CN114212890A - High-value utilization method of microalgae energy - Google Patents
High-value utilization method of microalgae energy Download PDFInfo
- Publication number
- CN114212890A CN114212890A CN202111440337.0A CN202111440337A CN114212890A CN 114212890 A CN114212890 A CN 114212890A CN 202111440337 A CN202111440337 A CN 202111440337A CN 114212890 A CN114212890 A CN 114212890A
- Authority
- CN
- China
- Prior art keywords
- microalgae
- mineralized
- magnetic
- electrolyte
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000010865 sewage Substances 0.000 claims abstract description 30
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 13
- 238000012258 culturing Methods 0.000 claims abstract description 13
- 238000003306 harvesting Methods 0.000 claims abstract description 12
- 239000006249 magnetic particle Substances 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 10
- 239000003546 flue gas Substances 0.000 claims abstract description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 8
- 238000007885 magnetic separation Methods 0.000 claims abstract description 8
- 239000006148 magnetic separator Substances 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 239000003225 biodiesel Substances 0.000 claims abstract description 3
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229920000447 polyanionic polymer Polymers 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000010294 electrolyte impregnation Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- AWDMDDKZURRKFG-UHFFFAOYSA-N potassium;propan-1-olate Chemical compound [K+].CCC[O-] AWDMDDKZURRKFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000010842 industrial wastewater Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 210000004027 cell Anatomy 0.000 description 30
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 14
- 239000012075 bio-oil Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 241000195493 Cryptophyta Species 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 230000003592 biomimetic effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 239000001963 growth medium Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 240000009108 Chlorella vulgaris Species 0.000 description 4
- 235000007089 Chlorella vulgaris Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000002551 biofuel Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001766 physiological effect Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/59—Biological synthesis; Biological purification
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Genetics & Genomics (AREA)
- Water Supply & Treatment (AREA)
- Microbiology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Botany (AREA)
- Hydrology & Water Resources (AREA)
- Cell Biology (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Tropical Medicine & Parasitology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Virology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention discloses a high-value utilization method of microalgae energy, which comprises the following steps: step 1, culturing microalgae by using pretreated industrial sewage, and introducing coal-fired flue gas into the industrial sewage, wherein the coal-fired flue gas comprises CO2Nitrogen oxides and sulfur oxides; step 2, carrying out mineralization treatment on the microalgae cultured in the step 1 to obtain mineralized microalgae, generating magnetic particles on the surface of the mineralized microalgae in situ by adopting a coprecipitation method, and continuously culturing the obtained mineralized and magnetized microalgae in sewage; step 3, carrying out magnetic separation harvesting on the mineralized and magnetized microalgae, separating the mixed solution of the microalgae obtained by magnetic separation and magnetic nanoparticles by a magnetic separator, and liquefying the microalgae separated by the magnetic separator to obtain biodiesel; and 4, modifying the liquefied microalgae residues, wherein the modified microalgae residues are used for adsorbing heavy metal elements in the industrial sewage. The culture cost and the process energy consumption are reduced while the yield of the microalgae is improved.
Description
Technical Field
The invention belongs to the technical field of microalgae resource utilization, and particularly relates to a high-value utilization method of microalgae energy.
Background
Microalgae cells contain various unsaturated fatty acids, high-quality fuel can be prepared by thermochemical conversion technologies such as pyrolysis and hydrothermal technology, and byproducts such as residues can also be used as soil conditioners and biological adsorbents. In addition, the microalgae has wide application prospects in the fields of biological medicine, food safety, environmental monitoring and the like, and is an ideal renewable green biological resource. However, a large amount of water and nutrients are required in the microalgae cultivation stage, and efficient harvesting of microalgae biomass still faces challenges, resulting in higher production cost of microalgae biofuel and significantly reduced competitive advantages.
In addition to conventional raceway ponds and photobioreactor culture, microalgae can utilize a variety of speciesIndustrial, agricultural and domestic waste. Utilizing CO in flue gas2And nutrient substances such as nitrogen, phosphorus and the like in the sewage are used for culturing the microalgae, and meanwhile, the bioadsorption mechanism of the microalgae can also be used for deeply purifying heavy metal pollutants in the sewage, so that the dual purposes of high value-added energy output and low-cost pollutant removal are simultaneously met.
When the heavy metal sewage is used for culturing the microalgae, the physiological toxicity of the heavy metal sewage and the secondary release problem of the heavy metal in the energy utilization process of the microalgae cannot be ignored, and the tolerance of the microalgae needs to be improved by carrying out a necessary pretreatment method on the microalgae. The existing method comprises the following steps: the biotechnology such as radiation mutagenesis, gene improvement and the like theoretically provides a method for directionally transforming cells to improve the environmental tolerance, but the screening process is complicated and long, the time cost is high, and the problem cannot be solved in a short time. Therefore, a new improvement method needs to be explored to improve the survival capacity of the microalgae in the mercury-containing sewage and ensure that the physiological activity and the oil yield are not influenced; on the other hand, the influence of the modification method on the downstream production of biofuel by microalgae is also considered.
Development and utilization of microalgae biofuel technology are of great importance. The direct conversion of microalgae into fuel by the traditional thermal conversion technology (i.e. direct combustion, baking, pyrolysis, gasification, etc.) is difficult and uneconomical, and the hydrothermal liquefaction technology does not need the pretreatment of drying and cell disruption of the microalgae, thereby greatly reducing the process energy consumption. The common hydrothermal liquefaction has the defects that the products are not easy to separate, and a catalyst is required to be added for improving the oil yield. A large amount of residues after oil production are not fully utilized, so that the energy recovery efficiency is low.
Therefore, there is a need to develop a new technology, which can improve the yield of microalgae and reduce the culture cost and process energy consumption, and provide support for industrial application of microalgae oil production.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a high-value utilization method of microalgae energy, which aims to reduce the culture cost and the process energy consumption while improving the yield of microalgae, thereby solving the technical problem of low utilization efficiency of the existing microalgae energy.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for high-value utilization of microalgae energy, comprising the steps of:
step 1, culturing microalgae by using pretreated industrial sewage, and introducing coal-fired flue gas into the industrial sewage, wherein the coal-fired flue gas comprises CO2Nitrogen oxides and sulfur oxides;
step 2, carrying out mineralization treatment on the microalgae cultured in the step 1 to obtain mineralized microalgae, generating magnetic particles on the surface of the mineralized microalgae in situ by adopting a coprecipitation method, and continuously culturing the obtained mineralized and magnetized microalgae in sewage;
step 3, carrying out magnetic separation harvesting on the mineralized and magnetized microalgae, separating the mixed solution of the microalgae obtained by magnetic separation and magnetic nanoparticles by a magnetic separator, and liquefying the mineralized and magnetized microalgae (or the microalgae separated by the magnetic separator) to obtain biodiesel;
and 4, modifying the liquefied microalgae residues, wherein the modified microalgae residues are used for adsorbing heavy metal elements in the industrial sewage.
Wherein, the industrial sewage after primary treatment and filtration is utilized in the step 1, coal-fired flue gas is introduced into the industrial sewage, and microalgae cells can fix CO in the flue gas through photosynthesis2While absorbing NOXAnd SOXAs nitrogen source and sulfur source required by growth, and has certain adsorption and removal effect on low-concentration heavy metal ions in the wastewater. The device for culturing the microalgae in the step 1 can be at least one of an open raceway pond or a column type, a tubular type, a flat plate type, a spiral type, a stirring tank type and a mixed type photobioreactor.
In step 2, the microalgae cultured in step 1 is mineralized, preferably, the microalgae cells stably grown on day 5 are selected for culturing and then mineralized.
Preferably, the mineralization treatment comprises: and (2) forming a net-shaped inorganic salt mineralization crystallization site on the surface of the microalgae cell by electrolyte impregnation, then impregnating the microalgae impregnated with the electrolyte into a mineralization protection shell solution, and cleaning the microalgae after the impregnation is finished to obtain the mineralized microalgae.
Preferably, the electrolyte is a polycation electrolyte and a polyanion electrolyte, the concentration of the polycation electrolyte and the concentration of the polyanion electrolyte are both 0.5-2mg/mL, the dipping time is 15-30 minutes, the dipping temperature is 20-30 ℃, and the alternate dipping times are 3-6 times.
Preferably, the polycation electrolyte is one of polyvinylamine, polyethyleneimine and polyvinylpyridine, and the polyanion electrolyte is one of polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid and polyvinyl sulfonic acid.
Preferably, the mineralization protection shell solution is at least one of calcium phosphate solution, silicon dioxide solution, chitosan solution and alginate solution, and the mineralization protection shell solution is impregnated under the conditions that: pH 8-10.
Preferably, the magnetic particles are Fe3O4Nanoparticles of said Fe3O4The particle size of the nano particles is 10-50 nm; the method for generating the magnetic particles on the surface of the mineralized microalgae in situ by adopting a coprecipitation method comprises the following steps: at 20-30 deg.C, pH 8-10, and FeCl 0.5-1mol/L2·4H2O and 0.5-1mol/L FeCl3·6H2O is used as raw material, 0.3-0.8mol/L NH3·H2O is used as a precipitator to generate Fe on the surface of the mineralized microalgae in situ3O4Magnetic particles.
Preferably, the mineralized and magnetized microalgae are liquefied, specifically, the microalgae are liquefied under the condition of subcritical/supercritical methanol, the liquefaction temperature is 180-300 ℃, the liquefaction pressure is 5-15 MPa, the heat preservation time is 0.5-2 h, the solid-to-liquid ratio of the microalgae and the methanol is 1: 5-1: 20, and at least one of metal simple substances of Zn, Fe, Al, Mg, Na and Cu or metal salts thereof, the mass of which is 5 wt% of that of the microalgae, is added into a liquefaction solvent to serve as a hydrogen production catalyst.
Preferably, when the microalgae are cultured in the step 1, BG-11 culture medium and glucose are added into the industrial sewage, the culture temperature is 20-30 ℃, the pH value is 7.0-10, the illumination time is 12 hours of illumination and 12 hours of darkness, and the culture period is 12 days.
Preferably, when culturing microalgae in step 1: adding pure water with the volume ratio of 1:1 to the industrial sewage, mixing, and adding BG-11 culture medium and glucose.
Further preferably, the microalgae growth condition is best when the ratio of the sewage to the BG-11 culture medium is 1000: 1 and the mass concentration of the glucose is 0.5 g/L.
Preferably, the liquefied microalgae residue is modified by at least one of formic acid, acetic acid, propionic acid, sodium methoxide, sodium ethoxide, sodium propoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, potassium chloride, sodium chloride, iron chloride, magnesium chloride and zinc chloride.
Preferably, during the modification treatment, the solid-to-liquid ratio of the microalgae residue to the modification solvent is 1: 10-1: 3, the modification impregnation time is 12 hours, and 1mol/L NaOH and 1mol/L HNO are adopted3The solution pH was adjusted to neutral.
In general, at least the following advantages can be obtained by the above technical solution contemplated by the present invention compared to the prior art.
(1) According to the invention, firstly, microalgae culture and industrial sewage purification are combined, so that the dual purposes of high value-added energy output and low-cost pollutant removal are simultaneously met, then, mineralized microalgae is magnetized, the tolerance of microalgae cells to high-concentration sewage is improved, and simultaneously, under the action of an external magnetic field, the microalgae cells and floccules of magnetic nano materials are quickly separated from a culture medium, so that the efficient harvesting of the microalgae is realized. And finally, the microalgae residues are reused as byproducts after liquefaction, so that the process cost and the energy consumption are reduced while the yield of the microalgae is improved, and the energy recovery efficiency is greatly improved.
(2) The method adopts the magnetization treatment on the mineralized microalgae, and because the mineralized microalgae is soaked by two polyelectrolytes, namely polycation electrolyte and polyanion electrolyte, the two polyelectrolytes form reticular inorganic salt mineralized crystal sites on the surfaces of microalgae cells, the uniform generation of a mineralized layer on the surfaces of the microalgae is promoted, and meanwhile, in the magnetization process, the in-situ generated magnetic Fe is promoted3O4Binding of the particles to the algal cells. The reason is that the microalgae itself has negative electricity, and when the microalgae is directly magnetized conventionally, the negative electricity on the surface of the microalgae cell and the magnetic particles generate repulsion force to influence the combination of the microalgae cell and the magnetic particles, thereby reducing the harvesting efficiency of the microalgae cell. The method has the advantages that the mineralized microalgae is magnetized, the electrostatic affinity between the microalgae cells with positive charges and the nano particles with negative charges is increased through the modification of the cationic polymer, and the harvesting efficiency of the magnetic separation microalgae cells can reach more than 98%.
(3) In the invention, Fe is generated in situ on the surface of the modified microalgae3O4Nanoparticles of Fe3O4The bonding strength of the modified surface of the nano-particles and the microalgae is higher than that of Fe in the traditional process of directly magnetizing the microalgae3O4Bonding strength of nanoparticles to microalgae, and thus, magnetization of treated Fe3O4Part of the Fe can remain on the surface of the microalgae after magnetic separation, and in the subsequent liquefaction process, the Fe3O4Can be used as catalyst to improve liquefaction efficiency.
(4) In the invention, the microalgae is liquefied under the condition of methanol, and the methanol can not only carry out esterification reaction with acidic components in the microalgae to reduce the acidity of the bio-oil, but also reduce the viscosity of the bio-oil through ester exchange reaction. Methanol is used as a hydrogen donor in the liquefaction process, so that free radicals can be stabilized, the yield of the bio-oil is improved, and the repolymerization reaction is reduced. In addition, the oxygen content of the bio-oil can be reduced through the hydrodeoxygenation reaction, and the heat value of the bio-oil can be improved. The quality of the bio-oil is effectively improved.
(5) In the invention, the microalgae residues are reused as byproducts, so that the energy recovery efficiency of the microalgae oil-making process is improved. The micro-pore structure of the material is obviously improved through modification, pores are obviously formed in a 2-50 nm mesoporous range, and the pore volume and the specific surface area are obviously improved compared with those of an unmodified sample, so that the physical adsorption capacity of the material is greatly improved.
Drawings
FIG. 1 is a schematic process flow diagram of example 1 of the present invention;
FIG. 2 (a) is a scanning electron microscope photograph of Chlorella vulgaris and FIG. 2 (b) is a scanning electron microscope photograph of the magnetic biomimetic mineralized Chlorella vulgaris prepared in example 1;
FIG. 3 (a) is a graph showing fluorescence intensity of Chlorella naturalis in mercury-containing wastewater, and FIG. 3(b) is a graph showing fluorescence intensity of the magnetic biomimetic mineralized Chlorella prepared as in example 1 in mercury-containing wastewater of the same concentration, the fluorescence intensity representing physiological activity of the Chlorella;
FIG. 4 (a) shows the harvesting of Chlorella vulgaris (a), and FIG. 4 (b) shows the harvesting of the magnetic biomimetic mineralized Chlorella vulgaris prepared in example 1 in the same period of time;
FIG. 5 is a graph showing the yields of bio-oil from hydrothermal liquefaction and bio-oil from methanol liquefaction in example 1 under the same conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The microalgae culture reactor is a columnar bioreactor (the working volume of 200mm multiplied by phi 50mm is 300 mL), and industrial sewage after centrifugation and filtration and pure water 1:1 mixing, adding 1ml of BG11 mother liquor and 0.5g of glucose into 1L of sewage, adjusting the inoculation density of chlorella in a culture medium to be 0.4 g/L, adjusting the pH to 7, setting the temperature to be 25 ℃, setting the light intensity to be 6000lux, and continuously illuminating for 12h and 12h in darkness. Gas is introduced into the bottom of the reactor from a long steel pipe (210mm multiplied by phi 3mm), and CO with the volume fraction of 14 percent, 4 percent and 4.5 percent is introduced2、NO、SO2The aeration rate of the mixed gas (2) was 30 mL/min. The culture period is 5 d.
After the growth of the microalgae cells is stable, the chlorella solution is centrifuged for 7 minutes under the condition of 1200G.After centrifugation, supernatant is removed to obtain algae mud, and the algae mud is washed by 0.05mol/L NaCl solution for three times of centrifugation and harvest. Alternately soaking with 1mg/mL polydiallyldimethylammonium chloride (PDADMAC) and sodium Polyacrylate (PAAS) nontoxic electrolyte for 3 times (20 min at 30 deg.C) to eliminate physiological inhibition of electrolyte on algae cells, and forming polymer network structure on cell surface to provide inorganic salt mineralized crystallization sites. After the immersion, the cells are filtered, collected, washed by deionized water and placed in 0.1mol/L CaCl2Soaking in the solution for 6 hr to allow the cell surface polyelectrolyte layer to react with Ca2+Fully complexing; then separating and collecting the fully soaked cells, and washing the cells with deionized water until Ca in the eluent is contained2+If not detected, the washed cells were further immersed in 0.1mol/L Na3 PO3In S, the impregnation conditions were pH 9 and the impregnation temperature was 30 ℃. The cells were collected by filtration and washed with deionized water and then washed with 0.5mol/L FeCl2·4H2O and 0.5mol/L FeCl3·6H2O is used as raw material, 0.3mol/L NH3·H2O is used as a precipitator, and Fe with the grain diameter of about 20nm is generated on the surface of mineralized cells in situ at the temperature of 30 DEG C3O4And (3) separating and collecting the fully-soaked cells, and washing the cells by using deionized water until metal and ammonium ions in the eluent are not detected, so as to obtain the magnetically mineralized microalgae cells.
Expanding the treated algae liquid into a raceway pond, culturing for 3 days, standing for 3 hours in a magnetic field with the magnetic field intensity of 0.15T, and separating algae cells and Fe by a magnetic separator3O4Particle separation, 95% Fe3O4The particles are recycled, and the rest of 5 percent Fe which is not completely recycled3O4The particles flow downstream with the algal cells. The separated algal mud was left to air dry for 3 days. Drying the algae mud in the shade according to the sample/solvent ratio of 1:10 is placed in an intermittent reaction kettle system with a certain volume, the solvent is methanol, the operation pressure is 9MPa, the temperature is 260 ℃, and the reaction residence time is 30 minutes. And after the reaction is completed, carrying out centrifugal separation on residues in the kettle body to obtain solid residues and liquid phase products. Washing the solid residue with water to separate and drying to obtain solid algae baseBiological coke sample; the liquid phase product is fractionated to obtain the algae-based bio-oil, and the solvent which is excessive in reaction is recycled after being fractionated and condensed.
And (3) soaking and modifying the obtained solid residue sample and 1mol/L formic acid solution according to a solid-to-liquid ratio of 1:10 for 3 hours, drying, grinding uniformly, and sieving to obtain uniform powder with the particle size distribution of 75-150 mu m. Mixing the powder with a mixture containing 5mg/L Cu2+The industrial sewage is stirred in a sewage stirring tank according to the ratio of 1: 100 mass ratio, stirring for 2 hours, pH 5, temperature 25 ℃. And then, recovering solid residues through standing separation, enabling supernatant liquor to enter a subsequent sewage treatment unit, and recycling the adsorbed algae-based solid residues through an elution regeneration link. In this example, the data of the pore structure of the surface before and after modification of the microalgae residue are shown in Table 1.
In fig. 2, (a) and (b) compare the surface topography of natural chlorella with the magnetic biomimetic mineralized chlorella prepared in example 1, it can be seen that the chlorella obtained by the method of the present invention has a good surface formation of a uniform magnetic mineralized layer.
FIGS. 3 (a) and (b) are graphs showing fluorescence intensities of naturally occurring chlorella and the magnetic biomimetic mineralized chlorella prepared in example 1 in the same concentration mercury-containing sewage, and it can be seen that the magnetically mineralized chlorella obtained by the method of the present invention has a Cu concentration of 100 μ g/L2+The simulated wastewater still can keep better physiological activity.
In fig. 4, (a) and (b) show the harvesting conditions of the natural chlorella and the magnetic biomimetic mineralized chlorella prepared in example 1 in the same time, and the harvesting efficiency of the magnetically mineralized chlorella obtained by the method of the invention can reach more than 95% within 5 min.
FIG. 5 is a graph showing the yields of bio-oil obtained by hydrothermal liquefaction under the same conditions and bio-oil obtained by liquefaction of methanol prepared in example 1, and it can be seen that Fe3O4The particles play a catalytic role in liquefaction, and the oil yield is obviously improved.
Table 1 surface pore structure data before and after modification of microalgae residue prepared in example 1
Examples 2 to 6
Examples 2 to 6 the energy of microalgae was used for high value in the same manner as in example 1, except for the differences shown in Table 2.
Table 2 preparation conditions of example 2 to example 6
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A high-value utilization method of microalgae energy is characterized by comprising the following steps:
step 1, culturing microalgae by using pretreated industrial sewage, and introducing coal-fired flue gas into the industrial sewage, wherein the coal-fired flue gas comprises CO2Nitrogen oxides and sulfur oxides;
step 2, carrying out mineralization treatment on the microalgae cultured in the step 1 to obtain mineralized microalgae, generating magnetic particles on the surface of the mineralized microalgae in situ by adopting a coprecipitation method, and continuously culturing the obtained mineralized and magnetized microalgae in sewage;
step 3, carrying out magnetic separation harvesting on the mineralized and magnetized microalgae, separating the mixed solution of the microalgae obtained by magnetic separation and magnetic nanoparticles by a magnetic separator, and liquefying the microalgae separated by the magnetic separator to obtain biodiesel;
and 4, modifying the liquefied microalgae residues, wherein the modified microalgae residues are used for adsorbing heavy metal elements in the industrial sewage.
2. The method of claim 1, wherein the mineralization treatment comprises: and (2) forming a net-shaped inorganic salt mineralization crystallization site on the surface of the microalgae cell by electrolyte impregnation, then impregnating the microalgae impregnated with the electrolyte into a mineralization protection shell solution, and cleaning the microalgae after the impregnation is finished to obtain the mineralized microalgae.
3. The method of claim 2, wherein the electrolyte is a polycation electrolyte and a polyanion electrolyte, the concentration of the polycation electrolyte and the concentration of the polyanion electrolyte are both 0.5-2mg/mL, the dipping time is 15-30 minutes, the dipping temperature is 20-30 ℃, and the number of alternate dipping times is 3-6.
4. The method of claim 3, wherein the polycationic electrolyte is one of polyvinylamine, polyethyleneimine, and polyvinylpyridine, and the polyanionic electrolyte is one of polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid, and polyvinylsulfonic acid.
5. The method of claim 2, wherein the mineralization protection shell solution is at least one of a calcium phosphate solution, a silica solution, a chitosan solution, and an alginate solution, and the mineralization protection shell solution is impregnated under the following conditions: pH 8-10.
6. The method of any one of claims 1 to 5, wherein the magnetic particles are Fe3O4Nanoparticles of said Fe3O4The particle size of the nano particles is 10-50 nm; the method for generating the magnetic particles on the surface of the mineralized microalgae in situ by adopting a coprecipitation method comprises the following steps: at 20-30 deg.C, pH 8-10, and FeCl 0.5-1mol/L2·4H2O and 0.5-1mol/L FeCl3·6H2O is used as raw material, 0.3-0.8mol/LNH3·H2O as a precipitating agent inMineralized microalgae surface in-situ generation of Fe3O4Magnetic particles.
7. The method according to claim 1, wherein the mineralized and magnetized microalgae are liquefied, and specifically, the microalgae are liquefied under the condition of sub/supercritical methanol, the liquefaction temperature is 180-300 ℃, the liquefaction pressure is 5-15 MPa, the heat preservation time is 0.5-2 h, the solid-to-liquid ratio of the microalgae and the methanol is 1: 5-1: 20, and at least one of metal simple substances of Zn, Fe, Al, Mg, Na and Cu or metal salts thereof, the mass of which is 5 wt% of that of the microalgae, is added into a liquefaction solvent to serve as a hydrogen production catalyst.
8. The method of claim 1, wherein when culturing the microalgae in step 1, BG-11 medium and glucose are added into industrial wastewater, the culture temperature is 20-30 ℃, the pH is 7.0-10, the illumination time is 12h of illumination and 12h of darkness, and the culture period is 12 days.
9. The method of claim 1, wherein the liquefied microalgae residue is subjected to modification treatment by using at least one of formic acid, acetic acid, propionic acid, sodium methoxide, sodium ethoxide, sodium propoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, potassium chloride, sodium chloride, ferric chloride, magnesium chloride, and zinc chloride.
10. The method according to claim 9, wherein during the modification treatment, the solid-to-liquid ratio of the microalgae residue to the modification solvent is 1: 10-1: 3, the modification dipping time is 12 hours, and 1mol/L of LNaOH and 1mol/L of HNO are adopted3The solution pH was adjusted to neutral.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111440337.0A CN114212890A (en) | 2021-11-30 | 2021-11-30 | High-value utilization method of microalgae energy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111440337.0A CN114212890A (en) | 2021-11-30 | 2021-11-30 | High-value utilization method of microalgae energy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114212890A true CN114212890A (en) | 2022-03-22 |
Family
ID=80699028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111440337.0A Pending CN114212890A (en) | 2021-11-30 | 2021-11-30 | High-value utilization method of microalgae energy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114212890A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114733508A (en) * | 2022-04-29 | 2022-07-12 | 华中科技大学 | Microalgae biological Johnson catalyst and preparation method and application thereof |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362613A (en) * | 2007-08-10 | 2009-02-11 | 四川德美环境技术有限责任公司 | Agent for magnetically separating and purifying algal bloom and preparation method thereof |
| CN101962618A (en) * | 2010-06-10 | 2011-02-02 | 海南大学 | Method for harvesting microalgae by using polysaccharide |
| JP2011206016A (en) * | 2010-03-30 | 2011-10-20 | Fujifilm Corp | Method of extracting intracellular component of microalgae |
| CN102642987A (en) * | 2012-04-25 | 2012-08-22 | 中国农业大学 | High-concentration sewage treatment method |
| CN103030203A (en) * | 2012-12-27 | 2013-04-10 | 中国科学院合肥物质科学研究院 | Preparation method of composite inorganic polymer stable algaecide and algae removing method |
| CN103194394A (en) * | 2013-04-10 | 2013-07-10 | 中国科学院过程工程研究所 | Method for separating microalgae by taking polyethyleneimine modified Fe3O4 nanoparticles as flocculating agent |
| CN103333880A (en) * | 2013-06-19 | 2013-10-02 | 中国科学院过程工程研究所 | Method for harvesting microalgae with magnetic separator |
| KR20140133311A (en) * | 2013-05-10 | 2014-11-19 | 한국에너지기술연구원 | Flocculant composition comprising Magnetic Chitosan Nanocomposite and Recovery Method of Microalgae Using the same |
| CN104480016A (en) * | 2014-12-08 | 2015-04-01 | 北京林业大学 | Self-assembled magnetically modified flocculant for separating microalgae and preparation method and application thereof |
| CN104962585A (en) * | 2015-06-25 | 2015-10-07 | 浙江大学 | Method for cultivating microalgae to generate hydrogen |
| CN105506009A (en) * | 2015-12-23 | 2016-04-20 | 中国水产科学研究院南海水产研究所 | Method for preparing biodiesel from alage cultured by exhaust gas and ash of power plant as well as system |
| KR20160053565A (en) * | 2014-11-05 | 2016-05-13 | 한국에너지기술연구원 | Method for harvesting microalgae and subsequent extracting lipid using cationic surfactant-functionalized magnetic nanoparticle composite |
| KR20170007076A (en) * | 2015-07-07 | 2017-01-18 | 한국에너지기술연구원 | Magnetic flocculant for microalgae harvesting comprising magnetic core and dual functinalized shell |
| CN109294631A (en) * | 2018-09-14 | 2019-02-01 | 厦门大学 | A kind of method of microalgae catalytic liquefaction preparation bio oil |
| CN110684655A (en) * | 2019-10-18 | 2020-01-14 | 江苏大学 | Microalgae separation gradient magnetic stabilization fluidized bed device and microalgae harvesting method thereof |
| CN111235022A (en) * | 2020-03-11 | 2020-06-05 | 西安交通大学 | Microalgae carbon sequestration and energy utilization system and method for supercritical water treatment |
| CN112337442A (en) * | 2020-10-15 | 2021-02-09 | 华中科技大学 | Modified algae base, preparation thereof and application of modified algae base as mercury removal adsorbent |
-
2021
- 2021-11-30 CN CN202111440337.0A patent/CN114212890A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362613A (en) * | 2007-08-10 | 2009-02-11 | 四川德美环境技术有限责任公司 | Agent for magnetically separating and purifying algal bloom and preparation method thereof |
| JP2011206016A (en) * | 2010-03-30 | 2011-10-20 | Fujifilm Corp | Method of extracting intracellular component of microalgae |
| CN101962618A (en) * | 2010-06-10 | 2011-02-02 | 海南大学 | Method for harvesting microalgae by using polysaccharide |
| CN102642987A (en) * | 2012-04-25 | 2012-08-22 | 中国农业大学 | High-concentration sewage treatment method |
| CN103030203A (en) * | 2012-12-27 | 2013-04-10 | 中国科学院合肥物质科学研究院 | Preparation method of composite inorganic polymer stable algaecide and algae removing method |
| CN103194394A (en) * | 2013-04-10 | 2013-07-10 | 中国科学院过程工程研究所 | Method for separating microalgae by taking polyethyleneimine modified Fe3O4 nanoparticles as flocculating agent |
| KR20140133311A (en) * | 2013-05-10 | 2014-11-19 | 한국에너지기술연구원 | Flocculant composition comprising Magnetic Chitosan Nanocomposite and Recovery Method of Microalgae Using the same |
| CN103333880A (en) * | 2013-06-19 | 2013-10-02 | 中国科学院过程工程研究所 | Method for harvesting microalgae with magnetic separator |
| KR20160053565A (en) * | 2014-11-05 | 2016-05-13 | 한국에너지기술연구원 | Method for harvesting microalgae and subsequent extracting lipid using cationic surfactant-functionalized magnetic nanoparticle composite |
| CN104480016A (en) * | 2014-12-08 | 2015-04-01 | 北京林业大学 | Self-assembled magnetically modified flocculant for separating microalgae and preparation method and application thereof |
| CN104962585A (en) * | 2015-06-25 | 2015-10-07 | 浙江大学 | Method for cultivating microalgae to generate hydrogen |
| KR20170007076A (en) * | 2015-07-07 | 2017-01-18 | 한국에너지기술연구원 | Magnetic flocculant for microalgae harvesting comprising magnetic core and dual functinalized shell |
| CN105506009A (en) * | 2015-12-23 | 2016-04-20 | 中国水产科学研究院南海水产研究所 | Method for preparing biodiesel from alage cultured by exhaust gas and ash of power plant as well as system |
| CN109294631A (en) * | 2018-09-14 | 2019-02-01 | 厦门大学 | A kind of method of microalgae catalytic liquefaction preparation bio oil |
| CN110684655A (en) * | 2019-10-18 | 2020-01-14 | 江苏大学 | Microalgae separation gradient magnetic stabilization fluidized bed device and microalgae harvesting method thereof |
| CN111235022A (en) * | 2020-03-11 | 2020-06-05 | 西安交通大学 | Microalgae carbon sequestration and energy utilization system and method for supercritical water treatment |
| CN112337442A (en) * | 2020-10-15 | 2021-02-09 | 华中科技大学 | Modified algae base, preparation thereof and application of modified algae base as mercury removal adsorbent |
Non-Patent Citations (2)
| Title |
|---|
| 彭阳: "微藻生物材料对工业污水二价汞的脱除性能及机理研究" * |
| 蒋咏梅等: "利用纳米Fe3O4快速回收单细胞微藻" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114733508A (en) * | 2022-04-29 | 2022-07-12 | 华中科技大学 | Microalgae biological Johnson catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Beni et al. | Biosorption, an efficient method for removing heavy metals from industrial effluents: a review | |
| Law et al. | Microalgal-based biochar in wastewater remediation: Its synthesis, characterization and applications | |
| CN108311153B (en) | Nano-ZnO loaded magnetic biochar composite photocatalyst and preparation method thereof | |
| Li et al. | A review on mycelial pellets as biological carriers: wastewater treatment and recovery for resource and energy | |
| CN108144581B (en) | Alkali modified pig manure biochar and preparation method and application thereof | |
| CN109012589B (en) | A kind of urea-modified charcoal of selective absorption Cr (VI) and its preparation method and application method | |
| CN107262039B (en) | A kind of high-molecular biologic charcoal ball immobilized microalgae compound adsorbent and its preparation and application | |
| Ji et al. | Modified mussel shell powder for microalgae immobilization to remove N and P from eutrophic wastewater | |
| CN111807453A (en) | Modified biochar for adsorbing phosphorus in water body and preparation method and application thereof | |
| WO2013055887A1 (en) | Microalgae culture and harvest | |
| Lin et al. | Nitrogen-doped hydrochar prepared by biomass and nitrogen-containing wastewater for dye adsorption: effect of nitrogen source in wastewater on the adsorption performance of hydrochar | |
| CN107893064B (en) | Preparation method and application of biochar-polyvinyl alcohol combined immobilized microalgae pellets | |
| CN101402485A (en) | Cohesive action nutrient source SRB sewage sludge immobilization particle, production and uses in treating heavy metal wastewater thereof | |
| CN113233587B (en) | Microalgae culture pond-artificial wetland coupling system and method for deep purification of sewage | |
| CN104445816A (en) | Method for treating high-concentration ammonia nitrogen pig breeding biogas slurry | |
| Han et al. | Microalgae harvesting by magnetic flocculation for biodiesel production: current status and potential | |
| WO2016074409A1 (en) | Method for preparing vehicle biological fuel oil, biogas and fertilizer by utilizing microalgae full composition | |
| CN110801814A (en) | Preparation method of magnetic amino walnut shell biochar novel adsorbent | |
| CN112619600A (en) | Method for preparing modified biochar by utilizing plant wastes and application | |
| Liu et al. | Long-chain poly-arginine functionalized porous Fe3O4 microspheres as magnetic flocculant for efficient harvesting of oleaginous microalgae | |
| CN114212890A (en) | High-value utilization method of microalgae energy | |
| Vasantha et al. | Application of nanotechnology toward improved production of sustainable bioenergy | |
| CN106311148B (en) | A kind of charcoal composite material and preparation method | |
| CN115231684A (en) | Method for treating dye wastewater by using sludge hydrothermal biochar activated persulfate | |
| CN114410695A (en) | Hydroxyapatite, preparation method thereof and application thereof in hydrogen production by dark fermentation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220322 |