CN107055773B - Method for advanced treatment of anaerobic effluent of cassava alcohol waste liquid - Google Patents

Method for advanced treatment of anaerobic effluent of cassava alcohol waste liquid Download PDF

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CN107055773B
CN107055773B CN201710457535.5A CN201710457535A CN107055773B CN 107055773 B CN107055773 B CN 107055773B CN 201710457535 A CN201710457535 A CN 201710457535A CN 107055773 B CN107055773 B CN 107055773B
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赵明星
廖家林
卞志明
阮文权
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • 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

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Abstract

The invention discloses a method for advanced treatment of cassava alcohol waste liquid anaerobic effluent, and belongs to the technical field of sewage purification treatment. The inoculated sludge is the moderate-temperature anaerobic granular sludge of a food processing factory, an up-flow anaerobic sludge bed UASB is used as a reactor, the fermentation characteristic of the sludge is analyzed through continuous anaerobic treatment at the moderate temperature of 35 ℃, and meanwhile, a kinetic model is established to provide optimized operation parameters for the fermentation process and provide reliable operation management theoretical guidance for the actual cassava alcohol waste liquid treatment. The anaerobic deep fermentation of the wastewater can generate a large amount of methane, the high-temperature anaerobic effluent waste liquid in the first stage of the cassava spirit can be effectively treated, and the harmlessness, reduction and recycling of the high-concentration organic wastewater are realized. The method is simple and easy to operate, has high stability, and can effectively treat the waste liquid of high-temperature anaerobic effluent of the cassava alcohol in one stage.

Description

Method for advanced treatment of anaerobic effluent of cassava alcohol waste liquid
Technical Field
The invention relates to a method for advanced treatment of cassava alcohol waste liquid anaerobic effluent, and belongs to the technical field of sewage purification treatment.
Background
According to related reports, the cassava fuel ethanol will play an increasingly important role in the future energy configuration process. Because the roots and stems of cassava contain a large amount of carbohydrate and starch, a large amount of organic wastewater can be generated in the ethanol production process, and contains a large amount of renewable nutrient substances, so that the cassava is nontoxic and high-concentration organic wastewater. In the production process of cassava fuel ethanol, about 15t of alcohol wastewater can be discharged per ton of alcohol, the wastewater has the characteristics of high solid content, high COD (chemical oxygen demand), low pH (potential of hydrogen) and the like, is industrial high-concentration organic wastewater which is difficult to degrade, not only influences the ecological environment of a wastewater receiving water body, but also is one of influencing factors for restricting enterprise development, and therefore, how to solve the problem becomes an important subject in the enterprise development process. Anaerobic fermentation is a technology for converting biomass into biological energy, can generate renewable clean energy biogas, and is one of effective methods for treating alcohol wastewater
Compared with other treatment technologies, anaerobic digestion has more advantages, the cassava alcohol waste liquid can be effectively treated, clean biogas energy can be obtained, the cassava alcohol waste liquid is reduced, harmless and recycled, and the method has important significance for sustainable development of environment and economy.
In the anaerobic fermentation process of the cassava alcohol waste liquid, although partial organic matters can be degraded after primary anaerobic treatment, organic matters in primary anaerobic effluent are still high, biodegradability is good, SS content is low, pH is moderate, and therefore the treatment method of the effluent of the cassava alcohol waste liquid through one-stage anaerobic fermentation still needs to be improved. At present, a plurality of problems still exist in the anaerobic effluent treatment of a first-stage anaerobic fermentation with high organic concentration and high SS, and the problems are mainly shown in two aspects: on one hand, the treatment types of the adopted subsequent advanced treatment are different due to different water quality characteristics of the wastewater in the effluent of the one-stage anaerobic fermentation system; on the other hand, in the actual waste liquid treatment process, the principles of economy, operability and the like need to be considered, the subsequent advanced treatment unit is required to not only need high-efficiency treatment capacity, but also have the characteristics of low economic cost, simplicity and easiness in management and the like, and in addition, aiming at the problem of optimizing the operation conditions in the anaerobic fermentation process, how to establish an optimization mode and method is also a problem in the process of treating the alcohol waste liquid.
Disclosure of Invention
The invention aims to solve the technical problem of high content of soluble organic substances in effluent of a one-stage high-temperature CSTR reactor, and provides a method for deep treatment of anaerobic effluent of cassava alcohol waste liquor.
In one embodiment of the invention, the TS of the medium-temperature granular sludge is 100-110 mg/L, the VS is 80-90 mg/L, and the pH is 7.5-8.0.
In one embodiment of the invention, the inoculation amount is 8-10 gVS sludge/L wastewater.
In one embodiment of the invention, the inoculum size is 72gVS sludge in a 7.2L reactor volume.
In one embodiment of the invention, the mesophilic granular sludge is from a mesophilic anaerobic UASB reactor in a food processing plant, and the inoculum size is 72gVS strain in a reaction tank.
In one embodiment of the invention, VS of the anaerobic fermentation of the cassava alcohol waste liquid is 10g/L, the cassava alcohol anaerobic fermentation waste liquid is continuously fed by a peristaltic pump, and the reflux ratio of the effluent to the influent is 2:1, the pH is not adjusted in the reaction process.
In one embodiment of the invention, the pH of the inlet water of the reactor is 7.4-7.62, the total COD is 15000-15400 mg/L, the soluble COD is 10000-11000 mg/L, the alkalinity is 6200-6500 CaO mg/L, and the VFA is 2200-2700 mg/L.
In one embodiment of the invention, the operating temperature of the UASB anaerobic reactor is 33-35 ℃.
In one embodiment of the invention, the UASB anaerobic reactor is operated in a stepwise volumetric load increase mode at 3 kgCOD/(m)3D) running for 5-10 d, and lifting to 5 kgCOD/(m)3D) running for 10-15 d, and then lifting to 7 kgCOD/(m)3D) running for 30-35 d.
In one embodiment of the present invention, the HRT and gas production rate of the UASB reactor are calculated as follows: 5.2441x2+2.29 x; wherein y is y (t)/ym(ii) a y (t) is gas production rate per unit time, ymMaximum gas production rate; x is hydraulic retention time HRT; the required hydraulic retention time is calculated to achieve a given gas production rate.
The invention also provides a treatment device for anaerobic effluent of cassava alcohol waste liquid, which is designed and manufactured according to the method.
Has the advantages that: the invention takes the inoculated sludge from the mesophilic anaerobic granular sludge of a food processing factory, adopts an upflow anaerobic sludge blanket UASB reactor as a processing device, and adopts the concepts of maximized resource recovery waste treatment, simple operation, low cost and the like, through comprehensively analyzing intermediate metabolites generated in the growth and reproduction process of microorganisms, the TCOD concentration is reduced from 15000mg/L to 1327.9mg/L through the biological treatment of wastewater for nearly 60 days, and the removal rate of the TCOD reaches 83.0-84.1 percent. According to the invention, by adopting the anaerobic fermentation operation mode of increasing the volume load, the concentration of organic substances in the anaerobic fermentation effluent is further reduced, and the resource utilization degree of the anaerobic fermentation effluent is improved. The method has the advantages of simple process, easy control and operation, great significance for improving the treatment efficiency and the energy recovery rate of the cassava alcohol anaerobic fermentation waste liquid, and no secondary pollution, so the method can be used as a subsequent treatment means of effluent of the cassava alcohol waste liquid by one-stage anaerobic fermentation, and has good application and research prospects.
Drawings
FIG. 1 is a schematic diagram of a UASB anaerobic reactor;
FIG. 2 shows the change of COD in the effluent of the UASB reactor under different operating conditions;
FIG. 3 shows the performance of the UASB reactor under different conditions;
FIG. 4 shows the stability characteristics of organic acids and pH in UASB reactors;
FIG. 5 shows the dynamic change of organic acid composition in the UASB reaction system;
FIG. 6 is a fitting straight line of CSTR anaerobic reaction biogas gas production rate under different volume loads;
FIG. 7 is a straight line fit between HRT and y (t)/(ym-y (t));
FIG. 8 is a plot of the fit between k, HRT and y (t)/(ym-y (t)).
Detailed Description
The content of methane is measured by a portable methane measuring instrument, TCOD and SCOD are measured by a potassium dichromate titration method, and VFA is measured by a liquid phase method.
The basic characteristics of the cassava alcohol waste liquor, namely effluent from anaerobic fermentation of a stage of high-temperature CSTR are shown in Table 1:
TABLE 1 cassava alcohol waste liquor Water quality characteristics
Figure BDA0001324044400000031
The moderate temperature granular sludge inoculated by the UASB anaerobic reactor in the embodiment is taken from a moderate temperature anaerobic reaction tank of a food processing factory, and the basic characteristics of the sludge are shown in the table 2:
TABLE 2 Properties of the inoculated sludge
Figure BDA0001324044400000032
Example 1
The upflow anaerobic sludge blanket UASB reactor device shown in FIG. 1 is made of full glass material, the volume is 9.5L, and the actual effective reaction volume is 7.2L. The reaction temperature is 35 ℃, inlet water enters from the bottom of the reactor through a pump, biogas generated by the reaction is separated through a three-phase separator, the biogas is discharged from a gas discharge pipe to a gas collection bag for collection, outlet water and inlet water flow back according to the proportion of 2:1, a glass interlayer is arranged outside the reactor, and the reactor is operated in a water bath heating mode under the condition that the temperature is maintained at 35 ℃.
Example 2 change of COD in effluent from UASB reactor under different operating conditions
The operational performance of the UASB reactor is shown in FIG. 2. After being treated by a CSTR anaerobic reactor at a first stage, the effluent is diluted according to the set corresponding hydraulic retention time and volume load and enters a UASB reactor by a pump for anaerobic fermentation at 3 kgCOD/(m)3D) operating for 10d under load, and lifting to 5 kgCOD/(m)3D) running for 15d, and then lifting to 7 kgCOD/(m)3D) run 33 d. After nearly 60 days of treatment, the final reactor operating load was 7kgCOD/m3D, the concentration of TCOD and SCOD in the effluent is 1327.9 and 551.2mg/L respectively, and the removal rate of TCOD reaches 83.0-84.1%. During the treatment process, the concentration of organic matters in the effluent is increased along with the increase of the volume load of the inlet water.
As shown in FIG. 3, the daily biogas production increases with the increase of the volume load, and when the volume load of the reactor is 3, 5, 7kgCOD/m3D, when the biogas is stably operated under the condition, the daily biogas yield is respectively 6.9, 12 and 17.1L/d, the methane content respectively reaches 47.5%, 52.3% and 51%, and the biogas gas yield is respectively 0.358, 0.315 and 0.31mL/g TCOD. Along with the reaction, the daily methane yield does not fluctuate dramatically, which indicates that the reactor has good stable treatment capacity and effect under the volume load.
The methanogenic anaerobic fermentation system is easily impacted by VFA concentration, and under a high-load condition, the pH value of the system is reduced along with the accumulation of the VFA concentration, so that the activity of methanogens is inhibited, and the removal rate and the conversion rate of organic substrates are reduced. Therefore, VFA concentration and pH indexes are adopted to evaluate the fermentation characteristics of the anaerobic fermentation system.
As shown in figure 4, in the whole fermentation process of the UASB anaerobic reactor, the pH of the inlet water is always kept above 7.4, and the volume load is within the treatment capacity range of the reactor, so that the pH of the outlet water is always kept above 7.3, and the alkalinity is maintained at about 1660-2325 CaOmg/L, because the pH of the UASB inlet water is high, and the methanogenic activity of the inoculated microorganisms is high, which shows that under the adjustment of proper operation load, the reaction system has good buffering capacity, and no acidification phenomenon occurs in the operation process.
The composition of organic acid in the whole fermentation process was analyzed, and the results are shown in FIG. 5, where the lactic acid content was very low, the maximum value was 24.7mg/L, the main organic acid component was acetic acid, and the volume load was 7kgCOD/m3D, the concentration of acetic acid is 532.9-1168.1mg/L, the contents of propionic acid and butyric acid are lower and have smaller fluctuation in the stable stage of the system, and the pH change is more consistent with the dynamic change trend of the components of each organic acid. In conclusion, in the whole anaerobic fermentation process, when the volume load is 7kgCOD/m3D, the organic acid concentration in the reactor is kept in a stable state all the time, and the VFA concentration is 900-951.4 mg/L.
Example 3 dynamic model of CSTR anaerobic reaction biogas production rate under different volume loads
The operating parameters of the reactor were controlled according to the following kinetic model:
the establishment of the dynamic model is based on material conservation, and comprises the following steps:
Figure BDA0001324044400000041
in the above formula:
VRis the volume of the reactor (L); m isoThe amount of the added materials (L/d); c0Is the concentration (g/L) of organic substances of the added materials; c is the concentration of organic material in the reactor (g/L); r (c) is the rate at which the substrate is digested (g/L.d); y is the unit raw gas production rate (L/gTCOD); y ismMaximum unit gas production rate (L/gTCOD);
according to first order reaction kinetics:
Figure BDA0001324044400000051
wherein k is the first order reaction rate (d)-1)。
According to HRT ═ m0VR, under steady state conditions, obtainable from the two formulas (1) (2) above:
Figure BDA0001324044400000052
in addition, during the anaerobic reaction, under different time t conditions, the gas production rate and the concentration of the substrate organic substances have the following relationship:
Figure BDA0001324044400000053
can be obtained by converting the equation (4),
Figure BDA0001324044400000054
wherein y (t) is the unit feedstock gas yield (L/gTCOD).
From equations (3) and (5), we can derive:
Figure BDA0001324044400000055
furthermore, the relationship Fr ═ m according to the volume load and hydraulic retention time0HRT, formula (6) can be converted to:
Figure BDA0001324044400000056
under the condition of equation (7), the k value can be determined according to HRT and y (t)/(y)m-y (t)) as shown in FIG. 7.
In addition, k, HRT, and y (t)/(y) can also be obtained by fitting the graphsm-y (t) a relationship diagram of the three, let y (t)/ymFormula (6) can be converted to,
Figure BDA0001324044400000057
from the gas production rate fitting graph 6, the fitting equation can be obtained as y ═ 0.004x +0.396, and the maximum gas production rate is 0.396L/gTCOD, i.e. the unit feedstock gas production rate, by HRT and y (t)/(y)mFitting graph 7 (fitting equation is y ═ 34.49x-2.06) between (y), (t)) can result in first order kinetic parameter k × C0A value of 34.49g/L.d, organic matter concentration C according to UASB0At 15000mg/L, a k-value of 2.29d may further be obtained-1。
Let y (t)/ymFig. 8 is obtained from the relationship between the volume loading and the hydraulic retention time. Fitting the curve equation to y-5.2441 x2+2.29 x. Again from FIG. 8, at a k value of 2.29d-1Then, based on the given value of y (t) of 0.35L/gTCOD, the optimal HRT value under the condition of 3.3d and Fr value of 4.5 kgCOD/(m)3·d)。
Therefore, the model can calculate and obtain the optimal HRT and Fr reaching the corresponding gas production rate under the condition of the given gas production rate y, has certain guiding significance on the scale of engineering construction and cost budget, and can also provide certain theoretical technical support for actual engineering operation.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (4)

1. An anaerobic effluent advanced treatment method of cassava alcohol waste liquid, which is characterized in thatCharacterized in that the method is to carry out advanced treatment on anaerobic effluent of cassava alcohol waste liquid treated by a first-stage high-temperature CSTR anaerobic reactor, wherein the advanced treatment adopts an up-flow anaerobic sludge bed reactor UASB, and inoculates medium-temperature granular sludge to carry out medium-temperature continuous anaerobic fermentation to produce methane; the TS of the medium-temperature granular sludge is 108-110 mg/L, the VS is 86-88 mg/L, and the pH is 7.8-8.0; the operation mode of the UASB anaerobic reactor is a mode of lifting volume load in stages at 3 kgCOD/(m)3D) running for 5-10 d, and lifting to 5 kgCOD/(m)3D) running for 10-15 d, and then lifting to 7 kgCOD/(m)3D) running for 30-35 d; the operation temperature of the UASB anaerobic reactor is 33-35 ℃; the inoculation amount of the medium-temperature granular sludge is 8-10 gVS sludge/L wastewater.
2. The method according to claim 1, wherein the feed water pH of the UASB anaerobic reactor is 7.4-7.62, the total COD is 15000-15400 mg/L, the soluble COD is 10000-11000 mg/L, the alkalinity is 6200-6500 CaO mg/L, and the VFA is 2200-2700 mg/L.
3. The method according to claim 1, wherein the UASB anaerobic reactor effluent to influent reflux ratio is 2:1, the pH is not adjusted in the reaction process.
4. The method according to claim 1, wherein the HRT and the gas production rate of the UASB anaerobic reactor are calculated as follows: y =5.2441x2+2.29 x; wherein y is y (t)/ym(ii) a y (t) is gas production rate per unit time, ymMaximum gas production rate; x is the hydraulic retention time HRT.
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CN101250005A (en) * 2008-04-01 2008-08-27 同济大学 Cassava grain stillage anaerobic treatment method
CN106630132A (en) * 2016-12-29 2017-05-10 江南大学 Method for high-temperature anaerobic treatment on cassava alcohol waste liquor by different inocula

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CN101250005A (en) * 2008-04-01 2008-08-27 同济大学 Cassava grain stillage anaerobic treatment method
CN106630132A (en) * 2016-12-29 2017-05-10 江南大学 Method for high-temperature anaerobic treatment on cassava alcohol waste liquor by different inocula

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