Method for efficiently preparing enol by selective hydrogenation of alkynol
阅读说明：本技术 一种由炔醇选择性加氢高效制备烯醇的方法 (Method for efficiently preparing enol by selective hydrogenation of alkynol ) 是由 李建锋 鲍元野 张永振 黎源 于 2020-12-15 设计创作，主要内容包括：本发明提供一种由炔醇选择性加氢高效制备烯醇的方法。将常规釜式反应器与微通道反应器联用,微通道反应器固载稀土金属掺杂催化剂后可快速制备烯醇产品,缩短反应时长,提高生产效率。添加膦化合物作为副反应抑制剂,提高选择性。(The invention provides a method for efficiently preparing enol by selective hydrogenation of alkynol. The conventional kettle type reactor and the microchannel reactor are combined, and the rare earth metal doped catalyst is immobilized on the microchannel reactor, so that an enol product can be quickly prepared, the reaction time is shortened, and the production efficiency is improved. The phosphine compound is added as a side reaction inhibitor to improve the selectivity.)
1. A method for preparing enol by selective hydrogenation of alkynol with high efficiency comprises the following steps:
1) mixing alkynol, a solvent, an inhibitor and hydrogen in a kettle type reactor to obtain an alkynol raw material solution;
2) the alkynol raw material liquid enters a micro-channel reactor, and the alkynol is subjected to selective hydrogenation reaction rapidly under the action of a catalyst to obtain the enol.
2. The process according to claim 1, characterized in that the alkynol has the general structural formula i:
wherein R is1、R2Is hydrogen or a hydrocarbyl group, preferably, R1Or R2One of which is hydrogen and the other is a branched or straight chain C6-20 alkyl or alkenyl group;
more preferably, the alkynol is selected from 2-methyl-3-butyn-2-ol, dehydrolinalool, dehydronerolidol, tetrahydrodehydronerolidol, dehydroisophytol.
3. The method according to claim 1 or 2, wherein the inhibitor is a phosphine compound selected from one or more of triphenylphosphine, triphenylphosphine oxide, tri (p-methylphenyl) phosphorus oxide, diphenylphosphine and tri-tert-butylphosphine, and is used in an amount of 0.01-5% by mass of the alkynol.
4. A process according to any one of claims 1 to 3, characterised in that the hydrogen pressure in the tank reactor is between 0.1MPa and 20.0MPa (absolute), preferably between 2.0MPa and 10.0MPa (absolute).
5. The process according to any one of claims 1 to 4, wherein the solvent is selected from one or more inert aliphatic alkanes, aromatic hydrocarbons, ethers, alcohols which do not react with the feedstock, preferably one or more of n-heptane, toluene, ethanol; the dosage of the solvent is 0.5 to 50 times of the mass of the alkynol, and preferably 1 to 10 times.
6. The method of any one of claims 1-5, wherein the catalyst is immobilized within a microchannel reactor and comprises an active component and a polydopamine coating;
the active component comprises a main active component and rare earth elements, wherein the main active component is selected from at least one of nickel, palladium, ruthenium and copper, and the rare earth elements are selected from at least one of lanthanum, cerium and praseodymium.
7. The method according to claim 6, wherein the main active ingredient is present in an amount of 0.5 to 20%, preferably 2 to 10% by mass of the polydopamine coating.
8. The process according to claim 5 or 6, characterized in that the rare earth element is contained in an amount of 0.01 to 5%, preferably 0.1 to 2%, by mass of the main active component.
9. The process according to any one of claims 1 to 8, wherein the alkynol feedstock is retained in the microchannel reactor for a period of time of 1 to 600 seconds, preferably 10 to 120 seconds, and the reaction temperature is 20 to 200 ℃, preferably 60 to 110 ℃.
10. The method according to any one of claims 1 to 9, wherein the volume of the treated feedstock per gram of catalyst per second is 0.01 to 5cm3Preferably 0.05 to 1.5cm3。
Technical Field
The invention relates to a method for efficiently preparing enol by selective hydrogenation of alkynol.
Background
The enol is an important intermediate for synthesizing fine chemicals such as vitamin A, vitamin E, vitamin K1, carotenoid, pyrethrin and the like, and is also a synthetic rubber monomer and a perfume product. The alkynols are usually hydrogenated selectively to give the corresponding enols, which have the general reaction formula:
wherein R is1、R2Is hydrogen or a hydrocarbyl group.
The catalyst applied to the reaction industry is a poisoned Lindlar catalyst, and the Lindlar catalyst is prepared by depositing metal palladium on carriers such as barium sulfate or calcium carbonate and the like and carrying out initial poisoning treatment by using lead acetate. The purpose of poisoning is to reduce the reaction rate of the catalyst, inhibit excessive hydrogenation reaction and improve selectivity. In order to achieve good catalytic effect, the purchased Lindlar catalyst usually needs further poisoning treatment when in use, generally sulfur-containing and nitrogen-containing compounds are added to reduce the activity of the catalyst, and the commonly used compounds include quinoline, pyridine, mercaptan and the like.
In addition, terminal alkyne self-coupling reaction is also one of the side reactions of alkynol in the selective hydrogenation Process, and 2-methyl-3-butene-2-ol in the selective hydrogenation Process is reported in the document Organic Process Research & Development 2009,13, 991-998. The reaction path is as follows:
the prior art has the following defects:
1. the Lindlar catalyst is deeply poisoned in the selective hydrogenation process of alkynol, although the selectivity is ensured, the reaction rate is reduced, the whole reaction time is prolonged, and the reaction is difficult to operate continuously.
2. In the prior art, the content of reaction byproducts is high, the overall selectivity is reduced, and the quinoline poisoning treatment catalyst is used to influence the product quality.
Disclosure of Invention
The invention provides a method for preparing enol by selective hydrogenation of alkynol, aiming at solving the defects in the prior art. The catalyst is immobilized in the microchannel reactor by adopting a combination mode of combining a conventional kettle type reactor and the microchannel reactor, and the phosphine compound is added into the system to inhibit the generation of byproducts.
The invention adopts the following technical scheme:
a method for preparing enol by selective hydrogenation of alkynol with high efficiency comprises the following steps:
1) mixing alkynol, a solvent, an inhibitor and hydrogen in a kettle type reactor to obtain an alkynol raw material solution;
2) the alkynol raw material liquid enters a micro-channel reactor, and the alkynol is subjected to selective hydrogenation reaction rapidly under the action of a catalyst to obtain the enol.
In the invention, the alkynol has a structural general formula I, and forms an enol with a structural general formula II after selective hydrogenation reaction:
wherein R is1、R2Is hydrogen or a hydrocarbyl group, preferably, R1Or R2One of which is hydrogen and the other is a branched or straight chain C6-20 alkyl or alkenyl group;
the alkynol is, for example, 2-methyl-3-butyn-2-ol, dehydrolinalool, dehydronerolidol, tetrahydrodehydronerolidol, or dehydroisophytol, etc., and has the following molecular structure:
in the invention, the kettle reactor is used as a raw material pre-mixer, reactants of alkynol, solvent, inhibitor and hydrogen are uniformly mixed in the kettle reactor, and the kettle is gas-liquid two-phase. The alkynol is only present in the liquid phase because of its very low saturated vapor pressure in the reaction vessel. The liquid phase stream enters a micro-channel reactor, the micro-channel reactor takes an immobilized rare earth metal doped hydrogenation catalyst as a reaction main unit, the stream temporarily stays in the micro-channel reactor, the alkynol is quickly converted to generate selective hydrogenation reaction to generate enol, and the stream enters a gas-liquid separation tank to perform post-treatment operation.
In the present invention, the solvent is selected from one or more inert aliphatic alkanes, aromatic hydrocarbons, ethers, alcohols which do not react with the raw material, such as one or more of n-heptane, toluene, ethanol. The dosage of the solvent is 0.5 to 50 times of the mass of the alkynol, and preferably 1 to 10 times.
In the invention, the inhibitor is a phosphine compound, such as one or more of triphenyl phosphine, triphenyl phosphine oxide, tri (p-methylphenyl) phosphine oxide, diphenyl phosphine and tri-tert-butyl phosphine, and the amount of the inhibitor is 0.01-5%, preferably 0.1-2% of the mass of the alkynol.
In the present invention, the hydrogen pressure in the tank reactor is 0.1 to 20.0MPa (absolute pressure), preferably 2.0 to 10.0MPa (absolute pressure).
In the invention, the catalyst comprises an active component and a polydopamine coating. The active component comprises a main active component and rare earth elements, wherein the main active component is selected from at least one of nickel, palladium, ruthenium and copper, preferably palladium, the rare earth elements are selected from at least one of lanthanide elements such as lanthanum, cerium and praseodymium, and the content of the main active component is 0.5-20%, preferably 2-10% of the mass of the polydopamine coating. The content of the rare earth element is 0.01-5% of the mass of the main active component, and preferably 0.1-2%.
The catalyst is immobilized in a microchannel reactor, the microchannel reactor takes the immobilized catalyst as a reaction main unit, and the immobilized catalyst exists in a nanometer metal cluster state.
The preparation method of the catalyst (the immobilization method in the microchannel reactor) can be realized by a conventional method, for example, fixing a functional particle membrane on the inner wall of a microchannel, carrying out geometric structure modification on the microchannel by a micro-processing technology such as etching or photoetching, pretreating the inner wall of the microchannel by a chemical method, and then carrying out polymerization of an organic monomer or crystal growth.
The invention adopts the microchannel reactor with the inner wall fixedly carrying the nano-scale metal cluster, the pure heterogeneous metal cluster (main active component) has high catalytic hydrogenation reaction activity, but poor selectivity, is easy to generate excessive hydrogenation, and is easy to generate terminal alkyne self-coupling reaction of raw materials under the condition of low conversion rate, thereby reducing the overall selectivity. The rare earth metal is doped in the process of immobilizing the main active component metal, so that the content of excessive hydrogenation products can be reduced, and the selectivity is improved. The reason is presumed that the addition of the rare earth metal in the rare earth metal-doped catalyst destroys the original lattice structure, so that the olefinic bond generated after the acetylene bond hydrogenation is quickly separated from the surface of the catalyst, and the generation of further hydrogenation products is avoided. In addition, the characteristics of rapid and efficient mass and heat transfer of the microchannel reactor can be utilized to shorten the contact time of the catalyst and the raw material and avoid the generation of excessive hydrogenation products. On the other hand, the phosphine compound added in advance in the raw materials can effectively inhibit the terminal alkyne self-coupling reaction from occurring. The reason for this is presumed to be that the phosphine atom is easily polarized and can interact with the triple bond of the terminal alkyne, reducing the occurrence probability of the coupling reaction.
According to the invention, the retention time of the alkynol raw material liquid in the microchannel reactor is 1-600 seconds, preferably 10-120 seconds, and the reaction temperature is 20-200 ℃, preferably 60-110 ℃. The volume of the reaction liquid treated per gram of catalyst per second is 0.01-5 cm3Preferably 0.05 to 1.5cm3。
The invention has the positive effects that:
the rapid selective hydrogenation process is realized by combining a conventional reactor and a microchannel reactor, and the continuous operation is easy to realize. The inhibitor is added to realize the preparation of the alkynol product with high selectivity, and the selectivity can reach more than 99 percent.
Detailed Description
The process of the present invention will be further illustrated by the following examples, but the present invention is not limited to the examples listed, but also includes any other known variations within the scope of the claims of the present invention.
The analysis method comprises the following steps:
gas chromatograph: agilent7820A, column HP-5(30 m.times.320. mu.m.times.0.25 μm), injection port temperature: 150 ℃; the split ratio is 50: 1; carrier gas flow: 1.5 ml/min; temperature rising procedure: keeping at 40 deg.C for 1min, heating to 90 deg.C at 10 deg.C/min for 0min, heating to 160 deg.C at 5 deg.C/min for 0min, heating to 280 deg.C at 30 deg.C/min for 6 min. Detector temperature: 280 ℃.
Second, the source of the main raw materials
Dehydroisophytol, 99 wt%, alatin reagent, ltd;
linalool, 99 wt%, alatin reagent, ltd;
99 wt% of dehydronerolidol, alatin reagent, ltd;
99 wt% of tetrahydrodehydronerolidol, Aladdin reagent, Inc.;
triphenylphosphine, 98 wt%, welfare science and technology ltd;
tris (p-methylbenzene) oxyphosphorus, 98 wt%, larvic technologies ltd.
Example 1
Carrying a catalyst in the microreactor:
a pipeline with the length of 15.0m and the inner diameter of 1mm is used as a micro-channel reactor and is subjected to load treatment:
preprocessing the inner wall surface of a microchannel: flushing the reactor microchannel with 30% potassium hydroxide solution for 1h, then flushing with deionized water for 0.5h, and introducing nitrogen to blow off residual deionized water;
preparing a dopamine coating: preparing 5mg/mL dopamine aqueous solution, injecting the dopamine aqueous solution into a reactor micro-channel at the flow rate of 1mL/min, continuously introducing the dopamine solution for 6 hours, injecting deionized water for washing, and drying at 60 ℃ in a nitrogen atmosphere;
③ electrochemical deposition catalyst: the micro-channel with the polydopamine coating is filled with the solution containing 5mmol/L K2PdCl4、0.01mmol/L La(NO3)3、0.01mmol/L Pr(NO3)3Heating the aqueous solution to 60 ℃, introducing an aqueous solution with the same composition as the aqueous solution into the microchannel at the flow rate of 0.1mL/min, and continuously introducing the aqueous solution for 12 hours; injecting deionized water into the microchannel for washing, blowing off residual deionized water by using nitrogen, and placing in the nitrogen for later use;
fourthly, catalyst reduction: placing the microchannel reactor in a resistance furnace, protecting the microchannel reactor in an inert atmosphere, vacuumizing, introducing hydrogen to atmospheric pressure, continuously introducing the hydrogen into the resistance furnace tube while keeping the hydrogen flow at 50m L/min, setting the temperature rise rate of the resistance furnace to be 1 ℃/min, raising the temperature from room temperature to 200 ℃, continuing the reduction reaction for 4 hours after the temperature rise is finished, and taking out the reactor after the furnace chamber is cooled to room temperature. Detecting the solid loading capacity of the catalyst to be about 0.8g, wherein the Pd content is 4.2 percent, the La content is 0.082 thousandths, and the Pr content is 0.085 thousandths.
Preparation of enol:
firstly, 294.5g (purity is 99.78%) of dehydroisophytol, 500g of ethanol and 1.0g of triphenylphosphine are added into an autoclave, stirring is started, then 5.0MPa of nitrogen is substituted for 6 times, and then 5.0MPa of hydrogen is introduced, and the hydrogen pressure is kept at 5.0 MPa. The temperature of the reaction kettle is controlled to be 90 ℃, a flow limiting plate and a flow meter are arranged at the bottom of the reaction kettle, and the feeding rate of the mixed liquid phase flow is controlled to be 1.47cm per gram of the volume of the catalyst treated per second through the flow meter3And enters a microchannel reactor.
The microchannel reactor is immersed in a constant temperature cycle, the bath temperature of the constant temperature cycle is 90 ℃, the residence time of reaction liquid in the microreactor is 10s, and the system stably runs for 2h and then samples are taken. The composition (wt%) of the reaction solution is as follows: 98.66% of isophytol, 0.52% of dehydroisophytol, 0.39% of dihydroisophytol, 0.43% of other alkyne self-coupling products which are not detected.
Example 2
Carrying a catalyst in the microreactor:
a pipeline with the length of 15.0m and the inner diameter of 1mm is used as a micro-channel reactor for carrying out load treatment.
Preprocessing the inner wall surface of a microchannel: flushing the reactor microchannel with 30% potassium hydroxide solution for 1h, then flushing with deionized water for 0.5h, and introducing nitrogen to blow off residual deionized water;
preparing a dopamine coating: preparing 9mg/mL dopamine aqueous solution, injecting the dopamine aqueous solution into a reactor microchannel at the flow rate of 1mL/min, continuously introducing the dopamine solution for 8 hours, injecting deionized water for washing, and drying at 60 ℃ in a nitrogen atmosphere;
③ electrochemical deposition catalyst: the micro-channel with the polydopamine coating is filled with 10mmol/L K2PdCl4、0.03mmol/L La(NO3)3Heating the aqueous solution of (1) to 60 ℃ and introducing the aqueous solution having the same composition as the aqueous solution into the microchannel at a flow rate of 0.1mL/minContinuously introducing the aqueous solution for 12 hours; injecting deionized water into the microchannel for washing, blowing off residual deionized water by using nitrogen, and placing in the nitrogen for later use;
fourthly, catalyst reduction: placing the microchannel reactor in a resistance furnace, protecting the microchannel reactor in an inert atmosphere, vacuumizing, introducing hydrogen to atmospheric pressure, continuously introducing the hydrogen into the resistance furnace tube while keeping the hydrogen flow at 50m L/min, setting the temperature rise rate of the resistance furnace to be 1 ℃/min, raising the temperature from room temperature to 200 ℃, continuing the reduction reaction for 4 hours after the temperature rise is finished, and taking out the reactor after the furnace chamber is cooled to room temperature. The solid loading of the catalyst is detected to be about 1.9g, the Pd content is 7.8 percent, and the La content is 0.191 per mill.
Preparation of enol:
firstly, 184.3g (purity 99.52 percent) of dehydrolinalool, 200g of toluene and 3.5g of tris (p-methylphenyl) oxyphosphorus are added into an autoclave, stirring is started, 6.0MPa of nitrogen is used for replacing 6 times, and then 6.0MPa of hydrogen is used, and the pressure of the hydrogen is kept at 6.0 MPa. The temperature of the reaction kettle is controlled to be 80 ℃, a flow limiting plate and a flow meter are arranged at the bottom of the reaction kettle, and the mixed liquid phase flow controls the feeding rate per gram of catalyst by the flow meter and the volume treated per second is 0.52cm3And enters a microchannel reactor.
The microchannel reactor is immersed in a constant temperature cycle, the bath temperature of the constant temperature cycle is 80 ℃, the residence time of reaction liquid in the microreactor is 12s, and the system stably runs for 2h and then samples are taken. The composition of the reaction solution is as follows: linalool 98.83%, linalool 0.31%, dihydrolinalool 0.36%, terminal alkyne self-coupling product 0.01%, and others 0.49%.
Example 3
Carrying a catalyst in the microreactor:
a pipeline with the length of 15.0m and the inner diameter of 1mm is used as a micro-channel reactor for carrying out load treatment.
Preprocessing the inner wall surface of a microchannel: flushing the reactor microchannel with 30% potassium hydroxide solution for 1h, then flushing with deionized water for 0.5h, and introducing nitrogen to blow off residual deionized water;
preparing a dopamine coating: preparing 8mg/mL dopamine aqueous solution, injecting the dopamine aqueous solution into a reactor microchannel at the flow rate of 1mL/min, continuously introducing the dopamine solution for 12 hours, injecting deionized water for washing, and drying at 60 ℃ in a nitrogen atmosphere;
③ electrochemical deposition catalyst: the micro-channel with the polydopamine coating is filled with a solution containing 3mmol/L K2PdCl4、0.06mmol/L Ce(NO3)3Heating the aqueous solution to 60 ℃, introducing an aqueous solution with the same composition as the aqueous solution into the microchannel at the flow rate of 0.1mL/min, and continuously introducing the aqueous solution for 12 hours; injecting deionized water into the microchannel for washing, blowing off residual deionized water by using nitrogen, and placing in the nitrogen for later use;
fourthly, catalyst reduction: placing the microchannel reactor in a resistance furnace, protecting the microchannel reactor in an inert atmosphere, vacuumizing, introducing hydrogen to atmospheric pressure, continuously introducing the hydrogen into the resistance furnace tube while keeping the hydrogen flow at 50m L/min, setting the temperature rise rate of the resistance furnace to be 1 ℃/min, raising the temperature from room temperature to 200 ℃, continuing the reduction reaction for 6h after the temperature rise is finished, and taking out the reactor after the furnace chamber is cooled to room temperature. The solid loading capacity of the catalyst is detected to be about 2.3g, the Pd content is 2.1 percent, and the Ce content is 0.389 thousandth.
Preparation of enol:
firstly, 220.1g (purity is 99.01 percent) of dehydronerolidol, 200g of toluene and 0.22g of tri-tert-butylphosphine are added into an autoclave, 2.0MPa of hydrogen is used for replacing 6 times with 2.0MPa of nitrogen after stirring is started, and the pressure of the hydrogen is kept at 2.0 MPa. The temperature of the reaction kettle is controlled to be 60 ℃, a flow limiting plate and a flow meter are arranged at the bottom of the reaction kettle, and the mixed liquid phase flow controls the feeding rate per gram of catalyst by the flow meter and the volume treated per second is 0.04cm3And enters a microchannel reactor.
The microchannel reactor is immersed in a constant temperature cycle, the bath temperature of the constant temperature cycle is 60 ℃, the residence time of reaction liquid in the microreactor is 120s, and the system stably runs for 2h and then samples are taken. The composition of the reaction solution is as follows: 98.21 percent of nerolidol, 0.33 percent of dehydronerolidol, 0.29 percent of dihydronerolidol, 0.02 percent of terminal alkyne self-coupling product and 1.15 percent of others.
Example 4
Carrying a catalyst in the microreactor:
a pipeline with the length of 15.0m and the inner diameter of 1mm is used as a micro-channel reactor for carrying out load treatment.
Preprocessing the inner wall surface of a microchannel: flushing the reactor microchannel with 30% potassium hydroxide solution for 1h, then flushing with deionized water for 0.5h, and introducing nitrogen to blow off residual deionized water;
preparing a dopamine coating: preparing 8mg/m L dopamine aqueous solution, injecting the dopamine aqueous solution into a reactor microchannel at the flow rate of 1m L/min, continuously introducing the dopamine aqueous solution for 8 hours, injecting deionized water for washing, and drying at 60 ℃ in a nitrogen atmosphere;
③ electrochemical deposition catalyst: the micro-channel with the polydopamine coating is filled with RuCl with the concentration of 15mmol/L3、0.03mmol/L Pr(NO3)3Heating the aqueous solution to 60 ℃, introducing an aqueous solution with the same composition as the aqueous solution into the microchannel at the flow rate of 0.1mL/min, and continuously introducing the aqueous solution for 12 hours; injecting deionized water into the microchannel for washing, blowing off residual deionized water by using nitrogen, and placing in the nitrogen for later use;
fourthly, catalyst reduction: placing the microchannel reactor in a resistance furnace, protecting the microchannel reactor in an inert atmosphere, vacuumizing, introducing hydrogen to atmospheric pressure, continuously introducing the hydrogen into the resistance furnace tube while keeping the hydrogen flow at 50m L/min, setting the temperature rise rate of the resistance furnace to be 1 ℃/min, raising the temperature from room temperature to 200 ℃, continuing the reduction reaction for 6h after the temperature rise is finished, and taking out the reactor after the furnace chamber is cooled to room temperature. The solid loading of the catalyst is detected to be about 1.7g, the Ru content is 9.6 percent, and the Pr content is 0.105 thousandth.
Preparation of enol:
firstly, 224.1g (purity 99.18%) of tetrahydrodehydronerolidol, 200g of toluene and 2.2g of tris (p-methylphenyl) phosphorus are added into an autoclave, stirring is started, 2.0MPa of nitrogen is used for replacing 6 times, and then 2.0MPa of hydrogen is used, and the pressure of the hydrogen is kept at 2.0 MPa. The temperature of the reaction kettle is controlled to be 110 ℃, a flow limiting plate and a flow meter are arranged at the bottom of the reaction kettle, and the mixed liquid phase flow controls the feeding rate per gram of catalyst by the flow meter and the volume treated per second is 0.14cm3And enters a microchannel reactor.
The microchannel reactor is immersed in a constant temperature cycle, the temperature of a constant temperature cycle bath is 110 ℃, the residence time of reaction liquid in the microreactor is 50s, and the system stably runs for 2h and then samples are taken. The composition of the reaction solution is as follows: 98.56% of tetrahydronerolidol, 0.22% of tetrahydrodehydronerolidol, 0.28% of hexahydronerolidol, 0.01% of terminal alkyne self-coupling product and 0.93% of others.
Comparative example 1
Carrying a catalyst in the microreactor:
microreactor immobilized with catalyst of example 1
Preparation of enol:
294.5g (purity 99.78%) of dehydroisophytol and 500g of ethanol are added into an autoclave, stirring is started, then 5.0MPa of nitrogen is replaced for 6 times, and then 5.0MPa of hydrogen is introduced, and the pressure of the hydrogen is kept at 5.0 MPa. The temperature of the reaction kettle is controlled to be 90 ℃, a flow limiting plate and a flow meter are arranged at the bottom of the reaction kettle, and the feeding rate of the mixed liquid phase flow is controlled to be 1.47cm per gram of the volume of the catalyst treated per second through the flow meter3And enters a microchannel reactor.
The microchannel reactor is immersed in a constant temperature cycle, the bath temperature of the constant temperature cycle is 90 ℃, the residence time of reaction liquid in the microreactor is 10s, and the system stably runs for 2h and then samples are taken. The composition of the reaction solution is as follows: 95.51% of isophytol, 0.57% of dehydroisophytol, 0.41% of dihydroisophytol, 3.12% of terminal alkyne self-coupling product and 0.39% of others.
Comparative example 2
Carrying a catalyst in the microreactor:
a pipeline with the length of 15.0m and the inner diameter of 1mm is used as a micro-channel reactor and is subjected to load treatment:
pretreating the inner wall surface of the micro-channel: flushing the reactor microchannel with 30% potassium hydroxide solution for 1h, then flushing with deionized water for 0.5h, and introducing nitrogen to blow off residual deionized water;
preparing a dopamine coating: preparing 5mg/mL dopamine aqueous solution, injecting the dopamine aqueous solution into a reactor micro-channel at the flow rate of 1mL/min, continuously introducing the dopamine solution for 6 hours, injecting deionized water for washing, and drying at 60 ℃ in a nitrogen atmosphere;
electrochemical deposition catalyst: the micro-channel with the polydopamine coating is filled with 5mmol/L K2PdCl4Heating the aqueous solution to 60 ℃, introducing the aqueous solution with the same composition as the aqueous solution into the microchannel at the flow rate of 0.1mL/min, and keeping the aqueous solution for 12 hours; then injecting deionized water into the microchannel for washing, and blowing off residues by using nitrogenKeeping deionized water, and placing in nitrogen for later use;
and reduction of the catalyst: placing the microchannel reactor in a resistance furnace, protecting the microchannel reactor in an inert atmosphere, vacuumizing, introducing hydrogen to atmospheric pressure, continuously introducing the hydrogen into the resistance furnace tube while keeping the hydrogen flow at 50m L/min, setting the temperature rise rate of the resistance furnace to be 1 ℃/min, raising the temperature from room temperature to 200 ℃, continuing the reduction reaction for 4 hours after the temperature rise is finished, and taking out the reactor after the furnace chamber is cooled to room temperature. The catalyst loading was measured to be about 0.8g, with 4.2% Pd.
Preparation of enol:
firstly, 294.5g (purity is 99.78%) of dehydroisophytol, 500g of ethanol and 1.0g of triphenylphosphine are added into an autoclave, stirring is started, then 5.0MPa of nitrogen is substituted for 6 times, and then 5.0MPa of hydrogen is introduced, and the hydrogen pressure is kept at 5.0 MPa. The temperature of the reaction kettle is controlled to be 90 ℃, a flow limiting plate and a flow meter are arranged at the bottom of the reaction kettle, and the feeding rate of the mixed liquid phase flow is controlled to be 1.47cm per gram of the volume of the catalyst treated per second through the flow meter3And enters a microchannel reactor.
The microchannel reactor is immersed in a constant temperature cycle, the bath temperature of the constant temperature cycle is 90 ℃, the residence time of reaction liquid in the microreactor is 10s, and the system stably runs for 2h and then samples are taken. The composition of the reaction solution is as follows: 93.91 percent of isophytol, 0.23 percent of dehydroisophytol, 5.53 percent of dihydroisophytol, 0.01 percent of terminal alkyne self-coupling product and 0.32 percent of others.
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