CN104557811A - Method for producing furfural from pentose solution by adopting ultrasonic reactor - Google Patents
Method for producing furfural from pentose solution by adopting ultrasonic reactor Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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Abstract
The invention provides a method for producing furfural from a pentose solution serving as a raw material. The method comprises the steps: introducing the pentose solution and an extractant into an ultrasonic reactor, reacting under the condition that furfural is produced from pentose through reacting, enabling a reaction effluent to be subjected to cooling, standing and layering, so as to obtain a water phase, namely an upper layer, and an extracted phase, namely a lower layer, enabling the extracted phase to enter an extractant regeneration tower for further separation, enabling a tower top product to be subjected to phase separation, so as to obtain a regenerated extractant and a small volume of water, and enabling a tower reactor product to enter a furfural finishing column for further separation, so as to obtain acetic acid and formic acid from the column top and obtain furfural from a column reactor, wherein the water phase can be reused as water for hydrolyzing hemicellulose, and the extractant can be recycled; enabling acetic acid and formic acid to enter an acetic acid refining tower for further separation, so as to obtain formic acid from the tower top and obtain acetic acid from a tower reactor. According to the method provided by the invention, the ultrasonic reactor is adopted, and furfural is enabled to instantly achieve a balance in two phases, namely the extractant and the water, so that the yield of furfural is increased; the process flow is simple, meanwhile, furfural, acetic acid and formic acid are recovered, and no waste liquid is discharged, so that the method is an environment-friendly process.
Description
Technical field
The present invention relates to and a kind ofly produce the method for furfural by pentose, particularly a kind ofly adopt ultrasound reactor to produce furfural and the method for by-product formic acid and acetic acid simultaneously.
Background technology
Furfural, has another name called furtural.Owing to there is the functional groups such as aldehyde radical, diene, cyclic ethers in Furfural Molecule structure, so it has the character of aldehyde, ether, diene and arene compound concurrently, the reaction of number of different types can be participated in, synthesize multiple Chemicals, be widely used in multiple production fields such as food, medicine, synthetic resins, casting.
The raw material of current production furfural is the vegetable fibre being rich in piperylene, as corn cob, bagasse, cornstalk, rice husk etc.Its principle is that first piperylene is hydrolyzed to pentose, and then dehydration of pentoses cyclisation generates furfural.
According to pentosan hydralysis and this two-step reaction of dehydration of pentoses whether in same reactor, furfural production method can be divided into single stage method and two-step approach.The advantage of single stage method is that equipment is simple, simple to operate, but it is large that its main drawback is steam consumption, produce the steam that 1 ton of furfural consumes 18 ~ 24 tons, furaldehyde yield is low, only have about 45%, produce a large amount of waste water and dregs, produce 1 ton of furfural and produce 24 tons of high pollution waste water, raw material availability is low, produce 1 ton of furfural, consume corn cob 11 tons, waste residue turns black, and Mierocrystalline cellulose and xylogen destroy serious.Two-step approach is produced furfural technology due to pentosan hydralysis and dehydration of pentoses and is carried out in two reactors, the raw material availability that can solve existing furfural production is low, raw material sources are narrow, furaldehyde yield is low, processing wastewater is difficult, furfural dregs is difficult to continue the difficult problems such as utilization, and this method is considered to the furfural production novel method of most prospect.
" two-step approach " produces the first step in furfural technology at present; namely to produce pentose technology ripe in biomass material hydrolysis; under relatively mild reaction conditions; hemicellulose in biomass and hydrolyzable mainly generate pentose; ethanoyl simultaneously on half fiber molecule side chain and the oxidized generation acetic acid of formyl radical and formic acid, therefore in pentose solution also containing a certain amount of formic acid and acetic acid.But produce furfural process by pentose, due to furfural easily and its precursor generation side reaction thus cause furaldehyde yield very low, this also becomes " two-step approach " produces furfural technology and fails the basic reason of industrial application.
Only while pentose reaction generates furfural, fast the furfural fast transfer that reaction generates is gone out reaction system and fundamentally could reduce side reaction raising furaldehyde yield.Reaction, extraction is produced the pentose that furfural technology is considered to most industrial prospect and is produced furfural technology.Reaction, extraction is produced furfural technology and is referred to that generating furfural process in pentose reaction adds a kind of not dissolving each other with water and furfural is had to the solvent of highly selective, constantly furfural is extracted into solvent phase from water react system by solvent, thus greatly reduces side reaction raising furaldehyde yield.
CN101486695A discloses the method and apparatus that a kind of reaction, extraction prepares furfural.This invention take supercritical co as extraction agent, take solid acid as catalyzer, supercritical co and pentose solution counter current contact in packed extraction tower is reacted, temperature of reaction be 200 DEG C, xylose concentration 30% (wt), supercritical co pressure be 7 MPa time, furaldehyde yield is 70%.
CN102627618A discloses a kind of method that reaction, extraction produces furfural.This invention utilizes organic solvent and pentose solution counter current contact in packed extraction tower to react, temperature of reaction be 200 DEG C, pentose sugar concentration 1.56% (wt), solvent ratio 3:1 time, furaldehyde yield is 70%.
Adopt reaction, extraction technique to prepare in the process of furfural, pentose solution and extraction agent can mix efficiently contact to impel react the furfural that generates enough fast mass transfer be restrict furaldehyde yield most critical factor just to extraction phase.In above-mentioned patent, extraction agent and pentose solution are all counter current contact reactions in packed extraction tower, but packing tower mixed effect is poor, and side reaction seriously causes furaldehyde yield lower, and the highest only have 70%; The surface that the condensation product that side reaction generates also can be accumulated in filler causes filler to block, and production process cannot be carried out for a long time; Foregoing invention method cannot reclaim acetic acid and the formic acid of pentose solution simultaneously in addition, if the direct discharge of the aqueous solution reacted not only can cause serious environmental pollution, also can cause the waste of precious resources.
summary of the invention
For the deficiencies in the prior art, the invention provides a kind of ultrasound reactor that uses and produce the production unit of furfural technique as reaction, extraction, High-efficient Production furfural also reclaims the novel method of by product acetic acid and formic acid simultaneously.
The invention provides a kind of method of being produced furfural by pentose solution, comprise following content:
(1) raw material pentose solution and extraction agent are passed into ultrasound reactor respectively by handling equipment, hyperacoustic frequency is 10 ~ 300kHz, hyperacoustic power is 0.1 ~ 500W/L reaction mass, reaction used catalyst is formic acid and/or acetic acid, carries out mixing and contacting reaction under generating the reaction conditions of furfural at dehydration of pentoses;
(2) reaction effluent that step (1) obtains carries out cooling stratification, and upper strata is aqueous phase, the unreacted pentose of the furfural containing trace, acetic acid, formic acid and trace, and lower floor is extraction phase, the moisture mainly containing furfural, acetic acid, formic acid and trace;
(3) extraction phase that step (2) obtains enters extractant regeneration tower and is separated, and overhead product obtains the extraction agent of regeneration and a small amount of water through phase-splitting, and tower reactor obtains the mixture of water-free furfural, acetic acid and formic acid;
(4) in step (3), tower reactor gained furfural, acetic acid enter furfural finishing column with the mixture of formic acid and are separated, and tower reactor obtains furfural, and tower top obtains acetic acid and formic acid mixtures;
(5) acetic acid that in step (4), tower top obtains and formic acid mixtures enter acetic acid refining tower, and tower top obtains formic acid, and tower reactor obtains acetic acid.
It is 150 ~ 280 DEG C that dehydration of pentoses of the present invention generates furfural reaction temperature, is preferably 180 ~ 220 DEG C; Reaction time is 0.1 ~ 2 h.
The present invention, under reaction pressure should be greater than temperature of reaction, aqueous phase bubbling pressure is to ensure that reaction is carried out under liquid phase state, and reaction pressure scope is at 2 ~ 10 MPa, and preferred pressure is 2 ~ 6 MPa.
In the inventive method, extraction agent used is composite extractant, comprises the hydrochloric ether that benzene, vinyl acetic monomer and boiling point are less than formic acid boiling point.Wherein, benzene 10wt% ~ 60wt%, vinyl acetic monomer 10wt% ~ 30wt%, hydrochloric ether 10wt% ~ 60wt%.Be preferably benzene 20 ~ 40wt%, vinyl acetic monomer 15 ~ 25wt%, hydrochloric ether 20 ~ 40wt%.Described hydrochloric ether is the mixture of one or more in trichloromethane, trieline, 1，1，1-trichloroethane, vinyl trichloride.
In the inventive method, composite extractant also plays the effect of entrainer simultaneously, and in extractant regeneration tower, extraction agent and water form azeotrope and the moisture in furfural, formic acid, vinegar stock is taken to tower top.
In the inventive method, can also add a certain amount of inorganic salt in described pentose solution, can be specifically one or more in sodium sulfate, calcium sulfate, sodium-chlor, SODIUMNITRATE, preferably sulfuric acid sodium and/or sodium-chlor.Described inorganic salt consumption is the 1wt% ~ 5wt% of pentose solution.
In the inventive method, dehydration of pentoses catalysts is preferably acetic acid and formic acid, and described catalyst levels is the 1wt% ~ 5wt% of pentose solution.
Ultrasound reactor of the present invention is made up of reactor and ultrasonic wave oscillator, ultrasonic transducer, ultrasonic emitter.In reactor, be provided with two ultrasonic emitter, one end of ultrasonic emitter is respectively provided with ultrasonic transducer, and ultrasonic wave oscillator connects ultrasonic transducer respectively.Ultrasonic emitter is fixed on the flange of reactor top and the bottom by set screw nut, and flange is fixedly connected with reactor by mounting block.
The reactor that the present invention relates to directly can continue to use existing standard reaction still, the reactor of non-standard reactor and channel-shaped or tubular, the auxiliary facilitys such as agitator, pressurizing device, thermometer, tensimeter can be set up, and can according to the scale of the scale of device and operational condition determination reactor and form.Also the reactor of other form can be selected, as impact flow reactor, static mixer reactor etc.For improving reaction effect, can set up Matter Transfer between reactor outlet and entrance, circulated material quantity is 5% ~ 500% of inlet amount.
The inventive method adopts ultrasound reactor to produce the production unit of furfural technique as reaction, extraction, because supersonic transducer frequency is different, the ultrasonic wave that each ultrasonic transducer produces by the side of ultrasonic emitter and the other end to the reaction mass radiation in reactor, hyperacoustic radiation power can regulate, so just can utilize hyperacoustic dispersion, vibration, the multiple-effects such as activation, destroy the interface structure that in reactor, reaction mass is alternate, thus improve pentose reaction generate furfural at two alternate rate of mass transfer, greatly reduce side reaction, improve furaldehyde yield.
In the inventive method, have employed double solvents as extraction agent, wherein, vinyl acetic monomer all has very high selectivity to formic acid, acetic acid and furfural, benzene and hydrochloric ether all have very high selectivity to furfural, benzene and hydrochloric ether are water-soluble hardly and Dichlorodiphenyl Acetate ethyl ester has very high selectivity, and vinyl acetic monomer can be made water-soluble hardly, solve vinyl acetic monomer because of in water solubleness large and can not as the problem of extraction agent; Hydrochloric ether can also play the effect regulating composite extractant density and viscosity simultaneously; This composite extractant all has very high selectivity to furfural, acetic acid and formic acid, byproduct formic acid and acetic acid can be reclaimed while reaction, extraction produces furfural, furaldehyde yield is greater than 80%, and acetic acid and the formic acid rate of recovery are greater than 90%, and the aqueous phase reacted can be used as system reuse water.
The inventive method, in the composite extractant adopted, benzene and vinyl acetic monomer all can form azeotrope with water, therefore composite extractant can also play the entrainer effect of dehydration, this makes dehydration of the present invention need not add other entrainer, so present invention process flow process is simple, and be separated the furfural that obtains and acetate products purity high.
The inventive method, by adding a certain amount of inorganic salt in aqueous phase, inorganic salt greatly reduce the mutual solubility of extraction agent and aqueous phase under high temperature, solve at high temperature because extraction agent and water mutual solubility cause extraction agent to lose seriously greatly, finally cause reaction, extraction technique industrially cannot apply this key technical problem; Inorganic salt both had stronger catalytic activity to dehydration of pentoses reaction in addition, substantially increased again the selectivity of extraction agent to furfural, formic acid and acetic acid, contributed to reducing side reaction and improved furaldehyde yield.
The present invention generates the reaction mechanism of furfural by the reaction of research pentose, finds that pentose is under reaction generates furfural condition, furfural very easily with its precursor generation side reaction, this is the basic reason causing furaldehyde yield low.Tradition reaction, extraction is produced furfural technology and is often carried out in packing tower, aqueous phase and extraction agent mixed effect very poor, make furfural cannot be delivered to extraction phase enough fast, this causes furaldehyde yield still very low.The present invention adopts the reactor being provided with ultrasonic transmission device to produce the production unit of furfural technique as reaction, extraction, greatly enhance microcosmic mixing and microcosmic mass transfer effect, make furfural reach partition equilibrium instantaneously at extraction agent and water two-phase, reduce side reaction, improve furaldehyde yield.Solve because of extraction agent and pentose solution mixed effect poor, reaction system is two-phase, and the side reaction that furfural causes far above furfural content during biphase equilibrium at water react system concentration is serious, furaldehyde yield is low and the problem such as reactor plugs.Simplify technical process, reduce production cost and facility investment.Without discharging of waste liquid in production process, it is an environmental protection processing method.
accompanying drawing explanation
Fig. 1 is a kind of ultrasound reactor structural representation that the present invention uses.
Fig. 2 is a kind of process flow sheet of reaction system of the present invention.
Embodiment
As shown in Figure 1, ultrasound reactor of the present invention is made up of cylindrical reactor 5 and ultrasonic wave oscillator 1, ultrasonic transducer 3, ultrasonic emitter 4.In reactor 5, be provided with two ultrasonic emitter 4, one end of ultrasonic emitter 4 is respectively provided with ultrasonic transducer 3, and ultrasonic wave oscillator 1 connects ultrasonic transducer 3 respectively.Ultrasonic emitter 4 is fixed on the flange 10 of reactor 5 top and the bottom by set screw nut 2, and flange 10 is fixedly connected with reactor 5 by mounting block 12.Reactor 5 be respectively equipped with recycle feed mouth 13 and recycle feed mouth 14 up and down, the outside of reactor 5 is provided with the chuck 6 controlling temperature of reaction, and side, chuck 6 bottom is provided with circulation fluid entrance 7, and side, chuck top is provided with circulation fluid outlet 9.And the top of reactor 5 is provided with reacting material outlet 11; The bottom of reactor 5 is provided with reacting material outlet 8.
The transform electrical signals of ultrasonic wave oscillator 1 can be mechanical shock by ultrasonic transducer 3.And a kind of ultrasonic wave of frequency can be produced.The ultrasonic wave that this ultrasonic transducer 3 produces is by the side of above-mentioned ultrasonic emitter 4, or side and the other end radiate in reactor 5.
As shown in Figure 2, pentose solution 15 and the extraction agent 16 of reaction will be participated according to stoichiometric ratio, with pump or other equipment for liquid transportation, material is input in tundish 17 respectively, carry out pre-mixing, then by pump or other equipment for liquid transportation, be input to the opening for feed 19 of ultrasound reactor 18, 20, feed stream produces violent vibration under hyperacoustic effect in reactor 18,-the extraction process thus Homogeneous phase mixing reacts, material is from two side outlets 21, 22 flow to tundish B, the opening for feed 19 of ultrasound reactor is input to again by pump, 20, material produces vibration under ul-trasonic irradiation, thus Homogeneous phase mixing reacts-extraction process again, circulation like this, reactor pressure is controlled by pressure-regulator 23.Directly enter phase separation tank 24 from the reaction mass of pressure-regulator 23 discharge and carry out cooling stratification, upper strata is the aqueous phase 25 reacted, aqueous phase 25 can be used as hydrolysis of hemicellulose water, lower floor is for being rich in furfural, the extraction phase of acetic acid and formic acid, lower floor's extraction phase 26 directly enters extractant regeneration tower 27 and is separated, tower top obtains the extraction agent of regeneration and a small amount of water, extraction agent can be recycled, water-free furfural and mixture of carboxylic acids 29 is obtained at the bottom of tower, then bottom product 29 directly enters furfural finishing column 30 and is separated, furfural product 31 is obtained at the bottom of tower, purity is greater than 99.5%, tower top obtains formic acid and vinegar stock 32, overhead product 32 enters acetic acid refining tower 33 and is separated, tower top obtains formic acid product 34, its purity is greater than 99.5%, acetate products 35 is obtained at the bottom of tower, its purity is greater than 99.5%.
Method of the present invention and effect is further illustrated below by embodiment.The percentage composition related to is mass percentage.
In embodiment, pentose transformation efficiency, furaldehyde yield and acid recovering rate are calculated by following formula.
Embodiment 1
In raw material pentose solution, furfural, acetic acid, formic acid concn are respectively 4.9 wt %, 3.1 wt %, 0.6wt%, sodium sulfate concentration 3wt%.
Extraction agent is benzene, vinyl acetic monomer, 1，1，1-trichloroethane mixed solvent, and wherein, benzene accounts for 40wt%, and vinyl acetic monomer accounts for 20wt%, and 1，1，1-trichloroethane accounts for 40wt%.
Extraction agent and pentose solution charge ratio are 3:1 (volume ratio), and the feeding rate of extraction agent and pentose solution equals ultrasound reactor useful volume, and (namely feed volume air speed is 1 h
-1namely, also the reaction times is 1 h), squeezes in reactor respectively by extraction agent and pentose solution with pump, and to react in reactor extraction process with recycle stock, recycle stock speed is 200% of inlet amount.Controlling temperature of reaction is 200 DEG C, and reaction pressure is 3Mpa, and ultrasonic frequency is 50kHz, and power is 400W/L.
Experimental result shows that pentose transformation efficiency is 97.4%, and furaldehyde yield is 82.1%, and recovery rate is 90.9%, and the formic acid rate of recovery is 89.8%.
Embodiment 2
According to the method for embodiment 1,2 times of difference to be feeding rate be reactor useful volume, namely the reaction times is 0.5 h.
Experimental result shows that pentose transformation efficiency is 78.1%, and furaldehyde yield is 61.4%, and recovery rate is 93.8%, and the formic acid rate of recovery is 90.8%.
Embodiment 3
According to the method for embodiment 1,0.67 times of difference to be feeding rate be reactor useful volume, namely the reaction times is 1.5 h.
Experimental result shows that pentose transformation efficiency is 99%, and furaldehyde yield is 82.5%, and recovery rate is 93.9%, and the formic acid rate of recovery is 90.9%.
Embodiment 4
According to the method for embodiment 1, difference is recycle stream is 100% of inlet amount.
Experimental result shows that pentose transformation efficiency is 96.8%, and furaldehyde yield is 82.1%, and recovery rate is 92.3%, and the formic acid rate of recovery is 90.7%.
Embodiment 5
According to the method for embodiment 1, difference is recycle stream is 300% of inlet amount.
Experimental result shows that pentose transformation efficiency is 96.1%, and furaldehyde yield is 81.1%, and recovery rate is 93.4%, and the formic acid rate of recovery is 91.3%.
Embodiment 6
According to the method for embodiment 1, difference is that temperature of reaction becomes 180 DEG C.
Experimental result shows that pentose transformation efficiency is 45.5%, and furaldehyde yield is 38.7%, and recovery rate is 94.6%, and the formic acid rate of recovery is 92.7%.
Embodiment 7
According to the method for embodiment 1, difference is that temperature of reaction becomes 220 DEG C.
Experimental result shows that pentose transformation efficiency is 99.5%, and furaldehyde yield is 84.1%, and recovery rate is 93.7%, and the formic acid rate of recovery is 91.4%.
Embodiment 8
According to the method for embodiment 1, difference is sodium sulfate concentration vanishing.
Experimental result shows that pentose transformation efficiency is 94.1%, and furaldehyde yield is 76.4%, and recovery rate is 82.5%, and the formic acid rate of recovery is 81.4%.
Embodiment 9
According to the method for embodiment 1, difference is that sodium sulfate concentration becomes 5%.
Experimental result shows that pentose transformation efficiency is 97.8%, and furaldehyde yield is 83.5%, and recovery rate is 93.9%, and the formic acid rate of recovery is 93.1%.
Embodiment 10
According to the method for embodiment 1, difference is that extraction agent and pentose solution charge ratio become 1:1.
Experimental result shows that pentose transformation efficiency is 97.9%, and furaldehyde yield is 77.3%, and recovery rate is 83.5%, and the formic acid rate of recovery is 79.7%.
Embodiment 11
According to the method for embodiment 1, difference is that extraction agent and pentose solution charge ratio become 5:1.
Experimental result shows that pentose transformation efficiency is 97.5%, and furaldehyde yield is 85.3%, and recovery rate is 94.5%, and the formic acid rate of recovery is 92.8%.
Embodiment 12:
According to the method for embodiment 1, difference is that composite extractant composition becomes: benzene, vinyl acetic monomer, 1，1，1-trichloroethane mass ratio 3:1:1.
Experimental result shows that pentose transformation efficiency is 97.7%, and furaldehyde yield is 77.3%, and recovery rate is 85.5%, and the formic acid rate of recovery is 82.5%.
Embodiment 13:
According to the method for embodiment 1, difference is that composite extractant composition becomes: benzene, vinyl acetic monomer, 1，1，1-trichloroethane mass ratio 1:1:3.
Experimental result shows that pentose transformation efficiency is 97.8%, and furaldehyde yield is 82.7%, and recovery rate is 81.5%, and the formic acid rate of recovery is 79.8%.
Embodiment 14:
According to the method for embodiment 1, difference is that composite extractant composition becomes: benzene, vinyl acetic monomer, 1，1，1-trichloroethane mass ratio 1:0:1.
Experimental result shows that pentose transformation efficiency is 97.8%, and furaldehyde yield is 83.4%, and recovery rate is 71.9%, and the formic acid rate of recovery is 70.8%.
Embodiment 15:
According to the method for embodiment 1, difference is that composite extractant composition becomes: benzene, vinyl acetic monomer, 1，1，1-trichloroethane mass ratio 0:1:1.
Experimental result shows that pentose transformation efficiency is 97.7%, and furaldehyde yield is 73.8%, and recovery rate is 92.9%, and the formic acid rate of recovery is 89.8%.
Embodiment 16:
According to the method for embodiment 1, difference is that composite extractant composition becomes: benzene, vinyl acetic monomer, 1，1，1-trichloroethane mass ratio 1:1:0.
Experimental result shows that pentose transformation efficiency is 97.8%, and furaldehyde yield is 76.1%, and recovery rate is 89.5%, and the formic acid rate of recovery is 85.9%.
Embodiment 17:
According to the method for embodiment 1, difference is that ultrasonic frequency becomes 100 kHz.
Experimental result shows that pentose transformation efficiency is 98.8%, and furaldehyde yield is 79.1%, and recovery rate is 86.5%, and the formic acid rate of recovery is 84.2%.
Embodiment 18:
According to the method for embodiment 1, difference is that ultrasonic frequency becomes 200 kHz.
Experimental result shows that pentose transformation efficiency is 98.2%, and furaldehyde yield is 75.1%, and recovery rate is 85.5%, and the formic acid rate of recovery is 81.1%.
Embodiment 19:
According to the method for embodiment 1, difference is that ultrasonic generator power becomes 200 W/L.
Experimental result shows that pentose transformation efficiency is 98.2%, and furaldehyde yield is 80.2%, and recovery rate is 85.9%, and the formic acid rate of recovery is 83.1%.
Embodiment 20:
According to the method for embodiment 1, difference is that ultrasonic generator power becomes 300 W/L.
Experimental result shows that pentose transformation efficiency is 98.2%, and furaldehyde yield is 81.8%, and recovery rate is 87.9%, and the formic acid rate of recovery is 86.1%.
Claims (11)
1. produced a method for furfural by pentose solution, comprise following content:
(1) raw material pentose solution and extraction agent are passed into ultrasound reactor respectively by handling equipment, hyperacoustic frequency is 10 ~ 300kHz, hyperacoustic power is 0.1 ~ 500W/L reaction mass, reaction used catalyst is formic acid and/or acetic acid, carries out mixing and contacting reaction under generating the reaction conditions of furfural at dehydration of pentoses;
(2) reaction effluent that step (1) obtains carries out cooling stratification, and upper strata is aqueous phase, the unreacted pentose of the furfural containing trace, acetic acid, formic acid and trace, and lower floor is extraction phase, the moisture mainly containing furfural, acetic acid, formic acid and trace;
(3) extraction phase that step (2) obtains enters extractant regeneration tower and is separated, and overhead product obtains the extraction agent of regeneration and a small amount of water through phase-splitting, and tower reactor obtains the mixture of water-free furfural, acetic acid and formic acid;
(4) in step (3), tower reactor gained furfural, acetic acid enter furfural finishing column with the mixture of formic acid and are separated, and tower reactor obtains furfural, and tower top obtains acetic acid and formic acid mixtures;
(5) acetic acid that in step (4), tower top obtains and formic acid mixtures enter acetic acid refining tower, and tower top obtains formic acid, and tower reactor obtains acetic acid.
2. in accordance with the method for claim 1, it is characterized in that: in step (1), dehydration of pentoses generates furfural reaction temperature is 150 ~ 280 DEG C, and reaction time is 0.1 ~ 2 h.
3. in accordance with the method for claim 1, it is characterized in that: in step (1), dehydration of pentoses generates furfural reaction temperature is 180 ~ 220 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: under in step (1), dehydration of pentoses generation furfural reaction pressure is greater than temperature of reaction, aqueous phase bubbling pressure is to ensure that reaction is carried out under liquid phase state, and reaction pressure is 2 ~ 10MPa.
5. in accordance with the method for claim 1, it is characterized in that: described catalyst levels is the 1wt% ~ 5wt% of pentose solution.
6. in accordance with the method for claim 1, it is characterized in that: extraction agent is composite extractant, comprise the hydrochloric ether that benzene, vinyl acetic monomer and boiling point are less than formic acid boiling point.
7. in accordance with the method for claim 6, it is characterized in that: described hydrochloric ether is one or more in trichloromethane, trieline, 1，1，1-trichloroethane, vinyl trichloride.
8. in accordance with the method for claim 6, it is characterized in that: in composite extractant, benzene is 10wt% ~ 60wt%, vinyl acetic monomer is 10wt% ~ 30wt%, and hydrochloric ether is 10wt% ~ 60wt%.
9. according to the method described in claim 6 or 8, it is characterized in that: in composite extractant, benzene is 20wt% ~ 40wt%, vinyl acetic monomer is 15wt% ~ 25wt%, and hydrochloric ether is 20wt% ~ 40wt%.
10. in accordance with the method for claim 1, it is characterized in that: add inorganic salt in described pentose solution, described inorganic salt consumption is the 1wt% ~ 5wt% of pentose solution.
11. in accordance with the method for claim 10, it is characterized in that: inorganic salt are one or more in sodium sulfate, calcium sulfate, sodium-chlor, SODIUMNITRATE.
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| CN102627618A (en) * | 2012-03-22 | 2012-08-08 | 天津大学 | Method for producing furfural through biomass hydrolysis-reactive extraction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102627618A (en) * | 2012-03-22 | 2012-08-08 | 天津大学 | Method for producing furfural through biomass hydrolysis-reactive extraction |
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