CN109082446A - A kind of method that photocatalysis pretreatment improves Anaerobic Digestion of Straw gas generation property - Google Patents
A kind of method that photocatalysis pretreatment improves Anaerobic Digestion of Straw gas generation property Download PDFInfo
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- CN109082446A CN109082446A CN201810851339.0A CN201810851339A CN109082446A CN 109082446 A CN109082446 A CN 109082446A CN 201810851339 A CN201810851339 A CN 201810851339A CN 109082446 A CN109082446 A CN 109082446A
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- 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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Abstract
A kind of method that photocatalysis pretreatment improves rice straw anaerobic digestion gas production performance, it is characterised in that the rice straw of certain mass is weighed by 50gTS/L load, load is with rice straw TS calculating；Titanium dioxide is dissolved in water and is added in glass container, after stirring evenly, the stalk that certain mass is added continues to stir evenly, it is then placed in photo catalysis reactor, solution surface is opened Hg lamp irradiation 1h~8h, is stirred using blender always in During Illumination away from lamp source 40-50cm；Reaction solution temperature is maintained at 47 ± 2 DEG C；Pretreated rice straw is mixed with inoculum, and inoculum is the biogas slurry after anaerobic digestion, and pH is 7.0~8.0, and ammonia nitrogen is in 200~1500mg/L, and basicity is in 2000~6000mg/L, inoculum concentration 20gMLSS/L；It adds water, stirs evenly, constant volume sealing guarantees anaerobic environment；Mesophilic anaerobic digestion process 25d is carried out in 35 ± 1 DEG C of constant water bath box, is shaken every day 1 time.The present invention is nontoxic, harmless, and the anaerobic digestion period is obviously shortened, and unit TS methane production improves 12.87%~56.98%.
Description
Technical field
The invention belongs to organic solid castoff anaerobic digestion fields, and in particular to a kind of photocatalysis pretreatment raising straw
The method of gas generation property.
Background technique
China is large agricultural country, and annual all kinds of crop materials are up to 800,000,000 tons, and a large amount of stalk is abandoned by open burning or arbitrarily
It sets, has severely impacted China's ecological environment.It is to solve agricultural wastes by anaerobic digestion techniques by stover at biogas
The effective way that environmental pollution and realization waste resource recovery utilize.
Stalk is typical lignocellulose biomass, is mainly made of lignin, cellulose and hemicellulose, wherein wood
The cross-linked structure of quality, cellulose and hemicellulose, the presence of especially stalk surface texture lignin lead to anaerobic digestion efficiency
Low, gas producing efficiency is low.Wherein lignin is a kind of three-dimensional novolac polymer, and complicated structure causes it to be difficult to be dropped by microorganism
Solution, and also counteract that microorganism and enzyme wrap up contact utilization of the cellulose therein with cellulose to by lignin, therefore logical
It often needs to pre-process stalk before anaerobic fermentation.Preprocess method mainly have physical method, chemical method, physical-chemical process and
Bioanalysis etc..Wherein physical method is mainly the crystal structure for destroying lignin, and cannot achieve the trans-utilization of lignin, and
And high-temperature and high-pressure conditions are mostly used greatly, operation and device are more complicated.During chemical method is pretreated, chemicals can escape
It is dissipated in environment, therefore there are the pollution problems of chemical reagent.Although physico-chemical process effect is preferable, there are still certain objects
Common problem in reason, chemical method.And physics and chemical pretreatment means focus primarily upon destroy lignin and cellulose and
The cross-linked structure of hemicellulose, so that cellulose and hemicellulose is made to be easier to contact utilization by microorganism, however for lignin
Degradation effect it is poor, cause lignin that can not be fully used in anaerobic digestion process.Although bioremediation can be with
Lignin degrading, but lignin degradation microbe species are few, it is low to decompose the enzyme activity of enzyme, the processing time is long.The above pretreatment
Few method dissolved lignins based on oxidation in method, the organic moiety for keeping it obstinate are conducive to biodegrade, therefore this
Patent proposes a kind of method for pre-processing using photocatalysis and improving straw gas generation property, is degraded by photocatalysis preconditioning technique wooden
Quality discharges cellulose therein, and realizes that the degradation of lignin utilizes.
Previous research discovery photocatalysis oxidation-degradable lignin obtains vanillic aldehyde, the more small-molecule substances such as wound phenol, but
Mainly to the catalytic degradation of single lignin, without being directed to the preprocess method of agricultural crop straw, subsequent detest to improve
The research of oxygen digestic property.
Document: Chen Yun's equality nano-TiO2Photocatalytic degradation alkali lignin research [J] biomass chemical engineering, 2009,
43 (6): 31~35. research discovery: nano-TiO is used2As catalyst, catalyzing oxidizing degrading alkali is wooden under ultraviolet light
Element, discovery are 5g in lignin, and when catalyst amount 0.75g/L, light application time are 2.5h and pH value is 10, degradation rate is reachable
70% or more, the small-molecule substances such as lilac radical derivative, vanillic aldehyde, guaiacyl derivative have been obtained after degradation.
Summary of the invention
Therefore in anaerobic fermentation process, the problem of lignin is difficult to the digestion that is degraded, anaerobic digestion low efficiency, proposition
The present invention.The side for improving rice straw anaerobic digestion gas production performance is pre-processed the purpose of the present invention is to provide a kind of photocatalysis
Method has the following characteristics that
Technical solution of the present invention includes following content:
(1) raw material and reagent
Raw material: stalk prepares, and takes air-dried rice straw, is first cut into 3~4 centimetres, then with the powder of 40 mesh screen of band
It is spare that broken machine crushes kept dry；
Reagent: TiO2。
(2) preprocess method
The rice straw of certain mass is weighed, load is with rice straw TS calculating；0.2g~2g titanium dioxide is added water-soluble
Solution is added in glass container, and after stirring evenly, the stalk that certain mass is added continues to stir evenly, and it is anti-to be then placed in photocatalysis
It answers in device, using with long arc mercury lamp, as light source, solution surface opens long arc mercury lamp point away from lamp source certain distance in reactor
Not Zhao She 1h~8h, be stirred using blender always in During Illumination.In the process, since semiconductor particle has
Band structure, when the light for being equal to or more than forbidden bandwidth with energy irradiates semiconductor, the electronics in valence band, which is excited, to be transitted to
Conduction band can generate oxidation and the stronger electronics-hole pair of reproducibility, but due to TiO2Greater band gap (about 3.2eV), therefore
It is irradiated using ultraviolet light, generates the photohole of strong oxidizing property, to cause a series of redox reaction, and generated
Hydroxyl radical free radical, hydroxyl radical free radical are considered as the driving force of degradation oxidation of organic compounds.Research shows that the hydroxyl of strong oxidizing property is certainly
By base can by lignin side chain carbonyl and double bond destroy, further generate small-molecule substance.It is put after the completion of pretreatment
It sets spare in 4 DEG C of refrigerator storages.
(3) anaerobic digestion
Pretreated rice straw is mixed with inoculum, inoculum is the biogas slurry after anaerobic digestion, pH 7.0~
8.0, ammonia nitrogen is in 200~1500mg/L, and basicity is in 2000~6000mg/L, inoculum concentration 20gMLSS/L；It adds water, stirring is equal
Even, constant volume sealing guarantees anaerobic environment；Mesophilic anaerobic digestion process 25d is carried out in 35 ± 1 DEG C of constant water bath box, is shaken daily
It is 1 time dynamic.
The methane percentage composition and daily output methane quantity in anaerobic digestion process are measured, data are for evaluating photocatalysis pretreatment
The effect of rice straw anaerobic digestion afterwards.
Specific steps:
15.98g rice straw is weighed respectively by 50gTS/L load, and load is with rice straw TS calculating；Respectively by 0.2g,
1g, 2g titanium dioxide, which are dissolved in water, to be added in glass container, after stirring evenly, the stalk weighed up is added later and is settled to
200ml is then placed in photo catalysis reactor, using with long arc mercury lamp, as light source, solution surface is away from lamp source in reactor
41cm opens long arc mercury lamp and irradiates 1h, 2h, 4h, 8h respectively, this experiment uses external lighting type bar shaped fluorescent tube, and lamp source uses 500W long
Arc mercury lamp, a length of 365nm of primary waves；It is stirred using magnetic stirring apparatus always in During Illumination, blender uses Shanghai
Happy 85~2 type constant temperature blender with magnetic force are taken charge of, reaction solution temperature is maintained at 47 ± 2 DEG C；4 DEG C are placed it in after the completion of pretreatment
Refrigerator storage is spare.
Catalyst is the VK-T06S type white powder high-activity nano two bought from Shaoxing photocatalysis air-cleaning center
Titanium oxide, partial size are 20 ± 5.60nm, and specific area is 70~120m2/ g, crystal form are rutile and anatase mixing crystal form.It will be pre-
Treated, and rice straw is mixed with inoculum, and inoculum is the biogas slurry after pig manure anaerobic digestion, and 7.0~8.0, ammonia nitrogen exists pH
200~1500mg/L, basicity is in 2000~6000mg/L, inoculum concentration 20gMLSS/L；It adds water, stirs evenly, be settled to
0.3L, sealing guarantee anaerobic environment；Mesophilic anaerobic digestion process 25d is carried out in 35 ± 1 DEG C of constant water bath box, is shaken every day
1 time.
The methane percentage composition and daily output methane quantity in anaerobic digestion process are measured in experimentation, data are for evaluating light
The effect of rice straw anaerobic digestion after catalytic pretreatment.
Compared with prior art, the invention has the following advantages:
(1) compared to previous preprocess method, photocatalysis technology can be in mild condition --- under room temperature normal pressure carries out, and
And the engineering easy to operate that is easy to is promoted, the technology is nontoxic, harmless, is of great significance for protection environment.
(2) the anaerobic digestion period is obviously shortened, compared with blank group (22d), each Pretreatment Test group T80Time shortens 1
~4d, shortens 5%~18%.
(3) experimental group anaerobic digestion efficiency is decreased obviously after 25d, in anaerobic fermentation 25d, compared to the blank group, each reality
It tests a group unit TS gas production and improves 11.07%~38.86%, unit TS methane production improves 12.87%~56.98%.
(4) pretreatment time is obviously shortened.The invention patent pretreatment time is only 1~8h, works as TiO2Additive amount is 1g,
When light application time is 1h, pretreating effect is best, compares previous pretreatment time, pretreatment time is greatly saved, and saves
Time cost.
(5) compared to the blank group, each experimental group Lignin degradation rate is 13.59%~22.41%.
Specific embodiment
15.98g rice straw is weighed respectively by 50gTS/L load, and load is with rice straw TS calculating；Respectively by 0.2g,
1g, 2g titanium dioxide, which are dissolved in water, to be added in glass container, after stirring evenly, the stalk weighed up is added later and is settled to
200ml is then placed in photo catalysis reactor, using with long arc mercury lamp, as light source, solution surface is away from lamp source in reactor
41cm opens long arc mercury lamp and irradiates 1h, 2h, 4h, 8h respectively, this experiment uses external lighting type bar shaped fluorescent tube, and lamp source uses 500W long
Arc mercury lamp, a length of 365nm of primary waves.It is stirred using magnetic stirring apparatus always in During Illumination, blender uses Shanghai
Happy 85~2 type constant temperature blender with magnetic force are taken charge of, reaction solution temperature is maintained at 47 ± 2 DEG C.4 DEG C are placed it in after the completion of pretreatment
Refrigerator storage is spare.
Pretreated rice straw is mixed with inoculum, inoculum is the biogas slurry after pig manure anaerobic digestion, and pH is 7.0
~8.0, ammonia nitrogen is in 200~1500mg/L, and basicity is in 2000~6000mg/L, inoculum concentration 20gMLSS/L；It adds water, stirs
Uniformly, it is settled to 0.3L, is sealed；Mesophilic anaerobic digestion process 25d is carried out in 35 ± 1 DEG C of constant water bath box, is shaken every day 1
It is secondary.
The methane percentage composition and daily output methane quantity in anaerobic digestion process are measured in experimentation, and measure pretreatment
Cellulose, hemicellulose, content of lignin afterwards, data are used to evaluate the effect of rice straw anaerobic digestion after photocatalysis pretreatment
Fruit.
In following all experiments, anaerobic digestion experimental provision is that volume is 1L indigo plant lid bottle, 1L wide-mouth bottle, catch basin and glass
Glass pipe, emulsion tube connection composition.Stalk was the rice straw that 40 mesh screen pulverizers crush, and additive amount is 50g TS.Inoculation
Object is to operate normally pig manure anaerobic digester biogas slurry, and additional amount is 20g MLSS/L.
Embodiment 1
Taking 39 parts of weight is 15.98g rice straw；Be separately added into 0.2g, 1g, 2g titanium dioxide solids catalyst add it is water-soluble
Solution is added in glass container, after stirring evenly, the stalk weighed up is added later and is settled to 200ml, is then placed in photocatalysis
In reactor, using with long arc mercury lamp, as light source, solution surface opens long arc mercury lamp difference away from lamp source 41cm in reactor
1h, 2h, 4h, 8h are irradiated, this experiment uses external lighting type bar shaped fluorescent tube, and lamp source uses 500W long arc mercury lamp, and primary waves is a length of
365nm.It is stirred using magnetic stirring apparatus always in During Illumination, blender is using happy 85~2 type constant temperature magnetic of Shanghai department
Power blender, reaction solution temperature are maintained at 47 ± 2 DEG C.It is spare that 4 DEG C of refrigerator storages are placed it in after the completion of pretreatment.
Pretreated rice straw is mixed with inoculum, inoculum is the biogas slurry after pig manure anaerobic digestion, and pH is 7.0
~8.0, ammonia nitrogen is in 200~1500mg/L, and basicity is in 2000~6000mg/L, inoculum concentration 20gMLSS/L；It adds water, stirs
Uniformly, it is settled to 0.3L, sealing guarantees anaerobic environment；Mesophilic anaerobic digestion process is carried out in 35 ± 1 DEG C of constant water bath box
25d is shaken every day 1 time.
Daily gas production is recorded in experimentation by drainage, while methane percentage composition in measurement gas daily,
Data are used to evaluate the effect of rice straw anaerobic digestion after photocatalysis pretreatment.Total gas production and methane are calculated after experiment
Then total output calculates T80With methane production increase rate.Experimental result is as shown in table 1 below.
1. anaerobic fermentation 25d gas production of table and methane production
Table 1 show the gas production and methane production and T of anaerobic digestion 25d80, in 25d, different photocatalysis pretreatments
Under the conditions of TS methane production rate be 84.74~117.86mL/gVS, improve 12.87% than non-pretreated group (75.08mL/gVS)
~56.98%, T80For 18~20d, shorten 5%~18% than non-pretreated group (22d).Comprehensively consider, works as TiO2Additive amount is
1g, when light application time is 1h, pretreating effect is best, and anaerobic digestion TS methane production rate is 248.00mL/gVS, T80It is 18.83
It.As it can be seen that photocatalysis pretreatment can be obviously shortened anaerobic digestion time, load methane production rate early period is improved.
Straw property after table 2. pre-processes
Table 2 show cellulose, hemicellulose and lignin quality after pretreatment, with untreated RICE STRAW LIGNIN quality
(7.14%) it compares, each experimental group Lignin degradation rate is 13.59%~22.41%, it is seen that the preconditioning technique may be implemented
Lignin degrading.
The discharging property of table 3.
Table 3 the experimental results showed that, this experiment each group discharges pH, ammonia nitrogen and basicity in the optimum range of anaerobic bacteria growth
(ammonia nitrogen < 2000mg/L, 3000~5000mg/L of basicity), can effectively improve the buffer capacity of digestive system, maintain the steady of system
It is qualitative.
Claims (3)
1. a kind of method that photocatalysis pretreatment improves rice straw anaerobic digestion gas production performance, it is characterised in that:
(1) raw material and reagent prepare
Raw material: stalk prepares, and takes air-dried rice straw, is first cut into 3~4 centimetres, then with the pulverizer of 40 mesh screen of band
It is spare to crush kept dry；
Reagent: TiO2
(2) preprocess method
The rice straw of certain mass is weighed by 50gTS/L load, load is with rice straw TS calculating；By titanium dioxide plus water-soluble
Solution is added in glass container, and after stirring evenly, the stalk that certain mass is added continues to stir evenly, and it is anti-to be then placed in photocatalysis
It answers in device, the mass ratio of titanium dioxide and stalk is (0.2~2): (15-16)；Using with the conduct of long arc mercury lamp in reactor
Light source, solution surface are opened Hg lamp irradiation 1h~8h away from lamp source 40-50cm, are carried out using blender always in During Illumination
Stirring；Reaction solution temperature is maintained at 47 ± 2 DEG C；It is spare that 4 DEG C of refrigerator storages are placed it in after the completion of pretreatment；
(3) anaerobic digestion
Pretreated rice straw is mixed with inoculum, inoculum is the biogas slurry after anaerobic digestion, and pH is 7.0~8.0, ammonia
Nitrogen is in 200~1500mg/L, and basicity is in 2000~6000mg/L, inoculum concentration 20gMLSS/L；It adds water, stirs evenly, constant volume
Sealing guarantees anaerobic environment；Mesophilic anaerobic digestion process 25d is carried out in 35 ± 1 DEG C of constant water bath box, is shaken every day 1 time.
2. according to the method described in claim 1, it is characterized by: lamp source uses 500W long arc mercury lamp.
3. according to the method described in claim 1, it is characterized by:
Solution surface is away from lamp source 41cm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485988A (en) * | 2009-02-18 | 2009-07-22 | 南京工业大学 | Catalyst for catalysis treatment of biomass with microwave and ultraviolet light as well as preparation method and application thereof |
| CN101502782A (en) * | 2009-02-18 | 2009-08-12 | 南京工业大学 | Microwave electrodeless ultraviolet light catalysis pretreatment method for hard-to-degrade biomass |
| CN102268490A (en) * | 2011-06-16 | 2011-12-07 | 北京化工大学 | Clean technique for co-producing xylose, xylitol and arabinose from agricultural and forestal waste |
| WO2015006882A1 (en) * | 2013-07-17 | 2015-01-22 | 北京化工大学 | Method for implementing zero emission biogas slurry in pure straw anaerobic digestion |
| CN105420282A (en) * | 2015-12-15 | 2016-03-23 | 北京化工大学 | Method for improving straw and excrement mixed anaerobic digestion gas production performance by biochemical pretreatment of maize straw |
| CN105967474A (en) * | 2016-06-16 | 2016-09-28 | 安徽新生力生物科技有限公司 | Ultraviolet catalytic pretreatment method for degradation-resistant biomass |
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- 2018-07-30 CN CN201810851339.0A patent/CN109082446B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485988A (en) * | 2009-02-18 | 2009-07-22 | 南京工业大学 | Catalyst for catalysis treatment of biomass with microwave and ultraviolet light as well as preparation method and application thereof |
| CN101502782A (en) * | 2009-02-18 | 2009-08-12 | 南京工业大学 | Microwave electrodeless ultraviolet light catalysis pretreatment method for hard-to-degrade biomass |
| CN102268490A (en) * | 2011-06-16 | 2011-12-07 | 北京化工大学 | Clean technique for co-producing xylose, xylitol and arabinose from agricultural and forestal waste |
| WO2015006882A1 (en) * | 2013-07-17 | 2015-01-22 | 北京化工大学 | Method for implementing zero emission biogas slurry in pure straw anaerobic digestion |
| CN105420282A (en) * | 2015-12-15 | 2016-03-23 | 北京化工大学 | Method for improving straw and excrement mixed anaerobic digestion gas production performance by biochemical pretreatment of maize straw |
| CN105967474A (en) * | 2016-06-16 | 2016-09-28 | 安徽新生力生物科技有限公司 | Ultraviolet catalytic pretreatment method for degradation-resistant biomass |
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