CN105463031A - Method for cooperatively producing ethyl alcohol and methane through energy grass - Google Patents
Method for cooperatively producing ethyl alcohol and methane through energy grass Download PDFInfo
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- CN105463031A CN105463031A CN201510767425.XA CN201510767425A CN105463031A CN 105463031 A CN105463031 A CN 105463031A CN 201510767425 A CN201510767425 A CN 201510767425A CN 105463031 A CN105463031 A CN 105463031A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The invention relates to an ethyl alcohol and methane cooperative production method, and particularly discloses a method for cooperatively producing ethyl alcohol and methane through energy grass. The energy grass which is subjected to steam explosion is used as a raw material, a product obtained after enzymolysis of cellulase and beta-glucosidase is used as a substrate, batch type supplementary material high-substrate-concentration simultaneous saccharification and fermentation and alcoholic fermentation all-residue anaerobic digestion treatment are integrated for cooperative production of clean energy ethyl alcohol and methane, the main purpose is that the cellulosic ethanol conversion rate is improved as far as possible, and all ingredients, capable of being utilized by anaerobic digestion flora, in alcoholic fermentation residues are further converted and utilized, so that the energy grass holocellulos conversion rate is improved, meanwhile, multi-stage utilization of all components of the energy grass is achieved, and an effective solution is provided for solving the raw material utilization rate bottleneck problem produced when existing lignocellulose raw materials are used for producing clean energy.
Description
Technical field
The present invention relates to ethanol methane co-production, specifically, relate to a kind of method utilizing energy grass co-producing ethanol and methane.
Background technology
Be raw material with lignocellulose, utilize the biological substitution energy that modernization animal nutrition is developed, become world today's prosperity
countrythe important component part of energy strategy.Produce going deep into gradually of clean energy research along with to lignocellulosic material, built up both at home and abroad or built many cover pilot production lines and exemplary factory, industrialization initial stage is just being stepped in the development of fiber-like alcohol fuel.Wherein, take energy grass as the lignocellulosic material of representative, because its rich cellulose, wide adaptability, strong stress resistance, growth are fast, output high and become the substrate of the production renewable and clean energy resource comparatively had superiority.
Energy grass is perennial tall and big herbaceous plant or subshrub, mostly is drought-enduring, Salt And Alkali Tolerance, barren-resistant, adaptable grass seeds, comprises switchgrass, awns belongs to the tall and big herbaceous plant such as crop.At present, researcher both domestic and external has carried out large quantity research to the production that energy grass carries out clean energy ethanol, and different energy sources grass is after the modes such as ensiling, soda acid, steam explosion carry out pre-treatment, and its ethanol fermentation output is also not quite similar.The people such as Sun. in 2015 are with grassland cordgrass (Prairiecordgrass) for substrate, and it is 205.0 ~ 275.6gkg-1 that the high substrate synchronous saccharification ethanol fermentation through the laggard row of peracid treatment 20% (w/w) finally obtains ethanol production; The cellulose conversion rate of eelgrass (Eelgrass) simultaneous saccharification and fermentation is brought up to 90.3% by steam explosion pre-treatment by the people such as Viola, and obtaining ethanol production is accordingly 243gkg-1.But although imperatoria (Kinggrass) has been carried out alkaline purification and carried out substep diastatic fermentation and the simultaneous saccharification and fermentation that concentration of substrate is 10% by the people such as Gallego, final ethanol production has been only 8.7 ~ 10.4gL-1.Same, carry out to broom corn millet (PanicummiliaceumL.) the substep diastatic fermentation that concentration of substrate is 23% with Silaging method, its alcohol yied is also only 45%.But above prior art fermentation producing and ethanol concentration is lower, and energy consumption is higher, is unsuitable for amplifying, and wants to carry out large-scale industrial production, needs a kind of method utilizing energy grass to carry out batch feed supplement height concentration of substrate simultaneous saccharification and fermentation production ethanol badly.But because energy grass main component is Mierocrystalline cellulose, hemicellulose, xylogen, structure is hard, different energy sources straw fiber cellulose content and property of raw material difference, cause not all pretreated energy grass can be directly applied for batch feed supplement height concentration of substrate simultaneous saccharification and fermentation.
In addition, for the full residue of the fermentation after energy grass fermentative production of ethanol, in prior art, do not provide good treatment process, compared with the available composition in good utilisation residue, can be produced by lignocellulosic material substantially again and obtain clean energy.
Such as, publication number is the treatment process that the Chinese patent application of CN103102036A discloses fiber-like ethanol production wastewater, this method be applicable to ethanol fermentation terminate after wastewater treatment, output and the cellulose conversion rate of fiber-like ethanol can not be improved by this method.
For another example, publication number is that the Chinese patent application of CN101914576A discloses with paper mill sludge and monosodium glutamate waste liquid mixture as substrate carries out the strategy of ethanol methane coproduction, its raw material paper mill sludge is with fiber fines type organic for main component, and its content can reach 70-90%, can be easier to be degraded.Even and if energy grass raw material is after steam explosion pre-treatment, content of cellulose scope is also only 35-50%, not easily carries out enzymolysis and ethanol industryization is produced.
Summary of the invention
In order to solve problems of the prior art, the object of this invention is to provide a kind of method utilizing energy grass co-producing ethanol and methane, being produced by lignocellulosic material substantially and obtaining clean energy.
In order to realize the object of the invention, technical scheme of the present invention is as follows:
A kind of method utilizing energy grass co-producing ethanol and methane, with the energy grass after steam explosion for raw material, after cellulase and beta-glucosidase enzymolysis, carry out high concentration of substrate simultaneous saccharification and fermentation ethanol, and fermentation residue is carried out Anaerobic Digestion to produce methane.
Energy grass content of cellulose after described steam explosion is 30-55%, and hemicellulose level is 5-10%, and content of lignin is 25-40%, and ash oontent is 1-3%.
Further, described method comprises the steps:
1) raw materials pretreatment:
In the energy grass after steam explosion, add damping fluid, make its concentration be 10-30%, adjustment pH is 5.1-5.5, adds cellulase and beta-glucosidase carries out enzymolysis, obtains fermentation substrate;
2) high concentration of substrate simultaneous saccharification and fermentation ethanol:
In described fermentation substrate, inoculate yeast saccharomyces cerevisiae ferment, after fermentation ends, obtain mash, distillation is carried out to mash and obtains ethanol and fermentation residue;
3) with described fermentation residue for digestion substrate, utilize and carry out anaerobic digestion containing the anaerobic sludge of methanogen, collect methane gas.
Step 2) in terminate when the alcohol concn in reaction system is stablized fermentation.
Further, cellulose enzyme equivalent 20FPU/gcellulose, beta-glucosidase enzyme equivalent 20U/gcellulose.Further, described enzymatic hydrolysis condition is temperature 45 C-50 DEG C, pH5.1-5.5, time 6-18h.Containing a large amount of glucose in enzymolysis solution, be easy to contact with yeast saccharomyces cerevisiae and be utilized.Cellulose conversion in raw material after steam explosion pre-treatment, as fermentation substrate, better can be become clean energy ethanol by the enzymolysis product after above-mentioned enzymatic hydrolysis condition enzymolysis.
Further, described damping fluid is the citric acid-sodium citrate damping fluid containing yeast extract and peptone, and its pH value is 5.1-5.5.The effect of the yeast extract in this damping fluid is for the growth of yeast flora provides sufficient C source, and the overall growth can played as yeast flora of described damping fluid provides C source, N source, the effect that maintenance system pH is stable.
The compound method of described damping fluid is: configure citric acid, sodium citrate buffer solution mother liquor respectively, concentration is 1mol/L.Citric acid, sodium citrate mother liquor are diluted 20 times to 0.05mol/L by the used time, mixing, pH is adjusted to 5.5 (due to raw material generating portion small molecules acid after steam explosion, raw material is in acid, during fermentation, pH is 5.0, can reduce the use of calcium hydroxide during pH regulator when damping fluid after being heightened by pH mixes with raw material, calcium hydroxide is supersaturated solution).Add subsequently, 15g/L yeast extract, 30g/L peptone, mixing, regulate pH to 5.1-5.5.
The present invention utilizes above-mentioned damping fluid to provide stable reaction system to the energy grass after steam explosion, the energy grass after steam explosion can be made to be easy to enzymolysis, be more conducive to subsequent reactions.
Further, step 2) in fermentation time, adjustment fermentation substrate concentration (initial substrate concentration) is 8%-12%, inoculation yeast saccharomyces cerevisiae ferments, carry out batch feed supplement between yeast phase, what add is energy grass after steam explosion, makes the final concentration of fermentation substrate be 18%-22%.
When initial substrate concentration and whole concentration of substrate meet above-mentioned condition, more stable reaction system can be maintained, thus utilize Mierocrystalline cellulose to carry out the production of ethanol better.
Further, feed supplement 3-4 time between yeast phase, each feed supplement amount needs
according to claimdescribed in book, formula calculates.The effect of feed supplement is to improve substrate equivalent, makes to obtain larger ethanol production during fermentation ends.
As preferably, described yeast saccharomyces cerevisiae
preservationin Chinese microorganism strain
preservationmanagement
the councilcommon micro-organisms center,
preservationmay 6 2008 date,
preservationbe numbered CGMCCNo.2660.This bacterial classification has more excellent fermenting alcohol ability.
The inoculum size of described yeast saccharomyces cerevisiae is 1 ~ 3 × 10
8/ mL, if access flora concentration is lower, can affect alcohol yied, if access concentration is higher, need a large number of nutrients for flora growth, is unsuitable for maintaining stable reaction system.
Further, the condition of described anaerobic digestion is 30 DEG C-35 DEG C, pH6.8-7.4.Under this condition, the carrying out of anaerobic digestion can be promoted.
As preferably, the described anaerobic sludge containing methanogen is pH6.5-7.0, and solubility COD value is less than 20000mg/L, propionic acid content is lower than 1000mg/L, total solids TS content is 100-200g/Kg, and total volatile solid(s) (TVS) VS content is 100-200g/Kg, and VS/TS content is the mud of 80-85%.Inoculation anaerobic sludge amount is that every 10mL fermentation residue adds 150mL anaerobic sludge
Further, described energy grass is selected from one or more in wheatgrass, lyme grass, Chinese silvergrass, needle Rhizoma Imperatae, reed, switchgrass, Herba penniseti and eelgrass.
As preferably, described energy grass is one or more in switchgrass, wheatgrass and needle Rhizoma Imperatae.
Beneficial effect of the present invention is:
The invention provides a kind of method utilizing energy grass co-producing ethanol and methane, produced by lignocellulosic material substantially and obtain clean energy.
The present invention is using the energy grass after steam explosion as raw material, product after cellulase and beta-glucosidase enzymolysis is as substrate, carry out batch feed supplement height concentration of substrate simultaneous saccharification and fermentation to integrate mutually with the Anaerobic Digestion of the full residue of ethanol fermentation, carry out the combination producing of ethanol methane two kinds of clean energies, major objective is improving cellulosic ethanol transformation efficiency as far as possible while, pass through anaerobic digestion techniques, all compositions being anaerobically digested flora and utilizing in further trans-utilization ethanol fermentation residue, thus while raising energy grass holocellulose transformation efficiency, realize the Multi-class propagation of energy grass total composition, the raw material availability bottleneck problem of producing clean energy for existing lignocellulosic material proposes effective solution.
In addition, the present invention is applied to industrial production aspect tool and has the following advantages:
1, same set of production line can obtain ethanol methane two kinds of clean energies simultaneously, and existing liquid fuel also has geseous fuel, can meet different energy demands.
2, in the process of producing clean energy, can improve energy grass holocellulose utilization ratio by the mode of coproduction, be the clean energy that the world today is badly in need of as much as possible by available conversion.
3, by the scientific research strategy of ethanol methane coproduction, the total composition Multi-class propagation of energy grass can be realized, for the suitability for industrialized production of clean energy provides rational basis.
Accompanying drawing explanation
fig. 1for the cellulose conversion of the high substrate simultaneous saccharification and fermentation of embodiment of the present invention 1-4
figure.
fig. 2for the Biochemical Methane Potential test experiments result of embodiment of the present invention 1-4.
fig. 3for ethanol, the methane coproduction mass balance analysis result of embodiment of the present invention 1-4.
Embodiment
Below in conjunction with embodiment, the preferred embodiment of the present invention is described in detail.It will be appreciated that providing of following examples is only object in order to play explanation, being not used to limit scope of the present invention.Those skilled in the art, when not deviating from aim of the present invention and spirit, can carry out various amendment and replacement to the present invention.
The experimental technique used in following embodiment if no special instructions, is ordinary method.
The compound method of damping fluid used in following embodiment is:
Configure citric acid, sodium citrate buffer solution mother liquor respectively, concentration is 1mol/L.Before using, citric acid, sodium citrate mother liquor are diluted 20 times to 0.05mol/L, and both are mixed to pH is 5.1-5.5.Add yeast extract and peptone subsequently, concentration is respectively 15g/L and 30g/L.
Cellulase is purchased from SIGMAC2730-50mL, and beta-glucosidase is purchased from SIGMA49290-250MG.
Anaerobic sludge containing methanogen is pH7.0, and solubility COD value is 19200mg/L, and propionic acid content is 850mg/L, total solids TS content is 128g/Kg, total volatile solid(s) (TVS) VS content is 107g/Kg, and VS/TS content is the active sludge of 83.5%, takes from The Big Red Gate, Beijing sewage work.
In following embodiment, other material used, reagent etc., if no special instructions, all can obtain from commercial channels.
In the present invention required location parameter and measuring method as follows:
1: the measuring method of glucose, ethanol, volatile acid content: high performance liquid chromatograph (Agilent 1260).Chromatographic column is Hi-PlexH (300mm × 7.7mm), column temperature 60 DEG C, Agilent Composition distribution, detector temperature 40 DEG C, and moving phase is dilute sulphuric acid (0.005mol/L), flow velocity 0.6mLmin
-1, sample size 5 μ L.
2: the measuring method of methane gas: NaOH draining water gathering of gas law
3: solubility COD measuring method: COD measures and adopts Hash COD determinator to measure, first need sample to dilute, sample thief 2ml, add 1ml potassium bichromate standardized solution, 3ml sulfuric acid-silver sulfate solution, heating observes whether become green, if become green, then needs sample to dilute, until after nondiscoloration dilution, measure in pipe to COD and add sample 2ml successively, potassium bichromate standardized solution 1ml, sulfuric acid-silver sulfate solution 3ml.Control group (replacing sample with 2ml distilled water) is set simultaneously.Mixing, clears up 2h for 150 DEG C in COD digestion device.After having cleared up, when temperature is down to 120 DEG C, take out COD and measure pipe, be cooled to room temperature.Colorimetric estimation: first select to measure program accordingly, by tubing surfaces wiped clean, uses control group zero setting, then distinguishes the COD value of working sample group, obtains data.
4: total solids TS, volatile solid VS measuring method: adopt standard method APHA, 1998.
Involved by following embodiment
table 1-
table 4as follows:
table 1energy grass composition analysis
table (%, DM)
table 2fermentation residue and inoculum composition measurement
table 3biochemical Methane Potential test terminates rear parametric measurement analysis
table
table 4parameter clearance interpretation of result before and after Biochemical Methane Potential test
Embodiment 1 wheatgrass (Agropyroncristatum) batch feed supplement height substrate simultaneous saccharification and fermentation combines with anaerobic digestion techniques and produces clean energy ethanol methane.
1, experiment material
Steam explosion wheatgrass raw material comes from University Of Science and Technology Of Tianjin, its composition measurement result
as table 1.
2, experimental technique
Dry with baking oven after obtaining steam explosion wheatgrass (Agropyroncristatum) raw material, final water content is 6.4%.Taking steam explosion raw material 10.68g adds in 250mL triangular flask, adds damping fluid 89.32mL subsequently, makes its concentration reach 10%, fully stirs with glass stick, adds Ca (OH)
2, regulate pH to 5.5, at 105 DEG C after sealing, under 10min condition, carry out sterilizing, after sterilizing terminates, be down to after room temperature until temperature, add cellulase and beta-glucosidase at 50 DEG C, under 200rpm condition, carry out enzymolysis, after enzymolysis 18h, treat that temperature is down to room temperature, obtain fermentation substrate.
Add yeast saccharomyces cerevisiae (CGMCCNo.2660) and carry out ethanol fermentation, inoculum size is 1 × 10
10individual/mL, fermentation substrate starting point concentration is 10%, between yeast phase respectively 12,24,36,48h supplements steam explosion wheatgrass raw material, each feed supplement amount is 4.53g, and fermentation substrate concentration is increased to 20%, until 96h, terminates ethanol fermentation experiment.Fermentation liquid distillation is obtained ethanol, and fermentation residue is for subsequent use.
Subsequently, 10mL fermentation residue and 150mL anaerobic sludge is added in anaerobism bottle, control group is set up to add 10mL distilled water and 150mL anaerobic sludge, because anaerobic sludge self also can produce gas, therefore control group must be set up to judge the anaerobic digestion end time, and come from the methane production of residue.Finally fill N
2to get rid of the air at anaerobism bottle top, envelope bottle.Every day carries out collection and confinement of gases with NaoH drainage, with 10mL effuser metering methane gas production.
3, experimental result
After 96h ethanol fermentation, the highest ethanol production reaches 15.24gkg
-1, corresponding cellulose conversion rate reaches 30.49%,
as Fig. 1 (a) shown in.Can learn through Biochemical Methane Potential test, after 30d, final methane cumulative withdrawal reaches 562.4mL, and its methane production is 360.05mLgVS
-1, result
as Fig. 2 (a) shown in.Can be learnt by mass balance analysis, every 100g wheatgrass can obtain ethanol 7.5g after batch height substrate simultaneous saccharification and fermentation, and methane 17.44g, clean energy amounts to 24.94g.Holocellulose transformation efficiency can reach 91.42% (see
table 4), be 2.0 times that carry out separately alcohol production.
4, conclusion
By the strategy that batch height substrate simultaneous saccharification and fermentation combines with anaerobic digestion techniques, the production of lignocellulosic material clean energy ethanol methane can be realized, improve wheatgrass (Agropyroncristatum) holocellulose utilization ratio and total composition Multi-class propagation thereof.
Experimental example 1
After the distillation of embodiment 1 fermentation liquid obtains fermentation residue, composition measurement is carried out, result to fermentation residue and inoculum
as table 2shown in.
By
table 2known, ethanol fermentation residue contains the acid of a large amount of small molecules, and COD concentration is higher, there is more Mierocrystalline cellulose, is comparatively suitable for carrying out anaerobically fermenting.Control group is set up while experimental group experiment starts, for identical with fermentation residue volume, and the distilled water of the identical access methanogen of inoculum size.Fill N
2to get rid of the air at anaerobism bottle top, envelope bottle.Set time every day carries out aerogenesis mensuration with drainage.Composition analysis is carried out, result after experiment terminates
as table 3shown in.
By
table 3known, after anaerobic digestion, the content of cellulose in residue, COD content, hemicellulose level, small molecules acid content etc. with
table 2compare and significantly reduced.
Embodiment 2 lyme grass (Elymusdahuricusturcz) batch feed supplement height substrate simultaneous saccharification and fermentation combines with anaerobic digestion techniques and produces clean energy ethanol methane.
1, experiment material
Steam explosion lyme grass raw material comes from University Of Science and Technology Of Tianjin, its composition measurement result
as table 1.
2, experimental technique
Dry with baking oven after obtaining steam explosion lyme grass (Elymusdahuricusturcz) raw material, final water content is 4.4%.Taking steam explosion raw material 10.46g adds in 250mL triangular flask, adds damping fluid 89.54mL subsequently, makes initial substrate concentration reach 10%, fully stir with glass stick, adds Ca (OH)
2, regulate pH to 5.5, at 105 DEG C after sealing, under 10min condition, carry out sterilizing, after sterilizing terminates, be down to after room temperature until temperature, add cellulase and beta-glucosidase at 50 DEG C, under 200rpm condition, carry out enzymolysis, after enzymolysis 18h, treat that temperature is down to room temperature, obtain fermentation substrate.
Add yeast saccharomyces cerevisiae (CGMCCNo.2660) and carry out ethanol fermentation, inoculum size is 1 × 10
10individual/mL, fermentation substrate starting point concentration is 10%, between yeast phase respectively 12,24,36,48h supplements steam explosion lyme grass raw material, each feed supplement amount is 4.41g, and fermentation substrate concentration is brought up to 20%, until 96h, terminates ethanol fermentation experiment.Fermentation liquid distillation is obtained ethanol, and fermentation residue is for subsequent use.
Subsequently, 10mL fermentation residue and 150mL anaerobic sludge is added in anaerobism bottle, control group is set up to add 10mL distilled water and 150mL anaerobic sludge, because anaerobic sludge self also can produce gas, therefore control group must be set up to judge the anaerobic digestion end time, and come from the methane production of residue.Finally fill N
2to get rid of the air at anaerobism bottle top, envelope bottle.Every day carries out collection and confinement of gases with NaoH drainage, with 10mL effuser metering methane gas production.
3, experimental result
After 96h ethanol fermentation, the highest ethanol production reaches 13.04gkg
-1, corresponding cellulose conversion rate reaches 20.75%,
as Fig. 1 (b) shown in.Can learn through Biochemical Methane Potential test, after 30d, final methane cumulative withdrawal reaches 546.7mL, and its methane production is 382.04mLgVS
-1, result
as Fig. 2 (b) shown in.Can be learnt by mass balance analysis, every 100g lyme grass can obtain ethanol 6.5g after batch height substrate simultaneous saccharification and fermentation, and methane 16.21g, clean energy amounts to 22.71g.Holocellulose transformation efficiency can reach 95.84% (
table 4), be 3.6 times that carry out separately alcohol production.
4, conclusion
By the strategy that batch height substrate simultaneous saccharification and fermentation combines with anaerobic digestion techniques, the production of lignocellulosic material clean energy ethanol methane can be realized, improve lyme grass (Elymusdahuricusturcz) holocellulose utilization ratio and total composition Multi-class propagation thereof.
Experimental example 2
After the distillation of embodiment 2 fermentation liquid obtains fermentation residue, composition measurement is carried out, result to fermentation residue and inoculum
as table 2shown in.
By
table 2known, ethanol fermentation residue contains the acid of a large amount of small molecules, and COD concentration is higher, there is more Mierocrystalline cellulose, is comparatively suitable for carrying out anaerobically fermenting.
Control group is set up while experimental group experiment starts, for identical with fermentation residue volume, and the distilled water of the identical access methanogen of inoculum size.Fill N
2to get rid of the air at anaerobism bottle top, envelope bottle.Set time every day carries out aerogenesis mensuration with drainage.Composition analysis is carried out, result after experiment terminates
as table 3shown in.
By
table 3known, after anaerobic digestion, the content of cellulose in residue, COD content, hemicellulose level, small molecules acid content etc. with
table 2compare and significantly reduced.
Embodiment 3 needle Rhizoma Imperatae (Stipabaicalensisroshev) batch feed supplement height substrate simultaneous saccharification and fermentation combines with anaerobic digestion techniques and produces clean energy ethanol methane
1, experiment material
Steam explosion needle Rhizoma Imperatae raw material comes from University Of Science and Technology Of Tianjin, its composition measurement result
as table 1.
2, experimental technique
Dry with baking oven after obtaining steam explosion needle Rhizoma Imperatae (Stipabaicalensisroshev) raw material, final water content is 21.4%.Taking steam explosion raw material 12.72g adds in 250mL triangular flask, adds damping fluid 87.28mL subsequently, makes initial substrate concentration reach 10%, fully stir with glass stick, adds Ca (OH)
2, regulate pH to 5.5, at 105 DEG C after sealing, under 10min condition, carry out sterilizing, after sterilizing terminates, be down to after room temperature until temperature, add cellulase and beta-glucosidase at 50 DEG C, under 200rpm condition, carry out enzymolysis, after enzymolysis 18h, treat that temperature is down to room temperature, obtain fermentation substrate.
Add yeast saccharomyces cerevisiae (CGMCCNo.2660) and carry out ethanol fermentation, inoculum size is 1 × 10
10individual/mL, fermentation substrate starting point concentration is 10%, between yeast phase respectively 12,24,36,48h supplements steam explosion needle Rhizoma Imperatae raw material, each feed supplement amount is 4.41g, and fermentation substrate concentration is brought up to 20%, until 96h, terminates ethanol fermentation experiment.Fermentation liquid distillation is obtained ethanol, and fermentation residue is for subsequent use.
Subsequently, 10mL fermentation residue and 150mL anaerobic sludge is added in anaerobism bottle, control group is set up to add 10mL distilled water and 150mL anaerobic sludge, because anaerobic sludge self also can produce gas, therefore control group must be set up to judge the anaerobic digestion end time, and come from the methane production of residue.Finally fill N
2to get rid of the air at anaerobism bottle top, envelope bottle.Every day carries out collection and confinement of gases with NaoH drainage, with 10mL effuser metering methane gas production.
3, experimental result
After 96h ethanol fermentation, the highest ethanol production reaches 15.78gkg
-1, corresponding cellulose conversion rate reaches 29.53%,
as Fig. 1 (c) shown in.Can learn through Biochemical Methane Potential test, after 30d, final methane cumulative withdrawal reaches 566.7mL, and its methane production is 258.65mLgVS
-1, result
as Fig. 2 (c) shown in.Can be learnt by mass balance analysis, every 100g lyme grass can obtain ethanol 8.0g after batch height substrate simultaneous saccharification and fermentation, and methane 16.80g, clean energy amounts to 24.80g.Holocellulose transformation efficiency can reach 85.98% (
table 4), be 2.0 times that carry out separately alcohol production.
4, conclusion
By the strategy that batch height substrate simultaneous saccharification and fermentation combines with anaerobic digestion techniques, the production of lignocellulosic material clean energy ethanol methane can be realized, improve needle Rhizoma Imperatae (Stipabaicalensisroshev) holocellulose utilization ratio and total composition Multi-class propagation thereof.
Experimental example 3
After the distillation of embodiment 3 fermentation liquid obtains fermentation residue, composition measurement is carried out, result to fermentation residue and inoculum
as table 2shown in.
By
table 2known, ethanol fermentation residue contains the acid of a large amount of small molecules, and COD concentration is higher, there is more Mierocrystalline cellulose, is comparatively suitable for carrying out anaerobically fermenting.
Control group is set up while experimental group experiment starts, for identical with fermentation residue volume, and the distilled water of the identical access methanogen of inoculum size.Fill N
2to get rid of the air at anaerobism bottle top, envelope bottle.Set time every day carries out aerogenesis mensuration with drainage.Composition analysis is carried out, result after experiment terminates
as table 3shown in.
By
table 3known, after anaerobic digestion, the content of cellulose in residue, COD content, hemicellulose level, small molecules acid content etc. with
table 2compare and significantly reduced.
Embodiment 4 reed (Triarrhenasacchariflora) batch feed supplement height substrate simultaneous saccharification and fermentation combines with anaerobic digestion techniques and produces clean energy ethanol methane
1, experiment material
Steam explosion reed raw material comes from University Of Science and Technology Of Tianjin, its composition measurement result
as table 1.
2, experimental technique
Dry with baking oven after obtaining steam explosion reed (Triarrhenasacchariflora) raw material, final water content is 12.8%.Taking steam explosion raw material 11.47g adds in 250mL triangular flask, adds damping fluid 88.53mL subsequently, makes initial substrate concentration reach 10%, fully stir with glass stick, adds Ca (OH)
2, regulate pH to 5.5, at 105 DEG C after sealing, under 10min condition, carry out sterilizing, after sterilizing terminates, be down to after room temperature until temperature, add cellulase and beta-glucosidase at 50 DEG C, under 200rpm condition, carry out enzymolysis, after enzymolysis 18h, treat that temperature is down to room temperature, obtain fermentation substrate.
Add yeast saccharomyces cerevisiae (CGMCCNo.2660) and carry out ethanol fermentation, inoculum size is 3 × 10
10individual/mL, fermentation substrate starting point concentration is 10%, between yeast phase respectively 12,24,36,48h supplements steam explosion reed raw material, each feed supplement amount is 4.41g, and fermentation substrate concentration is brought up to 20%, until 96h, terminates ethanol fermentation experiment.Fermentation liquid distillation is obtained ethanol, and fermentation residue is for subsequent use.
Subsequently, 10mL fermentation residue and 150mL anaerobic sludge is added in anaerobism bottle, control group is set up to add 10mL distilled water and 150mL anaerobic sludge, because anaerobic sludge self also can produce gas, therefore control group must be set up to judge the anaerobic digestion end time, and come from the methane production of residue.Finally fill N
2to get rid of the air at anaerobism bottle top, envelope bottle.Every day carries out collection and confinement of gases with NaoH drainage, with 10mL effuser metering methane gas production.
3, experimental result
After 96h ethanol fermentation, the highest ethanol production reaches 14.96gkg
-1, corresponding cellulose conversion rate reaches 25.11%,
as Fig. 1 (d) shown in.Can learn through Biochemical Methane Potential test, after 30d, final methane cumulative withdrawal reaches 443.9mL, and its methane production is 309.12mLgVS
-1, result
as Fig. 2 (d) shown in.Can be learnt by mass balance analysis, every 100g lyme grass can obtain ethanol 7.5g after batch height substrate simultaneous saccharification and fermentation, and methane 13.33g, clean energy amounts to 20.83g.Holocellulose transformation efficiency can reach 85.08% (
table 4), be 2.4 times that carry out separately alcohol production.
4, conclusion
By the strategy that batch height substrate simultaneous saccharification and fermentation combines with anaerobic digestion techniques, the production of lignocellulosic material clean energy ethanol methane can be realized, improve reed (Triarrhenasacchariflora) holocellulose utilization ratio and total composition Multi-class propagation thereof.
Experimental example 4
After the distillation of embodiment 4 fermentation liquid obtains fermentation residue, composition measurement is carried out, result to fermentation residue and inoculum
as table 2shown in.
By
table 2known, ethanol fermentation residue contains the acid of a large amount of small molecules, and COD concentration is higher, there is more Mierocrystalline cellulose, is comparatively suitable for carrying out anaerobically fermenting.
Control group is set up while experimental group experiment starts, for identical with fermentation residue volume, and the distilled water of the identical access methanogen of inoculum size.Fill N
2to get rid of the air at anaerobism bottle top, envelope bottle.Set time every day carries out aerogenesis mensuration with drainage.Composition analysis is carried out, result after experiment terminates
as table 3shown in.
By
table 3known, after anaerobic digestion, the content of cellulose in residue, COD content, hemicellulose level, small molecules acid content etc. with
table 2compare and significantly reduced.Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. one kind utilizes the method for energy grass co-producing ethanol and methane, it is characterized in that, with the energy grass after steam explosion for raw material, after cellulase and beta-glucosidase enzymolysis, carry out high concentration of substrate simultaneous saccharification and fermentation ethanol, and fermentation residue is carried out Anaerobic Digestion to produce methane.
2.
according to claimmethod described in 1, is characterized in that, described method comprises the steps:
1) raw materials pretreatment:
In the energy grass after steam explosion, add damping fluid, make its concentration be 10%-30%, adjustment pH is 5.1-5.5, adds cellulase and beta-glucosidase carries out enzymolysis, obtains fermentation substrate;
2) high concentration of substrate simultaneous saccharification and fermentation ethanol:
In described fermentation substrate, inoculate yeast saccharomyces cerevisiae ferment, after fermentation ends, obtain mash, distillation is carried out to mash and obtains ethanol and fermentation residue;
3) with described fermentation residue for digestion substrate, utilize and carry out anaerobic digestion containing the anaerobic sludge of methanogen, collect methane gas.
3.
according to claimmethod described in 1 or 2, is characterized in that, described enzymatic hydrolysis condition is temperature 45 C-50 DEG C, pH5.1-5.5, time 6-18h.
4.
according to claimmethod described in 3, is characterized in that, the citric acid-sodium citrate damping fluid containing yeast extract and peptone, its pH value is 5.1-5.5.
5.
according to claimmethod described in 1 or 2, it is characterized in that, step 2) in fermentation time, adjustment fermentation substrate concentration is 8%-12%, inoculation yeast saccharomyces cerevisiae ferments, carry out batch feed supplement between yeast phase, what needs were added is the raw material obtained after steam explosion pre-treatment, makes the final concentration of fermentation substrate be 18%-22%.
6. want the method described in 5 according to right, it is characterized in that, feed supplement 3-4 time.
7. want the method described in 6 according to right, it is characterized in that, described yeast saccharomyces cerevisiae is preserved in China Committee for Culture Collection of Microorganisms's common micro-organisms center, preservation date on May 6th, 2008, and deposit number is CGMCCNo.2660.
8.
according to claimmethod described in 1 or 2, is characterized in that, the condition of described anaerobic digestion is 30 DEG C-35 DEG C, pH6.8-7.4.
9.
according to claimmethod described in 8, it is characterized in that, the described anaerobic sludge containing methanogen is pH6.5-7.0, solubility COD value is less than 20000mg/L, propionic acid content is lower than 1000mg/L, total solids TS content is 100-200g/Kg, and total volatile solid(s) (TVS) VS content is 100-200g/Kg, and VS/TS content is the mud of 80-85%.
10.
according to claimmethod described in 1 ~ 9 any one, is characterized in that, described energy grass be selected from wheatgrass, lyme grass, Chinese silvergrass, needle Rhizoma Imperatae, reed, switchgrass, Herba penniseti and eelgrass one or more.
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