CN106978448A - A kind of method and system of xylose residue efficient anaerobic producing methane - Google Patents
A kind of method and system of xylose residue efficient anaerobic producing methane Download PDFInfo
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Abstract
The invention discloses a kind of method for improving xylose residue anaerobic ferment for methane efficiency and reducing cost, step is as follows：(1) xylose residue and water are proportionally added into preatreating reactors, carry out heating stirring reaction, complete the pretreatment to xylose residue；(2) pretreated xylose residue in step (1) is transported in enzymolysis reactor, adds pH buffer solutions regulation pH, add surfactant, cellulase, auxiliary enzymes and accelerator and digested；(3) enzymolysis liquid and sludge in step (2) are input in anaerobic fermentation reactor in proportion, lasting stirring fermentation；(4) with the progress of fermentation, the biogas produced in collection step (3).Be also disclosed it is a kind of run this method system, including be sequentially connected preatreating reactors, pretreatment fluid storage tank, enzymolysis reactor, enzymolysis liquid storage tank, at least one anaerobic fermentation reactor, biogas upgrader, gas storage holder.The system will be digested and fermentation is separated, and improve reaction efficiency.
Description
Technical field
The invention belongs to biomass energy and resources technology field, a kind of xylose residue efficient anaerobic natural pond is related particularly to
The method and system of gas.
Background technology
Xylose residue is the production remaining acid solid discarded object of xylose/xylitol, the sulfate ion containing higher concentration
And moisture, air and water source are easily polluted, ecological environment is exerted heavy pressures on, while limiting the health of xylose industry, holding
Supervention exhibition.At present, xylose residue is mainly used in progress edible fungus culturing or directly does fuel, few applications in the prior art
Xylose residue produces biogas.Xylose residue main component is cellulose, hemicellulose and lignin, due to containing substantial amounts of cellulose money
Source, it has the potentiality applied to industrial production bioenergy.
Cellulase is the general name for being capable of cellulolytic class of enzymes.Xylose residue is handled using cellulase, can be by wood
Cellulose in sugar residue is hydrolyzed into the small molecules such as reduced sugar, and the enzymolysis liquid after processing is produced into biogas using anaerobic fermentation.Due to
It is a large amount of to be digested using cellulase, production cost can be increased.
The content of the invention
It is an object of the invention to provide a kind of raising xylose residue anaerobic ferment for methane efficiency and it can reduce the side of cost
Method.
To achieve the above object, the technical scheme is that：
A kind of method of xylose residue efficient anaerobic producing methane, comprises the following steps：
(1) pre-treatment step：It is proportionally added into after xylose residue is crushed with water in preatreating reactors, in 45-55 DEG C of temperature
Reaction treatment is stirred under degree, the pretreatment to xylose residue is completed；
(2) enzymolysis step：Pretreated xylose residue in step (1) is input in enzymolysis reactor, pH bufferings are added
Liquid adjusts pH, adds surfactant, cellulase, auxiliary enzymes and accelerator and is digested；
(3) fermentation step：Enzymolysis liquid and sludge in step (2) is input in anaerobic fermentation reactor in proportion, held
Continuous stirring fermentation；
(4) collecting methane step：With the progress of fermentation, the biogas produced in collection step (3).
Further, in pre-treatment step, the xylose residue after crushing presses 1 with water:8-1:15 are added to pretreatment reaction
In device, at a temperature of 45-55 DEG C, stir process 30-60 minutes.
Further, in enzymolysis step, add 0.1-0.2mL/g surfactant, 10-40u/g cellulase,
1-5u/g auxiliary enzymes, 0.05-1mmol/L accelerator, at a temperature of 45-50 DEG C, digest 12-48 hours.
Further, in enzymolysis step, by acid-base accommodation pH, pH is made to be maintained at 4.5-4.8.
Further, cellulase can be endoglucanase, exoglucanase, one kind of beta glucan glycosides enzyme
Or it is a variety of.
Further, auxiliary enzymes can be the one or more of pectase, hemicellulase.
Further, accelerator can be trace element, the one or more of L-AA.
Further, in fermentation step, the ratio of sludge and enzymolysis liquid is 2:5-3:5, at a temperature of 55-60 DEG C,
Persistently stirred, fermented 5-15 days with 100-150r/min speed.
Further, in fermentation step, by acid-base accommodation pH, pH is made to be maintained at 7.3-7.8.
Compared with prior art, it is an advantage of the invention that：
1st, the xylose residue utilized in the present invention in step (1) is that the remaining acid solid of production xylose/xylitol is discarded
Thing, the inside also remains more sulfuric acid, and the xylose residue after crushing and water are pressed 1 by the present invention:8-1:15 are added to pretreatment instead
Answer in device, stirring reaction enters back into the tune pH and enzymolysis process of next step afterwards for a period of time, can make full use of xylose residue raw material
In bring acidity and enzymolysis need 45-55 DEG C of higher temperature.Xylose residue is pre-processed, after processing not only in xylose residue
Hemicellulose some can be converted into pentose, and by being pre-processed to xylose residue after, raw material is easier to enzyme
Solution, it is possible to reduce the consumption of subsequent step (2) cellulase, reaches cost-effective purpose, while can also accelerate biogas hair
Ferment factor of created gase and shortening fermentation period；
2nd, xylose residue is pre-processed using cellulase, the ability of xylose residue fermentation methane production can be increased substantially, can be contracted
In the cycle of short xylose residue fermentation methane production, xylose residue is contributed to produce biogas industrialization；
3rd, xylose residue can be converted into the biomass energy of high-efficiency cleaning as trade waste by anaerobic digestion techniques,
Solve the problems, such as energy shortage and improve environmental problem.
A kind of system for running xylose residue efficient anaerobic producing methane method of the present invention, including the pretreatment reaction being sequentially connected
Device, pretreatment fluid storage tank, enzymolysis reactor, enzymolysis liquid storage tank, at least one anaerobic fermentation reactor, biogas upgrader, gas storage
Cabinet, wherein：
Between preatreating reactors and pretreatment fluid storage tank, between pretreatment fluid storage tank and enzymolysis reactor, enzyme digestion reaction
Device and enzymolysis liquid storage tank between, enzymolysis liquid storage tank and anaerobic fermentation reactor between be provided with drawing liquid pump；
Temp probe and pH probes are provided with enzymolysis reactor, anaerobic fermentation reactor；
Filter is provided with enzymolysis reactor, enzymolysis liquid storage tank；
Agitator is provided with preatreating reactors, anaerobic fermentation reactor.
Further, the system also include acid regulation tank, alkali regulation tank, and by pipeline respectively with enzyme digestion reaction
Device, anaerobic fermentation reactor connection；Wherein, it is provided with valve on pipeline.
Further, the system also includes central control system, the temperature value that temp probe and pH probes will be detected
Central control system, the opening and closing of central control system control drawing liquid pump and valve are transmitted to pH value.
Further, the system also includes transformed sludeg collecting tank, and is connected by pipeline and anaerobic fermentation reactor
Connect.
Compared with prior art, it is an advantage of the invention that：
1st, the present invention is by setting enzymolysis reactor and anaerobic fermentation reactor, by cellulase hydrolysis and biogas fermentation point
Open, realize that two-step reaction is separated, optimum condition is in respectively, reaction efficiency is improved, while biogas fermentation environment pair can also be released
The suppression of cellulase；
2nd, the enzymolysis reactor and anaerobic fermentation reactor that the present invention is set can control temperature and pH respectively, it is ensured that two steps
Reaction can be carried out efficiently；
3rd, the present invention can adjust pH to enzymolysis reactor and anaerobic fermentation reactor in real time by setting acid-base accommodation tank；
4th, the present invention can carry out continuous feed by setting pretreatment fluid storage tank and enzymolysis liquid storage tank, realize continuous production
Biogas；
5th, industrial waste is used to produce biogas by the present invention, realizes the efficient utilization of waste, is conducive to environmental protection and saves money
Source.
Brief description of the drawings
, below will be to embodiment or existing for the clearer explanation embodiment of the present invention or technical scheme of the prior art
There is the accompanying drawing used required in technology description to be briefly described, it is clear that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the flow chart of xylose residue efficient anaerobic producing methane method of the embodiment of the present invention；
Fig. 2 is the structural representation of xylose residue efficient anaerobic producing methane system of the embodiment of the present invention；
Fig. 3 is concentration of reduced sugar variation diagram in reaction solution under the conditions of the different enzyme amount of the embodiment of the present invention；
Wherein, 1- preatreating reactors, 2- pretreatment fluid storage tanks, 3- enzymolysis reactors, 4- enzymolysis liquid storage tanks, 5- anaerobism hair
Ferment reactor, 6- biogas upgraders, 7- gas storage holders, 8- acid regulation tanks, 9- alkali regulation tank, 10- transformed sludeg collecting tanks, 12- the
One drawing liquid pump, the drawing liquid pumps of 13- second, the drawing liquid pumps of 14- the 3rd, the drawing liquid pumps of 15- the 4th, 11- agitators, 31- temp probes, 32-
PH pops one's head in, 33- filters, 41- filters, 51- temp probes, 52-pH probes, 53- agitators.
Embodiment
The embodiment of the present invention is by providing a kind of xylose residue efficient anaerobic producing methane method and system, by high to xylose residue
The research of anaerobism producing methane method details and the adjustment of system equipment are imitated, the yield of xylose residue anaerobism producing methane is added, together
When the overall anaerobic fermentation time is substantially shortened, to using xylose residue anaerobic ferment for methane produce far-reaching influence.
In order to be better understood from above-mentioned technical proposal, below in conjunction with Figure of description and specific embodiment to upper
Technical scheme is stated to be described in detail.
As shown in figure 1, the xylose residue efficient anaerobic producing methane method of the embodiment of the present invention, is comprised the following steps that：
(1) pre-treatment step：It is proportionally added into after xylose residue is crushed with water in preatreating reactors, in 45-55 DEG C of temperature
Reaction treatment is stirred under degree, the pretreatment to xylose residue is completed；
(2) enzymolysis step：Pretreated xylose residue in step (1) is input in enzymolysis reactor, soda acid is added and delays
Fliud flushing adjusts pH, adds surfactant, cellulase, auxiliary enzymes and accelerator and is digested；
(3) fermentation step：Enzymolysis liquid and sludge in step (2) is input in anaerobic fermentation reactor in proportion, held
Continuous stirring fermentation；
(4) collecting methane step：With the progress of fermentation, the biogas produced in collection step (3).
Next the joining relation between the details of each processing step and two processing steps is discussed in detail：
(1) pre-treatment step：
Xylose residue is the production remaining acid solid discarded object of xylose/xylitol.Xylose residue after crushing presses 1 with water:8-
1:15 are added in preatreating reactors, at a temperature of 45-55 DEG C, stir process 30-60 minutes, complete to the pre- place of xylose residue
The first step pretreatment of reason process, as xylose residue.Now, the hemicellulose part in xylose residue is originally converted into pentose,
And it is easier to enzymolysis.
The xylose residue utilized in the step is the production remaining acid solid discarded object of xylose/xylitol, by xylose residue
Mixed in proportion with water after crushing, xylose residue in itself institute's band acidity equivalent to xylose residue acidification hydrolization.By to xylose residue
Acidification after, make raw material be easier to enzymolysis, it is possible to reduce the consumption of subsequent step (2) cellulase, reach saving
The purpose of cost.
(2) enzymolysis step：
Pretreated xylose residue in step (1) is input in enzymolysis reactor, add weak acid-salt of weak acid or weak base-
Weak base salt adjusts pH, add 0.1-0.2mL/g surfactant, 10-40u/g cellulase, 1-5u/g auxiliary enzymes,
0.05-1mmol/L accelerator, at a temperature of 45-50 DEG C, digests 12-48 hours.
Wherein, weak acid-salt of weak acid or weak base-weak base salting liquid are used as buffer solution, play initial regulation raw material pH work
With pH is in 4.5-4.8 for regulation.It is preferred that, Acetic acid-sodium acetate solution buffer solution can be selected.
Surfactant, the contact for promoting enzyme-to-substrate promotes enzyme digestion reaction, it is preferred that surfactant can be with
From Tween 80.
It is preferred that, cellulase can from endoglucanase, exoglucanase, one kind of beta glucan glycosides enzyme or
It is a variety of.
It is preferred that, auxiliary enzymes can select pectase, the one or more of hemicellulase.
Accelerator, for stablizing zymoprotein structure, extends the service life of enzyme.It is preferred that, accelerator can select micro
The one or more of element, L-AA.Wherein, trace element is from iron ion, cobalt ions, one kind of nickel ion or several
Kind.
In enzymolysis step, by acid-base accommodation pH, pH is set to remain at 4.5-4.8.
Obtained enzymolysis liquid is digested on this condition, the cellulose of 80-90% in xylose residue and hemicellulose can be changed
For small molecule carbohydrate.
(3) fermentation step：
By the sludge and enzymolysis liquid in step (2) according to 2:5-3:5 ratio is input in anaerobic fermentation reactor,
At a temperature of 55-60 DEG C, persistently stirred, fermented 5-15 days with 100-150r/min speed.
In fermentation step, by acid-base accommodation pH, pH is maintained at 7.3-7.8, prevent sludge to be acidified.
(4) collecting methane step：
With the progress of fermentation, the biogas produced in collection step (3).After after enzymolysis liquid, all fermentation is finished, input is new
Enzymolysis liquid, proceed anaerobic fermentation production biogas.Period detects biogas acidizing degree, after continuously fermenting 5-10 times, will
The sludge of acidifying denaturation is discharged into transformed sludeg collecting tank and post-processed, and adds new sludge, continuously produces biogas.
As shown in Fig. 2 the xylose residue efficient anaerobic producing methane system of the embodiment of the present invention, including the pretreatment being sequentially connected
Reactor 1, pretreatment fluid storage tank 2, enzymolysis reactor 3, enzymolysis liquid storage tank 4, at least one anaerobic fermentation reactor 5, biogas are carried
Matter device 6, gas storage holder 7, in addition to acid regulation tank 8, alkali regulation tank 9, transformed sludeg collecting tank 10.
With reference to the method for the xylose residue efficient anaerobic producing methane of the present invention, the xylose residue that the embodiment of the present invention is introduced item by item is high
Imitate the structure and function of each component devices in anaerobism producing methane system：
Preatreating reactors 1：Step (1) pre-treatment step is anti-in pretreatment in xylose residue efficient anaerobic producing methane method
Answer in device 1 and carry out, the top of preatreating reactors 1, which is provided with charging aperture, water inlet bottom, discharging opening.In preatreating reactors 1
Agitator 11 is additionally provided with, the xylose residue after crushing is fully mixed with water, accelerates the hydrolysis of xylose residue.
Because the temperature of pretreatment reaction in pre-treatment step is at 45-55 DEG C, therefore need to add preatreating reactors 1
Heat, it is preferred that heating coil can be provided with preatreating reactors 1.
Pretreatment fluid storage tank 2：Its charging aperture is connected with preatreating reactors 1, and is provided with and is taken out on pipeline therebetween
Liquid pump 12.The effect of pretreatment fluid storage tank 2 is set, is due to that the time of pretreatment is shorter, in order to realize continuous production, temporarily
Store pretreated xylose residue.The top of pretreatment fluid storage tank 2 is provided with charging aperture, bottom and is provided with discharging opening.
Enzymolysis reactor 3：Its charging aperture is connected with pretreatment fluid storage tank 2, and is provided with drawing liquid on pipeline therebetween
Step (2) enzymolysis step is carried out in enzymolysis reactor 3 in pump 13, xylose residue efficient anaerobic producing methane method.Enzyme digestion reaction
The top of device 3 is provided with xylose residue charging aperture and cellulase, auxiliary enzymes, accelerator charging aperture, and bottom sets discharging opening.
Enzymolysis reactor 3 is internally provided with temp probe 31 and pH probes 32, for monitoring in real time in enzymolysis reactor 3
Temperature and pH, to adjust the temperature and pH in enzymolysis reactor 3 at any time, make enzyme digestion reaction be in it is optimal under conditions of carry out.
Filter 33 is additionally provided with enzymolysis reactor 3, the bulk solid matters in enzymolysis reactor 3 are separated, is prevented
Only bulk solid matter blocks the drawing liquid pump 14 set between enzymolysis reactor 3 and enzymolysis liquid storage tank 4 on pipeline.
Because the temperature of enzyme digestion reaction in enzymolysis step is at 45-50 DEG C, therefore need to heat enzymolysis reactor 3, it is excellent
Choosing, heating coil can be provided with enzymolysis reactor 3.
Digest liquid storage tank 4：Its charging aperture is connected with enzymolysis reactor 3, and is provided with drawing liquid pump on pipeline therebetween
14, for temporarily storing enzymolysis liquid, to realize continuous production biogas.Enzymolysis liquid storage tank 4 top is provided with charging aperture, bottom and set
It is equipped with discharging opening.
Anaerobic fermentation reactor 5：Its charging aperture is connected with enzymolysis liquid storage tank 4, in xylose residue efficient anaerobic producing methane method
Step (3) fermentation step is carried out in anaerobic fermentation reactor 5, in order to realize continuous production, sets at least one anaerobism to send out
Ferment reactor 5.
Anaerobic fermentation reactor 5 is internally provided with temp probe 51 and pH probes 52, anti-for monitoring anaerobic fermentation in real time
The temperature and pH in device 5 are answered, to adjust the temperature and pH in anaerobic fermentation reactor 5 at any time, is in anaerobic fermentation reaction
Carried out under conditions of optimal.
Agitator is additionally provided with anaerobic fermentation reactor 5, for persistently giving fermentation stirring, accelerates reaction rate.
Because the fermentation temperature in anaerobic fermentation step is higher than the temperature digested in enzymolysis step, therefore need to anaerobic fermentation
Reactor 5 is heated, it is preferred that heating coil can be provided with anaerobic fermentation reactor 5.
Biogas upgrader 6：Its air inlet is connected with anaerobic fermentation reactor 5, in xylose residue efficient anaerobic producing methane method
Biogas first passes through upgrader 6 in step (4) collecting methane step, improves the purity of biogas.
Gas storage holder 7：Its air inlet is connected with biogas upgrader 6, step (4) natural pond in xylose residue efficient anaerobic producing methane method
Collection in gas collection step.
Acid regulation tank 8, alkali regulation tank 9：It is connected, is used with enzymolysis reactor 3, anaerobic fermentation reactor 5 respectively by pipeline
PH in regulation enzymolysis reactor 3, anaerobic fermentation reactor 5, is maintained under optimum and is reacted.And in main line
With valve is provided with bypass line, be easy to each reactor of separate regulation.
Transformed sludeg collecting tank 10：Its charging aperture is connected with anaerobic fermentation reactor 5, for collecting and handling anaerobic fermentation
Transformed sludeg after the fermentation of reactor 5, prevents direct exhaust emission environment.
Further, the system also includes central control system (not shown), and temp probe and pH visit a prisoner what is measured
Temperature value and pH value are transmitted to central control system, the opening and closing of central control system control drawing liquid pump and valve.Industry can be realized
The continuous production changed.
For the ease of the understanding of technical solution of the present invention, it is described in detail with reference to some embodiments：
Embodiment 1
Xylose residue is with water according to 1:8 ratio is added in preatreating reactors, at a temperature of 45 DEG C, 30 points of stir process
Clock, obtains pretreatment xylose residue.Pretreated xylose residue is input in enzymolysis reactor, Acetic acid-sodium acetate solution is added and adjusts
Save pH to 4.5, add 0.1mL/g Tween 80,10u/g cellulase, 1u/g pectase, 0.05mmol/L cobalt from
Son, digests 12 hours at a temperature of 55 DEG C, obtains enzymolysis liquid.By sludge and enzymolysis liquid according to 2:5 ratio is input to anaerobism hair
In ferment reactor, at a temperature of 55 DEG C, persistently stirred, fermented 5 days with 100r/min speed.In fermentation process, pH is adjusted, is made
PH is maintained at 7.3.With the progress of fermentation, the biogas produced is collected.
Aerogenesis result：
Raw material factor of created gase：659.20mL/g
Embodiment 2
Xylose residue is with water according to 1:10 ratio is added in preatreating reactors, at a temperature of 48 DEG C, stir process 37
Minute, obtain pretreatment xylose residue.Pretreated xylose residue is input in enzymolysis reactor, Acetic acid-sodium acetate solution is added
PH to 4.6 is adjusted, 0.15mL/g Tween 80,20u/g cellulase, 3u/g pectase, 0.45mmol/L L- is added
Ascorbic acid, digests 18 hours at a temperature of 47 DEG C, obtains enzymolysis liquid.By sludge and enzymolysis liquid according to 2.4:5 ratio input
Into anaerobic fermentation reactor, at a temperature of 56 DEG C, persistently stirred, fermented 8 days with 120r/min speed.In fermentation process,
PH is adjusted, pH is maintained at 7.5.With the progress of fermentation, the biogas produced is collected.
Aerogenesis result：
Raw material factor of created gase：689.18mL/g
Embodiment 3
Xylose residue is with water according to 1:12 ratio is added in preatreating reactors, at a temperature of 50 DEG C, stir process 42
Minute, obtain pretreatment xylose residue.Pretreated xylose residue is input in enzymolysis reactor, Acetic acid-sodium acetate solution is added
PH to 4.7 is adjusted, 0.18mL/g Tween 80,30u/g cellulase, 4u/g hemicellulase, 0.75mmol/L is added
Iron ion and L-AA, at a temperature of 48 DEG C digest 23 hours, obtain enzymolysis liquid.By sludge and enzymolysis liquid according to 2.8:
5 ratio is input in anaerobic fermentation reactor, at a temperature of 58 DEG C, is persistently stirred with 125r/min speed, is fermented 11 days.
In fermentation process, pH is adjusted, pH is maintained at 7.6.With the progress of fermentation, the biogas produced is collected.
Aerogenesis result：
Raw material factor of created gase：670.15mL/g
Embodiment 4
Xylose residue is with water according to 1:15 ratio is added in preatreating reactors, at a temperature of 55 DEG C, stir process 60
Minute, obtain pretreatment xylose residue.Pretreated xylose residue is input in enzymolysis reactor, Acetic acid-sodium acetate solution is added
Regulation pH to 4.8, addition 0.2mL/g Tween 80,40u/g cellulase, 5u/g pectase and hemicellulase,
1mmol/L iron ion, cobalt ions, nickel ion, digests 48 hours at a temperature of 50 DEG C, obtains enzymolysis liquid.By sludge and enzymolysis
Liquid is according to 3:5 ratio is input in anaerobic fermentation reactor, at a temperature of 60 DEG C, is persistently stirred with 150r/min speed,
Fermentation 15 days.In fermentation process, pH is adjusted, pH is maintained at 7.8.With the progress of fermentation, the biogas produced is collected.
Aerogenesis result：
Raw material factor of created gase：719.25mL/g
Embodiment 5
Xylose residue is added in enzymolysis reactor, is added Acetic acid-sodium acetate solution regulation pH to 4.5, is added 0.1mL/g's
Tween 80,10u/g cellulase, 1u/g pectase, 0.05mmol/L iron ion, digest 12 small at a temperature of 45 DEG C
When, obtain enzymolysis liquid.By sludge and enzymolysis liquid according to 2:5 ratio is input in anaerobic fermentation reactor, at a temperature of 55 DEG C,
Persistently stirred, fermented 5 days with 100r/min speed.In fermentation process, pH is adjusted, pH is maintained at 7.3.With entering for fermentation
OK, the biogas produced is collected.
Aerogenesis result：
Raw material factor of created gase：426.48mL/g
Embodiment 6
Xylose residue is with water according to 1:8 ratio is added in preatreating reactors, at a temperature of 45 DEG C, 30 points of stir process
Clock, obtains pretreatment xylose residue.Pretreated xylose residue is input in enzymolysis reactor, Acetic acid-sodium acetate solution is added and adjusts
Save pH to 7.5, add 0.1mL/g Tween 80,10u/g cellulase, 1u/g pectase, 0.05mmol/L iron from
Son, digests 12 hours at a temperature of 45 DEG C, obtains enzymolysis liquid.By sludge and enzymolysis liquid according to 2:5 ratio is input to anaerobism hair
In ferment reactor, at a temperature of 55 DEG C, persistently stirred, fermented 5 days with 100r/min speed.In fermentation process, pH is adjusted, is made
PH is maintained at 7.3.With the progress of fermentation, the biogas produced is collected.
Aerogenesis result：
Raw material factor of created gase：100.64mL/g
Embodiment 7
Xylose residue is with water according to 1:15 ratio is added in preatreating reactors, at a temperature of 55 DEG C, stir process 60
Minute, obtain pretreatment xylose residue.Pretreated xylose residue is input in enzymolysis reactor, Acetic acid-sodium acetate solution is added
Regulation pH to 4.8, addition 0.2mL/g Tween 80,45u/g cellulase, 5u/g pectase and hemicellulase,
1mmol/L iron ion, cobalt ions, zinc ion, digests 48 hours at a temperature of 50 DEG C, obtains enzymolysis liquid.By sludge and enzymolysis
Liquid is according to 3:5 ratio is input in anaerobic fermentation reactor, at a temperature of 60 DEG C, is persistently stirred with 150r/min speed,
Fermentation 15 days.In fermentation process, pH is adjusted, pH is maintained at 7.8.With the progress of fermentation, the biogas produced is collected.
Aerogenesis result：
Raw material factor of created gase：707.63mL/g
Comparative example 1
Xylose residue is with water according to 1:8 ratio is added in preatreating reactors, at a temperature of 45 DEG C, 30 points of stir process
Clock, obtains pretreatment xylose residue.By sludge and pretreatment xylose residue according to 2:5 ratio is input in anaerobic fermentation reactor,
At a temperature of 55 DEG C, persistently stirred, fermented 5 days with 100r/min speed.In fermentation process, pH is adjusted, pH is maintained at 7.3.
With the progress of fermentation, the biogas produced is collected.
Aerogenesis result：
Raw material factor of created gase：527.53mL/g
Comparative analysis：
1st, the xylose residue utilized in the present invention is the production remaining acid solid discarded object of xylose/xylitol, by xylose
Mixed in proportion with water after ground-slag is broken, at a temperature of 45-55 DEG C, stir process 30-60 minutes obtains pretreatment xylose residue.Place
A hemicellulose part after reason in xylose residue is converted into pentose.In follow-up enzyme digestion reaction, factor of created gase can be not only improved,
The consumption of cellulase can also be reduced, production cost is reduced.
The difference of embodiment 5 and embodiment 1 is to carry out acidolysis pretreatment either with or without to xylose residue, from embodiment 5 and in fact
Apply the aerogenesis Comparative result of example 1 to understand, factor of created gase can be improved to the pretreatment that xylose residue carries out acidification hydrolization, accelerate reaction speed
Rate, reduces cellulase consumption.
2nd, xylose residue is mainly cellulose and hemicellulose using composition, in marsh gas fermentation processes, microorganism pair
The decomposition of cellulose is slower, and cellulose is changed into small molecule reduced sugar, then can be utilized faster by microbial digestion, utilize fibre
The plain enzyme of dimension is fully hydrolyzed xylose residue, can improve the utilization rate of xylose residue.
From the figure 3, it may be seen that the amount for producing reduced sugar without cellulase and addition cellulase has very big difference, so adding
Plus cellulase can increase substantially the ability of xylose residue fermentation methane production, the cycle of xylose residue fermentation methane can be shortened.But
Be be not addition cellulose enzyme amount it is more many more be beneficial to the decomposition of cellulose, as can be seen from Figure 3, when the consumption of cellulase
During more than 40u/g, do not have apparent increase when consumption of the amount compared with cellulase of the reduced sugar of generation is 40u/g, so
When cellulase reaches 40u/g, enzymolysis efficiency reaches maximum.
The difference of comparative example 1 and embodiment 1 is carrying out enzyme digestion reaction either with or without to xylose residue, from comparative example 1 and in fact
Apply the aerogenesis Comparative result of example 1 to understand, after addition cellulase, the utilization rate of xylose residue can be improved, accelerate reaction rate.
Embodiment 7 and embodiment 4 are compared, and the cellulase used in embodiment 7 is 45u/g, from embodiment 7 and in fact
Apply the aerogenesis Comparative result of example 4 and understand that gas production and factor of created gase in embodiment 7 do not increase significantly compared with embodiment 4, on the contrary
It has been declined that, reason is that excessive cellulase remains in xylose residue and sludge can be caused to be acidified, and is unfavorable for aerogenesis on the contrary, so
When addition cellulase reaches 40u/g, enzymolysis efficiency reaches maximum, and raw material factor of created gase also reaches maximum.
3rd, the optimum reaction conditionses of cellulase are 45-50 DEG C, and pH value is 4.5-4.8.When pH value is 7.5, enzymatic activity
Almost all is lost.Therefore, it is 55 DEG C, under conditions of pH 4.5 in temperature, enters to adding cellulase in the xylose residue aqueous solution
Row enzymolysis.Therefore acid-base accommodation tank is provided with to pH is adjusted in enzymolysis step, make it ensure to enter in the range of optimum pH
Row enzymolysis.
By the pH regulations in enzyme digestion reaction 7.5 in embodiment 6, and the pH in 1~embodiment of embodiment 4 in enzyme digestion reaction
Regulation is in 4.5-4.8, it was found from aerogenesis Comparative result, and pH value is 4.5-4.8 in enzyme digestion reaction, and gas producing efficiency is high.
4th, the TS (total solid solid content) of embodiment 1~4 and comparative example 1, VS (volatility solid content) mass fraction
Change be shown in Table 1.From table 1 it was found from data, the zymotic fluid of embodiment 4 contains total solid 50.89g, total volatile solid(s) (TVS) 37.73g,
After fermentation ends, the total solid of embodiment 4 and total volatile solid(s) (TVS) reduce 20.09g and 16.42g, the raw material TS of embodiment 4 profits respectively
It is that 39.79%, VS utilization rates are 43.52% with rate；TS the and VS utilization rates of comparative example 1 are respectively 20.32% and 21.30%.
Illustrate that addition cellulase can effectively improve xylose residue utilization rate, be conducive to biogas fermentation.
Table 1
5th, mostly it is to prepare biogas with biomass materials such as stalk, cotton stalks in the prior art, and xylose residue is used as Industry Waste
Gurry easily pollutes air and water source, ecological environment is exerted heavy pressures on if do not dealt carefully with.Meanwhile, xylose residue mainly into
It is divided into cellulose, hemicellulose and lignin, because containing substantial amounts of cellulose resource, it, which has, is applied to industrial production biology
The potentiality of the energy.Therefore the present invention prepares biogas by raw material of xylose residue, first, xylose residue is trade waste in itself, with xylose
Slag saves cost as raw material；Secondly, trade waste has been handled, environmental problem is improved；Finally, produced by xylose residue
Biogas, can be used for prepare chemical products raw material, moreover it is possible to the problem of solving energy shortage.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright specification and accompanying drawing content are made, or directly or indirectly it is used in other related skills
Art field, is included within the scope of the present invention.
Claims (10)
1. a kind of method of xylose residue efficient anaerobic producing methane, it is characterised in that comprise the following steps：
(1) pre-treatment step：It is proportionally added into after xylose residue is crushed with water in preatreating reactors, at a temperature of 45-55 DEG C
Reaction treatment is stirred, the pretreatment to xylose residue is completed；
(2) enzymolysis step：Pretreated xylose residue in step (1) is input in enzymolysis reactor, pH buffer solutions is added and adjusts
PH is saved, surfactant, cellulase, auxiliary enzymes and accelerator is added and is digested；
(3) fermentation step：Enzymolysis liquid and sludge in step (2) is input in anaerobic fermentation reactor in proportion, persistently stirred
Mix fermentation；
(4) collecting methane step：With the progress of fermentation, the biogas produced in collection step (3).
2. the method for xylose residue efficient anaerobic producing methane according to claim 1, it is characterised in that the pre-treatment step
In, the xylose residue after crushing presses 1 with water:8-1:15 are added in preatreating reactors, at a temperature of 45-55 DEG C, at stirring
Reason 30-60 minutes.
3. the method for xylose residue efficient anaerobic producing methane according to claim 1, it is characterised in that the enzymolysis step
In, add 0.1-0.2mL/g surfactant, 10-40u/g cellulase, 1-5u/g auxiliary enzymes, 0.05-1mmol/L
Accelerator, at a temperature of 45-50 DEG C, digest 12-48 hours.
4. the method for xylose residue efficient anaerobic producing methane according to claim 1, it is characterised in that the enzymolysis step
In, by acid-base accommodation pH, pH is maintained at 4.5-4.8.
5. the method for xylose residue efficient anaerobic producing methane according to claim 1, it is characterised in that the cellulase can
To be the one or more of endoglucanase, exoglucanase, beta glucan glycosides enzyme；
The auxiliary enzymes can be the one or more of pectase, hemicellulase；
The accelerator can be trace element, the one or more of L-AA.
6. the method for xylose residue efficient anaerobic producing methane according to claim 1, it is characterised in that the fermentation step
In, the ratio of sludge and enzymolysis liquid is 2:5-3:5, at a temperature of 55-60 DEG C, persistently stirred with 100-150r/min speed,
Fermentation 5-15 days；By acid-base accommodation pH, pH is set to be maintained at 7.3-7.8.
7. a kind of system of xylose residue efficient anaerobic producing methane, it is characterised in that including the preatreating reactors being sequentially connected
(1), pretreatment fluid storage tank (2), enzymolysis reactor (3), enzymolysis liquid storage tank (4), at least one anaerobic fermentation reactor (5), natural pond
Gas upgrader (6), gas storage holder (7), wherein：
Between the preatreating reactors (1) and pretreatment fluid storage tank (2), pretreatment fluid storage tank (2) and enzymolysis reactor (3) it
Between, be all provided between enzymolysis reactor (3) and enzymolysis liquid storage tank (4), between enzymolysis liquid storage tank (4) and anaerobic fermentation reactor (5)
It is equipped with drawing liquid pump；
Temp probe and pH probes are provided with the enzymolysis reactor (3), anaerobic fermentation reactor (5)；
Filter is provided with the enzymolysis reactor (3), enzymolysis liquid storage tank (4)；
Agitator (53) is provided with the preatreating reactors (1), anaerobic fermentation reactor (5).
8. the system of xylose residue efficient anaerobic producing methane according to claim 7, it is characterised in that also including acid regulation tank
(8), alkali regulation tank (9), and being connected respectively with enzymolysis reactor (3), anaerobic fermentation reactor (5) by pipeline；Wherein, institute
State and valve is provided with pipeline.
9. the system of xylose residue efficient anaerobic producing methane according to claim 8, it is characterised in that also including central control
The temperature value monitored and pH value are transmitted to the central control system, the center by system, temp probe and the pH probe
Control system controls the opening and closing of the drawing liquid pump and valve.
10. the system of xylose residue efficient anaerobic producing methane according to claim 7, it is characterised in that also dirty including denaturation
Mud process tank (10), the transformed sludeg process tank (10) is connected with the anaerobic fermentation reactor (5).
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| CN116375521A (en) * | 2023-03-27 | 2023-07-04 | 吉林省东北亚硅藻土应用研究有限公司 | Production method for preparing biomass natural gas and co-producing organic fertilizer from straw |
| CN116731828A (en) * | 2023-06-12 | 2023-09-12 | 哈尔滨工业大学 | Hidden fermentation biological hydrogen production device and hydrogen production method thereof |
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