CN112813113A - Method for producing bio-oil by livestock and poultry manure synergism - Google Patents
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Abstract
The invention discloses a method for producing bio-oil by livestock and poultry manure synergism, and relates to the technical field of waste resource recycling in animal husbandry. The invention relates to a method for producing bio-oil by enhancing the efficiency of livestock and poultry manure, which comprises the steps of pre-fermenting the livestock and poultry manure, carrying out solid-liquid separation to obtain fermentation gas, a primary liquid product and a solid mixture, culturing microalgae by using the obtained primary liquid product and the fermentation gas, collecting the microalgae, mixing the microalgae with the solid mixture, and extracting by using an organic solvent to obtain the bio-oil. The invention discloses a method for producing bio-oil by livestock and poultry manure synergism, which is characterized in that livestock and poultry manure is fermented by microorganisms and then is used for culturing oil-producing microalgae, and finally bio-oil is obtained, so that the full recycling of wastes is realized, and the problem of treatment of manure and manure water is solved.
Description
Technical Field
The invention relates to the technical field of animal husbandry waste resource recycling, in particular to a method for producing bio-oil by livestock and poultry manure synergism.
Background
At present, the treatment direction of the livestock and poultry manure is single, and the production of methane and the preparation of organic fertilizer are mainly used. For example, the existing Chinese patent with publication number "CN 104649530B" relates to a method for producing biogas and organic fertilizer by underground treatment of livestock and poultry manure in a breeding house, the Chinese patent with publication number "CN 110452853B" discloses that bacillus is used for livestock and poultry manure treatment and organic fertilizer production, degradation products are mainly feed protein raw materials, the Chinese patent with publication number "CN 104876685B" discloses a method for efficiently and massively treating pig manure by fly maggots, the treated pig manure can be used for producing organic fertilizer, and the treatment method of the livestock and poultry manure is low in economic added value of the obtained products, can generate toxic and harmful gases and greenhouse gases, and the problem of treatment of sewage after manure treatment is not solved.
In addition, with the exhaustion of traditional fossil energy and the increasing environmental pollution, the search for a clean renewable energy source has become a hot point of research. With the development of research, the bio-oil is found to be capable of being used as a substitute of fossil fuel to generate heat, electricity and chemical substances, can be applied to boiler burning and thermoelectric power generation in a short term, and can be applied to a turbine and a diesel engine in a long term, so that the bio-oil is significant if waste livestock manure can be produced into high-value bio-oil.
Disclosure of Invention
Aiming at the problems, the invention aims to disclose a method for producing bio-oil by livestock and poultry manure synergism, which is characterized in that livestock and poultry manure is fermented by microorganisms and then is used for culturing oil-producing microalgae, and finally bio-oil is obtained, so that the full recycling of wastes is realized, and the problem of treatment of manure and manure water is solved.
The method comprises the steps of pre-fermenting livestock and poultry manure, performing solid-liquid separation to obtain fermentation gas, a primary liquid product and a solid mixture, culturing microalgae by using the obtained primary liquid product and the fermentation gas, mixing the microalgae and the solid mixture, and extracting by using an organic solvent to obtain the bio-oil.
According to the method for producing the bio-oil by synergically fermenting the livestock and poultry manure, the livestock and poultry manure is used as a raw material, the fermentation gas generated by fermentation is mainly carbon dioxide, the carbon dioxide is recycled to the microalgae culture and is used as a carbon source for photosynthesis of the microalgae, the emission reduction of CO2 is realized, and meanwhile, carbon element is introduced into microalgae cells through a biological means, so that the increment of energy is realized, and the method has the advantages of environmental protection, energy conservation and reproducibility.
Further, the method specifically comprises the following steps:
pre-fermentation: uniformly mixing the livestock and poultry manure and the edible fungus substrate, adding the mixture into a reaction kettle, adding cellulase, uniformly mixing, performing heat preservation fermentation, collecting fermentation gas generated by fermentation into a gas storage tank, and performing solid-liquid separation after fermentation to obtain a primary liquid product and a solid mixture; the edible fungus matrix and the livestock manure are mixed for use and are mutually supplemented, so that a better reaction environment can be provided for subsequent cellulase treatment, meanwhile, the livestock manure is pretreated by the cellulase, residual cellulose and partial nutrient substances in the livestock manure can be effectively decomposed, and a good culture matrix is provided for oil-producing microalgae culture.
Culturing microalgae: pumping the primary liquid product into a microalgae reactor, adding a nutrient additive, adding water, diluting to 2-3 times of the original volume to obtain a microalgae culture solution, inoculating microalgae into the microalgae culture solution, simultaneously adding a composite strain, starting the microalgae reactor, introducing air, intermittently introducing a fermentation gas, maintaining the pH value at 7.2-7.5, and culturing the microalgae for 18-25 d; the addition of the PH buffer solution, the nutrient additive and the composite strain provides a good growth environment for microalgae, improves the light transmittance, reasonably constructs the mutualistic symbiosis relationship of the microalgae and has synergistic effect on the biomass and metabolite yield of the microalgae.
Oil extraction: collecting the cultured microalgae, adding a solid mixture, uniformly mixing, adding the mixture into an oil extraction reaction kettle, removing air, extracting oil for 5-20h under the conditions that the temperature is 250-400 ℃ and the pressure is 1.5-2.5MPa, cooling the oil extraction reaction kettle to room temperature after oil extraction is finished, introducing a gas-phase product into a microalgae reactor, adding an organic solvent into a liquid-phase product for extraction, collecting an organic phase, removing the solvent from the organic phase through flash evaporation to obtain crude oil, and delivering the water phase into the microalgae reactor for recycling. The collected microalgae and the solid mixture are mixed for oil extraction, and the edible fungus substrate and the cellulase contained in the solid mixture can generate biological synergistic catalytic effect under the oil extraction condition of the invention, thereby promoting the conversion and extraction of the biological oil.
Further, the organic solvent is any one of amyl acetate, amyl formate and hexane.
Further, the microalgae reactor comprises three tubular reactors and a mixing tank which are connected in series, and a white fluorescent light source is arranged in the centers of the three tubular reactors.
Due to the structural arrangement of the microalgae reactor, microalgae can be better cultured and cultivated, and a way for fully utilizing tail gas after fermentation and oil extraction is provided.
Further, the light source for microalgae culture adopts a combined mode of a fluorescent light source and a solar light source, and is in light and shade cycle of 12:12h-14:10h, the time ratio of a white fluorescent light source to the solar light source is 1:1-1:4, the fluorescent light intensity is increased to 2500 plus 15000lux after the illumination intensity is 1000 plus 3000lux and 10-15 d.
The fluorescent light source and the solar light source are recycled, so that the range of an illumination wave band is expanded, and the microalgae can be grown to provide illumination energy; the light length in the later period is increased, and necessary energy is provided for the extended growth of the microalgae.
Further, the microalgae species is one or more of Scenedesmus obliquus, Chlorella, Spirulina and pseudocytomonas sp, and the inoculation density of microalgae in the microalgae culture solution is 8 × 106～11×106one/mL.
Furthermore, the consumption of the edible fungus matrix is 2-6% of the mass of the livestock and poultry manure, and the consumption of the cellulase is 0.8-2.0% of the mass of the livestock and poultry manure.
Further, the nutritional additive comprises NaHCO3、KH2PO4、NH2CONH2Said NaHCO3、KH2PO4、NH2CONH2The addition amounts of the components are respectively 1000mg/L-2000mg/L, 800mg/L-1800mg/L and 800mg/L-1800 mg/L.
Further, the composite strain is compounded by yeast, lactobacillus and bacillus, the addition amount of the composite strain is 200mg/L-500mg/L, and the proportion of the yeast, the lactobacillus and the bacillus is (1.1-1.3) to 1 (0.5-0.8).
Further, the culture temperature of the microalgae reactor is 25-30 ℃, the air ventilation amount is 2.5-3.5L/min, and CO is introduced every 6 hours2The ventilation amount is 4.5-5.5L/min, and the ventilation time is 30-60 min.
Further, in the step of culturing the microalgae, a small amount of aspergillus or wood mold is added after culturing the microalgae for 16-22d, and the addition amount is 100mg/L-200 mg/L.
In the late stage of microalgae culture, the addition of fungi such as aspergillus or trichoderma optimizes the culture conditions, so that the microalgae and the fungi form large-particle microalgae symbiotic spheres, and the bio-oil yield is improved.
The invention has the beneficial effects that:
1. the invention discloses a method for producing bio-oil by livestock and poultry manure synergism, which is characterized in that livestock and poultry manure is fermented by microorganisms and then is used for culturing oil-producing microalgae, and finally bio-oil is obtained, so that the full recycling of wastes is realized, and the problem of treatment of manure and manure water is solved.
2. The method for producing the bio-oil by synergically producing the livestock and poultry manure is characterized in that the structure of a microalgae reactor is designed, and the microalgae culture conditions are matched, so that the microalgae can be better cultured and cultivated, and a full utilization way of tail gas after fermentation and oil extraction is provided.
Drawings
FIG. 1 is a schematic block flow diagram of a method for the synergistic production of bio-oil from livestock and poultry manure according to the present invention;
FIG. 2 is a schematic structural diagram of a device for the method for producing bio-oil by enhancing livestock and poultry manure;
the device comprises a reaction kettle 1, an oil extraction reaction kettle 2, a gas phase outlet 21, a first solid-liquid separator 3, a tubular reactor 4, a mixing tank 5, a microalgae culture solution outlet 51, an air outlet 52, a fluorescent light source 6, an air outlet pipe 7, a second solid-liquid separator 8, a distillation kettle 9, an air storage tank 10, a bacteria filter 11 and an air speed adjusting valve 12.
Detailed Description
The present invention will be described in detail with reference to specific examples below:
the invention relates to a method for producing bio-oil by enhancing the efficiency of livestock and poultry manure, which comprises a reaction kettle 1 and an oil extraction reaction kettle 2 which are connected by a pipeline, wherein a first solid-liquid separator 3 is also arranged between the reaction kettle 1 and the oil extraction reaction kettle 2, a material inlet of the first solid-liquid separator 3 is communicated with a material outlet of the reaction kettle 1, a solid outlet is communicated with a material inlet of the oil extraction reaction kettle 2, a liquid outlet is connected with a microalgae reactor, the microalgae reactor comprises three tubular reactors 4 and a mixing tank 5 which are connected in series, a white fluorescent light source 6 is arranged at the center of the three tubular reactors 4, an immersion heater is arranged at the bottom of the mixing tank 5, an air outlet 52 is arranged at the top, a microalgae culture solution outlet 51 is arranged at a position 1/4 away from the top on the side wall of the mixing tank 5, an inlet of the tubular reactor 4 is arranged at the lower, the inlet is communicated with the microalgae culture solution outlet 51, the outlet is communicated with an air outlet pipe 7, the inlet of the tubular reactor 4 is also communicated with an air inlet pipe, used for introducing air, the pipe orifice of the air outlet pipe 7 extends into the mixing tank 5 and is positioned below the liquid level, the mixing tank 5 is communicated with the liquid outlet of the first solid-liquid separator 3, the discharge port is communicated with the second solid-liquid separator 8, the solid outlet of the second solid-liquid separator 8 is communicated with the oil extraction reaction kettle 2, the liquid outlet is communicated with the mixing tank 5, the discharge port pipeline on the oil extraction reaction kettle 2 is connected with a distillation kettle 9, the oil extraction reaction kettle 2 is also provided with a gas phase outlet 21, the gas phase outlet 21 is communicated with the mixing tank 5, wherein, still be connected with gas holder 10 on reation kettle 1, the gas outlet of gas holder 10 is linked together with tubular reactor 4's entry, is provided with fungus filter 11 and air speed regulating valve 12 on the pipeline between gas holder 10 and tubular reactor 4.
The first solid-liquid separator 3 and the second solid-liquid separator 8 may be a filter press, a membrane filter, or a centrifuge.
The method for producing bio-oil by synergically producing livestock and poultry manure uses the device, livestock and poultry manure is placed in a reaction kettle 1 to be pre-fermented to obtain fermented gas, the fermented gas is collected in a gas storage tank 10, then the fermented gas is subjected to solid-liquid separation by a first solid-liquid separator 3 to obtain a primary liquid product and a solid mixture, the obtained primary liquid product and the fermented gas are utilized to culture microalgae in a microalgae reactor, the microalgae is collected and mixed with the solid mixture, and then the bio-oil is extracted by an organic solvent.
The method comprises the following specific steps:
example one
Pre-fermentation: uniformly mixing 800kg of livestock and poultry manure and 50kg of edible fungus substrate, adding the mixture into a 1000L reaction kettle, adding 10kg of cellulase, uniformly mixing, heating the reaction kettle to 40 ℃, carrying out heat preservation and fermentation for 10 days, collecting fermentation gas generated in the fermentation process into a gas storage tank, and after the fermentation is finished, conveying the fermented mixture to a first solid-liquid separator for solid-liquid separation to obtain 580kg of primary liquid product and 275kg of solid mixture.
Culturing microalgae: pumping the primary liquid product into a mixing tank of a microalgae reactor, and adding 0.8kg of NaHCO3、 0.5kg KH2PO4、0.5kg NH2CONH2Diluting with water to 3 times of original volume to obtain microalgae culture solution, testing to obtain pH of 7.2, inoculating Chlorella and Scenedesmus in the culture solution at a mass ratio of 2:1, and inoculating to obtain microalgae culture solution with total inoculation density of 10 × 106Adding 0.3kg of composite strain into the culture medium per mL of the culture medium, mixing the composite strain with yeast, lactobacillus and bacillus according to the mass ratio of 1.1:1:0.8, stirring and uniformly mixing, starting a microalgae reactor, controlling the culture temperature to be 25-30 ℃, introducing air at the flow rate of 2.5L/min, intermittently introducing fermentation gas (carbon dioxide) into a gas storage tank every 6 hours, wherein the ventilation rate is 5.0L/min, the pH value is maintained at 7.2-7.5, and the ventilation time of the fermentation gas is 50min, namely culturing the micro-organismsWhen algae are cultured, a microalgae culture solution is conveyed to an inlet of a pipeline reactor through a pump from a mixing tank, mixed air and fermentation gas of the microalgae culture solution flow through three pipeline reactors from bottom to top, and then are conveyed back to the mixing tank from an outlet to start culturing the microalgae, 0.08kg of aspergillus is added after 18d of culturing the microalgae, so that the microalgae form a sphere with large granular bacteria and algae symbiotic, the microalgae are continuously cultured for 23d, a fluorescent light source is started during microalgae culturing, a solar light source alternative use mode is adopted, and light and shade circulation is carried out according to 12:12h, wherein a white fluorescent light source is used for 4h and then is converted to a solar light source for irradiating 8h, the fluorescent light intensity is 2000lux, and after 15d, the white fluorescent light source is lifted to 4000 lux;
oil extraction: collecting microalgae from a mixing tank after microalgae cultivation is finished, centrifuging, separating by a second solid-liquid separator, separating liquid, returning the separated liquid to the mixing tank, adding the remaining solid into a solid mixture, uniformly mixing, putting into an oil extraction reaction kettle, sealing, exhausting air, continuously stirring for 10 hours under the conditions that the temperature is 300 ℃ and the pressure is 2.0MPa, cooling the oil extraction reaction kettle to room temperature after oil extraction is finished, introducing a gas-phase product into the mixing tank of a microalgae reactor, adding 100L of amyl acetate into a liquid-phase product for extraction, collecting an organic phase, removing a solvent from the organic phase by flash evaporation to obtain crude oil, conveying a water phase into the mixing tank of the microalgae reactor for recycling, and detecting that the crude oil yield is 15%.
Example two
Pre-fermentation: uniformly mixing 800kg of livestock and poultry manure and 16kg of edible fungus substrate, adding the mixture into a 1000L reaction kettle, adding 6.5kg of cellulase, uniformly mixing, heating the reaction kettle to 35 ℃, carrying out heat preservation and fermentation for 8d, collecting fermentation gas generated in the fermentation process into a gas storage tank, and after the fermentation is finished, conveying the fermented mixture to a first solid-liquid separator for solid-liquid separation to obtain 545kg of primary liquid product and 267kg of solid mixture.
Culturing microalgae: pumping the primary liquid product into a mixing tank of a microalgae reactor, and adding 0.6kg of NaHCO3、 1kg KH2PO4、0.5kg NH2CONH2Diluting with water to 3 times of original volume to obtain microalgae culture solution, and detecting to obtain microalgae culture solutionThe pH value of the culture medium is 7.3, the microalgae culture medium is inoculated with the chlorella and the scenedesmus according to the mass ratio of 2:1, and the total inoculation density is 8 multiplied by 106Adding 0.1kg of composite strain into the reactor per mL at the same time, wherein the composite strain is prepared by mixing saccharomycetes, lactobacillus and bacillus according to the mass ratio of 1.3:1:0.6, stirring and uniformly mixing, starting a microalgae reactor, controlling the culture temperature to be 25-30 ℃, introducing air at the flow rate of 3.5L/min, intermittently introducing fermentation gas (carbon dioxide) into a gas storage tank every 6 hours, wherein the ventilation rate is 4.5L/min, the pH value is maintained to be 7.2-7.5, the ventilation time of the fermentation gas is 60min, namely, when culturing microalgae, conveying the microalgae culture solution from a mixing tank to an inlet of a pipeline reactor through a pump, conveying the mixed air and the fermentation gas of the microalgae culture solution to the mixing tank from an outlet after flowing through three pipeline reactors from bottom to top, starting culturing the microalgae, adding 0.05kg of aspergillus after culturing the microalgae for 16 days, and enabling the microalgae to form a large-particle algae symbiotic sphere, continuously culturing the microalgae, co-culturing the microalgae for 18d, starting a fluorescent light source during the culture of the microalgae, adopting a sunlight source alternate use mode, and circulating in a light and shade mode of 14:10h, wherein the white fluorescent light source is used for 3h and then is converted to be irradiated by the sunlight source for 11h, and the fluorescent light intensity is increased to 6000lux after 3000lux and 15 d;
oil extraction: collecting microalgae from a mixing tank after microalgae cultivation is finished, centrifuging, separating by a second solid-liquid separator, separating liquid, returning the separated liquid to the mixing tank, adding the remaining solid into a solid mixture, uniformly mixing, putting into an oil extraction reaction kettle, sealing, exhausting air, continuously stirring, extracting oil for 5 hours under the conditions that the temperature is 400 ℃ and the pressure is 2.5MPa, cooling the oil extraction reaction kettle to room temperature after oil extraction is finished, introducing a gas-phase product into the mixing tank of a microalgae reactor, adding 100L of hexane into a liquid-phase product for extraction, collecting an organic phase, removing a solvent from the organic phase by flash evaporation to obtain crude oil, conveying a water phase into the mixing tank of the microalgae reactor for recycling, and detecting that the crude oil yield is 18%.
EXAMPLE III
Pre-fermentation: uniformly mixing 800kg of livestock and poultry manure and 30kg of edible fungus substrate, adding the mixture into a 1000L reaction kettle, adding 16kg of cellulase, uniformly mixing, heating the reaction kettle to 30 ℃, carrying out heat preservation and fermentation for 5 days, collecting fermentation gas generated in the fermentation process into a gas storage tank, and after the fermentation is finished, conveying the fermented mixture to a first solid-liquid separator for solid-liquid separation to obtain 565kg of primary liquid product and 275kg of solid mixture.
Culturing microalgae: pumping the primary liquid product into a mixing tank of a microalgae reactor, and adding 1.1kg of NaHCO3、 0.6kg KH2PO4、0.8kg NH2CONH2Diluting with water to 3 times of original volume to obtain microalgae culture solution, testing to obtain pH 7.5, inoculating Chlorella and Scenedesmus in the culture solution at a mass ratio of 2:1, and inoculating to obtain microalgae culture solution with total inoculation density of 11 × 106Adding 0.2kg of composite strain into the reactor per mL at the same time, wherein the composite strain is prepared by mixing saccharomycetes, lactobacillus and bacillus according to the mass ratio of 1.1:1:0.5, stirring and uniformly mixing, starting a microalgae reactor, controlling the culture temperature to be 25-30 ℃, introducing air at the flow rate of 3.0L/min, intermittently introducing fermentation gas (carbon dioxide) into a gas storage tank every 6 hours, wherein the ventilation rate is 5.5L/min, the pH value is maintained to be 7.2-7.5, the ventilation time of the fermentation gas is 30min, namely when culturing the microalgae, conveying the microalgae culture solution from a mixing tank to the inlet of a pipeline reactor through a pump, conveying the mixed air and the fermentation gas of the microalgae culture solution to the mixing tank from the outlet after flowing through three pipeline reactors from bottom to top, starting culturing the microalgae, adding 0.11kg of aspergillus after culturing for 22 days to enable the microalgae to form a large-particle microalgae symbiotic sphere, continuously culturing microalgae, co-culturing microalgae for 25d, starting a fluorescent light source during microalgae culture, adopting a solar light source alternate use mode, and circulating in a light and shade mode of 13:11h, wherein a white fluorescent light source is used for 6h and then is converted to be irradiated by the solar light source for 7h, and the fluorescent light intensity is increased to 3000lux after 1000lux and 15 d;
oil extraction: collecting microalgae from a mixing tank after microalgae cultivation is finished, centrifuging, separating by a second solid-liquid separator, separating liquid, returning the separated liquid to the mixing tank, adding the remaining solid into a solid mixture, uniformly mixing, putting into an oil extraction reaction kettle, sealing, exhausting air, continuously stirring, extracting oil for 20 hours at the temperature of 250 ℃ and under the pressure of 1.5MPa, cooling the oil extraction reaction kettle to room temperature after oil extraction is finished, introducing a gas-phase product into the mixing tank of a microalgae reactor, adding 100L of amyl formate into a liquid-phase product for extraction, collecting an organic phase, removing a solvent from the organic phase by flash evaporation to obtain crude oil, conveying a water phase into the mixing tank of the reactor for recycling, and detecting that the yield of the crude oil is 16.5%.
Example four
Compared with the first embodiment, the difference between the first embodiment and the second embodiment is that after the microalgae culture is completed, the collected microalgae is pretreated before oil extraction, specifically:
after microalgae cultivation is finished, microalgae is collected from the mixing tank, after centrifugation, liquid is separated by the second solid-liquid separator, the separated liquid returns to the mixing tank, the rest solid is processed for 3 rounds by adopting steep pulse electric field processing and ultrasonic processing alternately, and the steep pulse electric field processing and the ultrasonic processing are taken as one round after each time of application, wherein when the first round of processing is carried out, microwave processing is also carried out between the steep pulse electric field processing and the ultrasonic processing, and the operation is as follows:
a first round: applying a steep pulse electric field with the pulse peak value of 750V, the pulse width of 75 mus, the pulse rise time of 60ns, the repetition frequency of 65Hz and the duty ratio of 50% to the remaining solid for processing for 1min, then adding 20 wt% ethanol solution with the mass of 5% of the solid, stirring for 2min, processing for 30s under the microwave condition with the microwave radiation power of 8W, immediately performing ultrasonic processing for 20min, wherein the ultrasonic processing is alternately performed by cosine state ultrasonic waves and variable frequency ultrasonic waves, the frequency of the cosine state ultrasonic waves is 30KHz, and the power is 150mW/cm2The frequency of the frequency conversion ultrasonic wave is 25KHz, and the power is 200mW/cm2. The applied steep pulse electric field is nanosecond-level pulse, can generate instantaneous high pressure to penetrate through microalgae cells to increase the osmotic pressure of intracellular organelles, ethanol solution is added, the ethanol solution can better absorb microwave radiation, the ethanol solution can be better immersed into the microalgae cells under the microwave condition, and finally the microalgae cells are alternately treated by cosine-state ultrasonic waves and frequency conversion ultrasonic waves to promote the leaching of biomass in the microalgae cells,meanwhile, the breaking of macromolecular chemical bonds in the microalgae can be promoted, and the macromolecular chemical bonds are converted into low-molecular substances, so that the subsequent oil extraction step is facilitated.
And (2) two rounds: the steep pulse electric field treatment is the same as the first round, ultrasonic treatment is carried out for 15min immediately after the steep pulse electric field treatment is finished, the ultrasonic treatment is carried out alternately by cosine state ultrasonic waves and frequency conversion ultrasonic waves, the frequency of the cosine state ultrasonic waves is 26KHz, and the power is 120mW/cm2The frequency of the frequency conversion ultrasonic wave is 22KHz, and the power is 160mW/cm2。
Three rounds of: the steep pulse electric field treatment is the same as the first round, ultrasonic treatment is immediately carried out for 10min after the steep pulse electric field treatment is finished, the ultrasonic treatment is alternately carried out by cosine state ultrasonic waves and frequency conversion ultrasonic waves, the frequency of the cosine state ultrasonic waves is 24KHz, and the power is 100mW/cm2The frequency of the frequency conversion ultrasonic wave is 20KHz, and the power is 120mW/cm2. Because the energy absorbed by the microalgae in the treatment process can be accumulated by the components, in the treatment process, the treatment time and the ultrasonic treatment intensity are gradually reduced during ultrasonic treatment and are matched with the total energy required in the microalgae treatment process, so that the premature liquefaction of the microalgae is prevented, and the loss is caused.
Adding the pretreated microalgae into the solid mixture, uniformly mixing, putting into an oil extraction reaction kettle, sealing, removing air, continuously stirring at the temperature of 300 ℃ and under the pressure of 2.0MPa for oil extraction for 10 hours, cooling the oil extraction reaction kettle to room temperature after oil extraction is finished, introducing a gas-phase product into a mixing tank of a microalgae reactor, adding 100L of amyl acetate into a liquid-phase product for extraction, collecting an organic phase, removing a solvent from the organic phase through flash evaporation to obtain crude oil, conveying a water phase into the mixing tank of the microalgae reactor for recycling, and detecting that the yield of the crude oil is 24%.
EXAMPLE five
Compared with the comparative example 1, the difference of the present example is that no solid mixture is added in the final oil extraction step, specifically:
collecting microalgae from a mixing tank after microalgae culture is finished, centrifuging, separating by a second solid-liquid separator, returning separated liquid to the mixing tank, putting the remaining solid into an oil extraction reaction kettle, sealing, exhausting air, continuously stirring at 300 ℃ and under the pressure of 2.0MPa for oil extraction for 10 hours, cooling the oil extraction reaction kettle to room temperature after oil extraction is finished, introducing a gas-phase product into the mixing tank of a microalgae reactor, adding 100L of amyl acetate into a liquid-phase product for extraction, collecting an organic phase, removing a solvent from the organic phase by flash evaporation to obtain crude oil, conveying a water phase into the mixing tank of the microalgae reactor for cyclic utilization, and detecting that the yield of the crude oil is 10%.
Through the first to third embodiments, the method of the invention can convert the waste livestock manure into the bio-oil with high added value, realize the reutilization of resources, and the gas and the waste water generated by fermentation are effectively utilized, the problems of waste gas, greenhouse gas emission and waste water caused by the traditional livestock manure fermentation are solved, and the comparison between the first embodiment and the fourth embodiment shows that, by pretreating the cultured microalgae, the cells of the microalgae can be effectively destroyed, the bio-oil in the microalgae cells can be better extracted, the comparison between the first embodiment and the fifth embodiment shows that the solid mixture can generate biological synergistic catalytic effect to promote the transformation and extraction of the bio-oil by mixing the solid mixture with the microalgae and extracting the oil.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (10)
1. A method for producing bio-oil by enhancing the efficiency of livestock and poultry manure is characterized by comprising the steps of pre-fermenting the livestock and poultry manure, performing solid-liquid separation to obtain fermentation gas, a primary liquid product and a solid mixture, culturing microalgae by using the obtained primary liquid product and the fermentation gas, collecting the microalgae, mixing the microalgae with the solid mixture, and extracting by using an organic solvent to obtain the bio-oil.
2. The method for producing bio-oil by enhancing livestock and poultry manure yield as claimed in claim 1, which comprises the following steps:
pre-fermentation: uniformly mixing the livestock and poultry manure and the edible fungus substrate, adding the mixture into a reaction kettle, adding cellulase, uniformly mixing, performing heat preservation fermentation, collecting fermentation gas generated by fermentation into a gas storage tank, and performing solid-liquid separation after fermentation to obtain a primary liquid product and a solid mixture;
culturing microalgae: pumping the primary liquid product into a microalgae reactor, adding a nutrient additive, adding water to dilute to 2-3 times of the original volume to obtain a microalgae culture solution, inoculating microalgae into the microalgae culture solution, simultaneously adding a composite strain, starting the microalgae reactor, introducing air, intermittently introducing a fermentation gas, maintaining the pH value at 7.2-7.5, and culturing the microalgae for 18-25 d;
oil extraction: collecting the cultured microalgae, adding a solid mixture, uniformly mixing, adding the mixture into an oil extraction reaction kettle, removing air, extracting oil for 5-20h under the conditions that the temperature is 250-400 ℃ and the pressure is 1.5-2.5MPa, cooling the oil extraction reaction kettle to room temperature after oil extraction is finished, introducing a gas-phase product into a microalgae reactor, adding an organic solvent into a liquid-phase product for extraction, collecting an organic phase, removing the solvent from the organic phase through flash evaporation to obtain crude oil, and delivering the water phase into the microalgae reactor for recycling.
3. The method for synergistic production of bio-oil from livestock and poultry manure according to claim 2, wherein the microalgae reactor comprises three tubular reactors and a mixing tank which are connected in series, and a white fluorescent light source is arranged at the center of the three tubular reactors.
4. The method for synergistic production of bio-oil from livestock and poultry manure according to claim 3, characterized in that the light source for microalgae cultivation adopts a combined manner of a fluorescent light source and a solar light source, and the light-dark cycle is performed at 12:12h-14:10h, the time ratio of the white fluorescent light source to the solar light source is 1:1-1:4, the fluorescent light intensity is 1000-.
5. The method for synergistic production of bio-oil from livestock and poultry manure according to claim 4, wherein the microalgae species is one or more of Scenedesmus obliquus, Chlorella vulgaris, Spirulina platensis and pseudocytomonas sp, and the inoculation density of microalgae in the microalgae culture solution is 8 x 106～11×106one/mL.
6. The method for producing bio-oil by enhancing the efficiency of livestock and poultry manure according to claim 5, wherein the amount of the edible fungus matrix is 2-6% of the mass of the livestock and poultry manure, and the amount of the cellulase is 0.8-2.0% of the mass of the livestock and poultry manure.
7. The method for synergistic production of bio-oil from livestock and poultry manure according to claim 6, wherein the nutritional additive comprises NaHCO3、KH2PO4、NH2CONH2Said NaHCO3、KH2PO4、NH2CONH2The addition amounts of the components are respectively 1000mg/L-2000mg/L, 800mg/L-1800mg/L and 800mg/L-1800 mg/L.
8. The method for synergistic production of bio-oil from livestock and poultry manure according to claim 7, characterized in that the composite strain is compounded from yeast, lactobacillus and bacillus, the addition amount of the composite strain is 200mg/L-500mg/L, and the ratio of yeast, lactobacillus and bacillus is (1.1-1.3):1 (0.5-0.8).
9. The method for synergistic production of bio-oil from livestock and poultry manure according to claim 8, wherein the culture temperature of the microalgae reactor is 25-30 ℃, the air ventilation is 2.5-3.5L/min, the fermentation gas is introduced every 6 hours, the air ventilation is 4.5-5.5L/min, and the air ventilation time is 30-60 min.
10. The method for synergistic production of bio-oil from livestock and poultry manure according to claim 9, wherein in the step of microalgae cultivation, a small amount of aspergillus or trichoderma is added after the microalgae cultivation for 16-22 days, and the addition amount is 100mg/L-200 mg/L.
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