Search

CN-121990883-A - Preparation process of 4-hydroxybutyl vinyl ether

CN121990883ACN 121990883 ACN121990883 ACN 121990883ACN-121990883-A

Abstract

The application relates to the technical field of chemical engineering and processes, and particularly discloses a preparation process of 4-hydroxybutyl vinyl ether. The preparation method comprises the steps of preparing an immobilized catalyst by mixing, loading and activating, constructing an inert environment by nitrogen replacement, carrying out reactive distillation, and carrying out multistage separation, secondary replacement, material purification circulation and byproduct directional hydrogenation conversion to realize efficient reuse of the raw materials, and reinforcing product purification by an organic vapor permeable membrane. The product can be used in the fields of high-grade coating, environment-friendly adhesive, high-end electronic chemicals and the like, meets the requirements of high-added-value fine chemical intermediate, and has the outstanding advantages of continuous and stable operation of the process, high separation precision, double excellent raw material utilization rate and product purity and byproduct recycling.

Inventors

  • WANG WEIHUI
  • WANG LIDONG
  • ZHAO XIAOSONG
  • TIAN HUA

Assignees

  • 焦作新景科技有限公司

Dates

Publication Date
20260508
Application Date
20260113

Claims (10)

  1. 1. A preparation process of 4-hydroxybutyl vinyl ether is characterized by comprising the following steps: s1, preparing a catalyst, namely mixing potassium hydroxide with 1, 4-butanediol, loading the mixture on a porous carrier to form an immobilized catalyst, and then performing activation treatment; S2, nitrogen replacement, namely sequentially vacuumizing and filling nitrogen for replacement of a reaction system where the activated catalyst is located; S3, reactive distillation, namely continuously introducing acetylene gas into the reaction system treated in the step S2, adding 1, 4-butanediol, and carrying out synthetic reaction in a reactive distillation tower under the action of an immobilized catalyst; S4, secondary replacement, namely transferring the liquid phase material after the synthesis reaction is completed to a separation system; S5, stripping, namely sending the material transferred in the step S4 into a stripping tower for separation, and returning part of the material after condensing the gas phase at the top of the tower to the step S3; S6, double ether rectification, namely sending the crude product obtained in the step S5 into a double ether rectifying tower for separation, and returning part of materials after condensing the gas phase at the top of the tower to the step S3; S7, recovering transition components, namely, distributing the liquid phase recombinant obtained in the step S6 into a recovery tower for separation, condensing the gas phase at the top of the tower, and returning to the step S6; S8, product rectification, namely, sending the tower kettle material in the step S7 into a product rectification tower for separation, wherein the tower kettle material is divided into two parts, namely, the first part is directly returned to the step S3, and the second part is the material containing the deactivated catalyst and is sent into a regeneration rectification tower for separation and recovery; s9, material purification, namely collecting the materials returned to the step S3, sequentially filtering, adsorbing and purifying, and then entering a synthesis reaction; S10, converting byproducts, namely performing catalytic hydrogenation conversion on the byproducts of the diether substances, and supplementing the obtained 1, 4-butanediol into the synthesis reaction in the step S3.
  2. 2. The process for preparing 4-hydroxybutyl vinyl ether according to claim 1, characterized in that in step S1, the porous carrier is one selected from modified alumina, molecular sieve or activated carbon, the load of potassium hydroxide on the immobilized catalyst is 5-25wt%, the mixing temperature is 80-120 ℃, and the activation treatment time is 1-4 hours.
  3. 3. The preparation process of 4-hydroxybutyl vinyl ether according to claim 1, wherein in the step S2, the vacuum is pumped to a vacuum degree of-0.08 MPa to-0.1 MPa, nitrogen is filled to a micro positive pressure state of the system and maintained at 0.05kPa to 0.5kPa, the replacement cycle is 2 times to 4 times, the oxygen content in the system in the replacement process is lower than 10ppm, the operation temperature of adsorption is 25-40 ℃ and the operation temperature of thermal regeneration is 120-150 ℃, in the step S4, the separation system is sequentially subjected to vacuum pumping and nitrogen filling replacement before the liquid phase material is transferred, and the operation is the same as the step S2.
  4. 4. The preparation process of 4-hydroxybutyl vinyl ether according to claim 1, characterized in that in step S3, the reaction temperature of the synthesis reaction is 120-180 ℃, the reaction pressure is 0.2-0.8MPa, in step S6, the tower top temperature of the diether rectifying tower is 65-85 ℃, the tower bottom temperature is 150-180 ℃, in step S10, the reaction temperature of the hydroconversion is 80-140 ℃, the reaction pressure is 1.0-3.0MPa, and the molar ratio of hydrogen to diether is 2:1-5:1.
  5. 5. The process for preparing 4-hydroxybutyl vinyl ether according to claim 1, characterized in that in step S3, the reaction rectifying column is operated at a pressure of 0.3-0.6MPa, a column top temperature of 70-95 ℃ and a column bottom temperature of 150-170 ℃, and the acetylene gas is introduced from the lower part of the column, and 1, 4-butanediol and the catalyst are fed from the upper part of the column.
  6. 6. A process for preparing 4-hydroxybutyl vinyl ether according to claim 1, characterized in that in step S3, when the basicity of the synthesis reaction system is lower than 60 to 80% of its initial value, a part of the catalyst slurry is discharged and a potassium hydroxide-butanediol solution having a concentration of 10 to 30% by weight is supplemented, and the regenerated slurry is returned to the reaction system.
  7. 7. The process for preparing 4-hydroxybutyl vinyl ether according to claim 1, characterized in that in step S8, the gas phase extracted from the top of the product rectifying tower is separated by an organic vapor permeation membrane and then condensed to obtain the product, the operation temperature of the separation of the organic vapor permeation membrane is 40-70 ℃, and the vacuum degree of the rear side of the organic vapor permeation membrane is maintained at 5-20kPa.
  8. 8. The process for preparing 4-hydroxybutyl vinyl ether according to claim 1, wherein in step S9, a filter with a pore diameter of 0.1-0.5 μm is used for the filtration, an adsorption column filled with neutral alumina is used for the adsorption, the operation temperature of the adsorption column is 50-80 ℃, the volume space velocity of the material passing through the adsorption column is 1-3h-1, and the particle size of the neutral alumina is 100-300 meshes.
  9. 9. The process for preparing 4-hydroxybutyl vinyl ether according to claim 1, wherein in step S10, the hydrogenation catalyst used for the catalytic hydrogenation is a palladium-based catalyst or a nickel-based catalyst supported on an alumina carrier, wherein the active metal is supported in an amount of 0.5-5wt%.
  10. 10. The process for preparing 4-hydroxybutyl vinyl ether according to claim 9, wherein the reactive rectifying tower in step S3, the diether rectifying tower in step S6 and the product rectifying tower in step S8 are used for correspondingly adjusting the heat medium supply amount of each tower reboiler according to the change of the feed composition of each rectifying tower and the recycling proportion of circulating materials.

Description

Preparation process of 4-hydroxybutyl vinyl ether Technical Field The application relates to the technical field of chemical engineering and processes, in particular to a preparation process of 4-hydroxybutyl vinyl ether. Background The 4-hydroxybutyl vinyl ether is used as an important fine chemical intermediate, is widely applied to the fields of paint, adhesive, electronic chemicals and the like, and the stability and the resource utilization efficiency of the preparation process are directly related to the economical efficiency and the feasibility of industrial production. At present, the 4-hydroxybutyl vinyl ether is prepared by mainly reacting 1, 4-butanediol with acetylene in a catalytic system in industry, and the process generally comprises core links such as reaction, separation, purification and the like, and the preparation and recovery of a target product are realized through multi-unit cooperation. In the existing preparation process, the core problems of poor process continuity and low comprehensive utilization efficiency of raw materials are common. On one hand, the catalytic system mostly adopts a homogeneous catalyst or a simple immobilized catalyst, the former is difficult to separate from a product, so that the catalyst cannot be recovered and reused, the treatment material is required to be frequently stopped to supplement a new catalyst, and the latter cannot be regenerated in time after the activity is attenuated, and the continuous promotion of the process is also influenced. Meanwhile, the rectification unit is operated by adopting fixed parameters, so that the dynamic change of the feed composition and the proportion of the circulating materials cannot be adapted, the incomplete separation or the energy consumption redundancy is easily caused, the process interruption risk and the raw material loss are further increased, and the economical efficiency and the stability of the industrial production are restricted. Disclosure of Invention In order to solve the core problems of poor continuity and low comprehensive utilization efficiency of raw materials in the preparation process of the 4-hydroxybutyl vinyl ether in the prior art, the application provides the preparation process of the 4-hydroxybutyl vinyl ether, and the collaborative optimization of continuous and stable operation of the process and efficient multiplexing of the raw materials is realized by constructing a closed-loop process system integrating catalytic regeneration, material circulation and dynamic regulation and control. A process for preparing 4-hydroxybutyl vinyl ether, comprising the steps of: s1, preparing a catalyst, namely mixing potassium hydroxide with 1, 4-butanediol, loading the mixture on a porous carrier to form an immobilized catalyst, and then performing activation treatment; S2, nitrogen replacement, namely sequentially vacuumizing and filling nitrogen for replacement of a reaction system where the activated catalyst is located; S3, reactive distillation, namely continuously introducing acetylene gas into the reaction system treated in the step S2, adding 1, 4-butanediol, and carrying out synthetic reaction in a reactive distillation tower under the action of an immobilized catalyst; S4, secondary replacement, namely transferring the liquid phase material after the synthesis reaction is completed to a separation system; S5, stripping, namely sending the material transferred in the step S4 into a stripping tower for separation, and returning part of the material after condensing the gas phase at the top of the tower to the step S3; S6, double ether rectification, namely sending the crude product obtained in the step S5 into a double ether rectifying tower for separation, and returning part of materials after condensing the gas phase at the top of the tower to the step S3; S7, recovering transition components, namely, distributing the liquid phase recombinant obtained in the step S6 into a recovery tower for separation, condensing the gas phase at the top of the tower, and returning to the step S6; S8, product rectification, namely, sending the tower kettle material in the step S7 into a product rectification tower for separation, wherein the tower kettle material is divided into two parts, namely, the first part is directly returned to the step S3, and the second part is the material containing the deactivated catalyst and is sent into a regeneration rectification tower for separation and recovery; s9, material purification, namely collecting the materials returned to the step S3, sequentially filtering, adsorbing and purifying, and then entering a synthesis reaction; S10, converting byproducts, namely performing catalytic hydrogenation conversion on the byproducts of the diether substances, and supplementing the obtained 1, 4-butanediol into the synthesis reaction in the step S3. By adopting the technical scheme, the potassium hydroxide and the 1, 4-butanediol are mixed and then are loaded on the por