CN113321312B - High concentration of CO 2 Method for atmosphere domestication of microalgae high ammonia nitrogen resistant biogas slurry - Google Patents
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Abstract
The invention discloses high concentration CO 2 The method for atmosphere domestication of high ammonia nitrogen resistant biogas slurry of microalgae is characterized by comprising the following steps: step one, algae seed collection and culture: collecting microalgae in a water area near a farm needing to treat biogas slurry, and culturing the microalgae; step two, microalgae enrichment culture: inoculating the microalgae solution obtained in the step one and the biogas slurry of a farm in a photobioreactor according to a certain proportion, and culturing under a proper condition, wherein CO is continuously introduced during culturing 2 Mixing the gas; step three, microalgae domestication: inoculating the microalgae solution obtained in the step two and the biogas slurry in the farm according to a certain proportion into a photobioreactor, and culturing under a proper condition, wherein CO is continuously introduced during culturing 2 Mixing the gas; step four, carrying out low-speed centrifugation treatment on the microalgae liquid obtained in the step three, and inoculating microalgae seeds at the bottom of a centrifugal tube and the biogas slurry in a farm to obtain finally domesticated high ammonia nitrogen resistant algae seeds; the invention can be widely applied to the fields of breeding industry, environmental protection and the like.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to high-concentration CO 2 A method for acclimatizing microalgae high ammonia nitrogen resistant biogas slurry.
Background
With the development of science and the progress of society, the living standard of people is continuously improved, the demand of people for meat food is increased day by day, and the livestock and poultry industry is developed in a large scale. However, the large-scale development of the livestock and poultry industry also brings a series of environmental problems. A large amount of sewage with high ammonia nitrogen, high COD and rich phosphorus needs to reach the discharge standard urgently, the instability of the water quality and the odor bring huge pressure to the environment, and the work of wastewater treatment faces more serious challenges.
Microalgae is a sewage purification organism with great potential, and can utilize nutrient substances such as ammonia nitrogen, phosphorus and the like in the livestock and poultry breeding sewage to grow so as to achieve the aim of purifying the sewage, so that the wastewater can be purified by culturing the microalgae. At the present stage, microalgae used by researchers for sewage treatment are generally pure algae cultured in laboratories, but the pure algae cannot be well adapted to complicated and variable biogas slurry environments with severe conditions, the sewage purification effect is not satisfactory, and the stability of the pure algae is greatly deficient when the pure algae is used for treating wastewater with high ammonia nitrogen and high concentration fluctuation. Based on the invention, natural microalgae are directly collected in a water area near a farm as the algae for treating biogas slurry. The water areas near the culturing farm are polluted by the biogas slurry of the culturing farm to different degrees, and can be approximately regarded as the biogas slurry diluted by many times, so that the microalgae growing in the water areas for a long time are adapted to the environment and have great potential for decomposing pollutants in the biogas slurry. In addition, the microalgae may be a collection of algal groups, and may also contain certain fungi. The fungi have certain protection and buffering effects on the wrapping of the microalgae, so that the microalgae has stronger adaptability to complex and variable environments, the characteristics of the microalgae adapting to the pig raising wastewater are facilitated, and higher denitrification and dephosphorization effects can be achieved. Therefore, the microalgae in the water area near the farm can be selected as the algae for treating the biogas slurry.
The problem that microalgae in a water area near a farm cannot adapt to a high ammonia nitrogen environment is also faced when the microalgae is used as the algae to treat biogas slurry. The pig farm wastewater has the characteristics of high concentration of organic matters and suspended matters, high ammonia nitrogen concentration, high treatment difficulty and the like, and although nutrient substances such as the rich ammonia nitrogen in the pig farm wastewater can be utilized by the growth of microalgae, researches show that when the concentration of the ammonia nitrogen exceeds 900mg/L, the growth of the microalgae can be obviously inhibited, and even death is caused. This is because too high a concentration of ammonia nitrogen will produce more ammonium ions that cannot be rapidly transferred to the synthesis of amino acids, resulting in retarded growth or death of the microalgae. At present, the anaerobic-aerobic combined process is a traditional treatment mode adopted by the wastewater of the large-scale pig farm in China, and the biogas slurry fermented by the method still contains high-concentration nutrient substances such as nitrogen and phosphorus, wherein the concentration of ammonia nitrogen can reach 17-2050 mg/L, the content of COD (chemical oxygen demand) is 1100-7100 mg/L, the content of total phosphorus is 2-300 mg/L, and the total phosphorus content is far higher than the water pollutant discharge standard GB 18596-2001 of livestock and poultry breeding industry in China (the concentration of ammonia nitrogen is less than 80mg/L, the content of COD is less than 400mg/L, and the total phosphorus is less than 8 mg/L). The ammonia nitrogen concentration of the fermented biogas slurry can still exceed 900mg/L, and the growth of microalgae can still be inhibited. Microalgae in a water area near a farm adapts to the environment of the biogas slurry pollutants, but the adapted concentration is very low and cannot reach the level of directly treating the biogas slurry, but the ammonia nitrogen tolerance of the microalgae can be trained in a mode of gradually increasing the concentration of the biogas slurry. The method improves the tolerance of microalgae to ammonia nitrogen by gradually improving the concentration gradient domestication of the biogas slurry, so that the microalgae adapts to a high ammonia nitrogen biogas slurry environment.
The problem of inhibition of microalgae on high ammonia nitrogen biogas slurry can be solved by adopting a gradient domestication mode, but the growth of microalgae needs to provide a corresponding carbon source. The content of carbon in microalgae cells reaches more than 50 percent, but the biogas slurry is only rich in nitrogen, phosphorus and other elements, and the content of carbon is low, so that the requirement of microalgae growth cannot be metAnd (4) demand. The waste water is treated by the traditional fermentation mode, a large amount of methane can be generated, the common utilization mode of the methane is direct combustion power generation, and the combustion of the methane can bring a large amount of high-concentration CO 2 Contaminated flue gas of containing CO 2 The flue gas is the optimal selection of the carbon source of the microalgae.
The microalgae in the invention can purify water by using pollutants such as ammonia nitrogen, phosphorus and the like in biogas slurry and can absorb CO in biogas combustion flue gas 2 And the mature microalgae can be processed after being harvested to obtain the algae-based multifunctional product. High concentration of CO 2 The method for acclimatizing the microalgae high ammonia nitrogen resistant biogas slurry has wide prospect in engineering application.
Disclosure of Invention
The technical problem to be solved by the invention is to provide high-concentration CO 2 A method for acclimatizing microalgae high ammonia nitrogen resistant biogas slurry.
The technical scheme of the invention is as follows: high concentration of CO 2 The method for acclimatizing microalgae high ammonia nitrogen resistant biogas slurry in atmosphere is characterized by comprising the following steps:
step one, algae seed collection and culture: collecting microalgae in a water area near a farm needing biogas slurry treatment, and culturing the microalgae;
step two, microalgae enrichment culture: inoculating the microalgae solution obtained in the step one and the biogas slurry of a farm in a photobioreactor according to a certain proportion, and culturing under a proper condition, wherein CO is continuously introduced during culturing 2 Mixing the gas;
step three, microalgae domestication: inoculating the microalgae solution obtained in the step two and the biogas slurry of the farm into a photobioreactor according to a certain proportion, placing the photobioreactor into a proper condition for culture, and continuously introducing CO during culture 2 Mixing the gas;
step four, carrying out low-speed centrifugation treatment on the microalgae liquid obtained in the step three, inoculating microalgae seeds and the livestock farm biogas liquid at the bottom of a centrifugal tube into a serum bottle, placing the serum bottle in a constant-temperature greenhouse for culture, and continuously and quantitatively introducing CO during culture 2 And (3) supplying the mixed gas to a carbon source to obtain the final domesticated high ammonia nitrogen resistant algae.
High concentration of CO according to the invention 2 Preferred scheme of method for atmosphere domestication of microalgae high ammonia nitrogen resistant biogas slurry, and culturing farm biogas slurry and CO-containing biogas slurry in steps two, three and four 2 The mixed gas is prepared by the following steps:
A. anaerobic fermentation is carried out on the waste water of the farm to obtain biogas and biogas slurry of the farm;
B. burning the marsh gas to obtain electric energy and CO 2 Mixing the gas.
High concentration CO according to the invention 2 The method for atmosphere domestication of the microalgae high ammonia nitrogen resistant biogas slurry has the beneficial effects that: the invention takes the natural microalgae in the water area around the farm to perform gradient acclimation treatment on the sewage, and continuously passes high-concentration CO 2 The purpose of deep purification of the sewage is achieved under the condition of (1), and the effect is obvious; the invention also utilizes high-concentration CO brought by the combustion of marsh gas generated by sewage fermentation 2 The flue gas is used as a carbon source, so that the treatment cost is reduced, and CO in the flue gas is treated 2 Besides, the invention can be widely applied to the fields of breeding industry, environmental protection and the like.
Drawings
FIG. 1 is a schematic view of a wastewater treatment process in a farm.
FIG. 2 shows high concentration CO according to the present invention 2 A flow schematic diagram of a method for acclimatizing microalgae high ammonia nitrogen resistant biogas slurry in atmosphere.
FIG. 3 is a statistical chart of ammonia nitrogen removal in examples 1, 2 and 3.
Detailed Description
The technical scheme of the invention is further explained in detail by combining the drawings and the concrete implementation examples. However, it should be noted that the present invention is not limited to the following embodiments.
Referring to FIGS. 1 and 2, high concentration CO 2 The method for acclimatizing microalgae high ammonia nitrogen resistant biogas slurry in atmosphere comprises the following steps:
step one, algae seed collection and culture: collecting microalgae in a water area near a farm needing biogas slurry treatment, and culturing the microalgae;
step two, microalgae enrichment culture: microalgae obtained in the first stepInoculating the liquid and the biogas slurry in a certain proportion into a photobioreactor, culturing under appropriate conditions while continuously introducing CO 2 Mixing the gas;
step three, microalgae domestication: inoculating the microalgae solution obtained in the step two and the biogas slurry of the farm into a photobioreactor according to a certain proportion, placing the photobioreactor into a proper condition for culture, and continuously introducing CO during culture 2 Mixing the gas;
step four, carrying out low-speed centrifugation treatment on the microalgae liquid obtained in the step three, inoculating microalgae seeds and the livestock farm biogas liquid at the bottom of a centrifugal tube into a serum bottle, placing the serum bottle in a constant-temperature greenhouse for culture, and continuously and quantitatively introducing CO during culture 2 And (3) supplying the mixed gas to a carbon source to obtain the final domesticated high ammonia nitrogen resistant algae.
In a specific embodiment, the biogas slurry and the CO-containing biogas slurry in the culturing farm in the second, third and fourth steps 2 The mixed gas is prepared by the following steps:
A. anaerobic fermentation is carried out on the waste water of the farm to obtain biogas and biogas slurry of the farm;
B. burning the marsh gas to obtain electric energy and CO 2 And (4) mixing the gases.
Example 1 high concentration of CO 2 The method for acclimatizing microalgae high ammonia nitrogen resistant biogas slurry in atmosphere comprises the following steps:
step 1: collecting and culturing algae
(1) Collection of algal species
Although the wastewater components in the pig farm plants are approximately the same, the wastewater components are different to some extent, and the microalgae groups most suitable for the wastewater characteristics should be present for the differences. The method directly collects and cultures the microalgae in the water area near the pig farm which needs to treat biogas slurry, and the microalgae can be an aggregate of various algal groups and can also contain certain fungi. The method is favorable for the characteristics of the microalgae which are suitable for the pig raising wastewater, and can achieve higher denitrification and dephosphorization effects.
(2) The culture conditions are as follows: the temperature is 20-30 ℃, the illumination is 80-170 mu mol/(m < 2 >. S), the pH value is 6-10, and the growth period is 5-12 days.
Step 2: enrichment culture
Inoculating the natural microalgae algae solution obtained in the step 1 and the piggery biogas in a serum bottle according to the volume ratio of 1 (the pig raising wastewater accounts for 50%) and placing the bottle in a constant-temperature greenhouse for culturing, wherein the culture temperature is set to be 20-30 ℃, and the illumination is set to be 80-170 [ mu ] mol/(m) mol 2 S) with constant quantitative introduction of CO 2 The carbon source was supplied with the mixed gas, and the algal solution was mixed, and the culture period was 6 days. 50 percent of pig wastewater is purified by microalgae, the COD content in the effluent is 230mg/L, (the discharge standard GB 18596-2001 of water pollutants for livestock and poultry farming in China) is 400 mg/L), the removal rate is 65.1 percent, and NH is added 3 The removal rates of-N and TP reached 94% and 53.8%, respectively.
The step not only enriches the microalgae, but also has certain screening and domestication effects.
And step 3: microalgae domestication
Inoculating the microalgae solution obtained in the step 2 and the hogpen biogas slurry into a serum bottle according to the volume ratio of 1 to 3 (the waste water in the farm accounts for 75 percent), and placing the bottle in a constant-temperature greenhouse for culturing, wherein the culture temperature is set to be 20-30 ℃, and the illumination is set to be 80-170 [ mu ] mol/(m) mol 2 S) with constant quantitative introduction of CO 2 The carbon source was supplied with the mixed gas, and the culture period was 7 days. 75 percent of the pig raising wastewater is decomposed by microalgae to obtain COD and NH in the effluent 3 The removal rates of-N and TP reach 86.7%, 98.5% and 100% respectively.
And 4, step 4: taking the microalgae liquid obtained in the step (3) for low-speed centrifugation treatment, taking microalgae seeds at the bottom of a centrifuge tube and a serum bottle inoculated with the biogas slurry in a farm (the culture wastewater accounts for 100%), placing the microalgae seeds and the biogas slurry in a constant-temperature greenhouse for culture, setting the culture temperature to be 20-30 ℃ and setting the illumination to be 80-170 [ mu ] mol/(m & lt/& gt) 2 S) with constant quantitative introduction of CO 2 Supplying carbon source to the mixed gas, mixing the algae solution, and culturing for 7 days to obtain final domesticated algae. 100 percent of the aquaculture wastewater is decomposed by microalgae, and COD and NH in the effluent 3 The removal rates of-N and TP reached 84.5%, 86.4% and 100%, respectively.
Example 2 high concentration of CO 2 Atmosphere domestication microalgae toleranceThe method for producing high ammonia nitrogen biogas slurry comprises the following steps:
step 1: collecting and culturing conditions of algae
Directly collecting microalgae in a water area near a cultivation plant which needs to treat biogas slurry for cultivation, wherein the cultivation conditions are as follows: the temperature is 20-30 ℃, and the illumination is 80-170 mu mol/(m) 2 S), pH 6 to 10, growth cycle 5 to 12 days.
And 2, step: enrichment culture
Inoculating the natural microalgae algae solution and the piggery biogas slurry in the step 1 into a serum bottle according to the volume ratio of 1 (the pig raising wastewater accounts for 50 percent), placing the bottle into a constant-temperature greenhouse for culturing, wherein the culture temperature is set to be 20-30 ℃, and the illumination is set to be 80-170 [ mu ] mol/(m) mol 2 S) with constant quantitative introduction of CO 2 The carbon source was supplied with the mixed gas, and the algal solution was mixed, and the culture period was 6 days. 50 percent of the pig raising wastewater is decomposed by microalgae, and COD and NH in the effluent 3 The removal rates of-N and TP reach 63.3%, 88.2% and 60%, respectively.
The step not only enriches the microalgae, but also has certain screening and domestication effects.
And 3, step 3: microalgae domestication
Inoculating the microalgae solution obtained in the step 2 and the hogpen biogas slurry into a serum bottle according to the volume ratio of 1 to 3 (the swine wastewater accounts for 75 percent), and placing the bottle in a constant-temperature greenhouse for culturing, wherein the culture temperature is set to be 20-30 ℃, and the illumination is set to be 80-170 [ mu ] mol/(m) mol 2 S) with constant quantitative introduction of CO 2 The carbon source was supplied with the mixed gas, and the algal solution was mixed, and the culture period was 7 days. 75 percent of the pig raising wastewater is decomposed by microalgae to obtain COD and NH in the effluent 3 The removal rates of-N and TP reach 89.9%, 82.7% and 100% respectively.
And 4, step 4: taking the microalgae liquid obtained in the step (3) for low-speed centrifugation treatment, taking microalgae seeds at the bottom of a centrifuge tube and the biogas slurry in a farm to inoculate into a serum bottle (pig breeding wastewater accounts for 100 percent), and placing the bottle in a constant-temperature greenhouse for culture, wherein the culture temperature is set to be 20-30 ℃, and the illumination is set to be 80-170 mu mol/(m mol) 2 S) with constant quantitative introduction of CO 2 The mixed gas supplies a carbon source, the algae liquid is mixed,culturing for 5-12 days to obtain the final domesticated algae. Decomposing 100 percent of pig raising wastewater by microalgae to obtain COD and NH in effluent 3 The removal rates of-N and TP reach 92%, 89.7% and 100% respectively.
Example 3 high concentration of CO 2 The method for acclimatizing microalgae high ammonia nitrogen resistant biogas slurry in atmosphere comprises the following steps:
step 1: collecting and culturing algae
Directly collecting microalgae in a water area near a cultivation plant needing biogas slurry treatment for cultivation, wherein the cultivation conditions are as follows: the temperature is 20-30 ℃, and the illumination is 80-170 mu mol/(m) 2 S), pH 6 to 10, growth cycle 5 to 12 days.
Step 2: enrichment culture
Inoculating the natural microalgae algae solution and the pig farm biogas slurry in the step 1 into a serum bottle according to the volume ratio of 1 (pig raising wastewater accounts for 50 percent), placing the serum bottle into a constant temperature greenhouse for culturing, wherein the culture temperature is set to be 20-30 ℃, and the illumination is set to be 80-170 [ mu ] mol/(m & lt/m & gt) 2 S) and continuously and quantitatively feeding a CO 2-containing mixed gas to supply a carbon source, and mixing the algae solution, wherein the culture period is 6 days. 50 percent of the pig raising wastewater is decomposed by microalgae, and COD and NH in the effluent 3 The removal rates of-N and TP reach 56.9%, 87.4% and 96.1%, respectively.
The step not only enriches the microalgae, but also has certain screening and domestication effects.
And step 3: microalgae domestication
Inoculating the microalgae solution obtained in the step 2 and the hogpen biogas slurry into a serum bottle according to the volume ratio of 1 to 3 (the pig raising wastewater accounts for 75 percent), and placing the bottle in a constant-temperature greenhouse for culturing, wherein the culture temperature is set to be 20-30 ℃, and the illumination is set to be 80-170 [ mu ] mol/(m ] mol 2 S) with continuous quantitative introduction of CO 2 The carbon source was supplied with the mixed gas, and the algal solution was mixed, and the culture period was 6 days. 75 percent of the pig raising wastewater is decomposed by microalgae to obtain COD and NH in the effluent 3 The removal rates of-N and TP reach 70%, 98.7% and 100% respectively.
Step 4, the microalgae liquid obtained in the step 3 is taken for low-speed centrifugation treatment, and the microalgae seeds at the bottom of a centrifuge tube and the piggery marsh are takenInoculating the solution into a serum bottle (the pig raising wastewater accounts for 100 percent), and culturing in a constant temperature greenhouse at the culture temperature of 20-30 ℃ and the illumination of 80-170 mu mol/(m) 2 S) and continuously and quantitatively feeding a CO 2-containing mixed gas to supply a carbon source, mixing the algae solution, and culturing for 7 days to obtain the final domesticated algae. Decomposing 100 percent of pig raising wastewater by microalgae to obtain COD and NH in effluent 3 The removal rates of-N and TP reached 84.5%, 86% and 100%, respectively.
Referring to fig. 3, the method of the invention has the advantages of low cost, simple operation, good denitrification and dephosphorization effect and extremely high success rate. While treating the biogas slurry wastewater, the device can also absorb CO generated by the combustion of biogas generated in the fermentation process 2 。
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (2)
1. High concentration of CO 2 The method for acclimatizing microalgae high ammonia nitrogen resistant biogas slurry in atmosphere is characterized by comprising the following steps:
step one, algae seed collection and culture: collecting microalgae in a water area near a farm needing to treat biogas slurry, and culturing the microalgae;
step two, microalgae enrichment culture: inoculating the microalgae solution obtained in the step one and the biogas slurry of a farm in a photobioreactor according to a certain proportion, and culturing under a proper condition, wherein high-concentration CO is continuously introduced during culturing 2 Flue gas;
step three, microalgae domestication: inoculating the microalgae solution obtained in the step two and the biogas slurry in the farm according to a certain proportion into a photobioreactor, and culturing under a proper condition, wherein high-concentration CO is continuously introduced during culturing 2 Flue gas;
step four, carrying out low-speed centrifugation treatment on the microalgae liquid obtained in the step three, and inoculating the microalgae seeds and the livestock farm biogas liquid at the bottom of a centrifugal tube to serumPlacing the serum bottle in a constant temperature greenhouse for culturing, and continuously and quantitatively introducing high concentration CO during culturing 2 And supplying the carbon source to the flue gas to obtain the finally domesticated high ammonia nitrogen resistant algae.
2. The high concentration CO of claim 1 2 The method for atmosphere domestication of high ammonia nitrogen resistant biogas slurry of microalgae is characterized by comprising the following steps: biogas slurry and high-concentration CO in culturing farms in the second, third and fourth steps 2 The flue gas is prepared by the following steps:
A. anaerobic fermentation is carried out on the waste water of the farm to obtain methane and the biogas slurry of the farm;
B. burning the marsh gas to obtain electric energy and high-concentration CO 2 Flue gas.
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