NL2031876A - Method for co-producing methane and bio-oil by coupling anaerobic digestion of domestic wastewater with microalgae cultivation - Google Patents
Method for co-producing methane and bio-oil by coupling anaerobic digestion of domestic wastewater with microalgae cultivation Download PDFInfo
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/06—Production of fats or fatty oils from raw materials by pressing
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- C11B1/00—Production of fats or fatty oils from raw materials
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- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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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
- C12P7/6436—Fatty acid esters
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Abstract
A method for co—producing methane and bio—oil by coupling anaerobic digestion of domestic wastewater with microalgae cultivation is provided, including: (1) removing suspended matters from domestic wastewater; (2) performing anaerobic digestion fermentation. reaction; (3) purifying, desulfurizing, and drying marsh gas: one part of the marsh gas is used for combustion for power generation, and the other part is used for separating CO2 and biomethane; CO2 generated by the combustion for power generation enters an oil—enriched, microalgae cultivation system; the combustion for power generation supplies electric energy to a light source; (4) adding water into biogas slurry for dilution, performing sterilization treatment and aeration treatment, and adjusting a pH value; (5) applying the pretreated biogas slurry to oil—enriched microalgae cultivation; and (6) squeezing oil— enriched, microalgae to obtain bio—oil, and returning remaining algae residues to the anaerobic digestion fermentation reaction.
Description
METHOD FOR CO-PRODUCING METHANE AND BIO-QIL BY COUPLING ANAEROBIC
DIGESTION OF DOMESTIC WASTEWATER WITH MICROALGAE CULTIVATION
The present invention belongs to the technical field of wastewater treatment and resource recovery, and specifically re- lates to a method for co-producing methane and bio-oil by coupling anaercbic digestion of domestic wastewater with microalgae culti- vation.
The rapid development of urbanization and the extensive use of organic fertilizers in modern agriculture have produced a large amount of domestic wastewater with high nitrogen, phosphorus, and organic matter content. Direct drainage of the domestic wastewater causes serious water pollution and brings a greater threaten to urban and agricultural water. At the same time, the domestic wastewater is also an excellent substrate for anaerobic digestion.
Anaerobic digestion can not only bring economic benefits, but also effectively solve the problem in treatment of the domestic sewage, thus truly achieving harmlessness and resource utilization.
Biogas slurry is a liquid residue of the anaerobic digestion, with complex compositions, including nutrients such as ammonia ni- trogen, nitrate nitrogen, nitrite nitrogen and a small amount of organic nitrogen, as well as trace elements and vitamins such as
Ca, Mg, Fe, and Zn required by crops. The biogas slurry plays an important role in regulating the growth and development of the crops, and, at the same time, will breed a large number of micro- organisms and miscellaneous algae.
The present invention aims to provide a method for co- producing methane and bio-oil by coupling anaerobic digestion of domestic wastewater with microalgae cultivation. High-quality me- thane and bio-cil are prepared by pretreatment and anaerobic di-
gestion of domestic wastewater, pretreatment of biogas slurry, pu- rification of biogas.
The method of the present invention includes the following steps: (1) pretreating domestic wastewater to remove suspended mat- ters, thus preparing pretreated wastewater; (2) introducing the pretreated wastewater into an anaerobic digestion fermentation reactor for anaerobic digestion reaction, thus producing bicgas and biogas slurry; {3) introducing the biogas into a desulfurizing tower for pu- rification and desulfurization, and then drying the biogas to form purified biogas: one part of the purified biogas is used for com- bustion for power generation, and the other part is introduced in- to a separation system to separate CO; and biomethane; the CO, serving as a gas fertilizer enters an oil-enriched microalgae cul- tivation system, and CO: generated by the combustion for power gen- eration and serving as a gas fertilizer enters the oil-enriched microalgae cultivation system; the combustion for power generation supplies electric energy to a light source; the light source irra- diates the oil-enriched microalgae cultivation system; (4) adding water into the biogas slurry for dilution to form diluted biogas slurry; adding trichloroisocyanuric acid into the diluted biogas slurry for sterilization treatment; using an aera- tion system to perform aeration treatment with air; then adding a sodium carbonate solution to adjust a pH value to 7.0-7.5, thus preparing pretreated biogas slurry; (5) delivering the pretreated biogas slurry into the oil- enriched microalgae cultivation system for oil-enriched microalgae cultivation under the gas fertilizer and the light source, thus producing oil-enriched microalgae; and (6) squeezing the oil-enriched microalgae to obtain bio-oil, and returning remaining algae residues to the anaerobic digestion fermentation reactor for anaerobic digestion fermentation reaction together with the pretreated wastewater.
In the above step (1), the pretreatment means that the domes- tic wastewater passes through a grating, then flows through a set- tling pit and a settling basin, and is then discharged, so that the suspended matters in the domestic wastewater are removed to form the pretreated wastewater.
In the above step (2), the anaerobic digestion fermentation reaction is carried out at a temperature of 30-40°C for at least 8 h.
In the above step (2), the organic matter content of the bio- gas slurry is less than that of the pretreated wastewater by 45% or above.
In the above step (3), the purification and desulfurization mean removing H,S in the biogas, and the drying means removing wa- ter vapor from the biogas.
In the above step (3), a main functional component of the separation system is a polydimethylsiloxane (PDMS) /polyetherimide (PEI) composite film.
In the above step (3), a volume concentration of CH,4 in the biomethane is greater than or equal to 85%.
In the above step (3), waste heat of the combustion for power generation is used for heating and thermal insulation of the an- aerobic digestion fermentation reaction.
In the above step (3), the purified biogas introduced into the separation system accounts for 55-65% of all the purified bio- gas.
In the above step (4), the sterilization treatment is carried out for at least 12 h.
In the above step (4), the aeration treatment is carried out for at least 12 h.
In the above step (4), the concentration of the sodium car- bonate is 1-3 mol/L.
In the above step (4), the concentration of the trichloroiso- cyanuric acid in the diluted biogas slurry is 12-18 mg/L.
In the above step (4), the adding amount of the water is 4-10 times the mass of the biogas slurry.
In the above step (5), the oil-enriched microalgae cultiva- tion is carried out for at least 24 h.
In the above step (6), the bio-oil is squeezed by a screw press.
In the above step (6), grease remaining on the surface of the algae residue is recovered by a solvent extraction method. Chloro- form is used as a solvent. The method is washing the microalgae with the chloroform to remove the grease.
The purification of the biogas slurry by the microalgae is mainly to remove TN (mainly NH*%-N), TP, COD, and antibiotics. The microalgae can convert, through photo-heterotrophy and chemohete- rotrophy, organic pollutants in the biogas slurry into a carbon source and energy for growth. Due to a growth requirement of the microalgae itself, the microalgae will absorb all kinds of inor- ganic nitrogen and convert them into genetic and metabolic sub- stances required by the microalgae. The microalgae can use phos- phorus salt in the wastewater and convert it into essential nucle- ic acids, proteins, carbohydrates, and lipids, etc., or can change the pH of the biogas slurry to increase dissolved oxygen to cause phosphate precipitation. Removing the antibiotics from the biogas slurry by the microalgae is achieved in two ways: adsorption and biodegradation. The adsorption efficiency is generally not more than 10%. Heterotrophic metabolism is a main removal way, and has the removal efficiency of 50-90% for the antibiotics in the biogas slurry.
The bio-oil is a renewable and environmentally-friendly fuel.
Raw materials for production change from a first generation of liquid biofuels coming from edible raw materials such as corn, soybean, and sugarcane, to a second generation of biofuels coming from inedible raw materials such as Jatropha, miscanthus, and switchgrass, to microalgae now. Microalgae has been determined as a raw material for industrial-scale production of bio-oil. The mi- croalgae is rich in species, grows and reproduces fast, and has higher photosynthetic efficiency that other energy crops, and will be the most suitable alternative of fossil fuels in the future.
The present invention provides a method for co-producing me- thane and bio-oil by coupling anaerobic digestion of domestic wastewater with microalgae cultivation, which has both a function of domestic wastewater treatment and a function of microalgae cul- tivation. The entire system is self-sufficient in energy, which not only solves the problem in treatment of the domestic wastewater, but also produces the high-quality biomethane and pro-
duces the bio-oil through the microalgae cultivation system.
FIG. 1 is a flow chart of a method for co-producing methane 5 and bic-0il by coupling anaerobic digestion of domestic wastewater with microalgae cultivation of the present invention.
The model of an anaerobic digestion fermentation reactor in the embodiment of the present invention is UASB.
During the anaerobic fermentation reaction in the embodiment of the present invention, an organic load is 3.5-4.5 gvs/Led.
In the embodiment of the present invention, the mass content of water in biogas slurry is 30-40%.
A desulfurization tower in the embodiment of the present in- vention is a spray desulfurization tower.
The separation system in the embodiment of the present inven- tion separates CO: and methane through a PDMS/PEI composite film.
In the embodiment of the present invention, combustion for power generation adopts a biogas internal combustion engine, an alternating-current generator, and a waste heat recovery device.
An oil-enriched microalgae cultivation system in the embodi- ment of the present invention adopts an open single-layer track- type photobioreactor. Agitation is mechanical agitation.
In the embodiment of the present invention, a volume concen- tration of CO: in biomethane is less than or equal to 2%.
In the embodiment of the present invention, the main composi- tions of bic-oil are C14-C22 long-chain fatty acids and triglycer- ides. At the same time, the bio-oil contains a large number of high value-added chemical substances: levoglucosan, levoglucosone, glycollic aldehyde, hydroxyacetone, methylol furfural, maltol, vanillin, furfural, oligosaccharides, etc.
In the embodiment of the present invention, a carbalkoxy of the long-chain fatty acid of the bio-oil has a heat value of 40-50
MJ/kg.
In the embodiment of the present invention, during aeration, a pressure of introduced air is 0.1-0.5 MPa, and an air flow rate is 0.3-0.6 in accordance with a volume ratio of the air introduced per minute to diluted biogas slurry.
The yield of the biogas in the embodiment of the present in- vention is 75-85%.
Embodiment 1
The flow is as shown in FIG. 1.
Domestic wastewater is pretreated to remove suspended mat- ters, thus preparing pretreated wastewater. The pretreatment means that the domestic wastewater passes through a grating, then flows through a settling pit and a settling basin, and is then dis- charged, so that the suspended matters in the domestic wastewater are removed.
The pretreated wastewater is introduced into an anaercbic di- gestion fermentation reactor for anaerobic digestion fermentation reaction to produce biogas and biogas slurry. The anaerobic diges- tion fermentation reaction is carried out at a temperature of 40°C for 8 h. The organic matter content of the biogas slurry is less than that of the pretreated wastewater by 45% or above.
The biogas is introduced into a desulfurizing tower for puri- fication and desulfurization, and is then dried, thus forming pu- rified bicgas. The purification and desulfurization mean removing
H;S in the biogas, and the drying means removing water vapor from the biogas. One part of the purified biogas is used for combustion for power generation, and the other part is introduced into a sep- aration system to separate CO: and biomethane; the CO, serving as a gas fertilizer enters an oil-enriched microalgae cultivation sys- tem, and CO: generated by the combustion for power generation and serving as a gas fertilizer enters the oil-enriched microalgae cultivation system; the combustion for power generation supplies electric energy to a light source; the light source irradiates the oil-enriched microalgae cultivation system. A volume concentration of CH4 in the biomethane is 87%. Waste heat of the combustion for power generation is used for heating and thermal insulation of the anaerobic digestion fermentation reaction. The purified biogas in- troduced into the separation system accounts for 60% of all the purified biogas.
Water is added into the biogas slurry for dilution, and the adding amount of the water is 8 times the mass of the biogas slur- ry to form diluted biogas slurry; trichloroisocyanuric acid is added into the diluted biogas slurry for agitation and steriliza- tion treatment for 14 h, and the concentration of the trichloroi- socyanuric acid in the diluted biogas slurry is 15 mg/L; an aera- tion system is used to perform aeration treatment with air for 15 h; then a sodium carbonate solution is added to adjust a pH value to 7.5, thus preparing pretreated biogas slurry; and the concen- tration of the sodium carbonate solution is 2 mol/L.
The pretreated biogas slurry is delivered into the oil- enriched microalgae cultivation system for oil-enriched microalgae cultivation for 36 h under the gas fertilizer and the light source, thus producing oil-enriched microalgae.
The oil-enriched microalgae is squeezed with a screw press to obtain bio-oil, and remaining algae residues is returned to the anaerobic digestion fermentation reactor for anaerobic digestion fermentation reaction together with the pretreated wastewater.
Embodiment 2
A difference between the method and Embodiment 1 is as fol- lows: (1) The anaerobic digestion fermentation reaction is carried out at a temperature of 35°C for 10 h. {2} The volume concentration of CH: in the biomethane is 86%, and the purified biogas introduced into the separation system ac- counts for 55% of all the purified biogas. (3) The adding amount of the water is 5 times the mass of the biogas slurry; the concentration of the trichloroisocyanuric acid in the diluted biogas slurry is 12 mg/L, and the sterilization treatment is carried out for 12 h; the aeration treatment is car- ried out for 18 h; the pH value is adjusted to 7.2; and the con- centration of the sodium carbonate solution is 1 mol/L. {4) The oil-enriched microalgae cultivation is carried out for 30 h.
Embodiment 3
A difference between the method and Embodiment 1 is as fol- lows: (1) The anaerobic digestion fermentation reaction is carried out at a temperature of 30°C for 12 h.
(2) The volume concentration of CH; in the biomethane is 88%, and the purified biogas introduced into the separation system ac- counts for 65% of all the purified biogas.
(3) The adding amount of the water is 10 times the mass of the biogas slurry; the concentration of the trichloroisocyanuric acid in the diluted biogas slurry is 18 mg/L, and the steriliza- tion treatment is carried out for 16 h; the aeration treatment is carried out for 17 h; the pH value is adjusted to 7.0; and the concentration of the sodium carbonate solution is 3 mol/L.
(4) The oil-enriched microalgae cultivation is carried out for 24 h.
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