Background
As fossil energy is decreasing and the greenhouse effect is increasing due to the use of fossil energy, more and more researchers are focusing on the development and utilization of renewable energy. Biomass can be the most important renewable energy on earth, and comprises forestry biomass, crops, aquatic plants, agricultural wastes and the like. Among the many biomass energy sources, microalgae are important renewable resources. They have the characteristics of wide distribution, large biomass, high photosynthesis efficiency, strong environment adaptability, short growth period, high biomass yield and the like. The cells contain unique primary or secondary metabolites and are chemically complex. The solar energy conversion efficiency of the microalgae can reach 3.5 percent, the microalgae is a potential resource for producing medicines, fine chemicals and novel fuels, and fatty acid obtained from the microalgae can be converted into fatty acid methyl ester, namely biodiesel. Therefore, biodiesel produced using microalgal oil as a feedstock is currently the most likely renewable energy source for fuels needed for world transportation.
With the development of the world economy, the use and consumption of a large amount of fossil energy, resulting in the shortage of energy and the increasing deterioration of the environment, particularly CO2The greenhouse effect is getting more and more serious due to the sharp increase of the amount of the organic compound. Short growth period of microalgae, high photosynthetic efficiency, and CO2High fixing efficiency which is more than 10 times of that of terrestrial plants under certain conditions, and can reduce CO2Discharge and simultaneously reduce the culture cost. CO removal2Besides, some microalgae have tolerance and removal capacity of SOx and NOx, and SOx and NOx in the exhaust gas can be purified along with metabolism of the microalgae, so that the emission of harmful gases is effectively reduced.
CN106467897A discloses a Scenedesmus (Scenedesmus) rich in oilDesmodesmus sp.) MH-04 with the preservation number of CGMCC number 10764. The Scenedesmus can tolerate high concentration of CO2And SO2Can use CO-containing2And SO2The waste gas or the flue gas is subjected to illumination autotrophic growth to obtain biomass, and the carbon sequestration efficiency is high. However, this strain is SO-deprived2Has limited capabilities.
CN109576315A discloses a method for producing microalgae oil by using smoke, firstly adding microalgae culture medium and quasi-chlorella cathayi FSH-Y3 or/and Scenedesmus obliquus FSH-Y2 seed liquid into a photobioreactorAdjusting the pH value to 10-12, and introducing CO2Culturing the smoke with the content of 1-5 v% for a certain time; then adjusting the pH value to 8-10, inoculating a chlorella SF-B1 seed solution, simultaneously inoculating at least one of Scenedesmus MH-04 seed solution and Monostroma SS-B1 seed solution, performing mixed culture, and introducing CO2And (3) culturing the smoke with the content of 5-45 v% to a stable period under the condition of continuous illumination, and harvesting the microalgae cells. The method improves the tolerance to SOx and NOx in the flue gas, can purify the flue gas, and has the NOx removal rate of over 80 percent but limited SOx removal effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for producing microalgae grease by using flue gas. The method improves the microalgae culture system to high-concentration CO2The tolerance and the solubility of the catalyst improve the carbon fixation efficiency, and simultaneously can remove SOx and NOx in the flue gas and purify the flue gas.
The method for producing the microalgae grease by using the flue gas comprises the following steps:
adding microalgae culture medium and Scenedesmus obliquus (Scenedesmus obliquus) (A) into a photobioreactorScenedesmus acutus) HY-D3 seed liquid, and Chlorella (Chlorella)Chlorella sp.) SF-B1 seed liquid, and introducing CO25-45% of volume content and SO2Flue gas with volume content not more than 0.06% and NOx volume content not more than 0.08%, culturing for 12-48 hr, adding Scenedesmus obliquus (Scenedesmus obliquus) (A. obliquus)Scenedesmus obliqnus) And performing mixed culture on the FSH-Y2 seed liquid.
Wherein Scenedesmus (A) and (B)Scenedesmus acutus) The accession number of HY-D3 is CGMCC number 15298; chlorella (Chlorella vulgaris)Chlorella sp.) The preservation number of SF-B1 is CGMCC No. 11005; scenedesmus obliquus (C. obliquus)Scenedesmus obliqnus) The preservation number of FSH-Y2 is CGMCC number 6551.
In the present invention, Scenedesmus (A) isScenedesmus acutus) HY-D3 has been deposited in China general microbiological culture Collection center (CGMCC) No. 15298 at 2018, 2.5.4 and deposited at Beijing Kogyang area, Xilu No.1 Hospital No. 3 of China academy of sciencesThe location was investigated.
In the present invention, the chlorella isChlorella sp.) SF-B1, which has been deposited in the general microbiological center of China Committee for culture Collection of microorganisms (CGMCC) No.11005 at 7/6/2015 with the deposition address of the institute for microbiology, China academy of sciences No. 3, North West Lu No.1 Hospital, Chaoyang, Beijing. Chlorella SF-B1 was filed as published in CN109576158A and submitted for deposit and proof of survival.
In the present invention, the microalgae culture medium is a liquid culture medium for culturing microalgae, such as BG11, SE, BBM, etc., which are well known to those skilled in the art.
The preparation method of the Scenedesmus HY-D3 seed liquid and the chlorella SF-B1 seed liquid comprises the following steps: adjusting the pH value of the culture medium to 7-9, performing shaking culture at the temperature of 20-30 ℃, the illumination period of 24h, the light-dark time ratio of 14:10 and the illumination intensity of 2000-10000 Lux until the logarithmic phase.
In the invention, the volume ratio of the scenedesmus HY-D3 seed solution to the microalgae culture medium added into the photobioreactor is 1: 20-1: 5.
In the invention, the volume ratio of the chlorella SF-B1 seed solution to the microalgae culture medium added into the photobioreactor is 1: 20-1: 5.
In the invention, the flue gas is derived from incineration tail gas, catalytic cracking regeneration tail gas or S-zorb regeneration tail gas of a sulfur recovery device, preferably, CO in the flue gas2The volume content is 10-30 percent, and SO2The volume content is 0.005-0.06%, and the volume content of NOx is 0.005-0.08%.
In the present invention, Scenedesmus obliquus (A), (B), (C) and (C)Scenedesmus obliqnus) FSH-Y2, which has been deposited in China general microbiological culture Collection center (CGMCC) at 11.9.2012, with the preservation number of CGMCC number 6551 and the preservation address of China academy of sciences (Ministry of sciences, China, No. 3, of Xilu 1, Beijing, Chaoyang, and the area of Tokyo. FSH-Y2 was filed as published in CN104611227A and submitted for deposit and proof of survival.
In the invention, the preparation method of the Scenedesmus obliquus FSH-Y2 seed liquid comprises the following steps: adjusting the pH value of the culture medium to 10-12, and carrying out shake culture to logarithmic phase under the conditions that the temperature is 20-30 ℃, the illumination period is 24 hours, the light-dark time ratio is 14:10, and the illumination intensity is 2000-10000 Lux.
In the invention, the volume ratio of the addition amount of the Scenedesmus obliquus FSH-Y2 seed liquid to the microalgae culture medium is 1: 40-1: 20. Preferably, the scenedesmus obliquus FSH-Y2 seed liquid is added to the photobioreactor in batches every 24-72 hours in the culture process, and the adding amount of each time is an average value according to the total adding amount.
In the invention, the temperature of a microalgae culture system is controlled to be 20-35 ℃, the illumination period is 24h, the light-dark time ratio is 14:10, the illumination intensity is 2000-20000 Lux, and the microalgae culture system is cultured until the growth stabilization period is finished. Preferably, the culture process is divided into two stages by taking Scenedesmus obliquus FSH-Y2 as a node, wherein the illumination intensity of the first stage is 2000-6000 Lux, the illumination period is 24h, and the light-dark time ratio is 14: 10; and in the second stage, the illumination intensity is improved by 3000-10000 Lux, and the illumination is continued until the culture is finished, so that the oil content is improved.
In the invention, microalgae cells are harvested by centrifugation, sedimentation and other modes, the dry weight of the cells and the oil content are measured, the dry weight of the cells can reach more than 11g/L, and the oil content can reach more than 46 percent of the dry weight of the cells.
Compared with the prior art, the invention can bring the following beneficial effects:
(1) in the invention, Scenedesmus HY-D3 and chlorella SF-B1 are added simultaneously in the process of producing microalgae oil by using smoke, and the two algae are matched with each other, so that the inhibiting factors in the smoke can be eliminated simultaneously, the carbon sequestration efficiency is higher, and the obtained biomass contains more oil.
(2) In the culture process of Scenedesmus HY-D3, the pH value is in a rising trend along with the culture, the tolerance capacity of Scenedesmus HY-D3 is unstable, Scenedesmus obliquus FSH-Y2 seed liquid is supplemented at certain time intervals under the condition, the improvement of the tolerance of Scenedesmus obliquus HY-D3 is facilitated, oil in algae cells can be stably accumulated, and finally the oil yield is improved.
(3) The mixed culture system can efficiently purify the flue gas, and the carbon dioxide removal rate in the purified flue gas is 50 percentAbove, SO2The removal rate is more than 90%, and the NOx removal rate is more than 80%.
Detailed Description
The present invention will be described in further detail by way of examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the present invention, CO is contained in the gas2、SO2、NOXThe concentration is detected by a flue gas analyzer.
Gas removal rate = (gas concentration at reactor inlet-gas concentration at reactor outlet)/gas concentration at reactor inlet × 100%.
The scenedesmus HY-D3 is a new strain separated and screened by the inventor and is preserved in the China general microbiological culture Collection center; address: the institute of microbiology, national academy of sciences No. 3, Xilu No.1, Beijing, Chaoyang, Beijing; the preservation number is: CGMCC number 15298; the preservation date is as follows: year 2018, month 2 and day 5. Scenedesmus HY-D3 can tolerate high concentration of SO2Can utilize CO in the exhaust gas2Autotrophic growth and CO fixation2And the problem of greenhouse effect brought by the current industrial society is solved. Under a microscope, algae cells are green and are often aggregated into groups, the groups are usually composed of 4-8 cells, and the cells of the groups are arranged in a straight line. The single cells are oval and oval, the single cells are oval, the cell walls are smooth, the single cells are internally provided with melanosomes, each cell contains a protein nucleus, and the length of each single cell is about 3-6 mu m, and the width of each single cell is about 2-3 mu m. The upper and lower ends of the cells on both sides of the population have 1 long or straight or slightly curved spikes, and both ends of the cells in the middle and the side free parts of the cells on both sides have no spikes. 4 cells with a group width of 10-24 microns and a puncture length of 10-13 microns.
BG11 medium was used in the examples of the present invention, and the medium formulations are shown in tables 1 and 2.
TABLE 1 BG11 culture Medium
Table 2 composition of a5+ Co solution in table 1
BG11 liquid medium was prepared according to tables 1 and 2, the pH of the medium for culturing Scenedesmus obliquus FSH-Y2 was adjusted to 10, the pH of the medium for culturing Scenedesmus obliquus HY-D3 and Chlorella vulgaris SF-B1 was adjusted to 8.0, and then Scenedesmus obliquus FSH-Y2, Scenedesmus obliquus HY-D3 and Chlorella vulgaris SF-B1 were inoculated into the above medium, respectively. Culturing in constant temperature light shaking table at 25 deg.C for 24 hr with light-dark time ratio of 14:10 and light intensity of 5000Lux at 120rpm until logarithmic phase to obtain Scenedesmus obliquus FSH-Y2 seed solution, Scenedesmus obliquus HY-D3 seed solution and Chlorella vulgaris SF-B1 seed solution, and storing the seed solutions at 15 deg.C under weak light.
Example 1
Adding 8L BG11 microalgae culture medium, 400mL Scenedesmus HY-D3 seed solution and 400mL Chlorella SF-B1 seed solution into 20L photobioreactor, and introducing CO240 volume percent of NO, 0.08 volume percent of SO2Smoke with the volume content of 0.06 percent is added into 300mL of Scenedesmus obliquus FSH-Y2 seed liquid once after being cultured for 24 hours. The culture temperature of the culture system is controlled at 25 ℃, the illumination period is 24h, the light-dark time ratio is 14:10, and the illumination intensity is 10000 Lux. And (3) finishing the culture after 7 days, centrifuging to collect algae liquid, measuring the dry weight of algae powder after vacuum freeze drying is carried out at the temperature of-60 ℃ to constant weight, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 12.3g/L, and the oil content is 46.5% of the dry cell weight. Detected and calculated, CO2The removal rate is 51.5 percent, and SO2The removal rate was 92.5%, and the NO removal rate was 82.8%.
Example 2
Adding 8L BG11 microalgae culture medium, 800mL Scenedesmus HY-D3 seed solution and 800mL Chlorella SF-B1 seed solution into 20L photobioreactor, and introducing CO240 volume percent of NO, 0.08 volume percent of SO2Smoke with the volume content of 0.06 percent is added into 200mL of Scenedesmus obliquus FSH-Y2 seed liquid once after culturing for 12 h. The culture temperature of the culture system is controlled to be 35 ℃, the illumination period is 24h, the light-dark time ratio is 14:10, and the illumination intensity is 10000 Lux. And (3) finishing the culture after 7 days, centrifuging to collect algae liquid, measuring the dry weight of algae powder after vacuum freeze drying is carried out at the temperature of-60 ℃ to constant weight, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 12.5g/L, and the oil content is 47.5 percent of the dry cell weight. Detected and calculated, CO2The removal rate is 52.3 percent, and SO2The removal rate was 93.2% and the NO removal rate was 83.1%.
Example 3
Adding 8L BG11 microalgae culture medium, 600mL Scenedesmus HY-D3 seed solution and 200mL Chlorella SF-B1 seed solution into 20L photobioreactor, and introducing CO240 volume percent of NO, 0.08 volume percent of SO2Smoke with the volume content of 0.06 percent is added into 400mL of Scenedesmus obliquus FSH-Y2 seed liquid once after culturing for 48 hours. The culture temperature of the culture system is controlled to be 20 ℃, the illumination period is 24h, the light-dark time ratio is 14:10, and the illumination intensity is 10000 Lux. And (3) finishing the culture after 7 days, centrifuging to collect algae liquid, measuring the dry weight of algae powder after vacuum freeze drying is carried out at the temperature of-60 ℃ to constant weight, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 12.1g/L, and the oil content is 46.2% of the dry cell weight. Detected and calculated, CO2The removal rate is 51.1 percent, and SO2The removal rate was 91.8%, and the NO removal rate was 81.7%.
Example 4
Adding 8L BG11 microalgae culture medium, 400mL Scenedesmus HY-D3 seed solution and 400mL Chlorella SF-B1 seed solution into 20L photobioreactor, and introducing CO240 volume percent of NO, 0.08 volume percent of SO2The volume content is 0.06% smoke, 50mL of Scenedesmus obliquus FSH-Y2 seed solution was added every 24h, for a total of 300 mL. The culture temperature of the culture system is controlled at 25 ℃, the illumination period is 24h, the light-dark time ratio is 14:10, and the illumination intensity is 10000 Lux. And (3) finishing the culture after 7 days, centrifuging to collect algae liquid, measuring the dry weight of algae powder after vacuum freeze drying is carried out at the temperature of-60 ℃ to constant weight, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 13.3g/L, and the oil content is 48.1 percent of the dry cell weight. Detected and calculated, CO2The removal rate is 54.1 percent, and SO2The removal rate was 93.3% and the NO removal rate was 84.6%.
Example 5
Adding 8L BG11 microalgae culture medium, 400mL Scenedesmus HY-D3 seed solution and 400mL Chlorella SF-B1 seed solution into 20L photobioreactor, and introducing CO240 volume percent of NO, 0.08 volume percent of SO2Smoke with volume content of 0.06 percent is added with 100mL of scenedesmus obliquus FSH-Y2 seed liquid every 48 hours, and 300mL is added totally. The culture temperature of the culture system is controlled at 25 ℃, the illumination period is 24h, the light-dark time ratio is 14:10, and the illumination intensity is 10000 Lux. And (3) finishing the culture after 7 days, centrifuging to collect algae liquid, measuring the dry weight of algae powder after vacuum freeze drying is carried out at the temperature of-60 ℃ to constant weight, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 13.2g/L, and the oil content is 47.9 percent of the dry cell weight. Detected and calculated, CO2The removal rate is 53.9 percent, SO2The removal rate was 93.1%, and the NO removal rate was 84.0%.
Example 6
Adding 8L BG11 microalgae culture medium, 400mL Scenedesmus HY-D3 seed solution and 400mL Chlorella SF-B1 seed solution into 20L photobioreactor, and introducing CO230 volume percent of NO, 0.04 volume percent of SO2Smoke with the volume content of 0.03 percent is added into 300mL of Scenedesmus obliquus FSH-Y2 seed liquid once after being cultured for 24 hours. The culture temperature of the culture system is controlled at 25 ℃, the illumination period is 24h, the light-dark time ratio is 14:10, and the illumination intensity is 10000 Lux. Culturing for 7 days, centrifuging to collect algae liquid, and culturing at-60 deg.CAnd (4) measuring the dry weight of the algae powder after vacuum freeze drying to constant weight, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 13.1g/L, and the oil content is 47.5 percent of the dry cell weight. Detected and calculated, CO2The removal rate is 65.1 percent, and SO2The removal rate was 95.3%, and the removal rate of NO was 88.8%.
Example 7
Adding 8L BG11 microalgae culture medium, 400mL Scenedesmus HY-D3 seed solution and 400mL Chlorella SF-B1 seed solution into 20L photobioreactor, and introducing CO240 volume percent of NO, 0.08 volume percent of SO2Smoke with the volume content of 0.06 percent, the culture temperature of a culture system is controlled to be 25 ℃, the illumination period is 24 hours, the light-dark time ratio is 14:10, and the illumination intensity is 5000 Lux; after 24h of culture, 300mL of Scenedesmus obliquus FSH-Y2 seed liquid is added at one time, the illumination intensity is increased by 10000Lux, and the illumination is continued until the culture is finished. And (3) finishing the culture after 7 days, centrifuging to collect algae liquid, measuring the dry weight of algae powder after vacuum freeze drying is carried out at the temperature of-60 ℃ to constant weight, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 12.9g/L, and the oil content is 48.5% of the dry cell weight. Detected and calculated, CO2The removal rate is 51.6 percent, and SO2The removal rate was 92.7%, and the NO removal rate was 83.1%.
Comparative example 1
The difference from example 1 is that: seed liquid without Chlorella SF-B1 added. After 7 days of culture, the dry weight of the cells can reach 10.8g/L after detection, and the oil content is 45.7 percent of the dry weight of the cells. Detected and calculated, CO2The removal rate is 50.6 percent, and SO2The removal rate was 90.5%, and the removal rate of NO was 10.1%.
Comparative example 2
The same as example 1, except that: no Scenedesmus HY-D3 seed solution was added. After 7 days of culture, the dry weight of the cells can reach 10.2g/L after detection, and the oil content is 43.4 percent of the dry weight of the cells. Detected and calculated, CO2The removal rate is 50.7 percent, SO2The removal rate is 50.5%, and the removal rate of NO is 80.1%.
Comparative example 3
The same as example 1, except that: scenedesmus obliquus FSH-Y2 was not added. After 7 days of culture, the dry weight of the cells can reach 11.5g/L after detection, and the oil content is 44.6 percent of the dry weight of the cells. Detected and calculated, CO2The removal rate is 51.7 percent, and SO2The removal rate is 85.5 percent, and the removal rate of NO is 82.1 percent.
Comparative example 4
The difference from example 1 is that: scenedesmus MH-04 with preservation number CGMCC No.10764 as CN106467897A is used to replace Scenedesmus HY-D3. After detection, the dry cell weight can reach 12.0g/L, and the oil content is 45.6% of the dry cell weight. Detected and calculated, CO2The removal rate is 51.7 percent, and SO2The removal rate was 60.5%, and the NO removal rate was 78.7%.
Comparative example 5
The difference from example 1 is that: adopts the unicladium SS-B1 with the preservation number of CGMCC No.7479 described in CN104611228A to replace scenedesmus HY-D3. After detection, the dry cell weight can reach 10.4g/L, and the oil content is 44.6% of the dry cell weight. Detected and calculated, CO2The removal rate is 50.7 percent, and SO2The removal rate was 65.5%, and the NO removal rate was 79.1%.
Comparative example 6
The same as example 1, except that: adopts the fibrophyta SS-B7 described in CN105713836A, the preservation number is CGMCC No.7478 to replace Scenedesmus SF-B1. After detection, the dry cell weight can reach 11.8g/L, and the oil content is 45.7% of the dry cell weight. Detected and calculated, CO2The removal rate is 51.7 percent, and SO2The removal rate is 90.3%, and the removal rate of NO is 20.3%.