CN113981011A - Method for synchronously realizing mineralization of azo dye and methanation of straw by ECMO-like device - Google Patents

Method for synchronously realizing mineralization of azo dye and methanation of straw by ECMO-like device Download PDF

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CN113981011A
CN113981011A CN202111199117.3A CN202111199117A CN113981011A CN 113981011 A CN113981011 A CN 113981011A CN 202111199117 A CN202111199117 A CN 202111199117A CN 113981011 A CN113981011 A CN 113981011A
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fermentation
biogas slurry
aeration
ecmo
fermentation reaction
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付善飞
解众
孙文鑫
邹华
王震宇
张云
丁剑楠
李祎飞
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Jiangnan University
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    • C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
    • C12P5/023—Methane
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
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    • C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
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    • C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
    • C12M29/26—Conditioning fluids entering or exiting the reaction vessel
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
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    • C02F2101/34—Organic compounds containing oxygen
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
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    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention discloses a method for synchronously realizing azodye mineralization and straw methanation by an ECMO-like device, belonging to the field of dye wastewater treatment and agricultural waste treatment. The method relies on the technical principle of ECMO in medicine, utilizes the straws as an electron donor for decoloring and reducing the azo dyes, removes carbon dioxide through external forced aeration to improve the concentration of methane and provide micro aerobic conditions in a digestion system, improves the degradation rate of aromatic amine and produces methane by synchronously digesting agricultural wastes, not only shortens the digestion period and treatment steps, but also truly realizes the harmless treatment of the azo dyes and the resource utilization of the agricultural wastes, and has good application prospect.

Description

Method for synchronously realizing mineralization of azo dye and methanation of straw by ECMO-like device
Technical Field
The invention relates to a method for synchronously realizing mineralization of azo dyes and methanation of straws by an ECMO-like device, belonging to the field of dye wastewater treatment and agricultural waste treatment.
Background
Azo dyes are used in various industries because of their wide chroma and stable structure. Worldwide, the amount of azo dye used is 50% of the total dye yield. Many reports indicate that the extensive use and discharge of teratogenic, carcinogenic and mutagenic azo dyes or degradation products poses a great threat to human health and the ecosystem. The natural biomass is used as the adsorbent, and compared with other materials, the natural biomass adsorbent has the advantages of simplicity, low price, reproducibility, easiness in obtaining and the like. The agricultural waste has rich porous structure and functional groups, such as amide, hydroxyl, carboxyl and the like, and can be used for adsorbing azo dyes in wastewater. Although agricultural stalks exhibit good adsorption properties for azo dyes in wastewater, post-treatment of the adsorbent composite requires complete degradation of the azo dyes before disposal, rather than simply transferring from a liquid to a solid phase.
Anaerobic digestion technology is a sustainable and renewable agricultural waste treatment technology. In addition, agricultural straw is widely considered as a potential substrate for biogas production, and anaerobic conditions can achieve higher bioconversion efficiency. At the same time, anaerobic conditions promote azo bonds (-N ═ N-) in azo dyesThe reductive cleavage of (3). Due to O under aerobic conditions2Has an electrophilic structure, has higher oxidation-reduction potential (+820mV), and preferentially accepts electrons to be reduced compared with azo dyes, thereby inhibiting the reduction of the azo dyes, so that the aerobic biological technology has poor effect on treating the azo dyes. The anaerobic treatment of azo dyes mainly comprises direct biological reduction and indirect biological reduction, wherein the direct biological reduction is to reduce the azo dyes by utilizing nonspecific azoreductase produced by bacterial secretion, and the azoreductase only has NADH, NADPH and FADH2And the reducing molecules play a catalytic role in the presence of reducing agents, and the reducing molecules serve as electron donors and participate in the breakage of azo bonds. Indirect biological is also the principle of effecting the reduction of azo dyes mediated by redox mediators, microorganisms producing electrons by oxidation of an electron donor, redox mediators receiving the electrons and being reduced, and subsequently reduced by the redox mediators in their reduced state reducing the azo dyes and decolorizing them. When the azo bond (-N ═ N-) undergoes reductive cleavage, aromatic amines with carcinogenic and mutagenic properties are produced. Aromatic compounds have large negative resonance energies, resulting in thermodynamic stability and because of the recalcitrant tendency of aromatic amines to anaerobic degradation, the treatment of azo dyes is usually combined with a two-step treatment of anaerobic decolorization and aerobic mineralization. The aromatic amines can be mineralized by hydroxylation and ring cleavage of aromatic compounds by aerobic treatment with non-specific enzymes.
The ECMO key technology widely reported in the period of new coronary epidemic rescues lives of a plurality of critical patients, and the principle is that extracorporeal membrane lung oxygenation is carried out on blood, carbon dioxide is discharged, and finally the blood flows back into the body. In addition, the anaerobic digestion treatment of the solid waste generally adopts low substrate concentration to carry out liquid fermentation, so that a large amount of biogas slurry generated from the liquid fermentation causes serious secondary environmental pollution, and further treatment is needed.
Disclosure of Invention
[ problem ] to provide a method for producing a semiconductor device
The decoloring reduction of the azo dye needs to add an additional carbon source, and the innocent treatment needs a complicated sequential process of anaerobic decoloring and aerobic mineralization.
[ technical solution ] A
Aiming at the problems, the invention provides a method for synchronously realizing the mineralization of azo dyes and the methanation of straws by an ECMO-like device, which takes the straws loaded with the azo dyes as a digestion substrate, simultaneously carries out the decolorization, the mineralization and the methanation of the straws synchronously under the micro-aerobic condition in a fermentation tank by aeration and decarbonization of biogas slurry external circulation, and simultaneously realizes the purification of methane.
Specifically, the technical scheme of the invention is as follows: a method for synchronously realizing azodye mineralization and straw methanation by an ECMO-like device comprises a fermentation reaction tank, a solid-liquid separation device, an aeration reactor, an aeration pump, a biogas slurry reflux device, a spraying device and a gas collection device, wherein the spraying device and the solid-liquid separation device are respectively positioned at the top and the bottom of the fermentation reaction tank, one end of the aeration reactor is connected with the bottom of the fermentation reaction tank through a pipeline, the other end of the aeration reactor is connected with the aeration pump, the biogas slurry reflux device is positioned outside the fermentation reaction tank, one end of the biogas slurry reflux device is connected with the aeration reactor, the other end of the biogas slurry reflux device is communicated with the spraying device, and the gas collection device is positioned at the top of the fermentation reaction tank;
the method is carried out in the ECMO-like device, and specifically comprises the following steps:
(1) mixing the agricultural wastes loaded with the azo dyes and anaerobic sludge, and placing the mixture into a fermentation reaction tank for anaerobic fermentation, wherein the content of the azo dyes in the system is 0-800 mg/L;
(2) and (2) separating the biogas slurry in the fermentation in the step (1) by using a solid-liquid separation device, allowing the separated biogas slurry to enter an aeration reactor, continuously aerating the interior of the aeration reactor by using an aeration pump, and spraying the aerated biogas slurry into a fermentation tank by using a spraying device after the biogas slurry reflows to the spraying device by using a biogas slurry reflowing device to perform micro-aerobic fermentation.
In one embodiment of the present invention, the fermentation tank in step (1) is purged with nitrogen to form an anaerobic environment before the reaction is started.
In one embodiment of the present invention, the azo dye used in step (1) is an anionic azo dye, preferably methyl orange; the agricultural waste is preferably straw, and can be corn straw, rice straw and the like.
In one embodiment of the invention, no additional carbon source is added in the step (1), and the solid content of the anaerobic fermentation liquid in the fermentation reaction tank is 8-15%.
In one embodiment of the present invention, the anaerobic nutrient solution is added to the anaerobic fermentation broth in step (1), and the anaerobic nutrient solution specifically comprises: solution A: NH (NH)4Cl100 g/L，NaCl10 g/L，CaCl2·2H2O5 g/L，MgCl2·6H2O10 g/L; and B, liquid B: k2HPO4·3H2O200 g/L; and C, liquid C: CoCl2·6H2O0.05 g/L，H3BO30.05 g/L，NiCl2·6H2O 0.092g/L，ZnCl20.05g/L, disodium ethylene diamine tetraacetate 0.5g/L, CuCl2·2H20.038g/L of O, 1mL/L of concentrated hydrochloric acid and MnCl2·4H2O 0.05g/L，Na2SeO3·5H2O 0.1g/L，(NH4)6Mo7O24·4H2O 0.05g/L，AlCl30.05 g/L; and (3) liquid D: 2mg/L of biotin, 2mg/L of folic acid, 10mg/L of pyridoxine acid, 5mg/L of riboflavin, 5mg/L of thiamine hydrochloride, 0.1mg/L of cyanocobalamine, 5mg/L of nicotinic acid, 5mg/L of p-aminobenzoic acid and 5mg/L of lipoic acid; wherein, 10mL of A solution, 2mL of B solution, 1mL of C solution, 1mL of D solution, and 2.6g NaHCO are added into 1L of nutrient solution3。
In one embodiment of the invention, the micro-aerobic fermentation in step (2) in the presence of azo dye is carried out at a temperature of 30-55 deg.C for a period of 35-50 days, and preferably at a pH of 6.5-8.
In one embodiment of the invention, the anaerobic sludge is from anaerobic granular sludge of a municipal sewage treatment plant.
In one embodiment of the present invention, it is preferred that the total solids content of the anaerobic sludge is 8.03% and the volatile solids are 81.76%.
In one embodiment of the invention, the mass ratio of anaerobic sludge to azo dye-loaded agricultural waste is 1:2 to 1: 4.
In one embodiment of the invention, the flow rate of the aeration pump is 10-60 mL/(L)RDay), i.e. an oxygen supply of 10-60mL per day per unit reaction volume.
The invention also provides an ECMO-like device for synchronously realizing azodye mineralization and straw methanation, which comprises a fermentation reaction tank, a solid-liquid separation device, an aeration reactor, an aeration pump, a biogas slurry reflux device, a spraying device and a gas collection device, wherein the spraying device and the solid-liquid separation device are respectively positioned at the top and the bottom of the fermentation reaction tank, one end of the aeration reactor is connected with the bottom of the fermentation reaction tank through a pipeline, the other end of the aeration reactor is connected with the aeration pump, the biogas slurry reflux device is positioned outside the fermentation reaction tank, one end of the biogas slurry reflux device is connected with the aeration reactor, the other end of the biogas slurry reflux device is communicated with the spraying device, and the gas collection device is positioned at the top of the fermentation reaction tank.
The invention also provides application of the method in azo dye wastewater treatment.
The invention also provides the application of the method in the agricultural field.
The invention has the advantages that:
the invention builds an ECMO-like micro-aerobic digestion device by relying on the ECMO principle, carries out anaerobic digestion on straws loaded with azo dyes, avoids adding an external carbon source by taking the straws as an electron donor for reducing and decoloring the azo dyes, realizes synchronous dye decoloring and straw methanation, and removes carbon dioxide by a method of leading biogas slurry out, aerating and then refluxing, on one hand, the purity of methane is improved, on the other hand, trace dissolved oxygen in the biogas slurry can build a micro-aerobic environment in an anaerobic system in a fermentation tank, further synchronously realizes the mineralization of aromatic amine as an intermediate product while not influencing the decoloring of the azo dyes and the yield of methane, greatly shortens the treatment process and simultaneously realizes the recycling of resources. The method has the advantages of simple operation, low economic cost and mild reaction condition;
(1) according to the invention, through the fermentation of the straw loaded with the azo dye, the problems of incomplete harmless treatment and resource waste in the process of adsorbing the azo dye are avoided;
(2) according to the invention, the straw is used for providing an electron donor for the anaerobic reduction of the azo dye, no additional carbon source is required to be added, and the operation cost is saved;
(3) the invention has the advantages of high methane yield and short digestion period, the period is shortened by 12.5-25%, and the methane yield is improved and the digestion period is shortened by removing carbon dioxide in the methane through the external circulation microaerobic of the biogas slurry;
(4) the invention can realize the recycling of fermentation byproducts and the mineralization of intermediate aromatic amine synergistically, and has obvious environmental and economic benefits.
Drawings
FIG. 1 is a diagram of an ECMO-like external circulation microaerobic digestion apparatus in example 1-4, wherein 1 is a fermentation reaction tank, 2 is a solid-liquid separation device, 3 is an aeration reactor, 4 is an aeration pump, 5 is a biogas slurry reflux device, 6 is a spraying device, and 7 is a gas collection device.
Figure 2 the methane content varies in examples 2-4.
Figure 3 cumulative methane production changes in examples 2-4.
FIG. 4 variation of methyl orange concentration in examples 3-4.
FIG. 5 aromatic amine 4-ABS concentration changes in examples 3-4.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The anaerobic sludge is anaerobic granular sludge from a stannless municipal sewage treatment plant, the total solid content of the anaerobic granular sludge is 8.03 percent, and the volatile solid content is 81.76 percent.
The detection method of the aromatic amine 4-ABS comprises the following steps: a high performance liquid chromatograph using a photoelectric two-stage rod detector (PAD) was used, about 2ml of the sample was immediately centrifuged at 4 ℃ and 8000rpm for 10 minutes, and the supernatant was quickly passed through a 0.45 water filter and subjected to HPLC measurement to measure the wavelength: 254nm
Mobile phase: acetic acid and ammonium acetate buffer/methanol 75: 25; preparing 0.1% (v/v) acetic acid and 0.1% (w/v) ammonium acetate solution; flow rate: 0.8mL/min column: SunAire C18 reverse phase column (4.6mm 150mm) column temperature: sample introduction at 25 ℃: 20 microliter.
Example 1
As shown in fig. 1, the ECMO-like biogas slurry external circulation microaerobic device of the present invention includes a fermentation reaction tank 1, a solid-liquid separation device 2, an aeration reactor 3, an aeration pump 4, a biogas slurry reflux device 5, a spray device 6, and a gas collection device 7. Wherein, spray set 6 and solid-liquid separation equipment 2 are located the top and the bottom of fermentation retort respectively, and aeration reactor 3 one end passes through the pipeline with fermentation retort and links to each other, and the other end links to each other with controllable flow's aeration pump 4, and natural pond liquid reflux unit 5 is located fermentation retort 1's outside and one end links to each other with aeration reactor, and the other end communicates with spray set. A gas collection device 7 is placed at the top of the reactor for collecting biogas and for determining the gas composition.
Specifically, the operation principle of the ECMO-like device of the present invention is as follows: mixing the agricultural wastes loaded with the azo dyes with anaerobic sludge, fermenting in a fermentation reaction tank, filtering biogas slurry in the fermentation process through a solid-liquid separation device, then feeding the biogas slurry into an aeration reactor, carrying out aeration decarburization on the biogas slurry in the aeration reactor under the forced ventilation of an aeration pump, introducing oxygen and removing carbon dioxide. The aerated biogas slurry enters the spraying device at the upper part through the biogas slurry reflux device and is uniformly sprayed into the fermentation reaction tank through the spraying device to complete reflux, trace dissolved oxygen in the biogas slurry can establish a microaerobic environment in an anaerobic system in the fermentation tank, and microaerobic fermentation is carried out in the fermentation reaction tank.
Example 2
(1) According to a solid content of 8%, the ratio of inoculum to substrate is 1: 3, uniformly mixing the straws and the anaerobic sludge, adding the mixture into a fermentation reaction tank, adding an anaerobic nutrient solution, blowing by nitrogen to form an anaerobic environment in the system, and carrying out anaerobic digestion at 37 ℃ for 40 days, wherein an aeration pump is always kept closed and micro-aerobic conditions are not given. The biogas slurry in the fermentation process is filtered by a solid-liquid separation device, directly enters a spraying device at the upper part through a biogas slurry reflux device, and is uniformly sprayed into a fermentation reaction tank through the spraying device to complete reflux;
(2) biogas generated during anaerobic digestion is collected at a gas collection device and the methane concentration is determined.
Example 3
(1) According to a solid content of 8%, the ratio of inoculum to substrate is 1: 3, uniformly mixing the straw loaded with methyl orange with anaerobic sludge, adding the mixture into a fermentation reaction tank, adding an anaerobic nutrient solution, blowing by nitrogen to form an anaerobic environment in the system, wherein the content of the azo dye is 628.61mg/L, carrying out anaerobic digestion at 37 ℃ for 40 days, and keeping an aeration pump closed all the time without giving microaerobic conditions. The biogas slurry in the fermentation process is filtered by a solid-liquid separation device, directly enters a spraying device at the upper part through a biogas slurry reflux device, and is uniformly sprayed into a fermentation reaction tank through the spraying device to complete reflux;
(2) collecting biogas generated in the anaerobic digestion process at a gas collecting device, and measuring the concentration of methane;
(3) collecting biogas slurry in the digestion process, and measuring the concentrations of methyl orange and aromatic amine after centrifugal filtration.
Example 4
(1) According to a solid content of 8%, the ratio of inoculum to substrate is 1: 3, uniformly mixing the straw loaded with methyl orange with anaerobic sludge, adding the mixture into a fermentation reaction tank, adding anaerobic nutrient solution, blowing by nitrogen to form an anaerobic environment in the system, wherein the content of azo dye is 628.61mg/L, carrying out anaerobic digestion at 37 ℃ for 40 days, wherein the flow rate of biogas slurry in an aeration reactor in an aeration pump is 25.81 mL/(L)RDay) aeration decarburization with forced ventilation, oxygen being introduced. The aerated biogas slurry enters a spraying device at the upper part through a biogas slurry reflux device and is uniformly sprayed into the fermentation reaction tank through the spraying device to complete reflux;
(2) collecting biogas generated in the anaerobic digestion process at a gas collecting device, and measuring the concentration of methane;
(3) collecting biogas slurry in the digestion process, and measuring the concentrations of methyl orange and aromatic amine after centrifugal filtration.
Fig. 2 and 3 respectively depict the variation of the accumulated methane yield and the methane concentration of each group in examples 2-4, and fig. 4 and 5 respectively depict the variation of the methyl orange concentration and the aromatic amine concentration of a methyl orange-loaded straw non-microaerobic group (example 3) and a methyl orange-loaded straw microaerobic group (example 4).
As can be seen from the above examples, anaerobic digestion of the straw loaded with azo dyes to produce methane and use of the straw as an electron donor for decolorization and reduction of the azo dyes are feasible, and no inhibition phenomenon occurs to the anaerobic digestion process. As can be seen from fig. 2 and fig. 3, the treatment of the azo dye-loaded straw by the ECMO-like biogas slurry external circulation microaerobic device not only increases the cumulative methane yield by 21.68% (fig. 3), but also significantly increases the methane concentration to 60-70% in the previous period (fig. 2), which is significantly higher than that of the original straw group (example 2) and the methyl orange-loaded straw microaerobic group (example 3), and significantly shortens the anaerobic digestion period.
As can be seen from fig. 4 and 5, the methyl orange concentration of the microaerobic group (example 4) can also achieve complete decolorization in a shorter time than the azo dye-loaded straw group (example 3) without biogas slurry external circulation, which indicates that in the present technology, the time required by the reduction and the decoloration of the azo dye is short, and the micro aerobic condition does not influence the decoloration process of the methyl orange, while the concentration of the aromatic amine as the intermediate product is not obviously degraded in the non-microaerobic group (example 3), which indicates that the aromatic amine is intractable under anaerobic conditions, the azo dye-loaded straw group treated by the ECMO-like biogas slurry extrinsic cycle microaerobic device (example 4) realizes the mineralization and degradation of the aromatic amine, the concentration of the aromatic amine is obviously reduced, at 35d the aromatic amine concentration was reduced to 14mg/L, which was 92% lower relative to the aromatic amine concentration of example 3.
According to the example and the result, the ECMO-like micro oxygen consumption external circulation device has excellent treatment performance on the straws loaded with the azo dyes, realizes harmless treatment of the azo dyes, reduces the azo dyes by taking the straws as an electron donor, saves economic cost, realizes resource utilization and biogas purification of agricultural wastes, obviously shortens the period of anaerobic digestion, obviously improves the yield of accumulated methane, simultaneously realizes micro aerobic fermentation without influencing the decolorization of methyl oranges, and simultaneously realizes the mineralization process of aromatic amine, thereby achieving three purposes at a time. Therefore, the method has higher environmental, economic and social benefits.
Example 5
(1) According to a solid content of 8%, the ratio of inoculum to substrate is 1: 3, uniformly mixing the straw loaded with methyl orange with anaerobic sludge, adding the mixture into a fermentation reaction tank, adding anaerobic nutrient solution, blowing by nitrogen to form an anaerobic environment in the system, wherein the content of azo dye is 628.61mg/L, carrying out anaerobic digestion at 37 ℃ for 40 days, wherein the flow rate of biogas slurry in the aeration reactor in an aeration pump is 10 mL/(L)RDay) aeration decarburization with forced ventilation, oxygen being introduced. The aerated biogas slurry enters a spraying device at the upper part through a biogas slurry reflux device and is uniformly sprayed into the fermentation reaction tank through the spraying device to complete reflux;
(2) collecting biogas generated in the anaerobic digestion process at a gas collecting device, and measuring the concentration of methane;
(3) collecting biogas slurry in the digestion process, and measuring the concentrations of methyl orange and aromatic amine after centrifugal filtration.
Example 6
(1) According to a solid content of 8%, the ratio of inoculum to substrate is 1: 3, uniformly mixing the straw loaded with methyl orange with anaerobic sludge, adding the mixture into a fermentation reaction tank, adding anaerobic nutrient solution, blowing by nitrogen to form an anaerobic environment in the system, wherein the content of azo dye is 628.61mg/L, carrying out anaerobic digestion at 37 ℃ for 40 days, wherein the flow rate of biogas slurry in the aeration reactor in an aeration pump is 60 mL/(L)RDay) aeration decarburization with forced ventilation, oxygen being introduced. The aerated biogas slurry enters a spraying device at the upper part through a biogas slurry reflux device and is uniformly sprayed into the fermentation reaction tank through the spraying device to complete reflux;
(2) collecting biogas generated in the anaerobic digestion process at a gas collecting device, and measuring the concentration of methane;
(3) collecting biogas slurry in the digestion process, and measuring the concentrations of methyl orange and aromatic amine after centrifugal filtration.
The cumulative methane yields obtained in examples 5 and 6 were 87mL/g VS and 96mL/g VS, respectively, and the degradation rates of aromatic amines were 12% and 95%, respectively, so that it was found that at a lower aeration rate, the increase in oxygen level in the system was insignificant, the interior was closer to the anaerobic environment, and the cumulative methane yield was not significantly improved, whereas when the aeration flow rate was 60 mL/(L)RDay), since the amount of dissolved oxygen in the liquid is limited, the cumulative methane production obtained in example 4 is not significantly different since the higher aeration rate does not introduce more oxygen into the reactor, and the energy consumption is considered when the aeration pump flow rate is 25.81 mL/(L)RDay) is the optimum aeration rate. In addition, methyl orange was significantly discolored in the two groups, but the degradation rate of aromatic amine in example 5 was significantly inferior to that in example 6. The oxygen content in the fermentation reaction tank is mainly determined by the oxygen content in the backflow biogas slurry, so that the micro-aerobic environment in the reactor is not influenced by the change of external environmental conditions, and the fermentation reaction tank has excellent stability.
Example 7
(1) According to a solid content of 15%, the ratio of inoculum to substrate is 1:4, uniformly mixing the straw loaded with methyl orange with anaerobic sludge, adding the mixture into a fermentation reaction tank, adding an anaerobic nutrient solution, blowing by nitrogen to form an anaerobic environment in the system, wherein the content of azo dye is 200mg/L, carrying out anaerobic digestion at 50 ℃ for 40 days, and the flow of biogas slurry in an aeration reactor in an aeration pump is 30 mL/(L)RDay) aeration decarburization with forced ventilation, oxygen being introduced. The aerated biogas slurry enters the spraying device at the upper part through the biogas slurry reflux device and is uniformly sprayed into the fermentation reaction tank through the spraying device to complete reflux.
Research finds that the improvement of the yield and the purity of the methane can be realized, and the methyl orange decoloring and aromatic amine mineralization processes are realized at the same time.
Comparative example 1
(1) According to a solid content of 8%, the ratio of inoculum to substrate is 1: 3, uniformly mixing the straw loaded with methyl orange with anaerobic sludge, adding the mixture into a fermentation reaction tank, adding an anaerobic nutrient solution, blowing by nitrogen to form an anaerobic environment in the system, wherein the content of the azo dye is 628.61mg/L, carrying out anaerobic digestion at 37 ℃ for 40 days, and directly carrying out aeration in the digestion reaction tank to introduce oxygen under the forced ventilation of an aeration pump with the flow rate of 25.81 mL/d.
(2) Collecting biogas generated in the anaerobic digestion process at a gas collecting device, and measuring the concentration of methane;
(3) collecting biogas slurry in the digestion process, and measuring the concentrations of methyl orange and aromatic amine after centrifugal filtration.
The cumulative methane yield obtained by the comparative example 1 is 82mL/g VS, and the methyl orange concentration is 44.76mg/L at 144h, so that the conventional microaerobic digestion straw can improve the methane yield and cannot be affected by the toxicity of azo dyes, but the decolorization rate of the methyl orange is far inferior to that of an external circulation microaerobic device or anaerobic digestion, because the methyl orange is uniformly distributed in a fermentation tank and the oxygen is concentrated at a few points and supplied to the inside of the reactor, so that the oxygen is not uniform, and the content difference of the oxygen in the inside of the reactor is large. In example 4, the methane yield is improved and the azo dyes are completely decolorized and mineralized by introducing and spraying the biogas slurry dissolved oxygen into the reactor.
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 (10)

1. The method for synchronously realizing azodye mineralization and straw methanation by using the ECMO-like device is characterized in that the ECMO-like device comprises a fermentation reaction tank, a solid-liquid separation device, an aeration reactor, an aeration pump, a biogas slurry reflux device, a spraying device and a gas collection device, wherein the spraying device and the solid-liquid separation device are respectively positioned at the top and the bottom of the fermentation reaction tank, one end of the aeration reactor is connected with the bottom of the fermentation reaction tank through a pipeline, the other end of the aeration reactor is connected with the aeration pump, the biogas slurry reflux device is positioned outside the fermentation reaction tank, one end of the biogas slurry reflux device is connected with the aeration reactor, the other end of the biogas slurry reflux device is communicated with the spraying device, and the gas collection device is positioned at the top of the fermentation reaction tank;
the method is carried out in the ECMO-like device, and specifically comprises the following steps:
(1) mixing the agricultural wastes loaded with the azo dyes and anaerobic sludge, and placing the mixture into a fermentation reaction tank for anaerobic fermentation, wherein the content of the azo dyes in the system is 0-800 mg/L;
(2) and (2) separating the biogas slurry in the fermentation in the step (1) by using a solid-liquid separation device, allowing the separated biogas slurry to enter an aeration reactor, continuously aerating the interior of the aeration reactor by using an aeration pump, and spraying the aerated biogas slurry into a fermentation tank by using a spraying device after the biogas slurry reflows to the spraying device by using a biogas slurry reflowing device to perform micro-aerobic fermentation.
2. The process according to claim 1, wherein the azo dye used in step (1) is an anionic azo dye; the agricultural waste is straw.
3. The method according to claim 1 or 2, wherein the solid content of the anaerobic fermentation liquid in the fermentation reaction tank in the step (1) is 8-15%.
4. A process according to any one of claims 1 to 3, wherein the microaerobic fermentation in step (2) in the presence of the azo dye is carried out at a temperature of 30 to 55 ℃ for a period of 35 to 50 days, and preferably at a pH of 6.5 to 8.
5. The method according to any one of claims 1 to 4, wherein the anaerobic sludge is anaerobic granular sludge from a municipal sewage treatment plant.
6. The method according to claim 5, wherein the mass ratio of anaerobic sludge to azo dye-loaded agricultural waste is 1:2 to 1: 4.
7. A method according to any one of claims 1 to 6, wherein the flow rate of the aeration pump is 10-60 mL/(L)R·day)。
8. The utility model provides a class ECMO type device for realizing azoic dye mineralize mineralization and straw methanation in step, a serial communication port, class ECMO type device includes fermentation reaction jar, solid-liquid separation equipment, aeration reactor, aeration pump, natural pond liquid reflux unit, spray set and gas collection device, wherein, spray set and solid-liquid separation equipment are located fermentation reaction jar's top and bottom respectively, and aeration reactor one end links to each other through the pipeline with fermentation reaction jar bottom, and the other end links to each other with the aeration pump, and natural pond liquid reflux unit is located fermentation reaction jar's outside, and its one end links to each other with aeration reactor, and the other end communicates with spray set, and gas collection device is located fermentation reaction jar's top.
9. Use of the method of any one of claims 1 to 7 or the ECMO-like device of claim 8 in azo dye wastewater treatment.
10. Use of the method of any one of claims 1 to 7 or the ECMO-like device of claim 8 in the agricultural field.
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