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

Abstract

The utility model 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 utility model further relates to continuous solid-liquid exothermic reaction equipment using the solid-liquid exothermic reaction device.

Description

TECHNICAL FIELD

[0001] The present application relates to a continuous solid-liquid exothermic reaction device and a continuous solid-liquid exothermic reaction equipment using the same. BACKGROUND

[0002] In the prior art, Grignard reagent is usually prepared by a batch reaction as follows: a reaction kettle is first dried, excess magnesium chips are added into the reaction kettle, an appropriate amount of initiator is added, halogenated hydrocarbon is added dropwise, after the dropwise addition is completed, the reaction is continued until the reaction is completed. The reaction has the following problems: each batch of reaction needs to be initiated; when the product is discharged or poured, the excess magnesium chips are easy to block the bottom of the reaction kettle; a large amount of unreacted material exists in the kettle per unit time, causing a large amount of reaction heat to accumulate, and the heat cannot be removed in time, which has a large safety hazard; the production efficiency of the batch method is low. SUMMARY

[0003] The purpose of the present application is to provide a novel solid-liquid exothermic reaction device and a continuous reaction equipment using the same, through which continuous feeding of solid-liquid raw materials, continuous discharge of products and continuous reuse of excess solid raw materials can be realized, and the operation is simple, safe and has high production efficiency.

[0004] When the continuous reaction equipment of the present application is used for producing Grignard reagent, the problems of the batch reaction, such as the excess magnesium chips blocking the bottom of the reaction kettle when the product is discharged or poured, the need for initiation for each batch of reaction, the large amount of reaction heat accumulation, the safety hazard and the low production efficiency, are effectively solved.

[0005] Specifically, the present application relates to:

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

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

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

[0010] (5) The reaction apparatus according to any one of (1) to (4), wherein the top of the reaction vessel is provided with a solid feeding bin.

[0011] (6) A continuous solid-liquid exothermic reaction apparatus, characterized in that the apparatus comprises the reaction apparatus according to any one of (1) to (5) as a first stage reaction unit, and further comprises a second stage reaction unit or more stages of reaction units connected to the second stage reaction unit, wherein the structure of the second stage or more stages of reaction units can be the same as that of the first stage reaction unit, or one or more than two of the first solid-liquid separator, the second solid-liquid separator, and the external heat exchanger can be removed from the structure of the first stage reaction unit.

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

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

[0014] (9) The reaction apparatus according to (8), wherein the first solid-liquid separator, the material feeding pump, and the second solid-liquid separator are sequentially arranged between the reaction vessel of the first stage reaction unit and the reaction vessel of the second stage reaction unit.

[0015] (10) The reaction apparatus according to (9), wherein the bottoms of the first and second solid-liquid separators of the second stage reaction unit are connected to the reaction vessel of the first stage reaction unit. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 Structure diagram of a preferred embodiment of the solid-liquid exothermic reaction apparatus of the present application.

[0017] Figure 2 Structure diagram of a preferred embodiment of the continuous solid-liquid exothermic reaction apparatus of the present application.

[0018] Explanation of reference signs:

[0019] 1 - first stage reaction unit, 11 - reactor, 12 - material guiding pipe, 13 - first solid-liquid separator, 14 - material guiding pump, 15 - second solid-liquid separator, 16 - external heat exchanger, 17 - solid feeding bin, 131 - reactant guiding inlet, 132 - first stage separated light component guiding outlet, 133 - first stage separated heavy component guiding outlet, 134 - liquid raw material feeding inlet, 135 - gas guiding inlet, 151 - second stage separated light component guiding outlet, 152 - second stage separated heavy component guiding outlet.

[0020] 2 - second stage reaction unit, 21 - reactor, 23 - first solid-liquid separator, 24 - material guiding pump, 25 - second solid-liquid separator, 27 - solid feeding bin. DETAILED DESCRIPTION

[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 in combination with the drawings, but the present application is not limited to this specific embodiment, and any modification and change within the scope of the main idea of the present application falls within the invention of the present application.

[0022] The present application relates to a novel solid-liquid exothermic reaction device. As shown in Figure 1 The solid-liquid exothermic reaction device of the present application comprises, in series: a reactor 11, a first solid-liquid separator 13, a material guiding pump 14, a second solid-liquid separator 15, and an external heat exchanger 16.

[0023] The first solid-liquid separator 13 is provided at the top or upper part thereof with a reactant guiding inlet 131 connected to the reactor 11 and a first stage separated light component guiding outlet 132 connected to the material guiding pump 14, and preferably also with a liquid raw material guiding inlet 134 and / or a gas guiding inlet 135, and at the bottom thereof with a first stage separated heavy component guiding outlet 133 connected to the reactor 11. The "first stage separated light component" refers to the reaction material after first stage separation, which contains only a small amount of solid, has a relatively light specific gravity, and is in the upper layer of the separator. The "first stage separated heavy component" refers to the reaction material after first stage separation, which contains a large amount of solid, has a relatively large specific gravity, and is in the lower layer of the separator.

[0024] The second solid-liquid separator 15 is provided at the top or upper part thereof with a second stage separated light component guiding outlet 151 connected to the external heat exchanger 16, and at the bottom thereof with a second stage separated heavy component guiding outlet 152 connected to the reactor 11. The "second stage separated light component" refers to the reaction material after second stage separation, which contains substantially no solid, has a relatively light specific gravity, and is in the upper layer of the separator. The "second stage separated heavy component" refers to the reaction material after second stage separation, which still contains a small amount of solid not separated completely, has a relatively large specific gravity, and is in the lower layer of the separator.

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

[0026] The first solid-liquid separator 13 performs the first solid-liquid separation on the reaction material to be cooled which is led out from the reaction kettle 11, and the heavy component after the first separation is led back to the reaction kettle 11 from the first separation heavy component leading-out port 133, and the light component is led into the second solid-liquid separator 15 by the leading pump 14 to perform the second solid-liquid separation, so as to more fully remove the unreacted solid raw material, and avoid the external heat exchanger 16 in the downstream from being blocked by the solid.

[0027] The first solid-liquid separator 13 and the second solid-liquid separator 15 can be any device capable of performing solid-liquid separation, and are preferably a settling tank, a rotary separator, a scraper filter, a precision filter, more preferably a settling tank and a rotary separator, and further preferably 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 pipeline of the first solid-liquid separator 13 and the second solid-liquid separator 15 can be provided as two pipelines, or can be combined into one pipeline to lead the separated heavy component back into the reaction kettle 11.

[0029] The reaction kettle 11 preferably further has a solid feeding bin 17 at the upper part or the bottom part. When used for a reaction requiring air tightness (such as Grignard reagent preparation reaction), the solid feeding bin 17 is preferably a closed solid feeding bin.

[0030] A liquid raw material feeding port 134 can be provided at the top or the upper part of the first solid-liquid separator 13, and a gas leading-in port 135 can also be provided at the top or the upper part of the first solid-liquid separator 13 when gas needs to be introduced for the reaction.

[0031] Another aspect of the present application relates to a continuous solid-liquid exothermic reaction device, which comprises the above-mentioned solid-liquid exothermic reaction device as the first stage reaction unit 1, and further comprises a second stage reaction unit 2 or more stage reaction units connected after the second stage reaction unit. The number of subsequent reaction units is determined according to the reaction species, the material quantity and other conditions. The structure of the second stage or more stage reaction unit can be the same as the first stage reaction unit 1, or one or more than two 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 exchanged by the jacket outside the reaction kettle 11 on one hand, and by the external heat exchanger 16 on the other hand. The external heat exchanger 16 is a heat exchanger with good heat dissipation effect, which is used to solve the problem of low heat exchange efficiency of the reaction kettle 11, reduce the accumulation of reaction heat, reduce the side reaction and safety hazards, and also make the reaction continuous. The external heat exchanger 16 is preferably a shell-and-tube heat exchanger and a coil heat exchanger, and more preferably a shell-and-tube heat exchanger, with the reaction material passing through the tube and the coolant passing through the shell.

[0033] The external heat exchanger 16 can be interlocked with its flow regulating valve and its temperature gauge indicating the temperature difference between the inlet and outlet, to control the flow of the coolant.

[0034] The temperature control device (not shown) in the reactor 11 can be interlocked with the regulating valve of the liquid raw material inlet 134, and when the temperature is higher than the required reaction temperature, the regulating valve opening is reduced, and when the temperature is lower than the required reaction temperature, the regulating valve opening is increased.

[0035] A liquid level gauge (not shown) is provided in the reactor 11, which is preferably interlocked with the start-stop switch of the material guiding pump 14. When the liquid level in the reactor 11 is higher than the inlet of the material guiding pipe 12, the material guiding pump 14 is started to guide the reaction liquid into the first solid-liquid separator 13 through the material guiding pipe 12; when the liquid level in the reactor 11 is lower than the inlet of the material guiding pipe 12, the material guiding pump 14 is stopped.

[0036] The solid-liquid exothermic reaction device and the continuous reaction equipment of the present application can be used in the preparation of Grignard reagent, for example. The operation of the reaction device and equipment of the present application will be described below by taking the preparation reaction of Grignard reagent as an example, but this example is only illustrative and does not constitute any limitation on the application of the device of the present application.

[0037] In the reactor 11, Grignard reagent reaction liquid is first added and the liquid level is higher than the inlet of the material guiding pipe 12, the material guiding pump 14 is started, then magnesium chips are added to the reactor 11 from the solid feeding bin 17, the reaction system is replaced with nitrogen, the chlorinated hydrocarbon solution dissolved in solvent is guided into the first solid-liquid separator 13 from the liquid raw material inlet 134, the liquid is mixed with the reaction liquid extracted from the reactor 11 by the material guiding pump 14 in the first solid-liquid separator 13, the heavy component (material containing a large amount of magnesium chips) after mixing is settled to the bottom of the first solid-liquid separator 13 and flows back to the reactor 11, the light component (material containing a small amount of magnesium chips) is further guided into the second solid-liquid separator 15 from the upper part or top of the separator by the material guiding pump 14 for secondary solid-liquid separation, the separated light component (material basically not containing magnesium chips) is guided into the external heat exchanger 16 for heat dissipation and cooling, and the heavy component (material still containing magnesium chips not removed by secondary solid-liquid separation) flows back to the reactor 11 from the bottom of the separator.

[0038] The reaction liquid is cooled by about 10°C after passing through the external heat exchanger 16, and then is returned to the reaction kettle 11. When the temperature in the reaction kettle 11 exceeds 30°C, the liquid feed inlet 134 adjusting valve is closed, when the temperature is between 20-30°C, the liquid feed inlet 134 adjusting valve is not operated, and when the temperature is below 20°C, the liquid feed inlet 134 adjusting valve is opened, and the liquid level in the reaction kettle 11 begins to slowly rise. When the liquid level reaches the set level, the guide pump 24 of the second stage reaction unit is started, and the reaction liquid is pumped into the solid-liquid separator 23, 25 and the reaction kettle 21 of the second stage reaction unit 2 for further reaction.

[0039] The reaction device or continuous equipment of the present application can be used for the preparation of Grignard reagent, and can be continuously fed, solving the problem of re-initiation of each batch in batch reaction.

[0040] As an application of the reaction device or continuous equipment of the present application, for example, the preparation of raw drug of boscalid, fluazinam, the preparation of water dispersible granules of boscalid, the preparation of suspension concentrate of boscalid, the preparation of wettable powder of boscalid, and the raw material pretreatment in the preparation of suspension concentrate of fluazinam, etc. can be listed, but are 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 vacuum pump (not shown), etc., can use conventional structures and settings known in the art, and are not particularly limited.

[0042] Example

[0043] The reaction equipment used in this example includes two reaction units, the first stage reaction unit 1 and the second stage reaction unit 2, for the preparation of Grignard reagent.

[0044] The magnesium chips 63 kg were added to the reactor 11 of the first reaction unit 1, and the reactor 21 of the second reaction unit 2 was not added with magnesium chips, and nitrogen was replaced respectively, and then the 50 L p-bromochlorobenzene toluene solution was added dropwise to the reactor 11, and then 27 L of tetrahydrofuran was added to the reactor 11, and the stirring of the reactor 11 was started, and after the reaction was initiated, the temperature was lowered to 20°C, and the continuous feeding was started, and at the same time, the p-bromochlorobenzene toluene solution was added to the reactor 11 at 100-255 L / h from the liquid raw material feeding port 134, and the tetrahydrofuran was added at 46-117 L / h, and the jacket cooling was started, and when the liquid level in the reactor was higher than the feeding port of the guide pipe 12, the material was pumped into the external circulation by the guide pump 14, and the solid-liquid separation was carried out through the settling tank as the first solid-liquid separator 13 and the rotating separator as the second solid-liquid separator 15, and the heat exchange was carried out in the external heat exchanger 16, and the temperature in the reactor 11 was controlled at 20-30°C, and after 4-10 h, when the liquid level in the reactor 11 was higher than the set liquid level, the guide pump 24 of the second reaction unit 2 was started, and the material in the reactor 11 of the first reaction unit 1 was fed at a speed of 146-372 L / h to the first solid-liquid separator 23 (settling tank) of the second reaction unit 2 and the second solid-liquid separator 25 (rotating separator) of the second reaction unit 2 for solid-liquid separation, and then the material was further reacted in the reactor 21 of the second reaction unit 2, and at the same time, the magnesium chips were added to the reactor 11 of the first reaction unit 1 from the solid feeding bin 17 at 9-22 kg / h.

[0045] The remaining amount of the raw material p-bromochlorobenzene in the material led out from the reactor 11 of the first reaction unit 1 was ≤1%, the remaining amount of the raw material p-bromochlorobenzene in the material led out from the reactor 21 of the second reaction unit 2 was ≤0.5%, the coupling impurity was ≤1%, the Grignard impurity was ≤1%, the p-chlorophenol was ≤1%, and the Grignard hydrolysis impurity was ≤1%, and the conversion product yield was ≥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 the continuous equipment of the present application are convenient, safe, and high in production efficiency.

Claims

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

2. The reaction device according to claim 1, wherein the first and second solid-liquid separators are sedimentation tanks, rotary separators, scraper filters, and precision filters.

3. The reaction device according to claim 2, wherein the first and second solid-liquid separators are settling tanks or rotary separators. The reaction device according to claim 3 , wherein the first solid-liquid separator is a sedimentation tank and the second solid-liquid separator is a rotary separator. 5 . The reaction device according to claim 1 , wherein the external heat exchanger is a shell and tube heat exchanger or a coil heat exchanger.

6. The reaction device according to any one of claims 1 to 4, wherein A liquid raw material feed port and / or a gas inlet port is also provided on the top or upper portion of the first solid-liquid separator.

7. The reaction device according to any one of claims 1 to 4, wherein A solid feeding bin is provided on the top of the reactor.

8. Continuous solid-liquid exothermic reaction equipment, characterized in that: The equipment comprises the reaction device described in any one of claims 1 to 4 as a first-stage reaction unit, and also includes a second-stage reaction unit or a multi-stage reaction unit connected to the second-stage reaction unit, wherein the structure of the second-stage or multi-stage reaction unit is 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 are subtracted from the structure of the first-stage reaction unit. The reaction equipment according to claim 8 , which is a Grignard reagent production equipment.

10. The reaction equipment according to claim 9, comprising first and second stage reaction units. 11 . The reaction equipment according to claim 10 , wherein a first solid-liquid separator, a feed pump and a second solid-liquid separator are sequentially arranged between the reactor of the first-stage reaction unit and the reactor of the second-stage reaction unit. 12 . The reaction equipment according to claim 11 , 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 reactor of the first-stage reaction unit.

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