CN114702367A - Continuous production process and production equipment of 1, 2-pentanediol - Google Patents
Continuous production process and production equipment of 1, 2-pentanediol Download PDFInfo
- Publication number
- CN114702367A CN114702367A CN202210339948.4A CN202210339948A CN114702367A CN 114702367 A CN114702367 A CN 114702367A CN 202210339948 A CN202210339948 A CN 202210339948A CN 114702367 A CN114702367 A CN 114702367A
- Authority
- CN
- China
- Prior art keywords
- fixed bed
- bed reactor
- stage fixed
- pentanediol
- storage tank
- 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
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
Abstract
The invention relates to a continuous production process and production equipment of 1, 2-pentanediol, belonging to the technical field of fine chemical engineering. The invention uses a fixed bed reactor as synthesis equipment, and realizes the continuous production of the 1, 2-pentanediol by adopting a continuous feeding mode. The raw materials and the solvent used in the production can be recycled at any time, thereby reducing the generation of three wastes to the maximum extent and reducing the pollution to the environment. The invention has simple process flow and mild reaction condition, and the content and yield of the obtained product are obviously higher than those of the prior production process.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a continuous production process and production equipment of 1, 2-pentanediol.
Background
1, 2-pentanediol is an important intermediate for preparing fine chemicals, and due to the special molecular structure, the 1, 2-pentanediol has important application in many fields. Firstly, 1, 2-pentanediol is used as a key intermediate for synthesizing propiconazole (systemic bactericide), and meanwhile, the 1, 2-pentanediol also has excellent antibacterial property and moisture retention property and is used for various skin care products such as skin cream, facial mask, eye cream, infant skin lotion and the like to replace ethanol; furthermore, 1, 2-pentanediol also has important applications in the production of polyester fibers, plasticizers, preservatives, emulsifiers, and the like. Currently, 1, 2-pentanediol has a great demand in China, but most of the 1, 2-pentanediol depends on import.
The main synthetic methods at home and abroad mainly comprise the following steps:
the synthesis method of acetic anhydride comprises the following steps: the method is mainly characterized in that the dosage of the concentrated sulfuric acid catalyst is difficult to control, if the dosage is too large or the dropping speed is too high, the reaction is difficult to control, a large amount of byproducts are increased, and finally the yield is reduced.
N-valeric acid method: n-valeric acid is used as a raw material, alpha-bromo-n-valeric acid is obtained through bromination, then alpha-hydroxyvaleric acid is obtained through hydrolysis, and finally 1, 2-pentanediol is obtained through reduction under the action of a catalyst, wherein the method has the defects that multi-brominated substances are easily generated in the bromination reaction process, the product yield and purity are influenced, the production cost is high, the technological process is complex, and industrialization is not easy to realize; furfuryl alcohol catalysis: furfuryl alcohol is used as a raw material and is hydrogenated and decomposed into 1, 2-pentanediol under the action of a skeletal nickel catalyst, and the method has the defects of wide raw material source, low yield and difficult separation of byproducts.
N-pentene oxidation process: the method comprises the steps of taking n-pentene, formic acid and hydrogen peroxide as raw materials, reacting the formic acid and the hydrogen peroxide in a certain molar ratio at a low temperature to prepare peroxyformic acid, generating 1, 2-epoxypentane from the n-pentene under the action of a strong oxidant peroxyformic acid, and hydrolyzing the 1, 2-epoxypentane under an alkaline condition to obtain the 1, 2-pentanediol.
The above routes all have the disadvantages of complex process, high cost for treating three wastes, serious pollution, difficult acquisition of raw materials, high cost and the like.
Disclosure of Invention
Aiming at the problems of complex process, high three-waste treatment cost, serious pollution and the like of the existing 1, 2-pentanediol synthesis process, the invention provides a continuous production process of 1, 2-pentanediol and production equipment thereof, so as to solve the technical problems.
The technical scheme of the invention is as follows: a continuous production process of 1, 2-pentanediol comprises the following specific steps:
(1) metering n-pentene, a solvent I and 30% hydrogen peroxide by a flowmeter, continuously feeding the mixture into the bottom of a first-stage fixed bed reactor I, and reacting in the reactor;
(2) in the step (1), the reaction liquid flows to the bottom of a second-stage fixed bed reactor I through an overflow pipe on the upper part of the first-stage fixed bed reactor I to continue to react, and unreacted n-pentene is circulated to a feeding section through a gas phase line;
(3) in the step (2), the reaction liquid overflows to a rectifying tower I through the upper part of a secondary fixed bed reactor I to be rectified and recycled for solvent I; obtaining an intermediate propyl oxirane at the bottom of the rectifying tower I;
(4) metering the intermediate propyl oxirane prepared in the step (3), water and a solvent II through a mass flow meter, continuously feeding the metered intermediate propyl oxirane, the water and the solvent II into the bottom of a first-stage fixed bed reactor II, and reacting in the reactor;
(5) in the step (4), the reaction liquid flows to the bottom of the second-stage fixed bed reactor through an overflow pipe at the upper part of the first-stage fixed bed reactor II to continue to react;
(6) and (5) overflowing the reaction liquid to a rectifying tower II through the upper part of the fixed bed to rectify and separate water in the 1, 2-pentanediol, flowing out of the bottom of the rectifying tower and allowing the solvent II, 1, 2-pentanediol to enter a separating tower, and separating the 1, 2-pentanediol in the separating tower through high negative pressure to obtain a product.
Preferably, the first-stage fixed bed reactor I and the second-stage fixed bed reactor I are filled with catalysts; the catalyst is a Ti/Si molecular sieve catalyst.
Preferably, the first-stage fixed bed reactor II and the second-stage fixed bed reactor II are filled with resin; the resin is a strong acid cation exchange resin.
Preferably, in the step (1), the solvent I is one of dichloroethane, methanol or ethanol, preferably methanol.
Preferably, the reaction temperature of the primary fixed bed reactor I is 40-55 ℃, and preferably 50 ℃; the reaction temperature of the second-stage fixed bed reactor I is 40-55 ℃, and preferably 50 ℃.
Preferably, the molar ratio of the dosage of the n-pentene to the dosage of the hydrogen peroxide is 1: 0.8-1; preferably 1: 0.9.
Preferably, the mass ratio of the n-pentene to the solvent I is 1: 3-5, and preferably 1: 4.
Preferably, the reaction temperature of the primary fixed bed reactor II is 50-80 ℃, and preferably 70 ℃; the reaction temperature of the second-stage fixed bed reactor II is 50-80 ℃, and preferably 70 ℃.
Preferably, in the step (4), the solvent II is one of toluene, benzene, xylene, dichloromethane and dichloroethane; dichloroethane is preferred.
The production equipment of the 1, 2-pentanediol comprises a first-stage fixed bed reactor I, a second-stage fixed bed reactor I, a first-stage fixed bed reactor II, a second-stage fixed bed reactor II, a rectifying tower I, a rectifying tower II and a separation tower. The bottom of the first-stage fixed bed reactor I is respectively connected with a n-pentene storage tank, a solvent I storage tank and a hydrogen peroxide storage tank through pipelines, and a flowmeter is arranged on the connected pipelines; the upper part of the first-stage fixed bed reactor I is connected with the bottom of the second-stage fixed bed reactor I; the top of the first-stage fixed bed reactor I is connected with a normal pentene storage tank; the top of the second-stage fixed bed reactor I is connected with a normal pentene storage tank; the upper part of the second-stage fixed bed reactor I is connected with the rectifying tower I; the top of the rectifying tower I is connected with a storage tank of a solvent I; the bottom of the rectifying tower I is connected with a propyl ethylene oxide storage tank; the bottom of the first-stage fixed bed reactor II is respectively connected with a propyl ethylene oxide storage tank, a solvent II storage tank and a water storage tank through pipelines, and a mass flowmeter is arranged on the connected pipelines; the upper part of the first-stage fixed bed reactor II is connected with the bottom of the second-stage fixed bed reactor II; the upper part of the second-stage fixed bed reactor II is connected with a rectifying tower II; the top of the rectifying tower II is connected with a solvent II storage tank; the bottom of the rectifying tower II is connected with the separation tower; the separation tower is connected with a finished product storage tank.
All the devices are connected through pipelines.
The invention has the beneficial effects that:
(1) the continuous production process of the 1, 2-pentanediol takes hydrogen peroxide as an oxidant and a byproduct of the oxidation of the n-pentene is water, so that the process does not cause pollution to the environment. The used reaction solvent and raw materials realize the real-time recovery of the production process and can be applied in production at any time, thereby reducing the generation of three wastes to the maximum extent and reducing the pollution to the environment.
(2) The invention adopts the Ti/Si molecular sieve as the catalyst, and the catalyst can be recycled, thereby fundamentally reducing the production cost; in addition, the method has simple process flow and mild reaction conditions, and the content and yield of the obtained product are obviously higher than those of the conventional production process.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a schematic view of the structure of a production apparatus of the present invention;
FIG. 2 is a gas phase detection spectrum of the product of example 2 of the present invention;
FIG. 3 is a gas phase detection spectrum of the product of example 3 of the present invention;
FIG. 4 is a gas phase detection spectrum of a product of example 4 of the present invention;
FIG. 5 is a gas phase detection spectrum of the product of example 5 of the present invention.
In the figure, 1-first-stage fixed bed reactor I, 2-second-stage fixed bed reactor I, 3-n-pentene storage tank, 4-solvent I storage tank, 5-hydrogen peroxide storage tank, 6-flowmeter, 7-rectifying tower I, 8-first-stage fixed bed reactor II, 9-second-stage fixed bed reactor II, 10-propyl ethylene oxide storage tank, 11-water storage tank, 12-solvent II storage tank, 13-mass flowmeter, 14-rectifying tower II, 15-separation tower and 16-finished product storage tank.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. 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
The utility model provides a production facility of 1, 2-pentanediol, includes first order fixed bed reactor I1, second grade fixed bed reactor I2, first order fixed bed reactor II 8, second grade fixed bed reactor II 9, rectifying column I7, rectifying column II 14 and knockout tower 15. The bottom of the first-stage fixed bed reactor I1 is respectively connected with a n-pentene storage tank 3, a solvent I storage tank 4 and a hydrogen peroxide storage tank 5 through pipelines, and a flow meter 6 is arranged on the connected pipelines; the upper part of the first-stage fixed bed reactor I1 is connected with the bottom of the second-stage fixed bed reactor I2; the top of the first-stage fixed bed reactor I1 is connected with a n-pentene storage tank 3; the top of the second-stage fixed bed reactor I2 is connected with a n-pentene storage tank 3; the upper part of the second-stage fixed bed reactor I2 is connected with a rectifying tower I7; the top of the rectifying tower I7 is connected with a solvent I storage tank 4; the bottom of the rectifying tower I7 is connected with a propyl ethylene oxide storage tank 10; the bottom of the first-stage fixed bed reactor II 8 is respectively connected with a propyl ethylene oxide storage tank 10, a solvent II storage tank 12 and a water storage tank 11 through pipelines, and a mass flowmeter 13 is arranged on the connected pipelines; the upper part of the first-stage fixed bed reactor II 8 is connected with the bottom of the second-stage fixed bed reactor II 9; the upper part of the second-stage fixed bed reactor II 9 is connected with a rectifying tower II 14; the top of the rectifying tower II 14 is connected with a solvent II storage tank 12; the bottom of the rectifying tower II 14 is connected with a separation tower 15; the separation column 15 is connected to a finished product storage tank 16.
All the devices are connected through pipelines.
Example 2
The apparatus of example 1 was used to prepare 1, 2-pentanediol by the following specific steps:
(1) continuously feeding n-pentene, methanol and 30% hydrogen peroxide into the bottom of a first-stage fixed bed reactor I at flow rates of 100Kg/h, 300Kg/h and 160Kg/h respectively, reacting in the reactor, filling a Ti/Si molecular sieve catalyst into the first-stage fixed bed reactor I, and controlling the reaction temperature in the first-stage fixed bed reactor I to be 55 ℃;
(2) overflowing the reaction liquid in the step (1) to the bottom of a second-stage fixed bed reactor I through the upper part of a first-stage fixed bed reactor I for continuous reaction, filling a Ti/Si molecular sieve catalyst in the second-stage fixed bed reactor I, controlling the reaction temperature in the second-stage fixed bed reactor I to be 55 ℃, and circulating unreacted n-pentene to an n-pentene storage tank;
(3) overflowing the reaction liquid in the step (2) to a rectifying tower I through the upper part of a second-stage fixed bed reactor I, and rectifying to recover dichloroethane; obtaining an intermediate propyl oxirane from the bottom of the rectifying tower I, and feeding the intermediate propyl oxirane into a propyl oxirane storage tank;
(4) continuously feeding the intermediate propyl ethylene oxide prepared in the step (3), water and dichloroethane to the bottom of a first-stage fixed bed reactor II at flow rates of 120Kg/h, 12Kg/h and 360Kg/h respectively, reacting in the reactor, filling the first-stage fixed bed reactor II with a strong acid cation exchange resin, and controlling the reaction temperature of the first-stage fixed bed reactor II to be 60 ℃;
(5) in the step (4), the reaction liquid flows to the bottom of a second-stage fixed bed reactor II through an overflow pipe on the upper part of the first-stage fixed bed reactor II to continue reacting, the second-stage fixed bed reactor II is filled with strong acid cation exchange resin, and the reaction temperature in the second-stage fixed bed reactor I is controlled to be 60 ℃;
(6) and (5) overflowing the reaction liquid to a rectifying tower II through the upper part of the fixed bed to rectify and separate water and dichloroethane in the 1, 2-pentanediol, returning the dichloroethane to a dichloroethane storage tank, allowing the 1, 2-pentanediol to flow out of the bottom of the rectifying tower and enter a separation tower, and removing the 1, 2-pentanediol in the separation tower under high negative pressure to obtain a product. The sample introduction is carried out continuously for 24h, 2400Kg of n-pentene is added totally, 3344.6Kg of 1, 2-pentanediol is obtained totally, and the total yield is 92%. The sampling was gas phase checked and the 1, 2-pentanediol content was 97.1%. The specific results are shown in the following table 1:
TABLE 1 results of the measurements
| Number of peak | Retention time | Area of | Height | Content (wt.) |
| 1 | 5.379 | 42698834 | 9504209 | 97.135％ |
| 2 | 9.111 | 1259403 | 92590 | 2.865％ |
| All are | 43958237 | 9596799 | 100.000％ |
Example 3
The apparatus of example 1 was used to prepare 1, 2-pentanediol by the following specific steps:
(1) continuously feeding n-pentene, methanol and 30% hydrogen peroxide into the bottom of a first-stage fixed bed reactor I at flow rates of 100Kg/h, 400Kg/h and 145Kg/h respectively, reacting in a reactor, filling a Ti/Si molecular sieve catalyst into the first-stage fixed bed reactor I, and controlling the reaction temperature in the first-stage fixed bed reactor I to be 50 ℃;
(2) overflowing the reaction liquid in the step (1) to the bottom of a second-stage fixed bed reactor I through the upper part of a first-stage fixed bed reactor I for continuous reaction, filling a Ti/Si molecular sieve catalyst in the second-stage fixed bed reactor I, controlling the reaction temperature in the second-stage fixed bed reactor I to be 50 ℃, and circulating unreacted n-pentene to an n-pentene storage tank;
(3) overflowing the reaction liquid in the step (2) to a rectifying tower I through the upper part of a second-stage fixed bed reactor I to rectify and recover methanol; obtaining an intermediate propyl oxirane at the bottom of the rectifying tower I, and feeding the intermediate propyl oxirane into a propyl oxirane storage tank;
(4) continuously feeding the intermediate propyl oxirane prepared in the step (3), water and dichloroethane to the bottom of a first-stage fixed bed reactor II at flow rates of 120Kg/h, 12Kg/h and 360Kg/h respectively, reacting in a reactor, filling a strong-acid cation exchange resin in the first-stage fixed bed reactor II, and controlling the reaction temperature of the first-stage fixed bed reactor II to be 70 ℃;
(5) in the step (4), the reaction liquid flows to the bottom of a second-stage fixed bed reactor II through an overflow pipe on the upper part of the first-stage fixed bed reactor II to continue reacting, the second-stage fixed bed reactor II is filled with strong acid cation exchange resin, and the reaction temperature in the second-stage fixed bed reactor I is controlled to be 70 ℃;
(6) and (5) overflowing the reaction liquid to a rectifying tower II through the upper part of the fixed bed to rectify and separate water and dichloroethane in the 1, 2-pentanediol, returning the dichloroethane to a dichloroethane storage tank, enabling the 1, 2-pentanediol to flow out of the bottom of the rectifying tower and enter a separating tower, and removing the 1, 2-pentanediol in the separating tower through high negative pressure to obtain a product. The sample is continuously injected for 24 hours, 2400Kg of n-pentene is added, 3494.7Kg of 1, 2-pentanediol is obtained, and the total yield is 98.9%. A sample was taken and examined for gas phase, and the 1, 2-pentanediol content was 99.986%. The specific results are shown in the following table 2:
TABLE 2 test results
| Peak number | Retention time | Area of | Height | Content (wt.) |
| 1 | 5.180 | 101600177 | 18971922 | 99.986％ |
| 2 | 9.230 | 14232 | 1580 | 0.014％ |
| All are | 101614409 | 18973502 | 100.000％ |
Example 4
The apparatus of example 1 was used to prepare 1, 2-pentanediol by the following specific steps:
(1) continuously feeding n-pentene, ethanol and 30% hydrogen peroxide into the bottom of a first-stage fixed bed reactor I at flow rates of 100Kg/h, 500Kg/h and 128Kg/h respectively, reacting in the reactor, filling a Ti/Si molecular sieve catalyst into the first-stage fixed bed reactor I, and controlling the reaction temperature in the first-stage fixed bed reactor I to be 40 ℃;
(2) overflowing the reaction liquid in the step (1) to the bottom of a second-stage fixed bed reactor I through the upper part of a first-stage fixed bed reactor I for continuous reaction, filling a Ti/Si molecular sieve catalyst in the second-stage fixed bed reactor I, controlling the reaction temperature in the second-stage fixed bed reactor I to be 40 ℃, and circulating unreacted n-pentene to an n-pentene storage tank;
(3) overflowing the reaction liquid in the step (2) to a rectifying tower I through the upper part of a second-stage fixed bed reactor I, and rectifying to recover ethanol; obtaining an intermediate propyl oxirane at the bottom of the rectifying tower I, and feeding the intermediate propyl oxirane into a propyl oxirane storage tank;
(4) continuously feeding the intermediate propylethylene oxide prepared in the step (3), water and toluene into the bottom of a first-stage fixed bed reactor II at flow rates of 120Kg/h, 12Kg/h and 360Kg/h respectively, reacting in a reactor, filling the first-stage fixed bed reactor II with a strong-acid cation exchange resin, and controlling the reaction temperature of the first-stage fixed bed reactor II to be 80 ℃;
(5) in the step (4), the reaction liquid flows to the bottom of a second-stage fixed bed reactor II through an overflow pipe on the upper part of the first-stage fixed bed reactor II to continue reacting, the second-stage fixed bed reactor II is filled with strong acid cation exchange resin, and the reaction temperature in the second-stage fixed bed reactor I is controlled to be 80 ℃;
(6) and (5) overflowing the reaction liquid to a rectifying tower II through the upper part of the fixed bed to rectify and separate water in the 1, 2-pentanediol, returning the toluene to a toluene storage tank, enabling the 1, 2-pentanediol to flow out of the bottom of the rectifying tower and enter a separating tower, and removing the 1, 2-pentanediol in the separating tower through high negative pressure to obtain a product. The sample is continuously injected for 24 hours, 2400Kg of n-pentene is added, 3303.9Kg of 1, 2-pentanediol is obtained, and the total yield is 93.5%. Sampling and gas phase detection show that the content of 1, 2-pentanediol is 99.9%. The specific results are shown in the following table 3:
TABLE 3 test results
| Peak number | Retention time | Area of | Height | Content (wt.) |
| 1 | 5.345min | 25574598 | 6090919 | 99.99％ |
| 2 | 9.809min | 1246 | 171 | 0.0049％ |
| All are | 25575844 | 6091090 | 100.000％ |
Example 5
The apparatus of example 1 was used to prepare 1, 2-pentanediol by the following specific steps:
(1) continuously feeding n-pentene, methanol and 30% hydrogen peroxide into the bottom of a first-stage fixed bed reactor I at flow rates of 100Kg/h, 400Kg/h and 145Kg/h respectively, reacting in a reactor, filling a Ti/Si molecular sieve catalyst into the first-stage fixed bed reactor I, and controlling the reaction temperature in the first-stage fixed bed reactor I to be 50 ℃;
(2) overflowing the reaction liquid in the step (1) to the bottom of a second-stage fixed bed reactor I through the upper part of a first-stage fixed bed reactor I for continuous reaction, filling a Ti/Si molecular sieve catalyst in the second-stage fixed bed reactor I, controlling the reaction temperature in the second-stage fixed bed reactor I to be 50 ℃, and circulating unreacted n-pentene to an n-pentene storage tank;
(3) overflowing the reaction liquid in the step (2) to a rectifying tower I through the upper part of a second-stage fixed bed reactor I to rectify and recover methanol; obtaining an intermediate propyl oxirane at the bottom of the rectifying tower I, and feeding the intermediate propyl oxirane into a propyl oxirane storage tank;
(4) continuously feeding the intermediate propyl ethylene oxide prepared in the step (3), water and benzene into the bottom of a first-stage fixed bed reactor II at flow rates of 120Kg/h, 12Kg/h and 360Kg/h respectively, reacting in a reactor, filling the first-stage fixed bed reactor II with a strong acid cation exchange resin, and controlling the reaction temperature of the first-stage fixed bed reactor II to be 80 ℃;
(5) in the step (4), the reaction liquid flows to the bottom of a second-stage fixed bed reactor II through an overflow pipe on the upper part of the first-stage fixed bed reactor II to continue reacting, the second-stage fixed bed reactor II is filled with strong acid cation exchange resin, and the reaction temperature in the second-stage fixed bed reactor I is controlled to be 80 ℃;
(6) and (5) overflowing the reaction liquid to a rectifying tower II through the upper part of the fixed bed to rectify and separate water in the 1, 2-pentanediol, returning the benzene to a benzene storage tank, enabling the 1, 2-pentanediol to flow out of the bottom of the rectifying tower and enter a separating tower, and removing the 1, 2-pentanediol in the separating tower through high negative pressure to obtain a product. The sample is continuously injected for 24 hours, 2400Kg of n-pentene is added, 3417.0Kg of 1, 2-pentanediol is obtained, and the total yield is 96.7%. Sampling and gas phase detection show that the content of 1, 2-pentanediol is 99.9%. The specific results are shown in the following table 4:
TABLE 4 test results
| Peak number | Retention time | Area of | Height | Content (wt.) |
| 1 | 5.339min | 21428557 | 5121100 | 99.9953％ |
| 2 | 9.08min | 1002 | 141 | 0.0047％ |
| All are | 21429559 | 5121241 | 100.000％ |
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A continuous production process of 1, 2-pentanediol is characterized by comprising the following specific steps:
(1) metering n-pentene, a solvent I and 30% hydrogen peroxide by a flowmeter, continuously feeding the mixture into the bottom of a first-stage fixed bed reactor I, and reacting in the reactor;
(2) in the step (1), the reaction liquid flows to the bottom of a second-stage fixed bed reactor I through an overflow pipe on the upper part of the first-stage fixed bed reactor I to continue to react, and unreacted n-pentene is circulated to a feeding section through a gas phase line;
(3) overflowing the reaction liquid in the step (2) to a rectifying tower I through the upper part of a second-stage fixed bed reactor I to rectify and recover a solvent I; obtaining an intermediate propyl oxirane at the bottom of the rectifying tower I;
(4) metering the intermediate propyl oxirane prepared in the step (3), water and a solvent II through a mass flow meter, continuously feeding the metered intermediate propyl oxirane, the water and the solvent II into the bottom of a first-stage fixed bed reactor II, and reacting in the reactor;
(5) in the step (4), the reaction liquid flows to the bottom of the second-stage fixed bed reactor through an overflow pipe at the upper part of the first-stage fixed bed reactor II to continue to react;
(6) and (5) overflowing the reaction liquid to a rectifying tower II through the upper part of the fixed bed to rectify and separate water in the 1, 2-pentanediol, flowing out of the bottom of the rectifying tower and allowing the solvent II, 1, 2-pentanediol to enter a separating tower, and separating the 1, 2-pentanediol in the separating tower through high negative pressure to obtain a product.
2. The continuous production process of 1, 2-pentanediol according to claim 1, wherein the first-stage fixed bed reactor i and the second-stage fixed bed reactor i are filled with a catalyst; the catalyst is a Ti/Si molecular sieve catalyst.
3. The continuous production process of 1, 2-pentanediol according to claim 1, wherein the first-stage fixed bed reactor ii and the second-stage fixed bed reactor ii are filled with resin; the resin is a strong acid cation exchange resin.
4. The continuous production process of 1, 2-pentanediol according to claim 1, wherein the solvent i in step (1) is one of dichloroethane, methanol, or ethanol.
5. The continuous production process of 1, 2-pentanediol according to claim 1, wherein the reaction temperature of the primary fixed bed reactor I is 40-55 ℃; the reaction temperature of the second-stage fixed bed reactor I is 40-55 ℃.
6. The continuous production process of 1, 2-pentanediol according to claim 1, wherein the molar ratio of the dosage of the n-pentene to the dosage of the hydrogen peroxide is 1: 0.8-1.
7. The continuous production process of 1, 2-pentanediol according to claim 1, wherein the mass ratio of the n-pentene to the solvent I is 1: 3-5.
8. The continuous production process of 1, 2-pentanediol according to claim 1, wherein the reaction temperature of the primary fixed bed reactor II is 50-80 ℃; and the reaction temperature of the second-stage fixed bed reactor II is 50-80 ℃.
9. The continuous process for producing 1, 2-pentanediol according to claim 1, wherein the solvent in step (4) is one of toluene, benzene, xylene, dichloromethane, and dichloroethane.
10. Production equipment of 1, 2-pentanediol is characterized by comprising a first-stage fixed bed reactor I, a second-stage fixed bed reactor I, a first-stage fixed bed reactor II, a second-stage fixed bed reactor II, a rectifying tower I, a rectifying tower II and a separation tower; the bottom of the first-stage fixed bed reactor I is respectively connected with a n-pentene storage tank, a solvent I storage tank and a hydrogen peroxide storage tank through pipelines, and a flowmeter is arranged on the connected pipelines; the upper part of the first-stage fixed bed reactor I is connected with the bottom of the second-stage fixed bed reactor I; the top of the first-stage fixed bed reactor I is connected with a normal pentene storage tank; the top of the second-stage fixed bed reactor I is connected with a n-pentene storage tank; the upper part of the second-stage fixed bed reactor I is connected with a rectifying tower I; the top of the rectifying tower I is connected with a storage tank of a solvent I; the bottom of the rectifying tower I is connected with a propyl ethylene oxide storage tank; the bottom of the first-stage fixed bed reactor II is respectively connected with a propyl ethylene oxide storage tank, a solvent II storage tank and a water storage tank through pipelines, and a mass flowmeter is arranged on the connected pipelines; the upper part of the first-stage fixed bed reactor II is connected with the bottom of the second-stage fixed bed reactor II; the upper part of the second-stage fixed bed reactor II is connected with a rectifying tower II; the top of the rectifying tower II is connected with a solvent II storage tank; the bottom of the rectifying tower II is connected with the separation tower; the separation tower is connected with a finished product storage tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210339948.4A CN114702367A (en) | 2022-04-01 | 2022-04-01 | Continuous production process and production equipment of 1, 2-pentanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210339948.4A CN114702367A (en) | 2022-04-01 | 2022-04-01 | Continuous production process and production equipment of 1, 2-pentanediol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114702367A true CN114702367A (en) | 2022-07-05 |
Family
ID=82173105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210339948.4A Pending CN114702367A (en) | 2022-04-01 | 2022-04-01 | Continuous production process and production equipment of 1, 2-pentanediol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114702367A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414872A (en) * | 2022-08-11 | 2022-12-02 | 安徽润衍科技有限公司 | Tubular isothermal reactor and process for producing 1,2-pentanediol from 1, 2-cyclopentane oxide |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605795A (en) * | 1984-11-24 | 1986-08-12 | Degussa Aktiengesellschaft | Continuous process for the production of pentanediol-1,2 |
| CN101885668A (en) * | 2010-07-20 | 2010-11-17 | 江苏扬农化工集团有限公司 | New method for preparing 1,2-pentadiol |
| CN102010293A (en) * | 2010-11-02 | 2011-04-13 | 云南大学 | Method for catalyzing and synthesizing 1, 2-pentanediol by using titanium silicalite |
| CN103896880A (en) * | 2012-12-26 | 2014-07-02 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
| CN105461511A (en) * | 2014-08-27 | 2016-04-06 | 中国石油化工股份有限公司 | Preparation of 1,2-pentanediol through oxidative hydrolysis of alpha-amylene |
| CN106478373A (en) * | 2015-08-25 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of method that vicinal diamines class compound is synthesized for catalyst with macroporous anion exchange resin |
| CN110283046A (en) * | 2019-07-31 | 2019-09-27 | 新乡市巨晶化工有限责任公司 | A kind of preparation method of 1,2- pentanediol |
| CN110724116A (en) * | 2018-07-16 | 2020-01-24 | 东营市海科新源化工有限责任公司 | Preparation method and production system of vicinal diol compound |
| CN113105414A (en) * | 2021-03-18 | 2021-07-13 | 浙江禾本科技股份有限公司 | Method for preparing 1, 2-epoxy pentane |
-
2022
- 2022-04-01 CN CN202210339948.4A patent/CN114702367A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605795A (en) * | 1984-11-24 | 1986-08-12 | Degussa Aktiengesellschaft | Continuous process for the production of pentanediol-1,2 |
| CN101885668A (en) * | 2010-07-20 | 2010-11-17 | 江苏扬农化工集团有限公司 | New method for preparing 1,2-pentadiol |
| CN102010293A (en) * | 2010-11-02 | 2011-04-13 | 云南大学 | Method for catalyzing and synthesizing 1, 2-pentanediol by using titanium silicalite |
| CN103896880A (en) * | 2012-12-26 | 2014-07-02 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
| CN105461511A (en) * | 2014-08-27 | 2016-04-06 | 中国石油化工股份有限公司 | Preparation of 1,2-pentanediol through oxidative hydrolysis of alpha-amylene |
| CN106478373A (en) * | 2015-08-25 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of method that vicinal diamines class compound is synthesized for catalyst with macroporous anion exchange resin |
| CN110724116A (en) * | 2018-07-16 | 2020-01-24 | 东营市海科新源化工有限责任公司 | Preparation method and production system of vicinal diol compound |
| CN110283046A (en) * | 2019-07-31 | 2019-09-27 | 新乡市巨晶化工有限责任公司 | A kind of preparation method of 1,2- pentanediol |
| CN113105414A (en) * | 2021-03-18 | 2021-07-13 | 浙江禾本科技股份有限公司 | Method for preparing 1, 2-epoxy pentane |
Non-Patent Citations (2)
| Title |
|---|
| 李亚男;何文军;俞峰萍;陈梁锋;戈军伟;: "离子交换树脂在有机催化反应中的应用进展" * |
| 罗岩;徐保明;汤国亮;陈坤;: "丙环唑中间体1,2-戊二醇的合成进展" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414872A (en) * | 2022-08-11 | 2022-12-02 | 安徽润衍科技有限公司 | Tubular isothermal reactor and process for producing 1,2-pentanediol from 1, 2-cyclopentane oxide |
| CN115414872B (en) * | 2022-08-11 | 2023-11-03 | 安徽润衍科技有限公司 | Tubular isothermal reactor and method for producing 1,2-pentanediol from 1, 2-epoxypentane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102008922B (en) | Process method and method for regenerating methyl nitrite in production of dimethyl oxalate | |
| CN108395422A (en) | A kind of the synthesis extracting process and device of metaformaldehyde | |
| CN114702367A (en) | Continuous production process and production equipment of 1, 2-pentanediol | |
| CN102351665A (en) | Preparation method of methylal | |
| CN110467595A (en) | A kind of no sulfuric acid process metaformaldehyde synthesizer and its synthesis route | |
| CN111499598A (en) | Production process for preparing epichlorohydrin by glycerol method | |
| CN107311868A (en) | A kind of method for preparing p-tert-butyl benzoic acid methyl esters | |
| CN106588590A (en) | Refinement method for polyoxymethylene dimethyl ether | |
| PL106455B1 (en) | METHOD OF MANUFACTURING UREA AND AMMONIA IN A COMMON PROCESS | |
| CN110483281A (en) | A kind of production method of ethyl difluoro | |
| CN213708194U (en) | Process unit for preparing cyclopentanol from cyclopentene | |
| CN210237495U (en) | Reactive distillation-steam permeation coupling device for synthesizing polymethoxy dimethyl ether | |
| CN114133330B (en) | Method for preparing methyl ethyl carbonate by adopting pipeline continuous reactor | |
| CN201862399U (en) | Regeneration device for methyl nitrite in production process of oxalic acid dimethyl ester | |
| CN102001938B (en) | Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid | |
| CN208717206U (en) | A kind of synthesis extraction equipment of metaformaldehyde | |
| CN210303646U (en) | Water adding inerting device for oxidation reaction of p-tert-butylbenzoic acid | |
| CN113214258A (en) | Method and device for synthesizing diquat dichloride | |
| CN109824498B (en) | Diacetone alcohol continuous production device and production process | |
| CN108299258B (en) | Synthetic method of p-methylsulfonylbenzoic acid | |
| CN102019164B (en) | Ethyl nitrite regeneration technological method in diethyl oxalate production process | |
| CN105732508A (en) | Continuous preparation method of N-methylimidazole | |
| CN201862400U (en) | Ethyl nitrite regenerating device in production process of diethyl oxalate | |
| CN216630783U (en) | Production device of natural delta-decalactone spice | |
| KR101813115B1 (en) | Integrated system comprising electrocatalytic reactor of glycerol and chemical catalyst reactor of biomass |
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 |