CN107151055B - Value-added utilization method for livestock and poultry wastewater environment - Google Patents
Value-added utilization method for livestock and poultry wastewater environment Download PDFInfo
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Abstract
The invention belongs to the technical field of environmental protection and new energy, and particularly relates to a livestock and poultry wastewater value-added utilization method based on microalgae culture and hydrothermal liquefaction, which comprises the following steps: 1) flocculating, precipitating and filtering the livestock and poultry wastewater, placing the diluted solution into a microalgae culture pond, and inoculating the domesticated microalgae into the solution; 2) culturing microalgae; 3) performing hydrothermal liquefaction; 4) and (3) separating a liquid product, filtering and separating the liquid mixture product to obtain a crude oil product and a water phase product, introducing the hydrothermal liquefied wastewater serving as a nutrient solution into the microalgae culture pond in the step (2) to supplement nutrient substances such as nitrogen, phosphorus and the like, and recycling the nutrient substances, wherein the hydrothermal liquefied wastewater is introduced into the microalgae culture pond to be mixed with the livestock wastewater, adjusting the concentration of total nitrogen TN and total phosphorus TP in the microalgae culture pond to 200-1000 mg/L and 20-500 mg/L respectively, and repeating the steps (2) to (4), so that the nutrient elements such as nitrogen, phosphorus and the like in the livestock wastewater can be recycled 3-10 times by supplementing the nutrient substances such as nitrogen, phosphorus and the like again through the hydrothermal liquefied wastewater.
Description
Technical Field
The invention belongs to the technical field of environmental protection and new energy, and particularly relates to a value-added utilization method of livestock and poultry wastewater based on microalgae culture and hydrothermal liquefaction.
Background
The livestock and poultry wastewater refers to fecaluria generated in the livestock and poultry breeding process, livestock and poultry house washing wastewater, livestock and poultry excrement fermentation liquor and the like. The livestock and poultry wastewater is rich in pollutants such as nitrogen, phosphorus, organic carbon, heavy metals and the like, and the wastewater is continuously generated in a large quantity in the production process. If the treatment is not timely and effective, the environment is polluted and the resource waste is caused.
Cases of treating wastewater (livestock wastewater, municipal wastewater, mine wastewater and the like) by culturing microalgae at home and abroad are abundant, and the microalgae cultured in the method is called wastewater microalgae. The wastewater microalgae absorb nitrogen and phosphorus resources in the wastewater in the growth process and simultaneously absorb a large amount of heavy metals. However, in the prior art, only the carbon and hydrogen organic elements in the wastewater microalgae are utilized by conversion, and the control and utilization of main pollutants such as nitrogen, phosphorus, heavy metals and the like are neglected. If the anaerobic fermentation converts carbon and hydrogen elements into methane and hydrogen, nitrogen, phosphorus and heavy metals still exist in the fermentation liquor, if the nitrogen and the phosphorus enter water, water bloom is caused to endanger the development of fishery, and the heavy metals enter a food chain to endanger the health of human beings.
Zhangming at university of Zhejiang utilizes blue algae fermentation to produce hydrogen alkane (research on mechanism of Zhangming and blue algae fermentation co-production of hydrogen and methane: doctor's academic paper, Zhejiang university, Zhejiang, 2011), the hydrogen production amount is 24mL/g, and the methane production amount is 84 mL/g. But lack control and management of nitrogen, phosphorus and heavy metals.
Experiments for preparing bio-crude oil by Hydrothermal liquefaction of mixed algae (macroalgae, microalgae, bacteria, etc.) directly harvested from municipal sewage were performed by Chen (Chen, W.T., et al., hydrotherl Liquefacial reaction of mixed-culture and water flow device system, 2014.152: p.130-139.) of U.S. UIUC. Experiments show that the maximum yield of the biological crude oil after the direct hydrothermal liquefaction is 49%, the biological crude oil mainly comprises carbon and hydrogen elements, and 75-80% of nitrogen elements enter a water-phase product in the form of ammonia nitrogen and nitrate nitrogen. But it uses bio-crude as the target product and lacks control and treatment of phosphorus and heavy metals.
Disclosure of Invention
The invention aims to provide a livestock and poultry wastewater environment value-added utilization method based on microalgae culture and hydrothermal liquefaction, so as to solve the problem of nutrient resource utilization of livestock and poultry wastewater at present.
The purpose of the invention is realized by the following technical scheme:
a method for value-added utilization of livestock and poultry wastewater environment comprises the following steps:
1) clarifying the livestock and poultry wastewater through flocculation precipitation, filtering, removing suspended matters in the wastewater, increasing the light transmittance, and further obtaining filtered livestock and poultry wastewater; diluting the filtered livestock and poultry wastewater, wherein the filtered livestock and poultry wastewater accounts for 5-10% of the total volume of the diluted solution, placing the diluted solution into a microalgae culture pond, inoculating the domesticated microalgae into the solution, and culturing in the microalgae culture pond under the illumination condition;
2) culturing microalgae: adjusting the pH value of a solution in a microalgae culture pond to 7.1 by using NaOH or HCl until the biomass reaches 0.5-5 g/L, harvesting microalgae, dehydrating and concentrating the harvested microalgae, and adjusting the water content to 75-90%;
3) hydrothermal liquefaction: adding the obtained microalgae into a hydrothermal liquefaction reaction kettle for hydrothermal liquefaction, pressurizing, heating and stirring in the hydrothermal liquefaction process, wherein the initial pressure is 0-2.5 MPa, the rotation speed of a stirrer is 100-800 rpm, the reaction temperature is 200-370 ℃, the residence time is 0-120 min, after the reaction is finished and the gas-phase product is collected, opening the hydrothermal liquefaction reaction kettle, and adding CO in the gas-phase product2The mass of the gas phase product is more than 90 percent of the total mass of the gas phase product, and the gas phase product is introduced into the microalgae culture pond in the step 2 to supplement CO2The carbon source is recycled to provide carbon source for the photosynthesis of the microalgae;
4) and (3) liquid product separation: filtering and separating the liquid mixture product to obtain a crude oil and a water phase product, wherein,
41) dissolving crude oil by using an organic solvent to obtain biological crude oil, wherein residues left after the crude oil is dissolved are solid residues containing Cu, Cr and Pb;
42) the obtained water phase product is hydrothermal liquefaction wastewater, and the total nitrogen content and the total phosphorus content in the hydrothermal liquefaction wastewater are respectively 4000-15000 mg/L and 300-10000 mg/L;
and (3) introducing the hydrothermal liquefied wastewater serving as nutrient solution into the microalgae culture pond in the step (2) to supplement nutrient substances such as nitrogen, phosphorus and the like for cyclic utilization, wherein the hydrothermal liquefied wastewater is introduced into the microalgae culture pond to be mixed with the livestock wastewater, the concentration of total nitrogen TN and total phosphorus TP in the microalgae culture pond is adjusted to 200-1000 mg/L and 20-500 mg/L respectively, the steps (2) -4) are repeated, and the nutrient elements such as nitrogen, phosphorus and the like in the livestock wastewater can be recycled for 3-10 times by supplementing the nutrient substances such as nitrogen, phosphorus and the like again through the hydrothermal liquefied wastewater.
In step 1, the filtration mode comprises ultrafiltration and nanofiltration; the livestock and poultry wastewater source places comprise breeding wastewater of chicken farms, pig farms and dairy farms and anaerobic fermentation liquor of a methane station, and the type of the livestock and poultry wastewater comprises at least one of livestock and poultry manure, flushing wastewater and livestock and poultry manure fermentation liquor.
In step 2, the microalgae is one of chlorella, spirulina, nannochloropsis, dunaliella salina, photosynthetic bacteria and mixed algae.
In step 2, the microalgae dehydration concentration mode comprises membrane filtration, centrifugation and flocculation.
In the step 3, the hydrothermal liquefaction reaction kettle is a batch reaction kettle, a semi-continuous reaction kettle or a continuous reaction kettle.
In step 4, the product separation means comprises filtration, extraction, distillation, centrifugation.
In step 4, the organic solvent comprises acetone, toluene, and dichloromethane.
In the step 4, the calorific value of the obtained biological crude oil is 30-40 MJ/kg.
The invention has the beneficial effects that:
1. the method for treating the livestock wastewater enriches the carbon, nitrogen and phosphorus resources in the organic wastewater into the hydrothermal liquefied water phase product, realizes the cyclic utilization of the carbon, nitrogen and phosphorus, and avoids environmental pollution caused by improper control and treatment.
2. The method is used for treating the livestock wastewater, so that the heavy metals in the livestock wastewater are immobilized, and the heavy metals are prevented from entering a food chain to harm human health.
3. The livestock and poultry wastewater is treated by the method, and the nutrient elements such as nitrogen, phosphorus and the like in the livestock and poultry wastewater can be recycled for 3-10 times, so that the biomass and the biological crude oil are increased by 3-10 times.
4. A large amount of biological crude oil is generated, and value-added energy is obtained while the environment is improved.
Drawings
FIG. 1 is a process flow diagram of the livestock and poultry wastewater environment value-added utilization method.
Detailed Description
The invention is further illustrated and described with reference to the following examples, which are not intended to limit the scope of the invention.
As shown in fig. 1, a method for increasing the value of livestock and poultry wastewater environment comprises the following steps:
1) clarifying the livestock and poultry wastewater through flocculation precipitation, then filtering, removing suspended matters in the wastewater, increasing the light transmittance, and further obtaining the filtered livestock and poultry wastewater, wherein the filtering mode comprises ultrafiltration and nanofiltration.
Diluting the filtered livestock and poultry wastewater, wherein the filtered livestock and poultry wastewater accounts for 5-10% of the total volume of the diluted solution.
Placing the diluted solution into a microalgae culture pond, inoculating the domesticated microalgae into the solution, and culturing in the microalgae culture pond under the illumination condition.
Wherein, the livestock wastewater source places comprise breeding wastewater of chicken farms, pig farms and dairy farms and anaerobic fermentation liquor of a biogas station, and the type of the livestock wastewater comprises at least one of livestock manure, flushing wastewater and livestock manure fermentation liquor.
2) Culturing microalgae: and adjusting the pH value of the solution in the microalgae culture pond to 7.1 by using NaOH or HCl until the biomass reaches 0.5-5 g/L, harvesting the microalgae, dehydrating and concentrating the harvested microalgae, and adjusting the water content to 75-90%.
Wherein the microalgae comprises one of Chlorella, Spirulina, Nannochloropsis, Dunaliella salina, photosynthetic bacteria and mixed algae.
The microalgae dehydration and concentration mode comprises membrane filtration, centrifugation and flocculation.
3) Hydrothermal liquefaction: adding the obtained microalgae into a hydrothermal liquefaction reaction kettle for hydrothermal liquefaction, and pressurizing, heating and stirring in the hydrothermal liquefaction process. The initial pressure is 0-2.5 MPa, the rotating speed of the stirrer is 100-800 rpm, the reaction temperature is 200-370 ℃, and the residence time is 0-120 min. After the reaction is finished and the gas phase product is collected after the reaction is cooled, the hydrothermal liquefaction reaction kettle is opened, and the gas phase productMiddle CO2The mass of the gas phase product is more than 90 percent of the total mass of the gas phase product, and the gas phase product is introduced into the microalgae culture pond in the step 2 to supplement CO2And the carbon source is recycled to provide carbon source for the photosynthesis of the microalgae.
Wherein, the hydrothermal liquefaction reaction kettle is an intermittent reaction kettle, a semi-continuous reaction kettle or a continuous reaction kettle.
4) And (3) liquid product separation: filtering and separating the liquid mixture product to obtain a crude oil and a water phase product, wherein,
41) and (3) dissolving the crude oil by using an organic solvent to obtain the biological crude oil, and modifying and upgrading the biological crude oil to be used as fuel and extraction chemicals. The residue left after the crude oil is dissolved is solid residue which contains Cu, Cr, Pb and the like, and the solid residue can be subjected to heavy metal immobilization and recycling treatment.
Wherein, the product separation mode includes but is not limited to filtration, extraction, distillation, centrifugation and the like.
Organic solvents include, but are not limited to, acetone, toluene, methylene chloride, and the like.
The heat value of the obtained biological crude oil is 30-40 MJ/kg, and transportation fuels and extracted chemicals can be produced through modification and upgrading.
42) The obtained water phase product is hydrothermal liquefaction wastewater, wherein the total nitrogen TN content in the hydrothermal liquefaction wastewater is 4000-15000 mg/L, the total phosphorus TP content in the hydrothermal liquefaction wastewater is 300-10000 mg/L, and nitrogen and phosphorus resources are obtained by converting microalgae.
And (3) introducing the hydrothermal liquefied wastewater serving as nutrient solution into the microalgae culture pond in the step (2) to supplement nutrient substances such as nitrogen, phosphorus and the like, and recycling. The hydrothermal liquefaction wastewater is introduced into a microalgae culture pond to be mixed with the livestock wastewater, the concentration of total nitrogen TN and total phosphorus TP in water in the microalgae culture pond is adjusted to 200-1000 mg/L and 20-500 mg/L respectively, the steps 2) -4 are repeated, nutrient elements such as nitrogen and phosphorus in the livestock wastewater can be recycled for 3-10 times by supplementing nutrient substances such as nitrogen and phosphorus again through the hydrothermal liquefaction wastewater, and the biomass and the biological crude oil are increased by 3-10 times.
The hydrothermal liquefaction reaction kettle used in the embodiment of the invention is an intermittent reaction kettle (4593/HT, 100ml, Parr, USA), the initial pressure is 0-2.5 MPa, and the reaction temperature is 220-350 ℃.
Example 1
(1) The chicken manure biogas slurry is clarified after flocculation precipitation, and then is ultrafiltered by using a UF (ultrafiltration) membrane to remove suspended matters in wastewater and increase the light transmittance, so that the filtered chicken manure biogas slurry is obtained.
Diluting the filtered chicken manure biogas slurry, wherein the filtered chicken manure biogas slurry accounts for 5-10% of the total volume of the diluted solution.
Placing the diluted solution into a microalgae culture pond, inoculating the domesticated chlorella into the solution, and culturing in the microalgae culture pond under the illumination condition.
(2) Harvesting chlorella when the biomass is 2g/L in a microalgae culture pond, adjusting the pH of water in the culture pond to 7.1 by using HCl, and adjusting the water content of the microalgae to 80 +/-0.2% after harvesting to be mud-shaped.
(3) Adding 50ml of microalgae mud into a 100ml hydrothermal liquefaction reaction kettle, and sealing the reaction kettle. The initial pressure of the reaction kettle is 2MPa, the rotating speed of the stirrer is 400rpm, the reaction kettle is heated to 290-320 ℃, the temperature is kept for 0-60 min, then the heating is stopped, after the reaction kettle is cooled to the room temperature, gas is collected firstly, then the reaction kettle is opened, and CO in the gas-phase product2Over 90% of the total mass of the gas phase product, introducing into a microalgae culture pond to supplement CO2And the carbon source is recycled to provide carbon source for the photosynthesis of the microalgae.
(4) Collecting the liquid mixture by using a beaker, and separating the liquid mixture by suction filtration through slow qualitative filter paper to obtain crude oil and hydrothermal liquefaction wastewater:
a. the crude oil was dissolved with acetone and the solid residue was isolated by filtration. The yield of the biological crude oil is 30-39.2%, and the yield of the solid residue is 12.35-23.2%. The solid residue has a Cu content of about 0.098 to 0.106 mg/g.
b. The total nitrogen TN content of the hydrothermal liquefaction wastewater is 13000-15000 mg/L, and the total phosphorus TP content is 1200-2500 mg/L. And (3) circularly returning the generated hydrothermal liquefaction wastewater into the microalgae culture pond, mixing the generated hydrothermal liquefaction wastewater with the chicken manure biogas slurry in the microalgae culture pond, adjusting the concentrations of total nitrogen TN and total phosphorus TP in the mixed culture pond to 800 +/-10 mg/L and 100 +/-10 mg/L respectively, repeating the steps 2) -4), continuously culturing the chlorella, circularly repeating the steps, wherein nutrient elements such as nitrogen, phosphorus and the like in the chicken manure biogas slurry can be recycled for 9-10 times by supplementing nutrient substances such as nitrogen, phosphorus and the like with the hydrothermal liquefaction wastewater, and further increasing the biomass and the biological crude oil by 9-10 times.
Example 2
(1) And clarifying the pig farm water-washed manure wastewater through flocculation precipitation, removing suspended matters in the wastewater through ultrafiltration, and increasing the light transmittance so as to obtain the filtered pig farm water-washed manure wastewater.
Diluting the filtered pig farm water excrement-washing wastewater, wherein the filtered pig farm water excrement-washing wastewater accounts for 5-6% of the total volume of the diluted solution.
Placing the diluted solution into a microalgae culture pond, inoculating the domesticated spirulina into the solution, and culturing in the microalgae culture pond under the illumination condition.
(2) Culturing in a microalgae culture pond until the biomass is 3.5g/L, harvesting spirulina, adjusting the pH of the solution to 7.1 with NaOH, and adjusting the water content of the microalgae to 85 +/-0.2% after harvesting to obtain mud.
(3) And (3) adding 45ml of microalgae mud into a 100ml reaction kettle, and sealing the hydrothermal liquefaction reaction kettle. The initial pressure of the reaction kettle is 1.5MPa, the rotating speed of the stirrer is 350rpm, the reaction kettle is heated to 220-290 ℃, the temperature is kept for 30min, then the heating is stopped, after the reaction kettle is cooled to the room temperature, gas is collected firstly, then the reaction kettle is opened, and CO in a gas-phase product2Over 90% of the total mass of the gas phase product, introducing into a microalgae culture pond to supplement CO2And the carbon source is recycled to provide carbon source for the photosynthesis of the microalgae.
(4) The liquid mixture was collected in a beaker. Separating the liquid mixture by slow qualitative filter paper suction filtration to obtain crude oil and hydrothermal liquefaction wastewater:
a. the crude oil was dissolved with toluene and the solid residue was isolated by filtration. The yield of the biological crude oil is 24.3-26.2%, and the yield of the solid residue is 18.35-20.2%. The solid residue contains Cu 0.056-0.070 mg/g and Cr 0.010-0.016 mg/g.
b. The total nitrogen TN of the hydrothermal liquefaction wastewater is 10000-11000 mg/L, and the total phosphorus TP is 500-700 mg/L. And (3) circularly returning the generated hydrothermal liquefaction wastewater into the microalgae culture pond, mixing the generated hydrothermal liquefaction wastewater with livestock and poultry pig farm wastewater in the microalgae culture pond, adjusting the concentrations of total nitrogen TN and total phosphorus TP in the mixed culture pond to 500 +/-10 mg/L and 60 +/-10 mg/L respectively, repeating the steps 2) -4), continuously culturing the spirulina, circularly repeating the steps, and circularly recycling the nutrient elements such as nitrogen, phosphorus and the like in the pig farm water-washed excrement wastewater for 3-4 times by supplementing nutrient substances such as nitrogen, phosphorus and the like through the hydrothermal liquefaction wastewater, so that the biomass and the biological crude oil are increased by 3-4 times.
Example 3
(1) And clarifying the pig farm water-soaked manure wastewater through flocculation precipitation, removing suspended matters in the wastewater through nanofiltration, and increasing the light transmittance so as to obtain the filtered pig farm water-soaked manure wastewater.
Diluting the filtered pig farm water-soaked manure wastewater, wherein the filtered pig farm water-soaked manure wastewater accounts for 6-7% of the total volume of the diluted solution.
Placing the diluted solution into a microalgae culture pond, inoculating the domesticated Dunaliella salina into the solution, and culturing in the microalgae culture pond under the illumination condition.
(2) Culturing Dunaliella salina in a microalgae culture pond until the biomass is 1.2g/L, harvesting Dunaliella salina, adjusting the pH of the solution in the culture pond to 7.1 by using HCl, and adjusting the water content of the microalgae to 90 +/-0.2% after harvesting to be mud-shaped.
(3) 60ml of microalgae mud is added into a 100ml hydrothermal liquefaction reaction kettle, and the reaction kettle is sealed. The initial pressure of the reaction kettle is 0.5MPa, the rotating speed of the stirrer is 400rpm, the reaction kettle is heated to 290-320 ℃, the temperature is kept for 10-60 min, then the heating of the reaction kettle is stopped, the reaction kettle is cooled to room temperature, gas is collected firstly, then the reaction kettle is opened, and CO in a gas-phase product2Over 90% of the total mass of the gas phase product, introducing into a microalgae culture pond to supplement CO2And the carbon source is recycled to provide carbon source for the photosynthesis of the microalgae.
(4) Collecting the liquid mixture by using a beaker, and performing suction filtration on the liquid mixture by using slow qualitative filter paper to separate the liquid mixture to obtain crude oil and hydrothermal liquefaction wastewater:
a. the crude oil was dissolved with toluene and the solid residue was isolated by filtration. The yield of the biological crude oil is 17.6-19.3%, and the yield of the solid residue is 20.25-23.82%. The solid residue has a Cu content of about 0.156 to 0.172 mg/g;
b. the total nitrogen TN of the hydrothermal liquefaction wastewater is 7000-9000 mg/L, and the total phosphorus TP is 300-500 mg/L. And (3) circularly returning the generated hydrothermal liquefied wastewater into the microalgae culture pond, mixing the generated hydrothermal liquefied wastewater with the water-soaked excrement wastewater in the microalgae culture pond, adjusting the concentration of total nitrogen TN and total phosphorus TP in the liquid in the mixed culture pond to 900 +/-10 mg/L and 200 +/-10 mg/L respectively, repeating the steps 2) -4), continuously culturing the dunaliella salina, and circularly repeating the steps, wherein the nutrient elements such as nitrogen, phosphorus and the like in the water-soaked excrement wastewater of the pig farm can be circularly utilized for 5-6 times by supplementing nutrient substances such as nitrogen, phosphorus and the like through the hydrothermal liquefied wastewater, so that the biomass and the biological crude oil are increased by 5-6 times.
Example 4
(1) Clarifying the pig manure fermentation liquor through flocculation precipitation, removing suspended matters in the wastewater through nanofiltration, and increasing the light transmittance so as to obtain the filtered pig manure fermentation liquor.
Diluting the filtered pig manure fermentation liquor, wherein the filtered pig manure fermentation liquor accounts for 8-9% of the total volume of the diluted solution.
Placing the diluted solution in a microalgae culture pond, inoculating the domesticated mixed microalgae (photosynthetic bacteria, microalgae, aquatic plants and the like) into the solution, and culturing in the microalgae culture pond under the illumination condition.
(2) Adjusting the pH value of the solution in the culture pond to 7.1 by using HCl, harvesting the mixed algae when the biomass is cultured to be 4.5g/L, and adjusting the water content of the microalgae to 75 +/-0.1% after harvesting to be in a mud shape.
(3) And (3) adding 40ml of microalgae mud into a 100ml supercritical reaction kettle, and sealing the reaction kettle. The initial pressure of the reaction kettle is 2.5MPa, the rotating speed of the stirrer is 700rpm, the reaction kettle is heated to 330-360 ℃, the temperature is kept for 5-10 min, and then the heating is stopped. After the reaction kettle is cooled to room temperature, firstly collecting gas, then opening the reaction kettle, and obtaining CO in the gas-phase product2Over 90% of the total mass of the gas phase product, introducing into a microalgae culture pond to supplement CO2And the carbon source is recycled to provide carbon source for the photosynthesis of the microalgae.
(4) The liquid mixture was collected in a beaker. Separating the liquid mixture by slow qualitative filter paper suction filtration to obtain crude oil and hydrothermal liquefaction wastewater:
a. the crude oil was dissolved with acetone and the solid residue was isolated by filtration. The yield of the biological crude oil is 18.3-21.2%, and the yield of the solid residue is 22.35-23.23%. The Cu content in the solid residue is about 0.026-0.050 mg/g;
b. the total nitrogen TN of the hydrothermal liquefaction wastewater is 4000-5000 mg/L, and the total phosphorus TP is 1200-1500 mg/L. And (3) circularly returning the generated hydrothermal liquefaction wastewater to the microalgae culture pond, mixing the generated hydrothermal liquefaction wastewater with the pig manure fermentation liquid in the microalgae culture pond, adjusting the concentration of total nitrogen TN and total phosphorus TP in the mixed culture pond to 300 +/-10 mg/L and 20 +/-1 mg/L respectively, repeating the steps 2) -4), continuously culturing the mixed microalgae, circularly repeating the steps, wherein nutrient elements such as nitrogen, phosphorus and the like in the pig manure fermentation liquid can be recycled for 6-7 times by supplementing nutrient substances such as nitrogen, phosphorus and the like again through the hydrothermal liquefaction wastewater, and further the biomass and the biological crude oil are increased by 6-7 times.
Example 5
(1) And clarifying the wastewater of the dairy farm by flocculation precipitation, removing suspended matters in the wastewater by ultrafiltration, and increasing the light transmittance so as to obtain the filtered wastewater of the dairy farm.
Diluting the filtered dairy farm wastewater, wherein the filtered dairy farm wastewater accounts for 5-7% of the total volume of the diluted solution.
Placing the diluted solution into a microalgae culture pond, inoculating domesticated mixed algae seeds into the solution, screening the mixed algae seeds from a pond near a cattle farm, and culturing in the microalgae culture pond under the illumination condition.
(2) The pH of the water in the culture pond was adjusted to 7.1 with HCl, and the mixed algae was harvested when the biomass was cultured to 2 g/L. After harvesting, adjusting the water content of the microalgae to 90 +/-10 percent to be mud-shaped.
(3) Adding 800ml of microalgae mud into 1800ml of reaction kettle, and sealing the reaction kettle. The initial pressure of the reaction kettle is 1.0MPa, the rotating speed of the stirrer is 750rpm, the reaction kettle is heated to 230-250 ℃, the temperature is kept for 90-120 min, and then the heating is stopped. After the reaction kettle is cooled to room temperature, firstly collecting gas, then opening the reaction kettle, and obtaining CO in the gas-phase product2Over 90% of the total mass of the gas phase product, introducing micro-particlesAlgae culture pond for supplementing CO2And the carbon source is recycled to provide carbon source for the photosynthesis of the microalgae.
(4) Collecting the liquid mixture by using a beaker, and separating the liquid mixture by suction filtration through slow qualitative filter paper to obtain crude oil and hydrothermal liquefaction wastewater:
a. the crude oil was dissolved with diethyl ether and the solid residue was isolated by filtration. The yield of the biological crude oil is 32.6-38.4%, and the yield of the solid residue is 13.55-15.23%. The solid residue contains Cu in an amount of about 0.189 to 0.195 mg/g;
b. the total nitrogen TN of the hydrothermal liquefaction wastewater is 4000-6000 mg/L, and the total phosphorus TP is 2200-2500 mg/L. And (3) circularly returning the generated hydrothermal liquefaction wastewater into the microalgae culture pond, mixing the generated hydrothermal liquefaction wastewater with the dairy farm wastewater in the microalgae culture pond, adjusting the concentration of total nitrogen TN and total phosphorus TP in the mixed culture pond to 800 +/-10 mg/L and 480 +/-10 mg/L respectively, repeating the steps 2) -4), continuously culturing the mixed algae, and circularly repeating the steps, wherein the nutrient elements such as nitrogen, phosphorus and the like in the dairy farm wastewater can be recycled 4-5 times by supplementing nutrient substances such as nitrogen, phosphorus and the like through the hydrothermal liquefaction wastewater, so that the biomass and the biological crude oil are increased by 4-5 times.
Claims (7)
1. A method for value-added utilization of livestock and poultry wastewater environment is characterized by comprising the following steps:
the method comprises the following steps:
1) clarifying the livestock and poultry wastewater through flocculation precipitation, filtering, removing suspended matters in the wastewater, increasing the light transmittance, and further obtaining filtered livestock and poultry wastewater; diluting the filtered livestock and poultry wastewater, wherein the filtered livestock and poultry wastewater accounts for 5-10% of the total volume of the diluted solution, placing the diluted solution into a microalgae culture pond, inoculating the domesticated microalgae into the solution, and culturing in the microalgae culture pond under the illumination condition;
the filtration mode comprises ultrafiltration and nanofiltration; the livestock and poultry wastewater source places comprise breeding wastewater of chicken farms, pig farms and dairy farms and anaerobic fermentation liquor of a methane station, and the type of the livestock and poultry wastewater comprises at least one of livestock and poultry manure, flushing wastewater and livestock and poultry manure fermentation liquor;
2) culturing microalgae: adjusting the pH value of a solution in a microalgae culture pond to 7.1 by using NaOH or HCl until the biomass reaches 0.5-5 g/L, harvesting microalgae, dehydrating and concentrating the harvested microalgae, and adjusting the water content to 75-90%;
3) hydrothermal liquefaction: adding the obtained microalgae into a hydrothermal liquefaction reaction kettle for hydrothermal liquefaction, pressurizing, heating and stirring in the hydrothermal liquefaction process, wherein the initial pressure is 0-2.5 MPa, the rotation speed of a stirrer is 100-800 rpm, the reaction temperature is 200-370 ℃, the residence time is 0-120 min, after the reaction is finished and the gas-phase product is collected, opening the hydrothermal liquefaction reaction kettle, and adding CO in the gas-phase product2The mass of the gas phase product is more than 90 percent of the total mass of the gas phase product, and the gas phase product is introduced into the microalgae culture pond in the step 2 to supplement CO2The carbon source is recycled to provide carbon source for the photosynthesis of the microalgae;
4) and (3) liquid product separation: filtering and separating the liquid mixture product to obtain a crude oil and a water phase product, wherein,
41) dissolving crude oil by using an organic solvent to obtain biological crude oil, wherein residues left after the crude oil is dissolved are solid residues containing Cu, Cr and Pb;
42) the obtained water phase product is hydrothermal liquefaction wastewater, and the total nitrogen content and the total phosphorus content in the hydrothermal liquefaction wastewater are respectively 4000-15000 mg/L and 300-10000 mg/L;
and (3) introducing the hydrothermal liquefied wastewater serving as a nutrient solution into the microalgae culture pond in the step (2) to supplement nitrogen and phosphorus nutrient substances for cyclic utilization, wherein the hydrothermal liquefied wastewater is introduced into the microalgae culture pond to be mixed with the livestock wastewater, the concentration of total nitrogen TN and total phosphorus TP in the microalgae culture pond is adjusted to 200-1000 mg/L and 20-500 mg/L respectively, and the steps (2) -4) are repeated), so that nitrogen and phosphorus nutrient elements in the livestock wastewater can be recycled for 3-10 times by supplementing nitrogen and phosphorus nutrient substances again through the hydrothermal liquefied wastewater.
2. The livestock and poultry wastewater environment value-added utilization method according to claim 1, characterized in that:
in step 2, the microalgae is one of chlorella, spirulina, nannochloropsis, and dunaliella salina.
3. The livestock and poultry wastewater environment value-added utilization method according to claim 1, characterized in that:
in step 2, the microalgae dehydration concentration mode comprises membrane filtration, centrifugation and flocculation.
4. The livestock and poultry wastewater environment value-added utilization method according to claim 1, characterized in that:
in the step 3, the hydrothermal liquefaction reaction kettle is a batch reaction kettle, a semi-continuous reaction kettle or a continuous reaction kettle.
5. The livestock and poultry wastewater environment value-added utilization method according to claim 1, characterized in that:
in step 4, the product separation means comprises filtration, extraction, distillation, centrifugation.
6. The livestock and poultry wastewater environment value-added utilization method according to claim 1, characterized in that:
in step 4, the organic solvent comprises acetone, toluene, and dichloromethane.
7. The livestock and poultry wastewater environment value-added utilization method according to claim 1, characterized in that:
in the step 4, the calorific value of the obtained biological crude oil is 30-40 MJ/kg.
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