CN106119295A - Utilize NH4hCO3the method of pretreatment corn straw and the anaerobic fermentation method of corn straw - Google Patents
Utilize NH4hCO3the method of pretreatment corn straw and the anaerobic fermentation method of corn straw Download PDFInfo
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- CN106119295A CN106119295A CN201610760837.5A CN201610760837A CN106119295A CN 106119295 A CN106119295 A CN 106119295A CN 201610760837 A CN201610760837 A CN 201610760837A CN 106119295 A CN106119295 A CN 106119295A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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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
Abstract
It is an object of the invention to provide one and utilize NH4HCO3The method of pretreatment corn straw and the anaerobic fermentation method of corn straw, cross 40 mesh sieves after corn straw smashing, adding mass concentration is the NH of 4% ~ 10%4HCO3Solution, after mix homogeneously, under room temperature, micro-oxygen processes a few days, the corn straw after then processing take out and add water stir after stand, filter, dry stand-by；Then gained corn straw is carried out anaerobic fermentation gas production.Getting a promotion through the gas production of the pretreated corn straw of the method for the invention, improve 30.6% compared with time untreated, the COD clearance in pretreated corn straw anaerobic fermentation process is also obviously improved.
Description
Technical field
The invention belongs to corn straw processing technology field, particularly relate to NH4HCO3The method of pretreatment corn straw and
The anaerobic fermentation method of corn straw.
Background technology
China is large agricultural country, is also straw yield big country, and only corn straw just has 2.2 hundred million tons.Corn straw is in the micro-life of anaerobism
Clean energy resource biogas can be produced under the effect of thing.And biogas is as a kind of high-grade clean energy resource, there is feed distribution
Extensively, construction cost is low, transformation efficiency is high, comprehensive benefit is good, it is raw at energy economy and discharge reduction in rural area and agricultural to be suitable for the features such as rural development
State environmental conservation is played a positive role.Development stalk fermentation engineering can effectively alleviate stalk resource waste problem, also can change
Kind rural energy structure, is the utilization ways of a clean and effective.
The preprocess method of straw is broadly divided into Physical, chemical method and bioanalysis and wherein two or more side at present
The coupling processing of method.But all there is the problems such as some the most relatively costly, treatment effect is not good enough, follow-up waste remediation.
Summary of the invention
It is an object of the invention to provide one and utilize NH4HCO3The method of pretreatment corn straw and the anaerobism of corn straw are sent out
Fermenting process, gets a promotion through the gas production of the pretreated corn straw of the method for the invention, raising compared with time untreated
30.6%, the COD clearance in pretreated corn straw anaerobic fermentation process is also obviously improved.
For achieving the above object, the present invention is by the following technical solutions:
One utilizes NH4HCO3The method of pretreatment corn straw, crosses 40 mesh sieves after corn straw smashing, add mass concentration and be
The NH of 4% ~ 10%4HCO3Solution, after mix homogeneously, under room temperature, micro-oxygen processes a few days, and the corn straw after then processing takes out also
Add water and stand after stirring, filter, dry stand-by.
Preferably, added NH4HCO3The mass concentration of solution is 8%.
Preferably, described NH4HCO3The addition of solution is the corn straw after just flooding pulverizing.
The anaerobic fermentation method of a kind of corn straw, comprises the following steps:
(1) corn straw pretreatment: cross 40 mesh sieves after corn straw smashing, adding mass concentration is the NH of 4% ~ 10%4HCO3Molten
Liquid, after mix homogeneously, under room temperature micro-oxygen process a few days, then will process after corn straw take out and add water stir after quiet
Put, filter, dry stand-by；
(2) take 60 ~ 100g step (1) gained and dry stand-by corn straw, add the inoculation liquid of 150 ~ 300mL and 700 ~
The water of 850mL, is configured to fermentation liquid that TS concentration is 8% ~ 12% and regulates pH to 7.0；
(3) then step (2) gained fermentation liquid is loaded in reactor and being placed on reactor sealing in constant incubator,
Fermentation temperature is set to 35 DEG C, the fermentation culture a few days.
Preferably, in step (1), added NH4HCO3The mass concentration of solution is 8%.
Preferably, in step (1), described NH4HCO3The addition of solution is the corn straw after just flooding pulverizing.
Preferably in step (2), the sodium carbonate using mass concentration to be 10% or sodium bicarbonate solution regulation fermentation liquid pH are extremely
7.0。
Beneficial effects of the present invention is as follows:
Corn straw is mainly made up of plant cell wall, and it is cellulose, hemicellulose, lignin that cell wall forms substantially, fiber
Element and hemicellulose are wrapped up layer by layer by lignin.Lignin to the protective effect of cellulose and cellulose by hemicellulose covering etc.
Structure determines, with the factor of chemical composition, the characteristic that corn straw is difficult to hydrolyze, and this is the anaerobic fermentation manufacture of corn straw
Obstacle so that anaerobic digestion time extends, digestibility reduces, gas production reduces.In order to ensure being smoothed out of anaerobic fermentation, right
Corn straw carries out pretreatment, makes the cellulose and the hemicellulose that are wrapped up by lignin come out, and destroys the structure of straw, makes
Fermentative microorganism increases with the contact area of cellulose, hemicellulose, and then improves gas production.
Ammonium hydrogen carbonate (NH4HCO3) solution shows alkalescence, the hydrogen bonded within corn stalk fiber can be made to die down, make fibre
Dimension molecule expands, and can saponification alduronic acid and the ester bond of acetic acid, neutralize free alduronic acid, make the fiber in cell wall constituent
Contact weakening and hemicellulose between element and lignin are dissolved, thus are more beneficial for anaerobic digestion.Ammonia nitrogen is microorganism weight
The nitrogen source wanted, will cause growth of microorganism slow if lacked, the underutilization to carbon source, the Semen Maydis after processing with ammonium hydrogen carbonate
Straw can also improve the nitrogen content of straw to a certain extent, thus improves the utilization rate of carbon source.
The corn straw utilizing method pretreatment of the present invention to obtain carries out anaerobic fermentation, the aerogenesis energy of corn straw
Power obtains a certain degree of raising, is embodied in the microstructure generation significant change through pretreated corn straw,
Under scanning electron microscope, considerable measuring substantially loses trace, and the highest effect of pretreatment concentration is the most obvious, in particular by mass concentration is
Ammonium hydrogen carbonate (the NH of 8%4HCO3) solution aerogenesis best results, improve 30.6% compared with time untreated；Additionally, after pretreatment
Corn straw COD clearance in anaerobic fermentation process be also obviously improved, wherein using mass concentration is the carbon of 8%
Acid hydrogen ammonium (NH4HCO3) solution, COD clearance reaches maximum, is 36%.So the method for the invention is at the pre-place of corn straw
Reason aspect achieves extraordinary effect.
Waste liquid after method the most of the present invention not only cost effective, and process can recycle, it is also possible to
Biogas slurry and biogas residue coordinates secondary to utilize, and there is not the features such as operation easier is big, processing cost is high, waste liquid is difficult.
To sum up, the present invention is the most with the obvious advantage in cost control, treatment effect and environmental friendliness degree, if it is possible to
To promoting, the high-quality and high-efficiency for corn straw utilizes significant, also can alleviate simultaneously corn straw the wasting of resources and
Arbitrarily abandoning of corn straw and the series of environmental problems that brings.
Accompanying drawing explanation
Fig. 1 is embodiment 1 to 5 and the scanning electron microscope (SEM) photograph of the pretreated corn straw of comparative example；
Fig. 2 is the daily gas amount change in embodiment 1 to 5 and comparative example pretreated corn straw anaerobic fermentation process
Figure；
Fig. 3 is methane in the daily output tolerance in embodiment 1 to 5 and comparative example pretreated corn straw anaerobic fermentation process
The variation diagram of content；
Fig. 4 is the cumulative gas production change in embodiment 1 to 5 and comparative example pretreated corn straw anaerobic fermentation process
Figure；
Fig. 5 is the pH of fermentation liquid in the anaerobic fermentation of embodiment 1 to 5 and the pretreated corn straw of comparative example starts a week
Value variation diagram.
Detailed description of the invention
In order to make the technical purpose of the present invention, technical scheme and beneficial effect clearer, below in conjunction with specific embodiment to this
The technical scheme of invention is further illustrated, but described embodiment is intended to explain the present invention, and it is not intended that to this
Bright restriction, unreceipted concrete technology or condition person in embodiment, according to the technology described by the document in this area or condition
Or carry out according to product description.
Embodiment 1
One utilizes NH4HCO3The method of pretreatment corn straw:
Crossing 40 mesh sieves after corn straw smashing, weigh 88g adding 300mL mass concentration is the NH of 4%4HCO3Solution, floods just
Corn straw after pulverizing, is positioned over after mix homogeneously in Plastic Drum, and (Plastic Drum was the completeest in 10 days for the process of the most micro-oxygen
Hermetically sealed, air can enter), the corn straw after then processing adds water after stirring and stands, filters, and dries stand-by.
The method using above-mentioned pretreated corn straw to carry out anaerobic fermentation is as follows:
Take the stand-by corn straw of above-mentioned drying in fermentation flask, add the inoculation liquid of 200mL, [the source of described inoculation liquid: will
Common fresh cattle manure (mainly utilizing the methanogen in cattle manure) adds water and is configured to TS concentration (the most total solid concentration, lower with) and is
The fermentation liquid of 8%, after being then charged in reactor (reactor purges through nitrogen, removes air) and being sealed by reactor
Being placed in constant incubator, fermentation temperature is set as 35 DEG C, and the anaerobic fermentation carried out 35 days by a definite date is cultivated；After fermentation ends,
Taking fermented supernatant fluid 2L, add 10g corn straw and carry out the prepared inoculation liquid of tamed strain cultivation, the condition that domestication is cultivated is permanent
Temperature incubator is cultivated one week for 35 DEG C], and add water to 1000mL, be configured to fermentation liquid that TS concentration is 8% and by mass concentration be
10% sodium carbonate or sodium bicarbonate solution regulation pH value are 7.0；Be then charged in reactor (reactor through nitrogen purge, remove
Remove air) and being placed on reactor sealing in constant incubator, fermentation temperature is set as 35 DEG C, uses draining water gathering of gas law to receive
Collection aerogenesis, stopping aerogenesis one week after, as the time of termination, thus records the change of daily gas amount and cumulative gas production changes, such as Fig. 2
Shown in Fig. 4.
The measurement of methane content uses gas chromatography, and concrete testing conditions is: Porapak N chromatographic column, the gas of 250 μ L
Body quantitative air inlet ring, sets detector 1500 DEG C, column temperature 80 DEG C, injection port 60 DEG C；It is 0.6s that methane goes out peak retention time, methane
The relation of content Y and peak area x is: while y%==0.0031*x+2.5029(methane content measures, it is also possible to detect CO2
Content, CO2Going out peak retention time is 1.2s, CO2The relation of content Y and peak area x is: y%==0.0147*x-10.6), thus
Record methane content, be then calculated the accounting of methane content, as shown in Figure 3.
Embodiment 2
Added NH4HCO3The mass concentration of solution is 6%, and remaining is with embodiment 1.
Embodiment 3
Added NH4HCO3The mass concentration of solution is 8%, and remaining is with embodiment 1.
Embodiment 4
Added NH4HCO3The mass concentration of solution is 10%, and remaining is with embodiment 1.
Embodiment 5
Added NH4HCO3The mass concentration of solution is 12%, and remaining is with embodiment 1.
Comparative example: the most preprocessed
Add and NH4HCO3The water of solution equal volume amounts replaces NH4HCO3Solution, remaining is with embodiment 1.
Testing embodiment 1 to 5 and comparative example, test result analysis is as follows:
Fig. 1 show the scanning electron microscope (SEM) photograph of the corn straw under variable concentrations processes.From Fig. 1 a-f it can be seen that matched group a
Straw structure is relatively smooth, smooth and has certain breakage, this is because the cellulose of composition corn straw main component, half fibre
Dimension element and lignin are chain structure, and its chain polymerization state makes the structure of corn straw may appear to the most whole under the microscope
Together, smoothing, corn straw carries out pulverizing simultaneously can have a certain degree of destruction to make it a certain degree of breakage occur structure.
Corn straw structure after being can be seen that process by Fig. 1 b-f seems mixed and disorderly, and many positions occur in that breakage and incompleteness, along with place
The increase of reason concentration, the damaged degree of corn straw is bigger, and erosion trace also becomes apparent from, and this shows the knot of pretreated corn straw
Structure there occurs that change, the lignin structure on corn straw surface are destroyed, NH4HCO3The pretreatment concentration of solution is the highest, Semen Maydis
The straw structure degree that is damaged is the most obvious.Owing to lignin can not be utilized by anaerobic fermentation Institute of Micro-biology, and its structure is very
Densification, but through NH4HCO3After process, lignin polymerization's body occurs in that fracture and damaged, wrap up cellulose therein, half
Cellulose then comes out, and the microorganism in fermentation liquid directly can contact with available material so that fermentation reaction can be carried out
More smoothly, quickly.
Fig. 2 show embodiment 1 to 5 variable concentrations NH4HCO3The corn straw processed and the anaerobic fermentation gas production of comparative example
Situation.The most after inoculation the 1st～2d, daily output tolerance is higher and increase along with pretreatment concentration, produces tolerance daily
Rise the most therewith, this and NH in pretreated straw4HCO3Residual relevant, the fermented feed liquid after inoculation carries out rapidly anaerobism and sends out
The acid-producing of ferment first stage, CO is accelerated in the accumulation of volatile fatty acid3 2-Ion is with CO2Form effusion, the most initially
Phase gas composition is mainly carbon dioxide, and methane content is negligible.Comparative example and through 4%, 6%, 8%NH4HCO3After process
Corn straw all can normal fermentation, and through mass concentration be the NH of 12%4HCO3Corn straw after process fermentation 3d it
After the most no longer aerogenesis.After fermentation is smoothed out, 10% NH4HCO3Corn straw after process reaches aerogenesis peak, time the soonest
It is 6d；The NH of 8%4HCO3Corn straw after process takes second place, and the time is 7d, and remaining all reaches aerogenesis peak at 9d.?
The front 15d of sweat, the NH of 8%4HCO3Straw daily output tolerance after process is in higher level, phase variable concentrations after fermentation
NH4HCO3The corn straw aerogenesis situation difference processed is little, and gas happening law is similar.As can be seen here, through NH4HCO3After pretreatment
Corn straw, the time arrived in its aerogenesis peak relatively early, along with NH4HCO3The increase of pretreatment concentration, arrives in aerogenesis peak
Time is the most early.Corn straw after higher concentration process receives destruction, the fibre that a part is wrapped up by lignin due to its structure
Dimension element and hemicellulose come out so that reaction is easier to make for, and available material increases, and whole fermentation period shortens, and produce
Tolerance also gets a promotion.
Fig. 3 is embodiment 1 to 5 variable concentrations NH4HCO3In the corn straw processed and the daily output tolerance of comparative example, methane contains
Amount situation of change.From figure 3, it can be seen that except being the NH of 12% through mass concentration4HCO3Corn straw after process does not produce
Outside raw methane, remaining respectively organizes methane content all 50%～about 60%, variable concentrations NH4HCO3Methane content under Chu Liing is slightly
Difference, the wherein NH of 8%4HCO3Straw corn straw fermentation initial stage methane content after process is slightly above remaining each group, methane content
Maximum is 62%, improves 6.9% than comparative example.
Fig. 4 show embodiment 1 to 5 variable concentrations NH4HCO3The corn straw processed and the cumulative gas production of comparative example become
Change situation, variable concentrations NH4HCO3Under process, each group of cumulative gas production Changing Pattern is similar, but mass concentration is the NH of 8%4HCO3
Pretreated group cumulative gas production is consistently higher than remaining each group.It is the NH of 8% through mass concentration4HCO3Tiring out of corn straw after process
Long-pending gas production is 14690mL, and unit TS gas production is the 183.6mL/g [calculating of unit TS gas production: cumulative gas production/(initial
The TS of the quality * corn straw of corn straw, the water content 9% of TS=1 corn straw of corn straw), lower with], and not
Pretreatment is compared and is improve 30.6%；It is the NH of 10% through mass concentration4HCO3The cumulative gas production of the corn straw after process
It, for 12890mL, unit TS gas production is 161.1mL/g, improves 14.7% compared with non-pretreatment, is 4% through mass concentration
NH4HCO3The total gas production of the straw after process is minimum, and for 11225mL, difference is little compared with non-pretreated straw.
From fig. 5, it can be seen that after fermentation reaction starts, embodiment 1 to 5 variable concentrations NH4HCO3The corn stalk of pretreatment
The pH value that stalk and comparative example are respectively organized is the most on a declining curve.Through NH in anaerobic fermentation process4HCO3The corn straw pH value of pretreatment
Higher state all can be maintained after decline.Work as NH4HCO3When pretreatment concentration is 6%, 8%, 10%, fermentation liquid pH value maintains
6.5 left and right；And comparative example and NH4HCO3When pretreatment concentration is 4%, it is relatively big that fermentation liquid pH value declines scope, is 5.5 left sides at pH
Right.In sweat, when aerogenesis effect is the best, the pH of fermentation liquid is the most stable, through NH that concentration is 6%, 8%, 10%4HCO3Pre-place
After reason, in corn straw anaerobic fermentation process, the pH of fermentation liquid is more stable, and ferment effect is also than the most preprocessed and NH4HCO3
Concentration is to do very well when 4%.
COD clearance in the pretreated corn straw of table 1 present invention and comparative example anaerobic fermentation process.
As shown in table 1, embodiment 1 to 4 pretreated corn straw COD clearance in anaerobic fermentation process also obtains
To being obviously improved, the ammonium hydrogen carbonate (NH wherein using mass concentration to be 8%4HCO3) solution, COD clearance reaches maximum, for
36%, it is the twice of the COD clearance (18%) of the most preprocessed corn straw.
The above is only the preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. one kind utilizes NH4HCO3The method of pretreatment corn straw, it is characterised in that: cross 40 mesh sieves after corn straw smashing, add
Enter the NH that mass concentration is 4% ~ 10%4HCO3Solution, after mix homogeneously, under room temperature, micro-oxygen processes a few days, the jade after then processing
Rice straw take out and add water stir after stand, filter, dry stand-by.
The most according to claim 1 utilize NH4HCO3The method of pretreatment corn straw, it is characterised in that: added
NH4HCO3The mass concentration of solution is 8%.
The most according to claim 1 and 2 utilize NH4HCO3The method of pretreatment corn straw, it is characterised in that: described
NH4HCO3The addition of solution is the corn straw after just flooding pulverizing.
4. the anaerobic fermentation method of a corn straw, it is characterised in that comprise the following steps:
(1) corn straw pretreatment: cross 40 mesh sieves after corn straw smashing, adding mass concentration is the NH of 4% ~ 10%4HCO3Molten
Liquid, after mix homogeneously, under room temperature micro-oxygen process a few days, then will process after corn straw take out and add water stir after quiet
Put, filter, dry stand-by；
(2) take 60 ~ 100g step (1) gained and dry stand-by corn straw, add the inoculation liquid of 150 ~ 300mL and 700 ~
The water of 850mL, is configured to fermentation liquid that TS concentration is 8% ~ 12% and regulates pH to 7.0；
(3) step (2) gained fermentation liquid is loaded in reactor and being placed on reactor sealing in constant incubator, fermentation
Temperature is set to 35 DEG C, the fermentation culture a few days.
The anaerobic fermentation method of corn straw the most according to claim 4, it is characterised in that in step (1), added
NH4HCO3The mass concentration of solution is 8%.
The anaerobic fermentation method of corn straw the most according to claim 4, it is characterised in that in step (1), described NH4HCO3
The addition of solution is the corn straw after just flooding pulverizing.
The most according to claim 4, the anaerobic fermentation method of corn straw, it is characterised in that in step (2), use quality dense
Degree is sodium carbonate or the sodium bicarbonate solution regulation fermentation liquid pH to 7.0 of 10%.
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| CN107311609A (en) * | 2017-07-05 | 2017-11-03 | 合肥市片叶装饰工程有限公司 | A kind of method that utilization discarded object prepares insulation material |
| CN111763272A (en) * | 2020-07-06 | 2020-10-13 | 福建农林大学 | Drying method and production method of hemicellulose |
| CN114772887A (en) * | 2022-04-11 | 2022-07-22 | 同济大学 | Method for increasing methane production amount of sludge anaerobic digestion by using ammonium bicarbonate |
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| CN107311609A (en) * | 2017-07-05 | 2017-11-03 | 合肥市片叶装饰工程有限公司 | A kind of method that utilization discarded object prepares insulation material |
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| CN114772887A (en) * | 2022-04-11 | 2022-07-22 | 同济大学 | Method for increasing methane production amount of sludge anaerobic digestion by using ammonium bicarbonate |
| CN114772887B (en) * | 2022-04-11 | 2023-07-21 | 同济大学 | Method for improving methane yield of anaerobic sludge digestion by using ammonium bicarbonate |
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