CN114105735A - Preparation method and production device of Guerbet alcohol ether - Google Patents
Preparation method and production device of Guerbet alcohol ether Download PDFInfo
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- CN114105735A CN114105735A CN202111364062.7A CN202111364062A CN114105735A CN 114105735 A CN114105735 A CN 114105735A CN 202111364062 A CN202111364062 A CN 202111364062A CN 114105735 A CN114105735 A CN 114105735A
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- guerbet alcohol
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- ethylene oxide
- mixer
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 91
- 239000007788 liquid Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 34
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- -1 alcohol ethers Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00873—Heat exchange
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00889—Mixing
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/0095—Control aspects
- B01J2219/00952—Sensing operations
- B01J2219/00954—Measured properties
- B01J2219/00961—Temperature
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/0095—Control aspects
- B01J2219/00952—Sensing operations
- B01J2219/00954—Measured properties
- B01J2219/00963—Pressure
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/0095—Control aspects
- B01J2219/00984—Residence time
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of Guerbet alcohol ether and a production device thereof, belonging to the technical field of alcohol ether preparation. The preparation method comprises the following steps: mixing Guerbet alcohol, potassium hydroxide and ethylene oxide in a mixer to obtain a mixture; transferring the mixture into a microchannel reactor to react for 0.5-1.5 min under the conditions of 140-200 ℃ and 1-6 MPa to obtain Guerbet alcohol ether; the Guerbet alcohol and the ethylene oxide are reactants, the potassium hydroxide is a catalyst, and the addition amount of the potassium hydroxide is 1.0-4.0 per mill of the total mass of the Guerbet alcohol and the ethylene oxide. The method for preparing the Guerbet alcohol ether has high production efficiency, high selectivity of a target product and low production cost.
Description
Technical Field
The invention belongs to the technical field of alcohol ether preparation, and particularly relates to a preparation method and a production device of Guerbet alcohol ether.
Background
The isomeric fatty alcohol polyoxyethylene ether series products are easy to disperse or dissolve in water, have excellent wettability, permeability and emulsibility, are used as components of degreasing agents, detergents, emulsifiers and refining agents in textile industry and leather industry, and can also be used as metal processing agents, multifunctional detergents, decontamination solubilizers, household care detergents, vehicles, public facilities, ultrasonic detergents and the like.
In the prior art, a semi-batch gas-liquid ethoxylation reactor is generally adopted to prepare alcohol ether, and the reactor generally takes raw materials and a catalyst as an initiator to be added into the reactor together, and then ethoxylation is carried out in a mode of continuously feeding EO. Of these, stirred reactors, Buss loop reactors and Press recirculating sparged reactors are the three more common semi-batch reactors. However, the reaction using the stirred reactor has the following disadvantages: a. the reaction rate is low, and the reaction time is long; b. explosion and electrostatic deflagration are easy to occur; c. the by-products are increased and the chain growth of the product is smaller. Buss loop reactors and Press circulating spray reactors are superior to stirred reactors in terms of safety and throughput. However, the reaction rate of the Press reactor ethoxylation process is relatively slow, increasing energy consumption. And the Buss reactor has less industrial devices. In addition to the above three reactors, there are also researchers who have carried out the production of alcohol ethers using a tubular reactor, but the tubular reactor has a small addition amount per stage of the reactor due to mixing problems, is difficult to produce a high molecular weight product, and has a low productivity due to a small reaction cross-sectional area.
Disclosure of Invention
The invention provides a preparation method of Guerbet alcohol ether and a production device thereof, which have the advantages of high reaction efficiency, high selectivity of target products and low production cost.
In order to achieve the above object, the present invention provides a method for preparing a guerbet alcohol ether, comprising the steps of:
mixing Guerbet alcohol, potassium hydroxide and ethylene oxide in a mixer to obtain a mixture;
transferring the mixture into a microchannel reactor to react for 0.5-1.5 min under the conditions of 140-200 ℃ and 1-6 MPa to obtain Guerbet alcohol ether;
the addition amount of the potassium hydroxide is 1.0-4.0 per mill of the total mass of the Guerbet alcohol and the ethylene oxide.
Preferably, the molar ratio of the Guerbet alcohol to the ethylene oxide is 1:2 to 1: 9.
Preferably, the Guerbet alcohol is a C12-18 Guerbet alcohol.
Preferably, the flow range of the microchannel reactor is 0-100 mL/min, and the liquid holdup of the reaction pipeline is 14 mL.
Preferably, the mixer is a microchannel reactor with a liquid hold-up of 8mL in the pipeline.
The invention provides a production device of the method in any scheme, which comprises a mixer, a microchannel reactor and a cooler;
the discharge hole of the mixer is connected with the feed hole of the microchannel reactor through a pipeline; and the discharge port of the microchannel reactor is connected with the cooler through a pipeline.
Preferably, the microchannel reactor is provided with a temperature sensor, a heat exchange main pipeline, a heat exchange medium inlet temperature sensor and a heat exchange medium outlet temperature sensor.
Preferably, a plunger pump is further included; the plunger pump is connected with the feeding pipeline of the mixer.
Preferably, the cooler further comprises a backpressure valve, and the backpressure valve is connected with the discharge hole of the cooler.
Compared with the prior art, the invention has the advantages and positive effects that:
the invention provides a preparation method of Guerbet alcohol ether, which comprises the steps of mixing Guerbet alcohol, potassium hydroxide and ethylene oxide in a mixer to obtain a mixture; and transferring the mixture into a microchannel reactor to react for 0.5-1.5 min under the conditions of 140-200 ℃ and 1-6 MPa to obtain the Guerbet alcohol ether. The invention takes the microchannel reactor as a mixer, and is connected with the microchannel reactor for reaction subsequently, the Guerbet alcohol and the ethylene oxide can be fully mixed in the mixer, the gas phase and the liquid phase enter the microchannel reactor again, and the gas phase and the liquid phase are further contacted, so that the reaction efficiency is improved. Meanwhile, the reaction residence time is greatly shortened, and the product selectivity is effectively improved.
Furthermore, the invention provides a production device of the method, which has the advantages of small volume, low cost, convenient operation and control and suitability for continuous production.
Drawings
FIG. 1 is a schematic view of the structure of a production apparatus for producing a Guerbet alcohol ether according to the present invention;
FIG. 2 is a schematic view of the internal structure of the microchannel reactor of the present invention;
FIG. 3 is a schematic view showing the structure of a Press recirculating spray reactor used in comparative example 8;
FIG. 4 is a schematic view of the structure of a stirred tank reactor used in comparative example 9;
wherein: 1-temperature sensor, 2-standby inlet, 3-raw material inlet, 4-product outlet, 5-heat exchange main pipeline, 6-heat exchange medium outlet temperature sensor, 7-heat exchange medium outlet, 8-heat exchange medium inlet and 9-heat exchange medium inlet temperature sensor.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments 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.
The invention provides a preparation method of Guerbet alcohol ether, which comprises the following steps:
mixing Guerbet alcohol, potassium hydroxide and ethylene oxide in a mixer to obtain a mixture;
transferring the mixture into a microchannel reactor to react for 0.5-1.5 min under the conditions of 140-200 ℃ and 1-6 MPa to obtain Guerbet alcohol ether;
the addition amount of the potassium hydroxide is 1.0-4.0 per mill of the total mass of the Guerbet alcohol and the ethylene oxide.
According to the invention, Guerbet alcohol, potassium hydroxide and ethylene oxide are mixed in a mixer to obtain a mixture. In the present invention, the Guerbet alcohol is preferably a C12-18 Guerbet alcohol. In the present invention, the molar ratio of the Guerbet alcohol to ethylene oxide is preferably 1:2 to 1: 9. In the present invention, the amount of potassium hydroxide added is 1.0 to 4.0%, preferably 3%, of the total mass of the Guerbet alcohol and ethylene oxide.
In the present invention, the mixer is preferably a microchannel reactor having a liquid hold-up of 8mL in a line, that is, the microchannel reactor is used as a mixing device of Guerbet alcohol and ethylene oxide. The reaction raw materials, Guerbet alcohol, are in a liquid phase and ethylene oxide is in a gas phase, so that the solubility of ethylene oxide in Guerbet alcohol is low during the reaction, and the reaction efficiency is low. The invention takes the microchannel reactor as a mixer, so that the Guerbet alcohol and the ethylene oxide can be fully mixed, and the reaction efficiency is improved.
After the mixture is obtained, the mixture is transferred into a microchannel reactor to react for 0.5-1.5 min under the conditions of 140-200 ℃ and 1-6 MPa, and the Guerbet alcohol ether is obtained. In the present invention, the reaction temperature is preferably 190 ℃, the pressure is preferably 3Mpa, and the reaction time is preferably 1 min. The reaction temperature is low, the pressure is low, the reaction time is too short, the conversion rate is not improved, the by-products are increased due to the high temperature, the high pressure and the long reaction time, and the energy consumption is high.
In the invention, the flow range of the microchannel reactor is preferably 0-100 mL/min, and the liquid holdup of a reaction pipeline is preferably 14 mL. In the invention, the reaction time of the materials in the microchannel reactor is controlled by adjusting the flow rate of the microchannel reactor. In the invention, the microchannel reactor is adopted for reaction, so that the reaction raw materials are further fully contacted, the reaction rate is improved, and the energy consumption is reduced. Meanwhile, the reaction residence time is greatly shortened, and the product selectivity is effectively improved.
The invention also provides a production device of the method in any scheme, which comprises a mixer, a microchannel reactor and a cooler;
the discharge hole of the mixer is connected with the feed hole of the microchannel reactor through a pipeline; and the discharge port of the microchannel reactor is connected with the cooler through a pipeline.
In the invention, the microchannel reactor is preferably provided with a temperature sensor, a heat exchange main pipeline, a heat exchange medium inlet temperature sensor and a heat exchange medium outlet temperature sensor. The internal structure of the microchannel reactor is shown in fig. 1.
In the present invention, the production apparatus preferably further comprises a plunger pump; the plunger pump is preferably connected to the feed line of the mixer. In the present invention, two plunger pumps are preferably included, one pumping ethylene oxide into the mixer and the other pumping Guerbet alcohol and catalyst into the mixer. In the invention, the range of the plunger pump is preferably 0.01-100 mL/min.
In the present invention, it is preferable that the cooling system further comprises a back pressure valve connected to a discharge port of the cooler.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of C12 guerbet alcohol ether (EO ═ 2).
3% o of the catalyst was dissolved in C12 Guerbet alcohol (M188 g/mol). The Guerbet alcohol and the ethylene oxide dissolved with the catalyst are respectively pumped into a mixer through a plunger pump to be mixed, and the obtained mixture is led into a micro-channel reactor (the temperature of the micro-channel reactor is set to be 190 ℃, the reaction pressure is controlled to be 3Mpa, and the residence time of the reaction is 1 min).
The product obtained from the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain a conversion of C12 Guerbet alcohol of 73.2%, the hydroxyl number was determined and the average EO addition number was calculated to be 2.08.
Example 2
The product and the process were the same as in example 1, except that: the temperature of the microchannel reactor was set at 165 ℃, the reaction pressure was controlled at 6Mpa, and the residence time of the reaction was 1.5 min. The product obtained from the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain a conversion of 72.76% of C12 Guerbet alcohol, the hydroxyl number was determined and the average EO addition number was calculated to be 2.2.
Example 3
The product and the process were the same as in example 1, except that: the dosage of the catalyst is 2 per mill. The product obtained from the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain C12 Guerbet alcohol with a conversion of 65.5%, a hydroxyl value was determined and the average EO addition number calculated to be 1.7.
Example 4
Preparation of C16 guerbet alcohol ether (EO ═ 5).
Respectively pumping C16 Guerbet alcohol (M is 243g/mol) and ethylene oxide which are dissolved with 3 thousandths of catalyst and cooled into a mixer through a plunger pump for mixing, and introducing the mixture into a microchannel reactor (the temperature of the microchannel reactor is set to be 190 ℃, the reaction pressure is controlled to be 3Mpa, and the residence time of the reaction is 1 min).
The product obtained from the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain a conversion of 92.55% of C16 Guerbet alcohol, the hydroxyl number was determined and the average EO addition number was calculated to be 5.05.
Comparative example 1
The product and the process were the same as in example 1, except that: a mixer is not used for mixing, and a plunger pump is directly adopted to pump reaction raw materials into the microchannel reactor. The specific operation steps are as follows:
3% o of the catalyst was dissolved in C12 Guerbet alcohol. Respectively pumping the catalyst-dissolved Guerbet alcohol and ethylene oxide into a microchannel reactor through a plunger pump, setting the temperature of the microchannel reactor to be 190 ℃, controlling the reaction pressure to be 3Mpa, and setting the residence time of the reaction to be 1min), measuring the content of free alcohol in a product obtained by the reaction by using n-nonanol as an internal standard to obtain the conversion rate of C12 Guerbet alcohol to be 44.62%, measuring the hydroxyl value, and calculating the average EO addition number to be 1.7.
Comparative example 2
The product and the process were the same as in example 1, except that: the guerbet alcohol and ethylene oxide with dissolved catalyst were mixed using a membrane dispersion mixer. The product obtained from the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain a conversion of 63.39% of C12 Guerbet alcohol, the hydroxyl number was determined and the average EO addition number was calculated to be 2.2.
Comparative example 3
The product and the process were the same as in example 1, except that: the reaction time in the microchannel reactor was 2 min. The product obtained from the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain a conversion of 75.35% of C12 Guerbet alcohol, the hydroxyl number was determined and the average EO addition number was calculated to be 2.3.
Comparative example 4
The product and the process were the same as in example 1, except that: the reaction time in the microchannel reactor was 0.4 min. The product obtained from the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain a conversion of C12 Guerbet alcohol of 45.48%, the hydroxyl number was determined and the average EO addition number was calculated to be 1.8.
Comparative example 5
The product and the process were the same as in example 1, except that: the dosage of the catalyst is 4.5 per mill. The product obtained from the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain a conversion of 72.76% of C12 Guerbet alcohol, the hydroxyl number was determined and the average EO addition number was calculated to be 2.5.
Comparative example 6
The product and the process were the same as in example 1, except that: the reaction temperature of the microchannel reactor was set at 210 ℃. The product obtained from the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain a conversion of C12 Guerbet alcohol of 73.11%, the hydroxyl number was determined and the average EO addition number was calculated to be 2.6.
Comparative example 7
The product and the process were the same as in example 1, except that: the reaction temperature of the microchannel reactor was set at 130 ℃. The product obtained by the reaction was measured for the content of free alcohol using n-nonanol as an internal standard to obtain a conversion of C12 Guerbet alcohol of 53.6%, the hydroxyl value was determined and the average EO addition number was calculated to be 1.7.
Comparative example 8
The product was prepared as in example 1, except that: c12 guerbet alcohol ether (EO ═ 2) was prepared using a Press recycle spray reactor (a schematic of the apparatus is shown in fig. 3). The specific operation is as follows:
dissolving 3 per thousand of catalyst in C12 Guerbet alcohol, sucking the solution into a reaction kettle by a vacuum pump, replacing air in the reaction kettle by high-purity nitrogen under the condition of stirring, continuously replacing for 3-4 times, charging nitrogen to 0.5MPa, setting the stirring speed to be 1200r/min, starting to heat up, when the temperature is raised to 135 ℃, closing the heating, when the temperature of the reaction kettle is raised to 140 ℃, discharging a part of nitrogen in the reaction kettle to 0.1MPa, starting to charge ethylene oxide to 0.50MPa, stopping charging ethylene oxide, starting to induce the reaction, when the pressure in the reaction kettle is lower than 0.2MPa when the ethylene oxide is consumed, starting to continuously charge ethylene oxide, and paying attention to the temperature change in the reaction kettle in the process of continuously charging ethylene oxide to ensure that the reaction temperature is not higher than 170 ℃, when the amount of charged ethylene oxide reaches a theoretical value, the ethylene oxide was turned off, the feed was stopped and the reaction was allowed to proceed fully. In order to make the reaction more complete, when the ethylene oxide is consumed until the pressure in the reaction kettle is lower than 0.2MPa, nitrogen is filled to the pressure of 0.5MPa, so that the ethylene oxide is fully reacted, when the temperature in the reaction kettle begins to drop or the pressure in the reaction kettle does not drop any more, the reaction is indicated to be completed, the heating is closed, the cooling water is opened, the temperature is started to drop, when the temperature in the reaction kettle drops to be lower than 50 ℃, the stirring is closed, the product in the reaction kettle is discharged, the reaction product is used as an internal standard to measure the content of free alcohol, the conversion rate of C12 Guerbet alcohol is calculated to be 68.04%, and the average EO addition number of the product is calculated to be 2.12 by measuring the hydroxyl value.
Comparative example 9
The product was prepared as in example 2, except that: c16 guerbet alcohol ether (EO ═ 5) was prepared using a conventional stirred tank (schematic of the apparatus shown in fig. 4). The specific operation is as follows:
dissolving 3 per thousand of catalyst in C16 Guerbet alcohol, sucking the solution into a reaction kettle by a vacuum pump, replacing air in the reaction kettle by high-purity nitrogen under the condition of stirring, continuously replacing for 3-4 times, charging nitrogen to 0.4MPa, setting the stirring speed to be 600r/min, starting to heat up, when the temperature is increased to 135 ℃, closing the heating, when the temperature of the reaction kettle is increased to 150 ℃, discharging a part of nitrogen in the reaction kettle to 0.1MPa, starting to charge ethylene oxide to 0.4MPa, stopping charging ethylene oxide, starting to induce the reaction, when the pressure in the reaction kettle is less than 0.2MPa, starting to continuously charge ethylene oxide, and paying attention to the temperature change in the reaction kettle in the process of continuously charging ethylene oxide, ensuring that the reaction temperature is not more than 170 ℃, the reaction pressure is 0.4MPa, and when the amount of charged ethylene oxide reaches a theoretical value, the ethylene oxide was turned off, the feed was stopped and the reaction was allowed to proceed fully. In order to make the reaction more complete, when the ethylene oxide is consumed until the pressure in the reaction kettle is lower than 0.2MPa, nitrogen is filled to the pressure of 0.4MPa to make the ethylene oxide fully react, when the temperature in the reaction kettle begins to drop or the pressure in the reaction kettle does not drop any more, the reaction is indicated to be completed, the heating is closed, cooling water is opened, the temperature is started to drop, when the temperature in the reaction kettle drops to below 50 ℃, the stirring is closed, the product in the reaction kettle is discharged, the content of free alcohol in the reaction product is measured by using n-nonanol as an internal standard, the conversion rate of C16 Guerbet alcohol is calculated to be 89.35%, and the average EO addition number of the product is calculated to be 6.19 by measuring the hydroxyl value.
As can be seen by comparing the comparative example with the inventive example, the process according to the invention not only increases the conversion of Guerbet alcohol, but also brings the average EO addition number of the product closer to the theoretical value.
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 (9)
1. A preparation method of Guerbet alcohol ether is characterized by comprising the following steps:
mixing Guerbet alcohol, potassium hydroxide and ethylene oxide in a mixer to obtain a mixture;
transferring the mixture into a microchannel reactor to react for 0.5-1.5 min under the conditions of 140-200 ℃ and 1-6 MPa to obtain Guerbet alcohol ether;
the addition amount of the potassium hydroxide is 1.0-4.0 per mill of the total mass of the Guerbet alcohol and the ethylene oxide.
2. The production method according to claim 1, wherein the molar ratio of the Guerbet alcohol to the ethylene oxide is 1:2 to 1: 9.
3. The method according to claim 1, wherein the Guerbet alcohol has 12 to 18 carbon atoms.
4. The preparation method of claim 1, wherein the flow rate of the microchannel reactor is in the range of 0-100 mL/min, and the liquid holdup of the reaction pipeline is 14 mL.
5. The method of claim 1, wherein the mixer is a microchannel reactor having a line liquid hold-up of 8 mL.
6. The apparatus for producing the method according to any one of claims 1 to 5, comprising a mixer, a microchannel reactor and a cooler;
the discharge hole of the mixer is connected with the feed hole of the microchannel reactor through a pipeline; and the discharge port of the microchannel reactor is connected with the cooler through a pipeline.
7. The production device according to claim 6, wherein the microchannel reactor is provided with a temperature sensor, a main heat exchange pipeline, a heat exchange medium inlet temperature sensor and a heat exchange medium outlet temperature sensor.
8. The production device of claim 6, further comprising a plunger pump; the plunger pump is connected with the feeding pipeline of the mixer.
9. The production apparatus as claimed in claim 6, further comprising a back pressure valve connected at the outlet of the cooler.
Priority Applications (1)
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