CN106146441A - A kind of preparation technology of furfural - Google Patents
A kind of preparation technology of furfural Download PDFInfo
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- CN106146441A CN106146441A CN201510183556.3A CN201510183556A CN106146441A CN 106146441 A CN106146441 A CN 106146441A CN 201510183556 A CN201510183556 A CN 201510183556A CN 106146441 A CN106146441 A CN 106146441A
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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
- C07D307/50—Preparation from natural products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
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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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Abstract
The invention discloses a kind of efficient production furfural and reclaim byproduct formic acid and the new technology of acetic acid simultaneously.Present invention uses a kind of impact flow reactor being particularly well-suited to this technique, realize fluid by multiple impact to mix, the microcosmic mixed effect having had, mixed liquid is in impingement region outer horizontal sliding flowing, the sufficient time of staying is provided for material, realize graduated response, and reach target conversion by runner and flow rate of liquid design.The present invention overcomes current impact flow reactor and cannot be realized the shortcoming of high conversion by single-reactor, simplify technological process, reduce production cost and equipment investment, it is ensured that the long-term operation of equipment.Without discharging of waste liquid in the inventive method production process, it it is an environmental protection process.
Description
Technical field
The present invention relates to the preparation technology of a kind of furfural, a kind of use high efficient mixed reactor to produce furfural by-product formic acid and the technique of acetic acid simultaneously.
Background technology
Furfural, has another name called furtural.Owing to Furfural Molecule structure existing the functional groups such as aldehyde radical, diene, cyclic ethers, so it has the character of aldehyde, ether, diene and arene compound concurrently, may participate in the reaction of number of different types, synthesize multiple chemical products, be widely used in multiple production fields such as food, medicine, synthetic resin, casting.
The raw material producing furfural at present is with the Plant fiber rich in pentosan, such as corn cob, bagasse, corn stalk, rice husk etc..Its principle is that first pentosan 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 one-step method and two-step method.The advantage of one-step method is that equipment is simple, simple to operate, but it is big that its major defect is steam consumption, producing 1 ton of furfural and consume the steam of 18～24 tons, furaldehyde yield is low, only about 45%, producing 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, consuming corn cob 11 tons, waste residue turns black, and cellulose and lignin destroy serious.Two-step method production furfural technology is carried out in two reactors due to pentosan hydralysis and dehydration of pentoses, the raw material availability that can solve the problem that existing furfural production is low, raw material sources are narrow, furaldehyde yield is low, technique waste water is difficult, furfural dregs is difficult to difficult problems such as continuing with, and this method is considered as the furfural production new method of most prospect.
The first step during " two-step method " produces furfural technology at present; i.e. to produce pentose technology the most ripe in biomass material hydrolysis; under relatively mild reaction condition; hemicellulose in biomass i.e. hydrolyzable mainly generates pentose; acetyl group on half fiber molecule side chain and formoxyl oxidized generation acetic acid and formic acid, therefore also contain a certain amount of formic acid and acetic acid in pentose solution simultaneously.But produced furfural process by pentose, due to furfural easily with its precursor generation side reaction thus cause furaldehyde yield the lowest, this also becomes " two-step method " generation furfural technology and fails the basic reason of commercial Application.
The reaction system that goes out the furfural fast transfer only quickly reaction generated while pentose reaction generates furfural could fundamentally reduce side reaction and improve furaldehyde yield.Reaction, extraction is produced the pentose that furfural technology is considered as most industrial prospect and is produced furfural technology.Reaction, extraction is produced furfural technology and is referred to add a kind of immiscible with water in pentose reaction generation furfural process and have high optionally solvent to furfural, constantly furfural is extracted into solvent phase from aqueous phase reactions system by solvent, thus is substantially reduced side reaction and improves furaldehyde yield.
CN101486695A discloses the method and apparatus that a kind of reaction, extraction prepares furfural.This invention is with supercritical carbon dioxide as extractant, with solid acid as catalyst, supercritical carbon dioxide and pentose solution counter current contacting in packed extraction tower is reacted, reaction temperature be 200 DEG C, xylose concentration 30% (wt), supercritical carbon dioxide 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 contacting in packed extraction tower to react, reaction temperature be 200 DEG C, pentose sugar concentration 1.56% (wt), solvent than 3:1 time, furaldehyde yield is 70%.
During using reaction, extraction technique to prepare furfural, can pentose solution mix the most critical factor that the sufficiently fast mass transfer of furfural contacting to promote reaction to generate is restriction furaldehyde yield height to extraction phase efficiently with extractant.In above-mentioned patent, extractant and pentose solution are all counter current contacting reactions in packed extraction tower, but packed tower mixed effect is poor, and side reaction seriously causes furaldehyde yield relatively low, the highest by only 70%；The condensation product that side reaction generates may also accumulate and causes filler to block on the surface of filler so that production process cannot be carried out for a long time；Additionally foregoing invention method cannot reclaim acetic acid and the formic acid of pentose solution simultaneously, if the aqueous solution reacted directly discharge not only results in serious environmental pollution, also can cause the waste of precious resources.
Percussion flow is the highly effective method of one realizing quickly mixing.It utilizes two strands of high-velocity fluids to clash in opposite directions, forms the impingement region of a high turbulence in the reactor, it is possible to effectively reduces the external drag in transmittance process, promotes mixing, enhancing mass and heat transfer.The chemical processes such as impact flow reactor is widely used for absorbing, mixes, conducts heat, crystallization.It is the effective means improving furaldehyde yield that exploitation be applicable to reaction, extraction technique efficiently to be prepared the impact flow reactor of furfural process.
Since the nineties in 20th century, the research in percussion flow field substantially turns to liquid continuous phase percussion flow (Liquid-continuous Impinging
Streams, LIS) attach most importance to.Patent CN 100364656C arrange in reactor shell two just to guide shell, after liquid flows separately through both sides guide shell by the driving effect of pump, center occur clash in opposite directions.Though this reactor simple in construction, only focus on the impact effects of two ends guide shell fluid, do not consider flow condition in the reactor after liquid knockout, easily cause reactor both sides and there is dead band.If two shock fluids exist solid-phase catalyst, then easily cause catalyst sedimentation, delay, directly affect reaction depth and product quality.
Patent CN 102989404 A arranges propeller in guide shell, utilizes the driving effect of two propellers that liquid in reactor is clashed in center, utilizes the effect of guide shell and flow deflector simultaneously, the problem solving mixing outside impingement region.But propeller needs power drive, it is therefore desirable to peripheral hardware motor, add the overall cost of reactor；It addition, the motor shaft installing propeller needs to install shaft seal structure on the reactor wall, long-term operating easily causes damage, affects the long-term operation of reactor.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation technology of a kind of furfural, the most efficiently produce furfural and reclaim byproduct formic acid and the new method of acetic acid simultaneously, and a kind of liquid liquid mixing impact flow reactor being particularly well-suited to this technique, it realizes fluid by multiple impact and mixes, the microcosmic mixed effect having had, mixed liquid is in impingement region outer horizontal sliding flowing, the sufficient time of staying is provided for material, realize graduated response, and reach target conversion by runner and flow rate of liquid design, overcome the shortcoming that current impact flow reactor cannot realize high conversion by single-reactor.
A kind of efficient production furfural that the present invention provides simultaneously recovery formic acid and the new technology of acetic acid, including herein below:
(1) a kind of liquid phase impact flow reactor is provided, including shell of reactor and guide shell；Shell of reactor includes cylinder and end socket；Arrange in the middle position of end socket outer wall two just to feed pipe；Be connected with feed pipe in shell of reactor inside is the first guide shell, first guide shell is made up of two truncated cone-shaped housings, two housings is just to placement, the axis of the first guide shell overlaps with reactor axis, the butt end of round table-like housing connects with feed pipe, at the outlet generation impingement mix of taper end after the liquid of feed pipe entrance is accelerated.The outside of the first guide shell is the second guide shell, and it is shaped as cylindrical shape, leaves gap between the two ends of the second guide shell and end socket, and the second guide shell axis overlaps with reactor axis.Being the 3rd guide shell in the outside of the second guide shell, the 3rd guide shell is made up of two truncated cone-shaped housings, and two housings is just to placement, and the 3rd guide shell axis overlaps with reactor axis, and the butt end of the 3rd guide shell is connected with end socket, and taper end outlet is staggered relatively.The outside of the 3rd guide shell is the 4th guide shell, and the 4th guide shell is cylindrical shape, leaves gap between the two ends of the 4th guide shell and end socket, and guide shell axis overlaps with reactor axis；
(2) enter hydrolysis kettle after being mixed according to mass ratio 0.05～1 with water by biomass material, under the conditions of 100～160 DEG C, hydrolyze 0.2～1 h, obtain pentose, acetic acid and formic acid mixed solution；
(3) with gained mixed solution Han pentose in step (2) as raw material, use the impact flow reactor in step (1) as reactor, mixed solution and extractant are each led into impact flow reactor by conveying 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 dehydration of pentoses generates the reaction condition of furfural；
(4) reaction effluent that step (3) obtains carries out cooling down stratification, upper strata is aqueous phase, the unreacted pentose of furfural, acetic acid, formic acid and trace containing trace, lower floor is extraction phase, mainly contains the water of extractant, furfural, acetic acid, formic acid and trace；
(5) extraction phase that step (4) obtains enters extractant regeneration tower and separates, and tower top obtains the mixture of the furfural containing minor amount of water, acetic acid and formic acid, and tower reactor obtains the extractant of regeneration, and described extractant enters reactor cycles and uses；
(6) furfural containing minor amount of water, acetic acid and the formic acid mixtures obtained in step (5) enters furfural treatment tower and separates, and tower reactor obtains furfural, and its purity is more than 99.5wt%, and tower top obtains acetic acid and formic acid mixtures；
(7) in step (6), gained acetic acid separates after contacting with entrainer with formic acid mixtures entrance azeotropy rectification column, tower top phase separator obtains water and entrainer mixture, water is from overhead extraction, entrainer returns in tower, tower reactor obtains acetic acid and formic acid, acetic acid and formic acid mixtures entrance finishing column and separates further, and tower top obtains finished product formic acid, tower reactor obtains finished product acetic acid, and its purity is all higher than 99.5wt%.
In the method for the present invention, the impact flow reactor described in step (1) can be vertical or horizontal.Shell of reactor cylinder is cylindrical shape or rectangle, and end socket is circular, oval, butterfly or flat cover shape.
In the method for the present invention, in step (1) described impact flow reactor, described guide shell can arrange more than 4, is advisable with 4～10, and when guide shell is shaped as round platform, the bus of round platform and axis angle are preferably 1 °～80 °.
In the method for the present invention, be wherein positioned at vertical plane at axis centre on shell of reactor is provided with discharge nozzle, and discharge nozzle typically arranges more than 2, is preferably provided with 2～6.Described discharge nozzle is symmetrical along reactor axis.
In the method for the present invention, in step (1) described impact flow reactor, 0.1～10 times that first guide shell two truncated cone-shaped housing taper end exit distance is taper end diameter, second guide shell two ends with end socket apart from equal, it it is 0.1～10 times of the first guide shell round platform housing taper end diameter, 3rd guide shell two truncated cone-shaped housing taper end exit distance is 0.1～10 times of the first guide shell taper end diameter, 4th guide shell two ends apart from equal, are 0.1～10 times of the first guide shell round platform housing taper end diameter with end socket.
In the method for the present invention, in step (1) described impact flow reactor, guide shell uses steel plate to roll, be welded, between guide shell and end socket and between two guide shells, use welding or riveting fixing, round platform guide shell butt end can perforate, make feed back under suction, strengthen mixing, improve reaction conversion ratio.Reaction raw materials is flowed into by truncated cone-shaped guide shell butt end, flow to taper end, fluid pressure potential changes into kinetic energy in the process, in taper end exit, kinetic energy reaches maximum and effect of impact occurs, mixed fluid is horizontal sliding flowing under round platform guide shell and the obstruct in cylinder next door and guide functions, after running into reactor shell, baffling is to next horizontal sliding runner, this runner is similar to a upper flow passage structure, fluid is flowed to taper end by butt end, in flow process, liquid accelerates and at taper end generation impingement mix, and so forth, reactor can arrange multiple horizontal sliding runner by increasing guide shell number.
In the inventive method, the conventional extraction agent that extractant is this area used in step (3).Further, extractant used is preferably composite extractant.Composite extractant is dimethyl phthalate, the carbon number alphanol (boiling point is higher than 180 DEG C) more than 7 and the compositions 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, on the basis of the weight of composite extractant, consisting of: dimethyl phthalate accounts for 10wt%～60wt%, alphanol accounts for 10wt%～40wt%, and ethyl triphenyl phosphine hexafluorophosphate accounts for 10wt%～50wt%.Composite extractant preferably constitute for: 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 (3), dehydration of pentoses generates furfural reaction temperature is 120～220 DEG C, preferably 140～200 DEG C；Reaction time is 0.1～2 h；Reaction pressure should be greater than aqueous phase bubble point pressure under reaction temperature and carries out under liquid phase state to ensure to react, and reaction pressure scope is 1～2 MPa at 1～3 MPa, preferably pressure.
In the inventive method, biomass material described in step (2) can be one or more in corn cob, wheat stalk, corn stalk, sorghum stalk, rice straw.
In the inventive method, the hydrolysis kettle during aqueous phase can enter step (2) described in step (4) recycles.
In the inventive method, in step (7), entrainer used by azeotropy rectification column is selected generally from the one in hexamethylene, ethyl acetate, isopropyl acetate, n-butyl acetate.
In the inventive method, can specifically determine the scale of impact flow reactor according to the scale of device and operating condition.For improving the mixed effect of impact flow reactor, it is also possible to set up Matter Transfer between impact flow reactor outlet and entrance；After a part for reaction effluent mixes with step (2) gained mixed solution raw material Han pentose obtained by step (3), looping back impact flow reactor, wherein circulated material quantity is the 5% ~ 500% of fresh feed amount.
Compared with prior art, the furfural preparation technology of the present invention has the advantages that
1, in the percussion flow Liquid-phase reactor that the present invention uses, logistics is clashed at impingement region after guide shell imports, and high efficient mixed occurs, and this region can be regarded as a complete mixing flow response system.After liquid after impingement mix flows out impingement region, the isolation of guide shell and water conservancy diversion issue life plug-flow and move, until there is secondary impact, this region is considered as a laminar flow response system.Reactor of the present invention occurs multiple impact mixing, enhances mass transfer, heat-transfer effect；Laminar flow response system runner volume accounting is high, and residence time of material is long, can reach target conversion by design, eliminates overreaction.The reactor of the present invention overcomes the deficiency of tradition impact flow reactor, makes reaction uniformly, fully, saves reactor volume, decrease overreaction, can reach target conversion by runner volume design, decrease equipment investment and have good economic benefit.It addition, guide shell has barrier fluid and lead the effect of transporting fluid, without arranging special fluid distribution flow guide system in reactor, compared with traditional flow guide system, have that liquid flowing is smooth and easy, pressure drop is little, without the advantage in dead band.
2, the percussion flow of the present invention enhances the impact effects of liquid liquid impact flow reactor, the microcosmic mixed effect making reactor is greatly enhanced, incorporation time is greatly shortened, improve production efficiency, and the existence in dead band is avoided by good horizontal sliding runner design, chemical reaction is improved at the synchronicity of space reactor each position, is favorably improved product quality；Reactor simple structure, it is not necessary to setting up other flow guide distribution system, apparatus processing difficulty is little, and equipment investment cost is low, has good economic benefit.
3, the present invention uses described impact flow reactor to produce the reactor of furfural technique as reaction, extraction, enhance microcosmic mixing and microcosmic mass transfer greatly, make furfural reach partition equilibrium in extractant and water biphase moment, improve production efficiency, reduce side reaction, improve furaldehyde yield.Solving because extractant and pentose solution mixed effect are poor, reaction system is biphase, furfural when aqueous phase reactions system concentration is far above biphase equilibrium furfural content and the side reaction that causes is serious, furaldehyde yield is low and the problem such as reactor plugs.
4, in the inventive method, use composite extractant, compound use by alphanol and ethyl triphenyl phosphine hexafluorophosphate and substantially increase the selectivity to furfural, and by the addition of ethyl triphenyl phosphine hexafluorophosphate, pentose is produced furfural reaction and is substantially accelerated, show that pentose is produced furfural reaction and had catalytic action by ethyl triphenyl phosphine hexafluorophosphate, pentose can be made to generate furfural reaction and occur under the operating condition relatively relaxed, thus reduce production cost.In composite extractant of the present invention, add alphanol and solve the problem of intersolubility difference between ethyl triphenyl phosphine hexafluorophosphate and Dichlorodiphenyl Acetate and formic acid selectivity high dimethyl phthalate, composite extractant the most of the present invention is respectively provided with the highest 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 more than 80%, acetic acid and the formic acid response rate are more than 90%, and the aqueous phase reacted can be as system recycle-water.
5, the inventive method, it is preferred to use high boiling composite extractant, extractant boiling point is far above furfural boiling point, can significantly reduce extractant regeneration process energy consumption.
6, the inventive method and equipment, substantially increases pentose and produces yield and the production efficiency of furfural, simplify technological process, reduce production cost and equipment investment, it is ensured that the long-term operation of equipment.Without discharging of waste liquid in production process, it it is an environmental protection process.
Accompanying drawing explanation
Fig. 1 is the structural representation of reactor of the present invention；
Fig. 2 is present invention process flow chart.
Detailed description of the invention
Below in conjunction with concrete accompanying drawing, the liquid phase impact flow reactor of the present invention is done more detailed description.
As it is shown in figure 1, a kind of liquid phase impact flow reactor for the mixing of liquid-liquid multiple-effect of the present invention, including shell of reactor and two parts of guide shell.Shell of reactor is made up of cylinder 12 and end socket 15.The middle position of shell of reactor end socket 15 outer wall arrange two just to feed pipe 16, be connected with feed pipe in the inner side of shell of reactor is the first guide shell 3 and 14, first guide shell 3 and 14 is respectively truncated cone-shaped housing, two truncated cone-shaped housings are just to placement, and the axis of the first guide shell (truncated cone-shaped housing) overlaps with reactor axis.The butt end of round table-like housing connects with feed pipe, in taper end outlet, impingement mix occurs after liquid is accelerated.The outside of the first guide shell 3 and 14 is the second guide shell 4.Second guide shell 4 is cylindric, leaves gap between itself and end socket 15, it is provided that the passage of fluid flowing.Second guide shell 4 can be fixed by supporting be connected with end socket 15 or the first guide shell 3 and 14.The axis of the second guide shell 4 overlaps with reactor axis.Being the 3rd guide shell 5 and 13 outside the second guide shell 4, the 3rd guide shell is truncated cone-shaped housing, and two housings is just to placement.The axis of the 3rd guide shell overlaps with reactor axis, the butt end of truncated cone-shaped housing and end socket 15 airtight connection, and taper end outlet is oppositely arranged.The outside of the 3rd guide shell 5 and 13 is the 4th guide shell 6, and it is cylindrical shape, and axis overlaps with reactor axis.Gap (passage) is left, it is provided that the passage of fluid flowing between the two ends of the 4th guide shell and end socket 15.4th guide shell 6 can be fixed by supporting be connected with end socket 15, cylinder 12 or the 3rd guide shell 5 and 13.Arranging discharge nozzle 8 on the shell of reactor axis center vertical plane, discharge nozzle 8 typically arranges two or more, is preferably provided with 2 to 6 discharge nozzles.Several discharge nozzles are symmetrical along reactor axis.
The liquid phase impact flow reactor form of the present invention can be vertical or horizontal type structure.Shell of reactor cylinder is cylindrical shape or rectangle, and end socket 15 is generally circular in cross section, oval, butterfly or flat cover shape.Guide shell can arrange more than 4, is advisable with 4～10.When guide shell is shaped as round platform, the bus of round platform and axis angle are generally 1 °～80 °.In first guide shell 3 and 14, distance is taper end outlet diameter 0.1～10 times between two truncated cone-shaped housing taper end outlets.The two ends of the second guide shell 4 with end socket apart from equal, 0.1～10 times of the round platform housing taper end outlet diameter of the generally first guide shell.In 3rd guide shell 5 and 13,0.1～10 times that distance is the first guide shell taper end (outlet) diameter of two truncated cone-shaped housing taper end exits.The distance with end socket at the 4th guide shell 6 two ends is equal, 0.1～10 times of the truncated cone-shaped housing taper end outlet diameter of the generally first guide shell.
Described guide shell typically uses steel plate to roll, be welded.Between guide shell and end socket 15, between two adjacent guide shells, general employing welding or riveting 7 are fixed.If the butt end at round platform guide shell can have dry hole, to make feed back under suction, strengthen mixing, thus improve reaction conversion ratio.
In conjunction with Fig. 1, operation principle or the work process of the liquid phase impact flow reactor of the present invention be: reaction feed 1 is after raw material pump 2 pressurizes, flowed into by the first guide shell 3 and 14 butt end, flow to taper end, fluid pressure potential changes into kinetic energy in the process, in taper end exit, kinetic energy reaches maximum and effect of impact occurs, and forms the first striking face 11.Mixed fluid flows along this runner (be spaced by the first guide shell and the second guide shell and formed) horizontal sliding under the obstruct and guide functions of first guide shell the 3,14 and second guide shell 4, after running into end socket 15, baffling is to next horizontal sliding runner, this runner is similar to a upper flow passage structure, by the second guide shell 4 and the 3rd guide shell 5,13 intervals are formed, fluid is flowed to taper end cross section by butt end cross section, and in flow process, liquid accelerates and at taper end generation impingement mix, forms striking face 10.Fluid after shock flows in the runner that the 3rd guide shell the 5,13 and the 4th guide shell 6 interval is formed, and carries out baffling after running into end socket 15, enters the 4th guide shell 6 and cylinder 12 is spaced the runner formed, and clash in outlet, form striking face 9.Fluid after shock is from exporting 8 outflow reactors.
Below in conjunction with concrete accompanying drawing, the technique of the present invention is done more detailed description.
As shown in Figure 2, according to metering ratio by fresh water 19 and biomass material 18, it is injected separately in hydrolysis kettle 20, pans 22 are entered after gained pentose solution 21 and extractant 28 converge after hydrolysis, carry out premixing, then by pump or other equipment for liquid transportation, it is input to the monosymmetric charging aperture of impact flow reactor 17 16, feed stream flows to container center through guide shell at a high speed under pressure, and clash in opposite directions in center, material after clashing into flows to pans 22 from outlet 8, it is input to the monosymmetric charging aperture of impact flow reactor 17 16 again by pump, again clash into, reactor pressure is controlled by pressure regulator 23.nullIt is directly entered phase separation tank 24 from the reaction mass of pressure regulator 23 discharge to carry out cooling down stratification，Upper strata aqueous phase 25 loops back hydrolysis kettle 20 and recycles，Lower floor's extraction phase 26 is directly entered extractant regeneration tower 27 and separates，Tower top obtains the water furfural containing trace、Acetic acid and formic acid mixtures 29，The extractant 28 of regeneration is obtained at the bottom of tower，Extractant 28 and the pentose solution 21 of regeneration converges Posterior circle and uses，Overhead product 29 then immediately proceeds to furfural treatment tower 30 and separates，Furfural product 31 is obtained at the bottom of tower，Purity is more than 99.5%，Formic acid and vinegar stock 32 that tower top obtains enter azeotropy rectification column 33 and separate，Overhead extraction aqueous phase 34，Water-free acetic acid and formic acid mixtures 35 is obtained at the bottom of tower，Tower bottom product 35 enters finishing column 36，Tower top obtains finished product formic acid 37，Finished product acetic acid 38 is obtained at the bottom of tower，Its purity is all higher than 99.5wt%.
Method and the effect of the present invention is further illustrated below by embodiment.The percentage composition related to is weight/mass percentage composition.
In embodiment, pentose conversion ratio, furaldehyde yield and acid recovering rate are calculated by following formula.
。
Embodiment 1
Injecting 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-octyl alcohol, ethyl triphenyl phosphine hexafluorophosphate mixed solvent, and wherein, dimethyl phthalate accounts for 40wt%, and n-octyl alcohol accounts for 20wt%, and ethyl triphenyl phosphine hexafluorophosphate accounts for 40wt%.
Extractant and pentose solution charge ratio are 3:1 (volume ratio), and equal to impact flow reactor volume, (i.e. feed volume air speed is 1h to the feed rate of extractant and pentose solution-1, namely the response time be 1h), recycle stock speed is the 200% of inlet amount.Controlling reaction temperature is 200 DEG C, and reaction pressure is 3MPa.
Test result indicate that pentose conversion ratio is 97.1wt%, furaldehyde yield is 82.3wt%, and recovery rate is 90.6wt%, and the formic acid response rate is 89.8wt%.
Embodiment 2
According to the method for embodiment 1, difference be feed rate be 2 times of impact flow reactor volume, i.e. response time be 0.5 h.
Test result indicate that pentose conversion ratio is 77wt%, furaldehyde yield is 60.9wt%, and recovery rate is 94.1wt%, and the formic acid response rate is 90.7wt%.
Embodiment 3
According to the method for embodiment 1, difference be feed rate be 0.67 times of impact flow reactor volume, i.e. response time be 1.5 h.
Test result indicate that pentose conversion ratio is 99%, furaldehyde yield is 82.4%, and recovery rate is 94.1%, and the formic acid response rate is 90.7%.
Embodiment 4
According to the method for embodiment 1, difference be circulation logistics be the 100% of inlet amount.
Test result indicate that pentose conversion ratio is 96.5%, furaldehyde yield is 82.2%, and recovery rate is 92.4%, and the formic acid response rate is 90.9%.
Embodiment 5
According to the method for embodiment 1, difference be circulation logistics be the 300% of inlet amount.
Test result indicate that pentose conversion ratio is 96.5%, furaldehyde yield is 80.9%, and recovery rate is 94.4%, and the formic acid response rate is 92.2%.
Embodiment 6
According to the method for embodiment 1, difference is that reaction temperature becomes 180 DEG C.
Test result indicate that pentose conversion ratio is 44.5%, furaldehyde yield is 37.2%, and recovery rate is 94.4%, and the formic acid response rate is 92.3%.
Embodiment 7
According to the method for embodiment 1, difference is that reaction temperature becomes 220 DEG C.
Test result indicate that pentose conversion ratio is 99.6%, furaldehyde yield is 83.9%, and recovery rate is 94.3%, and the formic acid response rate is 91.9%.
Embodiment 8
According to the method for embodiment 1, difference is that extractant becomes 1:1 with pentose solution charge ratio.
Test result indicate that pentose conversion ratio is 97.9%, furaldehyde yield is 77.8%, and recovery rate is 83.9%, and the formic acid response rate is 80.3%.
Embodiment 9
According to the method for embodiment 1, difference is that extractant becomes 5:1 with pentose solution charge ratio.
Test result indicate that pentose conversion ratio is 97.5%, furaldehyde yield is 85.8%, and recovery rate is 94.9%, and the formic acid response rate is 93.2%.
Embodiment 10:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-octyl alcohol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 3:1:1.
Test result indicate that pentose conversion ratio is 97.5%, furaldehyde yield is 75.8%, and recovery rate is 84.9%, and the formic acid response rate is 82.5%.
Embodiment 11:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-octyl alcohol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 1:1:3.
Test result indicate that pentose conversion ratio is 97.8%, furaldehyde yield is 83.3%, and recovery rate is 77.9%, and the formic acid response rate is 77.5%.
Embodiment 12:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-octyl alcohol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 1:0:1.
Test result indicate that pentose conversion ratio is 97.8%, furaldehyde yield is 74.6%, and recovery rate is 71.9%, and the formic acid response rate is 70.4%.
Embodiment 13:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-octyl alcohol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 0:1:1.
Test result indicate that pentose conversion ratio is 97.2%, furaldehyde yield is 83.6%, and recovery rate is 78.9%, and the formic acid response rate is 77.5%.
Embodiment 14:
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-octyl alcohol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 1:1:0.
Test result indicate that pentose conversion ratio is 97.4%, furaldehyde yield is 70.6%, and recovery rate is 88.9%, and the formic acid response rate is 85.8%.
Embodiment 15
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-octyl alcohol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 1:0:0.
Test result indicate that pentose conversion ratio is 97.0%, furaldehyde yield is 75.6%, and recovery rate is 48.9%, and the formic acid response rate is 45.8%.
Embodiment 16
According to the method for embodiment 1, difference is that composite extractant composition becomes: dimethyl phthalate, n-octyl alcohol, ethyl triphenyl phosphine hexafluorophosphate mass ratio 0:0:1.
Test result indicate that pentose conversion ratio is 97.9%, furaldehyde yield is 86.6%, and recovery rate is 49.9%, and the formic acid response rate is 50.8%.
Comparative example 1
Using the impact flow reactor of routine, such as the impact flow reactor introduced in CN 102989404 A, other are with embodiment 1.
Test result indicate that pentose conversion ratio is 97.1wt%, furaldehyde yield is 77.3wt%, and recovery rate is 86.6wt%, and the formic acid response rate is 86.8wt%.
Claims (22)
1. efficient production furfural simultaneously recovery formic acid and a technique for acetic acid, including herein below:
(1) providing a kind of liquid phase impact flow reactor, it includes shell of reactor and guide shell, and shell of reactor includes cylinder and end socket；Arrange in the middle position of end socket outer wall two just to feed pipe, be connected with feed pipe in the inner side of shell of reactor is the first guide shell, first guide shell is made up of two round table-like housings, two housings is just to placement, the axis of truncated cone-shaped housing overlaps with reactor axis, and the butt end of round table-like housing connects with feed pipe；Being the second guide shell in the outside of the first guide shell, the second guide shell is cylindric, leaves passage between two ends and end socket, and axis overlaps with reactor axis；Being the 3rd guide shell in the outside of the second guide shell, the 3rd guide shell is made up of the housing of two truncated cone-shaped, and two housings is just to placement, and guide shell axis overlaps with reactor axis, and the butt end of the 3rd guide shell is connected with end socket, and taper end outlet is oppositely arranged；Being the 4th guide shell in the outside of the 3rd guide shell, the 4th guide shell is cylindrical shape, leaves gap between its two ends and end socket, and axis overlaps with reactor axis；
(2) enter hydrolysis kettle after being mixed according to mass ratio 0.05～1 with water by biomass material, under the conditions of 100～160 DEG C, hydrolyze 0.2～1 h, obtain pentose, acetic acid and formic acid mixed solution；
(3) with gained mixed solution Han pentose in step (2) as raw material, use the impact flow reactor in step (1) as reactor, mixed solution and extractant are each led into impact flow reactor by conveying 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 dehydration of pentoses generates the reaction condition of furfural；
(4) reaction effluent that step (3) obtains carries out cooling down stratification, upper strata is aqueous phase, the unreacted pentose of furfural, acetic acid, formic acid and trace containing trace, lower floor is extraction phase, mainly contains the water of extractant, furfural, acetic acid, formic acid and trace；
(5) extraction phase that step (4) obtains enters extractant regeneration tower and separates, and tower top obtains the mixture of the furfural containing minor amount of water, acetic acid and formic acid, and tower reactor obtains the extractant of regeneration, and described extractant enters reactor cycles and uses；
(6) furfural containing minor amount of water, acetic acid and the formic acid mixtures obtained in step (5) enters furfural treatment tower and separates, and tower reactor obtains furfural, and tower top obtains acetic acid and formic acid mixtures；
(7) in step (6), gained acetic acid separates after contacting with entrainer with formic acid mixtures entrance azeotropy rectification column, tower top phase separator obtains water and entrainer mixture, water is from overhead extraction, entrainer returns in tower, tower reactor obtains acetic acid and formic acid, acetic acid and formic acid mixtures enter finishing column and separate further, and tower top obtains finished product formic acid, and tower reactor obtains finished product acetic acid.
2. according to the technique described in claim 1, it is characterised in that arrange discharge nozzle on the shell of reactor axis center vertical plane.
3. according to the technique described in claim 2, it is characterised in that described discharge nozzle arranges 2～6, and discharge nozzle is symmetrical along reactor axis.
4. according to the technique described in claim 1, it is characterised in that described reactor types is vertical or horizontal type structure.
5., according to the technique described in claim 1, it is characterised in that described shell of reactor cylinder is cylindrical shape or rectangle, end socket is circular, oval, butterfly or flat cover shape.
6. according to the technique described in claim 1, it is characterised in that the number 4 of described guide shell～10.
7. according to the technique described in claim 1, it is characterised in that the bus of described round platform and axis angle are 1 °～80 °.
8. want it seek the technique described in 1 according to right, it is characterised in that described first guide shell two truncated cone-shaped housing taper end exit separation is from for 0.1～10 times of taper end outlet diameter.
9. according to the technique described in claim 1, it is characterised in that the second described guide shell two ends are with end socket apart from equal, and this distance is 0.1～10 times of the first guide shell round platform housing taper end diameter.
10. according to the technique described in claim 1, it is characterised in that described 0.1～10 times that the 3rd guide shell two truncated cone-shaped housing taper end exit distance is the first guide shell taper end diameter.
11. according to the technique described in claim 1, it is characterised in that the two ends of the 4th described guide shell are with end socket apart from equal, and this distance is 0.1～10 times of the first guide shell round platform housing taper end diameter.
12. want it seek the technique described in 1 according to right, it is characterised in that between described guide shell and end socket, between adjacent two guide shells, use welding or riveting fixing.
13. according to the technique described in claim 1, it is characterised in that if the butt end at the first guide shell and the truncated cone-shaped housing of the 3rd guide shell has dry hole.
14. according to the technique described in claim 1, it is characterized in that, extractant described in step (3) is composite extractant, and composite extractant is that more than 7 and boiling point is higher than alphanol and the compositions of ethyl triphenyl phosphine hexafluorophosphate composition of 180 DEG C for dimethyl phthalate, carbon number.
15. according to the technique described in claim 14, it is characterized in that, on the basis of the weight of composite extractant, consisting of: dimethyl phthalate accounts for 10wt%～60wt%, alphanol accounts for 10wt%～40wt%, and ethyl triphenyl phosphine hexafluorophosphate accounts for 10wt%～50wt%.
16. according to the technique described in claim 14, it is characterised in that described ethyl triphenyl hexafluorophosphate is ethyl triphenyl sodium hexafluoro phosphate and/or ethyl triphenyl Potassium Hexafluorophosphate.
17. according to the technique described in claim 1, it is characterised in that in step (3), the reaction condition of dehydration of pentoses generation furfural is: reaction temperature is 120～220 DEG C, and reaction time is 0.1～2 h, and reaction pressure is more than aqueous phase bubble point pressure under reaction temperature.
18. according to the technique described in claim 17, it is characterised in that described reaction pressure is 1～3 MPa.
19. according to the technique described in claim 1, it is characterised in that the biomass material described in step (2) is one or more in corn cob, wheat stalk, corn stalk, sorghum stalk, rice straw.
20. according to the technique described in claim 1, it is characterised in that the aqueous phase obtained in step (4) enters the hydrolysis kettle in step (2) and recycles.
21. according to the technique described in claim 1, it is characterised in that in step (7), the entrainer used by azeotropy rectification column is selected from one or more in hexamethylene, ethyl acetate, isopropyl acetate, n-butyl acetate.
22. according to the technique described in claim 1, it is characterized in that, after a part for reaction effluent mixes with step (2) gained mixed solution raw material Han pentose obtained by step (3), looping back impact flow reactor, wherein circulated material quantity is the 5% ~ 500% of fresh feed amount.
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| CN201510183556.3A CN106146441A (en) | 2015-04-19 | 2015-04-19 | A kind of preparation technology of furfural |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851595A (en) * | 2019-04-18 | 2019-06-07 | 四川金象赛瑞化工股份有限公司 | A kind of technique of producing furfural by bagasse |
| CN110004194A (en) * | 2019-04-18 | 2019-07-12 | 四川金象赛瑞化工股份有限公司 | A method of production xylose and furfural are digested using bagasse |
| CN113999192A (en) * | 2021-11-19 | 2022-02-01 | 安徽金轩科技有限公司 | Method for extracting furfural from pentose produced by furfural |
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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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| 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851595A (en) * | 2019-04-18 | 2019-06-07 | 四川金象赛瑞化工股份有限公司 | A kind of technique of producing furfural by bagasse |
| CN110004194A (en) * | 2019-04-18 | 2019-07-12 | 四川金象赛瑞化工股份有限公司 | A method of production xylose and furfural are digested using bagasse |
| CN113999192A (en) * | 2021-11-19 | 2022-02-01 | 安徽金轩科技有限公司 | Method for extracting furfural from pentose produced by furfural |
| CN113999192B (en) * | 2021-11-19 | 2024-01-12 | 安徽金轩科技有限公司 | Method for extracting furfural from pentose |
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