CN101199944B - Cellulose biomimetic catalysis hydrolysis system and application in liquid fuel production thereof - Google Patents
Cellulose biomimetic catalysis hydrolysis system and application in liquid fuel production thereof Download PDFInfo
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Abstract
The invention discloses a novel catalyst of biomimetic catalytic hydrocellulose and hemicellulose, and the designing method of the catalyst. The catalyst can be used both in normal temperature and the high temperature. The novel invented catalyst does not resolve glucose and xylose, can hydrolyze cellulose and hemicellulose simultaneously, and can be effectively recycled. The novel invented catalyst can combine with the current producing technics, and the producing technics revealed in the invention can also be used to make full use of all the main components in biomass, thereby manufacturing the liquid fuel and the other products with high added value.
Description
Technical field
The present invention relates to the quick refining of a kind of brand-new cellulose bionic catalysis system and living beings and produce the liquid fuel method, more specifically to a kind of at normal temperatures and pressures Quick Pretreatment cellulose biomass, with the bionic catalyst of quick catalysis cellulose, the reaction of hydrolysis of hemicellulose saccharogenesis, and the recovery method of bionic catalyst.
Background technology
Industrialized the developing rapidly in the whole world causes the mankind to fossil energy such as coal, oil, and nuclear energy, the depletion rate of the non-renewable energy such as natural gas increases rapidly, but the peak value of its supply has been come into or moved towards to fossil energy.The shortage of fossil energy and the global warming because using fossil energy to cause are the difficult problems that the mankind guarantee to survive and must overcome with sustainable development.And cellulose biomass to produce liquid fuel be the reliable guarantee that the mankind overcome these difficult problems.
Use all three kinds of main components of cellulose biomass: cellulose, hemicellulose and lignin are for the production of liquid fuel such as gasoline comprehensively, diesel oil, the technology of the fuel energies such as ethanol, (WO/2007/095787 is invented out and discloses comprehensively in our comparatively complete success, CN200710084896.6, and CN200710006858.9).
But because the exploitation of cellulolytic enzyme initial success just, the production of cellulolytic enzyme and use also exist series of problems to overcome, as the production of cellulolytic enzyme also need with pure cellulose as carbon source, must ferment etc. with purity oxygen, this causes the production cost of cellulolytic enzyme to be difficult to be reduced in the short period of time proper level.In addition, the catalytic performance of cellulolytic enzyme is also lower, the time of cellulose hydrolysis is grown (above 48 hours), cellulolytic enzyme is subjected to the inhibition of product glucose comparatively serious, make the sugar concentration of hydrolysis gained lower, and the cellulose that cellulolytic enzyme can be hydrolyzed needs to remove more up hill and dale lignin and hemicellulose, and these problems are all more serious on the suitability for industrialized production impact.Moreover, use cellulolytic enzyme to make the catalyst hydrocellulose, also without comparatively ideal simple and easy sterilizing methods, if all use antibiosis usually to sterilize, its consumption will be very huge, and consequence is difficult to expect.
And hemicellulose is because its structure is very complicated, variety classes, one species is in different local growths even, its structure is not identical, the exploitation of hydrolysis of hemicellulose enzyme is not also to the stage that is successful on the whole, the cost of catalytic effect and hydrolysis of hemicellulose enzyme all goes back so that it is difficult to use in suitability for industrialized production, does not also have the hydrolysis of hemicellulose enzyme of commercialization supply on the market.
In a word, the hydrolase of current cellulose and hemicellulose all is difficult to carry out suitability for industrialized production.
For this reason, this area is in the urgent need to the bionic catalyst of a kind of hydrocellulose and hemicellulose, when this catalyst uses cellulose biomass to produce liquid fuel at fermentation method, possesses the quick catalysis effect of high selectivity and the strong acid catalyst of cellulolytic enzyme.
Summary of the invention
The first purpose of the present invention is to obtain a kind of bionic catalyst for catalyzing hydrolysis cellulose and/or hemicellulose, when this catalyst uses cellulose biomass to produce liquid fuel at fermentation method, possesses the quick catalysis effect of high selectivity and the strong acid catalyst of cellulolytic enzyme.
The present invention's the second purpose is to obtain a kind of method of hydrolysis fiber cellulosic biomass, and it has high selectivity and quick catalysis effect.
The 3rd purpose of the present invention is to obtain a kind of purposes of bionic catalyst.
A first aspect of the present invention provides a kind of bionic catalyst for catalyzing hydrolysis cellulose and/or hemicellulose, and described catalyst comprises bisgallic acid base catalysis region and cellulose binding domain.
In specific embodiment of the present invention, described bionic catalyst has the structure shown in molecular formula 1:
Wherein,
M is bisgallic acid base catalysis region, and described bisgallic acid base catalysis region is iron or zinc;
L
1, L
2, L
3Be cellulose binding domain, described cellulose binding domain is the part of single coordination, two coordination, three-fold coordination and/or four-coordination, and they can be identical, also can be different;
A, B are respectively C, N, S, B, Si or P, and wherein A can be identical with B, also can be different, and be singly-bound or two key between A and the B;
N represents integer, is selected from 0,1 or 2.
In specific embodiment of the present invention,
Described single ligand is selected from: take N, O, S, P, halogen, C, Si, B etc. as coordination atom or take two keys, triple bond, aromatic rings etc. as the material that contains a part point, and preferred CO, Cp
-, organophosphor ligand, halogen ion (Cl
-, Br
-, I
-), PF
6 -, BF
4 -, maleic acid (maleic acid), itaconic acid (itaconic acid), fumaric acid (fumaric acid) or its combination;
Described pair of ligand is selected from: N-N part, N-P part, P-O part, P-P part, O-N part, O-S part, S-N part, O-O part, P-S part, S-S part and other are take N, O, S, P, C, B, Si, as the material of containing of coordination atom of any two part points, and be preferred
Described three-fold coordination part is selected from: N-N-N part, N-P-N part, P-N-N part, P-P-N part, P-N-P part, O-N-N part, S-N-N part, O-N-O part, P-N-S part, P-P-P part, S-S-S part, O-O-O part, other N, O, S, P, C, B, Si, be the material that contains any three part points of coordination atom, the terpyridyl of preferred three nitrogen (terpyridine), use maltol (maltol) or its combination of nitrogen and oxygen.
Second aspect present invention provides a kind of method of hydrolysis fiber cellulosic biomass, and described cellulose biomass contains cellulose, hemicellulose and/or lignin, and the method comprises the steps:
(a) provide the mixture of bionic catalyst and cellulose biomass;
(b) mixture with step (a) is hydrolyzed, and obtains containing the hydrolysate of monose;
(c) hydrolysate of described step (b) ferments, degrades or liquefies, and obtains liquid fuel, and described liquid fuel comprises ethanol, gasoline, aromatic or its combination.
Preferably, the concentration of bionic catalyst in mixture is 5-200mM in the step (a).
Preferably, in the step (a) in the mixture between the consumption and the ratio 1-2mM/g between the cellulose biomass of bionic catalyst.
Preferably, cellulose and the weight/volume of hemicellulose in hydrolysate can reach 10-25% in the step (b).
Preferably, hydrolysate contains monose and/or lignin in the step (c), and described monose ferments and obtains ethanol, and described lignin is degraded or liquefied and obtains gasoline, aromatic or its combination.
In specific embodiment of the present invention, described step (b) is carried out in thermal field.
In specific embodiment of the present invention, described cellulose biomass is the pretreated cellulose biomass of process, and strong acid or highly basic high temperature and high pressure method, strong acid or highly basic decrepitation method, ammonia decrepitation method, normal temperature and pressure Chemical Physics field method or its combination are adopted in described preliminary treatment;
Preferably, the physical field of described normal temperature and pressure Chemical Physics field method is ultrasonic wave, microwave, magnetic force or tool combination;
Preferably, the material of the chemical reagent in the method for described normal temperature and pressure Chemical Physics field for being easy to recycle by distillation, more preferably ammoniacal liquor, SPA.
In specific embodiment of the present invention, when the chemical reagent in the method for described normal temperature and pressure Chemical Physics field was SPA, preliminary treatment may further comprise the steps:
The mixture of cellulose biomass and SPA as for processing in the physical field, is obtained pretreated cellulose biomass;
Described pretreated cellulose biomass separates, and obtains phosphoric acid and the organic solvent of cellulose and recovery;
Preferably, described separation method adopts extract and separate, precipitate and separate or its combination.
In specific embodiment of the present invention, adopt normal temperature and pressure Chemical Physics field method that cellulose biomass is carried out preliminary treatment in the described step (b), wherein said physical field is ultrasound field, frequency range at 17kHz between the 300MHz, only frequency range at 18kHz between the 100MHz, strength range between 0.1W-10kW/L, preferred 0.1Watts/cm
2To 300Watts/cm
2Between, only strength range between 2-6kW, preferred 80Watts/cm
2To 200Watts/cm
2Between, the ultrasonic wave of 2kW/20kHz most preferably; And/or described physical field is microwave field, and to 300 gigahertzs (GHz), strength range is between 0.1W-10kW/L at 300 megahertzes (MHz) for microwave frequency, and preferred microwave intensity scope is between 100-3000W/L; And/or described physical field is field of magnetic forece, and field of magnetic forece intensity is 0.2-12T.
In specific embodiment of the present invention, also comprise the recycling step (d1) of catalyst: adopt the hydrolysate of organic solvent extraction step (b), the catalyst that is recycled.
In specific embodiment of the present invention, also comprise the recycling step (d2) of catalyst: by using the hydrolysate of exchanger resin treatment step (b), the catalyst that is recycled;
Preferably, resin uses macroporous absorbent resin, macroporous absorption type weakly base resin, heat regenerative resin or its combination.
Third aspect present invention provides the purposes of bionic catalyst of the present invention, is used for hydrocellulose and/or hemicellulose.
Preferably, be used for the cellulose that hydrolysis contains lignin.
Preferably, be used for simultaneously hydrocellulose and hemicellulose.
Summary of drawings
Accompanying drawing 1 is a specific embodiment of the present invention, and this embodiment uses bionic catalyst of the present invention system to produce the process chart of high value added product such as liquid fuel ethanol and gasoline, xylitol, aromatic than the full use cellulose biomass.
Accompanying drawing 2 is another specific embodiments of the present invention, before the hydrolysis cellulose biomass is at first carried out preliminary treatment among this embodiment, then use bionic catalyst of the present invention system than the process chart of full use cellulose biomass production high value added product such as liquid fuel ethanol and gasoline, xylitol, aromatic.
Accompanying drawing 3 is another specific embodiments of the present invention, wherein the technological process of production is that cellulose biomass is at first carried out the field preliminary treatment of normal temperature and pressure Chemical Physics, isolated cellulose solids uses antigravity system of the present invention to be converted into alcohol fuel, the lignin that is present in the liquid is converted into gasoline or aromatic through precipitate and separate after out, and also the hemicellulose in liquid is converted into xylitol.
Optimum implementation of the present invention
The inventor has found a kind of bionic catalyst of ad hoc structure through large quantity research, and it possesses the quick catalysis effect of high selectivity and the strong acid catalyst of cellulolytic enzyme.Finished on this basis the present invention.
The inventor has developed artificial synthetic bionic catalyst according to the Catalysis Principles of the hydrolase that naturally exists.For example, with regard to cellulolytic enzyme, although its catalytic mechanism is also fully not clear, it possesses three different functional areas (domain) by basic confirmation: a catalysis region (catalytic domain), a cellulose binding domain (cellulose binding domain) and an attachment areas (linking region).General common cellulolytic enzyme catalysis region is comprised of two seed amino acids that contain sour residue: glutamic acid (glutamic acid) and asparatate (aspartic acid).One of them sour residue is as the donor of hydrogen proton, and another sour residue is as the nucleophilic functional group.
Common hydrolase generally is the protein complex that contains zinc or iron content, and iron and zinc are occurring in nature content enriches very much, be easy to obtain and transition metal that price is lower, active force between the transition metal ions such as iron and zinc and the hydroxyl is stronger, is suitable for as the cellulose binding domain in the catalyst (cellulosebinding domain).
The present invention has designed a kind of bionic catalyst, makes it contain bisgallic acid base catalysis region and cellulose binding domain.The inventor finds, the byproduct of the single and reaction of selectivity, the catalytic reaction that artificial synthetic bionic catalyst of the present invention generally possesses biological enzyme formulation seldom.And bionic catalyst can tolerate comparatively harsh reaction condition, and such as high temperature, high pressure and high acid-base value etc., it is Reaction time shorten greatly, thereby the inhibition that seldom is subject to product can obtain the product of higher concentration.And bionic catalyst can work under the condition that mushroom can't be survived, and the bionic catalyst catalysis system does not generally need sterilization.
Below describe in detail to various aspects of the present invention:
Cellulolytic enzyme bionic catalyst of the present invention has the structure shown in the following molecular formula 1:
Wherein, M be iron (Fe, oxidation state 0 ,+2 or+3) or zinc (Zn, oxidation state 0 ,+2);
L
1, L
2, L
3Be the complex compound part, they can be the parts of single coordination, two coordination, three-fold coordination, four-coordination, pentacoordinate, hexa-coordinate, and they can be identical, also can be different.
The example of single ligand includes but not limited to: take N, O, S, P, halogen, C, Si, B etc. as coordination atom or take two keys, triple bond, aromatic rings etc. as the material that contains a part point, such as CO, Cp
-, organophosphor ligand, halogen ion (Cl
-, Br
-, I
-), PF
6 -, BF
4 -, maleic acid (maleic acid), itaconic acid (itaconicacid), fumaric acid (fumaric acid), etc.
The example of two ligands includes but not limited to: N-N part, N-P part, P-O part, P-P part, O-N part, O-S part, S-N part, O-O part, P-S part, S-S part, etc. take N, O, S, P, C, B, Si, as the material of containing of coordination atom of any two part points, as
Deng.
The example of three-fold coordination part includes but not limited to: N-N-N part, N-P-N part, P-N-N part, P-P-N part, P-N-P part, O-N-N part, S-N-N part, O-N-O part, P-N-S part, P-P-P part, S-S-S part, O-O-O part, etc. take N, O, S, P, C, B, Si, as the material of containing of coordination atom of any three part points, as the terpyridyl (terpyridine) of three nitrogen, use nitrogen and oxygen maltol (maltol), etc.
As used herein, " three-fold coordination part " refers to that a molecule can provide three to join a little, is not single coordination.Particularly for example, " N-N-N " represents that three coordination sites that this part uses all are N.
A, B are respectively C, N, S, B, Si, O or P in the complex compound, and A and B can be identical, also can be different; Can be singly-bound between A and the B, also can be two keys.
N in the complex compound represents integer, can be 0,1 and 2.Both can be singly-bound between A and the B in the ligand molecular, also can be two keys or triple bond.
All complex compounds all have higher water-soluble.
All complex compounds all have at least two acid functional groups, and one of them sour residue is as the donor of hydrogen proton, and another sour residue is as the nucleophilic functional group, and they are catalysis regions of bionic catalyst.
The object lesson of above-mentioned complex compound includes but not limited to following molecular formula 2 and formula 3 compounds:
In the formula 2,
M=Fe, L1=Cp (cyclopentadiene), L2=CO, L3=BF
4 -, A, B are carbon, are that two keys connect between A and the B, and n=0.
In the formula 3,
M=Fe, L1=COONHNHCOOH (two coordination), L2=Cl
-, L3=Cl
-,
A, B are nitrogen, are singly-bound connection and n=2 between A and the B.
The synthetic method of above-mentioned these complex compounds is restriction not, all can use the known method for preparing complex compound.Concrete example includes but not limited to: use known simple complex compound to be starting material, in not affecting reaction and the solvent of product stability such as ether, then use the method for part displacement to change needed part into, according to the need and possibility the oxidation state of central metal is adjusted at last, perhaps first the oxidation state of central metal is adjusted, then use the method for part displacement to change needed part into, at last according to the need and possibility, the product of gained is purified, dry and get.Particularly as using di-iron enneacarbonyl complex compound [Fe
2(CO)
9] and maleic acid under the protection of nitrogen, prepare [Fe (CO)
4(maleic acid)] complex compound, reaction normal operation ether or benzene are as solvent, and reaction temperature is normal temperature or slightly high.Perhaps, use iron pentacarbonyl complex compound [Fe (CO)
5] as starting material, under the higher condition of ligand concentration, the Low Temperature Photochemistry reaction can obtain [Fe (CO)
3(maleic acid)
2], [Fe (CO)
2(maleic acid)
3].Perhaps use di-iron enneacarbonyl complex compound, iron pentacarbonyl complex compound etc. to prepare first cyclopentadiene dicarbapentaborane iron dimer, carry out again subsequent reactions; Also can buy and directly use cyclopentadiene dicarbapentaborane iron dimer { [CpFe (CO)
2]
2, Cyclopentadienyliron dicarbonyl dimer} changes the oxidation state of iron as starting material by the bromine oxidation, then carry out the part displacement; Can certainly use the simple salt of required oxidation state such as ferric acetate etc. to be starting material, progressively carry out the complexation reaction preparation.Etc..
The complex compound of two parts generally carries out in the larger solvent of polarity, such as alcohols as solvent.
In order to obtain comparatively ideal hydrolysis rate, these complex compounds are as the bionic catalyst of cellulose and hydrolysis of hemicellulose, general consumption concentration in hydrolyzation system is 0.1mM-10M, preferred 5-200mM, because it is slower to be lower than the speed of this interval hydrolysis, then catalyst costs is too high to be higher than this interval.
These complex compounds are as the bionic catalyst of cellulose and hydrolysis of hemicellulose, and they all are not found to cause the degraded of the monose such as glucose, wood sugar.These complex compounds are as the bionic catalyst of cellulose and hydrolysis of hemicellulose, and the catabolite of glucose, wood sugar all is lower than glucose, the wood sugar palliating degradation degree under (without any catalyst) same reaction temperature in pure water.
In order to obtain comparatively ideal hydrolysis effect, reduce the glucose that water causes, the degraded of wood sugar as far as possible, hydrolysis rate is fast as best one can, these complex compounds are as the bionic catalyst of cellulose and hydrolysis of hemicellulose, ratio between consumption in hydrolyzation system and cellulose or the hemicellulose, generally at 0.1-1000mmol/g, preferably be controlled between the 1-2 (mmol/g), when particularly accelerating extent of reaction with thermal field, the degraded that is lower than glucose that this interval water causes, wood sugar is more, and then catalyst costs is too high to be higher than this interval.
Cellulose biomass of the present invention can be pretreated, also can be without preliminary treatment.
These complex compounds of the present invention are as the bionic catalyst of cellulose and hydrolysis of hemicellulose, and general equal can the needs carried out preliminary treatment to cellulose biomass, although the hydrolysis progress is accelerated in the preliminary treatment meeting.
The cellulose biomass preliminary treatment can be adopted all known preprocess methods, such as Physical, chemical method, bioanalysis, chemicals logos, they all with the present invention in the bionic catalyst coupling that discloses.
The preferred chemicals logos of preprocess method, include but not limited to common as strong acid or highly basic high temperature and high pressure method, strong acid or highly basic decrepitation method, ammonia decrepitation method, normal temperature and pressure Chemical Physics field method, etc.
Normal temperature and pressure Chemical Physics field method, preferably, physical field includes but not limited to ultrasonic wave, microwave and field of magnetic forece.In a preferred embodiment, to 300 gigahertzs (GHz), strength range is between 0.1W-10kW/L at 300 megahertzes (MHz) for described microwave frequency, and preferred microwave intensity scope is between 100-3000W/L.To between the 300MHz, preferred 18kHz is between the 100MHz at 17kHz for described ultrasonic frequency scope; Strength range is at 0.1Watts/cm
2To 300Watts/cn
2Between, preferred 40Watts/cm
2To 100Watts/cm
2Between; Described field of magnetic forece generally is more strong better, but because economic reason, the field of magnetic forece intensity that preferably adopts is between the 0.2-12T (tesla).
Chemical reagent in the method for normal temperature and pressure Chemical Physics field can be common acid or alkali, preferably is generally the material that can be easy to recycle by distillation, include but not limited to ammoniacal liquor, SPA, etc.;
We announce the preprocess method of use ammoniacal liquor at patent WO/2007/095787, chemical reagent in the method for normal temperature and pressure Chemical Physics field is if during SPA, preliminary treatment may further comprise the steps: after cellulose biomass and SPA mix, mixture placed carry out preliminary treatment in the physical field, pretreatment time is generally 5 seconds to 18 hour, preferably 1 minute to 90 minutes.After preliminary treatment is finished, generally adopt extraction to separate, extractant for and the immiscible material of phosphoric acid, but with water preferably intersolubility is arranged again, these extractants include but not limited to acetone, MEK etc.Use the ketone extractant, cellulose is settled out from phosphoric acid, the cellulose available water washing that precipitates and isolates, and the phosphoric acid that uses in the preprocessing process and organic solvent all can be easy to recycling by distillation.
These complex compounds that disclose among the present invention are as the bionic catalyst of cellulose and hydrolysis of hemicellulose, and hydrolysis both can be carried out in the physical field of normal temperature and pressure, also can carry out in thermal field.
Different with the cellulolytic enzyme now, these complex compounds are as the bionic catalyst of cellulose and hydrolysis of hemicellulose, and cellulose and the hemicellulose content in hydrolyzate can reach 25% (weight/volume).And using present cellulolytic enzyme, its high level cadre's heavy substance content is difficult to reach 10% in the hydrolyzate.
Described physical field is microwave, ultrasonic wave or its combination.In a preferred embodiment, to 300 gigahertzs (GHz), strength range is between 0.1W-10kW/L at 300 megahertzes (MHz) for described microwave frequency.Preferred microwave intensity scope is between 100-3000W/L, and between the 300MHz, preferred 18kHz is between the 100MHz at 17kHz for described ultrasonic frequency scope; Strength range is at 0.1Watts/cm
2To 300Watts/cm
2Between, preferred 40Watts/cm
2To 100Watts/cm
2Between.
To hydrolysis of hemicellulose, thermal field refers to temperature between 110-170 ℃, because in the decomposition of the pentose of this temperature range seldom; To cellulose hydrolysis, thermal field refers to temperature between 120-195 ℃, and the decomposition that the water of this temperature range causes glucose seldom.Catalyst of the present invention also can be used for very high hydrolysis temperature, such as temperature range 200-260 ℃.
These complex compounds are as the bionic catalyst of cellulose and hydrolysis of hemicellulose, can produce in order to now known use cellulose biomass the production technology combination of liquid fuel, only for this reactions steps of hemicellulose of removing cellulose biomass, perhaps only be used for this reactions steps of cellulose of hydrolysis fiber cellulosic biomass such as bionic catalyst.
When bionic catalyst only is used for the cellulose of hydrolysis fiber cellulosic biomass, different with cellulolytic enzyme, because the catalytic performance of bionic catalyst is not subjected to the impact of lignin basically, cellulose biomass need not remove delignification, and whole production technology is greatly simplified.The reaction technological process of production as shown in Figure 1, cellulose biomass at first is crushed to suitable granularity, then approximately sloughing phytochrome in the pure water between 90-100 ℃, the cellulose biomass of depigmentation gained (120-230 ℃) in the pure water of higher temperature is sloughed basically whole hemicelluloses, the main component of the cellulose biomass that this moment is prepared is cellulose and lignin, this solid discharges all hydrolyzable glucose under the effect of bionic catalyst, lignin does not dissolve and is filtered off as solid product.The hemicellulose that produces in the production procedure is converted into xylitol, and lignin is converted into aromatic or gasoline.Remove pigment in the technological process of production and can make very shallow that the color of reaction system becomes, and the decolouring step that can help to make the more shallow lignin of color and simplify xylitol.
The bionic catalyst as cellulose and hydrolysis of hemicellulose among the present invention can also combine with existing preconditioning technique, and obviously simplify whole technological process of productions.For example, shown in the legend 2, the present invention can be behind the cellulose biomass granule decoloration that crushes, directly in physical field, use SPA that cellulose, hemicellulose are dissolved out, then use acetone that mixture is carried out layering, can tell lignin, wash at last the cellulose that from SPA, is settled out with water, it is fermentable monose that the cellulose solids of gained can be used bionic catalyst catalyzing hydrolysis of the present invention, and then monose is converted into alcohol by fermentation; And be present in lignin and hemicellulose in the liquid phase, after telling the lignin solid, the hemicellulose that water solubility is high can be told for the preparation of xylitol.The production technology of this invention selects SPA to make extract, be because its corrosivity much smaller than other inorganic acids such as the concentrated sulfuric acid, concentrated hydrochloric acids, also be concentrated again because it after using acetone etc. to produce cellulose and hemicellulose, is easy to be divested very much acetone and water and use.And if the color chin-deep appears after long-time the use, high-temperature calcination can be sloughed the overwhelming majority and be produced the materials that looks become.
Although the cellulose that foundation discloses in the present invention and the technological process of production on the hydrolysis of hemicellulose bionic catalyst basis, shown in legend 1 and 2, be very beneficial for the production of xylitol and ethanol, but because in these two kinds of neoteric technological process of productions, ash content in the cellulose biomass all is in the same place with lignin, and being the production technology of gasoline, lignin conversion all uses higher pressure and temperature, the ash content that as far as possible reduces reactant is extremely important, and the production technology shown in the legend 1 and 2 needs other step to come except ash content.And institute's invention preprocess method (W0/2007/095787) that we have announced, then can a direct step this problem be solved, in the technological process of production of legend 3, ash content is deposited together at cellulose, after cellulose was hydrolyzed and is converted into ethanol, the ash content in the cellulose biomass can be removed by simple filtration.
The inventor can use under the sharp pressure of higher temperature through the bionic catalysis system of extensive and deep research institute invention, and catalytic rate is higher than cellulolytic enzyme far away, thereby is subjected to the inhibition degree of product can get the liquid glucose of higher concentration far below cellulolytic enzyme.And bionic catalysis of the present invention system to the degraded of monose far below inorganic acid, hydrolysis gained liquid glucose can be directly used in alcohol prepared by fermenting.In addition, bionic catalyst of the present invention can recycle on higher degree ground, contrasts existing cellulolytic enzyme cost and obviously reduces; And the contrast inorganic acid, bionic catalyst of the present invention does not need to take the neutralizing hydrolysis liquid glucose with the alkali of correspondence, obviously reduces the consumption of water, and has reduced the pressure of environmental protection.
The bionic catalyst as cellulose and hydrolysis of hemicellulose that discloses among the present invention generally has very high lipophilicity, after hydrolysis finishes, can use with the immiscible organic solvent of water they to be extracted again and use.The organic solvent of extraction bionic catalyst complex compound commonly used includes but not limited to carrene, chloroform, benzene, toluene, ether, dimethylbenzene etc.
The bionic catalyst as cellulose and hydrolysis of hemicellulose that discloses among the present invention can also use exchanger resin to reclaim.Through resin column catalyst is adsorbed on the resin behind the hydrolyzate cool to room temperature, the monose solution of gained is used for fermentation.It is in parallel that resin column is generally two covers, wherein after the full profit of resin adsorption in the cover, carries out desorb and/or regeneration, and the another set of resin column of production and application carries out, and can not affect production so at once.Resin normal operation macroporous absorbent resin, macroporous absorption type weakly base resin, heat regenerative resin.These resins all can have been bought from the market, such as the TRR resin of XAD-2 resin, D301 resin, Amberlite XAD-4 resin and Novation company.Reclaim and preferably to use nonionic macroporous absorbent resin and heat regenerative resin because the product of these two kinds of resins reclaim can be with an organic solvent or hot water come wash-out.Organic solvent is generally selected ethanol, because one of major product of cellulose biomass refining is ethanol, can reduce production costs like this.Hot water between 70-95 ℃ of the heat regeneration normal operation, the too low recovery of temperature is too slow, and the too high meeting of temperature causes the structural damage of resin.
Heat regenerative resin is a kind of amphoteric resin, also can oneself oneself prepare as the case may be.Preparation method commonly used is to contain two amino amino acid, to pass through one of them amino covalent bond reaction, an amount of amino acid chain is received on the macroreticular resin matrix.Behind polyphenyl olefine resin chloromethylation, then make with amino acid such as lysine reaction.
Can be biomass solid through pulverizing in living beings of the present invention, including, but not limited to: particle diameter between 0.01-8mm, preferred 0.1-5mm, water content 1-50wt%, the living beings of preferred 5-30wt% are with the total weight of described living beings.
To between the 300MHz, between the 100MHz, strength range is (0.1Watts/cm between 0.1W-10kW/L at 18kHz for only frequency range at 17kHz for the ultrasonic frequency scope that is used for hydrolysis of using among the present invention
2To 300Watts/cm
2Between), only strength range (80Watts/cm between 2-6kW/L
2To 200Watts/cm
2Between), the ultrasonic wave of preferred 2kW/20kHz.
Below given embodiment be for the present invention is described better, be not that disclosed content only limits to the following examples.
Below the cellulose biomass that uses in the given example be the natural drying corn stalk (also being stalk) that crushes.In embodiments; the beta glucan that constitutes 36.4wt% of corn stalk particle (β-glucan); the xylan of 18.8wt% (xylan); the Arabic polysaccharide (arabinan) of 2.8wt%; the Glucomannan of 1.8wt% (mannan); the galactan of 2.2wt% (galactan); Carson's lignin (Klasonlignin) of 20.2wt%; the ash of 7.0wt% (ash); the acetyl group component of 3.2wt% (acetyl group); the protein of 4.0wt% (protein), and the glycuronic acid of 3.8wt% (Uronic acid).
Embodiment 1: catalyst [CpFeCO (maleic acid)] BF
4Synthetic
Under nitrogen protection; to the cyclopentadiene dicarbapentaborane iron dimer (Cyclopentadienyl iron dicarbonyl dimer) without adding 10mmol in the benzene solvent of water deoxygenation; after stirring lower all dissolvings; after reaction solution is cooled to about 10 ℃; in solution, add equimolar bromine; after being stirred to the whole disappearances of aubergine, adding the 20mmol alchlor in reactant liquor, is thereafter the maleic acid of 21mmol.The reactant liquor mixture slowly is warmed up to 60 ℃, and keeps this temperature approximately after four hours, behind the cool to room temperature, adds the tetrafluoro borated amine (NH of 21mmol
4BF
4), after precipitation formation, leaching sediment, vacuum is removed solution benzene and is got crude product.This crude product obtains pure product through the ether recrystallization, and productive rate is 91%.
Molecular structural formula is C
11H
9BF
4FeO
6, elementary analysis gets content C%:44.8, H%:3.21, Fe%:19.2 (deserved C%:45.09, H%:3.10, Fe%:19.06).
1H-NMR(CDCl
3，δppm)：11.7(br，2H)；6.68(s，2H)；5.21(s，5H)。
13C-NMR (CDCl
3, δ ppm): 218 (CO); 174 (carboxyls); 137.8 (C=C); 89.6 (Cp).
Embodiment 2: catalyst second diamino oxalic acid iron complex synthetic
Under nitrogen protection; 0.5mmol four hydration ferrous chloride be dissolved in 10 milliliters the deionized water; then slowly be added drop-wise to second diamino oxalic acid (the ethylenediamine diacetic acid that closely boils; 1.0mmol) in the tetrahydrofuran solution; aubergine begins to manifest after splashing into the aqueous solution of iron; carry out after two hours under stirring; after reaction solution is cooled to about 10 ℃; the ether that adds 20 milliliters in the solution comes precipitated product; after ether and the washing of acetone mixed liquor; drying obtains pure product under the vacuum, and productive rate is 90%.
Molecular structural formula is C
8H
16Cl
2FeN
4O
2, elementary analysis gets content C%:21.98, H%:3.96, N%:13.16, Fe%:13.1 (deserved C%:22.72, H%:3.81, N%:13.25, Fe%:13.20).
1H-NMR(CDCl
3，δppm)：11.2(br，4H)；6.68(br，4H)；3.21(m，8H)。
13C-NMR (CDCl
3, δ ppm): 158 (carboxyls); 23.8 (CH
2).
Embodiment 3: catalyst [CpFeCO (maleic acid)] BF
4Catalyzing hydrolysis cellulose at normal temperatures and pressures
Catalyst [CpFeCO (maleic acid)] BF to 100 milliliters of 50mM
4Microcrystalline cellulose about 200 orders of middle adding 5 grams, after reaction vessel is sealed mouth, reaction is hydrolyzed in the ultrasound reactor of 2kW/20kHz, constantly rock the container of containing microcrystalline cellulose in the reaction, whole microcrystalline cellulose solids disappeared after 4 hours, use HPLC to measure the concentration of reduced sugar of reactant liquor, concentration is 50.1mg/ml.Do not detect the catabolite of glucose in the hydrolyzate.
Embodiment 4: catalyst [CpFeCO (maleic acid)] BF
4The catalyzing hydrolysis cellulose
In suitable container, add 20.0 and restrain the natural drying corn stalk that crushes (5.8% moisture), then add respectively 100 ml deionized water, stir and lower mixture to be heated to nearly 100 ℃ and maintained this temperature approximately 30-60 minute, be cooled to the rear centrifugal dark brown yellow liquid of removing below 50 ℃, remaining solid is encased in the suitable stainless steel high temperature autoclave, after adding 100 ml deionized water, seal tight reactor, then be heated to 170 ℃ and maintained this temperature approximately 120 minutes.The centrifugal weak yellow liquid of removing after being cooled to below 50 ℃, weak yellow liquid finds it is whole hemicelluloses basically by analysis.
Remaining near-white solid, the solid analysis that takes a morsel, gained solid containing cellulose 6.5 grams, lignin 3.8 grams, cellulosic loss is 5.2%, lignin is loss not.
The solid of gained is divided into uniform two parts, installs to respectively in two 60 milliliters of suitable stainless steel high temperature high-pressure reactors, and making the cumulative volume in two reactors after the adding deionized water is 50 milliliters, seals tight reactor, is heated to 180 ℃.With high pressure nitrogen with a certain amount of catalyst [CpFeCO (maleic acid)] BF
4Saturated solution is compressed into the A reactor, makes its concentration reach 50mM, and maintains these 180 ℃ of temperature approximately 6 hours.Add the concentrated sulfuric acid in the B reactor, also make its concentration reach 50mM, and maintain these 180 ℃ of temperature approximately 6 hours, then two reactor A and B are cooled to below 30 ℃.
Cellulose hydrolysis degree in the reactor A is 81%, and concentration of glucose is 53mg/ml.Cellulose hydrolysis degree in the reactor B is 86%, and concentration of glucose is 13mg/ml.This result shows, bionic catalyst [CpFeCO (maleic acid)] BF
4Catalytic effect very near inorganic acid, and the glucose of gained is the yield more than four times far above sulfuric acid.
Embodiment 5: catalyst [CpFeCO (maleic acid)] BF
4The sharp hemicellulose of while catalyzing hydrolysis cellulose
In suitable container, add 20.0 and restrain the natural drying corn stalk that crushes (5.8% moisture), then add respectively 100 ml deionized water, stir and lower mixture to be heated to nearly 120 ℃ and maintained this temperature approximately 30-60 minute, be cooled to the rear centrifugal dark brown yellow liquid of removing below 50 ℃, getting behind the evaporate to dryness is the solid of hemicellulose basically entirely, can be directly used in the preparation xylitol.And the remaining solid of boiling is after vacuum drying, be encased in the corrosion resistant reactor, add 150 milliliter of 85% phosphoric acid in reactor, in the ultrasound reactor of 2kW/20kHz, stir after 30 minutes, the acetone that adds 400 milliliters, after thoroughly mixing, centrifugation goes out supernatant liquid, repeat once to tell upper liquid, upper liquid is lignin and hemicellulose.Then descend and add the washing of 300 ml pure waters in the category solids.Acetone extract liquid behind Distillation recovery acetone, the centrifugal lignin solid of telling, residual liquid is for containing a small amount of dilute phosphoric acid solution.This method among the present invention, two solvents of phosphoric acid and acetone all are recovered for re-use.
The cellulose solids of gained can directly be hydrolyzed to fermentable monose.
Cellulose solids is divided into two parts, the hemicellulose solid of boiling gained also is divided into two parts, one minute cellulose and hemicellulose solid are installed in 100 milliliters of suitable stainless steel high temperature high-pressure reactors, making the cumulative volume in the reactor after the adding deionized water is 90 milliliters, seal tight reactor, be heated to 180 ℃.With high pressure nitrogen with a certain amount of catalyst [CpFeCO (maleic acid)] BF
4Saturated solution is compressed into reactor, makes its concentration reach 100mM, and maintains these 180 ℃ of temperature approximately 6 hours, then reactor is cooled to below 30 ℃.
Cellulose hydrolysis degree in the reactor is＞99%, and concentration of glucose is 38mg/ml, productive rate 91%; Xylose concentration in the solution is 18mg/ml, productive rate 83%.This result's demonstration, the bionic catalyst that discloses among the present invention is hydrocellulose and hemicellulose simultaneously, and the degraded of hemicellulose is very low.
Get in the pure water that another part cellulose 2 gram that is divided is suspended in 50 milliliters, with dilute sulfuric acid pH is adjusted to 5.5 after, after 121 ℃ of sterilizations in a hour, in solution, add the NS50013 of 200 microlitres, the cellulolytic enzymes such as NS50010 of 20 microlitres.The discovery of monitoring hydrolysis progress, after 23 hours, all dissolvings of all fibres element, concentration of glucose is 43.3mg/ml, the cellulose of the cellulose extracting method gained in this invention is highly susceptible to by the cellulose hydrolysis enzyme hydrolysis.
Embodiment 6: bionic catalyst is to the degraded of glucose and wood sugar
Use respectively [CpFeCO (maleic acid)] BF of pure water, 100mM
4Glucose and the xylose solution of the sulfuric acid solution preparation 10% of solution and 100mM.For glucose solution, under nitrogen protection, all be rapidly heated to 190 ℃, measure respectively the sugared concentration of 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours and 6 hours, result such as following table 1; For xylose solution, under nitrogen protection, all be rapidly heated to 170 ℃, the sugared concentration when measuring respectively 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, result such as following table 2:
Table 1, concentration of glucose change (mg/ml)
| 30 minutes | 1 hour | 2 hours | 3 hours | 4 hours | 6 hours | |
| The aqueous solution | 98.2 | 96.1 | 94.2 | 91.8 | 89.4 | 84.1 |
| Bionic catalyst | 99.7 | 97.5 | 96.3 | 95.1 | 94.3 | 91.6 |
| Sulfuric acid | 87.6 | 57.8 | 40.5 | 35.8 | 29.1 | 23.3 |
Table 2, xylose concentration change (mg/ml)
| 10 minutes | 20 minutes | 30 minutes | 40 minutes | 50 minutes | 60 minutes | |
| The aqueous solution | 96.2 | 94.9 | 93.2 | 92.1 | 91.1 | 89.7 |
| Bionic catalyst | 97.7 | 96.3 | 95.8 | 94.6 | 94.1 | 93.7 |
| Sulfuric acid | 83.1 | 67.7 | 56.8 | 49.3 | 47.2 | 36.9 |
Embodiment 7: the recovery of bionic catalyst hydrolysis fiber cellulosic biomass and catalyst, liquid glucose fermentation
In suitable container, add 40.0 and restrain the natural drying corn stalk that crushes (5.6% moisture), then add respectively 200 ml deionized water, stir and lower mixture to be heated to nearly 100 ℃ and maintained this temperature approximately 30-60 minute, be cooled to the rear centrifugal dark brown yellow liquid of removing below 50 ℃, remaining solid joins in 30% the ammoniacal liquor, then adding pure water makes the content of solid in the mixture be about 10% (400 milliliters of cumulative volumes, ammonia concn 18-20%), after reaction vessel is sealed mouth, in the ultrasound reactor of 2kW/20kHz, carry out the preliminary treatment abstraction reaction, constantly rock the container of containing microcrystalline cellulose in the reaction.Sampling detects after 1 hour, 95% lignin has been dissolved in ammoniacal liquor, filter separately solid and product liquid, product liquid is behind Distillation recovery ammoniacal liquor, it is 2.5 also constantly stirrings that the lower liquid of cooling is adjusted to pH with sulfuric acid, filter to get brown color lignin solid product, wash twice final vacuum dry very pure lignin.
Separating obtained solid product used the pure water washing near after the neutrality after preliminary treatment was extracted, install in 100 milliliters of suitable stainless steel high temperature high-pressure reactors, making the cumulative volume in the reactor after the adding deionized water is 90 milliliters, seals tight reactor, is heated to 200 ℃.With high pressure nitrogen with a certain amount of catalyst [CpFeCO (maleic acid)] BF
4Saturated solution is compressed into reactor, makes its concentration reach 200mM, and maintains these 200 ℃ of temperature 1 hour, then reactor is cooled to below 25 ℃.Cellulose hydrolysis degree in the reactor is＞99%, and concentration of glucose is 136mg/ml, productive rate 90%.This result shows, the cellulolytic ability of the bionic catalyst that discloses among the present invention is very high, and the degraded of glucose is few when at high temperature using.
Above-mentioned gained glucose solution is divided equally is two parts of equating, a extracted with diethyl ether 3 times (each 50 millimeters) of using 150 milliliters, and combining extraction liquid boils off the catalyst that must reclaim behind the ether, and the rate of recovery can reach 69%.After the logical nitrogen of the aqueous solution after the extraction was sloughed residual ether, transferring pH was approximately 1.5% beancake powders of 5.5 rear addings, and 121 ℃ of sterilizations add 1% efficient Angel brewer's dried yeast after 30 minutes, 34 ℃ of bottom fermentations 24 hours.Sampling detects, and concentration of glucose can't detect substantially, and alcohol concentration is 5.9%.This result's demonstration, extracted with diethyl ether does not affect the liquid glucose fermentation.
Another part glucose solution is by the XAD-4 large pore resin absorption column of 3cm * 60cm, flow velocity 2 ml/min, basically can't detect catalyst in the D/W of gained, then transferring pH is approximately 1.5% beancake powders of 5.5 rear addings, 121 ℃ of sterilizations add 1% efficient Angel brewer's dried yeast after 30 minutes, 34 ℃ of bottom fermentations 24 hours.Sampling detects, and concentration of glucose can't detect substantially, and alcohol concentration is 5.9%.This result's demonstration, macroporous absorbent resin reclaims catalyst does not affect the liquid glucose fermentation.
Embodiment 8: lignin conversion is gasoline products
The 330-380 ℃ of dehydration after one hour under blanket of nitrogen of dry lignin, and the weight ratio such as naphthane mixes.In a Ha Shi (Hastolly C) pressure reactor, add Ni/C catalyst (catalyst content 10%), under the Hydrogen Vapor Pressure of 12Mpa, be heated to 390-400 ℃ and kept this temperature 1 hour.Reaction uses magnetic to stir, after reaction finishes, and cool to room temperature.Analyze the liquid part and find, the molecule carbon atoms is C
6-C
12The constituent content of boiling point between 60-200 ℃ is 86.8% (gasoline).Result's demonstration, the lignin of gained of the present invention is the raw material of well producing gasoline.
Industrial applicability
(1) the invention provides a kind of brand-new cellulolytic enzyme bionic catalysis system, this system can become glucose at the normal temperature and pressure rapidly hydrolyzing cellulose, can under HTHP, operate rapidly hydrolyzing cellulose again and become glucose, and can guarantee that the Glucose Liquid of the higher concentration of rapidly hydrolyzing cellulose gained can be directly used in alcoholic fermentation.In addition, the bionic catalysis system should be insensitive to existing of lignin and hemicellulose, bionic catalyst is compared generally with enzyme catalyst all be very little molecule, they are easy near the rapid hydrocellulose in cellulosic surface very much, these 2 so that when using the bionic catalyst hydrolysis, the preliminary treatment of cellulose biomass can be unnecessary thorough especially.Simultaneously, this bionic catalysis system can the catalyzing hydrolysis hemicellulose, and the catabolite in the gained hydrolysate does not affect the fermentation of hydrolysate.
(2) the present invention also provides the production technology of the cellulolytic enzyme bionic catalysis system that effective use invents, so that all main active ingredient all obtains the embodiment of maximum commercial value in the cellulose biomass raw material.Because according to our preresearch estimates, if fermentable sugars all in the cellulose biomass raw material all are converted into alcohol fuel, lignin is as the substitute of coal, contrast brand-new production technology of the present invention: cellulose is converted into that alcohol fuel, lignin are converted into gasoline, hemicellulose is converted into xylitol and fat-free feed, and the raw-material product value of the former cellulose biomass per ton is less than the product value 20 percent of this institute invention new production process.
(3) the present invention also provides a kind of feasible catalyst recovery method, further reduces the production cost of biorefinery factory.
(4) the present invention also provides a kind of quick normal temperature and pressure cellulose biomass preprocess method, and the cellulose of gained is easy to hydrolysis very much, and used solvent is easy to reclaim, and further reduces the production cost of biorefinery factory.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (18)
1. a bionic catalyst that is used for catalyzing hydrolysis cellulose and/or hemicellulose is characterized in that, comprises bisgallic acid base catalysis region and cellulose binding domain, has the structure shown in molecular formula 1:
Wherein,
M is bisgallic acid base catalysis region, and described bisgallic acid base catalysis region is iron or zinc;
L
1, L
2, L
3Be cellulose binding domain, described cellulose binding domain is the part of single coordination, two coordination, three-fold coordination and/or four-coordination, and they can be identical, also can be different; Described single ligand is selected from: take N, O, S, P, halogen, C, Si, B as coordination atom or take two keys, triple bond, aromatic rings as the material that contains a part point; Described pair of ligand is selected from: N-N part, N-P part, P-O part, P-P part, O-N part, O-S part, S-N part, O-O part, P-S part, S-S part and other are take N, O, S, P, C, B, Si, as the material of containing of coordination atom of any two part points; Described three-fold coordination part is selected from: N-N-N part, N-P-N part, P-N-N part, P-P-N part, P-N-P part, O-N-N part, S-N-N part, O-N-O part, P-N-S part, P-P-P part, S-S-S part, O-O-O part, other N, O, S, P, C, B, Si, be the material that contains any three part points of coordination atom;
A, B are respectively C, N, S, B, Si or P, and wherein A can be identical with B, also can be different, and be singly-bound or two key between A and the B;
N represents integer, is selected from 0,1 or 2.
2. catalyst as claimed in claim 1 is characterized in that, the preferred CO of described single ligand, Cp
-, organophosphor ligand, Cl
-, Br
-, I
-, PF
6 -, BF
4 -, maleic acid, itaconic acid, fumaric acid or its combination.
3. catalyst as claimed in claim 1 is characterized in that, and is described take N, O, S, P, C, B, Si, as the material of containing of coordination atom of any two part points
Preferably
4. catalyst as claimed in claim 1 is characterized in that, other N, O, S, P, C, B, Si, is the preferred terpyridyl of the material that contains any three part points of coordination atom.
5. the method for a hydrolysis fiber cellulosic biomass, described cellulose biomass contains cellulose, hemicellulose and/or lignin, and the method comprises the steps:
(a) provide the mixture of bionic catalyst and cellulose biomass,
Described bionic catalyst is catalyst claimed in claim 2;
(b) mixture with step (a) is hydrolyzed, and obtains containing the hydrolysate of monose;
(c) hydrolysate of described step (b) ferments, degrades or liquefies, and obtains liquid fuel, and described liquid fuel comprises ethanol, gasoline, aromatic or its combination.
6. method as claimed in claim 5 is characterized in that, described step (b) is carried out in thermal field.
7. method as claimed in claim 5, it is characterized in that, described cellulose biomass is the pretreated cellulose biomass of process, and strong acid or highly basic high temperature and high pressure method, strong acid or highly basic decrepitation method, ammonia decrepitation method, normal temperature and pressure Chemical Physics field method or its combination are adopted in described preliminary treatment.
8. method as claimed in claim 7 is characterized in that, the physical field of described normal temperature and pressure Chemical Physics field method is ultrasonic wave, microwave, magnetic force or its combination, the material of chemical reagent for being easy to recycle by distillation.
9. method as claimed in claim 8 is characterized in that, the described material that can be easy to recycle by distillation is ammoniacal liquor, SPA.
10. method as claimed in claim 9 is characterized in that, when the chemical reagent in the method for described normal temperature and pressure Chemical Physics field was SPA, preliminary treatment may further comprise the steps:
The mixture of cellulose biomass and SPA as for processing in the physical field, is obtained pretreated cellulose biomass;
Described pretreated cellulose biomass separates, and obtains phosphoric acid and the organic solvent of cellulose and recovery.
11. method as claimed in claim 7 is characterized in that,
Adopt normal temperature and pressure Chemical Physics field method that cellulose biomass is carried out preliminary treatment in the described step (b), wherein said physical field is ultrasound field, and between the 300MHz, strength range is between 0.1W-10kW/L at 17kHz for frequency range; And/or described physical field is microwave field, and to 300 gigahertzs (GHz), strength range is between 0.1W-10kW/L at 300 megahertzes (MHz) for microwave frequency; And/or described physical field is field of magnetic forece, and field of magnetic forece intensity is 0.2-12T.
12. method as claimed in claim 11 is characterized in that, between the 100MHz, strength range is between between the 2-6kW/L at 18kHz for the frequency range of ultrasound field.
13. method as claimed in claim 12 is characterized in that, the ultrasonic wave of preferred 2kW, 20kHz.
14. method as claimed in claim 11 is characterized in that, preferred microwave intensity scope is between 100-3000W/L.
15. method as claimed in claim 5 is characterized in that, also comprises the recycling step (d1) of catalyst: adopt the hydrolysate of organic solvent extraction step (b), the catalyst that is recycled.
16. method as claimed in claim 5 is characterized in that, also comprises the recycling step (d2) of catalyst: by using the hydrolysate of exchanger resin treatment step (b), the catalyst that is recycled.
17. method as claimed in claim 16 is characterized in that, described exchanger resin is macroporous absorbent resin, heat regenerative resin or its combination.
18. the purposes of bionic catalyst as claimed in claim 1 is used for hydrocellulose and/or hemicellulose.
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