Dynamic reactor device for solid-liquid and gas-liquid non-uniformity

Abstract

The invention discloses a dynamic reactor device for solid-liquid and gas-liquid non-uniformity, which comprises a premixing device, a feeding device and a reaction device, the reaction device comprises a solid homogeneous batching unit, a liquid batching unit, a weighing feeding pipeline, a pre-heat exchanger and a reaction unit, and the reactor unit can be one section, the invention provides the continuous reaction device which is safe in reaction process, simple to operate, high in product yield and suitable for industrial production, and the continuous reaction device can be used for realizing efficient mixing of materials and improving elements such as mass transfer and heat transfer in chemical reaction, so that the reaction rate can be obviously increased, and the production cost can be reduced. And the continuous production of the bis (chlorosulfonyl) imide is realized.

Description

Technical Field

[0001] The invention belongs to the field of chemical equipment, and in particular relates to a dynamic reactor device for solid-liquid, gas-liquid and other heterogeneous conditions, which can be applied to the continuous production of bischlorosulfonyl imide. Background Art

[0002] When using traditional intermittent methods for solid-liquid, gas-liquid and other heterogeneous chemical reactions, there are problems such as low mixing efficiency, poor mass transfer and heat transfer, and long reaction time.

[0003] Microchannel chemical continuous reaction devices can currently only be used for liquid-liquid homogeneous reactions, and are not very effective for solid-liquid heterogeneous reactions with high solid-liquid content, as well as gas-liquid two-phase reactions. Because the microchannel structure is fixed and the channel is very small, it cannot pass solid solutions, and the mixing effect on heterogeneous substances is poor.

[0004] In chemical production, solid-liquid and gas-liquid heterogeneous reactions account for a very large proportion of reactions. Due to the limitations of current technology, it is impossible to achieve continuous reactions through equipment such as microchannels.

[0005] With the development of the chemical industry, there is an urgent need for an efficient continuous reaction device to improve the mass transfer and heat transfer of the reaction, improve the reaction efficiency and product quality, and reduce production costs.

[0006] Bischlorosulfonyl imide is an important intermediate of lithium bisfluorosulfonyl imide, an electrolyte additive. In its production, chlorosulfonic acid, thionyl chloride and chlorosulfonic acid are used as raw materials, and it is obtained through high-temperature and long-term reaction. Due to the use of highly corrosive and highly volatile materials, the requirements for reaction equipment are very high. At the same time, a large amount of hydrogen chloride, sulfur dioxide and other gases are produced during the reaction, which affects the reaction balance. Long-term reaction under high temperature conditions is prone to produce polymers, resulting in an increase in product by-products and a low yield. An efficient and reliable device is urgently needed to solve the above problems.

[0007]

[0008] Patent CN101747242A discloses a method for preparing bischlorosulfonyl imide using aminosulfonic acid, dichlorothionyl and chlorosulfonic acid as raw materials, with a yield of 82%.

[0009] Patent CN103664712A discloses mixing concentrated sulfuric acid with potassium bis(fluorosulfonyl)imide and silicon dioxide, and distilling out bis(fluorosulfonyl)imide at 85-150° C., but the raw material potassium bis(fluorosulfonyl)imide is difficult to obtain.

[0010] Patent CN106044718A discloses a method for preparing bischlorosulfonyl imide from chlorosulfonic acid and chlorosulfonic acid isocyanate in the presence of a catalyst (NiCl2, concentrated sulfuric acid, anhydrous FeCl3), reacting at 100-150°C for 20-30h with a yield of 83-95%. However, this method requires the use of a catalyst and has a long reaction time.

[0011] Patent CN104925765A discloses placing bis(chlorosulfonyl)imide and a catalyst (SbCl5, TiCl4, SnCl4, MoCl5, etc.) in a reaction device, introducing HF gas for reaction, and the yield is 90%. However, this method has high requirements on equipment, and the use of catalyst introduces impurity ions, the process operation is cumbersome, and the risk is high.

[0012] Patent CN106829891A discloses a method for preparing bis(fluorosulfonyl)imide by direct reaction of fluorosulfonyl isocyanate and fluorosulfonic acid. However, the raw materials of this method are difficult to obtain and thus it is not suitable for industrial production.

[0013] Patent CN106430129A discloses a method for preparing bis(chlorosulfonyl)imide using aminosulfonic acid, dichlorothionyl and chlorosulfonic acid as raw materials. The reaction is stirred at 120° C. for 24 hours, and the product yield is 90%. However, the method takes a long time to react.

[0014] In summary, the preparation methods of bis(fluorosulfonyl)imide disclosed in the prior art are all traditional intermittent preparation methods, which have the problems of long reaction time, difficulty in obtaining raw materials, introduction of impurities by catalysts, cumbersome process operation, high risk, and unsuitability for industrial production. Summary of the invention

[0015] In order to overcome the technical problems mentioned above, the present invention aims at the problems existing in existing heterogeneous reactions and proposes a continuous reaction device with safe reaction process, simple operation, high product yield and suitability for industrial production. The continuous reaction device can achieve efficient mixing between materials, improve mass transfer, heat transfer and other factors in chemical reactions, thereby significantly improving the reaction rate.

[0016] The technical solution provided by the present invention is specifically:

[0017] A dynamic reactor device for non-uniform solid-liquid, gas-liquid, etc., comprises a premixing device, a feeding device and a reaction device. The reaction device comprises a solid homogenizing batching unit, a liquid batching unit, a weighing feeding pipeline, a preheat exchanger and a reaction unit. The reactor unit can be one section or can be divided into multiple sections connected in series or in parallel.

[0018] The reaction unit comprises a mixer, a heat exchanger, a reactor and a back pressure valve. The reactor is provided with a feed port and a discharge port. The weighing feed pipeline is connected to the reactor feed port, and the discharge port reactor outlet is connected to the heat exchanger or the back pressure valve.

[0019] The reactor is provided with a feed port and a discharge port, the reactor feed port is connected to the feed pump outlet, the reaction temperature is -50 to 350°C, and the pressure is -0.9 to 10MPa;

[0020] The heat exchanger feed port is connected to the first stage reactor discharge port, and the heat exchanger discharge port is connected to the second stage reactor feed port, and is used to heat up the material from the first stage to the second stage reactor.

[0021] Preferably, the mixers are arranged at the bottom, middle and top of the reactor for sufficient mixing of materials.

[0022] Preferably, the feed port of the back pressure valve is connected to the outlet of the reactor or the heat exchanger to control the pressure of the entire reaction system.

[0023] Preferably, the solid homogenizing batching unit comprises a batching kettle and a homogenizing device. The homogenizing device used is one or more combinations of an emulsifying pump, a homogenizing pump, a pipeline pump, a mortar pump, a rotor pump, a screw pump, etc. The bottom outlet of the batching kettle is connected to the inlet of the homogenizing device, and the outlet of the homogenizing device is connected to the inlet of the batching kettle, which is used for raw material circulation homogenization and subsequent feeding.

[0024] The solid homogenizing batching unit comprises two reaction tanks arranged side by side.

[0025] Preferably, the mixer is a combination of one or more dynamic mixers and static mixers, the dynamic mixer is a combination of one or more screw type, high-speed stirring, impeller, gear, the dynamic reactor speed is 0 to 8000 r / min, and the residence time is 1 to 400 min.

[0026] Preferably, the static mixer can be a SK type, SH type, SV type or other mixing device or a combination of metal / non-metal filler, ceramic particle filler, etc., which is installed in the reactor in sections, and baffles can also be installed in the reactor. By combining with the dynamic mixer, the mixing efficiency of the reactor is improved, and the mass transfer and heat transfer effects are improved.

[0027] Preferably, the reaction unit is made of iron, nickel-based alloy, silicon carbide, glass, Hastelloy or manganese-nel alloy, or titanium, zirconium, niobium, tantalum and alloys thereof.

[0028] Preferably, the reaction unit can be installed vertically or horizontally to improve fluidity and ensure mixing effect. Each device unit can be set separately or combined into a pry device.

[0029] Preferably, the weighing feeding pipeline includes a weighing tank, a weighing module, and a feed pump. The weighing tanks are used in a backup mode and are both placed on the weighing module. The feed port of the weighing tank is connected to the discharge port of the batching kettle, the discharge port of the weighing tank is connected to the inlet of the feed pump, and the outlet of the feed pump is connected to the inlet of the preheater. The feed pump is also used in a backup mode and is used to input raw materials into the preheater. The outlet of the preheater is connected to the inlet of the reactor and is used for preheating or precooling the materials before the reaction. The temperature of the preheater is -40 to 300°C.

[0030] Preferably, the feed pump is a diaphragm pump, a screw pump, a rotor pump, an emulsifying pump, a plunger pump, a peristaltic pump or a centrifugal pump.

[0031] Beneficial effects of the present invention:

[0032] 1. The reaction rate and product quality of the present invention are improved. The dynamic mixer is used to produce a violent and efficient mixing effect between the solid and the liquid, thereby significantly improving the reaction rate. As the reaction time is shortened (from 36 hours to 2 hours), the heavy components of the reaction by-products are greatly reduced, thereby making the product impurities lower (high boiling substances are reduced from 20% to 3%) and the yield higher (from 83% to 93%).

[0033] 2. The production process of the present invention is safer. The present invention continuously prepares bis(chlorosulfonyl)imide and bis(fluorosulfonyl)imide through automatic control systems such as automatic batching, automatic feeding and discharging, thereby simplifying complicated operations, reducing human errors, and greatly improving the safety factor.

[0034] 3. The present invention transforms the intermittent reaction of the traditional process into a continuous reaction. After the degree of automation is improved, labor intensity and working hours can be saved, which is more conducive to industrialization.

[0035] 4. The reaction unit of the present invention adopts special materials with good acid resistance and low equipment loss, thus avoiding the problem of conventional reactors being not resistant to corrosion. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is a structural schematic diagram of the present invention;

[0037] Among them: 1. Solid homogenizing batching unit, 2. Homogenizing device, 3. Liquid batching unit, 4. Weighing feed pipeline, 5. Preheat exchanger, 6. Level I reaction unit, 7. Level II reaction unit, 8. Heat exchanger, 9. Back pressure valve. DETAILED DESCRIPTION

[0038] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0039] In the description of the present invention, it should be understood that the terms "center", "length", "width", "height", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "side" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the drawings, and are only for the convenience of describing the present invention 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 limiting the present invention. In the description of the present invention, unless otherwise specified, "plurality" means two or more.

[0040] like Figure 1 As shown, a dynamic reactor device for non-uniform solid-liquid, gas-liquid, etc. includes a premixing device, a feeding device and a reaction device. The reaction device includes a solid homogenizing batching unit 11, a liquid batching unit 3, a weighing feed pipeline 4, a preheat exchanger 5 and a reaction unit. The reactor unit can be one section or can be divided into multiple sections connected in series or in parallel. The reaction unit includes a stage I reaction unit 6 and a stage II reaction unit 7.

[0041] The reaction unit includes a mixer, a heat exchanger 8, a reactor and a back pressure valve 9. The reactor is provided with a feed port and a discharge port. The weighing feed pipeline 4 is connected to the reactor feed port, and the discharge port reactor outlet is connected to the heat exchanger 8 or the back pressure valve 9.

[0042] The reactor is provided with a feed port and a discharge port, the reactor feed port is connected to the feed pump outlet, the reaction temperature is -50 to 350°C, and the pressure is -0.9 to 10MPa;

[0043] The feed port of the heat exchanger 8 is connected to the discharge port of the first stage reactor, and the discharge port of the heat exchanger 8 is connected to the feed port of the second stage reactor, which is used to heat up the material from the first stage to the second stage reactor.

[0044] The solid homogenizing batching unit 1 includes a batching kettle and a homogenizing device 2. The homogenizing device 2 used is one or more combinations of an emulsifying pump, a homogenizing pump, a pipeline pump, a mortar pump, a rotor pump, a screw pump, etc. The bottom outlet of the batching kettle is connected to the inlet of the homogenizing device 2, and the outlet of the homogenizing device 2 is connected to the inlet of the batching kettle, which is used for raw material circulation homogenization and subsequent feeding.

[0045] The solid homogenizing and dosing unit 1 comprises two reaction tanks arranged side by side.

[0046] The mixers are located at the bottom, middle and top of the reactor to fully mix the materials.

[0047] The feed port of the back pressure valve 9 is connected to the outlet of the reactor or the heat exchanger 8 to control the pressure of the entire reaction system.

[0048] The mixer is a combination of one or more dynamic mixers and static mixers. The dynamic mixer is a combination of one or more screw, high-speed stirring, impeller, and gear. The speed of the dynamic reactor is 0 to 8000 r / min, and the residence time is 1 to 400 min.

[0049] Static mixers can be SK, SH, SV and other mixing devices or metal / non-metal fillers, ceramic particle fillers, or a combination of several of them, which are installed in the reactor in sections, or baffles can be installed in the reactor. By combining with dynamic mixers, they work together to improve the mixing efficiency of the reactor and enhance the mass transfer and heat transfer effects.

[0050] The material of the reaction unit is iron, nickel-based alloy, silicon carbide, glass, Hastelloy or manganese nel alloy, or titanium, zirconium, niobium, tantalum and their alloys.

[0051] The reaction unit can be installed vertically or horizontally to improve fluidity and ensure mixing effect. Each device unit can be set up separately or combined into a skid device.

[0052] The weighing feed pipeline 4 includes a weighing tank, a weighing module, and a feed pump. The weighing tanks are used in a backup mode and are placed on the weighing module. The feed port of the weighing tank is connected to the discharge port of the batching kettle, the discharge port of the weighing tank is connected to the inlet of the feed pump, and the outlet of the feed pump is connected to the inlet of the preheater. The feed pump is also used in a backup mode and is used to input the raw materials into the preheater. The outlet of the preheater is connected to the inlet of the reactor and is used for preheating or precooling the materials before the reaction. The temperature of the preheater is -40 to 300°C.

[0053] The feed pump is a diaphragm pump, a screw pump, a rotor pump, an emulsifying pump, a plunger pump, a peristaltic pump or a centrifugal pump.

[0054] Embodiment 1 of the present invention:

[0055] 1. Add thionyl chloride, chlorosulfonic acid and aminosulfonic acid into the batching kettle successively. The molar ratio of thionyl chloride, chlorosulfonic acid and aminosulfonic acid is 6:2:1. Turn on the emulsification pump for 0.5 hours and put the materials into the first group of weighing tanks as the first raw material.

[0056] 2. Add thionyl chloride to the second group of weighing tanks as the second raw material, wherein the molar ratio of thionyl chloride to the aminosulfonic acid is 2:1.

[0057] 3. The first and second raw materials are respectively fed into the preheater for preheating through the feed pump, and the preheater is set to 120°C; the flow rate of the first raw material is 20Kg / min, and the flow rate of the second raw material is 60Kg / min.

[0058] 4. The first and second raw materials are preheated and then enter the first stage reactor for full stirring and mixing reaction by a dynamic mixer. The speed of the dynamic mixer is 5000r / min, the reaction temperature is 120°C, and the residence time is 10min;

[0059] 5. After the feed liquid comes out of the first stage, it enters the heat exchanger to be heated to 120°C, and then enters the second stage reactor for reaction at a reaction temperature of 180°C; the residence time is 240 minutes.

[0060] 6. The set pressure of the back pressure valve at the reactor outlet is 0.1 MPa. The product at the outlet of the back pressure valve of the reaction unit is separated by gas-liquid separation and distilled to obtain bischlorosulfonyl imide with a yield of 93.8%.

[0061] Embodiment 2 of the present invention:

[0062] Into a 250 ml three-necked flask, weigh and add 30.05 g of aminosulfonic acid, 39.78 g of chlorosulfonic acid and 110.59 g of thionyl chloride, slowly raise the temperature to 115°C, and reflux.

[0063] The reaction was kept warm for 36 hours, and 64.06 g of the product was obtained after vacuum distillation, with a yield of 73.85%.

[0064] It should be understood that the purpose of these embodiments is only to illustrate the present invention and is not intended to limit the protection scope of the present invention. In addition, it should also be understood that after reading the technical content of the present invention, those skilled in the art can make various changes, modifications and / or variations to the present invention, and all of these equivalent forms also fall within the protection scope defined by the claims attached to this application.

Claims

1. A dynamic reactor device for solid-liquid and gas-liquid heterogeneity, characterized in that: The invention comprises a premixing device, a feeding device and a reaction device, wherein the reaction device comprises a solid homogenizing batching unit (1), a liquid batching unit (3), a weighing feeding pipeline (4), a preheat exchanger (5) and a reaction unit, and the reactor unit is one section or divided into multiple sections connected in series or in parallel; The solid homogenizing batching unit (1) comprises a batching kettle and a homogenizing device (2), wherein the bottom outlet of the batching kettle is connected to the inlet of the homogenizing device (2), and the outlet of the homogenizing device (2) is connected to the inlet of the batching kettle; The reaction unit comprises a mixer, a heat exchanger (8), a reactor and a back pressure valve (9); the reactor is provided with a feed port and a discharge port; a weighing feed pipeline (4) is connected to the reactor feed port; and the discharge port reactor outlet is connected to the heat exchanger (8) or the back pressure valve (9); The reactor is provided with a feed inlet and a discharge inlet, and the reactor feed inlet is connected to the feed pump outlet; The feed port of the heat exchanger (8) is connected to the discharge port of the first stage reactor, and the discharge port of the heat exchanger (8) is connected to the feed port of the second stage reactor.

2. The dynamic reactor device for solid-liquid and gas-liquid heterogeneity according to claim 1, characterized in that: The homogenizing device (2) is one or more combinations of an emulsifying pump, a homogenizing pump, a pipeline pump, a mortar pump, a rotor pump, a screw pump, etc., and the solid homogenizing batching unit (1) includes two reaction tanks arranged side by side.

3. The dynamic reactor device for solid-liquid and gas-liquid heterogeneity according to claim 1, characterized in that: The mixers are arranged at the bottom, the middle and the top of the reactor.

4. The dynamic reactor device for solid-liquid and gas-liquid heterogeneity according to claim 1, characterized in that: The feed port of the back pressure valve (9) is connected to the outlet of the reactor or the heat exchanger (8).

5. The dynamic reactor device for solid-liquid and gas-liquid heterogeneity according to claim 1, characterized in that: The mixer is a combination of a dynamic mixer and a static mixer or several thereof, and the dynamic mixer is a combination of a screw type, a high-speed mixer, an impeller, and a gear or several thereof.

6. The dynamic reactor device for solid-liquid and gas-liquid heterogeneity according to claim 5, characterized in that: The static mixer is a mixing device of SK type, SH type, SV type, etc., or a combination of metal / non-metal filler, ceramic particle filler, or several of them, which is installed in the reactor in sections, or a baffle is installed in the reactor.

7. The dynamic reactor device for solid-liquid and gas-liquid heterogeneity according to claim 1, characterized in that: The reaction unit is made of iron, nickel-based alloy, silicon carbide, glass, Hastelloy or manganese-nel alloy, or titanium, zirconium, niobium, tantalum and alloys thereof.

8. The dynamic reactor device for solid-liquid and gas-liquid heterogeneity according to claim 1, characterized in that: The reaction unit is installed vertically or horizontally.

9. The dynamic reactor device for solid-liquid and gas-liquid heterogeneity according to claim 1, characterized in that: The weighing feed pipeline (4) comprises a weighing tank, a weighing module, and a feed pump. The weighing tanks are placed on the weighing module, one for backup and the other for use. The feed port of the weighing tank is connected to the discharge port of the batching kettle, the discharge port of the weighing tank is connected to the inlet of the feed pump, the outlet of the feed pump is connected to the inlet of the preheater, and the outlet of the preheater is connected to the inlet of the reactor.

10. The dynamic reactor device for solid-liquid and gas-liquid heterogeneity according to claim 1, characterized in that: The feed pump is a diaphragm pump, a screw pump, a rotor pump, an emulsifying pump, a plunger pump, a peristaltic pump or a centrifugal pump.

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