CN104557812A - Method for producing furfural from biomass - Google Patents
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- CN104557812A CN104557812A CN201310503596.2A CN201310503596A CN104557812A CN 104557812 A CN104557812 A CN 104557812A CN 201310503596 A CN201310503596 A CN 201310503596A CN 104557812 A CN104557812 A CN 104557812A
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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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- 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 biomass serving as a raw material. The method comprises the steps: hydrolyzing the biomass and water, so as to obtain a mixed solution of pentose, acetic acid and formic acid; introducing the mixed solution and an extractant into a static mixer for reaction, enabling a reaction effluent to be subjected to cooling, standing and layering, so as to obtain a water phase and an extracted phase, and enabling the extracted phase to enter an extractant regeneration tower for separation, so as to obtain a mixture, containing a trace volume of water, of furfural, acetic acid and formic acid from the tower top and obtain a regenerated extractant from the tower bottom; enabling the tower top product to enter a furfural refining tower for separation, so as to obtain acetic acid and formic acid, containing a trace volume of water, from the tower top and obtain furfural from a tower reactor; enabling the tower top product to enter an azeotropic rectifying tower, so as to extract the water phase from the tower top and obtain acetic acid and formic acid from a tower reactor; enabling the tower reactor product to enter a finishing column for separation, thereby obtaining formic acid and acetic acid. According to the method provided by the invention, the static mixer is adopted as a reaction vessel, 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 a kind of method of being produced furfural by pentose, particularly a kind of static mixer that adopts produces furfural and the method for by-product acetic acid and formic acid as reactor.
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 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 " generates 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 static mixer that uses as reactor, High-efficient Production furfural also reclaims the method for by product acetic acid and formic acid simultaneously.
Method of being produced furfural by biomass material of the present invention, comprises following content:
(1) enter hydrolysis kettle after being mixed according to mass ratio 0.05 ~ 1 with water by biomass material, at 100 ~ 160 DEG C of Water Under solution 0.2 ~ 1 h, obtain pentose, acetic acid and formic acid mixing solutions;
(2) with gained pentose solution in step (1) for raw material, adopt static mixer as reactor, pentose solution and extraction agent are passed into static mixer respectively by handling equipment, reaction used catalyst is formic acid and/or the acetic acid of biomass by hydrolyzation by-product, carries out mixing and contacting reaction under generating the reaction conditions of furfural at dehydration of pentoses;
(3) reaction effluent that step (2) obtains carries out cooling stratification, upper strata is aqueous phase, the unreacted pentose of the furfural containing trace, acetic acid, formic acid and trace, lower floor is extraction phase, the water mainly containing extraction agent, furfural, acetic acid, formic acid and trace;
(4) extraction phase that step (3) obtains enters extractant regeneration tower and is separated, and tower top obtains the mixture of furfural, acetic acid and formic acid containing minor amount of water, and tower reactor obtains the extraction agent regenerated, and described extraction agent enters reactor cycles and uses;
(5) furfural containing minor amount of water obtained in step (4), acetic acid enter furfural treatment tower with formic acid mixtures and are separated, and tower reactor obtains furfural, and its purity is greater than 99.5wt%, and tower top obtains acetic acid and formic acid mixtures;
(6) the middle gained acetic acid of step (5) enters after azeotropy rectification column contacts with entrainer with formic acid mixtures and is separated, tower top phase splitter obtains water and entrainer mixture, water is from overhead extraction, entrainer returns in tower, tower reactor obtains acetic acid and formic acid, and acetic acid and formic acid mixtures enter finishing column and be separated further, and tower top obtains finished product formic acid, tower reactor obtains finished product acetic acid, and its purity is all greater than 99.5wt%.
In the inventive method, extraction tower extraction agent used is composite extractant, described extraction agent is dimethyl phthalate, carbon number is greater than the alphanol (boiling point is higher than 180 DEG C) of 7 and the composition of ethyl triphenyl phosphine hexafluorophosphate composition, and described ethyl triphenyl hexafluorophosphate can be ethyl triphenyl sodium hexafluoro phosphate and/or ethyl triphenyl Potassium Hexafluorophosphate.Wherein, dimethyl phthalate accounts for 10wt% ~ 60wt%, and alphanol accounts for 10wt% ~ 40wt%, and ethyl triphenyl phosphine hexafluorophosphate accounts for 10wt% ~ 50wt%.Preferably, dimethyl phthalate accounts for 20wt% ~ 40wt%, and alphanol accounts for 20wt% ~ 30wt%, and ethyl triphenyl phosphine hexafluorophosphate accounts for 20wt% ~ 40wt%.
In the inventive method, in step (2), dehydration of pentoses generates furfural reaction temperature is 120 ~ 220 DEG C, is preferably 140 ~ 200 DEG C; Reaction time is 0.1 ~ 2 h; 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 1 ~ 3 MPa, and preferred pressure is 1 ~ 2 MPa.
In the inventive method, biomass material described in step (1) can be one or more in corn cob, wheat stalk, cornstalk, sorghum stalk, rice straw.
In the inventive method, aqueous phase described in step (3) can enter hydrolysis kettle and recycle.
In the inventive method, in step (6), azeotropy rectification column entrainer used is the one in hexanaphthene, vinyl acetic monomer, Iso Butyl Acetate, n-butyl acetate.
The static mixer that the present invention relates to can use various types of static mixer in prior art, can according to the scale of the scale of device and operational condition determination static mixer.Specifically can comprise standard or off-gauge static mixers such as SV type, SX type, SL type, SY type, SH type, SK type, SD type, and what preferentially select is the SK type static mixer of standard.For improving the mixed effect of static mixer, can set up Matter Transfer between static mixer outlet and entrance, recycle stock volumetric flow rate is 5% ~ 500% of inlet amount.Also can by the volume space velocity controlled circulation amount of recycle stock, the volume space velocity as recycle stock is 1 ~ 20 h
-1.
The inventive method adopts static mixer to produce the production unit of furfural technique as reaction, extraction, due to the effect of static mixer mixed cell, left-handed when making material, time and dextrorotation, continuous change flow direction, not only push central liquid stream to periphery, and push peripheral fluid to center, thus cause good radial mixed effect, the meanwhile turning effort of material self also can occur on the interface of adjacent elements junction, this perfect radial circular flow mixing effect, enhance microcosmic mixing and microcosmic mass transfer process greatly, thus substantially increase furfural rate of mass transfer, reduce side reaction, improve furaldehyde yield, realize the method for continuous seepage furfural.
Compared with prior art, the present invention adopts static mixer to produce the reactor of furfural technique as reaction, extraction, enhances microcosmic mixing greatly, makes 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.
In the inventive method, use composite extractant, the selectivity to furfural is substantially increased by alphanol and the composite use of ethyl triphenyl phosphine hexafluorophosphate, and adding by ethyl triphenyl phosphine hexafluorophosphate, pentose is produced furfural reaction and is obviously accelerated, show that ethyl triphenyl phosphine phosphofluoric acid salt pair pentose is produced furfural reaction and had katalysis, pentose can be made to generate furfural reaction and occur under the operational condition relatively relaxed, thus reduce production cost.In composite extractant of the present invention, add the problem that alphanol solves mutual solubility difference between ethyl triphenyl phosphine hexafluorophosphate and Dichlorodiphenyl Acetate and formic acid selectivity high dimethyl phthalate, therefore composite extractant of the present invention 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%, 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, have employed high boiling composite extractant, and extraction agent boiling point, far above furfural boiling point, in furfural and extraction agent sepn process, significantly can reduce the energy consumption of sepn process, and it is high to be separated the furfural product purity obtained.
Accompanying drawing explanation
Fig. 1 is static mixer structure schematic diagram in the present invention.
Fig. 2 is a kind of concrete technology schematic flow sheet of the inventive method.
Embodiment
As shown in Figure 1, static mixer 3 of the present invention, does not have moving parts in pipeline 24, only has stationary element 25, its stationary element 25 is welded by the left-handed of several distortions 180 degree and right-hand(ed)screw plate, its principle of work makes material impact stationary element 25 in the conduit 24, time and left-handed, time and dextrorotation, continuous change flow direction, not only push central liquid stream to periphery, and push peripheral fluid to center, thus cause good radial mixed effect.The meanwhile turning effort of material self also can occur on the interface of adjacent elements junction, this perfect radial circular flow mixing effect, makes extraction agent and water reach the object mixed, thus improves rate of mass transfer, reduce side reaction, improve furaldehyde yield.
As shown in Figure 2, according to metering than by fresh water 1 and biomass material 2, be injected in hydrolysis kettle 26 respectively, enter static mixer by static mixer 3 opening for feed 5 after the rear gained pentose solution 27 of hydrolysis converges with extraction agent 28 and carry out mixing and contacting reaction, the material flowed out by static mixer discharge port 6 enters in tundish 8, be recycled in static mixer opening for feed 4 by high-pressure gear pump, logistics impacts stationary element 25 again with fresh material under pressure in static mixer 3, produce violent eddy current, then reaction mass under pressure, continuous change flow direction, to static mixer discharge port 6, 7 direction flowings, reaction mass enters phase separation tank 9 and carries out cooling stratification after static mixer discharge port 7 discharge, upper strata aqueous phase 10 loops back hydrolysis kettle 26 and recycles, lower floor's extraction phase 11 directly enters extractant regeneration tower 12 and is separated, tower top obtains the water furfural containing trace, acetic acid and formic acid mixtures 14, the extraction agent 13 regenerated is obtained at the bottom of tower, extraction agent 13 and the pentose solution 27 of regeneration converge Posterior circle and use, then overhead product 14 directly enters furfural treatment tower 15 and is separated, furfural product 16 is obtained at the bottom of tower, purity is greater than 99.5%, the formic acid that tower top obtains and vinegar stock 17 enter azeotropy rectification column 18 and are separated, overhead extraction aqueous phase 19, water-free acetic acid and formic acid mixtures 20 is obtained at the bottom of tower, bottom product 20 enters finishing column 21, tower top obtains finished product formic acid 22, finished product acetic acid 23 is obtained at the bottom of tower, its purity is all greater than 99.5wt%.
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
Inject hydrolysis kettle with water according to mass ratio 1:1 after corn straw smashing, prehydrolysis temperature 160 DEG C, prehydrolysis time 30 min, after reaction, in gained pentose solution, pentose, acetic acid, formic acid mass concentration are respectively 5.2%, 2.5%, 0.7%.
Composite extractant used is dimethyl phthalate, n-Octanol, ethyl triphenyl phosphine hexafluorophosphate mixed solvent, and wherein, dimethyl phthalate accounts for 40wt%, and n-Octanol accounts for 20wt%, and ethyl triphenyl phosphine hexafluorophosphate 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 static mixer volume, and (namely feed volume air speed is 1h
-1namely, also the reaction times is 1h), squeeze in static mixer with pump respectively by extraction agent and pentose solution, in static mixer, impact stationary element short mix with recycle stock and to react-extraction process, recycle stock speed is 200% of inlet amount.Controlling temperature of reaction is 200 DEG C, and reaction pressure is 3MPa.Static mixer is the SK type static mixer of standard.
Experimental result shows that pentose transformation efficiency is 97.1wt%, and furaldehyde yield is 81.8wt%, and recovery rate is 90.1wt%, and the formic acid rate of recovery is 89.3wt%.
Embodiment 2
According to the method for embodiment 1,2 times of difference to be feeding rate be static mixer volume, namely the reaction times is 0.5 h.
Experimental result shows that pentose transformation efficiency is 77wt%, and furaldehyde yield is 60.4wt%, and recovery rate is 93.6wt%, and the formic acid rate of recovery is 90.2wt%.
Embodiment 3
According to the method for embodiment 1,0.67 times of difference to be feeding rate be static mixer volume, namely the reaction times is 1.5 h.
Experimental result shows that pentose transformation efficiency is 99%, and furaldehyde yield is 81.9%, and recovery rate is 93.6%, and the formic acid rate of recovery is 90.2%.
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 96.5%, and furaldehyde yield is 81.7%, and recovery rate is 91.9%, and the formic acid rate of recovery is 90.5%.
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 96.5%, and furaldehyde yield is 80.7%, and recovery rate is 93.9%, and the formic acid rate of recovery is 91.7%.
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 44.5%, and furaldehyde yield is 36.7%, and recovery rate is 93.9%, and the formic acid rate of recovery is 91.7%.
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 99.6%, and furaldehyde yield is 83.5%, 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 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 9
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 10:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-Octanol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 3:1:1.
Experimental result shows that pentose transformation efficiency is 97.5%, and furaldehyde yield is 75.3%, and recovery rate is 84.5%, and the formic acid rate of recovery is 81.8%.
Embodiment 11:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-Octanol, ethyl triphenyl phosphine hexafluorophosphate 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 77.5%, and the formic acid rate of recovery is 76.8%.
Embodiment 12:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-Octanol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 1:0:1.
Experimental result shows that pentose transformation efficiency is 97.8%, and furaldehyde yield is 74.1%, and recovery rate is 71.5%, and the formic acid rate of recovery is 69.8%.
Embodiment 13:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-Octanol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 0:1:1.
Experimental result shows that pentose transformation efficiency is 97.2%, and furaldehyde yield is 83.1%, and recovery rate is 78.5%, and the formic acid rate of recovery is 76.8%.
Embodiment 14:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-Octanol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 1:1:0.
Experimental result shows that pentose transformation efficiency is 97.4%, and furaldehyde yield is 70.1%, and recovery rate is 88.5%, and the formic acid rate of recovery is 85.1%.
Claims (12)
1. produced a method for furfural by biomass material, comprise following content:
(1) enter hydrolysis kettle after being mixed according to mass ratio 0.05 ~ 1 with water by biomass material, at 100 ~ 160 DEG C of Water Under solution 0.2 ~ 1h, obtain pentose, acetic acid and formic acid mixing solutions;
(2) with gained pentose solution in step (1) for raw material, adopt static mixer as reactor, pentose solution and extraction agent are passed into static mixer respectively by handling equipment, reaction used catalyst is formic acid and/or the acetic acid of biomass by hydrolyzation by-product, carries out mixing and contacting reaction under generating the reaction conditions of furfural at dehydration of pentoses;
(3) reaction effluent that step (2) obtains carries out cooling stratification, upper strata is aqueous phase, the unreacted pentose of the furfural containing trace, acetic acid, formic acid and trace, lower floor is extraction phase, the water mainly containing extraction agent, furfural, acetic acid, formic acid and trace;
(4) extraction phase that step (3) obtains enters extractant regeneration tower and is separated, and tower top obtains the mixture of furfural, acetic acid and formic acid containing minor amount of water, and tower reactor obtains the extraction agent regenerated, and described extraction agent enters reactor cycles and uses;
(5) furfural containing minor amount of water obtained in step (4), acetic acid enter furfural treatment tower with formic acid mixtures and are separated, and tower reactor obtains furfural, and its purity is greater than 99.5wt%, and tower top obtains acetic acid and formic acid mixtures;
(6) the middle gained acetic acid of step (5) enters after azeotropy rectification column contacts with entrainer with formic acid mixtures and is separated, tower top phase splitter obtains water and entrainer mixture, water is from overhead extraction, entrainer returns in tower, tower reactor obtains acetic acid and formic acid, and acetic acid and formic acid mixtures enter finishing column and be separated further, and tower top obtains finished product formic acid, tower reactor obtains finished product acetic acid, and its purity is all greater than 99.5wt%;
Wherein, in step (2), extraction tower extraction agent used is composite extractant, described composite extractant is dimethyl phthalate, carbon number is greater than 7 alphanol and ethyl triphenyl phosphine hexafluorophosphate.
2. in accordance with the method for claim 1, it is characterized in that: in step (2), dehydration of pentoses generates furfural reaction temperature is 120 ~ 220 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 (2), dehydration of pentoses generates furfural reaction temperature is 140 ~ 200 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: under in step (2), 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.
5. according to the method described in claim 1 or 4, it is characterized in that: in step (2), dehydration of pentoses generates furfural reaction stress reaction pressure is 1 ~ 3MPa, preferably 1 ~ 2MPa.
6. in accordance with the method for claim 1, it is characterized in that: the alphanol boiling point in described composite extractant is higher than 180 DEG C.
7. in accordance with the method for claim 1, it is characterized in that: in described composite extractant, ethyl triphenyl hexafluorophosphate is ethyl triphenyl sodium hexafluoro phosphate and/or ethyl triphenyl Potassium Hexafluorophosphate.
8. in accordance with the method for claim 1, it is characterized in that: in described composite extractant, dimethyl phthalate accounts for 10wt% ~ 60wt%, and alphanol accounts for 10wt% ~ 40wt%, ethyl triphenyl phosphine hexafluorophosphate accounts for 10wt% ~ 50wt%.
9. in accordance with the method for claim 1, it is characterized in that: in described composite extractant, dimethyl phthalate accounts for 20wt% ~ 40wt%, and alphanol accounts for 20wt% ~ 30wt%, ethyl triphenyl phosphine hexafluorophosphate accounts for 20wt% ~ 40wt%.
10. in accordance with the method for claim 1, it is characterized in that: biomass material described in step (1) is one or more in corn cob, wheat stalk, cornstalk, sorghum stalk, rice straw.
11. in accordance with the method for claim 1, it is characterized in that: aqueous phase described in step (3) enters hydrolysis kettle and recycles.
12. in accordance with the method for claim 1, it is characterized in that: azeotropy rectification column entrainer used is the one in hexanaphthene, vinyl acetic monomer, Iso Butyl Acetate, n-butyl acetate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418552A (en) * | 2015-12-15 | 2016-03-23 | 林康艺 | Method for extracting furan formaldehyde from cyclohexane |
| CN110105313A (en) * | 2019-04-18 | 2019-08-09 | 肖兵 | A kind of Two-way Cycle furfural production system and technique |
| CN112876435A (en) * | 2021-03-02 | 2021-06-01 | 安徽金轩科技有限公司 | Refining method of furfural |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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- 2013-10-24 CN CN201310503596.2A patent/CN104557812A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627618A (en) * | 2012-03-22 | 2012-08-08 | 天津大学 | Method for producing furfural through biomass hydrolysis-reactive extraction |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418552A (en) * | 2015-12-15 | 2016-03-23 | 林康艺 | Method for extracting furan formaldehyde from cyclohexane |
| CN110105313A (en) * | 2019-04-18 | 2019-08-09 | 肖兵 | A kind of Two-way Cycle furfural production system and technique |
| CN112876435A (en) * | 2021-03-02 | 2021-06-01 | 安徽金轩科技有限公司 | Refining method of furfural |
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