CN101143881B - Method for synchronously extracting hemicellulose, cellulose and lignin and reclaiming phenolic acid compounds - Google Patents
Method for synchronously extracting hemicellulose, cellulose and lignin and reclaiming phenolic acid compounds Download PDFInfo
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- CN101143881B CN101143881B CN2007101757432A CN200710175743A CN101143881B CN 101143881 B CN101143881 B CN 101143881B CN 2007101757432 A CN2007101757432 A CN 2007101757432A CN 200710175743 A CN200710175743 A CN 200710175743A CN 101143881 B CN101143881 B CN 101143881B
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Abstract
The present invention provides a technique method which separates lignose, hemicellulose, cellulose and phenolic acid from lignocellulosic biomass. Under the selected pH value and temperature, the lignocellulosic biomass is processed by hot water, so that the hemicellulose and the phenolic acid are preferentially resolved in aqueous solution, delignification processing is carried out, organic solvent or alkaline solution is applied to carry out high-temperature cooking, the generated liquid-solid phase product can be easily and effectively separated, and thus the hemicellulose, the cellulose and the phenolic acid can be respectively obtained. Moreover, enzymatic treatment can be selectively added, and a solid phase product is obtained at the first stage of a group of enzymatic treatment with a cooperative effect. Because the ferulic acid linkage between the hemicellulose and the lignose can be selectively broken, the separation of the chemical components has a high yield rate and high purity.
Description
Technical field
The present invention relates to from lignocellulose-like biomass, be extracted into simultaneously the method for each useful component.More particularly, the present invention relates to a kind of processing lignocellulose-like biomass, and therefrom extract hemicellulose simultaneously, xylogen and Mierocrystalline cellulose, and the multistage method of recovery phenolic acid.
Background technology
Lignocellulose-like biomass is organic resource the abundantest on the earth, and it is reproducible, also is referred to as biomass usually.Biomass comprise all agriculture residues (as the stalk of cereal, shell and chaff, corn stalk, bagasse), special-purpose fibre crops (as the withy grass, reed, bamboo, flax, hemp and bluish dogbane), timber and forest residue.
Three main components of lignocellulose-like biomass are Mierocrystalline celluloses, hemicellulose and xylogen.In the cell walls of vegetable fibre, the xylogen of cross bracing and the complex body of hemicellulose are a kind of matrix material of cellulosic fibre formation glued together, i.e. lignocellulose.Mierocrystalline cellulose (40%-60% by weight) is the glucose polymer that exists with crystallization and amorphous form a kind of while.Hemicellulose (20%-40% by weight) is made up of hyperbranched short sugar chain (five-carbon sugar and hexose).Wood sugar (five-carbon sugar) is a kind of topmost hemicellulose sugar, especially agro-ecology matter and leaf wood.Xylogen (10%-30% by weight) is the unbodied three-dimensional polymer of a complexity of being made up of phenylpropyl alcohol alkane unit, and it is glued together with the cellulose micro-fibers in the cell walls, makes ligno-cellulosic materials have physical strength.Lignocellulose biomass also contains various low molecular organic materials, phenolic acids for example, and wherein the effect of forulic acid is extremely important, and it is bound up xylogen in the plant cell wall and hemicellulose.
Now, people see the unprecedented challenge that we faced more and more significantly, promptly satisfy growing energy demand and protection environment.Biomass are a kind of cheapnesss, reproducible resource, can be used as the energy, the raw material of chemical industry and material industry, on behalf of a continuable way, it is converted into Industrial products satisfy the growing fuel and the demand of Chemicals, especially in view of the limited mineral wealth of supply, the rise of oil price and to the concern of environment.
Extract these three kinds of main chemical compositions from biomass efficiently and remain a difficult problem as the starting material of high added value, this is owing to the chemical structure of biomass complexity and is difficult to process optimization and is difficult for making the product of acquisition that enough productive rates and commercial value are arranged.
In paper industry, pulping process is used for separating compositions such as the Mierocrystalline cellulose of lignocellulosic material and xylogen, in these processes, the value of hemicellulose and xylogen does not obtain enough utilizations, 40% the material of only having an appointment reclaims with the available form, with widely used kraft process technology is example, and most hemicellulose and lignin dissolution and are burnt in black liquor subsequently.
The separating technology scheme of many lignocellulosic materials that are used for production of cellulosic ethanol is all ignored other of xylogen may purposes, and just suggestion is burned its and reclaimed heat energy.These produce the pattern of single bulk product, owing to do not make full use of biomass material, a common characteristic are arranged, the non-constant of economic benefit.The biorefinery notion is an approach that gets a good chance of seemingly, makes the biomass industry have more commercial appeal.Be similar to refining of petroleum, biorefinery factory is a complex, and wherein biomass are processed, and classification transforms and produces a series of high value added product, and according to this notion, the combination of nearly all biomass obtains utilizing.
Therefore, need an easy industrialized technological process, can separate three main components of lignocellulose biomass separately.Simultaneously, be necessary to set up a perfect technological process, and available conventional equipment, extract hemicellulose, xylogen and the cellulosic component of high quality and high yield successively.
Especially be necessary to set up a kind of effective separation method, can reduce the degraded of hemicellulose and xylogen to greatest extent, and it is reclaimed with useful form.In addition, also needing a method that reclaims phenolic acids, mainly is forulic acid, as the joint product of high value.
Summary of the invention
Technical problem solved by the invention has provided the processing method of a multistage, can be with high efficiency single chemical composition, promptly high yield and highly purified hemicellulose, xylogen, Mierocrystalline cellulose and the phenolic acids of being separated into of lignocellulose.Another target of the present invention provides a kind of high-level efficiency and easy industrialized processing method, extracts high-quality hemicellulose from lignocellulose, and xylogen and Mierocrystalline cellulose simultaneously, reclaim these products to greatest extent and reduce their degraded.
Method of the present invention relates to lignocellulose-like biomass earlier with hot-water cure, this section handled and produced first liquid product and one first solid product that is rich in hemicellulose and phenolic acids, and first liquid product that then this is obtained separates with first solid product.
Second section processing is delignification.Above first solid product that obtains is resolved into one be rich in second liquid product of xylogen and second solid product of a rich cellulose.Then this second liquid product is separated with second solid product.
Between hot-water cure section and delignification's processing section, can optionally increase by one section enzyme and handle.First solid product that enzyme obtains more than handling and inciting somebody to action resolves into an enzyme hydrolyzate and first solid product that enzyme was handled that is rich in hemicellulose and phenolic acid.Then, first solid product that above-mentioned enzyme hydrolyzate and enzyme were handled is separated.The enzyme hydrolyzate and above-mentioned first liquid product are merged into bonded first liquid product.Next, this bonded first liquid product is separated into fraction that is rich in hemicellulose and the fraction that is rich in phenolic acid.
The hot-water cure section utilizes the aqueous solution of specific pH value and temperature that hemicellulose and phenolic acid are separated.Delignification's processing section can be dissolved in liquid phase with xylogen with the mixed solvent or the alkaline solution of organic solvent and water, and Mierocrystalline cellulose is stayed solid phase, and makes them obtain separating.It is to connect by means of one group of forulic acid that has synergistic enzyme optionally to disconnect between hemicellulose and the xylogen that enzyme is handled.
Second section of method of the present invention is that delignification handles.With organic solvent or alkaline solution lignin dissolution is come out to obtain to reclaim, Mierocrystalline cellulose is then stayed in the solid phase.Conventional solid separation method can be easy to dissolved xylogen and residual Mierocrystalline cellulose are separated, thereby reduces the loss of sepn process and improve xylogen and cellulosic productive rate.
The alternative enzyme that adds in this method is handled further advantage can be provided, and by means of the selectively acting of enzyme, separating of hemicellulose and xylogen can be more complete.Simultaneously, can adopt the processing condition of milder when hot-water cure and delignification's processing, therefore, the hemicellulose that obtains like this and the productive rate of lignin component are higher, more clean, and keep more original chemical structure.In addition, more the phenolic acid of volume, particularly forulic acid can discharge recovery then.
This shows no matter be first section or second section and handle liquid phase and the solid product that produces, can utilize existing liquid-solid isolation technique to separate effectively at an easy rate.Usually, liquid-solid isolation technique is to be easy in addition industrialization amplify.
Specifically, the present invention relates to a kind of xylogen, Mierocrystalline cellulose and hemicellulose of from lignocellulose-like biomass, extracting simultaneously, and reclaim the method for phenolic acid, specifically comprise the steps:
A) lignocellulose-like biomass is used hot-water cure, produced first liquid product and one first solid product that is rich in hemicellulose and phenolic acid;
B) this first liquid product and first solid product are separated;
C) first liquid product is separated into fraction that is rich in hemicellulose and the fraction that is rich in phenolic acid;
D) first solid product is carried out delignification and handle, produce one and be rich in second liquid product of xylogen and second solid product of a rich cellulose; With
E) this second liquid product and second solid product are separated, obtained xylogen fraction and Mierocrystalline cellulose fraction.
In the method, the pH value of water is lower than 7 in the hot-water cure, and temperature about 100 is to about 220 ℃, and the time about 2 was to about 240 minutes.
In the method, the pH value can be regulated by adding acid, and this acid is optional from sulfuric acid, nitric acid, hydrochloric acid, one or more in phosphoric acid and the acetate; The pH value also can be regulated by adding alkali, and this alkali can be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, one or more in yellow soda ash and the sodium bicarbonate.
In the method, delignification handles and comprises the mixed solvent that adopts alkaline solution or organic solvent and water.Wherein alkali can be selected from sodium, potassium, ammonia, one or more in the oxyhydroxide of calcium; And organic solvent can be selected from a kind of lower fat family's alcohol or a kind of low fat aliphatic carboxylic acid or a kind of ketone.The temperature that delignification handles can be selected in 100 to 200 ℃ scope, but not above 220 ℃, temperature is preferably selected to about 200 ℃ scope at about 120 ℃, is preferably in about 140 ℃ and selects to about 180 ℃ scope, and the time can be about 30 minutes to about 6 hours scope; Delignification handles also and can carry out having under the condition of catalyzer, and this catalyzer can be selected from a kind of acid, as sulfuric acid, and hydrochloric acid and acetic acid, or a kind of alkali, as sodium hydroxide, or a kind of salt of neutral alkali earth metal, as sodium, magnesium, aluminium salt.
In the method, between handling, the delignification of first section hot-water cure and second section can also optionally add an enzyme treating processes, enzyme handle to adopt is one group synergistic enzyme, they take effect as the leading factor with feruloyl esterase, add in xylosidase, arabinase or the polygalacturonase one or more again and play synergy, the pH value scope that enzyme is handled is 3 to 10, preferably 4 to 6, temperature range can from 30 to 80 ℃, be preferably in 40 to 60 ℃, treatment time is about 2 hours to about 72 hours, preferably about 12 hours to about 48 hours.
This method both can be that gap operating technology also can be continous way operating procedure or semi continuous operation technology.
It is in order to improve the extraction yield of hemicellulose to greatest extent, to reduce the dissolving of xylogen simultaneously as far as possible that the processing parameter of hot-water cure is selected.It is in order to extract xylogen to greatest extent that delignification handles, and separated fiber element simultaneously.For the technology that has the stage casing enzyme to handle, can before delignification's processing section, obtain hemicellulose extraction more completely, and reduce deviating from of xylogen.
The processing parameter of hot-water cure comprises the pH value of water, temperature and time.These are the structural units of the sugar of some different chain length from the hemicellulose component that lignocellulose biomass is soluble in the aqueous phase, and comprise monomer, oligomer and polymkeric substance (being monose, oligose and polyose).The processing parameter of hot-water cure has not only determined the sugared rate of recovery, and has determined their structure formation.
Hot-water cure relates to difference but additional mutually mechanism comprises dissolving and hydrolysis. and each mechanism depends on the processing parameter that is adopted to a great extent to effect and contribution that hemicellulose extracts.The processing parameter of hot-water cure section can have very big range of choice, can make technology of the present invention be applicable to as previously described various lignocellulose biomass raw materials like this, but and the sugar of production particular demands or hemicellulose unit.
The pH of hot-water cure section can from 1 to 7, and it can be mineral acid or organic acid by adding acid or alkali is regulated.Mineral acid comprises any carbon atom acid that do not contain, as sulfuric acid, and nitric acid, hydrochloric acid and phosphoric acid.Organic acid can comprise any one or more carbon atom acid that contain, such as acetate and carboxylic-acid.Alkali include but not limited to, alkali-metal oxyhydroxide or carbonate, and as sodium hydroxide, potassium hydroxide, calcium hydroxide and yellow soda ash.
Hot-water cure also can be finished by autocatalytic mode.Because contain spontaneous catalyzer in this process, need not add catalyzer.For example, in the hot-water cure process, the acetate that discharges on the hemicellulose, but its hydrolysis of catalysis and solubilizing reaction.
Can affirm that the pH value is formed with structure formation and played great function for the yield of the hemicellulose that reclaims.For example, in the scope of pH value from 1 to 4, acid hydrolysis is a prevailing reaction mechanism, and promptly principal product is the monose of hemicellulose.When producing the hemicellulose product of oligose if desired, hot-water cure is preferably carried out under slightly acidic condition, and promptly the pH value is in 5 to 7 scopes.
In used lignocellulose-like biomass, some raw material has self-surge capability, and also some lignocellulose raw material is slight alkalinity natively.These features that exist naturally can be brought some technologic advantages, make hot-water cure oversimplify and low-cost, because very little or do not regulate the extra needs of pH value.
The sugar chain of hemicellulose can be by the cracking that is used for of certain enzyme.Similar with above-mentioned acid hydrolysis, the hydrolysis reaction of enzyme guiding strips down sugar unit from the hemicellulose chain gradually, and is dissolved into aqueous phase.These enzymes can be optionally on the hemicellulose chain certain specific position react, therefore, can produce the hemicellulose product of special procuring sugar chain length.
Therefore, adopt one group to have synergistic enzyme processing to play supplementary function to hot-water cure.Because it is optionally that enzyme is handled, and carries out under relatively mild condition, this can bring many advantages.At first, can adopt relatively mild processing condition, only need open up passage in the enzyme processing that the easily molten hemicellulose of this section stripping water reaches below being in the hot-water cure section.Because mild condition no matter be the degraded of hemicellulose, or the stripping of xylogen all can reduce to minimum.The second, in delignification's stage, can extract more and purer xylogen.The 3rd, more phenolic acid can discharge and obtain to reclaim.Add together, can be with biomass with higher yield and purity separation and Extraction hemicellulose, phenolic acid, xylogen and Mierocrystalline cellulose.
The hot-water cure temperature of lignocellulose biomass is preferably in 100 to 220 ℃ scope.Temperature controlled mode can be used the heating and the monitoring equipment of standard, as the electrically heated that people are familiar with, and decatize or microwave heating.
The time of hot-water cure comprises heating-up time and soaking time two parts, and it is the biomass material kind used according to hot-water cure, temperature and other factors and decide.Generally speaking, extraction yield that adequate time reaches hemicellulose offer 50% (accounting for the total amount in the raw material) at least be arranged, preferably reach about 80% (accounting for the total amount in the raw material), and the stripping quantity of xylogen surpass about 10% (accounting for the total amount in the raw material).
The Best Times scope of hot-water cure is that temperature and time often can exchange at about about 2 minutes to 4 hours, and as general rule, comparatively high temps preferably combines with the short period, and is perhaps opposite.
In some cases, can adopt slowly the hot-water cure thing is heated to desired temperature, then, immediately with its cooling (hot water is handled does not have soak at the top temperature place).Under other situation,, the hot-water cure thing need be incubated for some time in top temperature in order to make the variation that on biomass material, obtains anticipation.
The carrying out of hot-water cure needs to select and above these processing parameters are carried out suitable cooperation.For instance, when adopting comparatively high temps, the extraction of hemicellulose will cooperate with solutions of weak acidity and short reaction times.More than these processing parameters be fit to the combination of the higher limit of scope, promptly high temperature adds long-time and strong acidic condition, and is normally worthless.Because under such condition, the possibility of Mierocrystalline cellulose and the unnecessary degraded of xylogen in the lignocellulosic material will appear.Under this condition, the degraded that the hemicellulose component that obtains also can be subjected to a certain degree destroys.Certainly, the top temperature in the appropriate value scope can be used for the hydrolysis of hemicellulose when near neutral, does not promptly add the reaction conditions of acid.The hot-water cure section can comprise a mixing step, but this is not the key of this technology.Any suitable mixing machinery device can use, and is a kind of general knowledge for the professional person of this technical field.
Enzyme is handled to relate to and is used at least a enzyme to include but not limited to feruloyl esterase, xylosidase, arabinase and polygalacturonase.The pH value scope that enzyme is handled is 3 to 10, preferably 4 to 6.Temperature range can from 30 to 80 ℃, are preferably in 40 to 60 ℃.Treatment time is about 2 hours to about 72 hours, preferably about 12 hours to about 48 hours.
It can be alkaline process or organic solvent method or their combination that delignification handles.The target that this delignification's processing section will reach is the extraction yield offer 80% (accounting for the total amount in the raw material) at least of xylogen, preferably reaches about 90% (accounting for the total amount in the raw material).Alkaline process delignification handles and carries out in alkaline solution, and selected processing parameter comprises basicity, temperature, time and liquid-solid ratio.Alkali include but not limited to, alkali-metal oxyhydroxide or carbonate, and as sodium hydroxide, potassium hydroxide, calcium hydroxide and yellow soda ash.
Alkaline process delignification treatment temp can be selected in 100 to 200 ℃ scope, but does not surpass 220 ℃, and temperature is more preferably at about 120 ℃ and selects to about 200 ℃ scope, is preferably in about 140 ℃ and selects to about 180 ℃ scope.
The time that alkaline process delignification handles can be about 30 minutes to about 6 hours scope.
Organic solvent method delignification handles and can carry out in the mixed solvent of organic solvent and water, and the processing parameter of selection comprises temperature, time, pH value, the ratio of solvent-water and liquid-solid ratio.
Organic solvent include but not limited to, alcohols, organic acid and ketone.Alcohols can be selected from methyl alcohol, ethanol, propyl alcohol, butanols and ethylene glycol.Optional formic acid of organic acid and acetate.Ketone include but not limited to, acetone.
The ratio of organic solvent-water can be in the scope of about 10% (by weight) to anhydrous solvent.Yet its better scope is that about 40% (calculating by weight) is to about 60% (calculating by weight).
Organic solvent method delignification treatment temp can be selected in 100 to 200 ℃ scope, but does not surpass 220 ℃, and temperature is more preferably at about 120 ℃ and selects to about 200 ℃ scope, is preferably in about 140 ℃ and selects to about 180 ℃ scope.The time that organic solvent method delignification handles can be about 30 minutes to about 6 hours scope.
This organic solvent method delignification handles and can carry out having under the condition of catalyzer.The available catalyzer comprises inorganic and organic acid, as sulfuric acid, and hydrochloric acid and acetic acid.Alkali also can be used as catalyzer, as sodium hydroxide.In addition, the salt of neutral alkali earth metal, as sodium, magnesium, aluminium salt also can be used as catalyzer.
This organic solvent method delignification handles and also can finish by autocatalytic mode.Because contain spontaneous catalyzer in this process, as acetate, so need not add catalyzer.
Fig. 1 has shown an embodiment of the invention, and it comprises in the mode of multistage and separating in order, produces each liquid, solid product.First section of treatment of lignocellulosic biomass is that it is carried out hot-water cure, and its pH value of aqueous solution is lower than 7.About 100 to 220 ℃ of temperature, about 2 to 240 minutes of time.Regulate the sour optional of pH value from sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and acetate, the alkali of regulating the pH value can be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash and sodium bicarbonate.
Another embodiment of the invention is, preferably before hot-water cure, biomass material carried out pre-treatment, i.e. the mechanical disintegration of raw material, and as grinding, cutting, crushing or pulverize.
Before hot-water cure preferably stops at lignin dissolution significantly and begins a bit on, this section processing is to specify to be used for extracting the easily molten hemicellulose of water and to improve that lignocellulosic material is handled by enzyme subsequently and the easy degree of delignification's processing.
Hot-water cure produces one first liquid product and one first solid product, then, adopts solid separation method with this two-phase product separately, and first liquid product is made up of hemicellulose and phenolic acid.
A better implement mode of the present invention is, the hot-water cure section is before delignification's processing section, and then one section enzyme is handled, this stage casing is handled the hot-water cure section is played supplementary function, by optionally cutting off the connection of hemicellulose and xylogen, remaining hemicellulose in the biomass is separated.The kind that this enzyme is handled biomass is targetedly, employing be one group synergistic enzyme arranged that they include, but are not limited to feruloyl esterase, xylosidase, arabinase and polygalacturonase.Enzyme is handled and is produced an enzyme hydrolyzate and first solid product that enzyme was handled that is rich in hemicellulose and phenolic acid.Then, adopt solid separation method with this two-phase product separately, first solid product that this enzyme hydrolyzate and enzyme were handled is separated.
This enzyme hydrolyzate and above first liquid product merge into bonded first liquid product.Next, adopt the liquid liquid separating method that this bonded first liquid product is separated into fraction that is rich in hemicellulose and the fraction that is rich in phenolic acid.Separating this two fraction can be with the liquid liquid isolation technique of any routine, and these technology include but not limited to, organic solvent extraction, membrane sepn, chromatogram and absorption.As shown in Figure 1, this hemicellulose and phenolic acids can adopt existing technology further to process as required.First solid product that first solid product of this technological process or enzyme were handled will carry out delignification to be handled, and alkali is a kind of common chemical that is used for dissolving xylogen in the biomass, and this delignification method extensively is used in pulp and paper industry.The source of alkali can be a sodium, potassium, ammonia, the oxyhydroxide of calcium.
Another kind of delignification method is that organic solvent is handled used organic solvent and preferably a kind of lower fat of the organic solvent in water mixed solvent family's alcohol or low fat aliphatic carboxylic acid or a kind of ketone.The organic solvent that adds delignification's processing section can reclaim and but recirculation is used, and its method can be the technology that any this technical field professional person is familiar with, for example flash distillation and distillation.
This delignification's processing section produces one and is rich in second liquid product of xylogen and second solid product of a rich cellulose.The characteristics of xylogen are that it is that a hydrophobic polymer and its solubleness also are that pH is dependent.Therefore, the xylogen in second liquid phase is easy to precipitatedly come out to reclaim.Handle for the alkaline process delignification, the pH value of this liquid phase can be reduced (for example, by adding acid or carbon dioxide).For organic solvent method delignification, the organic solvent in this liquid phase can be removed or thin up.Xylogen that reclaims and Mierocrystalline cellulose can adopt existing technology to do further processing as required.
Separate the liquid-solid isolation technique that these liquid phases and solid product can be familiar with any this technical field professional person, for example those all can be used for this in the used technology of biomass and fiber process and separate purpose, comprise filtering and centrifugal.
This technological process can the gap, and continuous or semi-continuous mode operates, and these function modes are widely used in biomass and fiber process industry.
With the gap operating is example, and hot-water cure is handled and can be carried out at same reactor or two different reactors with delignification.The liquid mixing of biomass material and capacity promptly is respectively liquid and delignified alkaline solution or the organic solvent and the water mixed solvent of hot-water cure.This liquid-solid mixture is remained on certain pH value, temperature and required time, after finishing, carry out liquid-solid phase and separate, to reclaim hemicellulose, phenolic acid, xylogen and Mierocrystalline cellulose.
If the continous way operation, hot-water cure and delignification handle and can or carry out in two independent reactors at the single reaction vessel that two reaction zones are arranged.Biomass material is to add reactor with a direction, and simultaneously, liquid-flow is in the opposite direction, and this countercurrent mode is well-known technology to the professional person of this technical field.
When semi continuous operation, earlier biomass material is contained in the column reactor, and heating.At first processing section, the liquid of hot-water cure adds in the reactor with pump earlier through preheating, and the liquid of this hot-water cure carries out contacting of certain hour with biomass material, produces a liquid stream that is rich in hemicellulose.At second processing section, delignified alkali lye or organic solvent and water mixed solvent add in the reactor through preheating, produce a liquid stream that is rich in xylogen.This liquid flow point that is rich in hemicellulose and xylogen does not obtain reclaiming, the solid residue in the reactor, i.e. cellulosic component.
No matter be any operating method, optionally the stage casing enzyme is handled to be preferably in the independent reactor and is carried out.Any equipment that is suitable for enzymic hydrolysis and processing can use, and is a kind of general knowledge for the professional person of this technical field.
According to processing method provided by the invention, at first hemicellulose is separated from lignocellulose biomass, then, carry out delignification and handle and extract xylogen and Mierocrystalline cellulose.The chemical structure of hemicellulose has been protected in a kind of like this technological design effectively, compares with Mierocrystalline cellulose with xylogen, and the easier chemical degradation that is subjected to of hemicellulose destroys.In addition,, make hemicellulose not experience all chemical treatments in the whole technological process, therefore, reduce its degraded and unnecessary byproduct to greatest extent and produce also just because of such design.Processing method provided by the invention can gap operating or operate continuously or semi continuous operation, and the product of producing can be used to deep processing and becomes a series of high value-added products.Because hemicellulose destroys than xylogen and the easier chemical degradation that is subjected to of Mierocrystalline cellulose, this technology is separated the hemicellulose component at first section from lignocellulose biomass, the hemicellulose component reclaims with liquid product, separates with solid phase before delignification's processing section.Therefore, hemicellulose does not experience all chemical treatments in the whole technological process, reduces its degraded and unnecessary byproduct to greatest extent and produces.The product that this processing method is produced, i.e. hemicellulose, phenolic acid, xylogen and Mierocrystalline cellulose can be widely used as and produce various fuel, chemical industry, the industrial raw material of the material and the energy.
Description of drawings
Fig. 1 is the process flow diagram of one embodiment of the present invention.
Embodiment
For the ease of understanding and cognition the present invention, existing some first-selected embodiment to it is described.It will be understood that, only be the description of carrying out preferred embodiment here.The professional person of association area of the present invention may make amendment and further utilization to these embodiments, but all such modifications and utilization all will be to belong to a part of the present invention.
Embodiment 1
The corn stalk raw materials stainless steel pressure reactor (capacity is 1 liter) of packing into of 80 gram (oven-dry weight) air-dry pulverizing adds 800 milliliters deionized water.Begin to stir and heating, with the rate of heating that pre-sets, in 30 minutes, reactor is risen to 180 degrees centigrade from room temperature, and 180 degrees centigrade of insulations 30 minutes, use reactor inner coil refrigerating unit then, the temperature of reactor is dropped to rapidly about 50 degrees centigrade, open reactor, to carry out liquid-solid separation in reactant transfer to a funnel, and with hot wash fiber solid substance for several times.Reclaim all filtrate and fiber solid substance, the Chemical Composition analysis is done in record total amount and sampling separately.
Get fiber solid substance that 50 grams obtain more than (oven-dry weight) and pack in the identical reactor, (15% concentration is with NH to add 500 milliliters solution of ammonium hydroxide
3The weight meter), be heated to 170 degrees centigrade by same mode, and 170 degrees centigrade of insulations 60 minutes.After reaction finishes, fiber remnants earlier once with the diluted sodium hydroxide solution washing, then for several times with hot wash, the product weighing that obtains and do the Chemical Composition analysis.
The hemicellulose sugar of first section dissolved in filtrate (xylan and arabinan) be in the raw material total amount 83%, second section xylogen of handling stripping be in the raw material total amount 81%, fiber remnants after second section processing is carried out enzymic hydrolysis, and the transformation efficiency of glucose is 95%.
Embodiment 2
Reaction unit is identical with example 1 with working method.
Raw material is the wheat straw bar
First section processing: identical with example 1
Second section processing: be to add 1% sulfuric acid (in the weight of raw material) with 50% aqueous ethanolic solution, 170 degrees centigrade of soaking times are 30 minutes.
The dissolved hemicellulose is about 70% of a total amount in the raw material in first section hydrolyzed solution.
The xylogen that reclaims in second section treatment solution accounts for about 75% of total amount in the raw material.
It is 96% that second section fiber remnants that processing obtains, enzymic hydrolysis become the transformation efficiency of glucose
Embodiment 3
Reaction unit is identical with example 1 with working method.
Raw material is the wheat straw bar.
First section processing: 0.5N aqueous sulfuric acid, 100 degrees centigrade, 60 minutes.
Second section processing: 75% aqueous ethanolic solution (1N sulfuric acid concentration), 120 degrees centigrade, 90 minutes.
First section processing obtains 72% hemicellulose.
Second section processing obtains the Mierocrystalline cellulose of 69% xylogen and 97%.
Embodiment 4
By the continuous reaction apparatus of two helical reactors series combinations, throughput is 100 kilograms of raw material treatment capacities every day.The raw material of this test is the wheat straw stalk.
First section processing (hot water processing) is to carry out in a double-helical reactor, the ratio of water and wheat straw stalk raw material is 6:1 (weight), water and wheat straw stalk raw material are countercurrent flow in reactor, and temperature of reaction is 195 degrees centigrade, and the time that solid phase stops in reactor is 5 minutes.Hemicellulose accounts for 62% of former total amount in the liquid product that this section processing is reclaimed.
Second section processing (being that delignification handles) is to carry out in a single-screw reactor, the ratio of alkali lye and solid phase is 6:1 (weight), liquid-solid is coflow in reactor, sodium hydroxide concentration is 10% (in over dry wheat straw stalk weight), temperature of reaction is 195 degrees centigrade, and the residence time of solid phase in reactor is 15 minutes.The lignin recovery rate (liquid product) of this section processing is more than 80%, and the rate of recovery of Mierocrystalline cellulose (solid product) surpasses 86%.
Embodiment 5
Semi-continuous reactor thereof, raw material are poplars.
Reactor capacity is 100 milliliters, in adorn the poplar sheet of 10 grams (oven-dry weight), the preheating of treatment solution elder generation is gone in the reactor with infusion, the liquid that flows out from reactor reclaims after heat exchanger cooling.
First section is hot water extraction, and temperature is 180 degrees centigrade, and the time is 30 minutes.Subsequently, change with second section treatment solution (60% aqueous ethanolic solution, 1.25% sulfuric acid), temperature is 170 degrees centigrade, and the time is 120 minutes.
The extraction yield that first section hemicellulose productive rate that extracts is 90%, the second section xylogen is 85%.After two sections processing, the Mierocrystalline cellulose residue is through enzymic hydrolysis, and the rate of recovery of its glucose is 86%.
Embodiment 6
Reaction unit is identical with example 5, and raw material is a falx straw.
First section hot-water cure temperature is 150 degrees centigrade, and the time is 15 minutes.The hemicellulose of this section stripping accounts for 50% of former total amount.The condition that the stage casing enzyme is handled: the ferulic acid ester enzyme dosage is 20 unit of enzyme/gram raw material, and the xylosidase consumption is 4 unit of enzyme/gram raw material, and temperature is 50 degrees centigrade, pH5, and the time is 18 hours.
This section stripping 80% forulic acid and 40% hemicellulose (accounting for former total amount).
Second section processing (being delignification) is identical with example 5.The extraction yield of xylogen and cellulosic extraction yield all surpass 90%.
The explanation of used definition herein:
Term herein " gap operating " is meant a technological process, and its biomass are to pack into before reaction beginning in the container, and just remove when finishing, in whole process, with the exchange of surrounding environment without any material.
Term herein " operate continuously " is meant a technological process, and its biomass flow in whole process and flow out.
Term herein " catalyzer " is meant a kind of chemical substance, and its add-on is compared seldom with biomass material, and its effect is the chemical reaction velocity that changes or improve these biomass, and self is not consumed during the course.
Claims (11)
1. the method extracting hemicellulose, Mierocrystalline cellulose and xylogen simultaneously and reclaim phenolic acid from lignocellulose-like biomass is characterized in that: comprise the steps:
A) lignocellulose-like biomass is used hot-water cure, produced first liquid product and one first solid product that is rich in hemicellulose and phenolic acid, wherein the pH value of water is lower than 7 in the hot-water cure, 100 to 220 ℃ of temperature, 2 to 240 minutes time;
B) this first liquid product and first solid product are separated;
C) first solid product that obtains more than the general adds the feruloyl esterase processing, one or more that adopt xylosidase, arabinase or polygalacturonase are simultaneously handled, produce an enzyme hydrolyzate and first solid product that enzyme was handled that is rich in hemicellulose and phenolic acid, wherein the pH value scope of enzyme processing is 3 to 10, the temperature that enzyme is handled is at 30 ℃ to 80 ℃, and the time that enzyme is handled is 2 hours to 72 hours;
D) first solid product that the enzyme hydrolyzate that obtains and enzyme were handled is separated;
E) enzyme hydrolyzate and above-mentioned first liquid product are merged into bonded first liquid product;
F) bonded first liquid product is separated into fraction that is rich in hemicellulose and the fraction that is rich in phenolic acid;
G) first solid product of enzyme being handled carries out delignification to be handled, and wherein delignification handles the mixed solvent that adopts alkaline solution or organic solvent and water, and temperature is at 100 to 200 ℃, and the time was at 30 minutes to 6 hours; Produce one and be rich in second liquid product of xylogen and second solid product of a rich cellulose; With
H) this second liquid product and second solid product are separated, obtained xylogen fraction and Mierocrystalline cellulose fraction.
2. method according to claim 1, wherein the pH value scope of enzyme processing is 4 to 6.
3. method according to claim 1, wherein the temperature of enzyme processing is at 40 ℃ to 60 ℃.
4. method according to claim 1, wherein the time of enzyme processing is 12 hours to 48 hours.
5. method according to claim 1, its technological process are interval type or continous way or semi continuous.
6. method according to claim 1 wherein before hot-water cure, is ground lignocellulose biomass, cutting, crushing or the pre-treatment of pulverizing.
7. method according to claim 1, wherein the temperature of delignification's processing is in 120 ℃ to 200 ℃ scope.
8. method according to claim 7, wherein the temperature of delignification's processing is in 140 ℃ to 180 ℃ scope.
9. method according to claim 1, organic solvent wherein are selected from a kind of lower fat family's alcohol or a kind of low fat aliphatic carboxylic acid or a kind of ketone.
10. method according to claim 9, in the organic solvent wherein and the mixed solvent of water, the shared part by weight of organic solvent is 10% to 100%.
11. method according to claim 10, in the organic solvent wherein and the mixed solvent of water, the shared part by weight of organic solvent is 40% to 60%.
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