CN106977473B - A method of hemicellulose being prepared into furfural using continuous flow micro passage reaction - Google Patents
A method of hemicellulose being prepared into furfural using continuous flow micro passage reaction Download PDFInfo
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- CN106977473B CN106977473B CN201710244800.1A CN201710244800A CN106977473B CN 106977473 B CN106977473 B CN 106977473B CN 201710244800 A CN201710244800 A CN 201710244800A CN 106977473 B CN106977473 B CN 106977473B
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Abstract
The invention belongs to organic synthesis field, specially a kind of method that hemicellulose is prepared into furfural using continuous flow micro passage reaction.Method includes the following steps: hemicellulose aqueous solution and catalyst containing polymerization inhibitor are controlled molar ratio via metering pump；Into carrying out hybrid reaction in micro passage reaction, after hybrid reaction, continue through a series of mass transfer enhancement type microchannel modules and flow pattern microchannel module, after the completion of reaction process, product enters gas-liquid separator after the outlet of reactor outflow and carries out gas-liquid separation, furfural and vapor mixed gas be discharged into fractionating column by throttle valve by upper airway, and liquid falls into separator.It is raw material that this method, which is utilized with the hemicellulose that chemical fibre industry spent lye recycles, hemicellulose is directly translated by furfural using continuous micro passage reaction, by separation, the mode of catalyst is recycled, make yield, economic benefit, reduce pollution, improve the ecological environment etc. is improved a lot.
Description
Technical field
The invention belongs to organic synthesis applied technical field, it is related to using a kind of hemicellulose from chemical fibre waste fluid recycling
Continuity method manufactures furfural technology, specially a kind of method that hemicellulose is prepared furfural using continuous flow micro passage reaction.
Background technique
It cannot be still at present from carbohydrate by the important basic organic chemical raw material being chemically synthesized that furfural, which is a kind of,
Unique a kind of unsaturated big specific volume organic chemicals obtained in compound, chemical property is very active, furfural and its spreads out
Biology is all widely used organic chemical industry's intermediate.In addition, furfural can also be by generating 5- with the hydroxymethylation of formaldehyde
Hydroxymethylfurfural also can be used as raw material and prepare gasoline, diesel oil and aviation kerosine, the methyl four generated by furfural by hydrogenation
Hydrogen furans can be directly as the base-material of gasoline.With increasingly serious, each chemical industry of energy crisis in world wide and environmental problem
It field will sustainable growth to the demand of furfural.But existing furfural production technology energy consumption is huge, environmental pollution is extremely tight
Weight, production cost is higher and yield is low, and above many unfavorable factors make European Union and the U.S. give strict orders taboo in over the past several decades
Furfural is only home produced in range.China is furfural production and big export country, accounts for world's furfural total output 70% or so.In view of
Important function of the furfural in organic chemical industry and energy field, existing furfural production technology urgently improve.
The reaction mechanism of biomass by hydrolyzation furfural is the H that acid ionizes out in water+H3O is combined into water+, it makes half fiber
The oxygen atom of glycosidic bond in dimension element protonates rapidly, and glycosidic bond is broken because of decrease, the carbonium ion and water phase that end is formed
Interaction ultimately forms monosaccharide, while releasing H+, continue in conjunction with water.Water can also ionize out H under high-temperature and high-pressure conditions+
With OH?, have soda acid self-catalysis function, therefore reaction mechanism of the biomass half cellulose in high-temperature high pressure water also complies with biology
The mechanism of matter hydrolysis.The hydroxyl on xylose that hydrolysis of hemicellulose generates sloughs a molecular water in conjunction with hydrogen ion, while ring is disconnected
Split to form carbon-carbon double bond and C=O bond, slough again two molecular waters it is cyclic furfural.
Industrially, by the hemicellulose in lignocellulose biomass in diluted acid, commonly used catalyst is furfural
H2SO4.Theoretically, all biomass rich in pentosan all can serve as raw material to produce furfural, wherein contracts in corncob more
The content highest of pentose is to produce the commonly used raw material of furfural.Currently, the industrial production of furfural is made using batch process reactor
Raw material mixes in hydrolyzer with dilute acid solution, and is provided using high steam and react required heat, meanwhile, steam
Another important function is to remove furfural in time from reaction system, reduces furfural yield caused by due to secondary response and drops
Low, common process conditions are reaction 6~10h, H under high temperature (140~185 DEG C) high pressure (0.5~1MPa)2SO4Dosage is
3%, solid-to-liquid ratio is in (2~3): 1, it is limited by a variety of conditions, maximum furaldehyde yield can only achieve theoretical value in industrial production
45%~55%.The mass fraction of furfural is about 3% in reactor outlet steam, and the mixture (i.e. thick aldehyde) of furfural and water passes through
Stripper is concentrated, and the steam for being rich in furfural is formed.Since the solvability of furfural in water is limited (20 DEG C, 8.3%), phase
Clearly, lower layer is mutually further refined and is purified by continuous rectifying column rich in furfural segregation phenomenon, to obtain
Furfural finished product, upper layer aqueous phase are then back to stripper.During the separation process, methanol and acetic acid are valuable by-products.After hydrolysis
Waste residue (main component is cellulose and lignin) as boiler oil produce steam.
The mechanism of furfural is generated by hemicellulose and hydrolysis dynamics hemicellulose hydrolyzes under the action of acid and water
Pentose is generated, then xylose generates furfural by isomerization and continuous three steps dehydration.It is catalyst by wooden with acid
The furfural and xylose further occurrence side reaction that the hemicellulose fraction of cellulose generates.Firstly, under the action of an acid, glycosidic bond
It is broken, hydrolysis of hemicellulose is pentose, this step reaction condition is mild, and reaction speed is very fast.Then, the xylose of generation is in acid
3 molecular waters are sloughed under effect generates furfural.Since furfural property is unstable, can further occur with xylose and reaction intermediate
Reaction generates humin, and furfural itself also can tree esterification reaction.When longer or temperature is higher between when reacted, humin
It generates particularly evident.In water phase, the activation energy (EA=124kJ/mol) of xylose dehydration is higher than furfural and interacts with xylose
The activation energy (EA=72kJ/mol) of reaction and the activation energy (EA=68kJ/mol) of furfural itself resinification reaction, and all
In side reaction, furfural is the main path for generating humin with reacting for xylose.Using acid as catalyst, furfural is generated by xylose
Reaction process is that the isomerization of wherein xylose is the rate-limiting step entirely reacted.By the above Analysis on Mechanism it is found that there are two types of ways
The yield and selectivity of furfural can be improved in diameter, first is that optimization reaction condition reduces the generation of side reaction, second is that finding appropriate urge
The isomerization reaction of agent quickening xylose.
There are many drawbacks in existing furfural production technology: being yield first, at present about 70% in world wide
Furfural production enterprise uses batch process reactor, and furaldehyde yield only has 50% of theoretical value or so, but consumes quantity of steam and be
30~50 times of furfural yield, and the reaction time is longer.Existing catalyst system side reaction is more, water phase, strong acid, high temperature, with
Oxygen contact, longer reaction time etc. can all lead to the condensation and resinification of furfural, meanwhile, among furfural and xylose and reaction
Also cross polymerization reaction can occur between product, furfural can also further degrade and generate pyroracemic aldehyde, formaldehyde, glyceraldehyde, glycolaldehyde
The selectivity that pentose generates furfural can be reduced Deng, these side reactions.Secondly, diluted acid corrosive equipment, and its separation and circulation make
With extremely difficult, and dilute acid hydrolysis method also results in a large amount of acid furfural waste-waters and generates, and difficulty of governance is very big.Again, using steaming
Vapour is as heat source and extractant huge energy consumption.Therefore someone wishes to solve the above problems, and discloses in patent CN102391218A
A kind of method that the dehydration of fixed-bed catalytic xylose prepares furfural: enter the acid catalyst solutions of -3mol/L in reaction kettle, then plus help
Catalyst n aCl is warming up to reflux to being saturated, and stirring forms the rotation liquid level of the catalyst layer of a fixed volume and concentration, then
The xylose of the 10-20% obtained through diluted acid catalyzing hydrolysis stalk is added in reaction kettle by certain speed spray, carries out xylose dehydration
Reaction, furfuryl aldehyde solution are rectifying to obtain the furfural that purity reaches 99% or more, and yield reaches 50~70wt%.Patent CN
102399203A discloses a kind of dissolving pulp wood chip hydrolysis molten sulfur acid continuity method manufacture furfural technology, specifically utilizes production
The pre-hydrolyzed solution of the leaf wood Eucalyptus of dissolving pulp, poplar etc. is raw material, the technology of continuous hydrolysis, continuous production furfural.Its technology
Scheme are as follows: a kind of dissolving pulp wood chip hydrolysis molten sulfur acid continuity method manufacture furfural technology, pre-hydrolyzed solution use continuous acid-free condition
It is lower to be made, it is separated by filtration hydrolyzate and a small amount of dissolved lignin；Pre-hydrolyzed solution dehydration produces furfural, uses and is with sulfuric acid
Catalyst, continuous production technology.Biomass used is resourceful leaf wood Eucalyptus, poplar etc., is opened up for furfural production
New raw material resources and method abundant；Hydrolyzate is for producing furfural, and the wood chip after hydrolyzing further produces dissolving pulp,
And then realize the high-efficiency resource recycling of hemicellulose and cellulose in timber；The hydrolysis process of serialization and continuous furfural are raw
Production. art, furfural high conversion rate reach 76.6%；The hydrolysis process of anacidity, hydrolyst are the second that wood chip itself hydrolyzes generation
Acid, formic acid etc. substantially reduce the corrosion to equipment.Above method does not provide the reaction time, while yield is still lower.
Summary of the invention
The present invention is based on the above technical problem, provide it is a kind of using continuous flow micro passage reaction by hemicellulose system
The method of standby furfural.This method can be raw material using the hemicellulose of chemical fibre industry spent lye recycling, using continuous microchannel plate
It answers device that hemicellulose is directly translated into furfural, by separation, recycles the mode of catalyst, make yield, economic benefit, reduce dirt
Contaminate, improve the ecological environment etc. is improved a lot.Micro- reaction process replaces traditional chemistry using micro passage reaction
The technique that reactor is chemically reacted, and realize industrial technology.
The technical solution of the present invention is as follows:
A method of hemicellulose being prepared into furfural using continuous flow micro passage reaction, this method includes following step
It is rapid:
(1) to make reaction reach best yield, it is 8-15wt% that the raw material of hemicellulose, which is configured to hemicellulose level,
Aqueous solution, catalyst is made into the aqueous solution of 6-12wt%, super to go beyond the scope, and will have solid precipitation, blocks reactor, influences
The progress of reaction；
(2) water-soluble by middle addition polymerization inhibitor to hemicellulose, then by the hemicellulose aqueous solution containing polymerization inhibitor and catalysis
Agent controls via respective metering pump, respectively enters the mixing module of micro passage reaction, enter back into warm-up block channel and carry out
Preheating, set temperature are 180-220 DEG C, 1.6~2.2MPa of pressure, and resynchronisation, which enters in mass transfer enhancement pattern block, mix instead
It answers, reaction temperature is controlled at 180-220 DEG C；The temperature of the step reaction is carried out by external heat exchanger, and heat transferring medium is thermally conductive
Oil；The aqueous solution or 70- that the hemicellulosic material is 10-15wt% from the hemicellulose level that chemical fibre waste fluid recycles
80% solids.The catalyst is sulfuric acid or hydrochloric acid, the weight of hemicellulose aqueous solution and catalyst containing polymerization inhibitor
Amount is than being 1:0.2~4.The polymerization inhibitor is hydroxyanisol, p-tert-Butylcatechol, hydroquinone, the substitution of N- phenyl
The mixture of any one or more in urea, thiocarbamide, naphthylamines and triphenyl phosphorus, additive amount are 0.1wt%~1wt%.
(2) in the module after the raw reaction of hybrid concurrency, continue through a series of mass transfer enhancement type microchannel modules with
And once-through type microchannel module, reaction time 5-30min, after the completion of reaction process, outlet stream of the product from micro passage reaction
Out；
(3) reaction solution exported from micro passage reaction is entered into separator, is pre-filled with 2-5mol/ in separator
The sulfuric acid or aqueous hydrochloric acid solution of L, and 180-220 DEG C of temperature of maintenance is heated, the furfural and water vapour of generation are entered by throttle valve
Fractionating column obtains finished product furfural by rectifying again after obtaining chaff aldehyde.
Separator is entered with tangential way by the reaction solution that micro passage reaction comes out, carries out gas-liquid separation, furfural herein
With vapor mixed gas, fractionating column is discharged by throttle valve by upper airway, liquid is fallen into separator, the liquid
For unreacted hemicellulose and acidic catalyst, fall into separator lower liquid that the reaction was continued, with pump from separator bottom
Liquid material a part is returned to separator, while maintaining separator liquid level, extra liquid by recirculation reactor by portion's extraction
Body is returned in micro passage reaction mixing reactor, adds catalyst according to measurement result, maintains the concentration of catalyst to be
2-5mol/L。
Micro passage reaction used be Corning Incorporated mass transfer enhancement type micro passage reaction, the reaction system by
Muti-piece module assembled forms；The material of the module is silicon carbide or special glass；Microchannel structure divides once-through type channel in module
Two kinds of mixed type channel design of structure and enhancing, once-through type channel are tubular structure, and enhancing mixed type channel design is cardioid knot
Structure, channel hydraulic diameter are 0.5mm~10mm.
The separator is the material separator for flow reactor, which includes separator tank body and circulation
Reactor, is equipped with steam jacket outside the separator tank body and recirculation reactor, the feed inlet of product pump with separate
The bottom of device tank body is connected to, and the discharge port of product pump is by threeway, and lead to mixer for one end, in addition an outlet by flow divider with
Recirculation reactor connection, recirculation reactor are connected to by pipeline with separator tank body, and blender is arranged in separator pot body, temperature
Degree meter is arranged on separator tank body.
The separator tank body is cylindrical cone structure, has dome head, is arranged at the top of separator tank body
There is pressure sensor, pressure sensor is connected with pressure display unit；Gas material is arranged on the separator tank body to arrange
Throttle valve out, material are discharged throttle valve and are arranged at gas discharge outlet.
The reaction mass enters separator top by recirculation reactor with tangential direction；In the recirculation reactor
Equipped with SV type original part；The blender is turbine agitator, apart from the separator tank body cylinder straight tube bottom 5cm-
10cm。
Compared with prior art, the invention has the benefit that
(1), micro fluidic techniques process is continuous, and system is closed, and moment reactant doses is small, accurately controls reaction condition
Automatic control degree is high, preferably realizes reaction process.Yield, selectivity or in terms of be improved.This hair
Bright to use continuous flow micro passage reaction, reaction time from traditional a few hours shorten to 3 to 10 minutes, significantly improve reaction
Efficiency.
(2), mixed in microchannel due to raw material splendid, temperature accurately controls, in reaction process, the dosage of the concentrated sulfuric acid
Can greatly reduce, can also reuse, reduce costs, and the selectivity of product significantly improves.
It (three), the use of continuous flow micro passage reaction material is special glass in the present invention, the material of metering pump is poly- four
Vinyl fluoride and silicon carbide or glass, excellent corrosion resistance solve the problems, such as that corrosion equipment is serious in conventional reactor.
(4), in micro passage reaction, it is continuous flow reaction from charging, preheating, mixing and reaction process whole process, keeps away
The leakage for needing to occur in additional configuration device and transfer in Conventional batch reaction, Environmental Safety, high production efficiency are exempted from.
(5), main reaction is that xylose cyclodehydration generates furfural, while having side reaction in furfural production, main pair
Reaction has the furfural polymerization under high mild acidic conditions to generate the reaction such as furfural decomposition under oligomerization product and high temperature.So if
The furfural of generation can be removed from reaction system (acid, high temperature) immediately, reduce its residence time in the reactor, Ying Shi
One of the effective approach of furfural yield is improved, the operation can be completed in device described herein.
(6), we are using being raw material with the hemicellulose that chemical fibre industry spent lye recycles, using continuous flow microchannel plate
It answers device that hemicellulose is directly translated into furfural, by separation, recycles the mode of catalyst, in yield, economic benefit, reduce dirt
Improve the ecological environment etc. is contaminated to be enhanced.
(7), there is no acid pickle discharge in reaction, fully recovering reduces the pollution to environment.
Detailed description of the invention:
Fig. 1 is to be illustrated the process that hemicellulose prepares furfural method using continuous flow micro passage reaction in the present invention
Figure.
Fig. 2 is the structural schematic diagram of the heretofore described material separator for flow reactor.
Wherein, 1 --- Membrane Separator Cylinder for CFB Boiler；2 --- recirculation reactor；3 --- steam jacket；4 --- flow divider；5——
Product pump；6 --- blender；7 --- thermometer；8 --- throttle valve.
Specific embodiment
In order to make the contents of the present invention easily facilitate understanding, below in conjunction with the drawings and specific embodiments in the present invention
The technique is further elaborated.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following implementations
Example.
% in present specification, unless otherwise specified, expression wt%.
It is water-soluble by middle addition polymerization inhibitor to hemicellulose, then by hemicellulose aqueous solution and catalyst containing polymerization inhibitor,
It is controlled via respective metering pump, respectively enters the mixing module of micro passage reaction, entered back into warm-up block channel and carry out in advance
Heat, set temperature are 180-220 DEG C, 1.6~2.2MPa of pressure, and resynchronisation, which enters in mass transfer enhancement pattern block, mix instead
It answers, reaction temperature is controlled at 180-220 DEG C；The temperature of the step reaction is carried out by external heat exchanger, and heat transferring medium is thermally conductive
Oil；The aqueous solution or 70- that the hemicellulosic material is 10-15wt% from the hemicellulose level that chemical fibre waste fluid recycles
80% solids.The catalyst is sulfuric acid or hydrochloric acid, the weight of hemicellulose aqueous solution and catalyst containing polymerization inhibitor
Amount is than being 1:0.2~4.The polymerization inhibitor is hydroxyanisol, p-tert-Butylcatechol, hydroquinone, the substitution of N- phenyl
The mixture of any one or more in urea, thiocarbamide, naphthylamines and triphenyl phosphorus, additive amount are 0.1wt%~1wt%.
In the module after the raw reaction of hybrid concurrency, a series of mass transfer enhancement type microchannel modules and straight are continued through
Flow pattern microchannel module, reaction time 5-30min, after the completion of reaction process, product from the outlet of micro passage reaction flow out into
Enter separator,
A kind of material separator for continuous current micro-reactor, including separator tank body and recirculation reactor, described
Separator tank body on be provided with feed inlet, discharge port, gas material discharge throttle valve and blender；The gas material row
Throttle valve is arranged at the gas discharge outlet on separator tank body top out, and the azeotropic mixture discharge of the furfural and water that generate reaction is simultaneously
It is constant to control pressure in separator.The feed inlet of product pump is connected to the bottom of separator tank body, and the outlet of product pump is connected with
Threeway, one end are connect by pipeline with mixer, and other end is connect by flow divider with recirculation reactor bottom, circular response
The outlet of device enters the top of separator tank body by pipeline with tangential direction, can make a part of material by recirculation reactor into
Enter separator, a part of material returns to mixer to guarantee that liquid level in separator is constant.Discharge port and object on separator tank body
Expect pump intake connection, discharging control valve is arranged in material pump discharge, and material extraction in separator is entered recirculation reactor by product pump,
Unreacted material is mixed more preferably to be reacted.Blender is arranged in separator pot body, and blender makes the object into separator
The reaction was continued for unreacted reactant in material.
Outside separator pot body and the outside of tubular reactor is respectively provided with steam heating jacket, maintains needed for separator
Temperature.
The separator tank body is cylindrical cone structure, has dome head, is arranged at the top of separator tank body
Pressure sensor, pressure sensor are connected with pressure display unit, while having scene display pressure gauge.
The feed inlet is set to the separator top with tangential direction.
The blender is turbine agitator, which is arranged in separator pot body, apart from the separator
Tank body cylinder straight drum part bottom 5cm~10cm.
The thermometer is arranged on separator tank body, for measuring temperature in separator.
Separator employed in following embodiment is the separator recorded in embodiment.
Embodiment 1:
Continuous flow micro passage reaction used is the mass transfer enhancement type micro passage reaction of the Corning Incorporated, (reaction
The mode of device is " straight channel functional module "+" cardioid " structure function module) water conservancy diameter 10mm, referring to Fig.1, determine microchannel
Reactor connection mode, hybrid reaction number of modules determine that heat medium is conduction oil according to flow velocity and reaction time.
The dirty solution or 70-80% that hemicellulosic material is 15-25% from the hemicellulose level that chemical fibre waste fluid recycles
Solids, be made into hemicellulose level be 12wt% aqueous solution, polymerization inhibitor is added into hemicellulose aqueous solution, will
Hemicellulose aqueous solution and the catalyst concentrated sulfuric acid containing polymerization inhibitor control hemicellulose aqueous solution through metering pump and catalyst are dense
Sulfuric acid weight ratio is 1:0.3；It respectively enters and enters warm-up block, set temperature after mixing in mixing module in micro passage reaction
It is 190 DEG C, pressure 1.8MPa is controlled by external heat exchanger, and heat transferring medium is conduction oil, and resynchronisation enters mass transfer enhancement type
Hybrid reaction is carried out in module, mixing temperature is equally controlled by external heat exchanger at 190 DEG C, pressure 1.8MPa,；Furfural turns
Rate 88%.
In the module after the raw reaction of hybrid concurrency, a series of mass transfer enhancement type microchannel modules and straight are continued through
Flow pattern microchannel module, reaction time 6min, after the completion of reaction process, product is flowed out from the outlet of reactor.By microchannel plate
The reaction solution for answering device to come out enters gas-liquid separator with tangential way, carries out gas-liquid separation, furfural and vapor gaseous mixture herein
Body is discharged into fractionating column by throttle valve by upper airway, and liquid is fallen into separator, which is unreacted half
Cellulose and acidic catalyst, fall into separator lower liquid that the reaction was continued, are extracted out with pump from separator bottom, by liquids
Material a part returns to separator by recirculation reactor, and while maintaining separator liquid level, surplus liquid is returned micro- logical
In road reactor mixing reactor, catalyst is added according to measurement result, maintains the concentration of catalyst；In gas-liquid separator in advance
It is placed in the aqueous sulfuric acid of 3mol/L, and heats 190 DEG C of temperature of maintenance, pressure 1.8MPa.
The micro passage reaction used reaction system is formed by muti-piece module assembled；The material of the module be silicon carbide and
Special glass etc.；Microchannel structure is divided to two kinds of mixed type channel design of once-through type channel design and enhancing in module, and once-through type is logical
Road is tubular structure, and enhancing mixed type channel design is heart-shaped structure, and channel hydraulic diameter is 8mm；
To prevent the polymerization of reaction product in the process, addition polymerization inhibitor is the mixture (mixing of hydroxyanisol, thiocarbamide
Mass ratio is 1:1), additive amount 0.2wt%.
The method of the present invention and traditional conversion ratio of still reaction and the comparison in reaction time, see the table below:
Influence of the differential responses method to conversion ratio and reaction time
| Min when reaction | Furfural conversion ratio rate % | |
| Batch still hydrolysis | 240 | 75 |
| Present invention hydrolysis | 6 | 88 |
Embodiment 2
Micro passage reaction is the mass transfer enhancement type micro passage reaction of Corning Incorporated, and the reaction system is by muti-piece mould
Block assembles；The material of the module is silicon carbide and special glass etc.；Microchannel structure divides once-through type channel design in module
With two kinds of mixed type channel design of enhancing, once-through type channel is tubular structure, and enhancing mixed type channel design is heart-shaped structure, is led to
Road hydraulic diameter is 8mm；Continuous flow micro passage reaction (straight channel functional module+" cardioid " structure function module) stream used
Journey referring to Fig.1, determines micro passage reaction connection mode, and hybrid reaction number of modules is determined according to flow velocity and reaction time,
Heat medium is conduction oil.
Dirty solution that the hemicellulose level that the hemicellulosic material is recycled from chemical fibre waste fluid is 15-25wt% or
The solids of 70-80%, being made into hemicellulose level is 12wt% aqueous solution, cellulose aqueous solution and the catalyst concentrated sulfuric acid
Weight ratio be 1:2；Hemicellulose aqueous solution and the catalyst concentrated sulfuric acid containing polymerization inhibitor, through metering pump control hemicellulose with
Hydrochloric acid weight ratio: 1:0.3；Mixing module in micro passage reaction is respectively enterd to mix, it is pre- subsequently into being carried out in warm-up block
Heat, set temperature are 180 DEG C, and pressure 1.8MPa is controlled by external heat exchanger, and heat transferring medium is conduction oil, and resynchronisation enters
Hybrid reaction is carried out in mass transfer enhancement pattern block, mixing temperature is equally controlled by external heat exchanger in 180 DEG C of pressure
1.8MPa；
In the module after the raw reaction of hybrid concurrency, a series of mass transfer enhancement type microchannel modules are continued through, are reacted
Time 5min, after the completion of reaction process, product is flowed out from the outlet of reactor.The reaction solution come out by micro passage reaction is to cut
Line mode enters gas-liquid separator, carries out gas-liquid separation, furfural and vapor mixed gas herein, passes through section by upper airway
Stream valve is discharged into fractionating column, and liquid is fallen into separator, which is unreacted hemicellulose and acidic catalyst, falls
Enter in separator lower liquid that the reaction was continued, is extracted out with pump from separator bottom, liquid material a part is passed through into circular response
Device returns to separator, and while maintaining separator liquid level, surplus liquid is returned in micro passage reaction mixing reactor,
Catalyst is added according to measurement result, maintains the concentration of catalyst；The hydrochloric acid that 2mol/L is pre-filled in gas-liquid separator is water-soluble
Liquid, and heat 190 DEG C of temperature of maintenance, pressure 1.8MPa.Furfural conversion ratio 90%.
To prevent the polymerization of reaction product in the process, addition polymerization inhibitor is the mixture (mixing of hydroxyanisol, thiocarbamide
Weight ratio is 1:1), additive amount 0.2wt%.
The method of the present invention and traditional conversion ratio of still reaction and the comparison in reaction time, see the table below:
Influence of the differential responses method to furfural conversion ratio and reaction time
| Min when reaction | Furfural conversion ratio % | |
| Batch still hydrolysis | 220 | 77 |
| Present invention hydrolysis | 5 | 90 |
It is elaborated although the present invention has passed through specific embodiment, this profession ordinary skill
Personnel should be understood that made on this basis without departing from any form of claims and the variation of details,
Belong to invention which is intended to be protected.
Claims (9)
1. a kind of method that hemicellulose is prepared furfural using continuous flow micro passage reaction, it is characterised in that including following step
It is rapid:
(1) raw material containing hemicellulose is configured to the aqueous solution that hemicellulose level is 8-15wt%, catalyst is made into 6-
The aqueous solution of 12wt%；
(2) polymerization inhibitor is added into hemicellulose aqueous solution, the hemicellulose aqueous solution and catalyst that will contain, via respective meter
Amount pump control, into after the mixing module in micro passage reaction, enters back into the channel of micro passage reaction and is preheated, if
Determining temperature is 180-220 DEG C, 1.6~2.2MPa of pressure, and resynchronisation, which enters in mass transfer enhancement type microchannel module, mix instead
It answers, mixing temperature is controlled at 180-220 DEG C；The temperature of the step reaction is carried out by external heat exchanger, and heat transferring medium is thermally conductive
Oil；
(3) in the module after the raw reaction of hybrid concurrency, a series of mass transfer enhancement type microchannel modules and straight are continued through
Flow pattern microchannel module, reaction time 3-20min, after the completion of reaction process, product is flowed out from the outlet of micro passage reaction；
(4) reaction solution exported from micro passage reaction is entered into separator, is pre-filled with 2-5mol/L's in separator
Sulfuric acid or aqueous hydrochloric acid solution, and 180-220 DEG C of temperature of maintenance is heated, the furfural and water vapour of generation enter fractionation by throttle valve
Tower obtains finished product furfural by rectifying again after obtaining chaff aldehyde.
2. according to the method described in claim 1, it is characterized by: the reaction solution come out by micro passage reaction is with tangential way
Into separator, carry out gas-liquid separation herein, furfural and vapor mixed gas, by upper airway by throttle valve be discharged into
Enter fractionating column, liquid is fallen into separator, which is unreacted hemicellulose and acidic catalyst, falls into separator lower part
The reaction was continued in liquid, is extracted out with pump from separator bottom, and liquid material a part is returned to separator by recirculation reactor,
While maintaining separator liquid level, surplus liquid is returned in micro passage reaction mixing reactor, is added according to measurement result
Catalyst, maintaining the concentration of catalyst is 2-5mol/L.
3. according to the method described in claim 1, it is characterized by: what the hemicellulosic material was recycled from chemical fibre waste fluid
Hemicellulose level is the aqueous solution of 15-25wt% or the solids of 70-80%.
4. the method according to claim 1, it is characterised in that: the catalyst is sulfuric acid or hydrochloric acid, contains polymerization inhibitor
Hemicellulose aqueous solution and catalyst weight ratio be 1:0.1~0.4.
5. the method according to claim 1, it is characterised in that: micro passage reaction used is Corning Incorporated
Mass transfer enhancement type micro passage reaction, the reaction system are formed by muti-piece module assembled；The material of the module is silicon carbide or spy
Kind glass；Microchannel structure is divided to two kinds of mixed type channel design of once-through type channel design and enhancing in module, and once-through type channel is
Tubular structure, enhancing mixed type channel design are heart-shaped structure, and channel hydraulic diameter is 0.5mm ~ 10mm.
6. the method according to claim 1, it is characterised in that: the polymerization inhibitor is hydroxyanisol, to tert-butyl o
The mixture of any one or more in benzenediol, hydroquinone, N- phenyl substituted urea, thiocarbamide, naphthylamines and triphenyl phosphorus, adds
Dosage is 0.1wt%~1wt%.
7. the method according to claim 1, it is characterised in that: the separator is the material for flow reactor
Separator, the separator include separator tank body (1) and recirculation reactor (2), in the separator tank body (1) and are recycled anti-
It answers and is equipped with steam jacket (3) outside device (2), the feed inlet of product pump (5) is connected to the bottom of separator tank body (1), material
The discharge port of (5) is pumped by threeway, lead to mixer for one end, and in addition an outlet passes through flow divider (4) and recirculation reactor (2) even
It connects, recirculation reactor (2) is connected to by pipeline with separator tank body (1), and blender (6) setting is in separator tank body (1), temperature
Degree meter (7) is arranged on separator tank body (1).
8. the method for claim 7, it is characterised in that: the separator tank body (1) is cylindrical cone structure, tool
There is dome head, is provided with pressure sensor at the top of separator tank body (1), pressure sensor is connected with pressure display unit
It connects；Gas material is set on the separator tank body (1), throttle valve (8) are discharged, material is discharged throttle valve (8) and is arranged in gas
At body outlet.
9. method according to claim 8, it is characterised in that: the reaction mass by recirculation reactor with tangential direction into
Enter separator top；The recirculation reactor (2) is provided with SV type original part；The blender (6) is turbine agitator,
Apart from separator tank body (1) the cylinder straight tube bottom 5cm- 10cm.
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| CN113402486A (en) * | 2021-07-27 | 2021-09-17 | 江苏清泉化学股份有限公司 | Method for generating (Z) -2-methoxyimino-2-furylacetic acid |
| CN113956219A (en) * | 2021-11-01 | 2022-01-21 | 上海昶法新材料有限公司 | Process flow for producing furfural from papermaking wastewater |
| CN114315767B (en) * | 2021-11-29 | 2023-07-28 | 青岛三力本诺新材料股份有限公司 | Preparation method and preparation device of 5-hydroxymethylfurfural |
| CN114671832B (en) * | 2022-03-08 | 2024-01-19 | 南京工业大学 | Method for continuously preparing furfural by utilizing microchannel reaction device |
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