CN104031949A - Method for improving acid production quality and acetic acid proportion in anaerobic fermentation of residue active sludge - Google Patents
Method for improving acid production quality and acetic acid proportion in anaerobic fermentation of residue active sludge Download PDFInfo
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- CN104031949A CN104031949A CN201410256182.9A CN201410256182A CN104031949A CN 104031949 A CN104031949 A CN 104031949A CN 201410256182 A CN201410256182 A CN 201410256182A CN 104031949 A CN104031949 A CN 104031949A
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Abstract
The invention relates to a method for improving acid production quality and acetic acid proportion in anaerobic fermentation of residue active sludge. The method comprises the following steps of firstly, adding calcium peroxide into concentrated residual sludge in a wastewater treatment plant, wherein adding amount of the calcium peroxide is 5%-20% of the weight of the volatile suspended solid in the residual active sludge; then, sealing at 30-40 DEG C, carrying out anaerobic digestion in an anaerobic digestion tank with stirring speed of 100-200rpm, wherein the anaerobic digestion time is 5-10 days. The result indicates that calcium peroxide can promote dissolution of particulate organic substances, can improve acidification degree of deliquescent organic substances and can inhibit a methane production process, so that accumulation of volatile short-chain fatty acid is facilitated and transformation of other acids to acetic acid is promoted; meanwhile, a plurality of harmful organic substances in the sludge are effectively removed, so that the acid production quality in anaerobic fermentation of the residue active sludge is improved. The method disclosed by the invention is simple to operate and gentle in reaction condition, is used for recycling and carrying out harmless disposal on the concentrated residual sludge of the sewage treatment plant, and has very good economic and social benefits.
Description
Technical field
The present invention relates to a kind of method that improves residual active sludge anaerobic fermentation and acid production quality and proportion of acetic acid.Belong to sludge treatment and application technology as the second resource field.
Background technology
At present, in world wide, apply active sludge treatment technology the most widely and produced a large amount of mud (comprising primary sludge and residual active sludge).The treatment and disposal cost of residual active sludge is higher, is one of main bugbear of sewage work.In residual active sludge, organic content is high, if the part that can reclaim wherein can be utilized material, by cost-saving and reach the object of sludge reduction, resource utilization.The residual active sludge treatment process being most widely used is at present anaerobically fermenting.The intermediate product of anaerobic fermentation process is volatility short chain fatty acid (comprising acetic acid, propionic acid, isopropylformic acid, butyric acid, isovaleric acid, valeric acid), the alternative methyl alcohol of intermediate product of this anaerobic fermentation process, the additional carbons such as sugar are applied to biological denitrification denitrogenation and the Biological Phosphorus Removal Process of sewage work, and obtain good effect, thereby solve the especially problem of Shelter in South China Cities sewage work carbon source deficiency of China city.
Residual active sludge anaerobically fermenting generally comprises hydrolysis, produces acid, produces methane three phases.Strengthen hydrolysis and produce sour effect and suppress and produce methane process, can reach the object of accumulation volatility short chain fatty acid.Abroad to the research starting of residual active sludge anaerobic fermentation and acid production early, thereby mainly reach by parameters such as the pH value in control anaerobic digestion process, temperature, HRT, SRT speed and the efficiency object of carrying high acid, in addition, the different pretreatment mode such as ultrasonic wave, heat, microwave, advanced oxidation also can improve anaerobic fermentation and acid production speed and efficiency.The domestic research to residual active sludge anaerobic fermentation and acid production shows, adds alkali, salt, trace oxygen, humic acid and tensio-active agent etc. and can improve anaerobic fermentation and acid production.Wherein: Chinese patent CN101768609A has announced a kind of method that improves sludge anaerobic fermentation and acid production, by controlling hyperacoustic operating parameters, sludge microbe is carried out to broken wall effect, make a large amount of strippings of organism in microorganism cells, and under the combined action of the alkali lye adding and microorganism, to make mud be farthest liquid phase by solid phase transformation and produce VFA.Chinese patent CN102583917A has announced a kind of municipal sludge pretreatment process of reinforcement sludge anaerobic fermentation and acid production, add neutral protease and disodium EDTA (EDTA-2Na) by combining, and regulate pH and temperature of reaction, make mud cell rupture, organism obtains farthest discharging and high-quality transforms, and has significantly improved organic acid content that follow-up anaerobically fermenting produces.Chinese patent CN102583927A has announced a kind of method of micro-oxygen hydrolysis acidification mud, the mud that inoculation contains acid-producing bacteria in reactor for hydrolysis and acidification, intermittently passing into air to reactor for hydrolysis and acidification stirs, and auxiliary machinery stirs simultaneously, under the micro-oxygen condition that keeps dissolved oxygen 0.4-0.8mg/L, to the mud acidifying that is hydrolyzed, mud produces acid amount and improves 38-50%.Chinese patent CN102586344A has announced a kind of method of heating cycle sludge anaerobic fermentative production voltaile fatty acid, thickened sludge and dewatered sludge are made into mixing sludge and carry out alkaline anaerobic fermentation and acid production as charging, carry out heat pre-treatment at the mud while of output same volume returned sluge, alkaline anaerobically fermenting is carried out in recirculation, can collect high acid content mixed solution.Chinese patent CN102586345A has announced a kind of method of producing volatile fatty acid by using microwave circulation sludge anaerobic fermentation, the mixing sludge of thickened sludge and dewatered sludge composition is carried out to alkaline anaerobic fermentation and acid production as charging, returned sluge carries out Microwave Pretreatment simultaneously, alkaline anaerobically fermenting is carried out in recirculation, can collect high acid content mixed solution.Chinese patent CN102776240A has announced a kind of method that improves sludge fermentation volatile acid output, municipal sludge is joined in reactor, and add 0.2-200mg humic acid/g volatile suspended solid, pH value is controlled at 7.5-11,25 DEG C or 35 DEG C of temperature, fermentation number of days is 2-10d, and the volatile acid amount that can make sludge fermentation produce improves 60% left and right.Chinese patent CN102796764A has announced a kind of method of rhamnolipid biological surface activator promotion excess sludge anaerobic fermentation and acid production, in mud sample by natural subsidence 24-30h under 4 DEG C of conditions, add the rhamnolipid of 0.005-0.10g/g volatile suspended solid and carry out anaerobically fermenting, promoting the object of excess sludge anaerobic fermentation and acid production to reach rhamnolipid biological surface activator.Chinese patent CN103276023A has announced a kind of method of bio-surfactant promotion excess sludge anaerobic fermentation and acid production, adopt bio-surfactant alkyl polyglycoside to have the characteristic of common nonionic and anion surfactant concurrently, there is high surface, good ecological security and intermiscibility, can strengthen organic stripping, promote excess sludge fermentation and acid.Chinese patent CN103588373A has announced a kind of method of acidogenesis of waste activated sludge dehydration, and heat pre-treatment mud under 35-60 DEG C of condition, then adds calcium oxide and bodied ferric sulfate, can reach the object of putting forward high acid amount.Chinese patent CN103663890A has announced a kind of NaCl of interpolation strengthening excess sludge alkaline fermentation and has produced sour method, add after NaCl stirs 30-50min and add again NaOH, microorganism cells osmotic pressure raises, cellular component discharges in a large number, in addition, hypersaline environment suppresses methanogen growth, makes sludge fermentation stop at souring stage.Above patented technology has only been paid close attention to sludge anaerobic fermentation and acid production and has been ignored the difficult degradation harmful organic substance in sludge fermentation liquid, a lot of research shows, in sewage treatment process, mud can adsorb a large amount of organic pollutants, as: tensio-active agent, personal-care supplies, medicine, oestrogenic hormon etc., and simple anaerobically fermenting or alkali formula, hot fermentation etc. are difficult to remove the Persistent organic pollutants in sewage sludge solid particle surface and fermented liquid, therefore when fermented liquid is recycled as carbon source, still contain a large amount of organic pollutants, reduced the quality of fermented liquid.In addition, above these patented technologies have only been paid close attention to the total product acid amount in sludge anaerobic fermented liquid, do not pay close attention to the wherein content of moiety, the especially acetic acid of acid.Research shows, acetic acid plays an important role in biological carbon and phosphorous removal process, when therefore sludge fermentation liquid is utilized as carbon source, improves the effect that the ratio of acetic acid is wherein conducive to improve biological carbon and phosphorous removal.
Summary of the invention
The object of the present invention is to provide a kind of sludge fermentation that can improve to produce acid and measure and promote acetic acid conversion and removed the method for sludge treatment of noxious pollutant in mud.
In order to achieve the above object, the present invention is through for a long time to calcium peroxide (CaO
2) research discovery: CaO
2be a kind of white or light yellow solid powder, in moist medium, can discharge slowly H
2o
2, 1gCaO in theory
2can discharge 0.47g H
2o
2with 1.03g Ca (OH)
2.H
2o
2and Ca (OH)
2all there is the mud of promotion and dissolve, improve the function of anaerobically fermenting speed, and H
2o
2by producing the organism in all right oxidized sludge of hydroxyl radical free radical isoreactivity oxyradical.Therefore, adopt CaO
2both can promote sludge fermentation to produce acid, can remove again the difficult degradation harmful organic substance on mud, put forward high acid quality.
Although as a kind of " solid-state hydrogen peroxide ", CaO
2be widely used in during in-situ chemical repairs, wherein to the Persistent organic pollutants in soil, settling, surface water as hydrocarbon polymer, polychlorobiphenyl, phthalic ester, zellons etc. have good removal effect, and than liquid H
2o
2there is higher utilising efficiency.And soil, surface sediments, surface water are also made up of water and solid matter.But the organic substance containing in soil in the solid matters of a large amount of particulate minerals, organic substance, microorganism etc. is mainly made up of humic acid; Solid matter in surface sediments mainly comprises the destruction product of rock decay effect and abtragung, as detrital material, dissolved substance and newborn substance, also may contain biological remains, biological detritus and vulcanism product; Solid matter content in surface water is relatively less, mainly comprise that some intrinsic materials are as biological metabolite, resolvent, remains and chip etc., comprise in addition the material that mankind's activity enters, as dissolved organic matter, particulate state organism and volatile organic matter etc.
The residual active sludge that the present invention is pending and soil, settling, surface water all belong to complex system, and existing similarity also has feature separately.Similarity is that residual active sludge of the present invention is mainly also made up of water and solid matter, excess sludge water ratio after concentrated is up to more than 96%, solid matter comprises organism and inorganics, and the ratio that wherein organism (volatile solid material (VSS)) accounts for total suspended solid material (SS) is generally 60%-80%.But the organism in residual active sludge is mainly made up of microorganism cells, extracellular polymeric and organic pollutant of adsorbing in sewage treatment process etc.Therefore, we find suitable proportioning and other conditions by CaO from the character of residual active sludge
2be applied to the removal of poisonous and harmful organic pollutant in excess sludge, improve excess sludge anaerobic fermentation and acid production amount and promote other voltaile fatty acid to transform to acetic acid, thereby raising acetic acid amount accounts for the ratio of general volatile lipid acid amount.
The present invention is hydrolyzed three-stage theory according to anaerobically fermenting, and facilitation of hydrolysis and acid process suppress to produce methane process.Concrete steps are as follows:
First the residual active sludge in sewage work's second pond is concentrated into volatile suspended solid concentration VSS more than 8g/L, then calcium peroxide is added wherein, calcium peroxide dosage is the 5%-20% of volatile suspended solid quality in residual active sludge, then being positioned over temperature is 30-40 DEG C, stirring velocity is to carry out anaerobically fermenting in the anaerobic fermentation tank of 100-200rpm, and fermentation number of days is 5-10d; Last centrifugation, obtain fermented liquid and mud cake, through detecting, in fermented liquid volatile acid total concn be do not add calcium peroxide blank group 2.8-4.6 doubly, the concentration of acetic acid is 3.5 times-6.1 times of blank group, in fermented liquid, semi-volatile organic matter is 0-3 kind, illustrates that semi-volatile organic matter is effectively removed, and fermented liquid can be used as carbon source and be back to the process such as denitrification denitrogenation and biological phosphate-eliminating of sewage work; Mud cake after further processing, can be used as acid soil improving agent or as material of construction for paving the way, brickmaking etc.
Above-mentioned calcium peroxide is commercially available analytical pure calcium peroxide;
Above-mentioned semi-volatile organic matter is phenyl aldehyde, phenylcarbinol, phenylacetic aldehyde, phenylethyl alcohol, acrylamide, 1-19 alkene, amine hydroxybenzene, benzene.
The invention has the beneficial effects as follows:
1, the present invention adds calcium peroxide (CaO in mud
2) carry out anaerobically fermenting, calcium peroxide can promote the organic dissolving of graininess, improve the acidizing degree of dissolved organic matter, suppress to produce methane process, thereby be conducive to the accumulation of volatility short chain fatty acid and promote the conversion of other acid to acetic acid, compared with not adding the control group of calcium peroxide, total volatile fatty acids output improves more than 3 times, meanwhile, in mud, many harmful organic substances are also effectively removed, and have improved residual active sludge anaerobic fermentation and acid production quality.
2, calcium peroxide of the present invention promotes the voltaile fatty acid of other kind to transform to acetic acid, and therefore, compared with not adding the control group of calcium peroxide, acetic acid amount improves 5.4 times of left and right.
3, can make many noxious pollutants in mud as benzene, cresols, medicine and personal hygiene article, endocrine disrupter etc. are effectively removed by the inventive method, be conducive to the recycling of fermented liquid.
4, operational condition of the present invention is simple and easy to implement, and compares ozone, and the high-level oxidation technology lignin-sludges such as Fenton, without extras, thereby reduce costs.Calcium peroxide powder used is easy to get and safety non-toxic.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is CaO of the present invention
2on the impact of volatile suspended solid concentration in mud.
Fig. 3 is CaO of the present invention
2the impact of the general volatile fatty acid concentration that anaerobic sludge digestion is produced.
Fig. 4 is CaO of the present invention
2anaerobic sludge digestion is produced to the impact that acetic acid accounts for general volatile fatty acid ratio.
Fig. 5 is not for adding CaO
2the GC/MS of semi-volatile organic matter figure in anaerobic sludge digestion 20d secondary fermentation liquid.
Fig. 6 adds CaO for implementing mud in 1
2process the GC/MS figure of the semi-volatile organic matter in 5d secondary fermentation liquid.
Fig. 7 adds CaO for implementing mud in 2
2process the GC/MS figure of the semi-volatile organic matter in 5d secondary fermentation liquid.
Fig. 8 adds CaO for implementing mud in 3
2process the GC/MS figure of the semi-volatile organic matter in 5d secondary fermentation liquid.
Embodiment
Be described in further detail in conjunction with the embodiments, be to be understood that the example of lifting, just for the present invention that explains, does not comprise all the elements of the present invention below.
Embodiment 1
The residual active sludge of first sewage work being discharged is concentrated into VSS=8.8g/L, (TSS is 13g/L, pH is 6.89), add commercially available analytical pure calcium peroxide, calcium peroxide dosage is that every g volatile suspended solid correspondence adds 0.05g calcium peroxide, then sealing is positioned over 35 DEG C of temperature, carries out anaerobically fermenting in the anaerobic fermentation tank that stirring velocity is 150rpm, and fermentation number of days is 5d.Blank group does not add calcium peroxide, and other operational condition is identical.After testing, add the dissolution rate of mud of calcium peroxide group higher than blank group, show that the volatile suspended solid concentration that adds calcium peroxide group has declined respectively 16.3% and 25.5% at anaerobically fermenting 2d and 4d, and blank group volatile suspended solid concentration declines respectively 14.0% and 18.3% at anaerobically fermenting 2d and 4d; Adding calcium peroxide group gained volatile acid total concn is 1293mg/L, is 2.8 times of blank group; The concentration that adds calcium peroxide group gained acetic acid is 702mg/L, is 3.5 times of blank group, and the ratio that acetic acid accounts for general volatile lipid acid is 54.3%, higher than blank group 25.9%.In blank group sludge anaerobic fermentation 20d secondary fermentation liquid, the GC/MS collection of illustrative plates of semi-volatile organic matter shows (please see Figure 5), and semi-volatile organic matter kind is more, mainly comprises: phenyl aldehyde, phenylcarbinol, phenylacetic aldehyde, phenylethyl alcohol, acrylamide, 1-19 alkene, amine hydroxybenzene, totally 8 kinds of benzene.Add CaO
2after processing, in sludge fermentation liquid, the GC/MS collection of illustrative plates of semi-volatile organic matter shows (please see Figure 6), does not detect semi-volatile organic matter, illustrates that semi-volatile organic matter is effectively removed.
Embodiment 2
The residual active sludge that sewage work is discharged is concentrated into VSS=9.8g/L, (TSS is 14.48g/L, pH is 6.89), add commercially available analytical pure calcium peroxide, calcium peroxide dosage is that every g volatile suspended solid correspondence adds 0.1g calcium peroxide, then sealing is positioned over 35 DEG C of temperature, carries out anaerobically fermenting in the anaerobic fermentation tank that stirring velocity is 150rpm, and fermentation number of days is 5d.Blank group does not add calcium peroxide, and other operational condition is identical.Through detection, add the dissolution rate of calcium peroxide group mud higher than blank group, show that adding calcium peroxide group volatile suspended solid concentration has declined respectively 20.8% and 34.4% at anaerobically fermenting 2d and 4d, and blank group be respectively 14.0% and 18.3%; Adding calcium peroxide group gained volatile acid total concn is 1681mg/L, is 3.6 times of blank group; The concentration that adds calcium peroxide group gained acetic acid is 1009mg/L, is 5 times of blank group, and the ratio that acetic acid accounts for general volatile lipid acid is 60%, higher than blank group 38.9%.And add CaO
2the kind of processing semi-volatile organic matter in secondary fermentation liquid is obviously less than the kind of semi-volatile organic matter in blank group anaerobic sludge digestion secondary fermentation liquid, mainly comprises totally 2 kinds of acrylamide and amine hydroxybenzenes (please see Figure 7).
Embodiment 3
The residual active sludge of first sewage work being discharged is concentrated into VSS=8.8g/L, (TSS is 13g/L, pH is 6.89), add commercially available analytical pure calcium peroxide, calcium peroxide dosage is that every g volatile suspended solid correspondence adds 0.2g calcium peroxide, then sealing is positioned over 35 DEG C of temperature, carries out anaerobically fermenting in the anaerobic fermentation tank that stirring velocity is 150rpm, and fermentation number of days is 6d.Blank group does not add calcium peroxide, and other operational condition is identical.Through detection, add the dissolution rate of calcium peroxide group mud higher than blank group, show that adding calcium peroxide group volatile suspended solid concentration has declined respectively 25.4% and 50.2% at anaerobically fermenting 2d and 4d, and blank group be respectively 14.0% and 18.3%; Adding calcium peroxide group gained volatile acid total concn is 2371mg/L, is 4.6 times of blank group; The concentration that adds calcium peroxide group gained acetic acid is 1488mg/L, is 6.1 times of blank group, and the ratio that acetic acid accounts for general volatile lipid acid is 61.8%, higher than blank group 43.1%.And add CaO
2after processing, in sludge fermentation liquid, the kind of semi-volatile organic matter is obviously less than the blank kind of organizing the semi-volatile organic matter in anaerobic sludge digestion secondary fermentation liquid, mainly comprise phenyl aldehyde, totally 3 kinds of amine hydroxybenzene and benzene, and can find out from the abundance of Tu Zhongfeng, the concentration of residual organic substances reduces (please see Figure 8) greatly.
Claims (1)
1. one kind is improved the method for residual active sludge anaerobic fermentation and acid production quality and proportion of acetic acid, it is characterized in that: the residual active sludge in Xian Shi sewage work second pond is concentrated into more than volatile suspended solid concentration VSS reaches 8g/L, then, calcium peroxide is added wherein, calcium peroxide dosage is the 5%-20% of volatile suspended solid quality in residual active sludge, then being positioned over temperature is 30-40 DEG C, stirring velocity is to carry out anaerobically fermenting in the anaerobic fermentation tank of 100-200rpm, and fermentation number of days is 5-10d; Last centrifugation, obtain fermented liquid and mud cake, through detecting, in fermented liquid volatile acid total concn be do not add calcium peroxide blank group 2.8-4.6 doubly, the concentration of acetic acid is 3.5-6.1 times of blank group, in fermented liquid, semi-volatile organic matter is 0-3 kind, illustrates that semi-volatile organic matter is effectively removed, and fermented liquid can be used as carbon source and be back to denitrification denitrogenation and the Biological Phosphorus Removal Process of sewage work; Mud cake after further processing, can be used as acid soil improving agent or as material of construction for paving the way, brickmaking.
Above-mentioned calcium peroxide is commercially available analytical pure calcium peroxide;
Above-mentioned semi-volatile organic matter is phenyl aldehyde, phenylcarbinol, phenylacetic aldehyde, phenylethyl alcohol, acrylamide, 1-19 alkene, amine hydroxybenzene and benzene.
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