阅读说明：本技术 一种格氏试剂的连续制备方法 (Continuous preparation method of Grignard reagent ) 是由 王修纲 刘爱民 李晓亮 于 2021-01-05 设计创作，主要内容包括：本发明涉及化工生产领域,特别是涉及一种格氏试剂的连续制备方法。本发明提供一种格氏试剂的连续制备方法,通过生产格氏试剂的管式连续装置制备格氏试剂,所述生产格氏试剂的管式连续装置包括环管反应装置,所述环管反应装置上设有用于驱动环管反应装置中的物料的驱动装置和用于加热环管反应装置中的物料的温度调节装置。本发明所提供的生产格氏试剂的管式连续装置,可以有效降低未反应物料累积量,整个装置除了启动时需要引发反应外,生产过程无需另外引发,保证生产安全。(The invention relates to the field of chemical production, in particular to a continuous preparation method of a Grignard reagent. The invention provides a continuous preparation method of a Grignard reagent, which is characterized in that the Grignard reagent is prepared by a tubular continuous device for producing the Grignard reagent, the tubular continuous device for producing the Grignard reagent comprises a loop reaction device, and the loop reaction device is provided with a driving device for driving materials in the loop reaction device and a temperature regulating device for heating the materials in the loop reaction device. The tubular continuous device for producing the Grignard reagent provided by the invention can effectively reduce the accumulation amount of unreacted materials, and the whole device needs to initiate reaction when being started, and does not need to initiate in the production process, thereby ensuring the production safety.)

1. A continuous preparation method of a Grignard reagent comprises the steps of preparing the Grignard reagent by a tubular continuous device for producing the Grignard reagent, wherein the tubular continuous device for producing the Grignard reagent comprises a loop reaction device (1), and the loop reaction device (1) is provided with a driving device (2) for driving materials in the loop reaction device (1) and a temperature regulating device (3) for heating the materials in the loop reaction device (1);

according to the flowing direction of materials, a gridlike raw material introducing pipeline (4), a slurry feeding device (5) and a grignard reagent leading pipeline (6) are sequentially arranged on the loop reaction device (1), or the slurry feeding device (5), the raw material introducing pipeline (4) and the gridlike reagent leading pipeline (6) are sequentially arranged on the loop reaction device;

the Grignard reagent leading-out pipeline (6) is also provided with a filtering device (61);

the continuous preparation method of the Grignard reagent specifically comprises the following steps:

1) introducing a Grignard raw material, a reaction solvent and a magnesium agent into a loop reaction device (1) through a grignard raw material introduction pipeline (4) and a slurry feeding device (5);

2) the materials in the loop reaction device (1) are driven by a driving device (2) to react;

3) the Grignard reagent product is led out through a Grignard reagent leading-out pipeline (6).

2. The continuous production method of Grignard reagent according to claim 1, wherein the residence time of the material in the loop reaction device (1) is 2 to 120 min.

3. The continuous production method of a grignard reagent according to claim 1, wherein the flow rate of the material in the loop reaction device (1) is 1 to 10m/s in the loop reaction device (1).

4. The continuous production method of a grignard reagent according to claim 1, wherein the circulation ratio in the loop reaction device (1) is 10 to 300.

5. The continuous production method of grignard reagent according to claim 1, wherein the slurry feeding device (5) and the grignard reagent lead-out conduit (6) are respectively close to the grignard raw material lead-in conduit (4).

6. The continuous production method of grignard reagent according to claim 1, wherein the grignard raw material introduction conduit (4) and the grignard reagent extraction conduit (6) are respectively close to the slurry feeding device (5).

7. The continuous production method of Grignard reagent according to claim 1, wherein the slurry feeding means (5) is provided with a liquid phase inlet (51).

8. The continuous production method of Grignard reagent according to claim 1, wherein the slurry feeding means (5) is provided with a solid phase inlet (52).

9. The continuous production method of Grignard reagents according to claim 1, wherein the Grignard reagent extraction conduit (6) is further provided with a flow rate adjusting device (62).

10. The continuous production method of a grignard reagent according to claim 1, wherein the temperature regulation device (3) is a jacket.

Technical Field

The invention relates to the field of chemical production, in particular to a continuous preparation method of a Grignard reagent.

Background

The grignard reaction is one of the important reactions in organic chemistry and has a large number of applications in fine chemical engineering and pharmaceutical engineering. Generally, an organic halogen compound (alkyl halide, active halogenated aromatic hydrocarbon) and magnesium metal react in a solvent such as dry ether to form an organic magnesium reagent. Most of the existing Grignard reagent preparation methods in the industry are intermittent operation, the Grignard reagent of the previous batch is used for inducing reaction, and the induced Grignard reaction can be performed by autocatalysis; however, in the production process, it is sometimes difficult to determine whether or not the initiation has occurred, and a failure in determination causes a large amount of unreacted materials to accumulate. However, the grignard reaction is a strongly exothermic reaction, and if the unreacted materials are accumulated in a large amount and are suddenly initiated, the reaction rate increases exponentially, so that the reactor flies warm and, in a severe case, an explosion is caused. If the continuous process is adopted for carrying out the Grignard reaction, the Grignard reaction is induced only once during the start-up, so that a large amount of unreacted substances are not accumulated, and the intrinsic safety is realized.

Chinese patent 201210019808.5 discloses a tower three-phase bubbling slurry bed reactor, which comprises filling the space in the tower with magnesium chips, continuously feeding solvent and grignard material into the reactor from the bottom of the tower, and discharging the reaction product from the bottom of the tower. However, the flow velocity in the bubbling bed is very low, the gas-liquid mass transfer efficiency is not high, in order to meet the requirement of longer retention time, the height and diameter of the tower need to be increased, and the increase of the diameter of the tower can bring about the problem of difficult heat transfer. In addition, the magnesium scrap feeding device is simple, online feeding cannot be realized, and the magnesium scrap feeding device is still semi-continuous in operation. Chinese patent 201480036803.0 discloses a fluidized bed grignard reactor, which is similar to a tower type three-phase bubble column reactor, and the semi-continuous operation mode of the reactor changes the induction mode of grignard reaction to a great extent, but the mass transfer and heat transfer performance of the reactor is not ideal. In order to solve the above problems, chinese patent 201520705587.6 adds an internal heat exchanger and an external circulation to improve the mass transfer and heat transfer performance of the tower reactor, but this change makes the equipment too complex and the fixed cost of the equipment too high, and is not an ideal continuous grignard reactor.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a tubular continuous apparatus for producing grignard reagents, which solves the problems of the prior art.

In order to achieve the above and other related objects, the present invention provides a method for continuously preparing a grignard reagent by a tubular continuous apparatus for producing a grignard reagent, the tubular continuous apparatus for producing a grignard reagent comprising a loop reaction apparatus, the loop reaction apparatus being provided with a driving apparatus for driving a material in the loop reaction apparatus and a temperature adjusting apparatus for heating the material in the loop reaction apparatus;

according to the flowing direction of the materials, a gridline raw material introducing pipeline, a slurry feeding device and a grignard reagent leading pipeline are sequentially arranged on the ring pipe reaction device, or the slurry feeding device, the raw material introducing pipeline and the grignard reagent leading pipeline are sequentially arranged on the ring pipe reaction device;

the Grignard reagent leading-out pipeline is also provided with a filtering device;

the continuous preparation method of the Grignard reagent specifically comprises the following steps:

1) introducing the Grignard raw material, the reaction solvent and the magnesium agent into a loop reaction device through a Grignard raw material introduction pipeline and a slurry feeding device;

2) the materials in the loop reaction device are driven by a driving device to react;

3) and the Grignard reagent product is led out through a Grignard reagent leading-out pipeline.

In some embodiments of the present invention, the residence time of the material in the loop reaction device is 2-120 min.

In some embodiments of the present invention, the flow rate of the material in the loop reaction device is 1-10 m/s.

In some embodiments of the present invention, the circulation ratio in the loop reaction apparatus is 10 to 300.

In some embodiments of the invention, the slurry feed means and the grignard reagent lead-out conduit are each located in close proximity to the grignard feed introduction conduit.

In some embodiments of the invention, the grignard feed introduction conduit and grignard reagent withdrawal conduit are each proximate to the slurry feed device.

In some embodiments of the invention, the slurry feed means is provided with a liquid phase inlet.

In some embodiments of the invention, the slurry feed means is provided with a solid phase inlet.

In some embodiments of the present invention, a flow regulating device is further disposed on the grignard reagent extraction conduit.

In some embodiments of the invention, the temperature regulating device is a jacket.

Drawings

FIG. 1 is a schematic view of the present invention.

FIG. 2 is a schematic view of the present invention.

Description of the element reference numerals

1 circular pipe reaction device

2 drive device

3 temperature regulating device

4-grid type raw material introducing pipeline

5 slurry feeding device

51 liquid phase inlet

52 solid phase inlet

6 Grignard reagent leading-out pipeline

61 Filter device

62 flow regulating device

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, and other advantages and effects of the present invention will be apparent to those skilled in the art from the disclosure of the present specification.

The inventor of the invention provides a tubular continuous device for producing the Grignard reagent through a large amount of practical research, can realize the efficient continuous preparation of the Grignard reagent by matching with specific process parameters, and has the advantages of high safety, low cost and the like, thereby completing the invention.

The first aspect of the present invention provides a tubular continuous apparatus for producing grignard reagent, as shown in fig. 1 and fig. 2, which may include a loop reaction apparatus 1, wherein the loop reaction apparatus 1 is provided with a driving apparatus 2 for driving materials in the loop reaction apparatus 1 and a temperature adjusting apparatus 3 for heating the materials in the loop reaction apparatus 1, and the loop reaction apparatus 1 is further provided with a grignard raw material introducing pipe 4, a slurry feeding apparatus 5 and a grignard reagent leading pipe 6 in sequence, or further provided with a slurry feeding apparatus 5, a raw material introducing pipe 4 and a grignard reagent leading pipe 6 in sequence, according to the flow direction of the materials. In the tubular continuous device for producing the grignard reagent, the grignard raw material can be continuously introduced into the loop reaction device 1 through the grignard raw material introduction pipe 4, and other raw materials can be mixed to form slurry and continuously introduced into the loop reaction device 1 through the slurry feeding device 5, the grignard raw material and other raw materials generally have a suitable ratio, the materials of the loop reaction device 1 can be driven by the driving device 2, the materials can be kept at a suitable temperature through the temperature adjusting device 3, the materials are sufficiently mixed and chemically reacted, and the obtained grignard reagent product can be continuously led out of the loop reaction device 1 through the grignard reagent leading pipe 6.

In the tubular continuous device for producing the grignard reagent, the loop reaction device 1 is mainly used for providing a reaction cavity. Suitable loop reactors 1 should be known to the person skilled in the art, for example loop reactor 1 generally refers to a pipe reactor comprising a loop reaction chamber, more particularly to a loop reactor or the like. The loop reactor apparatus 1 generally needs to be of suitable size to ensure a suitable residence time and flow rate of the material in the apparatus. For example, the length of the loop reaction apparatus 1 may be 0.2m to 1000m, 0.2m to 0.5m, 0.5m to 1m, 1m to 2m, 2m to 3m, 3m to 5m, 5m to 10m, 10m to 20m, 20m to 30m, 30m to 50m, 50m to 100m, 100m to 200m, 200m to 300m, 300m to 500m, or 500m to 1000m, and the inner diameter of the loop reaction apparatus 1 may be 0.1 to 2m, 0.1 to 0.2m, 0.2 to 0.4m, 0.4 to 0.6m, 0.6 to 0.8m, 0.8 to 1m, 1 to 1.5m, or 1.5 to 2 m. The shape, extension direction and the like of the loop reactor 1 should be suitably adjusted by those skilled in the art, for example, the loop reactor 1 may comprise a plurality of parallel straight tube sections, and may also extend in a meandering manner, and each straight tube section may be arranged vertically or horizontally.

In the tubular continuous apparatus for producing grignard reagent of the present invention, as described above, the driving device 2 is mainly used for driving the material in the loop reaction device 1 to flow in a certain direction. Suitable drive means 2 should be known to the person skilled in the art, for example, the drive means 2 may generally be a suitable pump body, more specifically a circulation pump, a vane pump, a centrifugal pump, an axial pump, a mixed flow pump, etc. The driving device 2 can drive the materials in the loop reaction device 1 to flow in a certain direction, and can also form a certain positive pressure environment in the loop reaction device 1.

In the tubular continuous device for producing the grignard reagent provided by the invention, as described above, the tubular loop reaction device 1 is further sequentially provided with the grignard raw material introduction pipeline 4, the slurry feeding device 5 and the grignard reagent extraction pipeline 6, or further sequentially provided with the slurry feeding device 5, the raw material introduction pipeline 4 and the grignard reagent extraction pipeline 6, according to the material flowing direction. Generally, the slurry feeding means 5 and the grignard reagent introduction conduit 6 may be respectively close to the grignard raw material introduction conduit 4, or the grignard raw material introduction conduit 4 and the grignard reagent introduction conduit 6 may be respectively close to the slurry feeding means 5, so that a sufficient distance between the slurry feeding means 5 or the grignard raw material introduction conduit 4 and the grignard reagent introduction conduit 6 can be secured, so that the two raw materials after mixing can have a sufficient residence time in the reaction conduit. For example, the length of the loop reaction apparatus 1 between the slurry feeding means 5 and the grignard reagent introduction line 6, or the length of the loop reaction apparatus 1 between the grignard reagent introduction line 4 and the grignard reagent introduction line 6 may be 50% or more, 60% or more, 70% or more, or 80% or more of the total length of the loop reaction apparatus 1.

In the tubular continuous apparatus for producing grignard reagent provided by the present invention, the slurry feeding apparatus 5 is generally used to provide a mixing and buffering space for the two liquid-solid feed streams, and can further introduce the slurry material into the loop reactor 1. Slurry feed means 5 may generally comprise a suitable vessel (e.g., tank, etc.), and slurry feed means 5 is also generally provided with a liquid phase inlet 51 and/or a solid phase inlet 52, so that liquid phase feedstock and solid phase feedstock may be introduced into slurry feed means 5 and, after being sufficiently mixed to form a slurry, further introduced into loop reaction means 1. The slurry feeding device 5 is usually operated under normal temperature, positive pressure, and inert gas blanket for the protection of the raw materials and the reaction system.

In the tubular continuous device for producing the Grignard reagent, the Grignard reagent leading-out pipeline 6 can be also provided with the filtering device 61, so that the unreacted magnesium reagent can be blocked in the cavity of the reactor when the Grignard reagent product is led out from the Grignard reagent leading-out pipeline 6. Suitable filter means 61 should be known to those skilled in the art, for example, the filter means 61 may generally comprise a filter medium of suitable pore size located in the duct.

In the tubular continuous device for producing the Grignard reagent, the Grignard reagent leading-out pipeline 6 is also provided with a flow regulating device 62, so that the leading-out amount of the material in the Grignard reagent leading-out pipeline 6 can be regulated. Suitable flow regulating devices 62 should be known to those skilled in the art, for example, the flow regulating devices 62 may generally be valves or the like.

In the tubular continuous apparatus for producing grignard reagent of the present invention, as described above, the temperature adjusting means 3 is mainly used for heat exchange, so that the material in the loop reaction apparatus 1 can be maintained in a suitable temperature range. Suitable temperature adjusting means 3 are known to those skilled in the art, for example, the temperature adjusting means 3 may be a jacket, which may be wrapped around the loop reactor 1, and for example, the temperature of the material in the loop reactor 1 may be maintained at 30-60 ℃, 30-40 ℃, 40-50 ℃, or 50-60 ℃.

The second aspect of the present invention provides a method for continuously preparing a grignard reagent by using the tubular continuous apparatus for producing a grignard reagent according to the first aspect of the present invention, wherein the method for continuously preparing a grignard reagent may specifically comprise:

1) introducing a Grignard raw material, a reaction solvent and a magnesium agent into a loop reaction device 1 through a Grignard raw material introduction pipe 4 and a slurry feeding device 5;

2) the materials in the loop reaction device 1 are driven by a driving device 2 to react;

3) the Grignard reagent product is led out through a Grignard reagent lead-out pipe 6.

The continuous preparation method of the Grignard reagent provided by the invention can comprise the following steps: the grignard raw material, the reaction solvent and the magnesium reagent are introduced into the loop reaction device 1 through the grignard raw material introduction pipe 4 and the slurry feeding device 5. Each stream as a reaction raw material generally needs to have certain fluidity so as to be smoothly introduced into the loop reaction device 1 to participate in the reaction, and for example, can be in the state of slurry, gas, liquid, etc. Suitable reaction starting materials which can serve as the Grignard, the reaction solvent and the magnesium reagent should be known to the person skilled in the art. For example, the Grignard reagent may generally include a compound of the formula R-X (formula I) wherein R is an aliphatic or aromatic hydrocarbon group and X is halogen, Cl, Br or I, etc., and specific examples thereof may be halogenated hydrocarbons, chlorobenzene, 3-chloropropene, cyclopropylbromide, bromomethane, 3, 5-difluorobromobenzene, 2, 3-difluoro-4-bromobenzene ethylether, etc. For example, the grignard raw material may further include a suitable reaction solvent (e.g., an ether solvent and/or an aromatic hydrocarbon solvent, the ether solvent may be diethyl ether, tetrahydrofuran, methyltetrahydrofuran, cyclopentylmethyl ether, dioxane, dimethoxyethane, or the like, and the aromatic hydrocarbon solvent may be toluene, or the like), and the ratio of the grignard raw material compound of formula I to the reaction solvent may be 1:0.1 to 20, 1:0.1 to 0.2, 1:0.2 to 0.4, 1:0.4 to 0.6, 1:0.6 to 0.8, 1:0.8 to 1, 1:1 to 1.5, 1:1.5 to 2, 1:2 to 3, 1:3 to 4, 1:4 to 6, 1:6 to 10, 1:10 to 15, or 1:15 to 20. For example, the grid material may be usually in a gaseous and/or liquid state, and the amount of the grid material introduced may be 0.1 to 10000kg/h, 0.1 to 0.2kg/h, 0.2 to 0.4kg/h, 0.4 to 0.6kg/h, 0.6 to 1kg/h, 1 to 2kg/h, 2 to 4kg/h, 4 to 6kg/h, 6 to 10kg/h, 10 to 20kg/h, 20 to 30kg/h, 30 to 50kg/h, 50 to 100kg/h, 100 to 200kg/h, 200 to 300kg/h, 300 to 500kg/h, 500 to 500kg/h, 500 kg/h-1000 kg/h, 1000 kg/h-2000 kg/h, 2000 kg/h-3000 kg/h, 3000 kg/h-5000 kg/h, or 5000 kg/h-10000 kg/h. For another example, a magnesium agent (e.g., magnesium chips, magnesium powder, etc., with a particle size of 0.5mm to 3mm) is usually mixed with a reaction solvent, and the magnesium agent and the reaction solvent are usually introduced into a slurry feeding device through a solid phase inlet 52 and a liquid phase inlet 51, respectively, to form a slurry, and then introduced into a loop reaction device 1 through a slurry feeding device 5, wherein the ratio of the magnesium agent to the reaction solvent in the slurry is 1:0.1 to 20, 1:0.1 to 0.2, 1:0.2 to 0.4, 1:0.4 to 0.6, 1:0.6 to 0.8, 1:0.8 to 1, 1:1 to 1.5, 1:1.5 to 2, 1:2 to 3, 1:3 to 4, 1:4 to 6, 1:6 to 10, 1:10 to 15, 1:15 to 20, 1:20 to 30, 1:30 to 40, 1:40 to 60, 1:60 to 80, 1:80 to 10, 1:10 to 100kg/h of the slurry, and 0.10 to 0.10 kg/h of the amount of the slurry introduced/1 to 0.10 kg/h of the slurry, 0.2kg/h to 0.4kg/h, 0.4kg/h to 0.6kg/h, 0.6kg/h to 1kg/h, 1kg/h to 2kg/h, 2kg/h to 4kg/h, 4kg/h to 6kg/h, 6kg/h to 10kg/h, 10kg/h to 20kg/h, 20kg/h to 30kg/h, 30kg/h to 50kg/h, 50 kg/h-100 kg/h, 100 kg/h-200 kg/h, 200 kg/h-300 kg/h, 300 kg/h-500 kg/h, 500 kg/h-1000 kg/h, 1000 kg/h-2000 kg/h, 2000 kg/h-3000 kg/h, 3000 kg/h-5000 kg/h, or 5000 kg/h-10000 kg/h. The amount of magnesium reagent phase introduced (molar amount) to the compound of formula I is substantially equivalent to the total amount of the reaction system, for example, the molar ratio of magnesium reagent to compound of formula I may be 1: 0.95-1.05, 1: 0.95-0.97, 1: 0.97-0.99, 1: 0.99 to 1.01, 1: 1.01 to 1.03, or 1: 1.03 to 1.05.

The continuous preparation method of the grignard reagent provided by the invention can also comprise the following steps: the materials in the loop reactor 1 are driven by the driving device 2 and reacted. The material is driven to flow circularly in the direction of the grid material inlet pipe 4, the slurry feeding device 5 and the Grignard reagent outlet pipe 6. The materials in the loop reactor 1 usually need to have proper residence time, material flow rate, pressure condition, etc., and especially need to have proper circulation ratio (ratio of circulation flow in the tube to total feed flow) to ensure the quality of the product. For example, the residence time of the material in the loop reaction device 1 (for example, the residence time of the material is the average time of the material passing through the reactor cavity under the total feeding flow) is usually not less than 2min, 2-120 min, 2-4 min, 4-6 min, 6-10 min, 10-15 min, 15-20 min, 20-30 min, 30-40 min, 40-60 min, 60-90 min, or 90-120 min. For another example, the flow rate of the material in the tube of the loop reactor 1 is usually not less than 1m/s, 1-10 m/s, 1-2 m/s, 2-4 m/s, 4-6 m/s, 6-8 m/s, or 8-10 m/s. For another example, the circulation ratio in the loop reactor 1 is usually not less than 10, 10 to 300, 10 to 15, 15 to 20, 20 to 30, 30 to 40, 40 to 60, 60 to 80, 80 to 100, 100 to 150, 150 to 200, 200 to 250, or 250 to 300. For another example, the loop reactor 1 is usually operated at a positive pressure, and the operating pressure may be 0.01 to 10.0MPa, 0.01 to 0.02MPa, 0.02 to 0.03MPa, 0.03 to 0.05MPa, 0.05 to 0.1MPa, 0.1 to 0.2MPa, 0.2 to 0.3MPa, 0.3 to 0.5MPa, 0.5 to 1MPa, 1 to 2MPa, 2 to 3MPa, 3 to 5MPa, or 5 to 10 MPa.

The continuous preparation method of the grignard reagent provided by the invention can also comprise the following steps: the Grignard reagent product is led out through a Grignard reagent lead-out pipe 6. After the reaction raw materials are fully reacted, the Grignard reagent product can be led out of the loop reaction device 1 through the Grignard reagent leading-out pipeline 6. The extracted Grignard reagent product mainly comprises a Grignard reagent, namely a compound with the general formula of R-Mg-X, and also can comprise a reaction solvent, and the Grignard reagent is usually dissolved in the reaction solvent.

The tubular continuous device for producing the Grignard reagent and the continuous preparation method of the Grignard reagent provided by the invention can effectively reduce the cumulant of unreacted materials, and the whole device needs to initiate reaction when being started, and does not need to initiate in the production process, thereby ensuring the production safety. In addition, the device can effectively miniaturize reaction equipment, realize longer retention time in the device, realize pressurizing conditions, is suitable for Grignard continuous reaction of halogenated substances with weaker activity or low boiling point, has wide application range, good universality and good industrialization prospect, and the conversion rate of raw materials can reach more than 95%.

The present application is further illustrated by the following examples, which are not intended to limit the scope of the present application.

Example 1

The Grignard raw material used in this example was chlorobenzene, the Grignard solvent was a mixture of toluene and tetrahydrofuran, and the magnesium agent was 0.5mm to 3mm magnesium chips.

The reaction equation is:

the loop reactors are vertically arranged in groups (DN150, 42 m);

the operation method comprises the following steps:

the magnesium agent and the solvent respectively enter a slurry feeder from a magnesium agent inlet and a solvent inlet, the magnesium agent and the solvent continuously enter a loop reactor after the slurry feeder is mixed, the Grignard raw material enters the loop reactor from a Grignard raw material inlet, a reaction material circulates at a high speed in the loop reactor under the push of a circulating pump (adopting an axial flow pump) and carries out chemical reaction, mass transfer and heat transfer, the generated Grignard reagent is continuously discharged from a Grignard reagent outlet, and a filter keeps the unreacted magnesium agent in the reactor.

In the reaction process, the magnesium agent, the solvent and the Grignard raw material continuously enter the loop reactor according to the proportion, and the temperature of the reaction material is controlled by the heat exchange medium through the jacket;

in the reaction process, the operation temperature of the loop reactor is 60 ℃, the operation pressure is 0.15MPa, the average retention time of the materials in the reactor is 120min, the circulation ratio is 100, and the average flow velocity of the materials in the tube is 5 m/s;

the feed flow rates of the grignard material, magnesium reagent, and solvent are shown in the following table;

material(s)	Substance(s)	Flow rate kg/h	Phase state
				Grignard feedstock	Chlorobenzene	450	Liquid phase
Magnesium agent	Magnesium chips	97	Solid phase particles
				Solvent 1	Toluene	700	Liquid phase
Solvent 2	Tetrahydrofuran (THF)	700	Liquid phase

The conversion of chlorobenzene at the outlet of the grignard reagent was 98%.

Example 2

Example 2 is substantially the same as example 1 except that the magnesium reagent is 100 mesh magnesium powder, the operating temperature is 55 ℃, the average flow rate of the material in the tube is 2m/s, and the conversion of chlorobenzene at the outlet of the grignard reagent is 98%.

Example 3

Example 3 is essentially the same as example 1 except that the circulation pump is a centrifugal pump, the average residence time of the reactor contents is 80min, the circulation ratio is 300, and the conversion of chlorobenzene at the grignard reagent outlet is 98%.

Example 4

The Grignard raw material used in the embodiment is 3-chloropropene, the solvent is tetrahydrofuran, and the magnesium agent is 0.5mm-3mm magnesium chips, and the feeding molar ratio of the three is 1:10: 1.

The reaction equation is:

the circulating pump is a centrifugal pump, the loop reactor is horizontally arranged in a single group, the operating temperature of the loop reactor is 35 ℃, the operating pressure is 0.25MPa, the average retention time of materials in the reactor is 120min, the circulating ratio is 180, the average flow velocity of the materials in the tube is 3m/s, and the conversion rate of 3-chloropropene at the Grignard reagent outlet is 98 percent in the reaction process.

Example 5

The Grignard raw material used in the embodiment is cyclopropyl bromide, the solvent is diethyl ether, and the magnesium agent is 100-mesh magnesium powder, and the feeding molar ratio of the cyclopropyl bromide, the diethyl ether and the magnesium agent is 1:6: 1.

The reaction equation is:

the circulating pump is an axial flow pump, the loop reactor is horizontally arranged in a single group, in the reaction process, the operating temperature of the loop reactor (1) is 58 ℃, the operating pressure is 0.5MPa, the average retention time of materials in the reactor is 20min, the circulation ratio is 120, the average flow velocity of the materials in the tube is 3m/s, and the conversion rate of cyclopropyl bromine at the outlet of the Grignard reagent is 96.8%.

Example 6

The Grignard raw material used in the present example is methyl bromide (gaseous), the solvent is diethyl ether, and the magnesium agent is 100 mesh magnesium powder, and the feeding molar ratio of the three is 1:8: 1.

The reaction equation is:

CH₃Br+Mg→CH₃MgBr

the circulating pump is an axial flow pump, the loop reactor is horizontally arranged in a single group, the operating temperature of the loop reactor is 30 ℃, the operating pressure is 0.3MPa, the average retention time of materials in the reactor is 30min, the circulating ratio is 120, the average flow velocity of the materials in the loop is 3m/s, and the conversion rate of the bromomethane at the outlet of the Grignard reagent is 95.5 percent in the reaction process.

Example 7

In the embodiment, the Grignard raw material is 3, 5-difluorobromobenzene, the solvent is tetrahydrofuran, and the magnesium agent is 200-mesh magnesium powder, the feeding molar ratio of the three is 1:12:1, wherein half of the flow of the solvent enters the reactor from the solvent inlet, and the other half of the solvent is mixed with the Grignard raw material and then enters the reactor from the Grignard raw material inlet.

The reaction equation is:

the circulating pump is an axial flow pump, the loop reactor is horizontally arranged in a single group, the operating temperature of the loop reactor is 45 ℃, the operating pressure is 0.13MPa, the average retention time of materials in the reactor is 90min, the circulating ratio is 80, the average flow velocity of the materials in the tube is 2m/s, and the conversion rate of 3, 5-difluorobromobenzene at the Grignard reagent outlet is 95.5 percent in the reaction process.

Example 8

The Grignard raw material used in the embodiment is 2, 3-difluoro-4-bromobenzene ethyl ether, the solvent is tetrahydrofuran, and the magnesium agent is 200-mesh magnesium powder, and the feeding molar ratio of the three is 1:8: 1.

The reaction equation is:

the circulating pump is an axial flow pump, the loop reactor is horizontally arranged in a single group, the operating temperature of the loop reactor is 36 ℃, the operating pressure is 0.18MPa, the average retention time of materials in the reactor is 160min, the circulating ratio is 600, the average flow velocity of the materials in the tube is 6m/s, and the conversion rate of 2, 3-difluoro-4-bromophenylether at the Grignard reagent outlet is 99.1 percent.

In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.