CN103288642B - Method for preparing vegetable oil polyalcohol by using continuous method - Google Patents
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- Fats And Perfumes (AREA)
Abstract
The invention discloses a method for preparing vegetable oil polyalcohol by using a continuous method, which comprises the steps of dissolving epoxy vegetable oil in an organic solvent, pumping the organic solvent and a catalyst aqueous solution into a micro-channel modular reaction device at the same time, keeping the reaction residence time for 2-12 min, reacting at normal pressure and 30-100 ℃, standing and separating the reaction product, recovering the water phase, and using Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary evaporation to obtain the vegetable oil polyalcohol. The preparation method of the vegetable oil polyalcohol provided by the invention is continuous operation, the preparation process is easy to operate and control, the reaction time is short, the raw materials are green and environment-friendly, the source is rich, the waste water and the organic solvent can be recycled, the pollution is small, the energy consumption is low, the side reaction is weakened, and the controllable hydroxyl value range of the product is larger. The device has the characteristics of simple production device, easy disassembly and assembly, portability and movement, can be adjusted by simply increasing or decreasing the number of the micro-channels, and does not have amplification effect similar to industrial production.
Description
Technical Field
The invention relates to a preparation method of vegetable oil polyalcohol, in particular to a method for preparing vegetable oil polyalcohol by using epoxidized vegetable oil as a raw material and utilizing a continuous method.
Background
With the increase of petroleum consumption, the storage of petrochemical resources is increasingly reduced, the price of petrochemical products is continuously increased, the production of materials and fuels from renewable resources is more and more important, and the use of renewable resources as raw materials of chemical products is concerned by people. The vegetable oil polyalcohol is a substitute of petroleum-based polyalcohol, and has outstanding environmental protection value. According to the analysis data of the biosphere, compared with petroleum-based polyol, the total energy consumption of the vegetable oil polyol is reduced by 23%, the non-renewable resource consumption is reduced by 61%, and the emission of greenhouse gases to the atmosphere is reduced by 36%. The vegetable oil polyalcohol has wide raw material sources, and the vegetable oil comprises edible oil such as peanut oil, rapeseed oil, soybean oil, castor oil, olive oil, palm oil and the like, and non-edible oil such as jatropha curcas oil, pistacia chinensis bunge oil and the like.
The vegetable oil polyalcohol is mainly applied to the field of polyurethane, and the prepared vegetable oil-based polyurethane material completely meets the requirement of environmental protection; and because of the hydrophobicity of the main component fatty glyceride of the vegetable oil, the vegetable oil-based polyurethane material has good physical and chemical properties, particularly better hydrolysis resistance and thermal stability. Thus, vegetable oil polyols and their polyurethane materials have been rapidly developed.
The vegetable oil mainly comprises fatty glyceride, and most vegetable oils contain 14-22 carbon chain fatty acids, and each fatty acid has 0-3 unsaturated double bonds. In addition to castor oil, vegetable oils must be hydroxyl functionalized to provide polyols for the synthesis of polyurethane materials. The vegetable oil polyol is mainly divided into the following 5 types according to different synthetic methods: an alcoholysis method comprises the following steps: the vegetable oil is alcoholyzed by using ester group in the vegetable oil and micromolecular alcohol with multiple functionality, and hydroxyl is introduced on a molecular chain. ② epoxy ring opening method: the carbon-carbon double bond of the vegetable oil is epoxidated by Prileshajev, and then the epoxy group is opened by a functional monomer to introduce hydroxyl. ③ ozone oxidation method: double bonds in the vegetable oil are oxidized by utilizing the strong oxidizing property of ozone, so that the double bonds are broken to form primary hydroxyl groups or carboxylic acid groups, and then the carboxylic acid groups are subjected to esterification and other reactions to prepare the vegetable oil polyol. (iv) hydroformylation process: double bonds of the vegetable oil are utilized, a noble metal catalyst is adopted to react with hydrogen and carbon monoxide under certain pressure to generate aldehyde, and then hydrogenation is carried out to convert the aldehyde into hydroxyl. Alkoxylation: the production method of the similar petroleum-based polyol is to prepare the vegetable oil polyol by directly mixing vegetable oil and small molecular alcohol as a starting agent (or directly using vegetable oil containing hydroxyl as the starting agent) and performing alkoxylation. The method for preparing the vegetable oil polyol by the epoxy ring-opening method is low in cost and is a currently accepted method which is most likely to realize industrialization in the polyurethane industry.
Under the catalysis of sulfuric acid or fluoboric acid, the vegetable oil polyol is prepared by ring opening of water, alcohol amine, carboxylic acid and the like. Wherein, the vegetable oil polyalcohol with the structure of ortho-dihydroxy can be generated by the ring opening of the epoxidized vegetable oil through water. CN1837180A and CN101139252A respectively disclose "a bio-based polyol prepared by using rapeseed oil" and "a bio-based polyol prepared by using jatropha curcas oil", wherein the vegetable oil polyol is prepared by using the rapeseed oil and the jatropha curcas oil as main raw materials and carrying out three-step reactions of alcoholysis/epoxidation/ring opening. CN1837181A and CN101108803A disclose "a bio-based polyol prepared from rapeseed oil" and "a bio-based polyol prepared from jatropha curcas oil", which are respectively prepared from rapeseed oil and jatropha curcas oil as main raw materials through three steps of epoxidation/ring opening/alcoholysis to obtain vegetable oil polyol. CN1907944A discloses a bio-based polyol prepared by epoxy rapeseed oil, which directly takes the epoxy rapeseed oil as a main raw material to prepare vegetable oil polyol through two steps of ring opening/alcoholysis reaction. CN101906016A discloses a rubber seed oil polyol and a preparation method thereof, which takes rubber seed oil as a main raw material and prepares the vegetable oil polyol through two-step reaction of epoxidation/ring opening. CN101659627A discloses a high hydroxyl value bio-based polyol prepared by one-step reaction of epoxidized vegetable oil, which is prepared by the epoxy group ring-opening reaction and ester amidation reaction of the epoxidized vegetable oil and glycol amine. CN101747184A and CN101230020A disclose respectively a method for preparing polyol from soybean oil by one-step method and a method for synthesizing macromonomer for polymer polyol by vegetable oil and application thereof, and vegetable oil polyol is prepared by one-step method by reacting epoxidation and ring opening under acidic condition.
The vegetable oil polyol prepared by the above patents is mainly based on epoxy group open loop and is synthesized by an intermittent reaction kettle, and the following disadvantages exist: the reaction time is long; secondly, the energy consumption is higher; the equipment and the automatic control level are low; and fourthly, the quality of the product is low due to the inevitable side reaction (the hydroxyl value of the product is low and the viscosity is large due to the crosslinking side reaction).
Based on the problems, the scheme provides that the vegetable oil polyol is quickly prepared by using the epoxidized vegetable oil as the raw material and adopting the microchannel modular reaction device, the preparation method is continuous operation, the preparation process is easy to operate and control, the reaction time is short, the wastewater and the organic solvent can be recycled, the pollution is small, the energy consumption is low, the side reaction is weakened, and the controllable hydroxyl value range of the product is large. The device has the characteristics of simple production device, easy disassembly and assembly, portability and movement, can be adjusted by simply increasing or decreasing the number of the micro-channels, and does not have amplification effect similar to industrial production.
Disclosure of Invention
The invention aims to solve the technical problem that the method for preparing the vegetable oil polyalcohol by using the continuous method is provided for overcoming the defects of long reaction time, high energy consumption, low product quality and incapability of continuous production in the batch method for producing the vegetable oil polyalcohol based on the epoxy group ring-opening principle at present.
In order to solve the technical problems, the idea of the invention is as follows:
the vegetable oil contains unsaturated carbon-carbon double bonds (figure 1), and the epoxy vegetable oil can be prepared by the Prileshajev epoxidation reaction of the double bonds. Under the catalysis of sulfuric acid or fluoroboric acid, the epoxidized vegetable oil can generate vegetable oil polyol with an ortho-dihydroxy structure through water ring opening (figure 2).
The microchannel reaction is a new synthesis technology, has certain application in the fields of medicine and fine chemical engineering, and is a research hotspot in the technical field of international fine chemical engineering at present. Compared with the conventional reaction system, the microchannel reaction has the advantages of high reaction selectivity, high mass and heat transfer efficiency, high reaction activity, short reaction time, high conversion rate, good safety, easy control and the like. The microchannel reaction has a certain application prospect in a synthetic system of vegetable oil polyalcohol: firstly, vegetable oil polyol prepared from water-boiling epoxy vegetable oil belongs to heterogeneous reaction, the reaction efficiency is low and the reaction time is long during intermittent reaction, so that the side reaction is accelerated, the specific surface area of reactants can be greatly increased by forced mixing in the microchannel reaction process, the adverse factors of two-phase reaction are ignored, and the reaction efficiency is improved; secondly, a cross-linking side reaction occurs in the preparation process of the vegetable oil polyalcohol, and the cross-linking side reaction occurring in the reaction process can be greatly weakened due to the characteristic of high reaction selectivity of the microchannel reaction; the high efficiency of the microchannel reaction ensures that the reaction can be completed in a short time, saves energy consumption and conforms to the low-carbon environmental protection concept.
The specific technical scheme of the invention is as follows:
a method for preparing vegetable oil polyalcohol by using a continuous method comprises the steps of dissolving epoxy vegetable oil in an organic solvent, pumping the organic solvent and an aqueous solution containing a catalyst into a microchannel modular reaction device at the same time, keeping the reaction residence time for 2-12 min, reacting at normal pressure and 30-100 ℃, standing and separating the reaction product, recovering the aqueous phase, and using Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary evaporation to obtain the vegetable oil polyalcohol.
Wherein the epoxy vegetable oil is at least one of epoxy olive oil, epoxy peanut oil, epoxy rapeseed oil, epoxy cottonseed oil, epoxy soybean oil, epoxy coconut oil, epoxy palm oil, epoxy sesame oil, epoxy sunflower seed oil, epoxy linseed oil, epoxy castor oil, epoxy tung oil, epoxy safflower oil, epoxy rice bran oil, epoxy corn oil and epoxy tea oil. Epoxidized soybean oil, epoxidized cottonseed oil or epoxidized castor oil are preferred.
Wherein, the organic solvent is tetrahydrofuran, pyridine, acetone or methyl isobutyl ketone, and tetrahydrofuran is preferred.
Wherein the volume ratio of the epoxy vegetable oil to the organic solvent is 1: 1.5-8, preferably 1: 2-6.
Wherein the catalyst is sulfuric acid or fluoroboric acid, the concentration of the sulfuric acid is 98wt%, and the concentration of the fluoroboric acid is 40 wt%.
Wherein the volume ratio of the catalyst to the epoxidized vegetable oil is 1: 10-20, preferably 1: 10-16.
Wherein the volume ratio of the catalyst to the water is 1: 15-40, preferably 1: 18-30.
The microchannel modular reaction device comprises a micro mixer, a microstructure heat exchanger, a tubular temperature control module and a microstructure reactor which are sequentially connected through pipelines, and reaction raw materials are input into the micro mixer and subsequent equipment through a precise low-pulsation pump, so that the materials can continuously pass through the microchannel modular reaction device and the residence time of the materials can be controlled simultaneously. And the head and the tail can be respectively connected with a raw material storage tank and a product collecting bottle according to requirements to realize continuous production. The micro mixer is a slit plate mixer LH25(Hastelloy C); the microstructure heat exchanger is a coax exchanger (Hastelloy C); the microstructure reactor is a meander reactor HC, a sandwich reactor HC, a fixed bed meander reactor HC and a Harmonic alloy microchannel reactor (the inner diameter is 2.1 mm), and preferably the sandwich reactor HC or the Harmonic alloy microchannel reactor.
Wherein, the Na is2CO3The mass percentage concentration of the aqueous solution is 5 percent.
Has the advantages that:
the preparation method has the advantages of continuous operation, easy operation and control of the preparation process, short reaction time, green and environment-friendly raw materials, rich sources, recyclable wastewater and organic solvent, low pollution, low energy consumption, weakened side reaction and larger controllable hydroxyl value range of the product. The device has the characteristics of simple production device, easy disassembly and assembly, portability and movement, can be adjusted by simply increasing or decreasing the number of the micro-channels, and does not have amplification effect similar to industrial production.
Drawings
FIG. 1 shows the chemical structure of vegetable oil.
FIG. 2 is a schematic of the synthesis of vegetable oil polyols.
FIG. 3 is a schematic view of a microchannel modular reaction apparatus; wherein, 1 is a raw material storage tank, 2 is a T-shaped mixer, 3 is a heat exchanger, 4 is a tubular temperature control module, 5 is a micro-structure reactor, and 6 is a product collecting bottle (the reaction is stopped by cooling with an ice-water mixture).
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
The microchannel modular reaction apparatus suitable for the following embodiments is shown in fig. 3, and comprises a raw material storage tank 1, a micromixer 2, a microstructure heat exchanger 3, a tubular temperature control module 4, a microstructure reactor 5 and a product collection bottle 6 which are sequentially connected through a pipeline. The reaction raw materials are input into the micro mixer and the subsequent equipment through a precise and low-pulsation pump, so that the materials can continuously pass through the micro-channel modular reaction device and the residence time of the materials is controlled at the same time. The micro-structure reactor 5 and the product collecting bottle 6 are connected by a section of capillary tube made of polytetrafluoroethylene, and the micro-structure reactor is immersed in an ice water bath to stop the reaction. The micromixer is slit plate mixer LH25(Hastelloy C) from Ehrfeld Mikrotechnik BTS; the microstructure heat exchanger is a coaxial heat exchanger (Hastelloy C) available from Ehrfeld Mikrotechnik BTS; the microstructure reactor is a meander reactor HC, a sandwich reactor HC, a fixed bedmeander reactor HC, a Harmoni alloy microchannel reactor (inner diameter is 2.1 mm), preferably a sandwich reactor HC or a Harmoni alloy microchannel reactor, wherein the sandwich reactor HC is purchased from Ehrfeld Mikrotechnik BTS; tubular temperature control module, available from Ehrfeld Mikrotechnik BTS.
Example 1:
dissolving 200mL of epoxy olive oil in 600mL of tetrahydrofuran to prepare an A component, dissolving 13mL of sulfuric acid in 240mL of water to prepare a B component, simultaneously pumping the A component and the B component into a microchannel modular reaction device, reacting in a sandwich reactivator HC at normal pressure and 50 ℃, keeping the reaction residence time for 10min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3Washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the olive oil polyalcohol with the hydroxyl value of 222 mgKOH/g.
Example 2:
dissolving 200mL of epoxy peanut oil in 1000mL of tetrahydrofuran to prepare a component A, dissolving 20mL of fluoroboric acid in 440mL of water to prepare a component B, and pumping the mixture into a microchannel dieReacting in a caking reaction device in a sandwichuractor HC at normal pressure and 80 ℃, wherein the sample injection rates of A, B components are 5.3mL/min and 2.1mL/min respectively, keeping the reaction residence time for 5min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the peanut oil polyol with the hydroxyl value of 265 mgKOH/g.
Example 3:
dissolving 200mL of epoxy rapeseed oil in 700mL of tetrahydrofuran to prepare a component A, dissolving 20mL of sulfuric acid in 600mL of water to prepare a component B, simultaneously pumping the component B into a microchannel modular reaction device, reacting in a Harphii alloy microchannel reactor at normal pressure and 70 ℃, keeping the reaction residence time for 3.5min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary evaporation to prepare the rapeseed oil polyalcohol, wherein the hydroxyl value of the rapeseed oil polyalcohol is 222 mgKOH/g.
Example 4:
dissolving 200mL of epoxy cottonseed oil in 400mL of tetrahydrofuran to prepare a component A, dissolving 14mL of sulfuric acid in 340mL of water to prepare a component B, simultaneously pumping the component B into a microchannel modular reaction device, reacting in a Harphii alloy microchannel reactor at normal pressure and 40 ℃, keeping the reaction residence time for 4.5min, standing the reaction product for liquid separation, recovering the water phase, and using 5% Na as the oil phase, wherein the sample injection rates of the A, B components are 2.8mL/min and 1.6mL/min respectively, and the liquid phase is obtained by standing the reaction product for liquid separation and recovering the water phase2CO3Washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the cottonseed oil polyol with the hydroxyl value of 232 mgKOH/g.
Example 5:
dissolving 200mL of epoxidized soybean oil in 800mL of tetrahydrofuran to prepare a component A, and dissolving 16mL of fluoroboric acid in 300Preparing the component B with mL of water, pumping into a microchannel modular reaction device, reacting in a sandwichureactor HC at normal pressure and 100 ℃, wherein the sample injection rates of the A, B components are 5.6mL/min and 1.8mL/min respectively, keeping the reaction retention time for 5min, standing and separating the reaction product, recovering the water phase, and using 5% Na as the oil phase2CO3Washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the soybean oil polyol with the hydroxyl value of 356 mgKOH/g.
Example 6:
dissolving 200mL of epoxy coconut oil in 600mL of tetrahydrofuran to prepare component A, dissolving 18mL of fluoroboric acid in 380mL of water to prepare component B, simultaneously pumping the component B into a microchannel modular reaction device, reacting in a sandwichuractor HC at normal pressure and 50 ℃, keeping the reaction residence time for 7min, standing and separating the reaction product, recovering the water phase, and using 5% Na as the oil phase2CO3And washing the coconut oil polyol with the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the coconut oil polyol with the hydroxyl value of 25 mgKOH/g.
Example 7:
dissolving 200mL of epoxy palm oil in 1100mL of tetrahydrofuran to prepare an A component, dissolving 15mL of fluoroboric acid in 330mL of water to prepare a B component, simultaneously pumping the B component into a microchannel modular reaction device, reacting in a sandwichureactor HC at normal pressure and 40 ℃, keeping the reaction residence time for 9min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary evaporation to obtain the palm oil polyol with the hydroxyl value of 136 mgKOH/g.
Example 8:
dissolving 200mL epoxy sesame oil in 400mL tetrahydrofuran to prepare group ADissolving 12.5mL of sulfuric acid in 250mL of water to prepare a component B, pumping the component B into a microchannel modular reaction device, reacting in a Harphii alloy microchannel reactor at normal pressure and 80 ℃, keeping the sample injection rates of A, B components at 7.0mL/min and 3.0mL/min respectively, keeping the reaction residence time for 2min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the sesame oil polyol with the hydroxyl value of 242 mgKOH/g.
Example 9:
dissolving 200mL of epoxy sunflower seed oil in 600mL of tetrahydrofuran to prepare an A component, dissolving 16mL of fluoroboric acid in 290mL of water to prepare a B component, simultaneously pumping the A component and the B component into a microchannel modular reaction device, reacting in a sandwichreactor HC at normal pressure and 70 ℃, keeping the reaction residence time for 5min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the sunflower seed oil polyol with the hydroxyl value of 343 mgKOH/g.
Example 10:
dissolving 200mL of epoxy linseed oil in 1200mL of tetrahydrofuran to prepare an A component, dissolving 17mL of fluoroboric acid in 340mL of water to prepare a B component, simultaneously pumping the B component into a microchannel modular reaction device, reacting in a sandwichureactor HC at normal pressure and 90 ℃, keeping the reaction retention time for 3min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the linseed oil polyol with the hydroxyl value of 415 mgKOH/g.
Example 11:
200mL of ringDissolving oxycastor oil in 600mL of tetrahydrofuran to prepare a component A, dissolving 16mL of sulfuric acid in 320mL of water to prepare a component B, simultaneously pumping the component B into a microchannel modular reaction device, reacting in a Harphii alloy microchannel reactor at normal pressure and 60 ℃, keeping the reaction residence time for 3min at the sample injection rates of A, B component of 4.7mL/min and 2.0mL/min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the castor oil polyol with the hydroxyl value of 312 mgKOH/g.
Example 12:
dissolving 200mL epoxy tung oil in 500mL tetrahydrofuran to prepare component A, dissolving 15mL sulfuric acid in 400mL water to prepare component B, simultaneously pumping into a microchannel modular reaction device, reacting in a Harphii alloy microchannel reactor at normal pressure and 50 ℃, wherein the sample injection rates of A, B components are 3.1mL/min and 1.9mL/min respectively, keeping the reaction residence time for 4min, standing and separating the reaction product, recovering the water phase, and using 5% Na as the oil phase2CO3Washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary evaporation to obtain the tung oil polyol with the hydroxyl value of 354 mgKOH/g.
Example 13:
dissolving 200mL of epoxy safflower oil in 600mL of tetrahydrofuran to prepare a component A, dissolving 17mL of sulfuric acid in 470mL of water to prepare a component B, simultaneously pumping the component B into a microchannel modular reaction device, reacting in a Harphii alloy microchannel reactor at normal pressure and 30 ℃, keeping the reaction residence time for 6min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3Washing the water solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the safflower oil polyalcohol with the hydroxyl value of 303 mgKOH/g.
Example 14:
dissolving 200mL of epoxy rice bran oil in 900mL of tetrahydrofuran to prepare an A component, dissolving 15mL of sulfuric acid in 300mL of water to prepare a B component, simultaneously pumping the A component and the B component into a microchannel modular reaction device, reacting in a sandwich reactivator HC at normal pressure and 90 ℃, keeping the reaction residence time for 2min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3Washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the rice bran oil polyol with the hydroxyl value of 275 mgKOH/g.
Example 15:
dissolving 200mL of epoxy corn oil in 400mL of tetrahydrofuran to prepare an A component, dissolving 18mL of sulfuric acid in 450mL of water to prepare a B component, simultaneously pumping the B component into a microchannel modular reaction device, reacting in a Harphii alloy microchannel reactor at normal pressure and 60 ℃, keeping the reaction residence time for 3min, standing and separating the reaction product, recovering the water phase, and using 5% Na as the oil phase, wherein the sample injection rates of the A, B components are 3.7mL/min and 3.0mL/min respectively, and the oil phase is obtained by recovering the 5% Na2CO3Washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the corn oil polyol with the hydroxyl value of 258 mgKOH/g.
Example 16:
dissolving 200mL of epoxy tea oil in 500mL of tetrahydrofuran to prepare an A component, dissolving 14mL of fluoroboric acid in 260mL of water to prepare a B component, simultaneously pumping the B component into a microchannel modular reaction device, reacting in a sandwich reactivator HC at normal pressure and 40 ℃, keeping the reaction residence time for 11min, standing and separating the reaction product, recovering the water phase, and using 5% Na as an oil phase2CO3And washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary steaming to obtain the tea oil polyalcohol with the hydroxyl value of 227 mgKOH/g.
Claims (5)
1. A method for preparing vegetable oil polyalcohol by using a continuous method is characterized in that epoxy vegetable oil is dissolved in an organic solvent, the organic solvent and an aqueous solution containing a catalyst are pumped into a micro-channel modular reaction device at the same time, the reaction retention time is kept for 2-12 min, the reaction is carried out at normal pressure and the temperature of 30-100 ℃, the reaction product is kept stand for liquid separation, the water phase is recovered, and the oil phase is prepared by using Na2CO3Washing the aqueous solution to be neutral, and then carrying out liquid separation and rotary evaporation to obtain vegetable oil polyalcohol;
wherein,
the organic solvent is tetrahydrofuran, pyridine, acetone or methyl isobutyl ketone;
the volume ratio of the epoxy vegetable oil to the organic solvent is 1: 1.5-8;
the catalyst is sulfuric acid or fluoroboric acid;
the volume ratio of the catalyst to the epoxy vegetable oil is 1: 10-20;
the volume ratio of the catalyst to the water is 1: 15-40.
2. The method of claim 1, wherein the epoxidized vegetable oil is at least one of epoxidized olive oil, epoxidized peanut oil, epoxidized rapeseed oil, epoxidized cottonseed oil, epoxidized soybean oil, epoxidized coconut oil, epoxidized palm oil, epoxidized sesame oil, epoxidized sunflower oil, epoxidized linseed oil, epoxidized castor oil, epoxidized tung oil, epoxidized safflower oil, epoxidized rice bran oil, epoxidized corn oil and epoxidized tea oil.
3. The method for preparing the vegetable oil polyol by the continuous process as claimed in claim 1, wherein the microchannel modular reaction device comprises a micromixer, a microstructure heat exchanger, a tubular temperature control module and a microstructure reactor which are sequentially connected through a pipeline, and the reaction raw materials are input into the micromixer and the subsequent equipment through a precise and low-pulsation pump.
4. The method for preparing the vegetable oil polyol by the continuous process as claimed in claim 3, wherein the micromixer is slit plate mixer LH 25; the microstructure heat exchanger is a coaxial heat exchanger; the micro-structure reactor is a meander reactor HC, sandwich reactor HC, fixed bed meander reactor HC or a Harcom alloy micro-channel reactor.
5. The method of claim 1, wherein the Na is selected from the group consisting of sodium, potassium, magnesium, and potassium2CO3Mass percent of aqueous solutionThe concentration of each component was 5%.
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| CN105712881B (en) * | 2014-12-05 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of high hydroxyl value tung oil polyalcohol and preparation method thereof |
| CN105713171B (en) * | 2014-12-05 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of tung oil polyalcohol and preparation method thereof |
| CN105713172B (en) * | 2014-12-05 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of tung oil polylol and its synthetic method |
| CN105713169B (en) * | 2014-12-05 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of tung oil polyalcohol and preparation method |
| CN105713170B (en) * | 2014-12-05 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of tung oil polylol and preparation method thereof |
| CN104610060A (en) * | 2015-02-05 | 2015-05-13 | 南京工业大学 | High hydroxyl value vegetable oil polyol and preparation method and application thereof |
| CN104610540A (en) * | 2015-03-17 | 2015-05-13 | 南京工业大学 | Vegetable oil polyalcohol and preparation method and application thereof |
| CN105461555B (en) * | 2015-11-11 | 2018-03-30 | 南京工业大学 | Vegetable oil polyalcohol and preparation method and application thereof |
| CN107151210B (en) * | 2016-03-03 | 2020-07-07 | 中国石油化工股份有限公司 | Method for preparing tung oil polyol under ultrasonic condition |
| CN107151214B (en) * | 2016-03-03 | 2020-07-07 | 中国石油化工股份有限公司 | Method and device for preparing tung oil polyol under hypergravity condition |
| CN107151520B (en) * | 2016-03-03 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of tung oil base water polyurethane coating and preparation method thereof |
| CN109320684B (en) * | 2018-09-29 | 2020-09-04 | 南京工业大学 | Polyurethane polyol and preparation method and application thereof |
| CN109265361B (en) * | 2018-10-08 | 2020-07-10 | 南京工业大学 | Method for carrying out micro-reaction continuous flow preparation by applying acylamino to vegetable oil-based plasticizer |
| CN109232195B (en) * | 2018-10-16 | 2021-09-10 | 南京工业大学 | Bio-based polyol and preparation method and application thereof |
| CN109610202A (en) * | 2018-10-29 | 2019-04-12 | 薛向东 | A kind of environment-protection coating printing adhesive and preparation method thereof |
| CN110746300A (en) * | 2019-10-31 | 2020-02-04 | 辽宁石油化工大学 | General method for preparing soybean oil-based polyol from epoxidized soybean oil |
| CN111905668B (en) * | 2020-09-04 | 2022-01-28 | 南京工业大学 | Reaction device and application thereof in continuous preparation of vegetable oil polyalcohol |
| CN113372548B (en) * | 2021-05-06 | 2022-06-24 | 华南农业大学 | Vegetable oil-based antifouling polyol and preparation method and application thereof |
| CN117603047B (en) * | 2024-01-23 | 2024-06-11 | 中建安装集团有限公司 | Preparation method and application of bio-based polyol |
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