CN114480367B - Electrochemical promotion of high concentration CO in nannochloropsis immobilization flue gas 2 Is a method of (2) - Google Patents
Electrochemical promotion of high concentration CO in nannochloropsis immobilization flue gas 2 Is a method of (2) Download PDFInfo
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- CN114480367B CN114480367B CN202210107541.9A CN202210107541A CN114480367B CN 114480367 B CN114480367 B CN 114480367B CN 202210107541 A CN202210107541 A CN 202210107541A CN 114480367 B CN114480367 B CN 114480367B
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- 241000224474 Nannochloropsis Species 0.000 title claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000003546 flue gas Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 48
- 241000195493 Cryptophyta Species 0.000 claims abstract description 40
- 239000001963 growth medium Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000002028 Biomass Substances 0.000 claims abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 12
- 239000004917 carbon fiber Substances 0.000 claims abstract description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 8
- 230000012010 growth Effects 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 238000005286 illumination Methods 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- 230000006872 improvement Effects 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000002835 absorbance Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000013535 sea water Substances 0.000 claims description 9
- 229910021654 trace metal Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 6
- 238000003306 harvesting Methods 0.000 claims description 6
- 238000011081 inoculation Methods 0.000 claims description 6
- 238000012258 culturing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 238000002703 mutagenesis Methods 0.000 claims description 4
- 231100000350 mutagenesis Toxicity 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 230000009261 transgenic effect Effects 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 229930003451 Vitamin B1 Natural products 0.000 claims description 3
- 229930003779 Vitamin B12 Natural products 0.000 claims description 3
- 229960002685 biotin Drugs 0.000 claims description 3
- 235000020958 biotin Nutrition 0.000 claims description 3
- 239000011616 biotin Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229960003495 thiamine Drugs 0.000 claims description 3
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 235000010374 vitamin B1 Nutrition 0.000 claims description 3
- 239000011691 vitamin B1 Substances 0.000 claims description 3
- 235000019163 vitamin B12 Nutrition 0.000 claims description 3
- 239000011715 vitamin B12 Substances 0.000 claims description 3
- 230000003698 anagen phase Effects 0.000 claims 1
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 claims 1
- 238000004659 sterilization and disinfection Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 abstract description 2
- 230000009919 sequestration Effects 0.000 abstract description 2
- 238000009630 liquid culture Methods 0.000 abstract 1
- 238000011160 research Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- 241000163984 Acutodesmus Species 0.000 description 1
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 1
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- 241000168517 Haematococcus lacustris Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 235000013793 astaxanthin Nutrition 0.000 description 1
- 239000001168 astaxanthin Substances 0.000 description 1
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 1
- 229940022405 astaxanthin Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004520 electroporation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N linoleic acid group Chemical class C(CCCCCCC\C=C/C\C=C/CCCCC)(=O)O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- -1 salt ions Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N13/00—Treatment of microorganisms or enzymes with electrical or wave energy, e.g. magnetism, sonic waves
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/12—Unicellular algae; Culture media therefor
Abstract
The invention relates to biomass energy utilization technology, and aims to provide an electrochemical promotion method for fixing high-concentration CO in flue gas by using nannochloropsis 2 Is a method of (2). Comprising the following steps: etching the conductive carbon fiber felt at high temperature to remove impurities, soaking the conductive carbon fiber felt in a mixed aqueous solution of 2-methylimidazole and cobalt nitrate, and growing Co-MOF; then circulating and aging in an electrochemical system to prepare a NiCoS-LDH coating; inoculating the original algae liquid of the nannochloropsis into a culture medium, and immersing a carbon felt as the anode and cathode of an electrochemical system of the nannochloropsis; continuous CO-containing feed 2 Algae liquid culture is carried out on the flue gas of the microalgae, and the accumulated biomass dry weight is obtained by utilizing the OD750 difference before and after culture so as to calculate the fixed CO of the nannochloropsis 2 Rate. The invention can effectively improve the high-concentration CO of the flue gas of the nannochloropsis in the power plant by an electrochemical treatment method 2 Lower growth carbon sequestration rate.
Description
Technical Field
The invention relates to biomass energy utilization technology, in particular to an electrochemical promotion method for fixing high-concentration CO in flue gas by nannochloropsis 2 Is a method of (2).
Background
The serious impact of the greenhouse effect has led to an increasing concern over CO 2 Emission reduction problem, CO in the atmosphere at present 2 The concentration has gradually increased>400ppm. The microalgae grow and reproduce rapidly, and a large amount of CO is consumed in the photosynthesis process 2 Therefore, the microalgae are utilized to fix CO in the flue gas of the coal-fired power plant 2 And has become a research hotspot in recent years. The economic cost for cultivating microalgae by utilizing waste water and waste gas is low, and the CO in the flue gas can be efficiently fixed 2 The microalgae biomass with higher economic value is obtained while the environmental benefit is obtained, and the method has important significance for developing new energy and low-carbon economy.
In recent years, the incoming call processing technology is increasingly applied to the technical field of microorganisms. Various methods of electrical treatment, including electrolysis and electrical stimulation, have been successfully applied to bacterial biotechnology systems to increase biomass production of high value added products. However, microalgae electrotreatment techniques have limited research and application, mainly focused on the collection of microalgae metabolites and products or electroporation. La et al applied a 10kV periodic PEF pulse (2/60 s on/off cycle for 15 minutes, 6 times per day for 5 days) to Acutodesmus dimorphus under air conditions, which showed a 28.8% increase in lipid production, but no significant increase in the algae growth rate. Kim et al, after 1 minute of electrical treatment of Haematococcus pluvialis at 25V (100 mA), followed by 7 days of incubation in air, showed only 7% and 10% increases in biomass dry weight and astaxanthin content, and did not promote significantly. Choi et al treated Chlorella with 4V (31 mA) cathodic current for 4h resulted in an increase in TAG, polyunsaturated linoleic acid (C18:2n6) and linolenic acid (C18:3n3) of 110%,36% and 57%, respectively, but a slight decrease in carbohydrate content.
Although the above research results discuss the performance change of microalgae after electric treatment, the accumulation of the dry weight of microalgae biomass is not obviously promoted, and the application research of electrochemistry on the high-concentration carbon dioxide of microalgae fixed smoke is lacking.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing the method for electrochemically promoting the nannochloropsis to fix the high-concentration CO in the flue gas 2 Is a method of (2).
In order to solve the technical problems, the invention adopts the following solutions:
provides an electrochemical method for promoting the fixation of high-concentration CO in flue gas by nannochloropsis 2 Specifically comprising the following steps:
(1) In static air, heating the conductive carbon fiber felt to 450 ℃, and then carrying out heat preservation and etching for 2 hours to remove impurities; an equal volume of 0.4M aqueous 2-methylimidazole solution and 5mM Co (NO) were taken 3 ·6H 2 The O aqueous solution is uniformly mixed under the condition of not stirring; vertically soaking the etched carbon felt in a mixed solution at 30 ℃ for 5 hours to obtain a purple carbon felt with Co-MOF grown; taking out, washing with ultrapure water and methanol, and drying at 60 ℃ overnight;
(2) By NiCl 3 And thiourea to prepare an electrolyte, wherein NiCl 3 Concentration was 0.5M, thiourea concentration was 0.25mM; immersing a purple carbon felt into an electrodeposition solution, wherein a reference electrode in an electrochemical system is Ag/AgCl; after 6 cycles at a rate of 5mV/s in the potential range of-1.2V to 0.2V, aging in the electrolyte for 12 hours, a green carbon felt with a NiCoS-LDH coating was produced; taking out, washing with ultrapure water and methanol, and drying in a vacuum oven;
(3) Inoculating the original algae liquid of the nannochloropsis into a culture medium, wherein the inoculation condition OD750 is 0.2-0.4, and the culture medium is a seawater culture medium consisting of an ESAW culture medium and an optimized f/2 culture medium;
(4) Cutting the green carbon felt obtained in the step (2) into two rectangular pieces, and respectively connecting a section of titanium wires in series; connecting titanium wires with the anode and the cathode of a constant voltage power supply respectively through wires, and immersing a green carbon felt into the algae liquid obtained in the step (3) to serve as the anode and the cathode of a microalgae electrochemical system; starting a stabilized voltage power supply, and setting the voltage to be 0.005-0.5V;
(5) Continuously introducing CO-containing material into the microalgae electrochemical culture system obtained in the step (4) 2 At 24-26 deg.C and illumination intensity of 80-90 mu mol.m 2 ·s -1 Culturing for 7-9 days under the illumination condition; harvesting microalgae solution after the culture period, and detecting algae liquid absorbance (OD) at 750nm with spectrophotometer 750 ) Obtaining accumulated biomass dry weight by utilizing the OD750 difference before and after the culture of the algae liquid so as to calculate the fixed CO of the nannochloropsis 2 Rate.
As an improvement, in the step (1), the temperature rising rate is 2 ℃/min.
As an improvement, in the step (3), the original algae liquid is yellow nannochloropsis algae liquid in a stable growth period; the algae is derived from natural algae screened in natural environment, mutant of algae obtained by physical and chemical mutagenesis or transgenic algae obtained by gene improvement; the specific acquisition mode is acquisition from natural environment of natural growth or acquisition from artificial open pond or closed reactor cultivation equipment.
As an improvement, in the step (3), each 1000mL of seawater culture medium comprises: 29.23g NaCl, 1.105g KCl, 11.09g MgSO 4 ·7H 2 O、1.21g Tris-base、1.83g CaCl 2 ·2H 2 O、0.25g NaHCO 3 3.0mL of trace metal solution and 997mL of distilled water;
wherein the trace metal solution is prepared by the following steps: 281.3mg NaNO was weighed out 3 、21.2mg NaH 2 PO 4 ·H 2 O、16.35mg Na 2 ·EDTA、11.8mg FeCl 3 ·6H 2 O、675μg MnCl 2 ·4H 2 O、37.5μg CoCl 2 ·6H 2 O、37.5μg CuSO 4 ·5H 2 O、82.5μg ZnSO 4 ·7H 2 O、22.5μg Na 2 MoO 4 0.375mg vitamin B1, 0.188. Mu.g of vitamin B12 and 0.188. Mu.g of biotin are dissolved in 1000mL of distilled water, heated at 105℃for 4 hours in an autoclave, and cooled to obtain a trace metal solution.
As an improvement, in the step (4), the rectangular green carbon felt serving as the anode and cathode of the microalgae electrochemical system has the dimensions of 40mm multiplied by 20mm multiplied by 3mm, and the distance between the two electrodes is 30mm.
As an improvement, in the step (5), CO contained in the flue gas 2 The volume concentration of the flue gas is 11-15%, and the flue gas inlet speed is controlled to be 2-4 mL/min.
As an improvement, absorbance (OD) is detected at 750nm with a spectrophotometer for the microalgae solution harvested in step (5) 750 ) The accumulated biomass dry weight is obtained according to the following formula to calculate the fixed CO of the nannochloropsis 2 Rate of:
description of the inventive principles:
the invention enhances the electron transfer rate in the process of the photosynthesis system PS II of the nannochloropsis cell through electrochemical treatment, promotes the absorption and utilization of nutrient salt ions such as nitrogen, phosphorus and the like by the cell, and simultaneously has a certain promotion effect on the division of the nannochloropsis cell by an electrical treatment means.
The conductive felt woven by the conductive carbon fibers (such as graphite carbon fibers) is commonly used for a conductive current collector in a flow battery. According to the invention, the carbon felt is subjected to hot oxygen etching (burning in static air), namely, the surface of the carbon felt is oxidized, so that impurities on the surface and the surface of the carbon fiber obtain more oxygen-containing groups, a coordination site with dimethyl imidazole is provided, and Co-MoF can conveniently grow on the surface in situ. The invention has no specific requirements on indexes such as the material, texture, warp and weft density, felt length and the like of the carbon felt, and various conductive carbon fiber felts commonly used in the market can be used.
When the cobalt nitrate solution is rapidly poured into the 2-methylimidazole aqueous solution, the two solutions are mixed by virtue of the kinetic energy of rapid pouring. Since the two aqueous solutions are dissolved before pouring, the two aqueous solutions can be fully and uniformly mixed after pouring, namely, the two aqueous solutions are uniformly mixed without stirring.
The reference electrode in the electrochemical system is Ag/AgCl, and is an electrode formed by immersing porous metal silver with the surface covered with silver chloride in a solution containing Cl-.
Compared with the prior art, the invention has the beneficial effects that:
the invention can effectively improve the flue gas of the nannochloropsis in the power plant by an electrochemical treatment method11-15% high concentration CO 2 Lower growth carbon sequestration rate. Fixing CO by using electrochemical treated nannochloropsis 2 The rate reaches 0.36-0.40 g/(L.d), compared with the nannochloropsis growing under the same environment without electric treatment and other culture conditions, the nannochloropsis fixing CO 2 The rate is 0.26 g/(L.d), and electrochemical treatment leads the nannochloropsis to fix CO 2 The speed is increased by 38-54%.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and detailed description:
the invention relates to an electrochemical promotion method for fixing high-concentration CO in flue gas by nannochloropsis 2 Is characterized by comprising the following steps:
(1) In static air, heating the conductive carbon fiber felt to 450 ℃ at a heating rate of 2 ℃/min, and then carrying out heat preservation and etching for 2 hours to remove impurities; an equal volume of 0.4M aqueous 2-methylimidazole solution and 5mM Co (NO) were taken 3 ·6H 2 The O aqueous solution is uniformly mixed under the condition of not stirring; vertically soaking the etched carbon felt in a mixed solution at 30 ℃ for 5 hours to obtain a purple carbon felt with Co-MOF grown; taking out, washing with ultrapure water and methanol, and drying at 60 ℃ overnight;
(2) By NiCl 3 And thiourea to prepare an electrolyte, wherein NiCl 3 Concentration was 0.5M, thiourea concentration was 0.25mM; immersing a purple carbon felt into an electrodeposition solution, wherein a reference electrode in an electrochemical system is Ag/AgCl; after 6 cycles at a rate of 5mV/s in the potential range of-1.2V to 0.2V, aging in the electrolyte for 12 hours, a green carbon felt with a NiCoS-LDH coating was produced; taking out, washing with ultrapure water and methanol, and drying in a vacuum oven;
(3) Inoculating the original algae liquid of the nannochloropsis into a culture medium, wherein the inoculation condition OD750 is 0.2-0.4, and the culture medium is a seawater culture medium consisting of an ESAW culture medium and an optimized f/2 culture medium;
the original algae liquid is yellow nannochloropsis algae liquid in a stable growth period; the algae is derived from natural algae screened in natural environment, mutant of algae obtained by physical and chemical mutagenesis or transgenic algae obtained by gene improvement; the specific acquisition mode is acquisition from natural environment of natural growth or acquisition from artificial open pond or closed reactor cultivation equipment.
Each 1000mL of seawater culture medium contains: 29.23g NaCl, 1.105g KCl, 11.09g MgSO 4 ·7H 2 O、1.21g Tris-base、1.83g CaCl 2 ·2H 2 O、0.25g NaHCO 3 3.0mL of trace metal solution and 997mL of distilled water; wherein the trace metal solution is prepared by the following steps: 281.3mg NaNO was weighed out 3 、21.2mg NaH 2 PO 4 ·H 2 O、16.35mg Na 2 ·EDTA、11.8mg FeCl 3 ·6H 2 O、675μg MnCl 2 ·4H 2 O、37.5μg CoCl 2 ·6H 2 O、37.5μg CuSO 4 ·5H 2 O、82.5μg ZnSO 4 ·7H 2 O、22.5μg Na 2 MoO 4 0.375mg vitamin B1, 0.188. Mu.g of vitamin B12 and 0.188. Mu.g of biotin are dissolved in 1000mL of distilled water, heated at 105℃for 4 hours in an autoclave, and cooled to obtain a trace metal solution.
(4) Cutting the green carbon felt obtained in the step (2) into two rectangular pieces with the size of 40mm multiplied by 20mm multiplied by 3mm, and connecting a section of titanium wires in series respectively; and (3) respectively connecting titanium wires with the anode and the cathode of a constant voltage power supply through wires, and immersing the green carbon felt into the algae liquid obtained in the step (3) to serve as the anode and the cathode of a microalgae electrochemical system, wherein the interval is 30mm. Starting a stabilized voltage power supply, and setting the voltage to be 0.005-0.5V;
(5) Continuously introducing CO-containing material into the microalgae electrochemical culture system obtained in the step (4) 2 Is characterized by comprising CO in the flue gas 2 The volume concentration of the flue gas is 11-15%, and the flue gas inlet speed is controlled to be 2-4 mL/min. At 24-26 deg.c and illumination intensity of 80-90 mu mol m 2 ·s -1 Culturing for 7-9 days under the illumination condition; harvesting microalgae solution after the culture period, and detecting algae liquid absorbance (OD) at 750nm with spectrophotometer 750 ) Cultivation by using algae liquidThe OD750 difference before and after the cultivation obtains the accumulated biomass dry weight so as to calculate the fixed CO of the nannochloropsis 2 Rate.
Detecting absorbance (OD) at 750nm with a spectrophotometer for the microalgae solution harvested in step (5) 750 ) The accumulated biomass dry weight is obtained according to the following formula to calculate the fixed CO of the nannochloropsis 2 Rate of:
the following examples will enable those skilled in the art to more fully understand the present invention and are not intended to limit the same in any way.
Example 1
And etching a piece of conductive carbon fiber felt in static air at the temperature rising rate of 2 ℃/min for 2 hours at the temperature of 450 ℃ to remove impurities. The Co-MOF was grown on carbon felt using the following method, which facilitates crystallization synthesis: 80mL of 2-methylimidazole (2-MIM) (0.4M) in water and 80mL of Co (NO) 3 ·6H 2 O (5 mM) aqueous solution was uniformly mixed without stirring, and then the etched carbon felt was vertically immersed in the mixture at 30 ℃ for 5 hours; then the obtained purple carbon felt is washed by ultrapure water and methanol and dried at 60 ℃ overnight;
then 100mL of electrolyte is prepared, wherein NiCl 3 A concentration of 0.5M and thiourea concentration of 0.25mM, placing a purple carbon felt into the electrodeposition solution, performing 6 cycles at a rate of 5mV/s in a potential range of-1.2V to 0.2V (vs Ag/AgCl), and then aging in the electrolyte for 12 hours; washing the prepared green NiCoS-LDH coated carbon felt with ultrapure water and methanol, and then drying in a vacuum oven;
then 300mL of original nannochloropsis alga liquid (natural alga species obtained by screening from natural environment) collected in natural growth natural environment is added into a triangular flask (500 mL), and the inoculation condition OD is adopted 750 0.2, the culture medium is a seawater culture medium consisting of ESAW culture medium and optimized f/2 culture medium;
finally, cutting the NiCoS-LDH coated carbon felt into 2 pieces of 40mmA section of titanium wires are respectively connected in series with cuboids with the length of multiplied by 20mm and multiplied by 3 mm; then connecting titanium wires with the anode and the cathode of a constant voltage power supply respectively through wires, and immersing a green carbon felt into the original nannochloropsis algae liquid to serve as the anode and the cathode of a microalgae electrochemical system; then starting a stabilized voltage power supply, and setting the voltage to be 0.005V; introducing CO-containing material 2 Is (CO) 2 The volume concentration is 11 percent), the smoke gas inlet speed is ensured to be 2mL/min, the temperature is 24 ℃, and the illumination intensity is 80 mu mol.m 2 ·s -1 Is cultured for 7 days under the illumination condition; then harvesting the microalgae solution after the culture period is finished, and detecting the absorbance (OD) of the microalgae solution at 750nm by using a spectrophotometer 750 ) Obtaining accumulated biomass dry weight by utilizing the OD750 difference before and after the culture of the algae liquid so as to calculate the fixed CO of the nannochloropsis 2 Rate.
Testing and calculating to obtain the immobilized CO of the nannochloropsis after electrochemical treatment 2 The rate reaches 0.36 g/(L.d), compared with the nannochloropsis growing under the same environment without electric treatment and other culture conditions, the nannochloropsis fixing CO 2 The rate is 0.26 g/(L.d), and electrochemical treatment leads the nannochloropsis to fix CO 2 The rate is increased by 38%.
Example 2
And etching a piece of conductive carbon fiber felt in static air at the temperature rising rate of 2 ℃/min for 2 hours at the temperature of 450 ℃ to remove impurities. The Co-MOF was grown on carbon felt using the following method, which facilitates crystallization synthesis: 80mL of 2-methylimidazole (2-MIM) (0.4M) in water and 80mL of Co (NO) 3 ·6H 2 O (5 mM) aqueous solution was uniformly mixed without stirring, and then the etched carbon felt was vertically immersed in the mixture at 30 ℃ for 5 hours; then the obtained purple carbon felt is washed by ultrapure water and methanol and dried at 60 ℃ overnight;
then 100mL of electrolyte is prepared, wherein NiCl 3 At a concentration of 0.5M and thiourea at a concentration of 0.25mM, placing a purple carbon felt in an electrodeposition solution at a potential of 5mV/s in the range of-1.2V to 0.2V (vs Ag/AgCl)The rate was cycled for 6 cycles and then aged in electrolyte for 12 hours; washing the prepared green NiCoS-LDH coated carbon felt with ultrapure water and methanol, and then drying in a vacuum oven;
then 300mL of original nannochloropsis alga solution (alga mutant obtained by physicochemical mutagenesis) cultivated in an artificial open pond is taken and added into a triangular flask (500 mL), and the condition of OD inoculation is adopted 750 0.3, the culture medium is a seawater culture medium consisting of ESAW culture medium and optimized f/2 culture medium;
finally, cutting the NiCoS-LDH coated carbon felt into 2 pieces of cuboids with the thickness of 40mm multiplied by 20mm multiplied by 3mm, and respectively connecting a section of titanium wires in series; then connecting titanium wires with the anode and the cathode of a constant voltage power supply respectively through wires, and immersing a green carbon felt into the original nannochloropsis algae liquid to serve as the anode and the cathode of a microalgae electrochemical system; then starting a stabilized voltage power supply, and setting the voltage to be 0.2V; introducing CO-containing material 2 Is (CO) 2 The volume concentration is 13 percent), the flue gas inlet speed is ensured to be 3mL/min, the temperature is 25 ℃, and the illumination intensity is 85 mu mol.m 2 ·s -1 Culturing for 8 days under the illumination condition; then harvesting the microalgae solution after the culture period is finished, and detecting the absorbance (OD) of the microalgae solution at 750nm by using a spectrophotometer 750 ) Obtaining accumulated biomass dry weight by utilizing the OD750 difference before and after the culture of the algae liquid so as to calculate the fixed CO of the nannochloropsis 2 Rate.
Testing and calculating to obtain the immobilized CO of the nannochloropsis after electrochemical treatment 2 The rate reaches 0.38 g/(L.d), compared with the nannochloropsis growing under the same environment without electric treatment and other culture conditions, the nannochloropsis fixing CO 2 The rate is 0.26 g/(L.d), and electrochemical treatment leads the nannochloropsis to fix CO 2 The rate was increased by 46%.
Example 3
And etching a piece of conductive carbon fiber felt in static air at the temperature rising rate of 2 ℃/min for 2 hours at the temperature of 450 ℃ to remove impurities. The carbon felt is produced by the following method which is easy to crystallize and synthesizeLong Co-MOF: 80mL of 2-methylimidazole (2-MIM) (0.4M) in water and 80mL of Co (NO) 3 ·6H 2 O (5 mM) aqueous solution was uniformly mixed without stirring, and then the etched carbon felt was vertically immersed in the mixture at 30 ℃ for 5 hours; then the obtained purple carbon felt is washed by ultrapure water and methanol and dried at 60 ℃ overnight;
then 100mL of electrolyte is prepared, wherein NiCl 3 A concentration of 0.5M and thiourea concentration of 0.25mM, placing a purple carbon felt into the electrodeposition solution, performing 6 cycles at a rate of 5mV/s in a potential range of-1.2V to 0.2V (vs Ag/AgCl), and then aging in the electrolyte for 12 hours; washing the prepared green NiCoS-LDH coated carbon felt with ultrapure water and methanol, and then drying in a vacuum oven;
then 300mL of original nannochloropsis algae liquid (transgenic algae species obtained by gene improvement) cultivated in a closed reactor is taken and added into a triangular flask (500 mL), and the inoculation condition OD is that 750 0.4, the culture medium is a seawater culture medium consisting of ESAW culture medium and optimized f/2 culture medium;
finally, cutting the NiCoS-LDH coated carbon felt into 2 pieces of cuboids with the thickness of 40mm multiplied by 20mm multiplied by 3mm, and respectively connecting a section of titanium wires in series; then connecting titanium wires with the anode and the cathode of a constant voltage power supply respectively through wires, and immersing a green carbon felt into the original nannochloropsis algae liquid to serve as the anode and the cathode of a microalgae electrochemical system; then starting a stabilized voltage power supply, and setting the voltage to be 0.5V; introducing CO-containing material 2 Is (CO) 2 The volume concentration is 15 percent), the flue gas inlet speed is ensured to be 4mL/min, the temperature is 26 ℃, and the illumination intensity is 90 mu mol.m 2 ·s -1 Culturing for 9 days under the illumination condition; then harvesting the microalgae solution after the culture period is finished, and detecting the absorbance (OD) of the microalgae solution at 750nm by using a spectrophotometer 750 ) Obtaining accumulated biomass dry weight by utilizing the OD750 difference before and after the culture of the algae liquid so as to calculate the fixed CO of the nannochloropsis 2 Rate.
Test meterObtaining the nannochloropsis fixed CO after electrochemical treatment 2 The rate reaches 0.40 g/(L.d), compared with the nannochloropsis growing under the same environment without electric treatment and other culture conditions, the nannochloropsis fixing CO 2 The rate is 0.26 g/(L.d), and electrochemical treatment leads the nannochloropsis to fix CO 2 The rate was increased by 54%.
Finally, it should be noted that the above list is only specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (6)
1. Electrochemical promotion of high concentration CO in nannochloropsis immobilization flue gas 2 Is characterized by comprising the following steps:
(1) In static air, heating the conductive carbon fiber felt to 450 ℃, and then carrying out heat preservation and etching for 2 hours to remove impurities; an equal volume of 0.4M aqueous 2-methylimidazole solution and 5mM Co (NO) were taken 3 ·6H 2 The O aqueous solution is uniformly mixed under the condition of not stirring; vertically soaking the etched carbon felt in a mixed solution at 30 ℃ for 5 hours to obtain a purple carbon felt with Co-MOF grown; taking out, washing with ultrapure water and methanol, and drying at 60 ℃ overnight;
(2) By NiCl 3 And thiourea to prepare an electrolyte, wherein NiCl 3 Concentration was 0.5M, thiourea concentration was 0.25mM; immersing a purple carbon felt into an electrodeposition solution, wherein a reference electrode in an electrochemical system is Ag/AgCl; after 6 cycles at a rate of 5mV/s in the potential range of-1.2V to 0.2V, aging in the electrolyte for 12 hours, a green carbon felt with a NiCoS-LDH coating was produced; taking out, washing with ultrapure water and methanol, and drying in a vacuum oven;
(3) Inoculating the original algae liquid of the nannochloropsis into a culture medium, wherein the inoculation condition OD750 is 0.2-0.4, and the culture medium is a seawater culture medium consisting of an ESAW culture medium and an optimized f/2 culture medium;
each 1000mL of seawater culture medium contains: 29.23g NaCl,1.105g KCl、11.09g MgSO 4 ·7H 2 O、1.21g Tris-base、1.83g CaCl 2 ·2H 2 O、0.25g NaHCO 3 3.0mL of trace metal solution and 997mL of distilled water;
wherein the trace metal solution is prepared by the following steps: 281.3mg NaNO was weighed out 3 、21.2mg NaH 2 PO 4 ·H 2 O、16.35mg Na 2 ·EDTA、11.8mg FeCl 3 ·6H 2 O、675μg MnCl 2 ·4H 2 O、37.5μgCoCl 2 ·6H 2 O、37.5μg CuSO 4 ·5H 2 O、82.5μg ZnSO 4 ·7H 2 O、22.5μg Na 2 MoO 4 Dissolving 0.375mg vitamin B1, 0.188 μg of vitamin B12 and 0.188 μg of biotin in 1000mL of distilled water, heating at 105 ℃ for 4 hours in a high-pressure steam sterilization pot, and cooling to obtain trace metal solution;
(4) Cutting the green carbon felt obtained in the step (2) into two rectangular pieces, and respectively connecting a section of titanium wires in series; connecting titanium wires with the anode and the cathode of a constant voltage power supply respectively through wires, and immersing a green carbon felt into the algae liquid obtained in the step (3) to serve as the anode and the cathode of a microalgae electrochemical system; starting a stabilized voltage power supply, and setting the voltage to be 0.005-0.5V;
(5) Continuously introducing CO-containing material into the microalgae electrochemical culture system obtained in the step (4) 2 At 24-26 deg.C and illumination intensity of 80-90 mu mol.m 2 ·s -1 Culturing for 7-9 days under the illumination condition; harvesting microalgae solution after the culture period, and detecting algae liquid absorbance (OD) at 750nm with spectrophotometer 750 ) Obtaining accumulated biomass dry weight by utilizing the OD750 difference before and after the culture of the algae liquid so as to calculate the fixed CO of the nannochloropsis 2 Rate.
2. The method according to claim 1, wherein in the step (1), the temperature rising rate is 2 ℃/min.
3. The method according to claim 1, wherein in the step (3), the raw algae liquid is an algae liquid of yellow nannochloropsis in a stationary growth phase; the algae is derived from natural algae screened in natural environment, mutant of algae obtained by physical and chemical mutagenesis or transgenic algae obtained by gene improvement; the specific acquisition mode is acquisition from natural environment of natural growth or acquisition from artificial open pond or closed reactor cultivation equipment.
4. The method according to claim 1, wherein in the step (4), the rectangular green carbon felt as the cathode and anode of the microalgae electrochemical system has a size of 40mm x 20mm x 3mm and a spacing between the two electrodes of 30mm.
5. The method according to claim 1, wherein in step (5), the CO contained in the flue gas is reduced 2 The volume concentration of the flue gas is 11-15%, and the flue gas inlet speed is controlled to be 2-4 mL/min.
6. The method according to claim 1, wherein absorbance (OD) is detected at 750nm for the microalgae solution harvested in step (5) using a spectrophotometer 750 ) The accumulated biomass dry weight is obtained according to the following formula to calculate the fixed CO of the nannochloropsis 2 Rate of:
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