Solid-liquid exothermic reaction device and continuous reaction equipment using same

Abstract

The invention relates to a solid-liquid exothermic reaction device which is characterized by comprising a reaction kettle, a first solid-liquid separator, a material guide pump, a second solid-liquid separator and an external heat exchanger which are sequentially connected in series, wherein the top or the upper part of the first solid-liquid separator is provided with a reactant lead-in port connected with the reaction kettle and a light component lead-out port connected with the material guide pump, and the bottom of the first solid-liquid separator is provided with a heavy component lead-out port connected with the reaction kettle; the top or the upper part of the second solid-liquid separator is provided with a light component leading-out port connected with the external heat exchanger, and the bottom of the second solid-liquid separator is provided with a heavy component leading-out port connected with the reaction kettle; and a discharge hole of the external heat exchanger is connected with the reaction kettle. The invention further relates to continuous solid-liquid exothermic reaction equipment using the solid-liquid exothermic reaction device.

Description

Technical Field

[0001] This application relates to a continuous solid-liquid exothermic reaction device and a continuous solid-liquid exothermic reaction equipment using the device. Background Art

[0002] In the prior art, the following batch reaction is often used to prepare Grignard reagents: first, dry the reaction kettle, add an excessive amount of magnesium chips into the reaction kettle, add an appropriate amount of initiator, start dropping halogenated hydrocarbons, and after the dropping is completed, continue the reaction until the reaction is completed. This reaction has the following problems: each batch of reaction requires initiation; when discharging or pouring the materials after the reaction is completed, the excessive magnesium chips are likely to block the bottom of the reaction kettle; there are a large number of unreacted materials in the kettle per unit time, resulting in a large accumulation of reaction heat and the inability to remove the heat in time, with great potential safety hazards; the production efficiency of the batch method is low. Summary of the Invention

[0003] The purpose of this application is to provide a novel solid-liquid exothermic reaction device and a continuous reaction equipment using the device, through which continuous feeding of solid-liquid raw materials, continuous discharging of products, and continuous recycling of excessive solid raw materials can be realized, with simple operation, safety, and high production efficiency.

[0004] When the continuous reaction equipment of this application is used for producing Grignard reagents, for example, it effectively solves the problems that excessive magnesium chips are likely to block the bottom of the reaction kettle during discharging or pouring in batch reactions, each batch of reaction requires initiation, there is a large accumulation of reaction heat with potential safety hazards, and the production efficiency is low.

[0005] Specifically, the present invention relates to:

[0006] (1) A solid-liquid exothermic reaction device, characterized in that the device includes: a reaction kettle, a first solid-liquid separator, a feed pump, a second solid-liquid separator, and an external heat exchanger connected in series in sequence; wherein, at the top or upper part of the first solid-liquid separator, there is a reactant inlet connected to the reaction kettle and a light component outlet connected to the feed pump, and at the bottom, there is a heavy component outlet connected to the reaction kettle; at the top or upper part of the second solid-liquid separator, there is a light component outlet connected to the external heat exchanger, and at the bottom, there is a heavy component outlet connected to the reaction kettle; the outlet of the external heat exchanger is connected to the reaction kettle.

[0007] (2) The reaction device according to the above (1), wherein the first and second solid-liquid separators are sedimentation tanks, rotary separators, scraper filters, precision filters, preferably sedimentation tanks or rotary separators, and further preferably the first solid-liquid separator is a sedimentation tank and the second solid-liquid separator is a rotary separator.

[0008] (3) The reaction device according to the above (1) or (2), wherein the external heat exchanger is a shell-and-tube heat exchanger or a coil heat exchanger.

[0009] (4) The reaction device according to any one of (1) to (3) above, wherein a liquid raw material inlet and / or a gas inlet is further provided at the top or upper part of the first solid-liquid separator.

[0010] (5) The reaction device according to any one of (1) to (4) above, wherein a solid charging bin is provided at the top of the reaction kettle.

[0011] (6) A continuous solid-liquid exothermic reaction device, characterized in that the device comprises the reaction device according to any one of (1) to (5) above as a first-stage reaction unit, and further comprises a second-stage reaction unit or optionally more reaction units connected after the second-stage reaction unit. The structure of the second-stage or more reaction units may be the same as that of the first-stage reaction unit, or one or more of the first solid-liquid separator, the second solid-liquid separator, and the external heat exchanger may be subtracted from the structure of the first-stage reaction unit.

[0012] (7) The reaction device according to (6) above, which is a Grignard reagent production device.

[0013] (8) The reaction device according to (7) above, which comprises first and second-stage reaction units.

[0014] (9) The reaction device according to (8) above, wherein a first solid-liquid separator, a feed pump, and a second solid-liquid separator are sequentially arranged between the reaction kettle of the first-stage reaction unit and the reaction kettle of the second-stage reaction unit.

[0015] (10) The reaction device according to (9) above, wherein the bottoms of the first solid-liquid separator and the second solid-liquid separator of the second-stage reaction unit are connected to the reaction kettle of the first-stage reaction unit. Description of the Drawings

[0016] Figure 1 It is a schematic structural diagram of a preferred embodiment of the solid-liquid exothermic reaction device of the present application.

[0017] Figure 2 It is a schematic structural diagram of a preferred embodiment of the continuous solid-liquid exothermic reaction device of the present application.

[0018] Description of the Reference Numerals:

[0019] 1 - First - stage reaction unit, 11 - Reactor, 12 - Feed pipe, 13 - First solid - liquid separator, 14 - Feed pump, 15 - Second solid - liquid separator, 16 - External heat exchanger, 17 - Solid feed bin, 131 - Reactant inlet, 132 - Light - component outlet of first - stage separation, 133 - Heavy - component outlet of first - stage separation, 134 - Liquid raw material inlet, 135 - Gas inlet, 151 - Light - component outlet of second - stage separation, 152 - Heavy - component outlet of second - stage separation.

[0020] 2 - Second - stage reaction unit, 21 - Reactor, 23 - First solid - liquid separator, 24 - Feed pump, 25 - Second solid - liquid separator, 27 - Solid feed bin. Specific embodiments

[0021] The structure of the solid - liquid exothermic reaction device and the continuous reaction equipment of the present application will be described in more detail below with reference to the accompanying drawings. However, the present application is not limited to this specific embodiment, and any modifications and changes within the scope of the main idea of the present application fall within the invention of the present application.

[0022] On the one hand, the present application relates to a novel solid - liquid exothermic reaction device. As Figure 1 shown, the solid - liquid exothermic reaction device of the present application includes: a reactor 11, a first solid - liquid separator 13, a feed pump 14, a second solid - liquid separator 15, and an external heat exchanger 16 connected in series in sequence.

[0023] At the top or upper part of the first solid - liquid separator 13, there are a reactant inlet 131 connected to the reactor 11 and a light - component outlet 132 of the first - stage separation connected to the feed pump 14. Preferably, there are also a liquid raw material inlet 134 and / or a gas inlet 135. At the bottom, there is a heavy - component outlet 133 of the first - stage separation connected to the reactor 11. "Light - component of the first - stage separation" refers to the reaction material that contains only a small amount of solid, has a relatively light specific gravity, and is in the upper layer of the separator after the first - stage separation. "Heavy - component of the first - stage separation" refers to the reaction material that contains a large amount of solid, has a relatively large specific gravity, and is in the lower layer of the separator after the first - stage separation.

[0024] At the top or upper part of the second solid - liquid separator 15, there is a light - component outlet 151 of the second - stage separation connected to the external heat exchanger 16. At the bottom, there is a heavy - component outlet 152 of the second - stage separation connected to the reactor 11. "Light - component of the second - stage separation" refers to the reaction material that basically does not contain solid, has a relatively light specific gravity, and is in the upper layer of the separator after the second - stage separation. "Heavy - component of the second - stage separation" refers to the reaction material that still contains a small amount of solid that has not been completely separated, has a relatively large specific gravity, and is in the lower layer of the separator after the second - stage separation.

[0025] The outlet of the external heat exchanger 16 is connected to the reactor 11, preferably connected to the bottom of the reactor 11, and the cooled reaction material is returned to the reactor 11.

[0026] The first solid-liquid separator 13 performs the first solid-liquid separation on the reaction material to be cooled exported from the reaction kettle 11. After the first separation, the heavy components are led back into the reaction kettle 11 through the heavy component outlet 133 of the first-stage separation. The light components are introduced into the second solid-liquid separator 15 by the feeding pump 14 for secondary solid-liquid separation, so as to more fully remove the unreacted solid raw materials therein and prevent the downstream external heat exchanger 16 from being blocked by solids.

[0027] The first solid-liquid separator 13 and the second solid-liquid separator 15 can be any devices capable of performing solid-liquid separation, preferably a settling tank, a rotary separator, a scraper filter, or a precision filter, more preferably a settling tank and a rotary separator, and further preferably a configuration combination in which the first solid-liquid separator 13 is a settling tank and the second solid-liquid separator 15 is a rotary separator.

[0028] The bottom heavy component discharge pipelines of the first solid-liquid separator 13 and the second solid-liquid separator 15 can be set as two pipelines or combined into one pipeline to lead the separated heavy components back into the reaction kettle 11 together.

[0029] The reaction kettle 11 is preferably further provided with a solid feeding bin 17 at the upper part or the bottom. When used in reactions requiring airtightness (such as the preparation reaction of Grignard reagent), the solid feeding bin 17 is preferably a closed solid feeding bin.

[0030] A liquid raw material inlet 134 can be arranged at the top or upper part of the first solid-liquid separator 13. When a gas needs to be introduced into the reaction, a gas inlet 135 can also be arranged at the top or upper part of the first solid-liquid separator 13.

[0031] On the other hand, the present application relates to a continuous solid-liquid exothermic reaction device, which includes the above-mentioned solid-liquid exothermic reaction device as the first-stage reaction unit 1, and also includes a second-stage reaction unit 2 or more optional reaction units connected after the second-stage reaction unit. The number of subsequent reaction units is determined according to conditions such as the types of reactants and the amount of materials. The structure of the second-stage or more reaction units can be the same as that of the first-stage reaction unit 1, or one or more of the first solid-liquid separator 13, the second solid-liquid separator 15, and the external heat exchanger 16 can be removed from the structure of the first-stage reaction unit 1.

[0032] The solid-liquid reaction is heat-exchanged on the one hand through the jacket outside the reaction kettle 11, and on the other hand through the external heat exchanger 16. The external heat exchanger 16 is a heat exchanger with good heat dissipation effect, which is used to solve the problem of heat accumulation caused by low heat exchange efficiency of the reaction kettle 11, reduce side reactions and potential safety hazards, and also enable the reaction to proceed continuously. The external heat exchanger 16 is preferably a shell-and-tube heat exchanger and a coil heat exchanger, more preferably a shell-and-tube heat exchanger, with the reaction material flowing through the tube side and the refrigerant flowing through the shell side.

[0033] The external heat exchanger 16 can interlock its flow regulating valve with the thermometer indicating the temperature difference between the inlet and outlet to control the flow rate of the refrigerant.

[0034] The temperature control device (not shown) in the reaction kettle 11 can be interlocked with the regulating valve of the liquid raw material inlet 134. When the temperature display is higher than the required reaction temperature, the opening of the regulating valve decreases; when it is lower than the required reaction temperature, the opening of the regulating valve increases.

[0035] A liquid level gauge (not shown) is provided in the reaction kettle 11. Preferably, the liquid level gauge is interlocked with the start-stop switch of the material guiding pump 14. When the liquid level in the reaction kettle 11 is higher than the inlet of the material guiding pipe 12 therein, the material guiding pump 14 is started, and the reaction liquid is introduced into the first solid-liquid separator 13 through the material guiding pipe 12; when the liquid level in the reaction kettle 11 is lower than the inlet of the material guiding pipe 12, the material guiding pump 14 stops.

[0036] The solid-liquid exothermic reaction device and the continuous reaction equipment of the present application can be used, for example, in the preparation of Grignard reagents. The following will take the preparation reaction of Grignard reagents as an example to illustrate the operation of the reaction device and equipment of the present application, but this example is only exemplary and does not constitute any limitation on the application of the device of the present application.

[0037] First, add the Grignard reagent reaction liquid into the reaction kettle 11 and make its liquid level higher than the inlet of the material guiding pipe 12, start the material guiding pump 14, then add magnesium chips into the reaction kettle 11 from the solid feeding bin 17, and carry out nitrogen replacement on the reaction system. The chlorohydrocarbon solution dissolved in the solvent is introduced into the first solid-liquid separator 13 from the liquid raw material inlet 134. The liquid is mixed with the reaction liquid pumped out from the reaction kettle 11 by the material guiding pump 14 in the first solid-liquid separator 13. The mixed heavy components (materials containing a large amount of magnesium chips) settle to the bottom of the first solid-liquid separator 13 and flow back to the reaction kettle 11. The light components (materials containing a small amount of magnesium chips) are further introduced into the second solid-liquid separator 15 from the upper part or the top of the separator by the material guiding pump 14 for secondary solid-liquid separation. The separated light components (materials basically free of magnesium chips) are introduced into the external heat exchanger 16 for heat dissipation and cooling. The heavy components (materials still containing magnesium chips not completely removed by the secondary solid-liquid separation) flow back to the reaction kettle 11 from the bottom of the separator.

[0038] The temperature of the reaction solution decreases by approximately 10 °C after passing through the external heat exchanger 16, and then it is returned to the reaction kettle 11. When the temperature in the reaction kettle 11 exceeds 30 °C, the regulating valve of the liquid raw material inlet 134 is closed slightly. When the temperature is between 20 - 30 °C, the regulating valve of the liquid raw material inlet 134 does not act. When the temperature is lower than 20 °C, the regulating valve of the liquid raw material inlet 134 is opened wide. The liquid level in the reaction kettle 11 starts to rise slowly. When the liquid level rises to the set level, the feeding pump 24 of the second-stage reaction unit starts, and the reaction solution is pumped into the solid-liquid separators 23 and 25 and the reaction kettle 21 of the second-stage reaction unit 2 for further reaction.

[0039] When the reaction device or continuous equipment of the present application is used to prepare Grignard reagents, continuous feeding can be carried out, solving the problem that each batch of feeding in batch reactions requires re-initiation.

[0040] As an application of the reaction device or continuous equipment of the present application, for example, it can be used for the preparation of active pharmaceutical ingredients such as boscalid and fluxapyroxad, the preparation of water dispersible granules of boscalid, the preparation of suspension concentrates of boscalid, the preparation of wettable powders of boscalid, the raw material pretreatment in the preparation of suspension concentrates of fluxapyroxad, etc., but is not limited to these.

[0041] Other conventional components required in the solid-liquid exothermic reaction device or continuous equipment of the present application, such as a vacuum pump (not shown), etc., can adopt well-known conventional structures and settings, and there are no special limitations.

[0042] Examples

[0043] The reaction equipment used in this example includes two reaction units, namely the first-stage reaction unit 1 and the second-stage reaction unit 2, and is used to prepare Grignard reagents.

[0044] Add 63 kg of magnesium chips to the reactor 11 of the first-stage reaction unit 1, and do not add magnesium chips to the reactor 21 of the second-stage reaction unit 2. Conduct nitrogen replacement respectively. Add 50 L of toluene solution of p-bromochlorobenzene dropwise to the reactor 11, and then add 27 L of tetrahydrofuran to the reactor 11. Start the stirring of the reactor 11. After the reaction is initiated, cool down to 20 °C and start continuous feeding. At the same time, add the toluene solution of p-bromochlorobenzene to the reactor 11 at a rate of 100 - 255 L / h and add tetrahydrofuran at a rate of 46 - 117 L / h from the liquid raw material feeding port 134. Start the jacket refrigeration. When the liquid level in the kettle is higher than the feeding port of the guide pipe 12, the material is pumped into the external circulation by the guide pump 14, and solid-liquid separation is carried out through the settling tank as the first solid-liquid separator 13 and the rotary separator as the second solid-liquid separator 15, and then enters the external heat exchanger 16 for heat exchange. The temperature in the reactor 11 is controlled at 20 - 30 °C. After 4 - 10 h, when the liquid level in the reactor 11 is higher than the set liquid level, the guide pump 24 of the second-stage reaction unit 2 starts, and the material in the reactor 11 of the first-stage reaction unit 1 is solid-liquid separated at a speed of 146 - 372 L / h through the first solid-liquid separator 23 (settling tank) of the second-stage reaction unit 2 and the second solid-liquid separator 25 (rotary separator) of the second-stage reaction unit 2, and then enters the reactor 21 of the second-stage reaction unit 2 for further reaction. At the same time, add magnesium chips to the reactor 11 of the first-stage reaction unit 1 from the solid feeding bin 17 at a rate of 9 - 22 kg / h.

[0045] Detect the residual amount of raw material p-bromochlorobenzene in the material derived from the reactor 11 of the first-stage reaction unit 1 by HPLC ≤ 1%, the residual amount of raw material p-bromochlorobenzene in the material derived from the reactor 21 of the second-stage reaction unit 2 ≤ 0.5%, the coupling impurities ≤ 1%, the double Grignard impurities ≤ 1%, p-chlorophenol ≤ 1%, and the Grignard hydrolysis impurities ≤ 1%. The product yield after conversion ≥ 95%.

[0046] The HPLC detection conditions are as follows:

[0047] Instrument: normal-phase high-performance liquid chromatograph

[0048] Detection wavelength: 254 nm (variable wavelength ultraviolet detector)

[0049] Flow rate: 1.0 ml / min

[0050] Column temperature: 30 °C

[0051] Mobile phase: acetonitrile: water = 50:50 (volume ratio).

[0052] Industrial applicability

[0053] The solid-liquid exothermic reaction device and continuous equipment of this application are convenient to operate, safe and have high production efficiency.

Claims

1. Solid-liquid exothermic reaction device, characterized in that, The device comprises: a reaction kettle, a first solid-liquid separator, a feed pump, a second solid-liquid separator and an external replacement heat exchanger connected in series in sequence; wherein, a reactant inlet connected to the reaction kettle and a light component outlet connected to the feed pump are provided at the top or upper part of the first solid-liquid separator, and a heavy component outlet connected to the reaction kettle is provided at the bottom; a light component outlet connected to the external replacement heat exchanger is provided at the top or upper part of the second solid-liquid separator, and a heavy component outlet connected to the reaction kettle is provided at the bottom; the outlet of the external replacement heat exchanger is connected to the reaction kettle.

2. The reaction device according to claim 1, wherein the first and second solid-liquid separators are sedimentation tanks, rotary separators, scraper filters, precision filters, preferably sedimentation tanks or rotary separators, and further preferably the first solid-liquid separator is a sedimentation tank and the second solid-liquid separator is a rotary separator.

3. The reaction device according to claim 1 or 2, wherein the external replacement heat exchanger is a shell-and-tube heat exchanger or a coil heat exchanger.

4. The reaction device according to any one of claims 1 to 3, wherein, A liquid raw material inlet and / or a gas inlet are further provided at the top or upper part of the first solid-liquid separator.

5. The reaction device according to any one of claims 1 to 4, wherein, A solid charging bin is provided at the top of the reaction kettle.

6. Continuous solid-liquid exothermic reaction equipment, characterized in that, The equipment comprises the reaction device according to any one of claims 1 to 5 as the first-stage reaction unit, and further comprises a second-stage reaction unit or optionally more reaction units connected after the second-stage reaction unit. The structures of the second-stage or more reaction units may be the same as that of the first-stage reaction unit, or one or more of the first solid-liquid separator, the second solid-liquid separator and the external replacement heat exchanger may be removed from the structure of the first-stage reaction unit.

7. The reaction equipment according to claim 6, which is a Grignard reagent production equipment.

8. The reaction equipment according to claim 7, which comprises first and second-stage reaction units.

9. The reaction equipment according to claim 8, wherein a first solid-liquid separator, a feed pump and a second solid-liquid separator are sequentially arranged between the reaction kettle of the first-stage reaction unit and the reaction kettle of the second-stage reaction unit.

10. The reaction equipment according to claim 9, wherein the bottoms of the first solid-liquid separator and the second solid-liquid separator of the second-stage reaction unit are connected to the reaction kettle of the first-stage reaction unit.

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