CN102174584A - Combined biological hydrogen production method by adopting sludge and fibers of recovered waste paper - Google Patents
Combined biological hydrogen production method by adopting sludge and fibers of recovered waste paper Download PDFInfo
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- CN102174584A CN102174584A CN2011100319136A CN201110031913A CN102174584A CN 102174584 A CN102174584 A CN 102174584A CN 2011100319136 A CN2011100319136 A CN 2011100319136A CN 201110031913 A CN201110031913 A CN 201110031913A CN 102174584 A CN102174584 A CN 102174584A
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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
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a combined biological hydrogen production method by adopting sludge and fibers of recovered waste paper, which comprises the following steps of: subjecting the fibers of the recovered waste paper to the pretreatment of dilute sulphuric acid hydrolysis to obtain hydrolysate and the recovered and hydrolyzed fibers of the waste paper; washing the recovered and hydrolyzed fibers of recovered waste paper to be neutral by using distilled water, airing and drying the fibers of recovered waste paper, mixing the fibers of recovered waste paper with anaerobic sludge and the distilled water to obtain a mixed solution, wherein the mass-to-volume ratio of the anaerobic sludge to the recovered fibers of recovered waste paper is 10-15ml/g, and the volume-to-mass ratio of the distilled water to the recovered fibers of recovered waste paper is 45-55ml/g; and regulating the initial reaction pH value of the mixed solution to be 7.0; guiding the mixed solution and the hydrolysate into a biological hydrogen production reactor, and filling inert gases into the reactor, wherein the reaction temperature of a constant-temperature shaking table is controlled as 35+/-1 DEG C, and the reaction time is 10-12d. The fibers in waste paper are hydrolyzed and fermented through anaerobic microorganisms in the sludge, and the fibers are decomposed to produce H2, CO2 and ethanol. In the invention, the biological hydrogen production can be realized successfully at a strict anaerobic environment, and a novel means of recovering and utilizing the fibers of the waste paper is provided.
Description
Technical field
The invention belongs to environmental technology field, relate to the method for biological hydrogen production, particularly relate to a kind of method with mud and recycled fiber blending in of fibers biological hydrogen production.
Background technology
Hydrogen Energy has the characteristics of high efficiency and environment friendly, will become the energy utilization form of future ideality.Hydrogen possesses following significant advantage: 1, fuel value height: hydrogen is the lightest element in the periodictable, compares with other material, has the highest energy ratio, reaches 34.15kcal/g; And gasoline only is 13kcal/g, and coal only is 4.837kcal/g; 2, cleanliness without any pollution: do not produce greenhouse gases and other harmful material during combustion of hydrogen, hydrogen-oxygen bonded products of combustion is the most purified material-water, can not produce any pollution to environment, more than the fossil oil cleaning.Therefore, hydrogen is efficient and can the regenerated secondary energy and receive much attention as cleaning.
The research of modern biological hydrogen production starts from the energy dilemma of the seventies in 20th century, and the nineties, biological hydrogen production caused people's attention once more as the industrial technology of Sustainable development because of the further understanding to Greenhouse effect.Bio-hydrogen production technology comprises optical drive process and two kinds of routes of anaerobically fermenting.The latter adopts the hydrogenogens anaerobically fermenting, and product hydrogen speed is fast, and reactor design is simple, and can utilize renewable resources and organic waste to produce, and has more development potentiality with respect to the former.The substrate that fermentative hydrogen production is used, great majority are sugar and starch, comprise the organic waste water that contains these simple carbohydrates.Although some research groups successfully are converted into hydrogen with the organic solid castoff (as potato starch slag, wheat drum, food waste thing, municipal organic solid castoff etc.) of some composition more complicated with Unareobic fermentation, hydrogen generation efficiency is not high.And for the biomass of cellulose family difficult for biological degradation, for example agricultural crop straw (cornstalk, wheat straw stalk and straw etc.) etc. has the report of its biological hydrogen production less so far both at home and abroad, and is in the laboratory study level.
But the waste paper huge reuse resource that is a kind of quantity.According to statistics, China's consumption Case Board was 1,605 ten thousand tons in 2008, calculated with 40% the waste paper rate of recovery, and the Case Board quantity of reuse more than 3 times also reaches about 1,000,000 tons/year.Waste paper is utilized again, not only can save a large amount of plant fiber materials, can also reduce the discharging of solid waste, reduce environmental pollution.The whole world mainly is to reclaim to produce low and middle-grade paper to the utilization of waste paper at present.Because after waste paper fibre utilizes through repeated multiple times, fibre content reduces, fiber shortens through process length such as polishing, manufacture paper with pulp, cause utilising efficiency low, and in paper-making process, added a large amount of chemical substances, the low-grade paper of retrieving should not be copied paper again, has lost its utility value as paper making raw material.But xylogen in the waste paper, hemicellulose level are low, exist with the Mierocrystalline cellulose attitude in a large number, if its hydrolysis can be produced glucose, with respect to the protofibre element, are more conducive to the hydrolysis utilization.If these secondary waste paper fibres can be converted into the cleaning Hydrogen Energy, not only can reduce the pollution of waste to environment, also help to improve energy structure.
People such as Yung-Chung Lo were research (Yung-Chung Lo, Ming-Der Bai, Wen-Ming Chen et al.Cellulosic hydrogen production with a sequencing bacterial hydrolysis and dark fermentationstrategy[J] .Bio-resource Technology, 2008,99:8299-8303), be about to NS, QS mud is mixed into the bacterium source, with rice husk, bagasse, wood fibres such as waste paper are substrate, 35 ℃ of controlled temperature, initial pH value 7.0, stirring velocity 100rpm, its hydrogen-producing speed reaches 23.8mL/L.Liu et al (Liu H., Zhang T., Fang, H.P.P.Thermophilic H2production from cellulose containing wastewater[J] .BiotechnologyLett.2003,25,365-369) use thermophile bacteria Thermoanaerobacterium sp 55 ℃ of temperature, under the condition of pH value 6.5, with sucrose waste water is substrate, and obtaining hydrogen generation efficiency is 7.56mgH
2/ g Mierocrystalline cellulose.
But utilize the method for anaerobic sludge mixing recycled fiber fiber fermentation biological hydrogen production at present, do not appear in the newspapers, because of recycled fiber fiber generation is huge, and it is low to recycle efficient, utilizes approach few, causes the present energy problem of the wasting of resources and China to become increasingly conspicuous.If can make full use of these recycled fiber fibers, turn waste into wealth, will produce very big economic and social benefit.
Summary of the invention
The present invention is directed to the problems referred to above, propose a kind of method with mud and recycled fiber blending in of fibers biological hydrogen production.
The object of the invention is achieved through the following technical solutions:
With the recycled fiber fiber through dilute sulphuric acid hydrolysis pre-treatment after, recycled fiber fiber after hydrolyzed solution and the hydrolysis; The recycled fiber fiber cleans to neutrality through distilled water after the described hydrolysis, mix with anaerobic sludge and distilled water, get mixed solution, described anaerobic sludge is 10～15ml/g with the volume mass ratio of recycled fiber fiber, and distilled water is 45～55ml/g with the volume mass ratio of recycled fiber fiber; The reaction initial pH value of regulating described mixed solution is 7.0; Described mixed solution and hydrolyzed solution are imported airtight biological hydrogen production reactor, charge into the inert gas warranty anaerobic environment, the temperature of reaction of constant temperature shaking table is controlled at 35 ± 1 ℃, reaction times 10～12d.
Described dilute sulphuric acid hydrolysis pretreatment condition is: 95 ℃～115 ℃ of temperature of reaction, dilute sulphuric acid massfraction 0.5%～1.5%, dilute sulphuric acid is 8～16ml/g with the volume mass ratio of recycled fiber fiber, and hydrolysis time is 20min～60min, and the waste paper fibre particle diameter is 0.35mm～1mm.
Above-mentioned pH value is regulated and is adopted 1mol/LHCl solution or 1mol/LNaOH solution.
With 3,5-dinitrosalicylic acid (DNS) method records reductive hydrolysis sugar yield.
In the hybrid reaction system of the present invention, anaerobic sludge is because of utilizing the recycled fiber fiber Decomposition of fermenting, and produces acetate, butyric acid voltaile fatty acid.After reaction of the present invention is finished, the end products that reacts is carried out qualitative and quantitative mensuration with gas-chromatography.
With respect to prior art, the present invention has the following advantages:
(1) the waste paper regenerated fiber that adopts of the present invention is compared with the thallophyta fiber, and xylogen etc. are basic to be removed, and hemicellulose level reduces, and exists with the Mierocrystalline cellulose form in a large number, and staple length shortens, and is hydrolyzed fermentation easilier.
(2) the present invention can realize the minimizing and the resource utilization of mud and recycled fiber fiber simultaneously, also can produce hydrogen, has very great Significance for Environment and society, economic implications.
(3) the present invention also can produce ethanol when producing hydrogen.If separated, purify, have great economic worth and social effect.
Description of drawings
The biological hydrogen production reactor synoptic diagram that Fig. 1 adopts for the present invention;
1-constant temperature shaking table; The 2-reactor; 3-fermented liquid thief hole; 4-gas sampling mouth; The 5-air collector; The 6-collection bottle.
Fig. 2 is the change curve of hydrogen output under the peak optimization reaction condition of the present invention with fermentation time.
Embodiment
Below in conjunction with embodiment the specific embodiment of the present invention is described in detail, but is not limited thereto.
Example 1:
The 200mL anaerobic sludge is put into biological hydrogen production reactor, and adding distil water is supplemented to 1L, after thorough mixing is even, regulates initial pH value to 7.0 with 1mol/L HCl solution, charges into nitrogen 15s, and airtight hydrogen-manufacturing reactor carries out fermentation reaction.The temperature of reaction of control constant temperature shaking table is 35 ℃, and shaking speed is 80r/min, behind the reaction 12d, obtains 27mL gas, after rare NaOH alkali lye absorbs, is CO from the sampling of gas sampling mouth
2, no H
2Produce.
Example 2:
Get 20g recycled fiber fiber and carry out dilute sulphuric acid hydrolysis pretreatment orthogonal test, recycled fiber fiber after hydrolyzed solution and the hydrolysis, waste paper fibre consists of: Mierocrystalline cellulose 64.8%, hemicellulose 7.70%, ash content 5.51%, water ratio 9.06%.Recycled fiber fiber after the hydrolysis is cleaned to neutrality through distilled water, mix with 200ml anaerobic sludge and 800ml distilled water, mud is taken from Sewage Plant, mud total solids level (TS) 88.9%, volatile solids content (VS) 87.5%, VS/TS 98.4%, pH value 7.41.Volume mass ratio, reaction times, 5 factors of waste paper fibre size of temperature, dilute sulphuric acid massfraction, dilute sulphuric acid and recycled fiber fiber are answered in the condition negate of dilute sulphuric acid pre-treatment hydrolysis, 3 levels of each factor, concrete orthogonal test level of factor is as shown in table 1:
Table 1
The orthogonal test of being undertaken by the arrangement of table 1 factor is carried out variance analysis, and hydrolysis effect is just estimated with the reducing sugar yield.The results of analysis of variance shows: the factor that influences reductive hydrolysis sugar yield maximum is dilute sulphuric acid massfraction and temperature of reaction, the R value is respectively 6.32,2.18 reaction times, dilute sulphuric acid influence not remarkable in the selected scope of experiment with volume mass ratio, waste paper fibre particle diameter 3 factors of recycled fiber fiber.Obtaining testing the peak optimization reaction condition is: 115 ℃ of temperature, dilute sulphuric acid massfraction 0.5%, dilute sulphuric acid compares 16mL/g with the volume mass of recycled fiber fiber, time 60min, recycled fiber after obtaining the hydrolysis that hydrolyzed solution 50ml and waste paper fibre particle diameter are 0.350mm (40 order) under this condition, recycled fiber cleans to neutral air-dry through distilled water after the hydrolysis.Record reductive hydrolysis sugar yield up to 56.28% with the DNS method.Concrete testing data is as shown in table 2:
Table 2
Under peak optimization reaction condition of the present invention, with the waste paper fibre of particle diameter 0.350mm (40 order) as fermentation raw material, get this waste paper 20g, with after the 200mL anaerobic sludge mixes mixed solution, mixed solution and 50ml hydrolyzed solution are imported in the biological hydrogen production reactor, adding distil water is supplemented to 1L, after thorough mixing is even, regulate initial pH value to 7.0 with 1mol/L HCl solution, charge into nitrogen 15s, closed reactor carries out fermentation reaction, as peak optimization reaction group of the present invention, compares with control group embodiment 1.The temperature of reaction of control constant temperature shaking table is 35 ℃, shaking speed 80r/min, reaction 12d.The fermentation time of control group and peak optimization reaction group of the present invention and the relation of hydrogen output are as shown in Figure 2.As can be seen from Figure 2, the control group no hydrogen produces, and peak optimization reaction group of the present invention obtains gas 2593.3mL at reaction 12d, gas sampling mouth sampling from air collector, record through gas chromatographic analysis, contain 749.5mL hydrogen, its hydrogen generation efficiency is 37.5mL/gVS.Simultaneously, because of taking from the anaerobic sludge of sewage work, anaerobically fermenting own has acetate, butyric acid voltaile fatty acid to produce, therefore before fermentation, voltaile fatty acid in the anaerobic sludge of peak optimization reaction group of the present invention is measured with gas-chromatography, get the fermented liquid sample from the fermented liquid thief hole of reactor, and simultaneously with gas Chromatographic Determination fermentation finish after product and content thereof in the reaction system of the present invention, its moiety is as shown in table 3.
Table 3
Claims (3)
1. with the method for mud and recycled fiber blending in of fibers biological hydrogen production, it is characterized in that specifically may further comprise the steps: the recycled fiber fiber through dilute sulphuric acid hydrolysis pre-treatment after, must hydrolyzed solution and hydrolysis after the recycled fiber fiber; The recycled fiber fiber mixes with anaerobic sludge and distilled water after distilled water flushing is air-dry to neutrality after the described hydrolysis, gets mixed solution, and described anaerobic sludge is 10～15ml/g with the volume mass ratio of recycled fiber fiber; Described distilled water is 45～55ml/g with the volume mass ratio of recycled fiber fiber; The reaction initial pH value of regulating described mixed solution is 7.0; Described mixed solution and hydrolyzed solution are imported airtight biological hydrogen production reactor, charge into the inert gas warranty anaerobic environment, the temperature of reaction of constant temperature shaking table is controlled at 35 ± 1 ℃, reaction times 10～12d.
2. the method with mud and recycled fiber blending in of fibers biological hydrogen production according to claim 1, it is characterized in that described dilute sulphuric acid hydrolysis pretreatment condition is: 95 ℃～115 ℃ of temperature of reaction, dilute sulphuric acid massfraction 0.5%～1.5%, dilute sulphuric acid is 8～16ml/g with the volume mass ratio of recycled fiber fiber, hydrolysis time is 20min～60min, and the waste paper fibre particle diameter is 0.35mm～1mm.
3. the method with mud and recycled fiber blending in of fibers biological hydrogen production according to claim 1 is characterized in that described pH value adopts 1mol/L HCl solution or 1mol/L NaOH solution to regulate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111235188A (en) * | 2020-02-28 | 2020-06-05 | 河海大学 | Method for producing volatile fatty acid by combining office waste paper and sludge through anaerobic fermentation |
| CN111334533A (en) * | 2020-02-28 | 2020-06-26 | 河海大学 | Method for producing volatile fatty acid by promoting anaerobic fermentation of office waste paper and sludge by cellulase |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381072A (en) * | 2008-10-15 | 2009-03-11 | 云南师范大学 | Hydrogen production method by sweet sorghum stalk anaerobic fermentation |
| CN101445810A (en) * | 2007-11-27 | 2009-06-03 | 中国科学院过程工程研究所 | Method for preparing hydrogen by fermenting biologically pretreated straw |
| CN101544450A (en) * | 2009-05-05 | 2009-09-30 | 浙江省环境保护科学设计研究院 | Method for treating and recycling waste paper making wastewater |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445810A (en) * | 2007-11-27 | 2009-06-03 | 中国科学院过程工程研究所 | Method for preparing hydrogen by fermenting biologically pretreated straw |
| CN101381072A (en) * | 2008-10-15 | 2009-03-11 | 云南师范大学 | Hydrogen production method by sweet sorghum stalk anaerobic fermentation |
| CN101544450A (en) * | 2009-05-05 | 2009-09-30 | 浙江省环境保护科学设计研究院 | Method for treating and recycling waste paper making wastewater |
Non-Patent Citations (3)
| Title |
|---|
| YUNG-CHUNG LO等: "Cellulosic hydrogen production with a sequencing bacterial hydrolysis and dark fermentation strategy", 《BIORESOURCE TECHNOLOGY》, 31 December 2008 (2008-12-31), pages 8299 - 8303 * |
| 肖领平等: "废瓦楞纸纤维素酶解条件及酶解时纤维结构的变化", 《林产化学与工业》, vol. 30, no. 2, 30 April 2010 (2010-04-30), pages 83 - 88 * |
| 詹怀宇: "我国造纸用非木材纤维、废纸原料供应与利用", 《第三届中日造纸技术交流会论文集》, 17 May 2010 (2010-05-17), pages 191 - 203 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111235188A (en) * | 2020-02-28 | 2020-06-05 | 河海大学 | Method for producing volatile fatty acid by combining office waste paper and sludge through anaerobic fermentation |
| CN111334533A (en) * | 2020-02-28 | 2020-06-26 | 河海大学 | Method for producing volatile fatty acid by promoting anaerobic fermentation of office waste paper and sludge by cellulase |
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Application publication date: 20110907 |