Tower reactor and preparation method of bis (fluorosulfonyl) imide triethylamine salt

Abstract

The invention relates to the technical field of chemical equipment, in particular to a tower reactor and a preparation method of bis (fluorosulfonyl) imide triethylamine salt. The tower reactor comprises: a reactor main body having a gas outlet and a liquid outlet; the liquid inlet pipe is arranged at the upper part of the reactor main body, the plurality of tower plates arranged at intervals are arranged in the reactor main body, and at least one tower plate is farther away from the gas outlet than the liquid inlet pipe; the first gas inlet pipe is arranged between any two adjacent tower plates; the second gas inlet pipe is arranged between any two adjacent tower plates and is farther away from the liquid inlet pipe than the first gas inlet pipe; the third gas inlet pipe is arranged between any two adjacent tower plates or mounted on one side, far away from the liquid inlet pipe, of the tower plate farthest away from the liquid inlet pipe, and is farther away from the liquid inlet pipe than the second gas inlet pipe; wherein at least one stirring mechanism is arranged on at least one tower plate. The at least one stirring mechanism is arranged on the tower plate, so that the temperature of the tower reactor does not need to be accurately controlled, and the reaction yield can be effectively improved.

Description

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 bis(fluorosulfonyl)imide triethylamine salt. Background Art

[0002] As a key part of lithium battery electrolyte, lithium salt has a huge impact on the electrochemical performance of electrolyte. Lithium bis(fluorosulfonyl)imide (LiFSI) has higher electrochemical stability and thermal stability than LiPF6, has good adaptability with lithium metal electrodes and graphite electrodes, is environmentally friendly, has high low temperature performance and safety performance, and is currently the most promising new lithium salt electrolyte for lithium batteries.

[0003] According to the patent CN102378755A, it is easier to derive lithium bis(fluorosulfonyl)imide by first preparing the triethylamine salt of bis(fluorosulfonyl)imide than by 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 records another method for preparing bis(fluorosulfonyl)imide triethylamine salt, but this method has 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. Summary of the invention

[0007] In view of the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a tower reactor that can be used for large-scale industrial production of bisfluorosulfonyl imide and a method for preparing bisfluorosulfonyl imide triethylamine salt using the tower reactor.

[0008] To achieve the above-mentioned and other related purposes, the present application provides, on one hand, a tower reactor, comprising: a reactor body having a gas outlet and a liquid outlet;

[0009] A liquid inlet pipe, disposed at the upper portion of the reactor body, and used for introducing liquid into the reactor body;

[0010] A plurality of spaced-apart trays are disposed in the reactor body and at least one tray is further away from the gas outlet than the liquid inlet pipe;

[0011] A first air inlet pipe is provided between any two adjacent plates and is used to introduce gas into the reactor body;

[0012] A second air inlet pipe is disposed between any two adjacent plates and is further away from the liquid inlet pipe than the first air inlet pipe;

[0013] a third air inlet pipe, disposed between any two adjacent plates, or disposed on a side of the plate farthest from the liquid inlet pipe, and further away from the liquid inlet pipe than the second air inlet pipe;

[0014] Wherein, at least one stirring mechanism is arranged on at least one tower plate.

[0015] In some embodiments of the present invention, a gas outlet is provided at the top of the reactor body.

[0016] 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.

[0017] In some embodiments of the present invention, a liquid outlet is provided at the bottom of the reactor body.

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

[0019] In some embodiments of the present invention, a portion of the liquid inlet pipe is disposed inside the reactor body, and a portion of the liquid inlet pipe is disposed outside the reactor body.

[0020] In some embodiments of the present invention, a spray head is provided at one end of the liquid inlet pipe in the reactor body.

[0021] In some embodiments of the present invention, the tower plates are arranged in a staggered manner.

[0022] 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.

[0023] In some embodiments of the present invention, each of the tower plates is arranged parallel to the horizontal plane.

[0024] In some embodiments of the present invention, a portion of the first air inlet pipe is located inside the reactor body, and a portion of the first air inlet pipe is located outside the reactor body.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] In some embodiments of the present invention, a portion of the third air inlet pipe is located inside the reactor body, and a portion of the third air inlet pipe is located outside the reactor body.

[0029] 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.

[0030] In some embodiments of the present invention, a stirring mechanism is provided on a tower plate opposite to the first air inlet hole of the first air inlet pipe. The tower plate opposite to the first air inlet hole is the tower plate to which the opening of the first air inlet hole faces.

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

[0032] In some embodiments of the present invention, each of the tower plates is provided with one or more stirring mechanisms.

[0033] In some embodiments of the present invention, the stirring mechanism is a gas stirring mechanism or a mechanical stirring mechanism.

[0034] In some embodiments of the present invention, each of the gas stirring mechanisms includes: an air pump, which is arranged outside the reactor body; an aeration pipe, which is connected to the air pump and is at least partially located inside the reactor body; and a plurality of aeration heads, which are arranged on the aeration pipe and are located inside the reactor body.

[0035] In some embodiments of the present invention, each of the mechanical stirring mechanisms includes: a power source; a plurality of stirring paddles electrically connected to the power source and located inside the reactor body; and a controller for controlling the rotation speed of the stirring paddles.

[0036] In some embodiments of the present invention, a first temperature control device is further included to control the internal temperature of the reactor body.

[0037] In some embodiments of the present invention, it also includes:

[0038] a filter, connected to the liquid outlet, for intercepting solids flowing out of the liquid outlet and allowing liquid flowing out of the liquid outlet to pass through;

[0039] A reflux pipe, connected to the liquid inlet pipe and the filter, respectively, and used to return part or all of the liquid passing through the filter to the reactor body;

[0040] The receiving kettle is connected with the filter and is used for receiving 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 bis(fluorosulfonyl)imide triethylamine salt, which is prepared using the tower reactor described in the first aspect of the present invention, comprising the following steps:

[0045] Introduce acetonitrile into the reactor body and make the liquid level submerge the first air inlet pipe;

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

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

[0048] introducing sulfuryl fluoride 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 in 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] Introduce acetonitrile into the reactor body, and make the liquid level at least submerge the first air inlet pipe;

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

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

[0055] introducing sulfuryl fluoride into the reactor body through a second air inlet pipe;

[0056] Ammonia gas is introduced into the reactor body through a 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] Using a receiving kettle to receive part or all of the filtrate;

[0060] Wherein, in any one step or in 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 introduced through the first air inlet pipe is (3-4): 1. Further, the molar ratio of triethylamine in the acetonitrile solution of triethylamine to the ammonia introduced through the first air inlet pipe can be, for example, (3-3.6): 1 or (3.6-4): 1, etc.

[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 ammonia gas introduced into the first air inlet pipe to ammonia gas introduced into the third air inlet pipe is 1:(2-3). Alternatively, the molar ratio of ammonia gas introduced into the first air inlet pipe to ammonia gas introduced into the third air inlet pipe may 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. Optionally, the ammonia gas introduced into the first air inlet pipe has 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. Optionally, 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. The ammonia gas introduced into the third air inlet pipe has an introduction rate of 700-710 mL / min or 710-800 mL / min, etc.

[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 in the reactor body is controlled to be 20-30° C. The temperature can be controlled by a first temperature control device.

[0070] Compared with the prior art, the beneficial effects of this application are:

[0071] According to the tower reactor involved in the present invention, since at least one stirring mechanism is also arranged 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, since a stirring mechanism is arranged on each tower plate, especially a stirring mechanism is arranged 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, each raw material can be fully stirred evenly during air intake to avoid the occurrence of side reactions caused by excessive local concentration of some raw materials, and on the other hand, the stirring speed can be accelerated to improve the reaction rate. In addition, since the third air inlet pipe is arranged 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 preparation method of bisfluorosulfonyl imide triethylamine salt involved in the present invention, because the above-mentioned tower reactor is used, the present invention can efficiently produce bisfluorosulfonyl imide triethylamine salt in large quantities under simple and mild conditions. In the preferred embodiment, since the liquid passing through the filter can re-enter the reactor body through the reflux pipe, it is not only possible to achieve a cyclic reaction to improve the reaction yield, but also to save the amount of acetonitrile and triethylamine to a certain extent, thereby achieving a green and environmentally friendly technical effect. In addition, ammonia is introduced from the first air inlet pipe and the third air inlet pipe respectively, so the low-value byproduct triethylamine fluoride produced in the reaction can be converted into a high-value byproduct ammonium fluoride, and separated in the subsequent process, which can not only promote the reaction to proceed continuously in the forward direction, but also achieve the co-production of the two. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] Figure 1Shown is a schematic diagram of the structure of the tower reactor in Example 1 of the present application.

[0074] Component number description

[0075] 1 Reactor body

[0076] 2 outlet

[0077] 3 liquid outlet

[0078] 4 Liquid inlet pipe

[0079] 5 trays

[0080] 6First intake pipe

[0081] 61 First air intake

[0082] 7 Second intake pipe

[0083] 71 Second air intake

[0084] 8Third intake pipe

[0085] 81 Third air intake

[0086] 9 sprinkler heads

[0087] 10. Mixing mechanism

[0088] 11 Filters

[0089] 12 Reflux pipe

[0090] 13 receiving kettle

[0091] 14 Production Pump

[0092] 15 Valves

[0093] 16 Flow meter DETAILED DESCRIPTION

[0094] The technical solutions in the embodiments of the present invention will be described clearly and completely 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.

[0095] In the description of the present application, it should be noted that the structures, proportions, sizes, etc. illustrated in the drawings of the present specification are only used to match the contents disclosed in the specification for people familiar with the technology to understand and read, and are not used to limit the limiting conditions that can be implemented in the present application, so they have no technical substantive significance. Any modification of the structure, change of the proportion relationship or adjustment of the size, without affecting the effects that can be produced by the present application and the purposes that can be achieved, should still fall within the scope of the technical content disclosed in the present application. At the same time, the orientation or position relationship indicated by the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc. is based on the orientation or position relationship shown in the drawings, which is only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation to the present application. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0096] In the description of this application, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0097] Furthermore, in the description of the present application, unless otherwise specified, “plurality” means two or more.

[0098] In the following examples, unless otherwise specified, all reaction raw materials are commercially available products.

[0099] <Example 1>

[0100] A tower reactor

[0101] 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.

[0102] like Figure 1As shown, the reactor body 1 is vertically arranged on a horizontal plane, and 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 is not necessarily 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, and the liquid in the reactor body 1 can be discharged. In the process of production using a tower reactor, the liquid outlet 3 is usually closed and will only be opened after the production is completed, while 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, etc. or requires a pressurized reaction, the gas outlet 2 should be closed during the reaction process, and if the reaction is not sensitive to the main components in the air, the gas outlet 2 may not be closed. A plurality of trays 5 are arranged at intervals inside the reactor body 1. In some embodiments, a plurality of trays 5 are evenly and staggeredly arranged inside the reactor body 1, and all trays 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 horizontality is measured with a level gauge and cannot exceed ±2mm. In the present embodiment, 6 tower plates 5 are provided in total, which are, from top to bottom, 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 less tower plates 5 can be provided according to actual needs.

[0103] The liquid inlet pipe 4, a part of which is inside the reactor body 1 and a part of which is outside the reactor body 1, is used to add liquid into 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 in the reactor body 1. After the spray head 9 is provided, the impact of the liquid on the first tray can be effectively reduced when the liquid is added, thereby extending the service life of the top tray 5.

[0104] 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 direction, 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 face 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.

[0105] The second air inlet pipe 7, a part of which is inside the reactor body 1, and a part of which is 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 the vertical direction, the projection of the part of the second air inlet pipe 7 inside the reactor body 1 is completely covered by the projection of the fourth tower plate. The part 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.

[0106] The third air inlet pipe 8, a part of which is inside the reactor body 1, and a part of which is 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 direction, the projection of the part of the third air inlet pipe 8 inside the reactor body 1 is completely covered by the projection of the sixth tower plate. The part 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 generating device (not shown in the figure) for introducing ammonia into the reactor body 1.

[0107] The stirring mechanism 10 is a gas stirring mechanism in this embodiment, but a mechanical stirring mechanism may also be used in other embodiments.

[0108] Each gas stirring mechanism includes: an air pump, an aeration pipe and a plurality of aeration heads.

[0109] An air pump is arranged outside the reactor body 1;

[0110] 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.

[0111] The aeration head is installed on the aeration pipe and is used to aerate the gas in the aeration pipe into the reactor body 1, disturbing the fluid in the reactor body 1 to achieve a stirring function. In this embodiment, five aeration heads are installed on each aeration pipe and all face upward. In other embodiments, the number of aeration heads installed on each aeration pipe can be selected according to actual needs, and can be more than six or less than six.

[0112] 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 will not affect the reaction is selected, such as nitrogen, argon, etc.

[0113] In other embodiments, the mechanical stirring mechanism comprises:

[0114] power supply;

[0115] A plurality of stirring paddles, electrically connected to the power supply and located inside the reactor body 1;

[0116] A controller is used to control the rotation speed of the stirring paddle.

[0117] The gas stirring mechanism or the mechanical stirring mechanism can adopt the common gas stirring mechanism or mechanical stirring mechanism in the prior art.

[0118] At least one stirring mechanism 10 is provided on at least one tower plate 5. In some embodiments, one or more stirring mechanisms 10 are provided on each of the tower plates 5. In this embodiment, each tower plate 5 is provided with a stirring mechanism 10, and a total of six stirring mechanisms 10 are provided, and the six stirring mechanisms 10 correspond to the six tower plates 5, that is, the first stirring mechanism is installed on the first tower plate, the second stirring mechanism is installed on the second tower plate, the third stirring mechanism is installed on the third tower plate, the fourth stirring mechanism is installed on the fourth tower plate, the fifth stirring mechanism is installed on the fifth tower plate, and the sixth stirring mechanism is installed on the sixth tower plate. In other embodiments, more or fewer stirring mechanisms 10 can be provided according to actual needs.

[0119] The first temperature control device (not shown in the figure) includes a first temperature control member and a first control member. The first temperature control member is installed inside the reactor body 1 and is used to exchange heat with the fluid in the reactor body 1 to adjust the temperature of the fluid inside the reactor. The first control member is used to adjust the working power of the first temperature control member to control the temperature of the fluid in the reactor body 1.

[0120] 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.

[0121] The filter 11, whose inlet is connected to the extraction pump 14 through a pipeline, and whose outlet is respectively connected to the receiving kettle 13 and the liquid inlet pipe 4 through the reflux pipe 12, is used to intercept the solids flowing out of the liquid outlet 3 and allow the liquid flowing out of the liquid outlet 3 to pass. In this embodiment, the filter 11 used has the function of adjusting the temperature, and can be controlled to perform filtering at a specific temperature.

[0122] The reflux pipe 12 includes 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 end is connected to the first branch pipe 122 and the second branch pipe 123 respectively. One end of the first branch pipe 122 is connected to the main pipe 121, and the other end is connected to the liquid inlet pipe 4. One end of the second branch pipe 123 is connected to the main pipe 121, and the other end is connected to the receiving kettle 13. There is a valve 15 on each of the main pipe 121, the first branch pipe 122 and the second branch pipe 123. In this embodiment, the connection between the first branch pipe 122 and the liquid inlet pipe 4 is a detachable connection.

[0123] A flow meter 15 is provided on the reflux pipe 12 . In this embodiment, a flow meter 16 is provided on the first branch pipe 122 .

[0124] The receiving tank 13 is connected to the filter 11 and is used for receiving part or all of the liquid passing through the filter 11 .

[0125] It is worth noting that in the present 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.

[0126] <Example 2>

[0127] Preparation method of bis(fluorosulfonyl)imide triethylamine salt

[0128] 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:

[0129] Step 1, opening the liquid outlet 3 and the gas outlet 2, connecting the liquid inlet pipe 4 with the container containing acetonitrile, and injecting 1L of acetonitrile into the reactor body 1 through the liquid inlet pipe 4;

[0130] Step 2, connecting the liquid inlet pipe 4 to the container containing the acetonitrile solution of triethylamine, and introducing 20.77L of acetonitrile solution of triethylamine (3.6eq, 5.4mol) with a concentration of 0.26mol / L into the reactor body 1 through the liquid inlet pipe 4;

[0131] 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 open all the gas stirring mechanisms, all the first air inlet holes 61 on the first air inlet pipe 6 are facing the fourth tower plate, and all the second air inlet holes 71 on the second air inlet pipe 7 are facing the fifth tower plate, so only the fourth stirring mechanism on the fourth tower plate and the fifth stirring mechanism on the fifth tower plate need to be opened to achieve similar technical effects. In other embodiments, a mechanical stirring mechanism can also achieve similar technical effects as a gas stirring mechanism.

[0132] Step 4, ammonia gas is introduced into the reactor body 1 through the first air inlet pipe 6 at a rate of 358.4 mL / min, and a total of 33.1 L (1.5 mol, 1.0 eq) is introduced. At the same time, sulfuryl fluoride is introduced into the reactor body 1 through the second air inlet pipe 7 at a rate of 713.3 mL / min, and a total of 86.3 L (3.15 mol, 2.1 eq) is introduced;

[0133] 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%, and then proceeding to step 6;

[0134] Step 6, introducing ammonia into the reactor body 1 through the third air inlet pipe 8 at a rate of 710 mL / min, and introducing a total of 69.45 L (3.15 mol, 2.1 eq). At the same time, the temperature in the reactor body 1 is controlled between 20-30° C. by the first temperature control device;

[0135] Step 7, the fluid in the reactor body 1 enters the filter 11, and the fluid is filtered to obtain solid and liquid respectively. The obtained solid is ammonium fluoride, and a total of 80.6 g is collected by the end of the reaction;

[0136] 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%, proceeding to step 10, otherwise proceeding to step 9;

[0137] Step 9, connect the liquid inlet pipe 4 with 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 proceed to step 8;

[0138] 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.

[0139] 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 bis(fluorosulfonyl)imide triethylamine salt with a yield of 95.0% and a purity of 99%.

[0140] In this embodiment, the main reaction formula of the reaction is as follows:

[0141]

[0142] 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.

[0143] <Comparative Example 1>

[0144] 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 bis(fluorosulfonyl)imide triethylamine salt is only 78.8%, and 94.4 g of ammonium fluoride is recovered.

[0145] <Comparative Example 2>

[0146] This comparative example is basically the same as Example 2, except that all ammonia is introduced from 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.

[0147] Functions and Effects of the Embodiments

[0148] According to the tower reactor involved in the above embodiment, since at least one stirring mechanism 10 is also arranged on the tower plate 5, the tower reactor of the present invention can effectively improve the reaction yield without precise temperature control.

[0149] Preferably, since 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 various raw materials can be fully stirred evenly during the air intake to avoid excessive local concentration of some raw materials resulting in side reactions, and on the other hand, the stirring speed can be accelerated to improve the reaction rate.

[0150] Preferably, since the third air inlet pipe 8 is arranged at the bottom of all the trays 5 , the by-product ammonium fluoride solid formed 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.

[0151] In the tower reactor of the present invention, the mechanical stirring mechanism and the gas stirring mechanism have similar technical effects.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] The above-mentioned embodiments are preferred examples of the present invention and are not intended to limit the protection scope of the present invention.

[0156] In summary, the present invention effectively overcomes various shortcomings of the prior art and has high industrial utilization value.

[0157] The above embodiments are merely illustrative of the principles and effects of the present application and are not intended to limit the present application. Anyone familiar with the technology may modify or change the above embodiments without violating the spirit and scope of the present application. Therefore, all equivalent modifications or changes made by a person of ordinary skill in the art without departing from the spirit and technical ideas disclosed in the present application shall still be covered by the claims of the present 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), arranged between any two adjacent plates (5) and 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); 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).

15. The tower reactor according to claim 14, characterized in that Also includes: It also includes at least one of the following features: D1) It also includes a production pump (14), and 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 extraction 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 the tower reactor described in any one of claims 1 to 15, comprising 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 bis(fluorosulfonyl)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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