CN101121735A - Plant fibre raw material hydrolysis solution and method for preprocessing plant fibre raw material using the same - Google Patents
Plant fibre raw material hydrolysis solution and method for preprocessing plant fibre raw material using the same Download PDFInfo
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- CN101121735A CN101121735A CNA2007100290540A CN200710029054A CN101121735A CN 101121735 A CN101121735 A CN 101121735A CN A2007100290540 A CNA2007100290540 A CN A2007100290540A CN 200710029054 A CN200710029054 A CN 200710029054A CN 101121735 A CN101121735 A CN 101121735A
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Abstract
The invention relates to a preparation method of the pentosan and organic lignin through the pretreatment of the raw material plant fiber. The invention uses the hydrolyzation solution made of the organic solvent, acid and aqueous solution; the hydrolysis of the hemicellulose and the dissolution of the lignin are combined in one technological process. The invention can nearly extract all the hemicellulose under the mild conditions and do the hydrolysis towards the hemicellulose to be the pentosan-based single sugar; at the same time, most of the lignin can be dissolved out to be the organic lignin soluble in the organic solvent; the left is basically separated to be the single-fibrous material with the cellulose as the main material.
Description
Technical field
The invention belongs to chemical field, is the method that the pre-treatment of a plant fiber raw material prepares pentose and organosolv lignin specifically.
Background technology
Plant fiber material is the very abundant renewable resources of occurring in nature, if plant fiber material can well be utilized, that will reduce the cost of industrial chemicals to a great extent.Yet up to now, people are but very insufficient to the utilization of plant fiber material.This is because main component Mierocrystalline cellulose, hemicellulose and xylogen in the plant fiber material are closely linked, and its processing characteristics is also poor.Cellulosic melt temperature is higher than decomposition temperature, does not also possess solvability and flowability so be heated to decomposition.Utilize plant fiber material just to need certain preprocessing process, whole hemicelluloses in the plant fiber material and part or all of xylogen and Mierocrystalline cellulose are separated, and make hydrolysis of hemicellulose become monose based on pentose, make remaining Mierocrystalline cellulose become a kind of short texture and be easy to, thereby realize the complete utilization of biomass by the material of acid or the quick hydrolysis of enzyme.
In recent years, the pretreatment process of plant material is mainly contained: the first, the diluted alkaline method: the dilute alkaline soln with heat can remove part xylogen and hemicellulose.But hot alkali treatment can cause the peeling reaction of Mierocrystalline cellulose and hemicellulose, reduce the reducing sugar yield, and need a large amount of water to come washing material after the alkaline purification, the hemicellulose that extracts also needs to be hydrolyzed again with diluted acid and just can obtain pentose, alkaline purification also makes gained liquid glucose color burn, has increased the aftertreatment cost.The second, diluted acid method: with the rare HCl or the H of heat
2SO
4Solution can be dissolved out the most hemicelluloses in the plant fiber material, and technology commonly used has two kinds, and one is not for being higher than 125 ℃ of down long-time insulations, and advantage is that the five-carbon sugar that hydrolysis obtains seldom is hydrolyzed into furfural, but can't extract xylogen; It two is an isothermal treatment for short time under 180 ℃～200 ℃ high temperature, and advantage is that speed is fast, but high temperature can make five-carbon sugar resolve into furfural, thereby the reducing sugar yield is reduced and also can't come out lignin extraction.The 3rd, organic solvent method: utilize organic solvent such as alcohols, ketone, phenols, DMSO, amine, carboxylic acid etc. to handle 1～2 hour down at 160～200 ℃, can be dissolved out most of xylogen and hemicellulose, but this method need be carried out under High Temperature High Pressure, high temperature can cause pentose to resolve into furfural and make the reducing sugar yield very low, and is also high to equipment requirements.The 4th: this method of steam explosion is isothermal treatment for short time moment pressure release then under the condition about 200 ℃, can be dissociated into single fiber to plant fiber material substantially, and simultaneously the carbohydrate of hydrolysis of hemicellulose one-tenth based on oligosaccharides, but the stripping of xylogen is less.Except these use the method for hydrolysis of mixed solvent in addition, as the quick hydrolysis process of the Dedini of Brazil (DHR method), but because this method is to use high-temperature and high-pressure conditions hydrolyzed hemicellulose and Mierocrystalline cellulose simultaneously, can make pentose be divided into furfural inevitably and hexose resolves into 5 hydroxymethyl furfural, make the reducing sugar yield lower, do not used so this method promotes.
Summary of the invention
In order to overcome the deficiency of above-mentioned plant fiber material pretreatment process, the invention provides the hydrolyzed solution of a plant fiber raw material and with the raw material pretreated method of this hydrolyzed solution.
For achieving the above object, plant fiber material hydrolyzed solution provided by the invention, described hydrolyzed solution comprise following component and content (weight) thereof:
Mineral acid: 0.5%～25%,
Alcohols: 30%～65%,
Water: surplus;
Perhaps, mineral acid: 0.5%～25%,
Ethers, ketone or carboxylic-acid or their mixtures (I): 30%～99%,
Water: 0.5%～69.5%;
Perhaps, mineral acid 0.5%～25%,
Alcohols and mixture (II) 30%～99% (I),
Water: 0.5%～69.5%,
Wherein the content (weight) of alcohols is not higher than 65% in (II).
Described mineral acid among the present invention is HCl or H
2SO
4Described alcohols comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol.Described ethers comprises tetrahydrofuran (THF), 1,4-dioxane, 1,3-dioxolane, 1,3-diox.Described ketone is an acetone.Described carboxylic-acid comprises formic acid, acetate, propionic acid.
Raw material pretreated method provided by the invention may further comprise the steps:
(1) get the raw materials ready, plant fiber material is cut into fines after, drying, standby;
(2) hydrolysis places the described hydrolyzed solution of claim 1 to the raw material handled well in (1) step, and reaction is 15 minutes～24 hours under 40 ℃～125 ℃ temperature;
(3) separate,, obtain Mierocrystalline cellulose filter residue and filtrate A the solution solid-liquid separation that step (2) obtains;
(4) precipitation, the xylogen among the precipitation filtrate A, solid-liquid separation obtains xylogen precipitation and liquor B;
(5) distillation, the distillation liquor B is not contained the liquid glucose of organic solvent up to organic solvent is all evaporated.
Wherein, when using H
2SO
4During as mineral acid preparation hydrolyzed solution, gained filtrate A CaCO
3Neutralize, filter, do not contained H
2SO
4Filtrate A.When with HCl during as mineral acid preparation hydrolyzed solution, the gained liquid glucose is with alkali or CaCO
3The residual HCl that neutralizes is not contained the liquid glucose of mineral acid.
In a specific embodiment of the raw material pretreated method of the present invention, the method of precipitation xylogen is in the described step (4): add an amount of water in filtrate A the concentration of organic solvent is reduced in the time of can not dissolving organosolv lignin again, make xylogen form precipitation; Perhaps, when using the hydrolyzed solution of higher water content, can the organic solvent concentration of filtrate A be reduced by distillation, xylogen be precipitated out because of solubleness reduces; But when using the hydrolyzed solution of lower water content, after filtrate A is distilled to a certain degree, add an amount of water, xylogen is precipitated out because of solubleness reduces to reduce organic solvent concentration.
If it is described plant fiber material is a wood material, after described wood material cuts into fines, after handling through steam explosion again, dry again; If described plant fiber material is the herbaceous stem raw material, after described herbaceous stem raw material cut into fines, convection drying was handled.
As an embodiment of the raw material pretreated method of the present invention, the filter residue that obtains in the step (3) washs with the mixed solution of above-mentioned organic solvent that does not contain mineral acid and water, and the washings of gained is used to prepare hydrolyzed solution, so that recycle.
As another embodiment of the raw material pretreated method of the present invention, the xylogen precipitation that obtains in the described step (4) washes with water, and distillation gained washings is so that recovery organic solvent wherein.
Raw material pretreated method of the present invention, after in dilute acid hydrolysis liquid, adding organic solvent, the hydrolysis of hemicellulose can promote the dissolving of xylogen, and the dissolving of xylogen can promote the hydrolysis of hemicellulose conversely, this stripping of mutually promoting can reach the purpose that reduces temperature of reaction or reduce the reaction times, thereby cut down the consumption of energy, the yield of pentose is improved, reduce cost; Handling sponge with organic solvent-acid-aqueous solution on the other hand can come out hemicellulose and lignin extraction simultaneously, except can obtaining two kinds of products of pentose and organosolv lignin, can also obtain the Mierocrystalline cellulose of the single fiber shape of short texture, its structure becomes loose, more help follow-up cellulosic enzyme or acid hydrolysis, particularly to the cellulosic acid hydrolysis, not only can reduce the condensation of sugar and xylogen, and significantly reducing of xylogen can also significantly reduce the dark matter that generates because of the xylogen acidolysis, thereby reduce the processing cost of liquid glucose; Also have, because temperature of reaction is lower, reaction conditions is gentle and the effect of organic solvent, xylogen is gone up substantially solvency action is only taken place, and Decomposition does not take place substantially, make the very slight color of gained pentose solution, can decolour and just can ferment or be further purified preparation wood sugar or Xylitol, so just reduce the processing cost of liquid glucose.Pentose is separated separately, thereby can be fermented separately, so just can avoid the yeast problem of ferment pentoses and hexose simultaneously; Organosolv lignin is because the xylogen that extracts than additive method has higher reactive behavior, and can be dissolved in organic solvent, so have purposes widely.
Description of drawings
Fig. 1 is the schema of the raw material pretreated method of the present invention;
Fig. 2 is the schema of a preferred embodiment of the raw material pretreated method of the present invention.
Embodiment
As shown in Figure 1, be the schema of raw material pretreated method of the present invention, its basic procedure is:
(1) get the raw materials ready, plant fiber material is cut into fines after, drying, standby;
(2) hydrolysis places the described hydrolyzed solution of claim 1 to the raw material handled well in (1) step, and reaction is 15 minutes～24 hours under 40 ℃～125 ℃ temperature;
(3) solid-liquid separation obtains fibrous filter residue and filtrate A;
(4) precipitation, the xylogen among the precipitation filtrate A, solid-liquid separation obtains xylogen precipitation and liquor B then;
(5) distillation, the distillation liquor B is not contained the liquid glucose of organic solvent up to organic solvent is all evaporated.
Fig. 2 is the schema of a preferred embodiment of raw material pretreated method of the present invention, and its detailed process is:
(1) get the raw materials ready: highly lignified plant fiber material (as needlebush, leaf wood, bamboo wood, shell etc.) passes through the steam explosion processing again and becomes single fiber shape material substantially after cutting into fines, and the straw or like vegetable fibrous material cuts into fines; These raw material dryings to water content about 15%.
(2) the good raw material of drying is placed contain by mineral acid (HCl or H
2SO
4), in the hydrolyzed solution that is mixed with of organic solvent (dissolving each other) and water with water.Wherein the concentration of mineral acid (all by weight) is 0.5%～25.0%, when mineral acid is H
2SO
4The time, its concentration in hydrolyzed solution is preferably 0.5%～1 5.0%.
The alcohols that organic solvent comprises is a lower alcohol, comprise methyl alcohol, ethanol, n-propyl alcohol, Virahol, the tetrahydrofuran (THF) of ethers, 1,4-dioxane, 1,3-dioxolane, 1,3-diox, the acetone of ketone, carboxylic-acid are lower fatty acid such as formic acid, acetate, propionic acid and the mixture be made up of them.These organic solvents shared weight percent in hydrolyzed solution is:
Alcohols: 30.0%～65.0%, or
Ethers, ketone or carboxylic-acid or their mixtures (I): 30%～99%, or
Alcohols and mixture (II) (I): 30%～99%, wherein, (II) content (weight) of middle alcohols is not higher than 65%.
(3) hydrolysis 15 minutes～24 hours under 40 ℃～125 ℃ temperature, hydrolysis time is decided according to inorganic acid concentration in the hydrolyzed solution and hydrolysis temperature, and inorganic acid concentration is higher and the higher then time of hydrolysis temperature is shorter.
(4) stop heating after fully to hydrolysis of hemicellulose, carry out solid-liquid separation by press filtration, obtain filter residue and filtrate A, then while stirring with the above-mentioned organic solvent-solution washing filter residue that does not contain mineral acid, to pentose wash substantially fully come out till, filter residue is separated into the single fiber shape substantially after this handles, and can be used as enzyme or acid-hydrolyzed material after the drying.Washings is used to prepare the hydrolyzed solution of next batch.
(5) the filtrate A that comes out of press filtration can be recycled and reused for repeatedly hydrolysis, until reaching suitable pentose and lignin concentration.
(6) when using sulfuric acid, use CaCO as mineral acid
3Sulfuric acid among the neutralization filtrate A generates CaSO
4Precipitation removes by filter precipitation, is not contained H
2SO
4Filtrate A.
(7) intermediate processing of xylogen among the filtrate A: all be to utilize organosolv lignin to be not dissolved in the characteristic of water.
(I) method one: can add an amount of water in filtrate A the concentration of organic solvent is reduced in the time of can not dissolving organosolv lignin again, make xylogen form precipitation;
(II) method two: when using the hydrolyzed solution of higher water content, can the organic solvent concentration of filtrate A be reduced by distillation, xylogen be precipitated out because of solubleness reduces; But when using the hydrolyzed solution of lower water content, be distilled to a certain degree to filtrate A after, can add an amount of water to reduce organic solvent concentration, xylogen is precipitated out because of solubleness reduces.
(8) obtain xylogen precipitation and liquor B by solid-liquid separation, the xylogen precipitation washes after drying with water and promptly obtains the organosolv lignin crude product, and washings reclaims and distills out organic solvent to recycle.
(9) liquor B continues distillation up to organic solvent is all evaporated, and when using HCl as mineral acid, the major part of HCl also can be distilled out with organic solvent and water, is not contained the liquid glucose of organic solvent.
(10) when during as mineral acid, still containing residual section H Cl in the liquid glucose with HCl, can be with alkali or CaCO
3Handle and do not contained the liquid glucose of acid.
Embodiment one
Preparation 100g hydrolyzed solution also places the 500ml flask, wherein contains ethanol 65wt%, HCl 0.5wt%, and all the other are water.The straw that is cut into 2cm length by solid-to-liquid ratio L/S=10 adding 10.0g air-dry (moisture 15%) connects prolong, places 70 ℃ of water-baths to be incubated 6h.Behind the stopped reaction, it is 1.75g that sampling records reducing sugar, and yield is 20.59%.Press filtration obtains tawny filtrate A and filemot Mierocrystalline cellulose filter residue.Filtrate A continue to add straw by solid-to-liquid ratio L/S=10 and repeats hydrolysis 6 times, pentose and lignin concentration among the filtrate A that final press filtration obtains are improved greatly, and significantly improving of sugar concentration can reduce fermentation and extraction cost.Add the water of 1 times of weight in filtrate A, form filemot precipitation, filter, obtain xylogen filter residue and liquor B, the xylogen filter residue washes 3 after drying with water and promptly gets thick organosolv lignin.The Mierocrystalline cellulose filter residue washs 3 times with the 75wt% ethanolic soln, Mierocrystalline cellulose filter residue dehydration after drying after the washing promptly gets the Mierocrystalline cellulose filter residue that is dispersed into the single fiber shape substantially, color is light yellow, can be used as the raw material of enzymolysis or acidolysis, be used to prepare new hydrolyzed solution behind the vapor condensation that produces in the drying process with after washings mixes.Liquor B is a yellow solution, after ethanol and section H Cl are removed in distillation, uses CaCO again
3The remaining HCl of neutralization promptly gets the neutral liquid glucose, and distillation gained ethanol then recycles.
Embodiment two
Preparation 20g hydrolyzed solution also places the 200ml flask, wherein contains methyl alcohol 30wt%, H
2SO
425wt%, all the other are water.Add the tabernaemontanus bulrush grass that is cut into 2cm length of 2.0g air-dry (moisture 15%), connect prolong, place 50 ℃ of water-baths to be incubated 15h.Behind the stopped reaction, it is 0.39g that sampling records reducing sugar, and yield is 22.94%.Press filtration obtains tawny filtrate A and filemot Mierocrystalline cellulose filter residue.In filtrate A, add CaCO
3In and H
2SO
4, remove by filter the deposit C aSO of generation
4, gained filtrate is 55～60 ℃ of distillations down, after methanol concentration reduces, xylogen no longer dissolves and is precipitated out, filter, obtain xylogen filter residue and liquor B, the xylogen filter residue washes 3 after drying with water and promptly gets thick organosolv lignin 0.34g (moisture 15%) yield 17.0%.The Mierocrystalline cellulose filter residue washs 3 times with the 40wt% methanol solution, Mierocrystalline cellulose filter residue dehydration after drying after the washing promptly gets the Mierocrystalline cellulose filter residue that is dispersed into the single fiber shape substantially, color is a canescence, heavy 1.22g, yield 61.0%, can be used as enzymic hydrolysis or acid-hydrolyzed raw material, be used to prepare new hydrolyzed solution behind the vapor condensation that produces in the drying process with after washings mixes.Liquor B is a yellow solution, behind the continuation distillation for removing methanol, promptly gets the neutral liquid glucose, and distillation gained methanol loop is used.
Embodiment three
Preparation 20g hydrolyzed solution also places the 200ml flask, wherein contains acetate 99wt%, H
2SO
410wt%, all the other are water.Add the tabernaemontanus bulrush grass that is cut into 2cm length of 20.0g air-dry (moisture 15%), connect prolong, place 90 ℃ of water-baths to be incubated 2h.Behind the stopped reaction, press filtration obtains tawny filtrate A and filemot Mierocrystalline cellulose filter residue.In filtrate A, add CaCO
3In and H
2SO
4, remove by filter the deposit C aSO of generation
4, gained filtrate is 80～90 ℃ of distillations down, and after acetic acid concentration reduced, xylogen no longer dissolved and is precipitated out, and filtered, and obtained xylogen filter residue and liquor B, and the xylogen filter residue washes 3 after drying with water and promptly gets thick organosolv lignin.The Mierocrystalline cellulose filter residue washs 3 times with glacial acetic acid liquid, Mierocrystalline cellulose filter residue dehydration after drying after the washing promptly gets the Mierocrystalline cellulose filter residue that is divided into the single fiber shape substantially, color is a canescence, can be used as the raw material of enzymolysis, be used to prepare new hydrolyzed solution behind the vapor condensation that produces in the drying process with after washings mixes.Liquor B is a yellow solution, after acetate is removed in the continuation distillation, promptly gets the neutral liquid glucose, and distillation gained acetate then recycles.
Embodiment four
Preparation 20g hydrolyzed solution also places the 200ml flask, wherein contains tetrahydrofuran (THF) 80wt%, HCl 15wt%, and the tabernaemontanus bulrush grass that is cut into 2cm length of adding 2.0g air-dry (moisture 15%) connects prolong, places 125 ℃ of water-baths insulations 15 minutes.Behind the stopped reaction, it is 0.38g that sampling records reducing sugar, and yield is 22.35%.Press filtration obtains tawny filtrate A and filemot Mierocrystalline cellulose filter residue.Add the water of 2 times of weight in filtrate A, form cervine sinking to the bottom, filter, obtain xylogen filter residue and liquor B, the xylogen filter residue washes 3 after drying with water and promptly gets thick organosolv lignin 0.42g (moisture 15%), yield 21.0%.The Mierocrystalline cellulose filter residue washs 3 times with the 90wt% tetrahydrofuran solution, Mierocrystalline cellulose filter residue dehydration after drying after the washing promptly gets the Mierocrystalline cellulose filter residue that is dispersed into the single fiber shape substantially, color is a canescence, heavy 1.12g, yield 56.0%, can be used as enzymic hydrolysis or acid-hydrolyzed raw material, be used to prepare new hydrolyzed solution behind the vapor condensation that produces in the drying process with after washings mixes.Liquor B is a yellow solution, after tetrahydrofuran (THF) and section H Cl are removed in distillation, uses CaCO again
3The remaining HCl of neutralization promptly gets the neutral liquid glucose, and distillation gained tetrahydrofuran (THF) then recycles.
Embodiment five
Preparation 100g hydrolyzed solution also places the 500ml flask, wherein contain acetate 20wt%, acetone 40wt%, HCl 25wt%, the needlebush that cuts into fines (handling) that adds 10.0g air-dry (moisture 15%) by solid-to-liquid ratio L/S=10 through steam explosion, connect prolong, place 100 ℃ of water-baths to be incubated 1h.Behind the stopped reaction, press filtration obtains tawny filtrate A and filemot Mierocrystalline cellulose filter residue.Gained filtrate is distilled, when acid concentration is reduced to 50%, add the water of 1 times of amount, xylogen no longer dissolves and is precipitated out, and filters, and obtains xylogen filter residue and liquor B, and the xylogen filter residue washes 3 after drying with water and promptly gets thick organosolv lignin.The Mierocrystalline cellulose filter residue washs 3 times with the acetic acid solution of 30wt%, Mierocrystalline cellulose filter residue dehydration after drying after the washing promptly gets the Mierocrystalline cellulose filter residue that is divided into the single fiber shape substantially, color is a canescence, can be used as the raw material of enzymolysis, be used to prepare new hydrolyzed solution behind the vapor condensation that produces in the drying process with after washings mixes.Liquor B is a yellow solution, after acetate is removed in the continuation distillation, adds among the NaOH and residual HCl, promptly gets the neutral liquid glucose, and distillation institute acetate promptly can be recycled.
Embodiment six
Preparation 100g hydrolyzed solution also places the 500ml flask, wherein contain ethanol 60wt%, tetrahydrofuran (THF) 39wt%, HCl0.5wt%, water 0.5wt%, the needlebush that cuts into fines (handling) that adds 10.0g air-dry (moisture 15%) by solid-to-liquid ratio L/S=10 through steam explosion, connect prolong, place 40 ℃ of water-baths to be incubated 24h.Behind the stopped reaction, press filtration obtains tawny filtrate A and filemot Mierocrystalline cellulose filter residue.Gained filtrate is distilled, when acid concentration is reduced to 50%, add the water of 1 times of amount, xylogen no longer dissolves and is precipitated out, and filters, and obtains xylogen filter residue and liquor B, and the xylogen filter residue washes 3 after drying with water and promptly gets thick organosolv lignin.The mixed solvent that the Mierocrystalline cellulose filter residue is formed with 70wt% ethanol and 50wt% tetrahydrofuran (THF) washs 3 times, Mierocrystalline cellulose filter residue dehydration after drying after the washing promptly gets the Mierocrystalline cellulose filter residue that is divided into the single fiber shape substantially, color is a canescence, can be used as the raw material of enzymolysis, be used to prepare new hydrolyzed solution behind the vapor condensation that produces in the drying process with after washings mixes.Liquor B is a yellow solution, after ethanol and tetrahydrofuran (THF) are removed in the continuation distillation, adds among the NaOH and residual HCl, promptly gets the neutral liquid glucose, and distillation gained ethanol and tetrahydrofuran (THF) can be recycled.
Embodiment seven
Preparation 100g hydrolyzed solution also places the 500ml flask, wherein contain formic acid 10wt%, 1,3-dioxolane 15wt%, acetone 5wt%, HCl0.5wt%, water 69.5wt%, the needlebush that cuts into fines (handling) that adds 10.0g air-dry (moisture 15%) by solid-to-liquid ratio L/S=10 through steam explosion, connect prolong, place 100 ℃ of water-bath insulations 45 minutes.Behind the stopped reaction, press filtration obtains tawny filtrate A and filemot Mierocrystalline cellulose filter residue.Gained filtrate is distilled, when acid concentration is reduced to 50%, add the water of 1 times of amount, xylogen no longer dissolves and is precipitated out, and filters, and obtains xylogen filter residue and liquor B, and the xylogen filter residue washes 3 after drying with water and promptly gets thick organosolv lignin.Mierocrystalline cellulose filter residue 20wt% formic acid, 30wt%1, the mixing solutions washing that 3-dioxolane and 20wt% acetone are formed 3 times, Mierocrystalline cellulose filter residue dehydration after drying after the washing promptly gets the Mierocrystalline cellulose filter residue that is divided into the single fiber shape substantially, color is a canescence, can be used as the raw material of enzymolysis, be used to prepare new hydrolyzed solution behind the vapor condensation that produces in the drying process with after washings mixes.Liquor B is a yellow solution, continues distillation and removes formic acid removal, 1, behind 3-dioxolane and the acetone, adds among the NaOH and residual HCl, promptly gets the neutral liquid glucose, distillation gained formic acid, 1, and 3-dioxolane and acetone can be recycled.
Claims (10)
1. a plant fiber raw material hydrolyzed solution is characterized in that, described hydrolyzed solution comprises following component and content (weight) thereof:
Mineral acid: 0.5%～25%,
Alcohols: 30%～65%,
Water: surplus;
Perhaps, mineral acid: 0.5%～25%,
Ethers, ketone or carboxylic-acid or their mixtures (I): 30%～99%,
Water: 0.5%～69.5%;
Perhaps, mineral acid 0.5%～25%,
Alcohols and mixture (II) 30%～99% (I),
Water: 0.5%～69.5%,
Wherein the content (weight) of alcohols is not higher than 65% in (II).
2. plant fiber material hydrolyzed solution as claimed in claim 1 is characterized in that, described mineral acid is HCl or H
2SO
4
3. plant fiber material hydrolyzed solution as claimed in claim 1 is characterized in that described alcohols comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol.
4. plant fiber material hydrolyzed solution as claimed in claim 1 is characterized in that described ethers comprises tetrahydrofuran (THF), 1,4-dioxane, 1,3-dioxolane, 1,3-diox.
5. plant fiber material hydrolyzed solution as claimed in claim 1 is characterized in that, described ketone is an acetone.
6. plant fiber material hydrolyzed solution as claimed in claim 1 is characterized in that described carboxylic-acid comprises formic acid, acetate, propionic acid.
7. raw material pretreated method is characterized in that it may further comprise the steps:
(1) get the raw materials ready, plant fiber material is cut into fines after, drying, standby;
(2) hydrolysis places the described hydrolyzed solution of claim 1 to the raw material handled well in (1) step, and reaction is 15 minutes～24 hours under 40 ℃～125 ℃ temperature;
(3) separate,, obtain Mierocrystalline cellulose filter residue and filtrate A the solution solid-liquid separation that step (2) obtains;
(4) precipitation, the xylogen among the precipitation filtrate A, solid-liquid separation obtains xylogen precipitation and liquor B;
(5) distillation, the distillation liquor B is not contained the liquid glucose of organic solvent up to organic solvent is all evaporated.
8. raw material pretreated method as claimed in claim 7 is characterized in that, when using H
2SO
4During as mineral acid preparation hydrolyzed solution, gained filtrate A CaCO
3Neutralize, filter, do not contained H
2SO
4Filtrate A.
9. raw material pretreated method as claimed in claim 7 is characterized in that, when with HCl during as mineral acid preparation hydrolyzed solution, the gained liquid glucose is with alkali or CaCO
3The residual HCl that neutralizes is not contained the liquid glucose of mineral acid.
10. raw material pretreated method as claimed in claim 7, it is characterized in that, the method of precipitation xylogen is in the step (4): add an amount of water in filtrate A the concentration of organic solvent is reduced in the time of can not dissolving organosolv lignin again, make xylogen form precipitation; Perhaps, when using the hydrolyzed solution of higher water content, can the organic solvent concentration of filtrate A be reduced by distillation, xylogen be precipitated out because of solubleness reduces; But when using the hydrolyzed solution of lower water content, after filtrate A is distilled to a certain degree, add an amount of water, xylogen is precipitated out because of solubleness reduces to reduce organic solvent concentration.
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| CN103819688A (en) * | 2008-03-14 | 2014-05-28 | 弗吉尼亚暨州立大学知识产权公司 | Method and apparatus for lignocellulose pretreatment by using super-cellulose-solvent and highly volatile solvents |
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| TWI642467B (en) * | 2016-12-08 | 2018-12-01 | 行政院原子能委員會核能研究所 | Separation method conducive to ?saccharification efficiency of high-lignin content lignocellulosic feedstock with mixed solvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| HU197774B (en) * | 1983-02-16 | 1989-05-29 | Laszlo Paszner | Organic solvent process for the hydrolytic saccharification of vegetable materials of starch type |
| BR9600672A (en) * | 1996-03-08 | 1997-12-30 | Dedini S A Administracao E Par | Acid hydrolysis process of lignocellulosic material and hydrolysis reactor |
| BRPI0505212A (en) * | 2005-11-01 | 2007-08-07 | Dedini Sa Ind De Base | improvements in fast acid hydrolysis process of lignocellulosic material and hydrolysis reactor |
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