Integrated high-safety mechanical-stirring-free Grignard reagent preparation device and process

Abstract

The invention discloses an integrated high-safety mechanical-stirring-free Grignard reagent preparation device and process, the device comprises a material feeding module, a Grignard reagent stirring-free preparation module and a Grignard reagent using module, aiming at the characteristics of a Grignard reagent preparation solid-liquid reaction, a tower type fixed bed reactor is used for replacing a traditional kettle type reactor, and the Grignard reagent stirring-free preparation module is used for preparing the Grignard reagent. The problem that the service life of equipment is influenced by collision between stirring of the tank reactor and solid magnesium is solved; by arranging the detachable preloaded solid magnesium filler layer, the safety problem of solid magnesium feeding in a class A workshop is solved; a plurality of reactors are connected in parallel, and the whole feeding and discharging rate is not influenced by single disassembly and assembly, so that the continuity of the whole fine chemical reaction process is realized; through reasonable integration of the tower type fixed bed reactor, the circulating cooler and the circulating pump, integration of the Grignard reagent stirring-free preparation module and modularization of the device are realized, the occupied area is reduced, and the operation process is solidified.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemical safety, and in particular relates to an integrated high-safety Grignard reagent preparation device and process without mechanical stirring. Background Art

[0002] The Grignard reaction is one of the most classic carbon-carbon bond formation reactions in organic chemistry. It plays an important role in organic synthesis and drug preparation. A variety of compounds with different structures and properties can be prepared through the Grignard reaction, and it is widely used in actual industrial production.

[0003] Grignard reagent, one of the raw materials of Grignard reaction, is extremely active and cannot be stored. It can only be prepared when it is used. However, there are still some problems in the preparation of Grignard reagent: The preparation of Grignard reagent is mainly carried out by halogenated hydrocarbons and metallic magnesium in a solvent system. Magnesium, as one of the reactants, is used in large amounts and its hardness cannot be ignored. In the most commonly used autoclave reactor, it collides and rubs against the stirring paddle severely, which greatly reduces the life of the stirring paddle.

[0004] Magnesium metal, the raw material for preparing Grignard reagent, reacts violently when it comes into contact with water or moisture, releasing hydrogen and heat, causing combustion and explosion. Currently, magnesium metal is fed through silos, and during the feeding process, it is exposed to the air in large quantities, posing a safety hazard.

[0005] The preparation of Grignard reagents is often a highly exothermic reaction. Preparation in a batch reactor is not only inefficient, but also has a large amount of material. If it gets out of control accidentally, the consequences are often serious.

[0006] The current reaction devices have a low degree of integration, occupy a large area, and have a variety of facility configurations and equipment layouts, which not only cause trouble for engineering design, but also are not conducive to the standardization of hazardous process operations.

[0007] Developing a safe, reliable, and continuous Grignard reagent preparation device and process not only has objective economic returns such as improving production efficiency and increasing equipment life, but also can effectively reduce the probability of accidents and increase the safety of the process. Summary of the invention

[0008] In view of the above problems, the object of the present invention is to provide an integrated high-safety Grignard reagent preparation device and process without mechanical stirring.

[0009] The specific technical solutions are as follows: The invention discloses an integrated high-safety Grignard reagent preparation device without mechanical stirring, comprising a material feeding module, a Grignard reagent preparation module without stirring and a Grignard reagent using module. The Grignard reagent preparation module without stirring comprises a plurality of tower fixed bed reaction systems connected in parallel, each tower fixed bed reaction system comprises a tower fixed bed reactor, a circulating cooler and a circulating pump, a top outlet pipeline of the tower fixed bed reactor is connected with the circulating cooler, a bottom outlet pipeline of the circulating cooler is divided into two pipelines, one pipeline is connected with the bottom of the tower fixed bed reactor through a circulating pump, and the other pipeline is connected with the Grignard reagent using module, the material feeding module is connected with the bottom of the tower fixed bed reactor through the circulating pump, the upper part and the lower part of the tower fixed bed reactor are respectively provided with detachable flanges, a metal magnesium filler layer is provided in the middle part of the tower fixed bed reactor between the detachable flanges, a filter screen is provided at the upper and lower ends of the metal magnesium filler layer, a discharge filter layer is provided in the top of the tower fixed bed reactor, a feed distributor is provided in the bottom of the tower fixed bed reactor, and the feed distributor is connected with the circulating pump through a pipeline.

[0010] Furthermore, the material feeding module includes a halogenated hydrocarbon / THF mixed liquid feed tank, a feed tank replenishment system, an initiator feed system and a quencher feed system. The feed tank replenishment system is connected to the halogenated hydrocarbon / THF mixed liquid feed tank. The discharge pipe of the halogenated hydrocarbon / THF mixed liquid feed tank is divided into multiple pipelines, each pipeline is respectively connected to a group of tower fixed bed reaction systems, the discharge pipe of the initiator feed system is divided into multiple pipelines, each pipeline is respectively connected to a group of tower fixed bed reaction systems, and the discharge pipe of the quencher feed system is divided into multiple pipelines, each pipeline is respectively connected to a group of tower fixed bed reaction systems.

[0011] Furthermore, the Grignard reagent use module includes two groups of Grignard reagent receiving systems, each group of Grignard reagent receiving systems includes a Grignard reagent feed control device and a Grignard reagent high-level tank, the Grignard reagent feed control device is arranged on the top of the Grignard reagent high-level tank, and the discharge pipes of multiple groups of tower fixed bed reaction systems are merged and connected into one pipeline, and the one pipeline is further divided into two pipelines, which are respectively connected to the Grignard reagent feed control devices of the two groups of Grignard reagent receiving systems, and the bottom discharge ports of the Grignard reagent high-level tanks of the two groups of Grignard reagent receiving systems are merged and connected to the Grignard reaction safety control component.

[0012] Furthermore, the Grignard reagent feed control device includes a remote level gauge arranged on the Grignard reagent high-level tank and a feed start switch valve interlocked with the remote level gauge; the Grignard reaction safety control component includes a drop addition pneumatic regulating valve and a discharge pneumatic switch valve.

[0013] Furthermore, both the halogenated hydrocarbon / THF mixed liquid feed tank and the Grignard reagent high-level tank are provided with nitrogen sealing and tail gas pipes.

[0014] Furthermore, multiple groups of tower fixed bed reaction systems are arranged on a movable bracket, and the movable bracket includes multiple groups of mounting frames, which are fixedly connected to each other. One group of tower fixed bed reaction systems is correspondingly installed on one group of mounting frames. The bottom of each group of mounting frames is provided with rotatable and foldable movable legs, and the inner side of the movable legs is provided with limit grooves. The bottom of the mounting frame is provided with sliding blocks, one end of the limit groove is a through opening, and the other end is a limit structure. The sliding block slides from the through opening to the limit structure, thereby realizing the limit fixation of the movable legs.

[0015] A Grignard reagent preparation process using an integrated high-safety Grignard reagent preparation device without mechanical stirring comprises the following steps: 1) Nitrogen replacement, start the circulating cooler, the halogenated hydrocarbon / THF mixed liquid is buffered by the halogenated hydrocarbon / THF mixed liquid feed tank, the halogenated hydrocarbon / THF mixed liquid enters the tower fixed bed reactor through the circulating pump and contacts the metal magnesium filler layer, and at the same time, the initiator is introduced into the tower fixed bed reactor through the initiator feeding system to initiate the Grignard reagent preparation reaction. After the reaction starts, the liquid phase fills the tower fixed bed reactor, and under the action of the circulating pump, it continuously passes through the tower fixed bed reactor to react with magnesium to release heat to generate the Grignard reagent, and then passes through the circulating cooler to control the temperature to a safe temperature; 2) Detect the product concentration at the outlet of the circulating cooler. When the product concentration reaches the requirement, close the circulating reaction pipeline and introduce the Grignard reagent at the outlet of the tower fixed bed reactor into the Grignard reagent high-level tank; 3) After the discharge of step 2) is completed, the circulating reaction pipeline is switched back, and the feed pipeline is switched to the quenching agent feed system to introduce the quenching agent into the tower fixed bed reactor. After the circulating quenching, the feed is switched to nitrogen, and the discharge is switched to sewage discharge to purge the liquid phase material in the tower fixed bed reaction system; 4) Remove the metal magnesium packing layer of the cleaned tower fixed bed reaction system by disassembling the detachable flange and replace it with a new packing; 5) After the packing is replaced, the tower fixed bed reaction system re-enters the next reaction cycle, and multiple groups of tower fixed bed reaction systems react and replace alternately to ensure the continuous reaction; 6) The Grignard reagent high-level tank of one group of Grignard reagent receiving systems is in a dripping and discharging state, and the discharging speed is controlled by the Grignard reaction safety control component. The Grignard reagent high-level tank of another group of Grignard reagent receiving systems is in a receiving state. When the Grignard reagent high-level tank in the receiving state reaches the upper limit of the receiving state, the Grignard reagent high-level tank in the dripping state has finished dripping, and the Grignard reagent feed control device switches the working state of the Grignard reagent high-level tank, and so on and so forth to achieve continuous production; the dripping state, that is, the feed start switch valve is closed, the dripping pneumatic regulating valve and the discharging pneumatic switch valve are opened, and the temperature signal of the discharge port is received to adjust the discharging opening, the receiving state, that is, the feed start switch valve is opened, and the dripping pneumatic regulating valve and the discharging pneumatic switch valve are closed.

[0016] Furthermore, the refrigerant of the circulating cooler is a non-aqueous phase refrigerant selected from thermal oil, Freon or ethanol.

[0017] The beneficial effects of the present invention are: 1) The present invention uses a tower fixed bed reactor to replace the traditional kettle reactor in view of the characteristics of the solid-liquid reaction in the preparation of Grignard reagents. A stirring paddle is no longer used to ensure the solid-liquid contact efficiency. Instead, a circulating pump and a feed distributor are used to ensure full solid-liquid contact, thereby solving the problem that the stirring of the kettle reactor and the collision of solid magnesium affect the equipment life. 2) The present invention aims at the hidden danger of explosion hazard caused by large amount of magnesium metal feeding and water and moisture when it comes into contact with air. By providing a detachable pre-installed solid magnesium filling layer, the dangerous magnesium metal filling process is transferred outside the production workshop, thereby avoiding secondary disasters caused by the explosion of magnesium metal in Class A and B media in the workshop, eliminating the possibility of accidents in the magnesium feeding process in the workshop, solving the possibility of accidents in the solid magnesium feeding process when preparing Grignard reagent, and solving the safety problem of solid magnesium feeding when preparing Grignard reagent; 3) The present invention aims at solving the problems existing in the current kettle process for preparing Grignard reagents. Multiple tower fixed bed reaction systems are connected in parallel. The disassembly and assembly of a single unit does not affect the overall feeding and discharging rate, thus realizing the continuity of the entire fine chemical reaction process. Due to the continuous production, the liquid holding volume of the entire device is greatly reduced, which not only increases the heat exchange effect, but also reduces the severity of the consequences of accidents. 4) The present invention rationally integrates the tower fixed reactor, the circulating cooler, and the circulating pump into a tower fixed bed reaction system and encapsulates it in a frame, thereby realizing the integration of the Grignard reagent non-stirring preparation module and the modularization of the device, and reducing the footprint of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a schematic diagram of the process of the present invention; Figure 2 It is a structural schematic diagram of a tower fixed bed reaction system; Figure 3It is a top view schematic diagram of the material feeding module and the Grignard reagent non-stirring preparation module after installation of the present invention; Figure 4 is a side view of the movable bracket; Figure 5 It is a schematic diagram of the working mode of the movable outrigger; Figure 6 It is a side view of the movable outrigger.

[0019] In the figure: 1. tower fixed bed reaction system; 11. tower fixed bed reactor; 111. detachable flange; 112. metal magnesium filler layer; 113. filter screen; 114. discharge filter layer; 115. feed distributor; 12. circulating cooler; 13. circulating pump; 2. halogenated hydrocarbon / THF mixed liquid feed tank; 3. feed tank replenishment system; 4. initiator feed system; 5. quencher feed system; 6. Grignard reagent receiving system; 61. Grignard reagent feed control device; 62. Grignard reagent high-level tank; 7. Grignard reaction safety control component; 8. movable bracket; 81. mounting frame; 811. movable support leg; 8111. limit groove; 8112. sliding block. DETAILED DESCRIPTION

[0020] The present invention is further described below in conjunction with the accompanying drawings and embodiments, but the protection scope of the present invention is not limited thereto.

[0021] like Figure 1 and Figure 2 As shown, an integrated high-safety non-mechanical stirring Grignard reagent preparation device includes a material feeding module ( Figure 1 A in), Grignard reagent non-stirring preparation module ( Figure 1 B) and Grignard reagent using module ( Figure 1C), the Grignard reagent non-stirring preparation module includes a plurality of tower fixed bed reaction systems 1 connected in parallel, each tower fixed bed reaction system 1 includes a tower fixed bed reactor 11, a circulating cooler 12 and a circulating pump 13, the top outlet pipeline of the tower fixed bed reactor 11 is connected to the circulating cooler 12, the bottom outlet pipeline of the circulating cooler 12 is divided into two pipelines, one pipeline is connected to the bottom of the tower fixed bed reactor 11 through the circulating pump 13, and the other pipeline is connected to the Grignard reagent using module, and the material feeding module is connected to the tower fixed bed reactor 1 through the circulating pump 13. 1 is connected to the bottom, the upper and lower parts of the tower fixed bed reactor 11 are respectively provided with detachable flanges 111, a metal magnesium filler layer 112 is provided in the middle part of the tower fixed bed reactor 11 between the detachable flanges 111, and a filter screen 113 is provided at the upper and lower ends of the metal magnesium filler layer 112, respectively, a discharge filter layer 114 is provided in the top of the tower fixed bed reactor 11, and a feed distributor 115 is provided in the bottom of the tower fixed bed reactor 11, and the feed distributor 115 is connected to the circulation pump 13 through a pipeline, and the material feeding module includes a halogenated hydrocarbon / THF mixed liquid feeding Tank 2, feed tank replenishment system 3, initiator feed system 4 and quencher feed system 5, the feed tank replenishment system 3 is connected to the halogenated hydrocarbon / THF mixed liquid feed tank 2, the discharge pipe of the halogenated hydrocarbon / THF mixed liquid feed tank 2 is divided into multiple pipelines, each pipeline is respectively connected to a group of tower fixed bed reaction systems 1, the discharge pipe of the initiator feed system 4 is divided into multiple pipelines, each pipeline is respectively connected to a group of tower fixed bed reaction systems 1, the discharge pipe of the quencher feed system 5 is divided into multiple pipelines, each pipeline is respectively connected to a group of tower fixed bed reaction systems 1, and the Grignard reagent use module package It includes two groups of Grignard reagent receiving systems 6, each group of Grignard reagent receiving systems 6 includes a Grignard reagent feeding control device 61 and a Grignard reagent high-level tank 62, the Grignard reagent feeding control device 61 is arranged on the top of the Grignard reagent high-level tank 62, the discharge pipes of multiple groups of tower fixed bed reaction systems 1 are merged and connected into a pipeline, and the pipeline is further divided into two pipelines, which are respectively connected to the Grignard reagent feeding control devices 61 of the two groups of Grignard reagent receiving systems 6, and the bottom discharge ports of the Grignard reagent high-level tanks 62 of the two groups of Grignard reagent receiving systems 6 are merged and connected to the Grignard reaction safety control component 7. Both the halogenated hydrocarbon / THF mixed liquid feed tank 2 and the Grignard reagent high-level tank 62 are provided with nitrogen seals and tail gas pipes. The Grignard reagent feed control device 61 includes a remote liquid level gauge provided on the Grignard reagent high-level tank 62 and a feed start switch valve interlocked with the remote liquid level gauge; the Grignard reaction safety control component 7 includes a drop addition pneumatic regulating valve and a discharge pneumatic switch valve.

[0022] like Figures 3 to 6As shown, multiple groups of tower fixed bed reaction systems 1 are arranged on a movable bracket 8, and the movable bracket 8 includes multiple groups of mounting frames 81, and the mounting frames 81 are fixedly connected. One group of tower fixed bed reaction systems 1 is correspondingly installed on one group of mounting frames 81, and the bottom of each group of mounting frames 81 is provided with a rotatable and foldable movable leg 811, and the inner side of the movable leg 811 is provided with a limiting groove 8111, and the bottom of the mounting frame 81 is provided with a sliding block 8112, one end of the limiting groove 8111 is a through opening, and the other end is a limiting structure. After the movable leg 811 is folded, the sliding block 8112 slides from the through opening to the limiting structure, thereby realizing the limiting fixation of the movable leg 811. At this time, a large space is reserved at the bottom of the movable bracket 8, which can be used to place the material feeding module.

[0023] A Grignard reagent preparation process using the above-mentioned integrated high-safety Grignard reagent preparation device without mechanical stirring comprises the following steps: 1) Nitrogen replacement, open the circulating cooler 12, the halogenated hydrocarbon / THF mixed liquid is buffered by the halogenated hydrocarbon / THF mixed liquid feed tank 2, the halogenated hydrocarbon / THF mixed liquid enters the tower fixed bed reactor 11 through the circulating pump 13 and contacts with the metal magnesium filler layer 112, and at the same time, the initiator is introduced into the tower fixed bed reactor 11 through the initiator feeding system 4 to initiate the Grignard reagent preparation reaction. After the reaction starts, the liquid phase fills the tower fixed bed reactor 11, and under the action of the circulating pump 13, it continuously passes through the tower fixed bed reactor 11 to react with magnesium to generate Grignard reagent by exothermic reaction, and then passes through the circulating cooler 12 to control the temperature to a safe temperature; 2) Detect the product concentration at the outlet of the circulating cooler 12. When the product concentration reaches the required level, close the circulating reaction pipeline and introduce the Grignard reagent at the outlet of the tower fixed bed reaction system 1 into the Grignard reagent high-level tank 62; 3) After the discharge of step 2) is completed, the circulating reaction pipeline is switched back, and the feed pipeline is switched to the quenching agent feeding system 5 to introduce the quenching agent into the tower fixed bed reactor 11. After the circulating quenching, the feed is switched to nitrogen, and the discharge is switched to sewage discharge to purge the liquid phase material in the tower fixed bed reaction system 1; 4) The cleaned metal magnesium filler layer 112 of the tower fixed bed reaction system 1 is removed by disassembling the removable flange 111 and replaced with a new filler; 5) After the packing is replaced, the tower fixed bed reaction system 1 re-enters the next reaction cycle, and multiple groups of tower fixed bed reaction systems 1 react and replace alternately to ensure the continuous progress of the reaction; 6) A Grignard reagent high-level tank 62 of one Grignard reagent receiving system 6 is in a dripping state, and the discharge speed is controlled by the Grignard reaction safety control component 7. Another Grignard reagent high-level tank 62 of the other Grignard reagent receiving system 6 is in a receiving state. When the Grignard reagent high-level tank 62 in the receiving state reaches the upper limit of the receiving, the Grignard reagent high-level tank 62 in the dripping state has finished dripping, and the Grignard reagent feeding control device 61 switches the working state of the Grignard reagent high-level tank 62. This cycle is repeated to achieve continuous production. In the dripping state, the feeding start switch valve is closed, and the dripping pneumatic regulating valve and the discharge pneumatic switch valve are opened. At the same time, the temperature signal of the discharge port is received to adjust the discharge opening. In the receiving state, the feeding start switch valve is opened, and the dripping pneumatic regulating valve and the discharge pneumatic switch valve are closed.

[0024] Example 1

[0025] The device and process of the present invention are used to produce a pesticide intermediate. The raw material of the Grignard reagent preparation process is butyl chloride, the raw material dosage is 60kg / h, the initiator is butyl bromide, the initiator dosage is 6kg / h, the solvent is tetrahydrofuran, the solvent amount is 348kg / h, and the metal magnesium dosage is 15kg / h; the reaction time required for a single tower fixed bed reaction system 1 is 6h, the number of tower fixed bed reaction systems 1 used is 6 sets, and the volume of the halogenated hydrocarbon / THF mixed liquid feed tank 2 is 3000L; the refrigerant used is -15°C heat transfer oil, the obtained reactant flow rate is 429kg / h, and the reaction product concentration is 18.88%.

[0026] Example 2

[0027] The device and process of the present invention are used to produce a certain raw material medicine. The raw material of the Grignard reagent preparation process is ethyl bromide, the raw material dosage is 40kg / h, the initiator is iodine, the initiator dosage is 4kg / h, the solvent is tetrahydrofuran, the solvent amount is 220kg / h, and the metal magnesium dosage is 10kg / h; the required reaction time of a single tower fixed bed reaction system 1 is 4h, the number of tower fixed bed reaction systems 1 used is 4 sets, and the volume of the feed tank is 2000L; the refrigerant used is -25°C heat transfer oil, the obtained reactant flow rate is 274kg / h, and the reaction product concentration is 19.71%.

[0028] Example 3

[0029] The device and process of the present invention are used to produce a health product. The raw material of the Grignard reagent preparation process is chloropropane, the raw material dosage is 20kg / h, the initiator is potassium iodide, the initiator dosage is 2kg / h, the solvent is methyltetrahydrofuran, the solvent amount is 120kg / h, and the metal magnesium dosage is 5kg / h; the reaction time required for a single tower fixed bed reaction system 1 is 8h, the number of tower fixed bed reaction systems 1 used is 8 sets, and the volume of the feed tank is 4000L; the refrigerant used is -35°C ethanol, the obtained reactant flow rate is 147kg / h, and the reaction product concentration is 18.37%.

[0030] Example 4

[0031] The device and process of the present invention are used to produce a food additive. The raw material of the Grignard reagent preparation process is butyl chloride, the raw material dosage is 25kg / h, the initiator is butyl bromide, the initiator dosage is 2.5kg / h, the solvent is methyltetrahydrofuran, the solvent amount is 125kg / h, and the amount of metal magnesium is 6.25kg / h; the reaction time required for a single tower fixed bed reaction system 1 is 6h, the number of tower fixed bed reaction systems 1 used is 6 sets, and the volume of the feed tank is 3000L; the refrigerant used is Freon, the obtained reactant flow rate is 158.75kg / h, and the concentration of the reaction product is 21.26%.

[0032] Example 5

[0033] The device and process of the present invention are used to produce a pesticide intermediate. The raw material of the Grignard reagent preparation process is ethyl bromide, the raw material dosage is 80kg / h, the initiator is iodine, the initiator dosage is 8kg / h, the solvent is ether, the solvent amount is 465kg / h, and the metal magnesium dosage is 20kg / h; the reaction time required for a single tower fixed bed reaction system 1 is 4h, the number of tower fixed bed reaction systems 1 used is 4 sets, and the volume of the feed tank is 2000L; the refrigerant used is -15°C heat transfer oil, the obtained reactant flow rate is 573kg / h, and the reaction product concentration is 18.85%.

[0034] Example 6

[0035] The device and process of the present invention are used to produce a certain raw material medicine. The raw material of the Grignard reagent preparation process is chloropropane, the raw material dosage is 100kg / h, the initiator is bromopropane, the initiator dosage is 10kg / h, the solvent is ether, the solvent amount is 600kg / h, and the metal magnesium dosage is 25kg / h; the reaction time required for a single tower fixed bed reaction system 1 is 8h, the number of tower fixed bed reaction systems 1 used is 8 sets, and the volume of the feed tank is 4000L; the refrigerant used is -25°C heat transfer oil, the obtained reactant flow rate is 735kg / h, and the reaction product concentration is 18.37%.

[0036] Example 7

[0037] The device and process of the present invention are used to produce a health product. The raw material of the Grignard reagent preparation process is chlorobutane, the raw material dosage is 80kg / h, the initiator is iodine, the initiator dosage is 8kg / h, the solvent is tetrahydrofuran, the solvent amount is 450kg / h, and the metal magnesium dosage is 20kg / h; the reaction time required for a single tower fixed bed reaction system 1 is 10h, the number of tower fixed bed reaction systems 1 used is 10 sets, and the volume of the feed tank is 5000L; the refrigerant used is -35°C ethanol, the obtained reactant flow rate is 558kg / h, and the reaction product concentration is 19.35%.

[0038] Example 8

[0039] The device and process of the present invention are used to produce a food additive. The raw material of the Grignard reagent preparation process is ethyl bromide, the raw material dosage is 25kg / h, the initiator is potassium iodide, the initiator dosage is 2.5kg / h, the solvent is tetrahydrofuran, the solvent amount is 130kg / h, and the metal magnesium dosage is 6.25kg / h; the required reaction time of a single tower fixed bed reaction system 1 is 12h, the number of tower fixed bed reaction systems 1 used is 12 sets, and the volume of the feed tank is 6000L; the refrigerant used is Freon, the obtained reactant flow rate is 163.75kg / h, and the concentration of the reaction product is 20.61%.

[0040] Example 9

[0041] The device and process of the present invention are used to produce a pesticide intermediate. The raw material of the Grignard reagent preparation process is chloropropane, the raw material dosage is 60kg / h, the initiator is potassium iodide, the initiator dosage is 6kg / h, the solvent is methyltetrahydrofuran, the solvent amount is 320kg / h, and the metal magnesium dosage is 15kg / h; the reaction time required for a single tower fixed bed reaction system 1 is 6h, the number of tower fixed bed reaction systems 1 used is 6 sets, and the volume of the feed tank is 3000L; the refrigerant used is -15°C heat transfer oil, the obtained reactant flow rate is 401kg / h, and the reaction product concentration is 20.20%.

[0042] Example 10

[0043] The device and process of the present invention are used to produce a certain raw material medicine. The raw material of the Grignard reagent preparation process is chlorobutane, the raw material dosage is 40kg / h, the initiator is iodine, the initiator dosage is 4kg / h, the solvent is methyltetrahydrofuran, the solvent amount is 250kg / h, and the metal magnesium dosage is 10kg / h; the required reaction time of a single tower fixed bed reaction system 1 is 4h, the number of tower fixed bed reaction systems 1 used is 4 sets, and the volume of the feed tank is 2000L; the refrigerant used is -25°C heat transfer oil, the obtained reactant flow rate is 304kg / h, and the reaction product concentration is 17.76%.

[0044] Embodiment 11

[0045] The device and process of the present invention are used to produce a health product. The raw material of the Grignard reagent preparation process is ethyl bromide, the raw material dosage is 50kg / h, the initiator is iodine, the initiator dosage is 5kg / h, the solvent is ether, the solvent amount is 300kg / h, and the metal magnesium dosage is 12.5kg / h; the reaction time required for a single tower fixed bed reaction system 1 is 8h, the number of tower fixed bed reaction systems 1 used is 8 sets, and the volume of the feed tank is 4000L; the refrigerant used is -35°C ethanol, the obtained reactant flow rate is 367.5kg / h, and the reaction product concentration is 18.37%.

[0046] Example 12

[0047] The device and process of the present invention are used to produce a food additive. The raw material of the Grignard reagent preparation process is chloropropane, the raw material dosage is 90kg / h, the initiator is bromopropane, the initiator dosage is 9kg / h, the solvent is ether, the solvent amount is 500kg / h, and the metal magnesium dosage is 22.5kg / h; the reaction time required for a single tower fixed bed reaction system 1 is 10h, the number of tower fixed bed reaction systems 1 used is 10 sets, and the volume of the feed tank is 5000L; the refrigerant used is Freon, the obtained reactant flow rate is 621.5kg / h, and the reaction product concentration is 19.55%.

Claims

1. An integrated high-safety Grignard reagent preparation device without mechanical stirring, characterized in that: The invention comprises a material feeding module, a Grignard reagent non-stirring preparation module and a Grignard reagent using module. The Grignard reagent non-stirring preparation module comprises a plurality of tower fixed bed reaction systems (1) connected in parallel. Each tower fixed bed reaction system (1) comprises a tower fixed bed reactor (11), a circulating cooler (12) and a circulating pump (13). The top outlet pipeline of the tower fixed bed reactor (11) is connected to the circulating cooler (12). The bottom outlet pipeline of the circulating cooler (12) is divided into two pipelines. One pipeline is connected to the bottom of the tower fixed bed reactor (11) through the circulating pump (13). The other pipeline is connected to the Grignard reagent using module. The material feeding module The tower fixed bed reactor (11) is connected to the bottom of the tower fixed bed reactor (11) via a circulation pump (13); the upper and lower parts of the tower fixed bed reactor (11) are respectively provided with detachable flanges (111); a metal magnesium filler layer (112) is provided in the middle part of the tower fixed bed reactor (11) between the detachable flanges (111); filter screens (113) are respectively provided at the upper and lower ends of the metal magnesium filler layer (112); a discharge filter layer (114) is provided in the top of the tower fixed bed reactor (11); a feed distributor (115) is provided in the bottom of the tower fixed bed reactor (11); and the feed distributor (115) is connected to the circulation pump (13) via a pipeline.

2. An integrated high-safety Grignard reagent preparation device without mechanical stirring as claimed in claim 1, characterized in that: The material feeding module comprises a halogenated hydrocarbon / THF mixed liquid feeding tank (2), a feeding tank replenishing system (3), an initiator feeding system (4) and a quenching agent feeding system (5). The feeding tank replenishing system (3) is connected to the halogenated hydrocarbon / THF mixed liquid feeding tank (2). The discharge pipe of the halogenated hydrocarbon / THF mixed liquid feeding tank (2) is divided into multiple pipes, each of which is respectively connected to a group of tower fixed bed reaction systems (1). The discharge pipe of the initiator feeding system (4) is divided into multiple pipes, each of which is respectively connected to a group of tower fixed bed reaction systems (1). The discharge pipe of the quenching agent feeding system (5) is divided into multiple pipes, each of which is respectively connected to a group of tower fixed bed reaction systems (1).

3. An integrated high-safety Grignard reagent preparation device without mechanical stirring as claimed in claim 2, characterized in that: The Grignard reagent using module comprises two groups of Grignard reagent receiving systems (6), each group of Grignard reagent receiving systems (6) comprises a Grignard reagent feeding control device (61) and a Grignard reagent high-level tank (62), the Grignard reagent feeding control device (61) is arranged on the top of the Grignard reagent high-level tank (62), the discharge pipes of multiple groups of tower fixed bed reaction systems (1) are merged and connected into a pipeline, and the pipeline is further divided into two pipelines, which are respectively connected to the Grignard reagent feeding control devices (61) of the two groups of Grignard reagent receiving systems (6), and the bottom discharge ports of the Grignard reagent high-level tanks (62) of the two groups of Grignard reagent receiving systems (6) are merged and connected and then connected to the Grignard reaction safety control component (7).

4. An integrated high-safety Grignard reagent preparation device without mechanical stirring as claimed in claim 3, characterized in that: The Grignard reagent feed control device (61) comprises a remote level meter disposed on the Grignard reagent high-level tank (62) and a feed start switch valve interlocked with the remote level meter; the Grignard reaction safety control component (7) comprises a drop addition pneumatic regulating valve and a discharge pneumatic switch valve.

5. An integrated high-safety Grignard reagent preparation device without mechanical stirring as claimed in claim 4, characterized in that: The halogenated hydrocarbon / THF mixed liquid feed tank (2) and the Grignard reagent high-level tank (62) are both provided with nitrogen seals and tail gas pipes.

6. An integrated high-safety Grignard reagent preparation device without mechanical stirring as claimed in claim 5, characterized in that: A plurality of tower-type fixed-bed reaction systems (1) are arranged on a movable support (8), the movable support (8) comprising a plurality of mounting frames (81), the mounting frames (81) being fixedly connected to each other, a group of tower-type fixed-bed reaction systems (1) being correspondingly mounted on a group of mounting frames (81), the bottom of each group of mounting frames (81) being provided with a rotatable and foldable movable leg (811), the inner side of the movable leg (811) being provided with a limiting groove (8111), the bottom of the mounting frame (81) being provided with a sliding block (8112), one end of the limiting groove (8111) being a through opening, and the other end being a limiting structure, the sliding block (8112) sliding from the through opening into the limiting structure, thereby achieving limiting fixation of the movable leg (811).

7. A process for preparing a Grignard reagent using the integrated high-safety Grignard reagent preparation device without mechanical stirring as claimed in claim 6, characterized in that: The steps include: 1) nitrogen replacement, opening the circulating cooler (12), buffering the halogenated hydrocarbon / THF mixed liquid through the halogenated hydrocarbon / THF mixed liquid feed tank (2), and entering the tower fixed bed reactor (11) through the circulating pump (13) to contact the metal magnesium filler layer (112). At the same time, an initiator is introduced into the tower fixed bed reactor (11) through the initiator feeding system (4) to initiate the Grignard reagent preparation reaction. After the reaction starts, the liquid phase fills the tower fixed bed reactor (11), and under the action of the circulating pump (13), it continuously passes through the tower fixed bed reactor (11) to react with magnesium to generate Grignard reagent by releasing heat, and then passes through the circulating cooler (12) to control the temperature to a safe temperature; 2) detecting the product concentration at the outlet of the circulating cooler (12); when the product concentration reaches the required level, closing the circulating reaction pipeline, and introducing the Grignard reagent at the outlet of the tower fixed bed reactor (11) into the Grignard reagent high-level tank (62); 3) After the discharge of step 2) is completed, the circulating reaction pipeline is switched back, and the feed pipeline is switched to the quenching agent feed system (5) to introduce the quenching agent into the tower fixed bed reactor (11). After the circulating quenching, the feed is switched to nitrogen, and the discharge is switched to sewage discharge to purge the liquid phase material in the tower fixed bed reaction system (1); 4) removing the metal magnesium filler layer (112) of the cleaned tower fixed bed reaction system (1) by disassembling the removable flange (111) and replacing it with a new filler; 5) After the packing is replaced, the tower fixed bed reaction system (1) re-enters the next reaction cycle, and the multiple tower fixed bed reaction systems (1) react and replace alternately to ensure the continuous progress of the reaction; 6) The Grignard reagent high-level tank (62) of one Grignard reagent receiving system (6) is in a dripping and discharging state, and the discharging speed is controlled by the Grignard reaction safety control component (7). The Grignard reagent high-level tank (62) of another Grignard reagent receiving system (6) is in a receiving state. When the Grignard reagent high-level tank (62) in the receiving state reaches the upper limit of the receiving, the Grignard reagent high-level tank (62) in the dripping state has finished dripping, and the Grignard reagent feeding control device (61) switches the working state of the Grignard reagent high-level tank (62), and so on and so forth to realize continuous production; in the dripping state, i.e., the feeding start switch valve is closed, the dripping pneumatic regulating valve and the discharging pneumatic switch valve are opened, and at the same time, the temperature signal of the discharging port is received to adjust the discharging opening, and in the receiving state, i.e., the feeding start switch valve is opened, and the dripping pneumatic regulating valve and the discharging pneumatic switch valve are closed.

8. An integrated high-safety Grignard preparation process without mechanical agitation as claimed in claim 7, characterized in that: The refrigerant of the circulating cooler (12) is a non-aqueous phase refrigerant selected from heat transfer oil, Freon or ethanol.

Images