CN107574268A - A kind of method of biomass Quick Pretreatment - Google Patents
A kind of method of biomass Quick Pretreatment Download PDFInfo
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- CN107574268A CN107574268A CN201610522114.1A CN201610522114A CN107574268A CN 107574268 A CN107574268 A CN 107574268A CN 201610522114 A CN201610522114 A CN 201610522114A CN 107574268 A CN107574268 A CN 107574268A
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- reactor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a kind of method of biomass Quick Pretreatment, the reactor that this method is not waited by the way that biomass material to be passed through to two pressure respectively, material is discharged into by lower pressure reactor from elevated pressures reactor by the unlatching of the coupling cock between reactor, the lasting charging in elevated pressures reactor can be realized with this, and can synchronously realize the hydrolysis pretreatment of biomass material.Pass through the implementation of this method, it is possible to achieve following purpose：(1) biomass material simple crushing, without crushing, to save power consumption；(2) being carried out continuously for hydrolysis pretreatment is realized；(3) processing speed is fast, can be completed in 3 10 minutes；(4) hemicellulose is largely utilized；(5) low liquid-solid ratio is used so that pretreatment heat loss drops to reduced levels；(6) the sugared concentration of pretreatment gained can regulate and control according to next step production requirement；(7) there is no mass loss substantially in preprocessing process.
Description
Technical field
The invention belongs to energy technology field, and in particular to a kind of method of biomass Quick Pretreatment.
Background technology
Biomass energy is low with energy density because of its dispersiveness so that scale utilizes and efficiently utilizes all more difficult, economy effect
Benefit is poor.Although there is certain development, the research and development stage is still on the whole, one-time investment is big, industry size
Small, earning capacity is low.Therefore, further development is realized, bio-energy industry must face to improve energy efficiency, reduce cost
Key issues of.
Conversion technology of biomass energy fails to realize that industrialized main cause is for a long time:1. stalk energy density is low,
Distribution is scattered, is not easy to focus on, these cause the collection of stalk and transport difficult；2. the density of stalk is low, takes up an area greatly, cause
The difficulty of storage；3. the structure of the cellulose, hemicellulose and lignin three in biomass straw causes it to be difficult to be disappeared
Change and decompose, it is necessary to be pre-processed to it to improve trans-utilization rate；4. hemicellulose dilute acid hydrolysis produces chaff in furfural production
Aldehyde time length, high energy consumption；5. hexose, which easily ferments, in alcohol production generates alcohol, pentose is but not easy to ferment complete；6. give birth to
Raw material of substance form of diverse, because the difference of the place of production, cultivation technique, kind etc. causes raw material components, structure different, so as to locate in advance
Manage bar part is also different.Although pretreatment of the scholars to raw material has carried out many researchs and has achieved some achievements, but without
Find ideal method.Therefore, preconditioning technique is the problem of current raising biomass trans-utilization rate needs letter to be solved.
The preconditioning technique of lignocellulosic, which can be divided into biological place, to be required to energy and the different of dynamics according to pretreatment
Logos, method of chemical treatment, physical treatment process and the multiclass method such as physics-chemical bond facture.Each processing method it is main
Processing intent is all to increase raw material endoporus area, reduces cellulose crystallity, remove lignin, remove several sides such as hemicellulose
Face.
A kind of straw of method (ZL200910116615.X) joint alkali cleaning processing using disposing straws by sulfur trioxide gas
Stalk preconditioning technique has mild condition, can be carried out under lower temperature and normal pressure；And stalk can not have to crush, such as straw and
Wheat Straw etc. only needs to be cut into 2~3cm length.Sulfur trioxide gas are diffused to inside stalk, make original with water combination very exothermic
The gas of position and water vapor expansion, the connection that can be destroyed in the original location between lignin and cellulose, and then explosion
Effect.Because the dosage of sulfur trioxide is no more than the 1% of stalk gross weight, throughput is low, therefore fluid bed class processing equipment is not conform to
Suitable；Because densified straw is small, with agitating paddle stir process, and it is difficult to operate continuously, production efficiency is too low.And use the work
Skill, it is that processing procedure can not reclaim hemicellulose degradation product, causes substantial amounts of wastage of material.
Cuzens and Farone passes through Arkenol method hydrolysing agricultural residues [23], institute using the dense H2SO4 aqueous solution
Method is stated just by BlueFire Ethanol (Irvine, California, USA) commodity production.In the method, biomass is used
77% H2SO4 solutions are brilliant, and it is about 40 weight % to be diluted to water content, then in 100 DEG C of hydrolysis.First one-step hydrolysis is almost
Whole hemicelluloses and some fibre element.Solid residue is through carrying out the second one-step hydrolysis to discharge remaining glucose.Concentrated acid
Method for hydrolysis can obtain high sugar yield, using simple catalyst, and only need the of short duration reaction time.But in spite of these
Advantage, operate the danger of concentrated acid and the complexity of its recycling is limited to the application of this technology.
The patent application WO2009047023 (date of publication on April 16th, 2009) announced is related to a kind of in hydration fuse salt
The method of transfer cellulose.Fuse salt is described as fusing point and is less than 200 DEG C of salt, more specifically refer to inorganic salts hydrate and
ZnCl2 hydrate.The method is it is said that can be applied to the material comprising lignin and hemicellulose in addition to cellulose.
It is fine that the patent application US20090020112 (date of publication on January 22nd, 2009) announced is related to a kind of pyrolysis lignin
The method for tieing up cellulosic material, the method include being combined lignocellulosic material with ionic liquid, then make this mixture through heated
Solution condition, such as about 150 DEG C to about 300 DEG C of temperature is heated to, wherein heating process can be anaerobism, to prepare a kind of production
Thing, this product can be 5 hydroxymethyl furfural, furfural, 2- methyl furfurals, levulic acid or laevoglucose, etc..
Although having carried out a large amount of effort to attempt to improve the hydrolysis by ligno-ccllulose to prepare the yield of required product,
It is that a pair wilderness demand for the method that can obtain high yield monose is still had in this area.The present invention provides a kind of hydrocellulose
With the method for the high yield of lignin fiber cellulosic biomass, the method produces the monose or oligosaccharide that easily reclaim, this sugar for
It is fabulous further to produce furfural, 5 hydroxymethyl furfural, 2- methyl furfurals, levulic acid or laevoglucose, alcohol production
Raw material.
The content of the invention
The purpose of the present invention is to propose to a kind of method for the continuous Quick Pretreatment of biomass, for by biomass by hydrolyzation
Produce polysaccharide, single carbohydrates and their derivative, or the method that pretreatment removes hemicellulose or lignin component., can using this method
To realize the purpose for reducing biomass material pretreatment time, raising target product yield, and realize and hydrolyzed instead under certain pressure
Answer the continuous feed of device.
The invention discloses a kind of method of biomass Quick Pretreatment, this method is by the way that biomass material is passed through respectively
The reactor that two pressure do not wait, by the unlatching of the coupling cock between reactor by material from elevated pressures reactor be discharged into compared with
Low-pressure reactor, the lasting charging in elevated pressures reactor can be realized with this, and can synchronously realize the water of biomass material
Solution pretreatment.
The method of the present invention by biomass material by passing through high temperature flashing reactor I and the steps of low temperature slow reaction device II two
Step pre-processes, and realizes the controllability conversion of biomass components, is connected, reacted by communicating valve between reactor I and reactor II
Pressure difference between device I and II>0.1MPa.
The invention discloses a kind of method of biomass Quick Pretreatment, specially in reactor I, maintenance reaction temperature
For：130-280 DEG C, liquid-solid ratio is：0.1-100, using being passed through high-temperature medium (such as water vapour) or directly heat mode by thing
Material quickly heats up to 130~280 DEG C, and the degraded of component is quickly realized under catalyst action, by using acid, alkali or ionic liquid
The variety classes catalyst such as body, hemicellulose, lignin, the degradation selectivity of cellulose can be achieved.
The invention discloses a kind of method of biomass Quick Pretreatment, pressure maintains lower value in reactor II
(below 0.7MPa) so that after the completion of being reacted in reactor I, open communicating valve so that material is under differential pressure action in reactor I
Quickly it is discharged into reactor II.
The invention discloses a kind of method of biomass Quick Pretreatment, after reaction mass enters reactor II, continues
Furfural, 5- methylol chaffs are further converted to compared with by the component do not reacted completely completion conversion under temperate condition or by catabolite
The downstream product such as aldehyde, levulic acid.
The invention discloses a kind of method of biomass Quick Pretreatment, in the reactor II products therefrom can be used for into
One one-step hydrolysis-dehydration production furfural and 5 hydroxymethyl furfural, enzymolysis-fermentative production of ethanol.
The invention discloses a kind of method of biomass Quick Pretreatment, the method bag of system pressure in rise reactor I
Include and directly heat increasing temperature and pressure, be passed through high-pressure water vapor, be passed through high pressure N2Or inert gas.
Catalyst in the reactor I is acid or base catalyst, the degraded for catalysis biomass component.
Acid or base catalyst, further degraded and degraded for catalysis biomass component are added in the reactor II
The further conversion of product.
The acid catalyst, including liquid acid, solid acid, be dissolved in water can produce acid gas, acidic ion liquid, and
Hydrolysis can produce H+Lewis acid.
The base catalyst, including liquid base, solid base, be dissolved in water and can produce the gas of alkali, alkali ionic liquid, and
Hydrolysis can produce OH-Lewis alkali.
Method in the biomass material input reactor I includes Geldart-D particle, spiral conveying and other modes.
Pressure is 0.2-6.5MPa in the reactor I, and pressure is 0-6.5MPa in reactor II.
Biomass material residence time in reactor I is 0.1-200min.
The present invention is to obtain including monose, oligosaccharide and its derivative products furfural, 5 hydroxymethyl furfural, levulic acid, fibre
The method for tieing up the products such as element.The method can apply to lignocellulosic pretreatment and remove hemicellulose or direct hydrolysis production chaff
Aldehyde, and by lignocellulosic alkali process removal lignin and hemicellulose, the pulp industries for the purpose of obtaining cellulose, or
Directly gathered by lignocellulosic production and the biomass glycan of correlation, such as galactan, mannosan, or araban and wood
Sugar and related biomass glycan.
Pass through the implementation of this method, it is possible to achieve following purpose：(1) biomass material simple crushing, without crushing,
To save power consumption；(2) being carried out continuously for hydrolysis pretreatment is realized；(3) processing speed is fast, can be completed within 3-10 minutes；(4) half
Cellulose is largely utilized；(5) low liquid-solid ratio is used so that pretreatment heat loss drops to reduced levels；(6) pretreatment gained
Sugared concentration can regulate and control according to next step production requirement；(7) there is no mass loss substantially in preprocessing process.
Brief description of the drawings
Fig. 1 is a kind of method schematic diagram of biomass Quick Pretreatment,
Wherein：1st, reactor I, 2, material inlet, 3, steam inlet, 4, exhaust outlet, 5, communicating valve, 6, reactor II, 7,
Exhaust outlet, 8, circulation fluid entrance, 9, circulation fluid outlet, 10, steam inlet, 11, discharge conveyor screw, 12, motor, 13, hydrolysis
Slag outlet.
Embodiment
In order that present disclosure is more likely to be clearly understood, specific embodiment and combination below according to the present invention
Accompanying drawing, the present invention is further detailed explanation.
The invention discloses a kind of method of biomass Quick Pretreatment, this method is by the way that biomass material is passed through respectively
The reactor that two pressure do not wait, by the unlatching of the coupling cock between reactor by material from elevated pressures reactor be discharged into compared with
Low-pressure reactor, the lasting charging in elevated pressures reactor can be realized with this, and can synchronously realize the water of biomass material
Solution pretreatment.
The method of the present invention by biomass material by passing through high temperature flashing reactor I and the steps of low temperature slow reaction device II two
Step pre-processes, and realizes the controllability conversion of biomass components, is connected, reacted by communicating valve between reactor I and reactor II
Pressure difference between device I and II>0.1MPa.
The invention discloses a kind of method of biomass Quick Pretreatment, by opening coupled reaction device I and reactor II
Between communicating valve, realize the band press-in material of material in reactor II.
The invention discloses a kind of method of biomass Quick Pretreatment, in reactor I, maintenance reaction temperature is：
130-280 DEG C, liquid-solid ratio is：0.1-100, using being passed through high-temperature medium (such as water vapour) or to directly heat mode fast by material
Speed is heated to 130~280 DEG C (0.8MPa), and the degraded of component is quickly realized under catalyst action, by using acid, alkali or from
The variety classes catalyst such as sub- liquid, hemicellulose, lignin, the degradation selectivity of cellulose can be achieved.
The invention discloses a kind of method of biomass Quick Pretreatment, pressure maintains lower value in reactor II
(below 0.7MPa) so that after the completion of being reacted in reactor I, open communicating valve so that material is under differential pressure action in reactor I
Quickly it is discharged into reactor II.
The invention discloses a kind of method of biomass Quick Pretreatment, after reaction mass enters reactor II, continues
Furfural, 5- methylol chaffs are further converted to compared with by the component do not reacted completely completion conversion under temperate condition or by catabolite
The downstream product such as aldehyde, levulic acid.
The invention discloses a kind of method of biomass Quick Pretreatment, in the reactor II products therefrom can be used for into
One one-step hydrolysis-dehydration production furfural and 5 hydroxymethyl furfural, enzymolysis-fermentative production of ethanol.
A kind of method of biomass Quick Pretreatment of the present invention, it is specific as shown in Figure 1：
It is then past from steam inlet 3 by biomass powder powder stock (particle diameter 3-20mm) by the input reactor I1 of feed(raw material)inlet 2
It is passed through more than 130 DEG C of saturated steam in reactor, after temperature reaches setting value in question response device, the maintenance reaction time, so
Communicating valve 5 is quickly opened afterwards, and material is quickly discharged into reactor II6.Communicating valve 5 is then shut off, remaining steaming is discharged from exhaust outlet 4
Vapour, then toward the saturated vapor for being passed through 120 DEG C in reactor II6 by steam inlet 10, when material reaches setting value in reactor II6
Afterwards, motor 12 is started, by material by the output-response system of discharge conveyor screw 11, the material exported is after separation of solid and liquid, liquid
Body exports the 9 and input reactor II6 of ring liquid entrance 8 by following circulation fluid, and solid slag is exported by discharge conveyor screw 11, finally by water
The discharge of slag outlet 13 is solved, solid can be used as the raw material of cellulosic ethanol enzymolysis.
It is described below exemplary only in nature, and the application and use of the present invention or the present invention are not limited.
Embodiment 1
By 10kg, moisture content 30% corn stalk powder powder stock (particle diameter 3-20mm) by Geldart-D particle input reactor I,
Then toward saturated steam of the acetic acid concentration for 5%, 200 DEG C of temperature is passed through in reactor, temperature reaches 200 DEG C in question response device
Afterwards, 10min is maintained, then quickly opens communicating valve 5, material is quickly discharged into reactor II.Communicating valve is then shut off, toward reactor
150 DEG C of saturated vapor is passed through by steam inlet 10 in II, when in reactor II material reach 150 DEG C after maintain 20min, start
Motor 12, by material by the output-response system of discharge conveyor screw 11.
Under the reaction conditions, feed components degradation rate is respectively：Cellulose 35%, hemicellulose 86%, lignin
16%.The xylose rate of recovery 78%.
Embodiment 2
By 10kg, moisture content 30% maize cob meal powder stock (particle diameter 3-20mm) by Geldart-D particle input reactor I, so
Afterwards toward the saturated steam that 220 DEG C of temperature is passed through in reactor, after temperature reaches 220 DEG C in question response device, 5min is maintained, then
Quick to open communicating valve 5, material is quickly discharged into reactor II.Communicating valve is then shut off, into reactor II by steam inlet 10
Be passed through 120 DEG C of saturated vapor, when in reactor II material reach 120 DEG C after maintain 30min, start motor 12, by material by
The output-response system of discharge conveyor screw 11, for the material exported after separation of solid and liquid, liquid inputs reaction by circulation fluid entrance 8
Device II, solid can be used as the raw material of cellulosic ethanol enzymolysis.
Under the reaction conditions, feed components degradation rate is respectively：Cellulose 40%, hemicellulose 92%, lignin
22%.The xylose rate of recovery 76%.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.
Claims (11)
- A kind of 1. method of biomass Quick Pretreatment, it is characterised in that this method by passing through two respectively by biomass material The reactor that individual pressure does not wait, material is discharged into from elevated pressures reactor by the unlatching of the coupling cock between reactor relatively low Pressure reactor, the lasting charging in elevated pressures reactor can be realized with this, and can synchronously realize the hydrolysis of biomass material Pretreatment.
- 2. according to a kind of method of biomass Quick Pretreatment described in claim 1, it is characterised in that this method is specially：It is first First by biomass material input reactor I, system pressure in reactor I, in reactor I, maintenance reaction temperature are then raised Spend and be：130-280 DEG C, liquid-solid ratio is：0.1-100；Using being passed through high-temperature medium or directly heat and other modes are fast by material 130-280 DEG C of speed heating, quickly realizes the degraded of component under catalyst action；Pressure is maintained in below 6.5MPa reactors I after the completion of reaction in reactor II, opens coupling cock so that reactor I Middle material is quickly discharged into reactor II under differential pressure action.
- 3. according to a kind of method of biomass Quick Pretreatment described in claim 2, it is characterised in that in rise reactor I The method of system pressure includes directly heating increasing temperature and pressure, being passed through high-pressure water vapor, be passed through high pressure N2Or other inert gases.
- 4. according to a kind of method of biomass Quick Pretreatment described in claim 2, it is characterised in that in the reactor I Catalyst for acid or base catalyst, the degraded for catalysis biomass component.
- 5. according to a kind of method of biomass Quick Pretreatment described in claim 2, it is characterised in that in the reactor II A certain amount of acid or base catalyst are added, for the further degraded of catalysis biomass component and further turning for catabolite Change.
- 6. according to a kind of method of biomass Quick Pretreatment described in claim 4 or 5, it is characterised in that the acid catalysis Agent, including liquid acid, solid acid, be dissolved in water can produce acid gas, acidic ion liquid, and hydrolysis can produce H+'s Lewis acid.
- 7. according to a kind of method of biomass Quick Pretreatment described in claim 4 or 5, it is characterised in that the base catalysis Agent, including liquid base, solid base, be dissolved in water and can produce the gas of alkali, alkali ionic liquid, and hydrolysis can produce OH-'s Lewis alkali.
- 8. according to a kind of method of biomass Quick Pretreatment described in claim 4 or 5, it is characterised in that the reactor Products therefrom can be used for further hydrolysis-dehydration production furfural and 5 hydroxymethyl furfural, enzymolysis-fermentative production of ethanol in II.
- 9. according to a kind of method of biomass Quick Pretreatment described in claim 2, it is characterised in that the biomass material Method in input reactor I includes Geldart-D particle, spiral conveying and other modes.
- 10. according to a kind of method of biomass Quick Pretreatment described in claim 1, it is characterised in that in the reactor I Pressure is 0.2-6.5MPa, and pressure is 0-6.0MPa in reactor II.
- 11. according to a kind of method of biomass Quick Pretreatment described in claim 1, it is characterised in that the biomass is former Material residence time in reactor I is 0.1-200min.
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| CN112442924A (en) * | 2019-09-03 | 2021-03-05 | 中国科学院大连化学物理研究所 | Method for preparing high-hardness environment-friendly material by using protogenic plant biomass as raw material |
| CN115053033A (en) * | 2020-02-03 | 2022-09-13 | 瑞典乙醇化工技术有限公司 | Apparatus and method for pretreatment of biomass |
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Application publication date: 20180112 |