CN102260754B - Method for preparing fermentable saccharide from cellulose wastes by differential expression filter bed low-acid hydrolysis - Google Patents
Method for preparing fermentable saccharide from cellulose wastes by differential expression filter bed low-acid hydrolysis Download PDFInfo
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Abstract
The invention discloses a method for preparing fermentable saccharide from cellulose wastes by differential expression filter bed low-acid hydrolysis for the purpose of solving the problem that in the existing diluted acid hydrolysis technology, the yield of hydrolysis saccharide is low, and hydrolysis byproduct is relatively high so as to inhibit the growth of microbial cells in the subsequent ethanol or butanol fermentation process, thereby causing the low yield of a target product. According to the invention, the method disclosed by the invention means that aiming at different structures and different hydrolysis difficulty, multi-section differential expression filter bed low-acid hydrolysis is used based on different hydrolysis temperatures, different acid concentrations and different reaction times, so that pentose, hexose, cellobiose, oligosaccharide and the like are obtained; and hydrolysis products are eliminated in time, the acid action time of hydrolysis saccharide at high temperature is reduced, and the byproducts are reduced, thereby improving the yield of saccharide. The method has the advantages of simple process, strong controllability, short reaction period, low cost, less pollution and the like and is easy to achieve industrial production on large scale, and waste liquid treatment is convenient.
Description
[technical field]
The present invention relates to technical field of biomass chemical engineering, relate in particular to a kind of method of utilizing the low acid hydrolysis of cellulose castoff differential expression diafiltration bed to become fermentable sugar.
[technical background]
China is large agricultural country, and existing various biomass resources comprise agricultural crop straw, corn straw, rice straw, wheat-straw, forestry waste, and by the various lignocelluloses that are rich in all applicable to this technology.In recent years, along with expanding economy and growth in the living standard, the peasant reduces the direct incendiary demand of biomass gradually; The residue that stalk resource occurred; So that arbitrarily burn, smoke pollution has constituted serious threat to traffic safety, and the traffic hazard that " burning the grass on waste land " causes emerges in an endless stream; Cause huge life security and property damage to the people, cause that each side pays close attention to.Agriculture and forestry organic waste material is converted into high-quality biochemical industry article and liquid fuel, forms the industrialization utilization, the straw refuse of can dissolving in a large number, environment and ecological hazard that agricultural wastes such as elimination stalk are burnt the grass on waste land and caused.
Cellulosic waste can generate liquid fuel or other Chemicals such as ethanol, butanols through biochemical conversion, and hydrolysis is crucial core technology.Be divided into acid hydrolysis and enzymic hydrolysis.Acid hydrolysis is divided into concentrated acid hydrolysis and dilute acid hydrolysis again, and they each have different reaction mechanisms.
The concentrated acid hydrolysis is representative with the Arkenol hydrolysis process; The report of concentrated acid hydrolysis is shown in 1883 the earliest; Its principle is that crystalline cellulose is dissolved under lower temperature in the phosphoric acid of 72% sulfuric acid, 42% hydrochloric acid or 77～83%; Cause cellulosic homogeneous hydrolysis, change into the oligose that contains several glucose units, with this solution thin up and heat certain hour and promptly be hydrolyzed to glucose.Vitriol oil hydrolysising reacting temperature and pressure are all low than dilute acid hydrolysis, have reduced the reducing sugar that generates and have continued degradation amount.Its major advantage is that the recovery of sugar is high, the sugar that recyclable about 90% Mierocrystalline cellulose, semicellulose transform.Adopt the acid of high density, more serious to equipment corrosion, need to adopt the corrosion material of anti-strong acid, this has increased the cost of equipment and materials greatly.And great deal of high concentration acid waste liquid contaminate environment, its recycling is difficulty, has increased the cost of concentrated acid hydrolysis from raw material, has restricted further developing of concentrated acid hydrolysis.
No acid hydrolysis can be claimed the high temperature liquid water hydrolysis, is to utilize high temperature liquid water to come the semicellulose in the hydrolyzing biomass to obtain methods such as wood sugar or low xylan.Its principle and dilute acid hydrolysis are similar, all are to come hydrolyzed hemicellulose through oxonium ion.Its main process is that the acetyl base class material hydrolysis on the semicellulose branched structure produces acetate in hydrolytic process, and the acetate disassociation produces the carrying out that oxonium ion promotes hydrolysis reaction again.The advantage of high temperature liquid water hydrolysis: but 1. high-level efficiency is dissolved semicellulose (more than 90%), part is removed wooden rate (10%～50%), and cellulosic loss is less.2. after having removed semicellulose and xylogen, improve the enzyme contact of biomass, can significantly improve the performance of enzymic hydrolysis.3. adopt water as catalyzer, running cost is lower, and does not have sour subsequent processes.But high temperature liquid water hydrolysis temperature and pressure are all than higher, and by product is also many, and fermentation inhibitor is more; And higher requirement has been proposed hydrolysis device; High temperature liquid water hydrocellulose efficiency ratio is lower in addition, and cellulose hydrolysis sugar yield is also lower, is suitable for the pre-treatment of enzymic hydrolysis most.
Extremely low acids hydrolysis is meant that with massfraction be the method that the acid below 0.1% is hydrolyzed to Mierocrystalline cellulose under comparatively high temps, proposed by U.S. renewable energy source laboratory (NREL).Ultralow acid is low to corrosion on Equipment property, reduces the subsequent disposal amount of acid, than other technology bigger advantage is arranged in the minimizing environmental pollution with aspect reducing production costs; Its shortcoming is to need high temperature, highly compressed reaction conditions; Harsh to equipment requirements, be difficult to industrialization, semicellulose is different with the cellulose hydrolysis performance in addition; Relatively easy hydrolysis of semicellulose and wood sugar at high temperature are prone to decompose, and cause lignocellulose hydrolysis sugar yield lower.
The enzyme hydrolysis process reaction conditions is gentle, hydrolysising by-product is few, the saccharification yield is high but its fatal problem is: low, the poor stability of organic efficiency of one side cellulase, and cost is high; Pretreated technology of enzymic hydrolysis and cost requirement are very high on the other hand, are difficult to realize industrialization.
The dilute acid hydrolysis method has advantages such as technology is simple, controllability is strong, reaction time is short, cost is low, liquid waste disposal is convenient, pollution is few, is the process method that is expected to realize large-scale industrial production most.In the Mierocrystalline cellulose dilute acid hydrolysis process, the acid effect makes cellulose hydrolysis mainly be converted into glucose; Semicellulose then generates multiple monose, mainly comprises wood sugar, pectinose, seminose etc.; Xylogen then is degraded into multiple monocyclic aromatic compound.Because these products and unstable under comparatively high temps and acid effect; The multiple reaction such as decomposition, oxidation that has various ways; These reactions have not only reduced the yield of fermentable sugar; Also generated multiple by product, mainly contained: formic acid, acetate, furfural, hydroxymethylfurfural, uronic acid, saccharinic acid, phenolic cpd, syringic acid, hydroxy-benzoic acid, Vanillin etc., the existence of these materials; Influence the yield of target product to suppressing in follow-up ethanol or the butylic fermentation process in the growth of microorganism cells.
In sum; Although the dilute acid hydrolysis method has advantages such as technology is simple, controllability is strong, reaction time is short, cost is low, liquid waste disposal is convenient, pollution is few, is the process method that is expected to realize large-scale industrial production most, exist the hydrolysis sugar yield low; By product is many; The fermentable sugars productive rate is low, has increased the difficulty that a lot of follow-up fermentable sugars utilize, and needs to solve as early as possible.
[summary of the invention]
The invention discloses the method that the low acid hydrolysis of a kind of cellulose castoff differential expression diafiltration bed prepares fermentable sugar; Low to solve in the existing dilute acid hydrolysis technology hydrolysis sugar yield; Hydrolysising by-product is than higher; Growth to microorganism cells in follow-up ethanol or the butylic fermentation process produces restraining effect, causes the low problem of target product yield.
Cellulose castoff is made up of Mierocrystalline cellulose, semicellulose and xylogen three, and structure is very complicated, and its structure of different raw materials is different, and the hydrolysis complexity is also different.The low acid hydrolysis of differential expression diafiltration bed is meant that and hydrolysis complexity different mining different with cellulosic structure carried out the differential expression diafiltration bed hydrolysis of multistage with different temperature, different acid concentrations with different hydrolysis times to the semicellulose in the raw material; Obtain pentose, hexose, cellobiose and oligose etc.; In time get rid of hydrolysate; The minimizing hydrolysis sugar is sour action time under high-temperature condition, thereby reduce production of by-products, improves the yield of sugar.Advantage and deficiency that the contriver combines the diafiltration bed to hang down acid hydrolysis process, high temperature liquid water, extremely low acids hydrolysis and enzyme hydrolysis process propose first; And make an experiment, reaction conditions is gentle, and the acid consumption is low; Aftertreatment is easy; By product is few after the hydrolysis, has improved sugared yield and sugared concentration, has reduced the inhibition concentration of follow-up biological fermentation.
The low acid hydrolysis of cellulose castoff differential expression diafiltration bed disclosed by the invention becomes the method for fermentable sugar; Be meant according to different raw materials and same raw material since semicellulose, cellulosic structure different water to separate the difficulty or ease degree also different; Reduce the hydrolysis sugar high-temperature residence time, reduce hydrolysising by-product, improve the yield of sugar; The cellulose castoff hydrolysis is divided into the hydrolysis process of differing temps or different acid concentration (containing different acids) or differential responses time, comprises the steps:
1) cellulose castoff is packed in the diafiltration bed hydrolytic reaction pot, add temperature greater than 50 ℃ hot water (or adding cold water with being steam heated to more than 50 ℃), solid-to-liquid ratio 2～12 was reacted after 10～100 minutes, and wash water is drained;
2) the adding acid concentration is 0.05～2% mineral acid; Or 0.1～2.5% organic acid, or 0.05～2.5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～12; With being steam heated to 85～130 ℃ of reactions after 30～200 minutes, hydrolyzed solution is entered the hydrolysis storage tank;
3) the adding acid concentration is 0.08～3% mineral acid; Or 0.15～3.5% organic acid, or 0.08～3.5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～12; With being steam heated to 90～135 ℃ of reactions after 30～200 minutes, hydrolyzed solution is entered the hydrolysis storage tank;
4) adding acid concentration is 0.1～3.5% mineral acid or 0.2～4% organic acid; Or 0.1～4% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～10 with being steam heated to 120～170 ℃ of reactions after 10～100 minutes, enters the hydrolysis storage tank with hydrolyzed solution;
5) adding acid concentration is 0.5～4% mineral acid or 0.8～4.5% organic acid; Or 0.5～4.5% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～12 with being steam heated to 130～200 ℃ of reactions after 10～100 minutes, enters the hydrolysis storage tank with hydrolyzed solution;
6) adding acid concentration is 0.8～4.5% mineral acid or 1.0～5% organic acid; Or 0.8～5% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～12 with being steam heated to 140～210 ℃ of reactions after 10～100 minutes, enters the hydrolysis storage tank with hydrolyzed solution;
7) adding acid concentration is 0.8～5% mineral acid or 1.0～5% organic acid, or 0.8～5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～10, be steam heated to 140～220 ℃ react 10～100 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
8) the water washing hydrolytic residue of adding solid-to-liquid ratio 2.5～12 is collected washing lotion and is entered the hydrolysis storage tank, drains hydrolytic residue then.
Concentration in the above-mentioned steps is mass percent concentration.
In the above-mentioned steps, also can take the way of following simplification:
Step 2) and 3) can replace with next procedure; For: the adding acid concentration is 0.05～3% mineral acid; Or 0.1～3.5% organic acid, or 0.05～3.5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～12; With being steam heated to 85～145 ℃ of reactions after 30～200 minutes, hydrolyzed solution is entered the hydrolysis storage tank.
Or; Step 4), 5), 6) and 7) can replace with following two steps; For: add acid concentration and be 0.1～4% mineral acid or 0.2～4.5% organic acid, or 0.1～4.5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～12; With being steam heated to 120～200 ℃ of reactions after 10～200 minutes, hydrolyzed solution is entered the hydrolysis storage tank.
Add acid concentration and be 0.8～5% mineral acid or 1.0～5% organic acid, or 0.8～5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～12, be steam heated to 140～220 ℃ react 10～200 minutes after, hydrolyzed solution is entered the hydrolysis storage tank.
Through above-mentioned simplification, the present invention can minimumly be reduced to the syllogic hydrolysis process.
Said cellulose castoff comprises agricultural wastes, as: stalk, shell, fruit stone, the waste of agricultural byproducts such as corn cob; Forestry waste, as: fuel wood, fallen leaves, bark, tree root and forestry processing waste; Waterplant, as: algae, duckweed, Herba Eichhorniae, jacinthe etc.; Energy crop, as: oil crops be rich in the plant of hydrocarbon polymer and other type biology of biomass.
In above-mentioned steps, dilute acid soln can also can be used the heating of other heating agent with steam heating, heating can be in reaction kettle direct heating, also can be heated to after the temperature of reaction earlier and then add in the reaction kettle.
Advantage of the present invention is:
The low acid hydrolysis of differential expression diafiltration bed is meant that and hydrolysis complexity different mining different with cellulosic structure carried out differential expression diafiltration bed hydrolysis step by step with different temperature, different acid concentrations to the semicellulose in the raw material; Obtain pentose, hexose, cellobiose and oligose etc.; In time get rid of hydrolysate; The minimizing hydrolysis sugar is sour action time under high-temperature condition, reduces production of by-products, has improved sugared yield; And advantage such as technology is simple, controllability is strong, reaction time is short, cost is low, liquid waste disposal is convenient, pollution is few, be easy to realize large-scale industrial production.
[embodiment]
Followingly the present invention is done detailed explanation through embodiment.
Embodiment 1
1) chooses the diafiltration bed hydrolytic reaction pot of 200L, 15 kilograms the straw that is cut into 2～3cm long moisture 10% is packed in the reaction kettle; Adding solid-to-liquid ratio 2,27 kilograms of temperature of meter are 70 ℃ hot water, react after 100 minutes, and wash water is drained;
2) add that solid-to-liquid ratio is 12, acid concentration is 162 kilograms of 0.6% aqueous hydrochloric acids, be steam heated to 100～105 ℃ react 100 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
3) adding acid concentration is that 50 kilograms of usefulness of aqueous hydrochloric acid of 0.8% were steam heated to 120～130 ℃ of reactions after 100 minutes, and hydrolyzed solution is entered the hydrolysis storage tank;
4) adding acid concentration is that 40 kilograms of usefulness of aqueous sulfuric acid of 1.8% were steam heated to 160 ℃ of reactions after 30 minutes, and hydrolyzed solution is entered the hydrolysis storage tank;
5) adding acid concentration is 30 kilograms of 2% aqueous sulfuric acids, be steam heated to 180 ℃ react 40 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
6) adding acid concentration is 30 kilograms of 2.1% aqueous sulfuric acids, be steam heated to 190 ℃ react 50 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
7) adding acid concentration is 25 kilograms of 2.2% aqueous sulfuric acids, be steam heated to 200 ℃ react 50 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
8) clear water that adds 20 kilograms washs hydrolytic residue, collects washing lotion and enters the hydrolysis storage tank, drains hydrolytic residue then.
Obtain about 3.8 kilograms of moisture 80% hydrolytic residue at last, 357 kilograms of hydrolyzed solutions, total sugar concentration is 2.42%, and the hydrolysis sugar yield is 85%, and the yield 60% greater than conventional dilute acid hydrolysis sugar has improved 25%.
Embodiment 2
1) chooses 2001 diafiltration bed hydrolytic reaction pot, moisture 12.5% 10 kilograms bagasse is packed in the reaction kettle; Adding 120 kg temperature is 50 ℃ a hot water, reacts after 10 minutes, and wash water is drained;
2) the adding acid concentration is 2.5% aqueous formic acid 120 kg, with being steam heated to 85 ℃ of reactions after 200 minutes, hydrolyzed solution is entered the hydrolysis storage tank;
3) adding acid concentration is that 25 kilograms of usefulness of acetic acid aqueous solution of 0.15% were steam heated to 135 ℃ of reactions after 30 minutes, and hydrolyzed solution is entered the hydrolysis storage tank;
4) adding acid concentration is 80 kilograms of 0.1% aqueous sulfuric acids, and solid-to-liquid ratio is about 12, be steam heated to 170 ℃ react 200 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
5) adding acid concentration is 20 kilograms of 4.5% acetic acid aqueous solutions, be steam heated to 200 ℃ react 10 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
6) adding acid concentration is 20 kilograms of 0.8% aqueous sulfuric acids, be steam heated to 210 ℃ react 100 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
7) adding acid concentration is 20 kilograms of 1.0% aqueous sulfuric acids, be steam heated to 220 ℃ react 10 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
8) clear water that adds 10 kilograms washs hydrolytic residue, collects washing lotion and enters the hydrolysis storage tank, drains hydrolytic residue then.
Obtain about 2.2 kilograms of moisture 80% hydrolytic residue at last, 290 kilograms of hydrolyzed solutions, total sugar concentration is 2.0%, the hydrolysis sugar yield is 86%, greater than conventional dilute acid hydrolysis sugar yield 60%, has improved 26%.
Embodiment 3
1) chooses 2001 diafiltration bed hydrolytic reaction pot, moisture 12.5% 28 kilograms bagasse is packed in the reaction kettle; Add 100 kilograms of temperature and be 50 ℃ hot water, react after 10 minutes, wash water is drained;
2) adding acid concentration is 100 kilograms of 0.1% aqueous hydrochloric acids, be steam heated to 110 ℃ react 100 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
3) adding acid concentration is that 70 kilograms of usefulness of aqueous hydrochloric acid of 0.3% were steam heated to 130 ℃ of reactions after 80 minutes, and hydrolyzed solution is entered the hydrolysis storage tank;
4) adding acid concentration is that 60 kilograms of usefulness of aqueous sulfuric acid of 0.8% were steam heated to 160 ℃ of reactions after 40 minutes, and hydrolyzed solution is entered the hydrolysis storage tank;
5) adding acid concentration is 50 kilograms of 0.8% hydrochloric acid aqueous acids, be steam heated to 170 ℃ react 35 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
6) adding acid concentration is 40 kilograms of 1.0% aqueous sulfuric acids, be steam heated to 180 ℃ react 30 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
7) adding acid concentration is 30 kilograms of 1.2% hydrochloric acid aqueous acids, be steam heated to 180 ℃ react 20 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
8) clear water that adds 30 kilograms washs hydrolytic residue, collects washing lotion and enters the hydrolysis storage tank, drains hydrolytic residue then.
Obtain about 7.6 kilograms of moisture 80% hydrolytic residue at last, 405 kilograms of hydrolyzed solutions, total sugar concentration is 4.0%, and the hydrolysis sugar yield is 87%, and the yield 60% greater than conventional dilute acid hydrolysis sugar has improved 27%.
Embodiment 4
1), choose 2001 diafiltration bed hydrolytic reaction pot, moisture 12.5% 28 kilograms bagasse is packed in the reaction kettle; Add 100 kilograms of temperature and be 50 ℃ hot water, react after 10 minutes, wash water is drained;
2), to add acid concentration be 100 kilograms of 0.1% aqueous hydrochloric acids, be steam heated to 130 ℃ react 100 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
3) adding acid concentration is that 90 kilograms of usefulness of aqueous hydrochloric acid of 1.0% were steam heated to 150 ℃ of reactions after 80 minutes, and hydrolyzed solution is entered the hydrolysis storage tank;
4) adding acid concentration is that 80 kilograms of usefulness of aqueous sulfuric acid of 1.5% were steam heated to 180 ℃ of reactions after 40 minutes, and hydrolyzed solution is entered the hydrolysis storage tank;
5), add 30 kilograms clear water washing hydrolytic residue, collect washing lotion and enter the hydrolysis storage tank, drain hydrolytic residue then.
Obtain about 7.8 kilograms of moisture 80% hydrolytic residue at last, 340 kilograms of hydrolyzed solutions, total sugar concentration is 4.6%, and the hydrolysis sugar yield is 84%, and the yield 60% greater than conventional dilute acid hydrolysis sugar has improved 24%.
Claims (5)
1. a cellulose castoff differential expression diafiltration bed hangs down the method that acid hydrolysis becomes fermentable sugar, it is characterized in that, hydrolysis is divided into differing temps or different acid and the multistage hydrolysis process of acid concentration or differential responses time, comprises the steps:
1) cellulose castoff is packed in the diafiltration bed hydrolytic reaction pot, adding temperature is 50～70 ℃ hot water, or adds cold water and use steam heating, and solid-to-liquid ratio 2～12 was reacted after 10～100 minutes, and wash water is drained;
2) the adding acid concentration is 0.05～2% mineral acid; Or 0.1～2.5% organic acid, or 0.05～2.5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～12; With being steam heated to 85～130 ℃ of reactions after 30～200 minutes, hydrolyzed solution is entered the hydrolysis storage tank;
3) the adding acid concentration is 0.08～3% mineral acid; Or 0.15～3.5% organic acid, or 0.08～3.5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～12; With being steam heated to 90～135 ℃ of reactions after 30～200 minutes, hydrolyzed solution is entered the hydrolysis storage tank;
4) adding acid concentration is 0.1～3.5% mineral acid or 0.2～4% organic acid; Or 0.1～4% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～10 with being steam heated to 120～170 ℃ of reactions after 10～100 minutes, enters the hydrolysis storage tank with hydrolyzed solution;
5) adding acid concentration is 0.5～4% mineral acid or 0.8～4.5% organic acid; Or 0.5～4.5% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～12 with being steam heated to 130～200 ℃ of reactions after 10～100 minutes, enters the hydrolysis storage tank with hydrolyzed solution;
6) adding acid concentration is 0.8～4.5% mineral acid or 1.0～5% organic acid; Or 0.8～5% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～12 with being steam heated to 140～210 ℃ of reactions after 10～100 minutes, enters the hydrolysis storage tank with hydrolyzed solution;
7) adding acid concentration is 0.8～5% mineral acid or 1.0～5% organic acid, or 0.8～5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～10, be steam heated to 140～220 ℃ react 10～100 minutes after, hydrolyzed solution is entered the hydrolysis storage tank;
8) the water washing hydrolytic residue of adding solid-to-liquid ratio 2.5～12 is collected washing lotion and is entered the hydrolysis storage tank, drains hydrolytic residue then.
2. the low acid hydrolysis of cellulose castoff differential expression diafiltration bed according to claim 1 becomes the method for fermentable sugar; It is characterized in that; Mineral acid is the mixing of sulfuric acid, hydrochloric acid or phosphoric acid or different mineral acid, and organic acid is the mixing of formic acid, acetate, propionic acid and toxilic acid or different organic acids.
3. a cellulose castoff differential expression diafiltration bed hangs down the method that acid hydrolysis becomes fermentable sugar, it is characterized in that, with the step 2 in the claim 1) and 3) replace with next procedure; For: the adding acid concentration is 0.05～3% mineral acid; Or 0.1～3.5% organic acid, or 0.05～3.5% mineral acid and organic acid mixture, solid-to-liquid ratio 2.5～12; With being steam heated to 85～145 ℃ of reactions after 30～200 minutes, hydrolyzed solution is entered the hydrolysis storage tank.
4. a cellulose castoff differential expression diafiltration bed hangs down the method that acid hydrolysis becomes fermentable sugar; It is characterized in that, with the step 4) in the claim 1,5), 6) and 7) replace with next procedure, for: add acid concentration and be 0.1～5% mineral acid or 0.2～5% organic acid; Or 0.1～5% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～12 with being steam heated to 120～220 ℃ of reactions after 10～200 minutes, enters the hydrolysis storage tank with hydrolyzed solution.
5. a cellulose castoff differential expression diafiltration bed hangs down the method that acid hydrolysis becomes fermentable sugar; It is characterized in that: with the step 2 in the claim 1) and 3) replace with next procedure, for: the adding acid concentration is 0.05～3% mineral acid, or 0.1～3.5% organic acid; Or 0.05～3.5% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～12 with being steam heated to 85～145 ℃ of reactions after 30～200 minutes, enters the hydrolysis storage tank with hydrolyzed solution;
With the step 4) in the claim 1,5) replace with next procedure; For: add acid concentration and be 0.1～4% mineral acid or 0.2～4.5% organic acid; Or 0.1～4.5% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～12 with being steam heated to 120～200 ℃ of reactions after 10～200 minutes, enters the hydrolysis storage tank with hydrolyzed solution;
With the step 6) in the claim 1 and 7) replace with next procedure; For: add acid concentration and be 0.8～5% mineral acid or 1.0～5% organic acid; Or 0.8～5% mineral acid and organic acid mixture; Solid-to-liquid ratio 2.5～12 with being steam heated to 140～220 ℃ of reactions after 10～200 minutes, enters the hydrolysis storage tank with hydrolyzed solution.
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