tower plates and even-numbered tower plates, the vertical projections of the odd-numbered tower plates on the horizontal plane overlap, the vertical projections of the even-numbered tower plates on the horizontal plane overlap, and the vertical projections of the odd-numbered tower plates and the even-numbered tower plates on the horizontal plane partially overlap.

[0024] In some embodiments of the present invention, each of the trays is arranged parallel to the horizontal plane.

[0025] In some embodiments of the present invention, a portion of the first air inlet pipe is located inside the reactor body, and a portion thereof is located outside the reactor body.

[0026] In some embodiments of the present invention, a portion of the first air inlet pipe inside the reactor body is provided with a plurality of first air inlet holes.

[0027] In some embodiments of the present invention, a portion of the second air inlet pipe is located inside the reactor body, and a portion of the second air inlet pipe is located outside the reactor body.

[0028] In some embodiments of the present invention, a portion of the second air inlet pipe inside the reactor body is provided with a plurality of second air inlet holes.

[0029] In some embodiments of the present invention, a portion of the third air inlet pipe is located inside the reactor body, and a portion thereof is located outside the reactor body.

[0030] In some embodiments of the present invention, a portion of the third air inlet pipe inside the reactor body is provided with a plurality of third air inlet holes.

[0031] In some embodiments of the present invention, a stirring mechanism is provided on a tower plate opposite to the first air inlet opening of the first air inlet pipe. The tower plate opposite to the first air inlet opening is the tower plate toward which the opening of the first air inlet opening faces.

[0032] In some embodiments of the present invention, a stirring mechanism is provided on a tray opposite to the second air inlet opening of the second air inlet pipe, wherein the tray opposite to the second air inlet opening is the tray toward which the second air inlet opening faces.

[0033] In some embodiments of the present invention, each of the tower plates is provided with one or more stirring mechanisms.

[0034] In some embodiments of the present invention, the stirring mechanism is a gas stirring mechanism or a mechanical stirring mechanism.

[0035] In some embodiments of the present invention, each of the gas stirring mechanisms includes: an air pump, arranged outside the reactor body; an aeration pipe, connected to the air pump and at least partially located inside the reactor body; and a plurality of aeration heads, arranged on the aeration pipe and located inside the reactor body.

[0036] In some embodiments of the present invention, each of the mechanical stirring mechanisms includes: a power supply; a plurality of stirring paddles electrically connected to the power supply and located inside the reactor body; and a controller for controlling the rotational speed of the stirring paddles.

[0037] In some embodiments of the present invention, the reactor further comprises a first temperature control device for controlling the internal temperature of the reactor body.

[0038] In some embodiments of the present invention, further comprising

[0039] The filter is connected to the liquid outlet and is used to intercept the solid flowing out of the liquid outlet and allow the liquid flowing out of the liquid outlet to pass through.

[0040] In some embodiments of the present invention, a reflux pipe is further included, which is respectively connected to the liquid inlet pipe and the filter, and is used to return part or all of the liquid passing through the filter to the reactor body. In some embodiments of the present invention, a receiving kettle is further included, which is connected to the filter and is used to receive part or all of the liquid passing through the filter.

[0041] In some embodiments of the present invention, a production pump is further included, and the production pump is connected to the liquid outlet and the filter respectively; a valve is provided on the connecting pipeline between the production pump and the filter.

[0042] In some embodiments of the present invention, the reflux pipe includes a main pipe, a first branch pipe and a second branch pipe, the first branch pipe or the second branch pipe is connected to the filter through the main pipe; the liquid inlet pipe is connected to the main pipe through the first branch pipe, and the receiving kettle is connected to the main pipe through the second branch pipe; valves are respectively provided on the main pipe, the first branch pipe and the second branch pipe.

[0043] In some embodiments of the present invention, a flow meter is provided on the reflux pipe.

[0044] Another aspect of the present invention provides a method for preparing triethylamine salt of bis(fluorosulfonyl)imide, which is prepared using the tower reactor described in the first aspect of the present invention, and the method comprises the following steps:

[0045] Acetonitrile is introduced into the reactor body until the liquid level submerges the first air inlet pipe;

[0046] Add triethylamine in acetonitrile solution into the reactor body through the liquid inlet tube;

[0047] Ammonia gas is introduced into the reactor body through the first air inlet pipe;

[0048] Sulfuryl fluoride is introduced into the reactor body through a second air inlet pipe;

[0049] Ammonia gas is introduced into the reactor body through the third air inlet pipe.

[0050] Wherein, in any one step or multiple steps, stirring is performed by a stirring mechanism.

[0051] In some embodiments of the present invention, the tower reactor is used for preparation, comprising the following steps:

[0052] Acetonitrile is introduced into the reactor body so that the liquid level at least covers the first air inlet pipe;

[0053] Add triethylamine in acetonitrile solution into the reactor body through the liquid inlet tube;

[0054] Ammonia gas is introduced into the reactor body through the first air inlet pipe;

[0055] Sulfuryl fluoride is introduced into the reactor body through a second air inlet pipe;

[0056] Ammonia gas is introduced into the reactor body through the third air inlet pipe;

[0057] The reaction mixture formed in the reactor body is discharged from the liquid outlet of the reactor body;

[0058] Filtering the reaction mixture using a filter to obtain an inorganic salt and a filtrate;

[0059] Use a receiving kettle to receive part or all of the filtrate;

[0060] Wherein, in any one step or multiple steps, stirring is performed by a stirring mechanism.

[0061] In some embodiments of the present invention, a portion or all of the filtrate re-enters the reactor body through the reflux pipe and the liquid inlet pipe.

[0062] In some embodiments of the present invention, the molar ratio of triethylamine in the acetonitrile solution of triethylamine to the ammonia gas introduced through the first air inlet pipe is (3-4): 1. Furthermore, the molar ratio of triethylamine in the acetonitrile solution of triethylamine to the ammonia gas introduced through the first air inlet pipe can be, for example, (3-3.6): 1 or (3.6-4): 1.

[0063] In some embodiments of the present invention, when the stirring mechanism is a gas stirring mechanism, the gas introduced is nitrogen, and the ventilation volume per unit tank cross section is 0.1 to 1 m 3 / (min·m 2 Optionally, the ventilation volume per unit tank cross section is 0.1 to 0.5 m 3 / (min·m 2 ) or 0.5~1m 3 / (min·m 2 )wait.

[0064] In some embodiments of the present invention, the molar ratio of ammonia introduced into the first air inlet pipe to sulfuryl fluoride introduced into the second air inlet pipe is 1:(2-3). Alternatively, the molar ratio of ammonia introduced into the first air inlet pipe to sulfuryl fluoride introduced into the second air inlet pipe can be, for example, 1:(2-2.1) or 1:(2.1-3).

[0065] In some embodiments of the present invention, the molar ratio of the ammonia gas introduced into the first air inlet pipe to the ammonia gas introduced into the third air inlet pipe is 1:(2-3). Alternatively, the molar ratio of the ammonia gas introduced into the first air inlet pipe to the ammonia gas introduced into the third air inlet pipe can be, for example, 1:(2-2.1) or 1:(2.1-3).

[0066] In some embodiments of the present invention, the ammonia gas introduced into the first air inlet pipe has an introduction rate of 300-400 mL / min. Alternatively, the ammonia gas introduced into the first air inlet pipe can have an introduction rate of, for example, 300-358.4 mL / min or 358.4-400 mL / min.

[0067] In some embodiments of the present invention, the introduction rate of sulfuryl fluoride into the second air inlet pipe is 700-800 mL / min. Alternatively, the introduction rate of sulfuryl fluoride into the second air inlet pipe is 700-710 mL / min or 710-800 mL / min.

[0068] In some embodiments of the present invention, the ammonia gas introduced into the third air inlet pipe has an introduction rate of 700-800 mL / min, 700-710 mL / min, or 710-800 mL / min.

[0069] In some embodiments of the present invention, when ammonia gas is introduced into the reactor body through the third gas inlet pipe, the temperature inside the reactor body is controlled to be 20-30° C. The temperature can be controlled by the first temperature control device.

[0070] Compared with the prior art, the present invention has the following advantages:

[0071] According to the tower reactor involved in the present invention, because at least one stirring mechanism is also provided on the tower plate, the tower reactor of the present invention can effectively improve the reaction yield without precise temperature control. In the preferred embodiment, because at least one stirring mechanism is provided on each tower plate, and in particular, a stirring mechanism is provided on the tower plate opposite to the first air inlet hole of the first air inlet pipe and the second air inlet hole of the second air inlet pipe, on the one hand, the various raw materials can be fully stirred evenly during the intake of air, thereby avoiding the occurrence of side reactions caused by excessive local concentrations of some raw materials, and on the other hand, the stirring speed can be accelerated to increase the reaction rate. In addition, because the third air inlet pipe is provided at the bottom of all the tower plates, the by-product ammonium fluoride solid will not be deposited on the tower plate, but can be smoothly discharged from the liquid outlet, thereby ensuring that the reactor will not be blocked.

[0072] According to the method for preparing bis(fluorosulfonyl)imide triethylamine salt, the tower reactor described above is used, enabling efficient, large-scale production of bis(fluorosulfonyl)imide triethylamine salt under simple and mild conditions. In a preferred embodiment, since the liquid passing through the filter can re-enter the reactor body via a reflux line, a cyclic reaction is achieved, improving the reaction yield and, to a certain extent, saving acetonitrile and triethylamine, thereby achieving a green and environmentally friendly technical effect. Furthermore, ammonia is introduced through the first and third air inlet pipes, respectively, so that the low-value byproduct triethylamine fluoride produced during the reaction can be converted into the high-value byproduct ammonium fluoride, which can be separated in subsequent steps. This not only promotes the continuous forward reaction, but also achieves the co-production of the two. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] FIG1 is a schematic structural diagram of a tower reactor in Example 1 of the present application.

[0074] Component Numbers Description 1 Reactor body 2 Gas outlet 3 Liquid outlet 4 Liquid inlet pipe 5 Tray 6 First gas inlet pipe 61 First gas inlet hole 7 Second gas inlet pipe 71 Second gas inlet hole 8 Third gas inlet pipe 81 Third gas inlet hole 9 Spray head 10 Stirring mechanism 11 Filter 12 Reflux pipe 13 Receiving kettle 14 Production pump 15 Valve 16 Flow meter DETAILED DESCRIPTION

[0075] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0076] In the description of this application, it should be noted that the structures, proportions, sizes, etc. illustrated in the drawings of this specification are only used to match the contents disclosed in this specification for understanding and reading by those familiar with the art, and are not intended to limit the conditions under which this application can be implemented. Therefore, they have no substantive technical significance. Any structural modifications, changes in proportional relationships, or adjustments in size, without affecting the efficacy and objectives of this application, should still fall within the scope of the technical content disclosed in this application. At the same time, the terms "center," "longitudinal," "transverse," "upper," "lower," "front," "back," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," etc., indicating directions or positional relationships, are based on the directions or positional relationships shown in the drawings and are only for the convenience of describing this application and simplifying the description. They do not indicate or imply that the devices or components referred to must have a specific orientation, be constructed or operate in a specific orientation, and therefore should not be construed as limiting this application. In addition, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0077] In the description of this application, it should be noted that, unless otherwise expressly specified or limited, the terms "installed," "connected," and "connected" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integral connections; mechanical connections or electrical connections; direct connections or indirect connections through an intermediate medium; and internal connections between two components. Those skilled in the art will understand the specific meanings of the above terms in this application based on specific circumstances.

[0078] Furthermore, in the description of the present application, unless otherwise specified, “plurality” means two or more.

[0079] The tower reactor of the present invention comprises a plurality of spaced trays, wherein the number of the trays is not particularly limited and can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or more. Preferably, the tower reactor of the present invention can comprise 5 to 10 (e.g., 6) spaced trays.

[0080] The introduction rate of ammonia gas introduced into the first air inlet pipe of the present invention is 300-400 mL / min, for example, it can be 310-390 mL / min, 320-380 mL / min, 330-370 mL / min, 340-360 mL / min, 300-360 mL / min, 340-400 mL / min, 350-400 mL / min, etc.

[0081] The introduction rate of sulfuryl fluoride into the second air inlet pipe of the present invention is 700-800 mL / min; the introduction rate of ammonia into the third air inlet pipe is 700-800 mL / min; wherein, 700-800 mL / min, for example, can be 700-790 mL / min, 700-780 mL / min, 700-770 mL / min, 700-760 mL / min, 700-750 mL / min, 700-740 mL / min, 700-730 mL / min, 700-720 mL / min, etc.

[0082] In the present invention, the terms "odd tray" and "even tray" refer to trays numbered sequentially based on their distance from the top or bottom of the tower reactor. For example, the tray closest to the top of the tower reactor may be designated as the first tray, and the tray second closest to the top of the tower reactor may be designated as the second tray. In this case, the first tray may be designated as an odd tray, and the second tray may be designated as an even tray.

[0083] In the present invention, "staggered arrangement" means that the vertical projections of two adjacent trays in the tower reactor of the present invention on the horizontal plane do not completely overlap.

[0084] In the present invention, the "horizontal plane" may refer to the liquid level of the reaction mixture in the tower reactor of the present invention.

[0085] In the following examples, unless otherwise specified, all reaction raw materials are commercially available products.

[0086] <Example 1>

[0087] A tower reactor

[0088] This embodiment provides a tower reactor, including: a reactor body 1, multiple tower plates 5, a liquid inlet pipe 4, a first air inlet pipe 6, a second air inlet pipe 7, a third air inlet pipe 8, a stirring mechanism 10, a first temperature control device (not shown in the figure), a production pump 14, a filter 11, a reflux pipe 12 and a receiving kettle 13.

[0089] As shown in Figure 1, the reactor body 1 is vertically arranged on a horizontal plane. The reactor body 1 has a gas outlet 2 at its top and a liquid outlet 3 at its bottom. In other embodiments, the gas outlet 2 can also be arranged on the side of the reactor body 1, as long as it is located above the liquid level during use. Similarly, the liquid outlet 3 does not have to be arranged at the bottom of the reactor body 1. In other embodiments, the liquid outlet 3 can also be arranged on the side of the reactor body 1, so as to discharge the liquid in the reactor body 1. In the production process using a tower reactor, the liquid outlet 3 is usually closed and will only be opened after the production is completed. The opening and closing of the gas outlet 2 needs to be determined according to the specific reaction type. If the reaction is sensitive to the main components in the air such as water, oxygen, carbon dioxide, or requires a pressurized reaction, the gas outlet 2 should be closed during the reaction. If the reaction is not sensitive to the main components in the air, the gas outlet 2 can be left open.

[0090] A plurality of tower plates 5 are arranged at intervals inside the reactor body 1. In some embodiments, a plurality of tower plates 5 are evenly and staggeredly arranged inside the reactor body 1, and all tower plates 5 are arranged parallel to the horizontal plane. A plurality of tower plates 5 are divided into odd-numbered tower plates and even-numbered tower plates. From the vertical direction, the projections of the odd-numbered tower plates overlap, the projections of the even-numbered tower plates overlap, and the projections of the odd-numbered tower plates and the even-numbered tower plates partially overlap. In the present embodiment, all tower plates 5 are located below the liquid inlet pipe 4. In other embodiments, the relative positions of the tower plates 5 and the liquid inlet pipe 4 are not specifically limited. The liquid inlet pipe 4 can be above all tower plates 5, below all tower plates 5, or between any two tower plates 5. The tower plates 5 require horizontality, and their levelness is measured with a spirit level and cannot exceed ± 2 mm. In the present embodiment, a total of 6 tower plates 5 are provided, which, from top to bottom, are sequentially the first tower plate, the second tower plate, the third tower plate, the fourth tower plate, the fifth tower plate, and the sixth tower plate. In other embodiments, more or fewer trays 5 may be provided according to actual needs.

[0091] The liquid inlet pipe 4, partially located inside the reactor body 1 and partially outside the reactor body 1, is used to add liquid to the reactor body 1. In this embodiment, the liquid inlet pipe 4 is located above the first tray. In this embodiment, a spray head 9 is installed at one end of the liquid inlet pipe 4 inside the reactor body 1. The installation of the spray head 9 effectively reduces the impact of liquid on the first tray during liquid addition, thereby extending the service life of the top tray 5.

[0092] The first air inlet pipe 6 has a portion inside the reactor body 1 and a portion outside the reactor body 1. In the present embodiment, the first air inlet pipe 6 is installed between the third tower plate and the fourth tower plate. From a vertical perspective, the projection of the portion of the first air inlet pipe 6 inside the reactor body 1 is completely covered by the projection of the third tower plate. The portion of the first air inlet pipe 6 inside the reactor body 1 has a plurality of first air inlet holes 61. In the present embodiment, all the first air inlet holes 61 on the first air inlet pipe 6 are facing the fourth tower plate. In the present embodiment, the first air inlet pipe 6 is connected to an ammonia generating device (not shown in the figure) for introducing ammonia into the reactor body 1.

[0093] The second air inlet pipe 7 has a portion inside the reactor body 1 and a portion outside the reactor body 1. In the present embodiment, the second air inlet pipe 7 is installed between the fourth tower plate and the fifth tower plate. From a vertical perspective, the projection of the portion of the second air inlet pipe 7 inside the reactor body 1 is completely covered by the projection of the fourth tower plate. The portion of the second air inlet pipe 7 inside the reactor body 1 has a plurality of second air inlet holes 71. In the present embodiment, all the second air inlet holes 71 on the second air inlet pipe 7 are facing the fifth tower plate. In other embodiments, the second air inlet pipe 7 can also be arranged on the same side of the reactor body 1 as the first air inlet pipe 6. In the present embodiment, the second air inlet pipe 6 is connected to a sulfonyl fluoride generating device (not shown in the figure) for introducing sulfonyl fluoride into the reactor body 1.

[0094] The third air inlet pipe 8 has a portion inside the reactor body 1 and a portion outside the reactor body 1. In the present embodiment, the third air inlet pipe 8 is installed below the sixth tower plate. From a vertical perspective, the projection of the portion of the third air inlet pipe 8 inside the reactor body 1 is completely covered by the projection of the sixth tower plate. The portion of the third air inlet pipe 8 inside the reactor body 1 has a plurality of third air inlet holes 81. In the present embodiment, all the third air inlet holes 81 on the third air inlet pipe 8 are facing the liquid inlet pipe 4. In other embodiments, the direction of the third air inlet holes 81 on the third air inlet pipe 8 is not limited. In other embodiments, the third air inlet pipe 8 can also be arranged on the same side of the reactor body 1 as the first air inlet pipe 6. In the present embodiment, the third air inlet pipe 6 is connected to an ammonia generator (not shown in the figure) for introducing ammonia into the reactor body 1.

[0095] The stirring mechanism 10 is a gas stirring mechanism in this embodiment, but a mechanical stirring mechanism may also be used in other embodiments.

[0096] Each gas stirring mechanism includes: an air pump, an aeration pipe and several aeration heads.

[0097] An air pump is arranged outside the reactor body 1;

[0098] The aeration pipe is embedded in the tower plate 5 to receive gas from the air pump and transport it to the aeration head. In other embodiments, the aeration pipe can also be directly laid above the corresponding tower plate 5.

[0099] Aeration heads, mounted on the aeration tubes, are used to introduce gas from the aeration tubes into the reactor body 1, disturbing the fluid within the reactor body 1 and thereby achieving a stirring function. In this embodiment, five aeration heads are mounted on each aeration tube, all facing upward. In other embodiments, the number of aeration heads mounted on each aeration tube can be selected based on actual needs, and can be more or less than six.

[0100] Generally speaking, the gas introduced into the reactor body 1 through the gas stirring mechanism needs to be related to the reaction carried out in the reactor body 1. Generally, a gas that does not affect the reaction is selected, such as nitrogen, argon, etc.

[0101] In other embodiments, the mechanical stirring mechanism comprises:

[0102] power supply;

[0103] A plurality of stirring paddles, electrically connected to the power supply and located inside the reactor body 1;

[0104] A controller is used to control the rotation speed of the stirring paddle.

[0105] The gas stirring mechanism or the mechanical stirring mechanism can adopt the common gas stirring mechanism or mechanical stirring mechanism in the prior art.

[0106] At least one stirring mechanism 10 is provided on at least one tray 5. In some embodiments, each tray 5 is provided with one or more stirring mechanisms 10. In this embodiment, each tray 5 is provided with one stirring mechanism 10, for a total of six stirring mechanisms 10, each corresponding to one of the six trays 5. Specifically, a first stirring mechanism 10 is provided on the first tray, a second stirring mechanism is provided on the second tray, a third stirring mechanism is provided on the third tray, a fourth stirring mechanism is provided on the fourth tray, a fifth stirring mechanism is provided on the fifth tray, and a sixth stirring mechanism is provided on the sixth tray. In other embodiments, more or fewer stirring mechanisms 10 may be provided as needed.

[0107] The first temperature control device (not shown) includes a first temperature control element and a first control element. The first temperature control element is installed inside the reactor body 1 and is used to exchange heat with the fluid in the reactor body 1 to regulate the temperature of the fluid inside the reactor. The first control element is used to adjust the operating power of the first temperature control element to control the temperature of the fluid in the reactor body 1.

[0108] The extraction pump 14 is connected to the liquid outlet 3 of the reactor body 1 and the filter 11, respectively, and is used to pump the fluid flowing out of the liquid outlet 3 into the filter 11. A valve 15 is provided on the pipeline between the extraction pump 14 and the filter 11 to control the opening and closing of the pipeline.

[0109] The filter 11 has an inlet connected to a production pump 14 via a pipeline, and an outlet connected to a receiving kettle 13 and a liquid inlet pipe 4 via a reflux pipe 12. The filter 11 is used to intercept solids flowing out of the liquid outlet 3 and allow liquid flowing out of the liquid outlet 3 to pass through. In this embodiment, the filter 11 has a temperature-regulating function and can be controlled to perform filtration at a specific temperature.

[0110] The reflux pipe 12 comprises a main pipe 121, a first branch pipe 122, and a second branch pipe 123. One end of the main pipe 121 is connected to the outlet of the filter 11, and the other ends are connected to the first branch pipe 122 and the second branch pipe 123, respectively. The first branch pipe 122 is connected to the main pipe 121 at one end and to the liquid inlet pipe 4 at the other end. The second branch pipe 123 is connected to the main pipe 121 at one end and to the receiving kettle 13 at the other end. Each of the main pipe 121, the first branch pipe 122, and the second branch pipe 123 has a valve 15. In this embodiment, the first branch pipe 122 is detachably connected to the liquid inlet pipe 4.

[0111] A flow meter 15 is provided on the return pipe 12 . In this embodiment, a flow meter 16 is provided on the first branch pipe 122 .

[0112] The receiving kettle 13 is connected to the filter 11 and is used to receive part or all of the liquid passing through the filter 11 .

[0113] It is worth noting that in this embodiment, the filter 11, the reflux pipe 12 and the receiving kettle 13 are connected to the reactor body 1 through pipelines. In other embodiments, these three may not be connected to the reactor body 1 through pipelines, but may be operated separately as one or more sets of equipment. In this case, the functions of other components of the tower reactor can operate normally and will not be affected.

[0114] <Example 2>

[0115] Preparation method of bis(fluorosulfonyl)imide triethylamine salt

[0116] This embodiment provides a method for preparing triethylamine salt of bis(fluorosulfonyl)imide. The method provided in this embodiment is carried out using the tower reactor provided in Example 1, and specifically comprises the following steps:

[0117] Step 1: Open the liquid outlet 3 and the gas outlet 2, connect the liquid inlet pipe 4 to the container containing acetonitrile, and inject 1L of acetonitrile into the reactor body 1 through the liquid inlet pipe 4;

[0118] Step 2: connect the liquid inlet pipe 4 to the container containing the acetonitrile solution of triethylamine, and introduce 20.77 L of acetonitrile solution of triethylamine (3.6 eq, 5.4 mol) with a concentration of 0.26 mol / L into the reactor body 1 through the liquid inlet pipe 4;

[0119] Step 3: Use the first temperature control device to control the temperature in the reactor body 1 between 0-10 ° C, and turn on all gas stirring mechanisms, wherein each gas stirring mechanism is fed with nitrogen gas, and the ventilation volume per unit tank cross section is 0.5m 3 / (min·m 2 ). In other embodiments, it is not necessary to activate all gas stirring mechanisms. All first air inlet holes 61 on the first air inlet pipe 6 face the fourth tray, and all second air inlet holes 71 on the second air inlet pipe 7 face the fifth tray. Therefore, similar technical effects can be achieved by activating only the fourth stirring mechanism on the fourth tray and the fifth stirring mechanism on the fifth tray. In other embodiments, a mechanical stirring mechanism can also achieve similar technical effects as a gas stirring mechanism.

[0120] Step 4: Ammonia gas was introduced into the reactor body 1 through the first air inlet pipe 6 at a rate of 358.4 mL / min, for a total of 33.1 L (1.5 mol, 1.0 eq). At the same time, sulfuryl fluoride was introduced into the reactor body 1 through the second air inlet pipe 7 at a rate of 713.3 mL / min, for a total of 86.3 L (3.15 mol, 2.1 eq).

[0121] Step 5, sampling and testing the liquid in the reactor body 1 until the liquid phase content of bis(fluorosulfonyl)imide triethylamine salt in the liquid in the reactor body 1 is greater than or equal to 20%, then proceeding to step 6;

[0122] Step 6: Ammonia gas was introduced into the reactor body 1 through the third air inlet pipe 8 at a rate of 710 mL / min, for a total of 69.45 L (3.15 mol, 2.1 eq). At the same time, the temperature in the reactor body 1 was controlled between 20° C. and 30° C. by the first temperature control device.

[0123] Step 7: The fluid in the reactor body 1 enters the filter 11 and is filtered to obtain a solid and a liquid, respectively. The obtained solid is ammonium fluoride, and a total of 80.6 g is collected by the end of the reaction.

[0124] Step 8, detecting the liquid flowing out of the filter 11. When the liquid phase content of bis(fluorosulfonyl)imide triethylamine salt in the liquid is greater than or equal to 25%, proceed to step 10; otherwise, proceed to step 9;

[0125] Step 9: Connect the liquid inlet pipe 4 to the first branch pipe 122, open the valves 15 on the main pipe 121 and the first branch pipe 122, close the valve 15 on the second branch pipe 123, and allow the liquid flowing out of the filter 11 to flow back into the reactor body 1, and then proceed to step 8;

[0126] Step 10: Open the valves 15 on the main pipe 121 and the second branch pipe 123, close the valve 15 on the first branch pipe 122, and transfer all the liquid passing through the filter 11 to the receiving kettle 13. The liquid is a mixed solution of bis(fluorosulfonyl)imide triethylamine salt, triethylamine and acetonitrile.

[0127] Subsequently, the mixed solution was transferred to a distillation apparatus to remove triethylamine and acetonitrile by distillation, and dried to obtain 401.85 g of bisfluorosulfonyl imide triethylamine salt with a yield of 95.0% and a purity of 99%.

[0128] In this embodiment, the main reaction formula of the reaction is as follows:

[0129] It is worth noting that the above reaction formula is the main reaction involved in this embodiment. In the actual reaction process, other known or unknown side reactions may also occur.

[0130] Comparative Example 1

[0131] This comparative example is basically the same as Example 2, except that the stirring mechanism 10 is not turned on during the entire reaction, the reaction speed is slow, and it takes 8 hours to complete the reaction. The final yield of bisfluorosulfonyl imide triethylamine salt is only 78.8%, and 94.4 g of ammonium fluoride is recovered.

[0132] Comparative Example 2

[0133] This comparative example is basically the same as Example 2, except that all ammonia gas is introduced through the first air inlet pipe 6, the third air inlet pipe 8 is not activated, the reaction system contains a large amount of reaction intermediates, and the final yield of bis(fluorosulfonyl)imide triethylamine salt is only 73.5%, and 105.2 g of ammonium fluoride is recovered.

[0134] Functions and Effects of the Embodiments

[0135] According to the tower reactor involved in the above embodiment, since at least one stirring mechanism 10 is further provided on the tower plate 5, the tower reactor of the present invention can effectively improve the reaction yield without precise temperature control.

[0136] Preferably, because a stirring mechanism 10 is provided on each tower plate 5, especially a stirring mechanism 10 is provided on the tower plate 5 opposite to the first air inlet hole 61 of the first air inlet pipe 6 and the second air inlet hole 71 of the second air inlet pipe 7, on the one hand, the raw materials can be fully stirred evenly during the intake of air to avoid the local concentration of some raw materials being too high, thereby causing the occurrence of side reactions; on the other hand, the stirring speed can be accelerated to improve the reaction rate.

[0137] Preferably, since the third air inlet pipe 8 is arranged at the bottom of all the trays 5 , the by-product ammonium fluoride solid will not be deposited on the tray 5 but can be smoothly discharged from the liquid outlet 3 , thereby ensuring that the reactor will not be blocked.

[0138] In the tower reactor of the present invention, the mechanical stirring mechanism and the gas stirring mechanism have similar technical effects.

[0139] According to the method for preparing bisfluorosulfonyl imide triethylamine salt involved in the above embodiment, since the above tower reactor is used, the present invention can efficiently produce bisfluorosulfonyl imide triethylamine salt in large quantities under simple and mild conditions.

[0140] Preferably, since the liquid passing through the filter 11 can re-enter the reactor body 1 through the reflux pipe 12, it can not only achieve a cyclic reaction to improve the reaction yield, but also save the amount of acetonitrile and triethylamine to a certain extent, thereby achieving a green and environmentally friendly technical effect.

[0141] Preferably, in the above embodiment, ammonia is introduced from the first air inlet pipe 6 and the third air inlet pipe 8 respectively. Compared with the case where ammonia is introduced only from the first air inlet pipe 6, the low-value by-product triethylamine fluoride produced in the reaction can be converted into a high-value by-product ammonium fluoride and separated in the subsequent process, which not only promotes the reaction to proceed in the forward direction, but also realizes the co-production of the two.

[0142] The above embodiments are preferred examples of the present invention and are not intended to limit the scope of protection of the present invention.

[0143] In summary, the present invention effectively overcomes various shortcomings of the prior art and has high industrial utilization value.

[0144] The above embodiments are merely illustrative of the principles and effects of this application and are not intended to limit this application. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of this application. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical concepts disclosed in this application shall be covered by the claims of this application.

Claims

1. A tower reactor, characterized in that: include: A reactor body (1) having a gas outlet (2) and a liquid outlet (3); A liquid inlet pipe (4), arranged at the upper part of the reactor body (1), and used for introducing liquid into the reactor body (1); A plurality of spaced-apart trays (5) are disposed in the reactor body (1), and at least one tray (5) is further away from the gas outlet (2) than the liquid inlet pipe (4); A first air inlet pipe (6), disposed between any two adjacent plates (5), for introducing gas into the reactor body (1); A second air inlet pipe (7) is disposed between any two adjacent plates (5) and is further away from the liquid inlet pipe (4) than the first air inlet pipe (6); a third air inlet pipe (8), arranged between any two adjacent tower plates (5), or arranged on a side of the tower plate (5) farthest from the liquid inlet pipe (4) and further away from the liquid inlet pipe (4) than the second air inlet pipe (7); At least one stirring mechanism (10) is arranged on at least one tower plate (5).

2. The tower reactor according to claim 1, characterized in that Also includes at least one of the following features: A1) a gas outlet (2) is provided at the top of the reactor body (1); A2) a gas outlet (2) is provided on the side of the reactor body (1), and the height of the gas outlet (2) is higher than the liquid level of the reactor body (1); A3) a liquid outlet (3) is provided at the bottom of the reactor body (1); A4) A liquid outlet (3) is provided on the side of the reactor body (1).

3. The tower reactor according to claim 1, characterized in that A portion of the liquid inlet pipe (4) is arranged inside the reactor body (1), and a portion of the liquid inlet pipe (4) is arranged outside the reactor body (1); a spray head (9) is arranged at one end of the liquid inlet pipe (4) inside the reactor body (1).

4. The tower reactor according to claim 1, characterized in that Also includes at least one of the following features: B1) the trays (5) are arranged in a staggered manner; B2) Each of the tower plates (5) is arranged parallel to the horizontal plane.

5. The tower reactor according to claim 4, characterized in that B11) In each of the tower plates (5), the tower plates (5) include odd-numbered tower plates and even-numbered tower plates, the vertical projections of the odd-numbered tower plates on the horizontal plane overlap, the vertical projections of the even-numbered tower plates on the horizontal plane overlap, and the vertical projections of the odd-numbered tower plates and the even-numbered tower plates on the horizontal plane partially overlap.

6. The tower reactor according to claim 1, characterized in that Also includes any one or more of the following features: C1) a portion of the first air inlet pipe (6) is located inside the reactor body (1), and a portion of the first air inlet pipe (6) is located outside the reactor body (1); C2) a portion of the second air inlet pipe (7) is located inside the reactor body (1), and a portion of the second air inlet pipe (7) is located outside the reactor body (1); C3) A portion of the third air inlet pipe (8) is located inside the reactor body (1), and a portion of the third air inlet pipe (8) is located outside the reactor body (1).

7. The tower reactor according to claim 6, characterized in that Also includes at least one of the following features: C11) the portion of the first air inlet pipe (6) inside the reactor body (1) is provided with a plurality of first air inlet holes (61); C21) the portion of the second air inlet pipe (7) inside the reactor body (1) is provided with a plurality of second air inlet holes (71); C31) The portion of the third air inlet pipe (8) inside the reactor body (1) is provided with a plurality of third air inlet holes (81).

8. The tower reactor according to claim 7, characterized in that A stirring mechanism (10) is provided on the tower plate (5) opposite to the first air inlet hole (61) of the first air inlet pipe (6); A stirring mechanism (10) is provided on the tower plate (5) opposite to the second air inlet hole (71) of the second air inlet pipe (7).

9. The tower reactor according to claim 1, characterized in that Each of the tower plates (5) is provided with one or more stirring mechanisms (10).

10. The tower reactor according to claim 1 or 9, characterized in that: The stirring mechanism (10) is a gas stirring mechanism or a mechanical stirring mechanism.

11. The tower reactor according to claim 10, characterized in that Each of the gas stirring mechanisms comprises: An air pump, arranged outside the reactor body (1); an aeration pipe, connected to the air pump and at least partially located inside the reactor body (1); A plurality of aeration heads are arranged on the aeration pipe and are located inside the reactor body (1).

12. The tower reactor according to claim 10, characterized in that Each of the mechanical stirring mechanisms comprises: power supply; A plurality of stirring blades, electrically connected to the power supply and located inside the reactor body (1); A controller is used to control the rotation speed of the stirring paddle.

13. The tower reactor according to claim 1, characterized in that It also includes a first temperature control device for controlling the internal temperature of the reactor body (1).

14. The tower reactor according to claim 1, characterized in that Also includes: a filter (11), which is in communication with the liquid outlet (3) and is used to intercept solids flowing out of the liquid outlet (3) and to allow liquid flowing out of the liquid outlet (3) to pass through; a reflux pipe (12), which is respectively connected to the liquid inlet pipe (4) and the filter (11), and is used to return part or all of the liquid passing through the filter (11) to the reactor body (1); A receiving kettle (13) is connected to the filter (11) and is used to receive part or all of the The liquid in the filter (11) 15. The tower reactor according to claim 14, characterized in that Also includes: Also includes at least one of the following features: D1) further comprises a production pump (14), wherein the production pump (14) is connected to the liquid outlet (3) and the filter (11) respectively; a valve (15) is provided on the connecting pipeline between the production pump (14) and the filter (11); D2) the reflux pipe (12) comprises a main pipe (121), a first branch pipe (122) and a second branch pipe (123); the first branch pipe (122) or the second branch pipe (123) is connected to the filter (11) through the main pipe (121); the liquid inlet pipe (4) is connected to the main pipe (121) through the first branch pipe (122); the receiving kettle (13) is connected to the main pipe (121) through the second branch pipe (123); valves (15) are respectively provided on the main pipe (121), the first branch pipe (122) and the second branch pipe (123); D3) A flow meter (16) is provided on the return pipe (12).

16. A method for preparing bis(fluorosulfonyl)imide triethylamine salt, characterized in that: The preparation is carried out using a tower reactor as described in any one of claims 1 to 15, and the method comprises the following steps: Introduce acetonitrile into the reactor body (1) so that the liquid level is above the first air inlet pipe (6); Adding a solution of triethylamine in acetonitrile into the reactor body (1) through a liquid inlet pipe (4); Ammonia gas is introduced into the reactor body (1) through a first gas inlet pipe (6); introducing sulfuryl fluoride into the reactor body (1) through a second air inlet pipe (7); Ammonia gas is introduced into the reactor body (1) through the third gas inlet pipe (8). In any one step or in multiple steps, stirring is performed by a stirring mechanism (10).

17. The method for preparing the bisfluorosulfonyl imide triethylamine salt according to claim 16, It is characterized in that Wherein, the tower reactor according to claim 14 is used for preparation, The steps include: Introduce acetonitrile into the reactor body (1) so that the liquid level at least covers the first air inlet pipe (6); Adding a solution of triethylamine in acetonitrile into the reactor body (1) through a liquid inlet pipe (4); Ammonia gas is introduced into the reactor body (1) through a first gas inlet pipe (6); introducing sulfuryl fluoride into the reactor body (1) through a second air inlet pipe (7); Ammonia gas is introduced into the reactor body (1) through a third gas inlet pipe (8); The reaction mixture formed in the reactor body (1) is discharged from the liquid outlet (3) of the reactor body (1); Using a filter (11) to filter the reaction mixture to obtain an inorganic salt and a filtrate; Using a receiving kettle (13) to receive a portion or all of the filtrate; In any one step or in multiple steps, stirring is performed by a stirring mechanism (10).

18. The method for preparing bisfluorosulfonyl imide triethylamine salt according to claim 17, characterized in that: A portion or all of the filtrate re-enters the reactor body (1) through the reflux pipe (12) and the liquid inlet pipe (4).

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