CN103288642A - Method for preparing vegetable oil polyalcohol by using continuous method - Google Patents
Method for preparing vegetable oil polyalcohol by using continuous method Download PDFInfo
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- CN103288642A CN103288642A CN2013102292160A CN201310229216A CN103288642A CN 103288642 A CN103288642 A CN 103288642A CN 2013102292160 A CN2013102292160 A CN 2013102292160A CN 201310229216 A CN201310229216 A CN 201310229216A CN 103288642 A CN103288642 A CN 103288642A
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- 239000008158 vegetable oil Substances 0.000 title claims abstract description 66
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- 238000011437 continuous method Methods 0.000 title abstract 2
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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 sources are 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 present invention relates to a kind of preparation method of vegetable oil polyol, relating in particular to a kind of is raw material with the epoxidized vegetable oil, utilizes continuous processing to prepare the method for vegetable oil polyol.
Background technology
Along with the consumption of petroleum amount increases, the minimizing day by day of petrochemical industry resource reserve, petroleum chemicals price continuous rise more and more causes people's attention with renewable resources production material and fuel, utilizes renewable resources to enjoy people to pay close attention to as the raw material of Chemicals.Vegetable oil polyol is the substitute of petroleum base polyvalent alcohol, and the value of environmental protection is outstanding.Show according to the biosphere analytical data, compare with the petroleum base polyvalent alcohol that the overall energy consumption of vegetable oil polyol reduces by 23%, nonrenewable resources consumption reduces by 61%, reduces 36% to the airborne release greenhouse gases.The vegetable oil polyol raw material sources are extensive, and vegetables oil comprises peanut oil, rapeseed oil, soybean oil, Viscotrol C, sweet oil, palm wet goods edible oil and Cortex jatrophae oil, Chinese pistache wet goods inedible oil.
Vegetable oil polyol is mainly used in polyurethane field, and the vegetable oil based polyurethane material of its preparation meets requirement on environmental protection fully; And because the hydrophobicity of plant main body of oil glycerin fatty acid ester, the vegetable oil based polyurethane material has good physicochemical performance, particularly possesses better hydrolytic resistance and thermostability.Therefore vegetable oil polyol and polyurethane material thereof have obtained developing rapidly.
Vegetables oil mainly is made up of glycerin fatty acid ester, and most of vegetables oil comprise the lipid acid of 14～22 carbochains, and each lipid acid has 0～3 unsaturated double-bond.Except Viscotrol C, vegetables oil must could be used for the synthetic of polyurethane material through obtaining polyvalent alcohol behind the hydroxy-functional.Vegetable oil polyol mainly is divided into following 5 kinds according to the difference of synthetic method: 1. alcoholysis method: utilize the ester group in the vegetables oil, with the small molecular alcohol of polyfunctionality vegetables oil is carried out alcoholysis, introduce hydroxyl at molecular chain.2. epoxy addition method: the carbon-carbon double bond of vegetables oil with functional monomer's open loop epoxide group, is introduced hydroxyl behind the Prileshajev epoxidation.3. ozone oxidation method: utilize the two keys in the strong oxidizing property oxidation vegetables oil of ozone, make two bond ruptures form primary hydroxyls or hydroxy-acid group, again hydroxy-acid group is carried out reaction such as esterification and make vegetable oil polyol.4. hydroformylation method: utilize two keys of vegetables oil, adopt noble metal catalyst to generate aldehyde with hydrogen, reaction of carbon monoxide under certain pressure, hydrogenation changes into hydroxyl with aldehyde then.5. alkoxylation process: the production method of similar petroleum base polyvalent alcohol, directly mix as initiator (or the vegetables oil that directly will contain hydroxyl is made initiator) with vegetables oil and small molecular alcohol and to prepare vegetable oil polyol through alkoxylate.Wherein to be equipped with the cost of vegetable oil polyol lower for the epoxy addition legal system, is the method that the urethane industry realizes industrialization that is most likely at of generally acknowledging at present.
Epoxidized vegetable oil is prepared vegetable oil polyol through open loops such as water, alcohol, hydramine, carboxylic acids under sulfuric acid or fluoroboric acid catalysis.Wherein, epoxidized vegetable oil can generate the vegetable oil polyol with adjacent two hydroxyl structures through the water open loop.CN1837180A and CN101139252A disclose " a kind of biopolyol that utilizes the rapeseed oil preparation " and " utilizing the biopolyol of Jatropha curcas oil preparation " respectively, be main raw material with rapeseed oil and Jatropha curcas oil respectively, make vegetable oil polyol through alcoholysis/epoxidation/open loop three-step reaction.CN1837181A and CN101108803A disclose " a kind of biopolyol that adopts the rapeseed oil preparation " and " a kind of biopolyol that adopts the Jatropha curcas oil preparation ", be main raw material with rapeseed oil and Jatropha curcas oil respectively, make vegetable oil polyol through epoxidation/open loop/alcoholysis three-step reaction.CN1907944A discloses " a kind of biopolyol that adopts the epoxy rapeseed oil preparation ", directly is main raw material with the epoxy rapeseed oil, makes vegetable oil polyol through open loop/alcoholysis two steps reaction.CN101906016A discloses " a kind of rubber seed oil polyalcohol and preparation method thereof ", is main raw material with the rubber seed oil, makes vegetable oil polyol through epoxidation/open loop two steps reaction.CN101659627A discloses " adopting the high hydroxyl value bio-base polyol of epoxidized vegetable oil through one-step reaction preparation ", by epoxidized vegetable oil and glycol amine epoxy group(ing) ring-opening reaction and ester group amidate action takes place simultaneously, prepares vegetable oil polyol.CN101747184A and CN101230020A disclose " single stage method is prepared the method for polyvalent alcohol by soybean oil " and " method of synthesizing macromonomer for polymer polyol by plant oil and uses thereof " respectively, utilize epoxidation and open loop all to react under acidic conditions, single stage method is prepared vegetable oil polyol.
The vegetable oil polyol of above patent preparation is mainly based on the epoxide group open loop, and is all synthetic by batch reactor, has following drawback: 1. long reaction time; 2. energy consumption is higher; 3. equipment and automatic control level are low; 4. the side reaction that is difficult to avoid causes product quality lower (crosslinking side reaction cause the product hydroxyl value is on the low side, viscosity is bigger than normal).
Based on above problem, it is raw material that this programme proposes with the epoxidized vegetable oil, adopt the microchannel module reaction unit to prepare vegetable oil polyol fast, the preparation method is operate continuously, preparation technology's easy operation control, reaction times is short, waste water and organic solvent reusable edible pollute for a short time, and energy consumption is low, side reaction is weakened, and the controlled hydroxyl value scope of product is bigger.It is simple to have production equipment, easy to assemble, and the characteristics that are easy to carry and move can be regulated by simple increase and decrease microchannel quantity, " scale effect " that does not exist similar industrial to produce.
Summary of the invention
Technical problem to be solved by this invention is, to produce that long reaction time, energy consumption that vegetable oil polyol exists are higher, product quality is not high, can not produce continuously and a kind of method of utilizing continuous processing to prepare vegetable oil polyol of proposing with interrupter method in order to overcome at present based on epoxide group open loop principle.
For solving the problems of the technologies described above, thinking of the present invention is as follows:
Contain unsaturated carbon-carbon double bond (Fig. 1) in the vegetables oil, two keys can make epoxidized vegetable oil through the Prileshajev epoxidation reaction.Epoxidized vegetable oil can generate the vegetable oil polyol (Fig. 2) with adjacent two hydroxyl structures through the water open loop under sulfuric acid or fluoroboric acid catalysis.
Microchannel reaction is as a new synthesis technology, at medicine, field of fine chemical has certain application, also is the research focus in present international fine chemical technology field.Compare with the popular response system, microchannel reaction has that reaction preference height, mass-and heat-transfer efficient height make the reactive behavior height, the reaction times is short, transformation efficiency is high, security is good and is easy to advantage such as control.The microchannel reaction will have certain application prospect in the synthetic system of vegetable oil polyol: 1. water open loop epoxidized vegetable oil prepares vegetable oil polyol and belongs to inhomogeneous reaction, reaction efficiency is not high when rhythmic reaction, the time is long, cause the side reaction aggravation, and the Forced Mixing by microchannel reaction process, can increase the specific surface area of reactant greatly, and then ignore the unfavorable factor of two phase reaction, reaction efficiency improves; 2. in the vegetable oil polyol preparation process crosslinking side reaction can appear, and the crosslinking side reaction that the high characteristics of reaction preference of microchannel reaction can weaken greatly and occur in the reaction process; 3. but the high-level efficiency of microchannel reaction has guaranteed to react and has finished within a short period of time, and energy efficient meets the low-carbon environment-friendly theory.
The concrete technical scheme of the present invention is as follows:
A kind of method of utilizing continuous processing to prepare vegetable oil polyol, epoxidized vegetable oil is dissolved in organic solvent, with the aqueous solution simultaneous pumping that contains catalyzer in a subtle way in the path modular reaction unit, keep reaction time 2～12min, under normal pressure and 30～100 ℃, react, reaction product is left standstill separatory, and water reclaims, oil phase Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make vegetable oil polyol.
Wherein, described epoxidized vegetable oil is at least a in epoxy sweet oil, epoxy peanut oil, epoxy rapeseed oil, epoxy Oleum Gossypii semen, epoxy soybean oil, epoxy coconut oil, epoxy palm oil, epoxy sesame oil, epoxy sunflower seed oil, epoxy oleum lini, epoxy Viscotrol C, epoxy tung oil, epoxy Thistle oil, epoxy Rice pollard oil, epoxy Semen Maydis oil and the epoxy tea oil.Preferred epoxy soybean oil, epoxy Oleum Gossypii semen or epoxy Viscotrol C.
Wherein, described organic solvent is tetrahydrofuran (THF), pyridine, acetone or mibk, preferred tetrahydrofuran (THF).
Wherein, described epoxidized vegetable oil is 1:1.5～8 with the volume of organic solvent ratio, preferred 1:2～6.
Wherein, described catalyzer is sulfuric acid or fluoroboric acid, and described sulfuric acid concentration is 98wt%, and described fluoroboric acid concentration is 40wt%.
Wherein, the volume ratio of catalyzer and epoxidized vegetable oil is 1:10～20, preferred 1:10～16.
Wherein, the volume ratio of catalyzer and water is 1:15～40, preferred 1:18～30.
Wherein, described microchannel module reaction unit comprises micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that is linked in sequence successively by pipeline, reaction raw materials passes through in the pump input micro mixer and equipment afterwards thereof of accurate and low pulsation, thereby the realization material can also be controlled its residence time by the microchannel module reaction unit continuously simultaneously.Can also connect raw material storage tank and product receiving flask end to end respectively to realize serialization production as required.Described micro mixer is slit plate mixer LH25 (Hastelloy C); The microstructure heat exchanger is coaxial heat exchanger (Hastelloy C); Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed meander reactor HC, breathe out kind alloy micro passage reaction (internal diameter 2.1mm), preferred sandwich reactor HC or breathe out kind alloy micro passage reaction.
Wherein, described Na
2CO
3Aqueous solution mass percentage concentration is 5%.
Beneficial effect:
The invention has the advantages that the preparation method is operate continuously, preparation technology's easy operation control, the reaction times is short, enrich in raw material environmental protection, source, and waste water and organic solvent reusable edible pollute little, energy consumption is low, and side reaction is weakened, and the controlled hydroxyl value scope of product is bigger.It is simple to have production equipment, easy to assemble, and the characteristics that are easy to carry and move can be regulated by simple increase and decrease microchannel quantity, " scale effect " that does not exist similar industrial to produce.
Description of drawings
Fig. 1 is the chemical structure of vegetables oil.
Fig. 2 is the synthetic synoptic diagram of vegetable oil polyol.
Fig. 3 is the synoptic diagram of microchannel module reaction unit; Wherein, 1 is raw material storage tank, and 2 is T type mixing tank, and 3 is heat exchanger, and 4 is the tubulose temperature control modules, and 5 is micro-structured reactor, and 6 are product receiving flask (cooling off termination reaction with mixture of ice and water).
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described content of embodiment only is used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
The microchannel module reaction unit that following examples were suitable for comprises the raw material storage tank 1, micro mixer 2, microstructure heat exchanger 3, tubulose temperature control modules 4, micro-structured reactor 5 and the product receiving flask 6 that are linked in sequence successively by pipeline as shown in Figure 3.Reaction raw materials passes through in the pump input micro mixer and equipment afterwards thereof of accurate and low pulsation, thereby the realization material can also be controlled its residence time by the microchannel module reaction unit continuously simultaneously.Connected by the kapillary of one section tetrafluoroethylene material between micro-structured reactor 5 and the product receiving flask 6, with its be immersed in the ice-water bath can termination reaction carrying out.Described micro mixer is slit plate mixer LH25 (Hastelloy C), available from Ehrfeld Mikrotechnik BTS; The microstructure heat exchanger is coaxial heat exchanger (Hastelloy C), available from Ehrfeld Mikrotechnik BTS; Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed meander reactor HC, Kazakhstan kind alloy micro passage reaction (internal diameter 2.1mm), preferred sandwich reactor HC or breathe out kind alloy micro passage reaction, wherein sandwich reactor HC is available from Ehrfeld Mikrotechnik BTS; The tubulose temperature control modules is available from Ehrfeld Mikrotechnik BTS.
Embodiment 1:
200mL epoxy sweet oil is dissolved in the 600mL tetrahydrofuran (THF) is made into the A component, 13mL sulfuric acid is dissolved in 240mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, under normal pressure and 50 ℃, in sandwich reactor HC, react, the sample rate of A, B component is respectively 2.8mL/min, 0.9mL/min, keeps reaction time 10min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the sweet oil polyvalent alcohol, its hydroxyl value is 222mgKOH/g.
Embodiment 2:
200mL epoxy peanut oil is dissolved in the 1000mL tetrahydrofuran (THF) is made into the A component, the 20mL fluoroboric acid is dissolved in 440mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, under normal pressure and 80 ℃, in sandwich reactor HC, react, the sample rate of A, B component is respectively 5.3mL/min, 2.1mL/min, keeps reaction time 5min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the peanut oil polyvalent alcohol, its hydroxyl value is 265mgKOH/g.
Embodiment 3:
The 200mL epoxy rapeseed oil is dissolved in the 700mL tetrahydrofuran (THF) is made into the A component, 20mL sulfuric acid is dissolved in 600mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, react in breathing out in the kind alloy micro passage reaction under normal pressure and 70 ℃, the sample rate of A, B component is respectively 3.4mL/min, 2.3mL/min, keeps reaction time 3.5min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the rapeseed oil polyvalent alcohol, its hydroxyl value is 222mgKOH/g.
Embodiment 4:
200mL epoxy Oleum Gossypii semen is dissolved in the 400mL tetrahydrofuran (THF) is made into the A component, 14mL sulfuric acid is dissolved in 340mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, react in breathing out in the kind alloy micro passage reaction under normal pressure and 40 ℃, the sample rate of A, B component is respectively 2.8mL/min, 1.6mL/min, keeps reaction time 4.5min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the Oleum Gossypii semen polyvalent alcohol, its hydroxyl value is 232mgKOH/g.
Embodiment 5:
The 200mL epoxy soybean oil is dissolved in the 800mL tetrahydrofuran (THF) is made into the A component, the 16mL fluoroboric acid is dissolved in 300mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, under normal pressure and 100 ℃, in sandwich reactor HC, react, the sample rate of A, B component is respectively 5.6mL/min, 1.8mL/min, keeps reaction time 5min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the soybean oil polyvalent alcohol, its hydroxyl value is 356mgKOH/g.
Embodiment 6:
The 200mL epoxy coconut oil is dissolved in the 600mL tetrahydrofuran (THF) is made into the A component, the 18mL fluoroboric acid is dissolved in 380mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, under normal pressure and 50 ℃, in sandwich reactor HC, react, the sample rate of A, B component is respectively 3.5mL/min, 1.8mL/min, keeps reaction time 7min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the Oleum Cocois polyvalent alcohol, its hydroxyl value is 25mgKOH/g.
Embodiment 7:
The 200mL epoxy palm oil is dissolved in the 1100mL tetrahydrofuran (THF) is made into the A component, the 15mL fluoroboric acid is dissolved in 330mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, under normal pressure and 40 ℃, in sandwich reactor HC, react, the sample rate of A, B component is respectively 3.2mL/min, 0.9mL/min, keeps reaction time 9min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the plam oil polyvalent alcohol, its hydroxyl value is 136mgKOH/g.
Embodiment 8:
200mL epoxy sesame oil is dissolved in the 400mL tetrahydrofuran (THF) is made into the A component, 12.5mL being dissolved in 250mL water, sulfuric acid is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, react in breathing out in the kind alloy micro passage reaction under normal pressure and 80 ℃, the sample rate of A, B component is respectively 7.0mL/min, 3.0mL/min, keeps reaction time 2min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the sesame oil polyvalent alcohol, its hydroxyl value is 242mgKOH/g.
Embodiment 9:
200mL epoxy sunflower seed oil is dissolved in the 600mL tetrahydrofuran (THF) is made into the A component, the 16mL fluoroboric acid is dissolved in 290mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, under normal pressure and 70 ℃, in sandwich reactor HC, react, the sample rate of A, B component is respectively 5.4mL/min, 2.0mL/min, keeps reaction time 5min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the sunflower seed oil polyvalent alcohol, its hydroxyl value is 343mgKOH/g.
Embodiment 10:
200mL epoxy oleum lini is dissolved in the 1200mL tetrahydrofuran (THF) is made into the A component, the 17mL fluoroboric acid is dissolved in 340mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, under normal pressure and 90 ℃, in sandwich reactor HC, react, the sample rate of A, B component is respectively 9.8mL/min, 2.5mL/min, keeps reaction time 3min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the oleum lini polyvalent alcohol, its hydroxyl value is 415mgKOH/g.
Embodiment 11:
200mL epoxy Viscotrol C is dissolved in the 600mL tetrahydrofuran (THF) is made into the A component, 16mL sulfuric acid is dissolved in 320mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, react in breathing out in the kind alloy micro passage reaction under normal pressure and 60 ℃, the sample rate of A, B component is respectively 4.7mL/min, 2.0mL/min, keeps reaction time 3min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make castor oil polyhydric alcohol, its hydroxyl value is 312mgKOH/g.
Embodiment 12:
200mL epoxy tung oil is dissolved in the 500mL tetrahydrofuran (THF) is made into the A component, 15mL sulfuric acid is dissolved in 400mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, react in breathing out in the kind alloy micro passage reaction under normal pressure and 50 ℃, the sample rate of A, B component is respectively 3.1mL/min, 1.9mL/min, keeps reaction time 4min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the tung oil polyvalent alcohol, its hydroxyl value is 354mgKOH/g.
Embodiment 13:
200mL epoxy Thistle oil is dissolved in the 600mL tetrahydrofuran (THF) is made into the A component, 17mL sulfuric acid is dissolved in 470mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, react in breathing out in the kind alloy micro passage reaction under normal pressure and 30 ℃, the sample rate of A, B component is respectively 2.1mL/min, 1.2mL/min, keeps reaction time 6min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the Thistle oil polyvalent alcohol, its hydroxyl value is 303mgKOH/g.
Embodiment 14:
200mL epoxy Rice pollard oil is dissolved in the 900mL tetrahydrofuran (THF) is made into the A component, 15mL sulfuric acid is dissolved in 300mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, under normal pressure and 90 ℃, in sandwich reactorHC, react, the sample rate of A, B component is respectively 14.4mL/min, 4.1mL/min, keeps reaction time 2min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the Rice pollard oil polyvalent alcohol, its hydroxyl value is 275mgKOH/g.
Embodiment 15:
200mL epoxy Semen Maydis oil is dissolved in the 400mL tetrahydrofuran (THF) is made into the A component, 18mL sulfuric acid is dissolved in 450mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, react in breathing out in the kind alloy micro passage reaction under normal pressure and 60 ℃, the sample rate of A, B component is respectively 3.7mL/min, 3.0mL/min, keeps reaction time 3min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the Semen Maydis oil polyvalent alcohol, its hydroxyl value is 258mgKOH/g.
Embodiment 16:
200mL epoxy tea oil is dissolved in the 500mL tetrahydrofuran (THF) is made into the A component, the 14mL fluoroboric acid is dissolved in 260mL water and is made into the B component, simultaneous pumping is in a subtle way in the path modular reaction unit, under normal pressure and 40 ℃, in sandwich reactor HC, react, the sample rate of A, B component is respectively 2.4mL/min, 1.0mL/min, keeps reaction time 11min, and reaction product is left standstill separatory, water reclaims, oil phase 5%Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make the tea oil polyvalent alcohol, its hydroxyl value is 227mgKOH/g.
Claims (10)
1. method of utilizing continuous processing to prepare vegetable oil polyol, it is characterized in that, epoxidized vegetable oil is dissolved in organic solvent, with the aqueous solution simultaneous pumping that contains catalyzer in a subtle way in the path modular reaction unit, keep reaction time 2～12min, under normal pressure and 30～100 ℃, react, reaction product is left standstill separatory, water reclaims, oil phase Na
2CO
3Solution washing is to neutral, again through separatory, revolve steaming, make vegetable oil polyol.
2. the method for utilizing continuous processing to prepare vegetable oil polyol according to claim 1, it is characterized in that described epoxidized vegetable oil is at least a in epoxy sweet oil, epoxy peanut oil, epoxy rapeseed oil, epoxy Oleum Gossypii semen, epoxy soybean oil, epoxy coconut oil, epoxy palm oil, epoxy sesame oil, epoxy sunflower seed oil, epoxy oleum lini, epoxy Viscotrol C, epoxy tung oil, epoxy Thistle oil, epoxy Rice pollard oil, epoxy Semen Maydis oil and the epoxy tea oil.
3. the method for utilizing continuous processing to prepare vegetable oil polyol according to claim 1 is characterized in that, described organic solvent is tetrahydrofuran (THF), pyridine, acetone or mibk.
4. the method for utilizing continuous processing to prepare vegetable oil polyol according to claim 1 is characterized in that, described epoxidized vegetable oil is 1:1.5～8 with the volume of organic solvent ratio.
5. the method for utilizing continuous processing to prepare vegetable oil polyol according to claim 1 is characterized in that, described catalyzer is sulfuric acid or fluoroboric acid.
6. the method for utilizing continuous processing to prepare vegetable oil polyol according to claim 1 is characterized in that, the volume ratio of catalyzer and epoxidized vegetable oil is 1:10～20.
7. the method for utilizing continuous processing to prepare vegetable oil polyol according to claim 1 is characterized in that, the volume ratio of catalyzer and water is 1:15～40.
8. the method for utilizing continuous processing to prepare vegetable oil polyol according to claim 1, it is characterized in that, described microchannel module reaction unit comprises micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that is linked in sequence successively by pipeline, in the pump input micro mixer and equipment afterwards thereof of reaction raw materials by accurate and low pulsation.
9. the method for utilizing continuous processing to prepare vegetable oil polyol according to claim 8 is characterized in that, described micro mixer is slit plate mixer LH25; The microstructure heat exchanger is coaxial heat exchanger; Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed meander reactor HC or breathes out kind alloy micro passage reaction.
10. the method for utilizing continuous processing to prepare vegetable oil polyol according to claim 1 is characterized in that, described Na
2CO
3Aqueous solution mass percentage concentration is 5%.
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