CN113800722A - Method for co-producing methane-bio-oil by coupling domestic sewage anaerobic digestion with microalgae culture - Google Patents

Method for co-producing methane-bio-oil by coupling domestic sewage anaerobic digestion with microalgae culture Download PDF

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CN113800722A
CN113800722A CN202111176188.1A CN202111176188A CN113800722A CN 113800722 A CN113800722 A CN 113800722A CN 202111176188 A CN202111176188 A CN 202111176188A CN 113800722 A CN113800722 A CN 113800722A
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oil
domestic sewage
microalgae
bio
biogas slurry
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张万里
孔天岐
邢万丽
李润东
杨天华
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Shenyang Aerospace University
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Shenyang Aerospace University
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    • C—CHEMISTRY; METALLURGY
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    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
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    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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    • C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
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    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
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    • C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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Abstract

A kind ofThe method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae culture comprises the following steps; (1) removing suspended components from domestic sewage; (2) carrying out anaerobic fermentation reaction; (3) purifying, desulfurizing and drying the biogas; one part is used for combustion power generation, and the other part is separated to obtain CO2And biomethane; combustion of CO produced by electricity generation2Entering an oil-rich microalgae culture system; the combustion power generation provides electric energy for the light source; (4) adding water into biogas slurry for dilution, sterilizing, aerating, and adjusting pH value; (5) culturing the pretreated biogas slurry oil-rich microalgae; (6) the oil-rich microalgae is squeezed to obtain bio-oil, and the residual algae residue is returned to the anaerobic fermentation reaction. The method of the invention is self-sufficient in energy, not only realizes the treatment of domestic sewage, but also produces high-quality biomethane and produces bio-oil through a microalgae culture system.

Description

Method for co-producing methane-bio-oil by coupling domestic sewage anaerobic digestion with microalgae culture
Technical Field
The invention belongs to the technical field of sewage treatment and resource utilization, and particularly relates to a method for co-producing methane-bio oil by coupling anaerobic digestion of domestic sewage with microalgae culture.
Background
The rapid development of urbanization and the wide use of organic fertilizers in modern agriculture generate a large amount of domestic sewage containing high content of nitrogen, phosphorus and organic matters, and the direct discharge causes serious water pollution and brings great threat to water for cities and agriculture. Meanwhile, the biological organic fertilizer is also an excellent substrate for anaerobic digestion, and the anaerobic digestion can not only bring economic benefits, but also effectively solve the problem of domestic sewage treatment and really realize harmless treatment and recycling.
The biogas slurry is liquid residue of anaerobic digestion, has complex components, contains nutrient substances such as ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and a small amount of organic nitrogen, and microelements and vitamins such as Ca, Mg, Fe, Zn required by crops, plays an important role in regulating the growth and development of the crops, and simultaneously can breed a large amount of microorganisms and other insects and other algae.
Disclosure of Invention
The invention aims to provide a method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion with microalgae cultivation.
The method of the present invention comprises the following steps;
(1) pretreating domestic sewage to remove suspended components to prepare pretreated sewage;
(2) introducing the pretreated sewage into an anaerobic fermentation reactor, and performing anaerobic fermentation reaction to generate biogas and biogas slurry;
(3) introducing the biogas into a desulfurizing tower for purification and desulfurization, and then drying to form purified biogas; purifying one part of the marsh gas for combustion power generation, introducing the other part into a separation system, and separating CO2And biomethane; CO 22The fertilizer is used as an air fertilizer to enter an oil-rich microalgae culture system; combustion of CO produced by electricity generation2The fertilizer is used as an air fertilizer to enter an oil-rich microalgae culture system; the combustion power generation provides electric energy for the light source, and the oil-rich microalgae culture system is irradiated by the light source;
(4) adding water into the biogas slurry for dilution to form diluted biogas slurry; adding strong chlorine essence into the diluted biogas slurry for sterilization treatment, then carrying out aeration treatment by adopting an aeration system through air, and then adding a sodium carbonate solution to adjust the pH value to 7.0-7.5 to prepare pretreated biogas slurry;
(5) sending the pretreated biogas slurry into an oil-rich microalgae culture system, and carrying out oil-rich microalgae culture under the conditions of an air fertilizer and a light source to generate oil-rich microalgae;
(6) and squeezing the oil-rich microalgae to obtain bio-oil, returning the residual algae residues to the anaerobic fermentation reactor, and carrying out anaerobic fermentation reaction with the pretreated sewage.
In the step (1), the pretreatment means that the domestic sewage passes through the grating, then flows through the grit chamber and the sedimentation tank, and is discharged, so that suspended matters in the domestic sewage are removed, and the pretreated sewage is formed.
In the step (2), the temperature of the anaerobic fermentation reaction is 30-40 ℃, and the time is at least 8 hours.
In the step (2), the organic matter content in the biogas slurry is lower than that of the pretreated sewage by more than 45%.
In the step (3), the step of purifying and desulfurizing is to remove H in the biogas2And S is removed, and the drying is to remove the water vapor in the methane.
In the step (3), the main functional component of the separation system is the PDMS/PEI composite membrane.
In the step (3), CH is contained in the biomethane4The volume concentration of (A) is more than or equal to 85 percent.
In the step (3), the waste heat generated by combustion power generation is used for heating and heat preservation of anaerobic fermentation reaction.
In the step (3), the purified biogas introduced into the separation system accounts for 55-65% of the total purified biogas.
In the step (4), the time for the sterilization treatment is at least 12 hours.
In the step (4), the time of the aeration treatment is at least 12 h.
In the step (4), the concentration of the sodium carbonate solution is 1-3 mol/L.
In the step (4), the concentration of the strong chlorine essence in the diluted biogas slurry is 12-18 mg/L.
In the step (4), the adding amount of water is 4-10 times of the mass of the biogas slurry.
In the step (5), the oil-rich microalgae is cultured for at least 24 hours.
In the step (6), a screw press is used to squeeze out the bio-oil.
In the step (6), the residual oil on the surface of the algae residue is recovered by a solvent extraction method, wherein the solvent is chloroform, and the method is to wash the algae residue with chloroform to remove the oil.
The microalgae for purifying the biogas slurry is mainly used for purifying TN (mainly NH)4+-N), TP, COD, antibiotic removal; microalgae can use photoheterotrophy and chemoheterotrophy to convert organic pollutants in biogas slurry into carbon sources and energy for growth, the microalgae can absorb various inorganic nitrogen to convert into genetic and metabolic substances required by the microalgae because of the growth requirement of the microalgae, the microalgae can convert phosphorus salts in the wastewater into nucleic acids, proteins, carbohydrates, lipids and the like which are necessary for the microalgae, or the pH of the biogas slurry is changed to increase dissolved oxygen so as to precipitate phosphate; the method for removing the antibiotics in the biogas slurry by the microalgae is implemented by two ways of adsorption and biodegradation, the adsorption efficiency is generally not more than 10%, heterotrophic metabolism is the main removal way, and the removal efficiency of the antibiotics in the biogas slurry is 50-90%.
Bio-oil is a renewable and environmentally friendly fuel, and the production raw material is from the first generation of liquid bio-fuel from edible raw materials such as corn, soybean, sugarcane, etc., and the second generation of bio-fuel from non-edible raw materials such as jatropha, miscanthus and switchgrass, to the present microalgae. Microalgae, which has been identified as a raw material for industrial scale production of bio-oil, is abundant in species, fast in growth and reproduction, and higher in photosynthetic efficiency compared with other energy crops, and will be the most suitable fossil fuel substitute in the future.
The anaerobic fermentation reaction process of the method has the functions of organic matter anaerobic fermentation, methane in-situ purification and synthetic gas anaerobic biological methanation, the anaerobic-pyrolysis coupling technology effectively improves the methane yield and concentration on the whole, obtains high value-added methane products, biological oil and biological carbon, and realizes zero waste discharge of the system; the whole system is self-sufficient in energy, not only realizes the treatment problem of domestic sewage, but also generates high-quality biomethane and biological oil through a microalgae culture system.
Drawings
FIG. 1 is a schematic flow chart of a method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae cultivation.
Detailed Description
The model of the anaerobic fermentation reactor in the embodiment of the invention is UASB.
In the embodiment of the invention, when the anaerobic fermentation reaction is carried out, the organic load is 3.5-4.5 gVS/L.d.
In the embodiment of the invention, the mass content of water in the biogas slurry is 30-40%.
The desulfurizing tower in the embodiment of the invention is a spray-type desulfurizing tower.
The separation system in the embodiment of the invention separates CO by PDMS/PEI composite membrane2And methane.
The system adopted by the combustion power generation in the embodiment of the invention comprises a methane internal combustion engine, an alternating-current generator and a waste heat recovery device.
The oil-rich microalgae culture system in the embodiment of the invention adopts an open single-layer runway type photobioreactor, wherein the stirring is mechanical stirring.
In the embodiment of the invention, CO in the biomethane2The volume concentration of the (C) is less than or equal to 2 percent.
In the embodiment of the invention, the bio-oil contains a large amount of chemical substances with high added values, including levoglucosan, levoglucosenone, hydroxyacetaldehyde, hydroxyacetone, hydroxymethylfurfural, maltol, vanillin, furfural and oligosaccharide.
In the embodiment of the invention, the heat value of the alkyl ester group of the long-chain fatty acid of the biological oil is 40-50 MJ/kg.
When the aeration is carried out in the embodiment of the invention, the introduced air pressure is 0.1-0.5 MPa, and the volume ratio of the air introduced by the air flow per minute to the diluted biogas slurry is 0.3-0.6.
The biogas yield in the embodiment of the invention is 75-85%.
Example 1
The flow is shown in figure 1;
pretreating domestic sewage to remove suspended components to prepare pretreated sewage; the pretreatment means that the domestic sewage passes through a grid, then flows through a grit chamber and a sedimentation tank, and is discharged, so that suspended matters in the domestic sewage are removed;
introducing the pretreated sewage into an anaerobic fermentation reactor, and performing anaerobic fermentation reaction to generate biogas and biogas slurry; the temperature of the anaerobic fermentation reaction is 40 ℃, and the time is 8 hours; the organic matter content in the biogas slurry is lower than that of the pretreated sewage by more than 45 percent;
introducing the biogas into a desulfurizing tower for purification and desulfurization, and then drying to form purified biogas; the purification and desulfurization are to remove H in the methane2S, removing, namely removing water vapor in the biogas; purifying one part of the marsh gas for combustion power generation, introducing the other part into a separation system, and separating CO2And biomethane; CO 22The fertilizer is used as an air fertilizer to enter an oil-rich microalgae culture system; combustion of CO produced by electricity generation2The fertilizer is used as an air fertilizer to enter an oil-rich microalgae culture system; the combustion power generation provides electric energy for the light source, and the oil-rich microalgae culture system is irradiated by the light source; CH in biomethane4The volume concentration of (d) is 87%; heating and heat preservation of anaerobic fermentation reaction by using waste heat generated by combustion; by passing through a separationThe purified marsh gas of the system accounts for 60 percent of the total purified marsh gas;
adding water into the biogas slurry for diluting, wherein the adding amount of the water is 8 times of the mass of the biogas slurry, so as to form diluted biogas slurry; adding strong chlorine essence into the diluted biogas slurry, stirring and sterilizing, wherein the concentration of the strong chlorine essence in the diluted biogas slurry is 15mg/L, and the time is 14 h; then an aeration system is adopted to carry out aeration treatment by air for 15 h; adding sodium carbonate solution to adjust the pH value to 7.5 to prepare the pretreated biogas slurry; the concentration of the sodium carbonate solution is 2 mol/L;
sending the pretreated biogas slurry into an oil-rich microalgae culture system, and carrying out oil-rich microalgae culture under the conditions of an air fertilizer and a light source for 36 hours to generate oil-rich microalgae;
and (3) squeezing the oil-rich microalgae oil out of the bio-oil by using a screw press, returning the residual algae residues to the anaerobic fermentation reactor, and carrying out anaerobic fermentation reaction with the pretreated sewage.
Example 2
The method is the same as example 1, except that:
(1) the temperature of the oxygen fermentation reaction is 35 ℃ and the time is 10 hours;
(2) CH in biomethane486% by volume; purified biogas introduced into the separation system accounts for 55% of the total purified biogas;
(3) the adding amount of water is 5 times of the mass of the biogas slurry; the concentration of the strong chlorine essence in the diluted biogas slurry is 12mg/L, and the sterilization treatment time is 12 h; the aeration treatment time is 18 h; adjusting the pH value to 7.2; the concentration of the sodium carbonate solution is 1 mol/L;
(4) the culture time of the oil-rich microalgae is 30 hours.
Example 3
The method is the same as example 1, except that:
(1) the temperature of the oxygen fermentation reaction is 30 ℃, and the time is 12 hours;
(2) CH in biomethane488% by volume; purified biogas introduced into the separation system accounts for 65% of the total purified biogas;
(3) the adding amount of water is 10 times of the mass of the biogas slurry; the concentration of the strong chlorine essence in the diluted biogas slurry is 18mg/L, and the sterilization treatment time is 16 h; the aeration treatment time is 17 h; adjusting the pH value to 7.0; the concentration of the sodium carbonate solution is 3 mol/L;
(4) the culture time of the oil-rich microalgae is 24 hours.

Claims (9)

1. A method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae culture is characterized by comprising the following steps;
(1) pretreating domestic sewage to remove suspended components to prepare pretreated sewage;
(2) introducing the pretreated sewage into an anaerobic fermentation reactor, and performing anaerobic fermentation reaction to generate biogas and biogas slurry;
(3) introducing the biogas into a desulfurizing tower for purification and desulfurization, and then drying to form purified biogas; purifying one part of the marsh gas for combustion power generation, introducing the other part into a separation system, and separating CO2And biomethane; CO 22The fertilizer is used as an air fertilizer to enter an oil-rich microalgae culture system; combustion of CO produced by electricity generation2The fertilizer is used as an air fertilizer to enter an oil-rich microalgae culture system; the combustion power generation provides electric energy for the light source, and the oil-rich microalgae culture system is irradiated by the light source;
(4) adding water into the biogas slurry for dilution to form diluted biogas slurry; adding strong chlorine essence into the diluted biogas slurry for sterilization treatment, then carrying out aeration treatment by adopting an aeration system through air, and then adding a sodium carbonate solution to adjust the pH value to 7.0-7.5 to prepare pretreated biogas slurry;
(5) sending the pretreated biogas slurry into an oil-rich microalgae culture system, and carrying out oil-rich microalgae culture under the conditions of an air fertilizer and a light source to generate oil-rich microalgae;
(6) and squeezing the oil-rich microalgae to obtain bio-oil, returning the residual algae residues to the anaerobic fermentation reactor, and carrying out anaerobic fermentation reaction with the pretreated sewage.
2. The method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae cultivation according to claim 1, wherein in the step (2), the temperature of the anaerobic fermentation reaction is 30-40 ℃ and the time is at least 8 hours.
3. The method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae cultivation according to claim 1, wherein in the step (3), the main functional component of the separation system is a PDMS/PEI composite membrane.
4. The method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae cultivation according to claim 1, wherein in the step (3), CH in bio-methane4The volume concentration of (A) is more than or equal to 85 percent.
5. The method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae cultivation according to claim 1, wherein in the step (3), purified biogas introduced into the separation system accounts for 55-65% of the total purified biogas.
6. The method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae cultivation according to claim 1, wherein in the step (4), the time of the sterilization treatment is at least 12 h.
7. The method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae cultivation according to claim 1, wherein in the step (4), the aeration treatment time is at least 12 h.
8. The method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae cultivation according to claim 1, wherein in the step (4), the concentration of the strong chlorine essence in the diluted biogas slurry is 12-18 mg/L.
9. The method for co-producing methane-bio oil by coupling domestic sewage anaerobic digestion and microalgae cultivation according to claim 1, wherein in the step (4), the addition amount of water is 4-10 times of the mass of the biogas slurry.
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