CN101914576B - Method for producing ethanol and methane by mixed fermentation of paper-making sludge and monosodium glutamate waste liquid - Google Patents

Method for producing ethanol and methane by mixed fermentation of paper-making sludge and monosodium glutamate waste liquid Download PDF

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Publication number
CN101914576B
CN101914576B CN2010102298021A CN201010229802A CN101914576B CN 101914576 B CN101914576 B CN 101914576B CN 2010102298021 A CN2010102298021 A CN 2010102298021A CN 201010229802 A CN201010229802 A CN 201010229802A CN 101914576 B CN101914576 B CN 101914576B
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fermentation
ethanol
monosodium glutamate
waste liquid
methane
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CN101914576A (en
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林云琴
王德汉
刘可星
王钍汀
吴少全
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South China Agricultural University
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/59—Biological synthesis; Biological purification
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/20—Sludge processing

Abstract

The invention belongs to the field of renewable energy sources and environmental protection and relates to a method for producing ethanol and methane by mixed fermentation of paper-making sludge and monosodium glutamate waste liquid. The method comprises the following steps of: mixing the monosodium glutamate waste liquid and the paper-making sludge according to a dry weight ratio of 3 to 10:100 to obtain a raw material mixture; adding cellulase, nutrient solution and the like into the mixture; adjusting the pH value so that the mixture is acid; inoculating saccharomyces cerevisiae to perform fermentation to produce the ethanol; after the fermentation is finished, distilling to obtain the ethanol; and adding anaerobic digestion inoculation sludge into the distillation remainder to perform anaerobic digestion to produce the methane. The method has the advantages that: the ethanol is produced by synchronous diastatic fermentation without any sterilization operation, the process is simple and the operability is strong; meanwhile, the ethanol and the methane are both produced under an intermediate-temperature condition, so the production condition is mild and the energy consumption is low; and besides, due to the adoption of the mixed fermentation of the paper-making sludge and the monosodium glutamate waste liquid, the living environment of the microorganisms can be improved in terms of trophic structure, the yield of ethanol and methane can be increased, and the harmlessness, reduction and recycling of the two major solid wastes are realized.

Description

A kind of method of utilizing paper mill sludge and monosodium glutamate waste liquid mixed fermentation producing and ethanol and methane
Technical field
The invention belongs to renewable energy source and field of environment protection, relate to a kind of method of utilizing paper mill sludge and monosodium glutamate waste liquid mixed fermentation producing and ethanol and methane.
Background technology
Pulping and paper-making is one of important industry of Chinese national economy; The paper of China's production at present and the output of cardboard leap to the first in the world; But in paper-making process, produced a large amount of paper mill sludges, with the existing papermaking scale of China, the YO of paper mill sludge has reached 2,389 ten thousand t dehydration paper mill sludge (water ratio is 80%); Expect the year two thousand twenty, China approximately will produce 3,088 ten thousand t dehydration paper mill sludge (water ratio is 80%).In the face of a large amount of paper mill sludge like this, traditional treatment and disposal method is: burning, landfill and soil utilization etc.; Paper waste owing to coagulation, absorption etc. act on most pollution substance enrichment in the waste water in mud, influences it directly to use in treating processes; The landfill paper mill sludge is capital not only, land occupation, and soil, underground water and air caused secondary pollution easily; Burn paper mill sludge and then need improve dewatering rate, but investment of boiler incineration system and working cost are higher, be prone to produce smoke pollution, be not suitable for general middle-size and small-size papermaking enterprise.
Paper mill sludge is meant the mixing sludge that the waste water in paper mill obtains in preliminary sedimentation tank and second pond in the biochemical treatment process; The organism that with the fiber fines is staple accounts for 70%～90%; With papermaking filler and coating is that the inorganics of staple accounts for 10%～30%; Because the organic content in the paper mill sludge is high, the bioremediation of seeking its recycling is significant.
Utilize anaerobic digestion techniques to handle organic solid waste; Because the anaerobic digestion energy consumption is low, secondary pollution is few; Can produce simultaneously methane instead of part oil fuel again, the current society at Global Greenhouse Effect aggravation, energy scarcity has crucial strategic importance.But because secondary stock content is high in the paper mill sludge, protein contnt is low, and higher C/N is unfavorable for normally carrying out of anaerobic digestion process, has restricted its anaerobic digestion is used.
Monosodium glutamate industry is one of the most ancient fermentation industry of China; Begin the eighties to get into the high speed development stage; 630,000 tons of China's monosodium glutamate YO in 2008 account for 47% of world's monosodium glutamate YO, a large amount of dischargings that also bring monosodium glutamate waste liquid when the glutamate production amount increases fast.Monosodium glutamate waste liquid mainly comprises the crystalline mother solution that the fermented waste fluid that extracts after the monosodium glutamate and condensing crystal abandon etc., and general every production 1t monosodium glutamate has the discharge of 25t waste liquid approximately, and this monosodium glutamate waste liquid contains large amount of organic, rich in protein, wet thallus and multiple K +, Na +, NH 4 +, Mg 2+, Ca 2+In nutritive salt, be a kind of more unmanageable high concentrated organic waste liquid, directly discharge the meeting serious environment pollution, it is one of the most active aspect of present monosodium glutamate waste liquid process field research that methane is produced in anaerobic digestion, but causes the NH of system easily because the waste liquid nitrogen content is too high 3-N poisons, and how to deal carefully with monosodium glutamate waste liquid becomes one of difficult problem of restriction China glutamate production enterprise development always.
Summary of the invention
The objective of the invention is to the deficiency to prior art, provide a kind of and can effectively handle paper mill sludge and changing food waste, alleviate environmental pressure and realize the method for resource reutilization.
The present invention realizes above-mentioned purpose through following technical scheme:
The invention provides a kind of method of utilizing paper mill sludge and monosodium glutamate waste liquid mixed fermentation producing and ethanol and methane, it is characterized in that may further comprise the steps: (1) with monosodium glutamate waste liquid and paper mill sludge according to dry weight than 3～10: 100 mixed becomes the raw materials mix material; (2) preparing nutrient solution; (3) get nutritive medium, inoculate yeast saccharomyces cerevisiae therein, after cultivating, become S. cervisiae liquid; (4) in the raw materials mix material, add cellulase, nutritive medium and water, regulating the pH value becomes fermentation materials for acidity, and inoculation S. cervisiae liquid, and producing and ethanol ferments; (5) after the fermentation ends, fermentation substrate distilled obtain ethanol; (6) the distillation surplus materials adds anaerobic digestion seed sludge (referring to one or more the kind mud that after domestication, obtain in the anaerobically digested sludge of septic tank mud, corrupt river silt or municipal sewage plant); Regulating the pH value is alkalescence, carries out the anaerobic digestion reaction and produces methane.(its method flow diagram is as shown in Figure 1.)
In the step (1), with before monosodium glutamate waste liquid mixes, paper mill sludge can also pass through pre-treatment in advance at paper mill sludge, and a kind of in the oxyhydroxide that basic metal forms adopted in pre-treatment, and alkaline concentration is 0.3%～1.0%, and pretreatment time is 15～24h.Monosodium glutamate waste liquid: paper mill sludge=3～10: 100 (w/w is in dry biomass) mix, the C/N=15 of adjustment fermentation substrate～25: 1.
Nutrient solution in the step (2) is yam-glucose culture solution; Be with the peeling potatoes stripping and slicing; After adding water boil 25～35 minutes and filtration; Add the nutritive medium of the glucose gained be equivalent to yam quality 5～15% in the filtrating, wherein the add-on of yam accounts for 10～20% of nutritive medium massfraction in the nutritive medium of step (3); The add-on of nutritive medium is 10～20% to be as the criterion with the massfraction of yam in fermentation materials in the step (4).
Can preferred following working method: be cut into the dice that the length of side is 1cm after the yam that is used to prepare nutritive medium need be removed the peel; Putting into 1000mL water then boiled 30 minutes; 8 layers of filtered through gauze, filtrating complements to 1000mL, adds the glucose that is equivalent to yam quality 5～15% again.
In the step (3), yeast saccharomyces cerevisiae is at 30 ± 1 ℃, and it is 10 that the following cultivation of 150rev/min 12～18h becomes concentration 8～10 9The bacterium liquid of cfu/mL.
In the step (4), the add-on of cellulase is 15～30U/gVS, wherein VS refer to the raw materials mix material in the quality (refer to raw material deduction moisture and ash content after remainder) of the volatile matter that contained; The add-on by volume of S. cervisiae liquid is 5～10% of a fermentation materials TV; Dry biomass mark in the fermentation materials counts 5～10%.
In order reaction to be carried out smoothly and to be obtained good co-producing ethanol and methane effect; There are specific requirement in the potential of hydrogen and the reaction times of step (4) and step (6); Wherein the acidity and the alkaline pH value of step (4) and step (6) are respectively 4.0～5.0 and 6.8～7.2, are respectively citric acid solution (10% citric acid solution) and alkali hydroxide soln (with the distillation residuum of 10% alkali hydroxide soln adjusting interpolation anaerobic digestion seed sludge) in order to what regulate pH value; The anaerobic digestion temperature of reaction of the fermentation of step (4) and step (6) is respectively 30 ± 1 ℃ and 37 ± 1 ℃.
In the step (5), the fermentation producing and ethanol time is 48-60h; After the raw material diastatic fermentation finishes; Fermentation substrate is distilled; Obtain concentration and be 8～10% alcohol fuel; Then carry out the anaerobic digestion reaction of step (6), add the anaerobic digestion seed sludge at distillation residue species earlier, the add-on of anaerobic digestion seed sludge accounts for 5～20% of distillation residuum dry-matter with dry weight basis; The anaerobic digestion reaction times is 40～50d, and a reaction residual part is as the seed sludge of new round anaerobic digestion, and another part is fertile as agricultural natural pond.
Carry out in order to guarantee to be reflected under the strict anaerobic condition; After material places in the reactor drum; Can utilize the tight reactor drum bottleneck of the rubbery plug lid that has ventpipe, and seal the interface of ventpipe and plug, feed nitrogen 2min in the reaction beginning forward reaction device with paraffin.
Invention has utilized prior art to be difficult to the paper mill sludge that rationally utilizes, through with monosodium glutamate waste liquid mixed fermentation, and, in the waste treatment harm reduction, can produce ethanol and methane through suitable adjusting.Along with the growth of world economy and the increase of population, the energy shortage problem is serious day by day, and the exploitation renewable energy source is called the focus that the whole world is paid close attention to.Ethanol has received national governments and numerous investigators' extensive attention as a kind of cleaning and the reproducible energy.Present stage, China's production of fuel ethanol was raw material with carbohydrate or grain all, further enlarged the restriction that output will receive resource, and therefore adopting cellulose raw material inexpensive, that be easy to get to produce ethanol will be the inexorable trend of Future Development.
Compared with prior art, the present invention has following advantage:
1, the present invention utilizes the simultaneous saccharification and fermentation producing and ethanol, and process need not any disinfecting action, and technology is simple, and is workable; The production of ethanol and methane is simultaneously all carried out under mesophilic condition, has realized that working condition is gentle, energy consumption is low.
2, the present invention utilizes alkaline solution pre-treatment paper mill sludge; Preprocessing process can realize that larger molecular organics is degraded to small-molecule substance in the mud; Thereby shorten the liquefaction hydrolysis time of follow-up anaerobically fermenting, improve the liquefaction percent hydrolysis of raw material and follow-up biological transformation ratio.
3, the present invention utilizes paper mill sludge and monosodium glutamate waste liquid mixed fermentation to produce alcohol fuel; Can not only improve the living environment of mikrobe from the trophic structure aspect; Improve the output of ethanol and methane, and can also realize " innoxious, minimizing and resource utilization " of two big solid waste simultaneously.
4, the present invention utilizes the organic substance in yeast decomposition paper mill sludge and the monosodium glutamate waste liquid to make ethanol earlier, further utilizes the organic substance in the methanobacteria destructive distillation residuum again, realizes raw-material making full use of, and has avoided the waste of resource.
5, also be that with the heat treatment phase ratio of material in the single product methane technology, the present invention has reduced energy consumption, has practiced thrift the energy to the heat treatment process of follow-up product methane digestion raw material ethanol distillation of the present invention the time.
6, the present invention has potential environmental benefit, social benefit and economic benefit, has huge market and application potential aspect production of renewable energy resources, waste resource regenerated using, industrial solid wastes processing and the disposal.
Description of drawings
Fig. 1 is the schematic flow sheet of paper mill sludge of the present invention and monosodium glutamate waste liquid mixed fermentation co-producing ethanol and methane.
Embodiment
Below further specify technical scheme of the present invention through concrete embodiment.
Embodiment 1
(1) test is taken from sludge dewatering workshop, paper mill, Guangdong Province with paper mill sludge, and the fresh sludge of fetching is uniformly dispersed, and adds 0.6%NaOH solution pre-treatment 24h then;
(2) monosodium glutamate waste liquid of test usefulness is taken from Guangdong Province Gourmet Powder Factory, and according to monosodium glutamate waste liquid: paper mill sludge=8: 100 (w/w is in dry mass) takes by weighing fresh monosodium glutamate waste liquid, adds in the paper mill sludge C/N=18 of adjustment fermentation substrate: 1 to;
(3) take by weighing the yam (peeling) of 300g, cut and put into 1000mL water behind the fritter and boil 30min, with 8 layers of filtered through gauze, filtrating complements to 1000mL, adds the glucose of 30g again, processes the required nutritive medium of fermentation system microorganism growth;
(4) select yeast saccharomyces cerevisiae bacterium colony on the solid medium, the concentration that is seeded to step (3) gained is 20% nutritive medium, cultivates behind the 15h inoculation bacterium liquid as the producing and ethanol test;
(5) mixture that step (2) is obtained (contains paper mill sludge dry-matter 35.8g; Monosodium glutamate waste liquid dry-matter 2.9g) adds in the reactor drum of 1000mL; The nutritive medium and the zero(ppm) water that obtain according to 30U/gVS adding cellulase, step (3) make the interior material total amount of reactor drum reach 600mL again, and total material solids content is 5% in the reactor drum; Utilize 10% citric acid solution to regulate pH value to 4.0～5.0 of above-mentioned material, and the cultured bacterium liquid of inoculation step (4) 60mL;
(6) with above-mentioned reactor drum with the tight bottleneck of consolidation cotton gag, place 30 ± 1 ℃ of isothermal vibration devices producing and ethanol that ferments;
(7) behind the diastatic fermentation 50h; Concentration of ethanol substantially constant in the reactor drum; Then fermentation substrate is distilled; Obtain concentration and be 8.7% alcohol fuel, simultaneously according to inoculum size: distillation residuum total amount=1: 10 (w/w is in dry mass); Add anaerobic digestion seed sludge (referring to one or more the kind mud that after domestication, obtain in the anaerobically digested sludge of septic tank mud, corrupt river silt or municipal sewage plant) in the distillation residuum, and to use the pH of 10%KOH solution adjustment material be 6.8;
(8) reactor drum of sealing step (7) carries out timing through whipping appts to fermented product and stirs, and places 37 ± 1 ℃ thermostat water bath to carry out anaerobic digestion product methane, and obtaining methane production is 0.27m 3CH 4/ kg VS (VS is the volatile matter quality of raw material, refers to the remainder after raw material is deducted moisture and ash content);
(9) the fermentation residuum in the step (8) is except that part is used as the seed sludge of new round anaerobic digestion, and it is directly agricultural that all the other can make natural pond fertilizer.
Embodiment 2
(1) test is taken from sludge dewatering workshop, paper mill, Guangdong Province with paper mill sludge, and the fresh sludge of fetching is uniformly dispersed, and adds 0.6%NaOH solution pre-treatment 24h then;
(2) monosodium glutamate waste liquid of test usefulness is taken from Guangdong Province Gourmet Powder Factory, and according to monosodium glutamate waste liquid: paper mill sludge=5: 100 (w/w is in dry mass) takes by weighing fresh monosodium glutamate waste liquid, adds in the paper mill sludge C/N=22 of adjustment fermentation substrate: 1 to;
(3) take by weighing the yam (peeling) of 300g, cut and put into 1000mL water behind the fritter and boil 30min, with 8 layers of filtered through gauze, filtrating complements to 1000mL, adds the glucose of 30g again, processes the required nutritive medium of fermentation system microorganism growth;
(4) select yeast saccharomyces cerevisiae bacterium colony on the solid medium, the concentration that is seeded to step (3) gained is 20% nutritive medium, cultivates behind the 15h inoculation bacterium liquid as the producing and ethanol test;
(5) mixture that step (2) is obtained (contains paper mill sludge dry-matter 35.8g; Monosodium glutamate waste liquid dry-matter 1.8g) adds in the reactor drum of 1000mL; The nutritive medium and the zero(ppm) water that obtain according to 30U/gVS adding cellulase, step (3) make the interior material total amount of reactor drum reach 600mL again, and total material solids content is 5% in the reactor drum; Utilize 10% citric acid solution to regulate pH value to 4.0～5.0 of above-mentioned material, and the cultured bacterium liquid of inoculation step (4) 60mL;
(6) with above-mentioned reactor drum with the tight bottleneck of consolidation cotton gag, place 30 ± 1 ℃ of isothermal vibration devices producing and ethanol that ferments;
(7) behind the diastatic fermentation 50h; Concentration of ethanol substantially constant in the reactor drum; Then fermentation substrate is distilled; Obtain concentration and be 8.1% alcohol fuel, simultaneously according to inoculum size: distillation residuum total amount=1: 10 (w/w is in dry mass); Add anaerobic digestion seed sludge (referring to one or more the kind mud that after domestication, obtain in the anaerobically digested sludge of septic tank mud, corrupt river silt or municipal sewage plant) in the distillation residuum, and to use the pH of 10%KOH solution adjustment material be 7.2;
(8) reactor drum of sealing step (7) carries out timing through whipping appts to fermented product and stirs, and places 37 ± 1 ℃ thermostat water bath to carry out anaerobic digestion product methane, and obtaining methane production is 0.25m 3CH 4/ kg VS (VS is the volatile matter quality of raw material, refers to the remainder after raw material is deducted moisture and ash content);
(9) the fermentation residuum in the step (8) is except that part is used as the seed sludge of new round anaerobic digestion, and it is directly agricultural that all the other can make natural pond fertilizer.

Claims (5)

1. method of utilizing paper mill sludge and monosodium glutamate waste liquid mixed fermentation producing and ethanol and methane is characterized in that may further comprise the steps: (1) with monosodium glutamate waste liquid and paper mill sludge according to dry weight than 3～10: 100 mixed becomes the raw materials mix material; (2) preparing nutrient solution; (3) get nutritive medium, inoculate yeast saccharomyces cerevisiae therein, after cultivating, become S. cervisiae liquid; (4) in the raw materials mix material, add cellulase, nutritive medium and water, regulating the pH value becomes fermentation materials for acidity, and inoculation S. cervisiae liquid, and producing and ethanol ferments; (5) after the fermentation ends, fermentation substrate distilled obtain ethanol; (6) the distillation surplus materials adds the anaerobic digestion seed sludge, and regulating the pH value is alkalescence, carries out the anaerobic digestion reaction and produces methane;
The described paper mill sludge of step (1) also passes through pre-treatment with before monosodium glutamate waste liquid mixes, and a kind of in the oxyhydroxide that basic metal forms adopted in pre-treatment, and alkaline concentration is 0.3%～1.0%, and pretreatment time is 15～24h;
The described nutritive medium of step (2) is yam-glucose nutritive medium, is with the peeling potatoes stripping and slicing, and after adding water boil 25～35 minutes and filtering, adding is equivalent to the nutritive medium of the glucose gained of yam quality 5～15% in the filtrating; The add-on of yam accounts for 10～20% of nutritive medium massfraction in the said nutritive medium of step (3); The add-on of nutritive medium is 10～20% to be as the criterion with the massfraction of yam in fermentation materials in the step (4);
It is 10 that the described yeast saccharomyces cerevisiae of step (3) is cultured to concentration 8～10 9Cfu/mL becomes described bacterium liquid; The described yeast saccharomyces cerevisiae of step (3) is at 30 ± 1 ℃, and 150rev/min cultivates 12～18h down becomes described bacterium liquid;
Step (4) and the described acidity of step (6) and alkaline pH value are respectively 4.0～5.0 and 6.8～7.2, are respectively citric acid solution and alkali hydroxide soln in order to what regulate the pH value.
2. the method for claim 1 is characterized in that the add-on of the described cellulase of step (4) is 15～30U/gVS, wherein VS refer to the raw materials mix material in the quality of the volatile matter that contained; The add-on by volume of S. cervisiae liquid is 5～10% of a fermentation materials TV; Dry biomass mark in the fermentation materials counts 5～10%,
3. the method for claim 1 is characterized in that described fermentation of step (4) and the described anaerobic digestion temperature of reaction of step (6) are respectively 30 ± 1 ℃ and 37 ± 1 ℃.
4. the method for claim 1 is characterized in that the said fermentation producing and ethanol time of step (5) is 48～60h; The add-on of step (6) anaerobic digestion seed sludge accounts for 5～20% of distillation residuum dry-matter with dry weight basis.
5. the method for claim 1 is characterized in that the described digestion reaction time of step (6) is 40～50d, and a reaction residual part is as the seed sludge of new round anaerobic digestion, and another part is fertile as agricultural natural pond.
CN2010102298021A 2010-07-16 2010-07-16 Method for producing ethanol and methane by mixed fermentation of paper-making sludge and monosodium glutamate waste liquid Expired - Fee Related CN101914576B (en)

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