CN111548256A - Preparation method of chlorohydrin ether - Google Patents
Preparation method of chlorohydrin ether Download PDFInfo
- Publication number
- CN111548256A CN111548256A CN202010424123.3A CN202010424123A CN111548256A CN 111548256 A CN111548256 A CN 111548256A CN 202010424123 A CN202010424123 A CN 202010424123A CN 111548256 A CN111548256 A CN 111548256A
- Authority
- CN
- China
- Prior art keywords
- raw material
- ring
- heat
- opening addition
- mixed raw
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chlorohydrin ether preparation, in particular to a preparation method of chlorohydrin ether. The preparation method of the chlorohydrin ether provided by the invention comprises the following steps: mixing and preheating a catalyst and fatty alcohol to obtain a preheated mixed raw material; introducing the preheated mixed raw material and epoxy chloropropane into a microchannel reactor to carry out a first ring-opening addition reaction to obtain a first ring-opening addition reaction product; and conveying the first ring-opening addition reaction product to a heat-preservation reaction unit for carrying out second ring-opening addition reaction and then purifying to obtain the chlorohydrin ether. The invention can improve the heat transfer and mass transfer efficiency by carrying out the ring-opening addition reaction in the microchannel reactor and the heat-preservation reaction unit, and has high yield and selectivity, few byproducts and high safety.
Description
Technical Field
The invention relates to the technical field of chlorohydrin ether preparation, in particular to a preparation method of chlorohydrin ether.
Background
The chlorohydrin ether is prepared by performing ring-opening addition reaction on fatty alcohol and epoxy chloropropane. The chlorohydrin ether and sodium hydroxide are subjected to ring-closing reaction to prepare aliphatic glycidyl ether, and the aliphatic glycidyl ether is a low-viscosity epoxy compound, can be used for reducing viscosity and toughening epoxy resin, is widely applied to coatings, adhesives, composite materials, chemical intermediates and the like, and is widely applied.
The ring-opening addition reaction of the fatty alcohol and the epichlorohydrin is a strong exothermic reaction, and the influence of heat transfer and mass transfer performance on the reaction is great. At present, the ring-opening addition reactor which is commonly adopted at home and abroad is a kettle type reactor. However, in the aspect of mass transfer, due to the reasons of uneven distribution of flow velocity in the system, dead zones, channeling, short circuit and the like, the retention time of materials in the system is inconsistent, various side reactions are easily caused to occur, and the yield and the product quality of a final product are affected; in the aspect of heat transfer, the temperature of the kettle reactor is generally controlled by a jacket and coil cooling method, the heat exchange area is small, once the ring-opening addition reaction is initiated, the reaction can be rapidly carried out, a large amount of heat is released, if the heat is not removed in time, a local hot spot is formed, the phenomena of self-polymerization and pot overflow of epoxy chloropropane can be generated, the explosion is very easy to occur, and great potential safety hazards exist.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing chlorohydrin ether, which can improve heat transfer and mass transfer efficiency by performing a ring-opening addition reaction in a microchannel reactor and a heat-preserving reaction unit, and has high yield and high safety.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of chlorohydrin ether, which is carried out in a chlorohydrin ether preparation device, wherein the device comprises a micro-channel reactor and a heat-preservation reaction unit communicated with an outlet of the micro-channel reactor, and the micro-channel reactor is respectively provided with a preheating mixed raw material inlet and an inlet of epichlorohydrin; the microchannel reactor is provided with a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure;
the heat-preservation reaction unit comprises a heat-preservation reaction kettle; the heat-preservation reaction kettle has a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure;
the preparation method comprises the following steps:
mixing and preheating a catalyst and fatty alcohol to obtain a preheated mixed raw material;
introducing the preheated mixed raw material and epoxy chloropropane into a microchannel reactor to carry out a first ring-opening addition reaction to obtain a first ring-opening addition reaction product;
and conveying the first ring-opening addition reaction product to a heat-preservation reaction unit for carrying out second ring-opening addition reaction and then purifying to obtain the chlorohydrin ether.
Preferably, the preheating temperature is 30-60 ℃.
Preferably, the molar ratio of the fatty alcohol to the epichlorohydrin is (0.4-5): 1.
preferably, the mass of the catalyst is 0.01-1% of the total mass of the fatty alcohol and the epoxy chloropropane.
Preferably, the temperature of the first ring-opening addition reaction is 50-130 ℃, the time is 15-300 s, and the pressure is less than or equal to 1.0 MPa.
Preferably, the temperature of the second ring-opening addition reaction is 50-90 ℃ and the time is 0.5-2 h.
Preferably, the microchannel reactor is internally provided with microchannel reaction sheets, and the number of the microchannel reaction sheets is 5-20.
Preferably, the single piece liquid holdup of the microchannel reaction plate is 0.8-2 mL independently.
The invention provides a preparation method of chlorohydrin ether, which is carried out in a chlorohydrin ether preparation device, wherein the device comprises a micro-channel reactor and a heat-preservation reaction unit communicated with an outlet of the micro-channel reactor, and the micro-channel reactor is respectively provided with a preheating mixed raw material inlet and an inlet of epichlorohydrin; the microchannel reactor is provided with a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure; the heat-preservation reaction unit comprises a heat-preservation reaction kettle; the heat-preservation reaction kettle has a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure; the preparation method comprises the following steps: mixing and preheating a catalyst and fatty alcohol to obtain a preheated mixed raw material; introducing the preheated mixed raw material and epoxy chloropropane into a microchannel reactor to carry out a first ring-opening addition reaction to obtain a first ring-opening addition reaction product; and conveying the first ring-opening addition reaction product to a heat-preservation reaction unit for carrying out second ring-opening addition reaction and then purifying to obtain the chlorohydrin ether. In the invention, the characteristic dimension of the microchannel in the microchannel reactor is in the micrometer scale range, the generated direct advantages are that the diffusion time is short, the mixing process of the fatty alcohol and the epichlorohydrin in the microchannel reactor is fast, the mass transfer and heat transfer processes are enhanced, the back mixing of reaction raw materials is eliminated, and the selectivity and the yield of the chlorohydrin ether are improved; the epichlorohydrin does not react completely in the microchannel reactor, the subsequent heat-preservation reaction unit can further prolong the retention time of reaction raw materials, ensure that a small amount of unreacted epichlorohydrin fully carries out ring-opening addition reaction with fatty alcohol, eliminate the explosion hazard caused by the small amount of unreacted epichlorohydrin, improve the reaction yield, and meanwhile, the heat-preservation reaction unit is also used as a feeding transition tank of a dealcoholization tower, improve the flexibility of operation, realize the continuous and efficient production of the epichlorohydrin ether, has good safety and is suitable for industrial production.
The equipment provided by the invention has high heat transfer and mass transfer efficiency, and can realize continuous and efficient production of chlorohydrin ether.
Drawings
FIG. 1 is a diagram of an apparatus for the preparation of chlorohydrin ethers;
wherein, 1 is a raw material preparation unit, 11 is a first mixed raw material preparation tank, 111 is a first fatty alcohol inlet, 112 is a first catalyst inlet, 113 is a first mixed raw material outlet, 114 is a first stirrer, 115 is a first heat exchange medium inlet, and 116 is a first heat exchange medium outlet; 117 is a first level gauge and 118 is a first level control pneumatic valve; 12 is a second mixed raw material preparation tank, 121 is a second fatty alcohol inlet, 122 is a second catalyst inlet, 123 is a second mixed raw material outlet, 124 is a second stirrer, 125 is a second heat exchange medium inlet, 126 is a second heat exchange medium outlet, 127 is a second liquid level meter, and 128 is a second liquid level control pneumatic valve; 13 is an epichlorohydrin preparation tank, 131 is an epichlorohydrin inlet, 132 is an epichlorohydrin outlet, 133 is a third liquid level meter, and 134 is a third liquid level control pneumatic valve; 14 is a first fatty alcohol metering tank, 15 is a first catalyst metering tank, 16 is a first flow controller, 17 is a second fatty alcohol metering tank, 18 is a second catalyst metering tank, 19 is a second flow controller, 20 is a mixed raw material pump, 21 is an epoxy chloropropane metering tank, 22 is a third flow controller, 23 is an epoxy chloropropane pump, and 24 is a first nitrogen storage tank;
2, a microchannel reactor, 211, 212, 213, 214, 215, a preheating mixed raw material inlet, an epichlorohydrin inlet, a third heat exchange medium inlet, a first ring-opening addition reaction product outlet and a third heat exchange medium outlet;
3, a heat preservation reaction unit, 31, a first heat preservation reaction kettle, 311, a first ring-opening addition reaction product inlet, 312, a first nitrogen inlet, 313, a first chlorohydrin ether crude product outlet, 314, a third stirrer, 315, a fourth heat exchange medium inlet and 316, wherein the first heat preservation reaction kettle is arranged in the heat preservation reaction unit; 32 is a second heat-preservation reaction kettle, 321 is a second first ring-opening addition reaction product inlet, 322 is a second nitrogen inlet, 323 is a second chlorohydrin ether crude product outlet, 324 is a fourth stirrer, 325 is a fifth heat exchange medium inlet, and 326 is a fifth heat exchange medium outlet; 33 is a second nitrogen storage tank;
and 4, a post-processing unit.
Detailed Description
The invention provides a preparation method of chlorohydrin ether, which is carried out in a chlorohydrin ether preparation device, wherein the device comprises a micro-channel reactor and a heat-preservation reaction unit communicated with an outlet of the micro-channel reactor, and the micro-channel reactor is respectively provided with a preheating mixed raw material inlet and an inlet of epichlorohydrin; the microchannel reactor is provided with a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure;
the heat-preservation reaction unit comprises a heat-preservation reaction kettle; the heat-preservation reaction kettle has a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure;
the preparation method comprises the following steps:
mixing and preheating a catalyst and fatty alcohol to obtain a preheated mixed raw material;
introducing the preheated mixed raw material and epoxy chloropropane into a microchannel reactor to carry out a first ring-opening addition reaction to obtain a first ring-opening addition reaction product;
and conveying the first ring-opening addition reaction product to a heat-preservation reaction unit for carrying out second ring-opening addition reaction and then purifying to obtain the chlorohydrin ether.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the apparatus comprises a microchannel reactor 2 and an incubation reaction unit 3 connected to a first ring-opening addition reaction product outlet 214 of the microchannel reactor 2; the outlet of the heat preservation unit 3 is connected with the post-treatment unit 4; the microchannel reactor is respectively provided with a preheating mixed raw material inlet and an epichlorohydrin inlet; the microchannel reactor is provided with a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure; the heat-preservation reaction unit comprises a heat-preservation reaction kettle; the heat preservation reaction kettle is of a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure.
As an embodiment of the invention, the apparatus further comprises a raw material preparation unit 1. In the invention, the raw material preparation unit 1 comprises a first mixed raw material preparation tank 11, a second mixed raw material preparation tank 12 and an epichlorohydrin metering tank 13 which are connected in parallel; the first mixed raw material outlet 113 of the first mixed raw material preparation tank 11 and the second mixed raw material outlet 123 of the second mixed raw material preparation tank 12 are respectively connected with the preheated mixed raw material inlet 211 of the microchannel reactor 2; the epichlorohydrin outlet 132 of the epichlorohydrin metering tank 13 is connected with the epichlorohydrin inlet 212 of the microchannel reactor 2.
As an embodiment of the present invention, a first fatty alcohol inlet 111 and a first catalyst inlet 112 are disposed on a wall of the first mixed raw material preparation tank 11, a first mixed raw material outlet 113 is disposed at a bottom of the first mixed raw material preparation tank 11, and a first stirrer 114 is further disposed in the first mixed raw material preparation tank 11.
In the present invention, the tank wall of the first mixed raw material preparation tank 11 has a double-layer structure, and a heat exchange medium is filled in an interlayer formed between the inner layer side wall and the outer layer side wall of the tank wall. As an embodiment of the present invention, the heat exchange medium is preferably steam or process water, the steam is used for heating the raw material, and the process water is used for cooling. As an embodiment of the present invention, the outer side wall of the tank wall of the first mixed raw material preparation tank 11 is further provided with a first heat exchange medium inlet 115 and a first heat exchange medium outlet 116; the heat exchange medium flows in the interlayer of the first mixed raw material preparation tank 11 and is used for preheating the mixed raw material of the fatty alcohol and the catalyst.
As an embodiment of the invention, the apparatus further comprises a first fatty alcohol metering tank 14 and a first catalyst metering tank 15; an outlet of the first fatty alcohol metering tank 14 is communicated with a fatty alcohol inlet 111 on the first mixed raw material preparation tank 11; the outlet of the first catalyst metering tank 15 is in communication with a first catalyst inlet 112 on the first mixed feed preparation tank 11; the first fatty alcohol metering tank 14 is used for metering the amount of fatty alcohol and the first catalyst metering tank 15 is used for metering the amount of catalyst.
In one embodiment of the present invention, the pipeline connecting the outlet of the first catalyst metering tank 15 and the first catalyst inlet 112 is preferably provided with a first valve for cutting, adjusting and throttling the mixed raw materials, wherein the first valve is opened when the feeding is performed and the first valve is closed when the feeding is completed.
As an embodiment of the present invention, a first liquid level meter 117 and a first liquid level control pneumatic valve 118 are further provided on the outer side wall of the first mixed raw material preparation tank 11, which are used for correctly measuring the volume or weight of the tank body (i.e. the liquid level measurement is used for metering and economic calculation), monitoring the liquid level of the tank body, and alarming the allowable upper and lower limits of the liquid level, thereby continuously monitoring the production and adjusting.
In the present invention, the second mixed raw material preparation tank 12 functions to uniformly mix the fatty alcohol raw material and the catalyst. As an embodiment of the present invention, the second mixed raw material preparation tank 12 is provided with a second fatty alcohol raw material inlet 121 and a second catalyst inlet 122 on the tank wall, the second mixed raw material preparation tank 12 is provided with a second mixed raw material outlet 123 on the bottom, and the second mixed raw material preparation tank 12 is further provided with a second stirrer 124 therein.
In the present invention, the tank wall of the second mixed raw material preparation tank 12 has a double-layer structure, and a heat exchange medium is filled in an interlayer formed between the inner layer side wall and the outer layer side wall of the tank wall. As an embodiment of the present invention, the heat exchange medium is preferably steam or process water, the steam is used for heating the raw material, and the process water is used for cooling. As an embodiment of the present invention, the outer sidewall of the tank wall of the second mixed raw material preparation tank 12 is further provided with a second heat exchange medium inlet 125 and a second heat exchange medium outlet 126; the heat exchange medium flows in the interlayer of the second mixed raw material preparation tank 12, and is used for preheating the mixed raw material of the fatty alcohol and the catalyst.
As an embodiment of the present invention, the first mixed raw material preparation tank 11 and the second mixed raw material preparation tank 12 are connected in parallel and can be switched to ensure that the reaction for preparing the chlorohydrin ethers is continuously performed.
As an embodiment of the present invention, the apparatus further comprises a second fatty alcohol metering tank 17 and a second catalyst metering tank 18; the outlet of the second fatty alcohol metering tank 17 is communicated with a fatty alcohol inlet 121 on the second mixed raw material preparation tank 12; the outlet of the second catalyst metering tank 18 is in communication with a second catalyst inlet 122 on the second mixed feed preparation tank 12; the second fatty alcohol metering tank 17 is used for metering the amount of fatty alcohol added and the second catalyst metering tank 18 is used for metering the amount of catalyst added.
In one embodiment of the present invention, the pipeline connecting the outlet of the second catalyst metering tank 18 and the second catalyst inlet 122 is preferably provided with a second valve for cutting, adjusting and throttling the mixed raw materials, wherein the second valve is opened when the feeding is performed and closed when the feeding is completed.
As an embodiment of the present invention, a second liquid level meter 127 and a second liquid level control pneumatic valve 128 are preferably further provided on the outer side wall of the second mixed raw material preparation tank 12, which are used for correctly measuring the volume or weight of the tank body (i.e. the liquid level measurement is used for metering and economic calculation), monitoring the liquid level of the tank body, and alarming the allowable upper and lower limits of the liquid level, thereby continuously monitoring the production and adjusting.
As an embodiment of the present invention, the apparatus further includes a first flow controller 16 and a second flow controller 19, the first flow controller 16 is disposed on the pipe where the first mixed raw material outlet 113 of the first mixed raw material preparation tank 11 and the second mixed raw material outlet 123 of the second mixed raw material preparation tank 12 communicate with the preheated mixed raw material inlet 211 of the microchannel reactor 2; the first flow controller 16 and the second flow controller 19 are used to control the amount of the mixed feed delivered to the microchannel reactor 2.
As an embodiment of the present invention, the top of the epichlorohydrin preparation tank 13 is provided with an epichlorohydrin inlet 131, and the bottom of the epichlorohydrin preparation tank 13 is provided with an epichlorohydrin outlet 132; the epichlorohydrin outlet 132 is connected with the epichlorohydrin inlet 212 of the microchannel reactor 2.
As an embodiment of the present invention, the apparatus further comprises an epichlorohydrin metering tank 21 and a first nitrogen storage tank 24; the outlet of the epichlorohydrin storage tank 21 is communicated with the epichlorohydrin inlet 131 of the epichlorohydrin preparation tank 13; the outlet of the first nitrogen storage tank 24 is respectively communicated with the mixed raw material inlet 211 and the epichlorohydrin inlet 212 of the microchannel reactor 2, and the nitrogen of the first nitrogen storage tank 24 is used for replacing the air in the device, so that potential safety hazards such as explosion caused by the air are prevented.
As an embodiment of the present invention, a third level meter 133 and a third level control pneumatic valve 134 are further disposed on the outer sidewall of the epichlorohydrin preparation tank 13, so as to be able to correctly measure the volume or weight of the tank (i.e. the level measurement is for the purpose of metering and economic accounting), monitor the liquid level of the tank, and give an alarm to the allowable upper and lower limits of the liquid level, thereby continuously monitoring production and performing adjustment.
As an example, the apparatus further comprises a mixed feedstock pump 20 and an epichlorohydrin pump 23 disposed between the feedstock preparation unit 1 and the flow line of the microchannel reactor 2; the fatty alcohol raw material pump 20 is disposed on a pipeline between the first mixed raw material outlet 113 of the first mixed raw material preparation tank 11 and the second mixed raw material outlet 123 of the second mixed raw material preparation tank 12 to the preheated mixed raw material inlet 211 of the microchannel reactor 2; the epichlorohydrin pump 23 is arranged on a pipeline between the epichlorohydrin outlet 132 of the epichlorohydrin metering tank 13 and the epichlorohydrin inlet 212 of the microchannel reactor 2.
The device provided by the invention comprises a microchannel reactor 2, wherein the side wall of the microchannel reactor 2 is provided with a mixed raw material inlet 211, the side wall of the microchannel reactor 2 is provided with an epichlorohydrin inlet 212, and the mixed raw material and epichlorohydrin enter the microchannel reactor 2, so that the raw materials can be rapidly and uniformly mixed; the microchannel reactor 2 has a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure; the heat exchange medium is preferably water vapor or process water, the water vapor is used for heating the raw materials, and the process water is used for cooling; the heat exchange medium flows in the interlayer of the microchannel reactor 2 and is used for controlling the temperature of the first ring-opening addition reaction. As an embodiment of the present invention, a third heat exchange medium inlet 213 is further disposed on the bottom outer sidewall of the microchannel reactor 2, and a third heat exchange medium outlet 215 is further disposed on the top outer sidewall of the microchannel reactor 2.
In the invention, the microchannel reactor 2 is provided with microchannels, and is preferably provided with microchannel reaction sheets; the shape of the microchannel preferably includes an umbrella structure, a T structure, a Y structure, a cross structure, or a co-flow structure.
In the invention, the number of reaction sheets in the microchannel reactor is preferably 5-20, and more preferably 10. In the present invention, the liquid holdup of each microchannel reaction plate is independently preferably 0.8 to 2mL, more preferably 1 to 1.5mL, and most preferably 1.18 mL.
The device provided by the invention comprises a heat-preservation reaction unit 3 communicated with a first ring-opening addition reaction product outlet 214 of the microchannel reactor 2.
In the present invention, the heat-preservation reaction unit 3 preferably includes a first heat-preservation reaction kettle 31 and a second heat-preservation reaction kettle 32 connected in parallel; the first heat-preservation reaction kettle 31 and the second heat-preservation reaction kettle 32 are of double-layer side wall structures, and heat exchange media are filled in an interlayer formed by the double-layer side wall structures; the heat exchange medium flows in the interlayer of the first heat-preservation reaction kettle 31 and the second heat-preservation reaction kettle 32, and is used for controlling the temperature of the second ring-opening addition reaction. As an embodiment of the present invention, the first adiabatic reactor 31 is provided with a first ring-opening addition reaction product inlet 311 and a first nitrogen inlet 312; the first heat preservation reaction kettle is provided with a first chlorohydrin ether crude product outlet 313; a third stirrer 314 is also arranged in the first heat-preserving reaction kettle 31. In the invention, the nitrogen is used for replacing the air in the heat-preservation reaction kettle, thereby preventing potential safety hazards such as explosion and the like caused by the existence of the air.
As an embodiment of the invention, the outer side wall of the bottom of the first heat-preserving reaction kettle 31 is further provided with a fourth heat exchange medium inlet 315 and a fourth heat exchange medium outlet 316,
as an embodiment of the present invention, the second insulated reaction vessel 32 is provided with a second first ring-opening addition reaction product inlet 321 and a second nitrogen inlet 322; the second heat-preservation reaction kettle 32 is provided with a second chlorohydrin ether crude product outlet 323; a fourth stirrer 324 is also arranged in the second heat-preservation reaction kettle 32. In the invention, the nitrogen is used for replacing the air in the heat-preservation reaction kettle, so that the safety of explosion and the like caused by the existence of the air is prevented.
In an embodiment of the present invention, the bottom outer sidewall of the second insulated reactor 32 is further provided with a fifth heat exchange medium inlet 325 and a fifth heat exchange medium outlet 326.
In an embodiment of the present invention, the apparatus is further provided with a second nitrogen storage tank 33, and an outlet of the nitrogen storage tank 33 is respectively communicated with the first nitrogen inlet 312 of the first thermal insulation reaction vessel 31 and the second nitrogen inlet 322 of the second thermal insulation reaction vessel 32, so as to replace air in the apparatus and prevent potential safety hazards such as explosion due to the existence of air.
In the invention, the first heat-preservation reaction kettle 31 and the second heat-preservation reaction kettle 32 are connected in parallel and can be switched to use or used simultaneously, so that the reaction for preparing the chlorohydrin ether is continuously carried out.
In the invention, the heat preservation reaction unit 3 is used for further prolonging the retention time of the unreacted fatty alcohol raw material and the epoxy chloropropane reaction raw material in the first ring-opening addition reaction product, ensuring that the unreacted fatty alcohol raw material and the epoxy chloropropane are subjected to sufficient ring-opening addition reaction, improving the reaction yield, realizing the continuous and efficient production of the chlorohydrin ether, having good safety and being suitable for industrial production.
As an embodiment of the present invention, the apparatus preferably further comprises a post-treatment unit 4 communicated with the first crude chlorohydrin ether outlet 313 of the first insulated reaction vessel and the second crude chlorohydrin ether outlet 323 of the second insulated reaction vessel, respectively. In the present invention, the post-treatment unit 4 is preferably provided with a rectification column. In the invention, the structure of the rectifying tower is preferably a packed tower, and the theoretical plate number of the rectifying tower is preferably 10-602.
The invention mixes and preheats the catalyst and the fatty alcohol to obtain the preheated mixed raw material.
In the present invention, the aliphatic alcohol preferably includes allyl alcohol, butanol, benzyl alcohol, octanol, ethylene glycol, propylene glycol, 1, 4-Butanediol (BDO), or C12-14An alcohol. In the present invention, the catalyst preferably comprises boron trifluoride etherate, tin tetrachloride or a mixture thereof (i.e., a built-up catalyst), perchlorate; the perchlorate preferably comprises zinc perchlorate or aluminum perchlorate.
In the present invention, the mixing of the catalyst and the fatty alcohol is preferably carried out by adding the catalyst to the fatty alcohol under stirring. The speed and time of stirring and mixing are not particularly limited, and the fatty alcohol and the catalyst can be uniformly mixed. In the invention, the preheating temperature is preferably 30-60 ℃, more preferably 40-60 ℃, and most preferably 40-50 ℃.
In the invention, the molar ratio of the fatty alcohol to the epichlorohydrin is preferably (0.4-5): 1, more preferably (1 to 4): 1, most preferably (1.1-3): 1. in the invention, the mass of the catalyst is preferably 0.01-1%, more preferably 0.1-0.9%, and most preferably 0.23-0.5% of the total mass of the fatty alcohol and the epichlorohydrin.
After the preheated mixed raw material is obtained, the preheated mixed raw material and epoxy chloropropane are subjected to a first ring-opening addition reaction in a microchannel reactor to obtain a first ring-opening addition reaction product.
In the invention, the temperature of the first ring-opening addition reaction is preferably 50-130 ℃, more preferably 60-110 ℃, and most preferably 60-90 ℃; the time of the first ring-opening addition reaction is preferably 15-300 s, more preferably 15-240 s, and most preferably 20-120 s; the pressure of the first ring-opening addition reaction is preferably less than or equal to 1.0 MPa. In the present invention, the time (i.e., residence time) for the first ring-opening addition reaction is preferably the time from when the raw material enters the microchannel reactor to when it leaves the microchannel reactor.
The microchannel reactor adopted by the invention can cut the flowing reaction raw material fluid, realizes the mixing and heat exchange of the reaction raw material fluid with the space-time size of micron or even smaller, and can improve the reaction yield. The characteristic dimension of the microchannel in the microchannel reactor is in the micrometer scale range, the mass transfer and heat transfer processes are enhanced by the generated direct advantages, the diffusion time of the raw materials is short, the full contact between the fatty alcohol and the epoxy chloropropane is facilitated, the reaction raw material mixing process is fast, the back mixing of the reaction raw materials is eliminated, the proportion of the reaction raw materials is accurate, the side reaction is avoided, and the selectivity of the product is improved; the reaction yield and selectivity are improved, the time of the ring-opening addition reaction is shortened from several hours to several minutes, and the reaction efficiency is improved; moreover, the micro-channel reactor has large specific surface area, greatly enhances the heat transfer in the chemical process, and simultaneously removes the reaction heat in time, thereby improving the safety.
In the present invention, the first ring-opening addition reaction product includes a chlorohydrin ether, an unreacted fatty alcohol, an unreacted epichlorohydrin, and a catalyst.
After the first ring-opening addition reaction product is obtained, the first ring-opening addition reaction product is conveyed to a heat preservation reaction unit to carry out second ring-opening addition reaction and then is purified, and the chlorohydrin ether is obtained.
In the invention, the pressure of the second ring-opening addition reaction is preferably normal pressure, and the reaction temperature is preferably 50-90 ℃, more preferably 50-80 ℃, and most preferably 50-70 ℃; the time of the second ring-opening addition reaction is preferably 0.5-2 h, more preferably 0.8-1.5 h, and most preferably 1 h.
In the invention, the heat-preservation reaction unit can further prolong the retention time of the unreacted fatty alcohol and epoxy chloropropane reaction raw materials in the first ring-opening addition reaction product, ensure that a small amount of unreacted epoxy chloropropane is fully subjected to the ring-opening addition reaction with the fatty alcohol, improve the reaction yield, and meanwhile, the heat-preservation reaction unit is also used as a feeding transition tank of the dealcoholization tower, thereby improving the flexibility of operation, realizing the continuous and efficient production of the chlorohydrin ether, having good safety and being suitable for industrial production.
In the present invention, the purification preferably comprises a continuous distillation to remove excess alcohol. In the invention, the excessive alcohol in the chlorohydrin ether is removed, and the alcohol is preferably subjected to ring closure by using sodium hydroxide to prepare the fatty alcohol glycidyl ether.
The specific method for preparing the chlorohydrin ether by using the device provided by the invention is described by combining the figure 1, and comprises the following steps:
(1) adding fatty alcohol metered by a fatty alcohol metering tank 14 into a mixed raw material preparation tank (a first mixed raw material preparation tank 11 or a second mixed raw material preparation tank 12), adding a catalyst metered by a catalyst metering tank 15 into the mixed raw material preparation tank (the first mixed raw material preparation tank 11 or the second mixed raw material preparation tank 12) under the stirring condition, and preheating the obtained mixed raw material under the heating action of a heat exchange medium flowing in an interlayer of the mixed raw material preparation tank after uniform mixing to obtain a preheated mixed raw material;
(2) pumping the preheated mixed raw material into the microchannel reactor 2 through a mixed raw material pump 20 via a preheated mixed raw material inlet 211, simultaneously pumping epichlorohydrin metered by an epichlorohydrin metering tank 14 into the microchannel reactor 2 through an epichlorohydrin pump 23 via an epichlorohydrin inlet 212, and carrying out a first ring-opening addition reaction under the heating action of a heat exchange medium flowing in an interlayer of the microchannel reactor 2 to obtain a first ring-opening addition reaction product;
(3) conveying the first ring-opening addition reaction product to a heat preservation reaction kettle (a first heat preservation reaction kettle 31 or a second heat preservation reaction kettle 32), and carrying out a second ring-opening addition reaction under the action of a heat exchange medium flowing in an interlayer of the heat preservation reaction kettle to obtain a crude chlorohydrin ether; and transferring the chlorohydrin ether crude product to a rectifying tower of a post-treatment unit 4 for purification to obtain a chlorohydrin ether pure product.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in fig. 1, (1) 901g of 1, 4-Butanediol (BDO) measured by an aliphatic alcohol measuring tank 14 was charged into a mixed raw material preparation tank (first mixed raw material preparation tank 11 or second mixed raw material preparation tank 12), 7.7g of boron trifluoride diethyl etherate measured by a first catalyst measuring tank 15 or second catalyst measuring tank 18 was charged into the mixed raw material preparation tank (first mixed raw material preparation tank 11 or second mixed raw material preparation tank 12) under stirring, and after uniform mixing, the resulting mixed raw material was preheated to 40 ℃ under the heating action of a heat transfer medium flowing in the interlayer of the mixed raw material preparation tank, to obtain a preheated mixed raw material.
(2) Pumping the preheated and mixed raw material into a microchannel reactor 2 through a mixed raw material pump 20 via a preheated and mixed raw material inlet 211, simultaneously pumping 2056g of epoxy chloropropane metered by an epoxy chloropropane metering tank 14 into the microchannel reactor 2 through an epoxy chloropropane inlet 212 via an epoxy chloropropane pump 23, mixing in the microchannel reactor 2, and carrying out a first ring-opening addition reaction for 47s under the conditions of 55 ℃ and less than or equal to 0.8MPa under the heating action of a heat exchange medium flowing in an interlayer of the microchannel reactor 2 to obtain a first ring-opening addition reaction product; wherein, the microchannel of the microchannel reactor has an umbrella-shaped structure, the number of the reaction plates is 10, the liquid holdup of a single reaction plate is 1.18mL, and the material is stainless steel 316L.
(3) Conveying the first ring-opening addition reaction product to a heat-preservation reaction kettle (a first heat-preservation reaction kettle 31 or a second heat-preservation reaction kettle 32), and carrying out second ring-opening addition reaction for 40min at 50 ℃ in a nitrogen atmosphere to obtain a crude chlorohydrin ether; transferring the chlorohydrin ether crude product to a rectifying tower of a post-treatment unit 4 for purification to obtain a chlorohydrin ether pure product;
the obtained pure chlorohydrin ether product was tested by gas chromatography under the following conditions: the model of a gas chromatograph is GC9800, the gas chromatograph is detected by a hydrogen flame ionization detector, the quantitative analysis is carried out by an area normalization method, the chromatographic column is SE-54(30m multiplied by 0.25mm), the column temperature is 100 ℃, the detector temperature is 260 ℃, the vaporization chamber temperature is 260 ℃, the programmed heating rate is 10 ℃/min, the final temperature is 260 ℃, the retention time is 10min, the sample injection amount is 0.2 mu L, and the test results are shown in Table 2.
Examples 2 to 15
Chlorohydrin ethers were prepared and tested according to the method of example 1, the reaction conditions of examples 2-15 are shown in table 1, and the preparation conditions not listed in table 1 were the same as the corresponding preparation conditions in example 1.
TABLE 1 examples 1 to 15 reaction conditions
Wherein, the mass ratio of the compound catalyst in the embodiment 14 is 1: 1, boron trifluoride diethyl etherate and stannic chloride; the mass ratio of the compound catalyst in the embodiment 15 is 1: 1 of boron trifluoride diethyl etherate and tin tetrachloride.
Comparative example 1
In a kettle-type reaction, the types and the dosage ratios of the raw materials are the same as those in example 1, 162g of 1, 4-butanediol, 166g of toluene and 1.4g of boron trifluoride diethyl etherate are added into a sealed 1000mL four-mouth bottle provided with a mechanical stirrer, a reflux condenser and a thermometer, the stirrer is started, the temperature is increased to 60 ℃, 370g of epichlorohydrin is added dropwise, the reaction is carried out for 6 hours at the temperature of 60 ℃, samples are tested by gas chromatography after the reaction is finished, and the test results are shown in Table 2.
Comparative example 2
Carrying out kettle type reaction: the kinds and the amount ratio of each raw material were the same as in example 3, and C was charged into a sealed 1000mL four-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer12～14300g of alcohol, 138g of toluene and 1.1g of boron trifluoride diethyl etherate, starting a stirrer, heating to 50 ℃, then dropwise adding 195g of epichlorohydrin, reacting for 6 hours at 55 ℃, testing a sample by using a gas chromatograph after the reaction is finished, and testing results are shown in Table 2.
Comparative example 3
The kettle type reaction, the kinds and the dosage ratio of the raw materials are the same as those of the example 7, in a sealed 1000mL four-mouth bottle provided with a mechanical stirrer, a reflux condenser and a thermometer, 377g of allyl alcohol and 2.9g of stannic chloride are added, the stirrer is started, 200g of epichlorohydrin is added dropwise after the temperature is raised to 85 ℃, the reaction is carried out for 6 hours at the temperature of 85 ℃, a sample is tested by gas chromatography after the reaction is finished, and the test results of the products prepared in the examples 1 to 15 and the comparative examples 1 to 3 are shown in Table 2.
TABLE 2 test results of examples 1 to 15 and comparative examples 1 to 3
As can be seen from comparison of examples (1, 3 and 7) and comparative examples (1, 2 and 3), the present invention, which performs a ring-opening addition reaction using a microchannel reactor and a temperature-maintained reaction unit, can improve the reaction yield and the selectivity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The preparation method of chlorohydrin ether is characterized by being carried out in a chlorohydrin ether preparation device, wherein the device comprises a microchannel reactor and a heat-preservation reaction unit communicated with an outlet of the microchannel reactor, and the microchannel reactor is respectively provided with a preheating mixed raw material inlet and an inlet of epichlorohydrin; the microchannel reactor is provided with a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure;
the heat-preservation reaction unit comprises a heat-preservation reaction kettle; the heat-preservation reaction kettle has a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure;
the preparation method comprises the following steps:
mixing and preheating a catalyst and fatty alcohol to obtain a preheated mixed raw material;
introducing the preheated mixed raw material and epoxy chloropropane into a microchannel reactor to carry out a first ring-opening addition reaction to obtain a first ring-opening addition reaction product;
and conveying the first ring-opening addition reaction product to a heat-preservation reaction unit for carrying out second ring-opening addition reaction and then purifying to obtain the chlorohydrin ether.
2. The method according to claim 1, wherein the preheating temperature is 30 to 60 ℃.
3. The preparation method according to claim 1, wherein the molar ratio of the fatty alcohol to the epichlorohydrin is (0.4-5): 1.
4. the method according to claim 1, wherein the mass of the catalyst is 0.01 to 1% of the total mass of the fatty alcohol and the epichlorohydrin.
5. The method according to claim 1, wherein the temperature of the first ring-opening addition reaction is 50 to 130 ℃, the time is 15 to 300s, and the pressure is less than or equal to 1.0 MPa.
6. The method according to claim 1, wherein the temperature of the second ring-opening addition reaction is 50 to 90 ℃ and the time is 0.5 to 2 hours.
7. The preparation method according to claim 1, wherein the microchannel reactor is provided with microchannel reaction plates, and the number of the microchannel reaction plates is 5-20.
8. The process of claim 7, wherein the microchannel reactor plate has a single piece liquid hold-up of 0.8 to 2mL independently.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010424123.3A CN111548256A (en) | 2020-05-19 | 2020-05-19 | Preparation method of chlorohydrin ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010424123.3A CN111548256A (en) | 2020-05-19 | 2020-05-19 | Preparation method of chlorohydrin ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111548256A true CN111548256A (en) | 2020-08-18 |
Family
ID=72000103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010424123.3A Pending CN111548256A (en) | 2020-05-19 | 2020-05-19 | Preparation method of chlorohydrin ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111548256A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416310A (en) * | 2021-05-31 | 2021-09-21 | 南京林业大学 | Preparation method of organic silicon modified acrylate |
| CN115677517A (en) * | 2022-11-01 | 2023-02-03 | 南京林业大学 | Quaternary ammonium salt glycerol ether and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0189247A1 (en) * | 1985-01-09 | 1986-07-30 | BP Chemicals Limited | Process for the preparation of glycol ethers and glycol ether esters |
| CN1927852A (en) * | 2006-09-26 | 2007-03-14 | 南京林业大学 | Synthesis method of butyl glycidyl ether |
| JP2010265193A (en) * | 2009-05-13 | 2010-11-25 | Yokkaichi Chem Co Ltd | Method for producing alkyl chlorohydrin ether and method for producing alkyl glycidyl ether |
| CN104744222A (en) * | 2013-12-31 | 2015-07-01 | 岳阳昌德化工实业有限公司 | Method for preparing 2-alkoxy cyclohexanol |
| CN106243344A (en) * | 2016-08-19 | 2016-12-21 | 浙江皇马科技股份有限公司 | A kind of epoxy radicals end capped polyether continuous open loop production technology |
| CN108033875A (en) * | 2017-12-14 | 2018-05-15 | 中国科学院过程工程研究所 | A kind of system and method for continuous production glycol ether |
| CN108752291A (en) * | 2018-07-11 | 2018-11-06 | 高化学（江苏）化工新材料有限责任公司 | The preparation method of 1,4- butanediol monoglycidyl ethers |
| CN108947779A (en) * | 2018-08-15 | 2018-12-07 | 南京红宝丽聚氨酯有限公司 | A kind of preparation method of tripropylene glycol |
| CN110655454A (en) * | 2018-06-29 | 2020-01-07 | 东营市海科新源化工有限责任公司 | Method and system for preparing dipropylene glycol with high selectivity |
-
2020
- 2020-05-19 CN CN202010424123.3A patent/CN111548256A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0189247A1 (en) * | 1985-01-09 | 1986-07-30 | BP Chemicals Limited | Process for the preparation of glycol ethers and glycol ether esters |
| CN1927852A (en) * | 2006-09-26 | 2007-03-14 | 南京林业大学 | Synthesis method of butyl glycidyl ether |
| JP2010265193A (en) * | 2009-05-13 | 2010-11-25 | Yokkaichi Chem Co Ltd | Method for producing alkyl chlorohydrin ether and method for producing alkyl glycidyl ether |
| CN104744222A (en) * | 2013-12-31 | 2015-07-01 | 岳阳昌德化工实业有限公司 | Method for preparing 2-alkoxy cyclohexanol |
| CN106243344A (en) * | 2016-08-19 | 2016-12-21 | 浙江皇马科技股份有限公司 | A kind of epoxy radicals end capped polyether continuous open loop production technology |
| CN108033875A (en) * | 2017-12-14 | 2018-05-15 | 中国科学院过程工程研究所 | A kind of system and method for continuous production glycol ether |
| CN110655454A (en) * | 2018-06-29 | 2020-01-07 | 东营市海科新源化工有限责任公司 | Method and system for preparing dipropylene glycol with high selectivity |
| CN108752291A (en) * | 2018-07-11 | 2018-11-06 | 高化学（江苏）化工新材料有限责任公司 | The preparation method of 1,4- butanediol monoglycidyl ethers |
| CN108947779A (en) * | 2018-08-15 | 2018-12-07 | 南京红宝丽聚氨酯有限公司 | A kind of preparation method of tripropylene glycol |
Non-Patent Citations (4)
| Title |
|---|
| 王光昆等: "1-烯丙氧基-2,3-环氧丙烷的制备", 《广东化工》 * |
| 王树民等: "1,4-丁二醇二缩水甘油醚的合成", 《广州化工》 * |
| 王树民等: "丙三醇缩水甘油醚的合成", 《广州化工》 * |
| 陈永福等: "液固相固定床催化合成丙二醇醚工艺的开发研究", 《精细石油化工进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416310A (en) * | 2021-05-31 | 2021-09-21 | 南京林业大学 | Preparation method of organic silicon modified acrylate |
| CN115677517A (en) * | 2022-11-01 | 2023-02-03 | 南京林业大学 | Quaternary ammonium salt glycerol ether and preparation method and application thereof |
| CN115677517B (en) * | 2022-11-01 | 2024-03-01 | 南京林业大学 | Quaternary ammonium salt glycerol ether and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111548256A (en) | Preparation method of chlorohydrin ether | |
| CN1331829C (en) | Process for preparing isobutene from tertiary butanol | |
| CN104788294B (en) | The device of a kind of reactive distillation synthesizing glycol monobutyl ether and process | |
| CN111635298A (en) | Method and device for preparing glycol ether | |
| CN109701293A (en) | A kind of method of solvent displacement condensation tower and production anhydrous formaldehyde | |
| CN109734601A (en) | A method of preparing 1,3- propane diamine | |
| CN111574335B (en) | Propylene glycol oligomer device and preparation method | |
| CN100491324C (en) | Method and apparatus for continuously preparing ethyl acetate by single tower | |
| CN103342624B (en) | Preparation method of high purity cyclopentene | |
| CN1330624C (en) | Process for the preparation of monochloroacetic acid | |
| CN111454156B (en) | Method for continuously synthesizing 4-ethyl nitrobenzene and 2-ethyl nitrobenzene | |
| CN104529730B (en) | A kind of method being prepared propione by 2-amylene | |
| CN218166975U (en) | System for continuously and efficiently preparing 2-chlorine-2-oxygen-1, 3, 2-dioxaphospholane without solvent | |
| CN112430188B (en) | Novel method for preparing isopropyl aniline by hydrogenation technology | |
| CN113548937B (en) | Continuous preparation method of high-purity perfluoro-2, 4-dimethyl-3-heptene | |
| CN110452083B (en) | Method and device for producing diisobutylene | |
| CN102701918A (en) | Method for producing MTBE (Methyl Tert Butyl Ether) by taking gas phase isobutene as raw material | |
| CN107055550A (en) | A kind of method for preparing dichlororosilane eiectronic grade | |
| CN110627751B (en) | Device and method for recycling bromine element in industrialized production of tetrahydrofurfuryl alcohol diethyl ether | |
| CN104447255A (en) | Method for preparing 2-pentanone from 2-amylene | |
| CN115317941B (en) | Method for preparing vinyl tri (beta-methoxyethoxy) silane by catalytic rectification | |
| CN112569620B (en) | Process system for preparing cyclopentyl methyl ether by using bulkhead reaction rectifying tower | |
| CN216703371U (en) | Integrated form reaction unit | |
| CN216573024U (en) | Maleic anhydride hydrogenation reaction system | |
| CN108299146A (en) | A kind of method of australene isomerization reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20231017 |