CN101798603B - Hydrolysis method of lignocellulosic biomass - Google Patents
Hydrolysis method of lignocellulosic biomass Download PDFInfo
- Publication number
- CN101798603B CN101798603B CN 201010128950 CN201010128950A CN101798603B CN 101798603 B CN101798603 B CN 101798603B CN 201010128950 CN201010128950 CN 201010128950 CN 201010128950 A CN201010128950 A CN 201010128950A CN 101798603 B CN101798603 B CN 101798603B
- Authority
- CN
- China
- Prior art keywords
- hydrolysis
- biomass
- acid
- lignocellulose
- hydrolysis reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention relates to a hydrolysis method of lignocellulosic biomass by using inorganic strong acid as a catalyst. The hydrolysis method mainly comprises the following steps: putting the lignocellulosic biomass into a hydrolysis reactor, and then, carrying out hydrolysis under the conditions that the temperature is 140 DEG C-200 DEG C, the pressure is 0.8MPa-2.0MPa and the inorganic strong acid with the mass percentage concentration of 0.1wt%-0.8wt% exists. The hydrolysis method of the lignocellulosic biomass, which is provided by the invention, not only can reduce generation of fermentation inhibitors but also can fully hydrolyze hemicellulose to obtain monosaccharide, and lays the foundation for high-efficiency utilization of the lignocellulosic biomass in the process of preparing ethanol by hydrolysis and fermentation of the lignocellulosic biomass.
Description
Technical field
The present invention relates to a kind of method for hydrolysis of lignocellulose-like biomass, specifically, relate to a kind of method for hydrolysis of the lignocellulose-like biomass take inorganic acid as catalyzer.
Background technology
Along with the increasing that various countries' ethanol petrol is used dynamics, the output that has driven world fuel ethanol is soaring year by year.But can not satisfy the great demand that bio-ethanol is produced based on sugar and starch class raw material, the various countries investigators more and more pay close attention to biomass resource-lignocellulose-like biomass the abundantest on the earth.
Lignocellulose-like biomass gets fermentable monose through enzymic hydrolysis, and because of advantages such as its inhibition with follow-up fermentation of impact in hydrolysising condition gentleness and the gained hydrolysate lack, and receive publicity.Yet because the complex structure of natural wooden fiber's element biolobic material (consists of the Mierocrystalline cellulose of biomass, twine mutually between hemicellulose and xylogen, and there is crystalline structure Mierocrystalline cellulose in itself, this crystalline texture, even if also being difficult to invade in its inside, goes water molecules), stoped (hydrolysis) enzyme near cellulose surface, the yield of the monose that causes fermenting is very low.Therefore, before the lignocellulose-like biomass enzymic hydrolysis, must carry out pre-treatment to it.
So far, the pretreatment process before the lignocellulose-like biomass enzymic hydrolysis mainly is divided into two classes, the first is steam explosion method for pretreating (Int JAgric ﹠amp; Biol Eng 2009; 2 (3): 51-68.), the method has certain requirement to raw material, and energy consumption is higher, is not easy large-scale production.It two is, the acid hydrolysis method for pretreating (it can the high-efficiency dissolution hemicellulose, the part xylogen, thus destroy the rock steady structure of lignocellulose-like biomass inside, thereby be conducive to improve the processing efficiency of enzymic hydrolysis).Such as ([J] chemical engineering, 2007,35 (10): the 49-52.) diluted acid of report (mass percentage concentration of acid is greater than 1.0wt%) hydrolysis method and [J] agricultural machine, 2006,37 (6), 27-31 and [J] Engineering Thermophysics journal, 2006,27 (5), the ultralow acid that 741-744 discloses (mass percentage concentration of acid is less than or equal to 0.1wt%) hydrolysis method.Wherein, described dilute acid hydrolysis method exists easy generation fermentation inhibitor (affecting follow-up fermentation) and the too much defective of sour usage quantity; And described extremely low acids hydrolysis rule exists hydrolysis effect not good (mostly being greatly oligose such as hydrolysate), affects the follow-up enzymic hydrolysis deficiency of (as also will increase the lytic enzyme of oligose in follow-up enzymic hydrolysis).
Given this, provide a kind of generation that had not only reduced fermentation inhibitor, but also with hydrolysis of hemicellulose fully the pretreatment process of the lignocellulose-like biomass enzymic hydrolysis of (acquisition monose) become the technical issues that need to address of the present invention.
Summary of the invention
Exist for overcoming in the prior art: adopt diluted acid (mass percentage concentration of acid is greater than 1.0wt%) for catalyzer, to the contained hemicellulose of the lignocellulose-like biomass appropriate to the occasion generation fermentation inhibitor that is hydrolyzed; And adopt ultralow acid (acid mass percentage concentration be less than or equal to 0.1wt%) that the contained hemicellulose of the lignocellulose-like biomass gained that is hydrolyzed mostly is greatly the defective of oligose, the present inventor finds after extensive and deep research: be that the acid of 0.1wt%～0.8wt% is catalyzer when adopting mass percentage concentration, and when under certain temperature condition, the contained hemicellulose of lignocellulose-like biomass being hydrolyzed, can realize not only reducing the generation of fermentation inhibitor, but also with the complete target of (acquisition monose) of hydrolysis of hemicellulose.To can obtain to greatest extent fermentable monose through enzymic hydrolysis (mainly being that Mierocrystalline cellulose is hydrolyzed) again through described acid-hydrolyzed material, thereby improve the utilization ratio of lignocellulose-like biomass.
The method for hydrolysis of the said lignocellulose-like biomass of the present invention, it is characterized in that, the key step of said method for hydrolysis is: lignocellulose-like biomass places hydrolysis reactor, is that 140 ℃～200 ℃, pressure are that 0.8MPa～2.0MPa and having under the acid catalyst existence condition is hydrolyzed in temperature;
Wherein: said acid catalyst is inorganic acid, and its mass percentage concentration is 0.1wt%～0.8wt%.
In the present invention, said inorganic acid can be (but being not limited to) sulfuric acid, hydrochloric acid or nitric acid etc., recommendation sulfuric acid or hydrochloric acid;
Said lignocellulose-like biomass is such as (but being not limited to): stalk biomass (such as agricultural crop straws such as maize straw, sorgo stalk or Wheat Straw etc.) and/or wood type biomass (such as wood fragments, timber or/and forestry products such as sawdusts) etc.
Description of drawings
Fig. 1 is the schematic flow sheet of lignocellulose biomass by hydrolyzation of the present invention;
Wherein: the 1-steam generator; The 2-acid storage tank; The 3-hydrolysis reactor; The 4-water cooler; The 5-temperature indicator; The 6-volume pump; 7---thermopair; 8-hydrolyzed solution products pot; The 9-pressure controller; V. valve; The P-tensimeter.
Embodiment
By reference to the accompanying drawings 1, content of the present invention is done into an explanation.
The method of hydrolysis of lignocellulose biolobic material of the present invention, its key step is: lignocellulose-like biomass is placed hydrolysis reactor 3, in hydrolysis reactor 3, add water vapor and inorganic acid by steam generator 1 and acid storage tank 2 (through volume pump 6) respectively, make in the hydrolysis reactor 3: pressure is 0.8MPa～2.0MPa, temperature is that the mass percentage concentration of 140 ℃～200 ℃ and inorganic acid is 0.1wt%～0.8wt%, the aqueous solution spray of inorganic acid is on wood fiber biomass, and gradually diafiltration to hydrolysis reactor 3 bottoms, open the bleeder valve of hydrolysis reactor 3 bottoms, and the flow velocity of control effluent liquid (hydrolysate), be that the volume of per minute effluent liquid (hydrolysate) and the ratio of hydrolysis reactor 3 volumes are 0.03～0.15, effluent liquid (hydrolysate) enters in the hydrolyzed solution products pot 8 through water cooler 4.
After finishing hydrolysis, pressurized air can be entered in the hydrolysis reactor 3 by the V. valve, the liquid that residues in hydrolysis reactor 3 is discharged.
The invention provides a kind of generation that not only can reduce fermentation inhibitor, but also can be with the complete method for hydrolysis of the lignocellulose-like biomass of (acquisition monose) of hydrolysis of hemicellulose, it is laid a good foundation for the lignocellulose biomass by hydrolyzation efficient utilization of lignocellulose-like biomass of fermenting in the ethanol process processed.
The present invention is further elaborated below by embodiment, and its purpose only is better to understand content of the present invention.Be understood that: following the cited case does not limit protection scope of the present invention.
Embodiment 1
120 gram maize straws are placed 1.5 premium on currency solution reactors, in this hydrolysis reactor, add respectively water vapor and sulphuric acid soln, and the mass percentage concentration that makes sulfuric acid in this hydrolysis reactor is 0.5wt%, hydrolysis pressure is 0.8MPa, hydrolysis temperature is 140 ℃, derives hydrolysate with 0.1 liter/min speed, and hydrolysate is through cooling off the laggard product storage tank that enters to be hydrolyzed, the monosaccharide concentration of hydrolysate is 2.0wt% in the hydrolysis prods storage tank, and the yield of monose is 71.4%.
The qualitative analysis by GC/MS of the fermentation inhibitor in the hydrolysate draws: mainly be these four kinds of materials of acetic acid, furfural, levulinic acid and 5 hydroxymethyl furfural.Concrete outcome sees Table 1
Table 1
The concentration of each compound adopts gas chromatography determination in the table 1, and is specific as follows:
Get the hydrolysis prods of 1mL, to 10mL, enter stratographic analysis, method of calculation: external standard method with the acetone diluted constant volume.At first prepare the standardized solution of acetic acid, furfural, levulinic acid and the 5 hydroxymethyl furfural of different concns, then at same sample size, measure under the same sampling condition, obtain experimental data, the drawing standard curve.Measure at last actual sample, with the concentration of each compound in the regression equation calculation sample,
Instrument parameter is as follows:
Analytical instrument: Agilent Agilent6820 gas chromatograph, flame ionization ditector (FID);
Chromatographic column: the Innowax polar column (30m * 0.32mm * 0.5um); Carrier gas: high pure nitrogen (99.999%); Carrier gas flux: 1.5ml/min; Splitting ratio: do not shunt; Injector temperature: 280 ℃; Detector temperature: 300 ℃;
Post case parameter: 120 ℃ of initial temperatures, keep 3min, rise to 250 ℃ with 50 ℃/min again, keep 10min; Sample size: 1ul.
As shown in Table 1: various inhibitor contents are lower in the hydrolyzed solution, do not affect the carrying out of follow-up fermentation.
Reducing sugar analysis:
Adopt high performance liquid chromatography to join the evaporative light detector to the hydrolysate in the hydrolysis prods storage tank of above-described embodiment 1 its contained monose is measured, the method can be measured contents of monosaccharides more accurately.Before entering liquid chromatography, need liquid sample is done necessary processing.
The method of sample pretreatment is: hydrolysate is neutralized to pH value 4.0 with calcium hydroxide, and centrifugal, with 0.22 micron membrane filtration, and the liquid after will filtering uses the ultrapure water of Millipore ultrapure water system produce to dilute 25 times as testing sample.
The moving phase that liquid chromatography adopts is the mixture of acetonitrile and ultrapure water, and the concrete operations parameter is as follows:
Chromatographic column: Intersil-NH2 250x4.6,5 μ;
Moving phase: acetonitrile/water=77/23, flow: 0.8ml/min; Sample size: 20ul;
Detector: the light scattering detector that Britain Polymer laboratories produces, model: PL-ELS2100, vaporization temperature: 70 ℃, atomization temperature: 40 ℃, detector uses nitrogen as atomization gas, and flow velocity is 1.2SLM;
Method of calculation: external standard method.At first prepare the wood sugar of different concns, the glucose standardized solution, by the concentration of each material and the double-log relation of corresponding chromatographic peak area, match obtains the typical curve equation.Bring the peak area of testing sample into concentration that the typical curve equation draws monose, the sugared concentration that the concentration of monose equals testing sample in the hydrolyzed solution multiply by corresponding extension rate.
The method of calculation of sugared yield are as follows in the hydrolyzed solution:
Symbology in the formula:
Y-monose yield (%);
The concentration of monose (g/ml) in the C-sample;
The mass fraction of hemicellulose in the A-sample;
The volume of V-sample (ml);
The quality of M-raw material (g);
The mass fraction of moisture in the m-raw material.
The hydrolysate that will be obtained by above-described embodiment 1 is after neutralization, again it is joined in the enzymic hydrolysis tank and to carry out enzymic hydrolysis with hydrolytic residue (enzyme dosage is 25FPU/g, and temperature is at 50 ℃, pH value 4.8, hydrolysis time 60 hours), the cellulose conversion rate reaches more than 83%.
Except the kind and concentration and hydrolysate derivation speed of feed change, hydrolysis temperature, hydrolysis pressure, acid, all the other conditions all with embodiment 1 identical (comprising the account form of sugared concentration and yield and the assay of fermentation inhibitor), concrete outcome sees Table 2 and table 3:
Table 2
Table 3
Claims (5)
1. the method for hydrolysis of a lignocellulose-like biomass is characterized in that, the key step of said method for hydrolysis is:
Lignocellulose-like biomass is placed hydrolysis reactor (3), in hydrolysis reactor (3), add water vapor and inorganic acid by steam generator (1) and acid storage tank (2) respectively, make in the hydrolysis reactor (3): pressure is 0.8MPa～2.0MPa, temperature is that the mass percentage concentration of 140 ℃～200 ℃ and inorganic acid is 0.1wt%～0.8wt%, the aqueous solution spray of inorganic acid is on wood fiber biomass, and gradually diafiltration to hydrolysis reactor (3) bottom, open the bleeder valve of hydrolysis reactor (3) bottom, and the flow velocity of control effluent liquid, be that the volume of per minute effluent liquid and the ratio of hydrolysis reactor (3) volume are 0.03～0.15, effluent liquid enters in the hydrolyzed solution products pot (8) through water cooler (4).
2. method for hydrolysis as claimed in claim 1 is characterized in that, wherein said inorganic acid is sulfuric acid, hydrochloric acid or nitric acid.
3. method for hydrolysis as claimed in claim 1 is characterized in that, wherein said lignocellulose-like biomass is: stalk biomass and/or wood type biomass.
4. method for hydrolysis as claimed in claim 3 is characterized in that, wherein said stalk biomass is: maize straw, sorgo stalk or Wheat Straw.
5. method for hydrolysis as claimed in claim 3 is characterized in that, wherein said wood type biomass are: wood fragments, timber are or/and sawdust.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010128950 CN101798603B (en) | 2010-03-22 | 2010-03-22 | Hydrolysis method of lignocellulosic biomass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010128950 CN101798603B (en) | 2010-03-22 | 2010-03-22 | Hydrolysis method of lignocellulosic biomass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101798603A CN101798603A (en) | 2010-08-11 |
| CN101798603B true CN101798603B (en) | 2013-02-27 |
Family
ID=42594447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010128950 Expired - Fee Related CN101798603B (en) | 2010-03-22 | 2010-03-22 | Hydrolysis method of lignocellulosic biomass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101798603B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676706A (en) * | 2011-03-09 | 2012-09-19 | 逢甲大学 | Preparation method and preparation equipment for reducing saccharide |
| DE102012020166A1 (en) * | 2012-10-13 | 2014-04-30 | Green Sugar Gmbh Produktinnovationen Aus Biomasse | Process for the hydrolysis of pelletable biomasses by means of hydrohalic acids |
| CN104655784A (en) * | 2015-03-19 | 2015-05-27 | 山东农业大学 | Method for determining lignocelluloses component content of plant straw |
| CN106083776A (en) * | 2016-07-04 | 2016-11-09 | 广西大学 | A kind of improve the method for furfural content in bagasse hydrolyzate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109100A (en) * | 1994-03-24 | 1995-09-27 | 冯文义 | Acid hydrolysis of plant cellulose |
| CN101627143A (en) * | 2007-03-08 | 2010-01-13 | 瑞典乙醇化工技术有限公司 | Apparatus for extraction of saccharides from lignocellulose material by means of hydrolysis and use of a certain material in the apparatus |
-
2010
- 2010-03-22 CN CN 201010128950 patent/CN101798603B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109100A (en) * | 1994-03-24 | 1995-09-27 | 冯文义 | Acid hydrolysis of plant cellulose |
| CN101627143A (en) * | 2007-03-08 | 2010-01-13 | 瑞典乙醇化工技术有限公司 | Apparatus for extraction of saccharides from lignocellulose material by means of hydrolysis and use of a certain material in the apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101798603A (en) | 2010-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ding et al. | Biobutanol production from corn stover hydrolysate pretreated with recycled ionic liquid by Clostridium saccharobutylicum DSM 13864 | |
| CN102224220B (en) | Bio-oil production method | |
| Rohowsky et al. | Feasibility of simultaneous saccharification and juice co-fermentation on hydrothermal pretreated sweet sorghum bagasse for ethanol production | |
| Klein‐Marcuschamer et al. | Renewable fuels from biomass: technical hurdles and economic assessment of biological routes | |
| Smuga-Kogut et al. | The use of ionic liquid pretreatment of rye straw for bioethanol production | |
| CN101736631B (en) | Process for efficiently preprocessing lignocellulose | |
| CN103502259A (en) | Enhanced soluble c5 saccharide yields | |
| NZ742430A (en) | Processes for enhancing saccharification of biomass materials | |
| Sonego et al. | Extractive fed-batch ethanol fermentation with CO2 stripping in a bubble column bioreactor: experiment and modeling | |
| CN101235392A (en) | Cellulose fuel ethanol and preparation method thereof | |
| CN101798603B (en) | Hydrolysis method of lignocellulosic biomass | |
| CN103502258A (en) | Cellulose hydrolysis with ph adjustment | |
| Nwakaire et al. | Production of cellulosic ethanol from wood sawdust | |
| Yang et al. | Influence of size reduction treatments on sugar recovery from Norway spruce for butanol production | |
| US11111513B2 (en) | Methods of removing one or more compounds from a lignocellulosic hydrolysate via gas stripping, and related systems | |
| Liu et al. | Preparation of hydrolytic liquid from dried distiller's grains with solubles and fumaric acid fermentation by Rhizopus arrhizus RH 7-13 | |
| Medina et al. | Ethanol production, current facts, future scenarios, and techno-economic assessment of different biorefinery configurations | |
| WO2015095255A1 (en) | Method of monitoring and controlling a bioprocess using near- and mid-infrared spectroscopy | |
| CN103502257A (en) | Multistage cellulose hydrolysis and quench with or without acid | |
| CN103313999A (en) | Mixed super critical fluid hydrolysis and alcoholysis of cellulose to form glucose and glucose derivatives | |
| CN102741418B (en) | For the method preparing the biological material rich in glucosan | |
| CN102559778A (en) | Fermentation culture medium and method for producing butyl alcohol by fermentation with culture medium | |
| KR101417836B1 (en) | Apparatus for producing cellulosic biomass hydrolysis material by Two-step acid treatment process and method thereof | |
| Kim et al. | Process design and evaluation of production of bioethanol and β-lactam antibiotic from lignocellulosic biomass | |
| Ren et al. | Optimizing steam explosion pretreatment conditions of corn stalk by response surface methodology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130227 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |