CN116621320A - Biological composite carbon source prepared from blue algae and preparation process thereof - Google Patents
Biological composite carbon source prepared from blue algae and preparation process thereof Download PDFInfo
- Publication number
- CN116621320A CN116621320A CN202310343515.0A CN202310343515A CN116621320A CN 116621320 A CN116621320 A CN 116621320A CN 202310343515 A CN202310343515 A CN 202310343515A CN 116621320 A CN116621320 A CN 116621320A
- Authority
- CN
- China
- Prior art keywords
- weight
- blue algae
- parts
- prepared
- halloysite
- 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.)
- Granted
Links
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 150
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 110
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000007788 liquid Substances 0.000 claims abstract description 139
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 139
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 137
- 238000000855 fermentation Methods 0.000 claims abstract description 102
- 230000004151 fermentation Effects 0.000 claims abstract description 101
- 238000000151 deposition Methods 0.000 claims abstract description 65
- 239000000843 powder Substances 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 241000193749 Bacillus coagulans Species 0.000 claims abstract description 43
- 229940054340 bacillus coagulans Drugs 0.000 claims abstract description 43
- 244000063299 Bacillus subtilis Species 0.000 claims abstract description 39
- 235000014469 Bacillus subtilis Nutrition 0.000 claims abstract description 39
- 229940088594 vitamin Drugs 0.000 claims abstract description 38
- 229930003231 vitamin Natural products 0.000 claims abstract description 38
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- 238000007710 freezing Methods 0.000 claims abstract description 26
- 230000008014 freezing Effects 0.000 claims abstract description 26
- 229920001690 polydopamine Polymers 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 230000005291 magnetic effect Effects 0.000 claims description 81
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 79
- 229910052757 nitrogen Inorganic materials 0.000 claims description 64
- 230000008021 deposition Effects 0.000 claims description 59
- 150000001875 compounds Chemical class 0.000 claims description 58
- 229910052751 metal Inorganic materials 0.000 claims description 56
- 239000002184 metal Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 53
- 238000005406 washing Methods 0.000 claims description 52
- 238000001035 drying Methods 0.000 claims description 48
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 35
- 238000001914 filtration Methods 0.000 claims description 33
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000001569 carbon dioxide Substances 0.000 claims description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 23
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 239000001110 calcium chloride Substances 0.000 claims description 20
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 20
- 235000011148 calcium chloride Nutrition 0.000 claims description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 238000012258 culturing Methods 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- 235000002639 sodium chloride Nutrition 0.000 claims description 19
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- 229930003451 Vitamin B1 Natural products 0.000 claims description 18
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 239000000661 sodium alginate Substances 0.000 claims description 18
- 235000010413 sodium alginate Nutrition 0.000 claims description 18
- 229940005550 sodium alginate Drugs 0.000 claims description 18
- 229960003495 thiamine Drugs 0.000 claims description 18
- 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 18
- 235000010374 vitamin B1 Nutrition 0.000 claims description 18
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- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 claims description 18
- 235000005282 vitamin D3 Nutrition 0.000 claims description 18
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 17
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 17
- 229960002089 ferrous chloride Drugs 0.000 claims description 16
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 15
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 15
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 230000001804 emulsifying effect Effects 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 13
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 13
- 230000001954 sterilising effect Effects 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002054 inoculum Substances 0.000 claims description 12
- 159000000003 magnesium salts Chemical class 0.000 claims description 12
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- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
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- 230000001502 supplementing effect Effects 0.000 claims description 11
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- 230000003213 activating effect Effects 0.000 claims description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 10
- 159000000007 calcium salts Chemical class 0.000 claims description 10
- 239000001963 growth medium Substances 0.000 claims description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
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- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- 238000007781 pre-processing Methods 0.000 claims description 9
- 238000004659 sterilization and disinfection Methods 0.000 claims description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
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- 206010021143 Hypoxia Diseases 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- UOELMDIOCSFSEN-FVZZCGLESA-N 7-Dehydrositosterol Chemical compound C1([C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)C=C[C@H](C)C(C)C)=CC=C1C[C@@H](O)CCC1=C.C1[C@@H](O)CCC2(C)C(CC[C@@]3([C@@H]([C@H](C)C=C[C@H](C)C(C)C)CC[C@H]33)C)C3=CC=C21 UOELMDIOCSFSEN-FVZZCGLESA-N 0.000 claims description 2
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- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 2
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 2
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- 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 claims description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 238000000354 decomposition reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
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- 241001148471 unidentified anaerobic bacterium Species 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- 241000709785 Hermetia illucens Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 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 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 239000011550 stock solution Substances 0.000 description 1
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- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
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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
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
Abstract
The invention provides a biological composite carbon source prepared by blue algae and a preparation process thereof, belonging to the technical field of sewage treatment. Adding blue algae powder into water, and repeatedly freezing and thawing to obtain blue algae wall-breaking liquid; soaking halloysite in alkali solution, and depositing MgO and Fe on the surface 3 O 4 Further depositing a polydopamine layer on the surface, adding the polydopamine layer, blue algae liquid, a vitamin composition and inorganic salt into water to prepare a fermentation substrate, inoculating bacillus subtilis and bacillus coagulans, and fermenting to prepare a fermentation product; the preparation method is simple, has good slow release effect, long acting time, low investment cost and low running cost, and is nitrified after being put into useHigh speed and good denitrification and dephosphorization effect.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a biological composite carbon source prepared by blue algae and a preparation process thereof.
Background
The sewage treatment plant is used as a town drainage receiving unit and is also the most critical link for finally discharging water. The current treatment process of more than 90% of sewage treatment plants adopts biological treatment method, biological denitrification is a core process for nitrogen removal, nitrogen in water is converted into gaseous nitrogen to be removed by utilizing nitrification and denitrification processes of microorganisms, when organic matters in water are insufficient, biological activity is reduced, denitrification process is blocked, denitrification effect is poor, especially water temperature is reduced in winter, activity of nitrifying bacteria and denitrifying bacteria is further reduced, and in order to improve activity, additional carbon supplement agent is needed to enhance denitrification effect.
The products currently on the market as carbon supplements are of a large variety, including glucose, organic acid salts, alcohols, by-products of chemical industry production enterprises, and the like. Glucose is generally used as an ideal carbon supplementing agent and is easy to be absorbed by microorganisms, but the control on the adding position and the adding amount is strict, if the control is improper, filamentous bacteria are easy to reproduce, sludge expansion is caused, and the water quality of effluent of a sedimentation tank is poor; the organic acid salt type carbon supplementing agent is mainly divided into low-molecular linear organic acid salt and aromatic benzene ring organic acid salt, the low-molecular direct organic acid salt is beneficial to microorganism absorption, the aromatic benzene ring organic acid salt can not be directly utilized by microorganisms, the organic acid salt type carbon supplementing agent is easy to cause the change of pH value and salt content, and the adding amount is greatly limited; alcohol carbon supplements are generally ethanol or methanol, and are used as dangerous chemicals, so that the use and management processes have great limitation; the byproducts of chemical industry production enterprises have low price, but the components are complex and unstable, and harmful and toxic substances easily cause fatal harm to a sewage treatment system, so that the whole biological system is crashed.
The main mode of treating blue algae outbreak at present is to salvage blue algae, then separate the blue algae from water and filter-press. The algae mud produced by filter pressing is mainly used for preparing organic fertilizer, producing biogas, raising hermetia illucens and the like. Because the recycling mode has low added value and cannot be widely popularized due to the influence of economic benefits, a recycling technology for efficiently utilizing blue algae resources and changing the blue algae resources into valuable is urgently needed. The blue algae is rich in organic matters, volatile organic acids mainly comprising acetic acid, propionic acid and butyric acid can be produced by breaking the wall of blue algae cells and anaerobic fermentation, and can be used as a high-quality carbon source of a sewage treatment plant, and the blue algae is wide in source and can be used as a raw material. Crude glycerol is a byproduct of the biodiesel production process, and green treatment and application thereof have been the subject of urgent research.
The Chinese patent application (application number 201810942764.0, publication date 2018, 12 month 11) discloses a preparation method of a composite adsorption filler containing a slow-release carbon source, which comprises the following steps: comprises the following components in percentage by weight: 28% -35% of cement, 14% -20% of fly ash, 10% -25% of zeolite powder, 20% -25% of diatomite, 8% -12% of bentonite and 3% of carbon source are used as solid raw materials, water is added and stirred into mud, and the mud is filled in a mould; demoulding for 3-5 days at 15-25deg.C and humidity of 50% -60%, maintaining for 7 days, and air drying. From the formula, the content of the slow-release carbon source is too small, and the denitrification effect is very limited.
The slow-release carbon source disclosed by the Chinese patent application No. 201811301778.0 (publication No. 2019, 1 month and 8 days) comprises or consists of 20-50 parts of carbon source components, 3-5 parts of alkalinity components, 30-60 parts of framework materials and 0.5-5 parts of forming aids, and is subjected to vacuum drying during preparation; and then uniformly mixing in a high-speed mixer, injecting into a double-screw extruder, carrying out melt blending granulation, and then carrying out extrusion molding to obtain the slow-release carbon source sheet.
The invention discloses a slow-release carbon source filler of biochar viscose fiber and a preparation method thereof (application number 201610671863.0, published day 2016, 12 months and 7 days), wherein the slow-release carbon source filler takes viscose fiber as a skeleton and a slow-release carbon source, and the slow-release carbon source filler comprises the following components in percentage by mass: 85-95% of viscose fiber and 5-15% of biochar, wherein the average particle size of the biochar is 50-100 mu m, the ratio of the biochar with the particle size smaller than 60 mu m is not lower than 30%, the ratio of the biochar with the particle size larger than 100 mu m is not more than 20%, and the maximum particle size of the biochar is not more than 200 mu m. In the technology, the viscose fiber is used as a slow-release carbon source filler skeleton and also used as a carbon source slow-release material. In fact, after the viscose fiber slow-release carbon source film is hung, the viscose fiber slow-release carbon source film is tightly contacted with the fiber to form a biological film formed by inner anaerobic bacteria, the degradation of the viscose fiber by the anaerobic bacteria is very slow, the utilization effect is not obvious, the contact area and the adding amount of the fiber need to be greatly improved, the filter material of the biological filter is blocked due to falling of the biological film, and the filtering efficiency of the filter material is also influenced by the fiber, so that the viscose fiber is not applicable to the denitrification biological filter. In addition, wet spinning not only needs various and huge stock solution preparation and preparation equipment before spinning, but also has coagulating bath, circulation and recovery equipment, and has complex process flow, large investment cost of factory buildings and equipment, low spinning speed and higher cost.
The existing slow-release carbon source has the following defects: 1) The slow release rate is uncontrollable; 2) The slow-release carbon chain is too long, can not be directly utilized, has low utilization rate and poor effect; 3) In the slow release process, pollutants such as nitrogen, phosphorus and the like are released simultaneously, so that secondary pollution is caused; 4) The large cellulose structure is easy to block filter material filter holes; 5) Complicated preparation process, high cost, and the like.
At present, higher requirements are put on the selection of the composite carbon source, so that the activity of microorganisms is improved, the stability of the original biological system is not affected, harmful and toxic substances are not brought, meanwhile, the safety and the economy of the use process are considered, and blue algae is a very intelligent choice.
Disclosure of Invention
The invention aims to provide a biological composite carbon source prepared by using blue algae and a preparation process thereof, wherein blue algae is used as a main raw material, waste is treated by waste, the preparation method of the prepared composite carbon source is simple, the preparation method has good slow release effect, long action time, low investment cost and low operation cost, and the prepared composite carbon source has high nitrification rate, good denitrification and phosphorus effects and wide application prospect after being put into use.
The technical scheme of the invention is realized as follows:
The invention provides a preparation process for preparing a biological composite carbon source by using blue algae, which comprises the steps of adding blue algae powder into water, and repeatedly freezing and thawing to obtain blue algae wall-breaking liquid; soaking halloysite in alkali solution, and depositing MgO and Fe on the surface 3 O 4 Further depositing a polydopamine layer on the surfaceAdding the prepared modified MgO deposited magnetic halloysite, blue algae liquid, a vitamin composition and inorganic salt into water to prepare a fermentation substrate, inoculating bacillus subtilis and bacillus coagulans strain seed liquid, and fermenting and culturing to prepare a fermentation product; adding aluminum salt, calcium salt and sodium carboxymethyl cellulose into water, reacting to obtain metal-containing lamellar compound, embedding the compound and fermented product into polyvinyl alcohol and sodium alginate shell, and preparing biological composite carbon source by blue algae.
As a further improvement of the invention, the method comprises the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, repeatedly freezing and thawing, and homogenizing to obtain blue algae wall breaking liquid;
s2, preprocessing halloysite: soaking halloysite powder in alkali liquor, filtering, washing and drying to obtain pretreated halloysite;
s3, preparing MgO deposition magnetic halloysite: dissolving magnesium salt, ferric chloride and ferrous chloride in water, adding the pretreated halloysite powder prepared in the step S2, dropwise adding ammonia water under the protection of inert gas, heating and stirring for reaction, filtering, washing and calcining to prepare MgO-deposited magnetic halloysite;
S4, modifying polydopamine: uniformly dispersing the MgO deposition magnetic halloysite prepared in the step S3 in water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, separating a magnet, washing and drying to prepare the modified MgO deposition magnetic halloysite;
s5, preparing a fermentation substrate: adding the blue algae wall-breaking liquid prepared in the step S1, the modified MgO deposition magnetic halloysite prepared in the step S4, the vitamin composition and the inorganic salt into water, and sterilizing to prepare a fermentation substrate;
s6, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture to obtain strain seed liquid;
s7, fermenting: inoculating the bacillus subtilis strain seed liquid and the bacillus coagulans strain seed liquid prepared in the step S6 to the fermentation substrate prepared in the step S5 for fermentation culture for a first time period, supplementing the modified MgO deposited magnetic halloysite prepared in the step S4, continuing fermentation culture for a second time period, filtering, concentrating the filtrate, and drying to obtain a fermented product;
s8, preparing a metal-containing lamellar compound: dissolving aluminum salt and calcium salt in water, adding sodium carboxymethylcellulose under the protection of inert gas, regulating the pH value of the solution, heating and stirring, cooling, centrifuging, washing, drying and grinding to obtain a metal-containing lamellar compound;
S9, preparing embedding liquid: dissolving polyvinyl alcohol and sodium alginate in water to obtain embedding liquid;
s10, preparing a biological composite carbon source by using blue algae: adding the metal-containing layered compound prepared in the step S8 and the fermented product prepared in the step S7 into the embedding liquid prepared in the step S9, uniformly mixing, emulsifying, dropwise adding a calcium chloride solution, solidifying at normal temperature, centrifuging, washing, and drying to prepare the biological composite carbon source by using blue algae.
As a further improvement of the invention, the solid-to-liquid ratio of the blue algae powder to the water in the step S1 is 1:5-10g/mL, the repeated freezing and thawing method is that the suspension is frozen for 2-4 hours at the temperature of minus 20 ℃ to minus 25 ℃ and then dissolved at room temperature, and then the operation is repeated for 1-2 times, the rotation speed of the homogenate is 12000-15000r/min, and the time is 15-20min; the solid-to-liquid ratio of the halloysite powder to the alkali liquor in the step S2 is 1:3-5g/mL, the alkali liquor is 7-10wt% NaOH or KOH solution, and the soaking time is 30-50min.
As a further improvement of the invention, in the step S3, the magnesium salt is at least one of magnesium chloride, magnesium nitrate and magnesium sulfate, the molar ratio of the magnesium salt to the ferric chloride to the ferrous chloride is 2-3:1:1, the mass ratio of the magnesium salt to the pretreated halloysite powder is 3-5:10, the concentration of the ammonia water is 22-25wt%, the temperature of the heating and stirring reaction is 40-50 ℃ for 1-2h, the calcining temperature is 300-500 ℃ for 2-3h; in the step S4, the mass ratio of the MgO deposition magnetic halloysite to the dopamine hydrochloride to the catalyst is 10:12-15:0.2-0.4, and the catalyst contains 3-5wt% of Co (NO 3 ) 2 The temperature of the heating and stirring reaction is 45-50 ℃ and the time is 30-50min.
As a further improvement of the invention, in the step S5, the mass ratio of the blue algae wall breaking liquid to the modified MgO deposition magnetic halloysite to the vitamin composition to the inorganic salt to the water is 20-30:7-12:2-4:1-3:100-120, wherein the vitamin composition is at least two of vitamin A, vitamin B1, vitamin B2, vitamin B3, vitamin B6, vitamin B12, vitamin C, vitamin D1, vitamin D3, vitamin K, vitamin E and folic acid, and the inorganic salt is at least one of sodium chloride, potassium chloride, calcium chloride, magnesium sulfate, ferric chloride, zinc sulfate, copper sulfate, manganese sulfate, zinc chloride, copper chloride, manganese chloride, ferric sulfate, copper nitrate, magnesium nitrate, copper nitrate and manganese nitrate; and step S6, the condition of the activation culture is that the activation culture is carried out for 12-18 hours under the micro-anoxic condition at the temperature of 36-38 ℃ and at the speed of 50-70r/min, wherein the micro-anoxic condition is that the oxygen content is 3-7v/v%, the carbon dioxide content is 3-5v/v%, and the balance is nitrogen.
As a further improvement of the invention, the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 3-5:2.
As a further improvement of the invention, the seed liquids of the bacillus subtilis and the bacillus coagulans in the step S7 have the inoculum sizes of 2-4% and 1-3% respectively, the conditions of fermentation culture are that under the micro-anoxic condition, the conditions of micro-anoxic condition are that the oxygen content is 3-7v/v%, the carbon dioxide content is 3-5v/v% and the balance is nitrogen, the first time period is 24-36h, the second time period is 12-18h, and the addition amount of the supplementary modified MgO deposited magnetic halloysite is 3-5g/L; in the step S8, the aluminum salt is selected from at least one of aluminum chloride, aluminum nitrate and aluminum sulfate, the calcium salt is selected from at least one of calcium chloride, calcium sulfate and calcium nitrate, the molar ratio of the aluminum salt to the calcium salt to the sodium carboxymethyl cellulose is 2:3:3-5, the pH is adjusted to 8.5-8.8, the temperature of heating and stirring is 70-80 ℃, and the time is 3-5h.
As a further improvement of the invention, the mass ratio of the polyvinyl alcohol, the sodium alginate and the water in the step S9 is 10-12:15-20:100; in the step S10, the mass ratio of the metal-containing layered compound to the fermentation product to the embedding liquid is 5-10:7-12:50-60, the emulsification condition is 10000-12000r/min, the time is 3-5min, the concentration of the calcium chloride solution is 10-15wt%, and the normal-temperature solidification time is 20-30min.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:5-10g/mL, repeatedly freezing and thawing, homogenizing for 15-20min at 12000-15000r/min, and obtaining blue algae wall-breaking liquid;
the repeated freezing and thawing method comprises the steps of placing the suspension in a temperature range of-20 to-25 ℃ for freezing for 2-4 hours, dissolving at room temperature, and repeating the operation for 1-2 times;
s2, preprocessing halloysite: immersing halloysite powder in 7-10wt% NaOH or KOH solution for 30-50min, wherein the solid-to-liquid ratio of the halloysite powder to alkali liquor is 1:3-5g/mL, filtering, washing and drying to obtain pretreated halloysite;
s3, preparing MgO deposition magnetic halloysite: dissolving 3-5 parts by weight of magnesium salt, ferric chloride and ferrous chloride in 50 parts by weight of water, wherein the molar ratio of the magnesium salt to the ferric chloride to the ferrous chloride is 2-3:1:1, adding 10 parts by weight of the pretreated halloysite powder prepared in the step S2, dropwise adding 10-12 parts by weight of 22-25wt% ammonia water under the protection of inert gas, heating to 40-50 ℃, stirring for reacting for 1-2 hours, filtering, washing, and calcining at 300-500 ℃ for 2-3 hours to prepare MgO-deposited magnetic halloysite;
s4, modifying polydopamine: uniformly dispersing 10 parts by weight of the MgO deposition magnetic halloysite prepared in the step S3 in 100 parts by weight of water, adding 12-15 parts by weight of dopamine hydrochloride and 0.2-0.4 part by weight of catalyst, heating to 45-50 ℃, stirring and reacting for 30-50min, separating by a magnet, washing and drying to prepare the modified MgO deposition magnetic halloysite;
The catalyst contains 3-5wt% Co (NO) 3 ) 2 Tris-HCl solution at ph=5.5-6;
s5, preparing a fermentation substrate: adding 20-30 parts by weight of blue algae wall-breaking liquid prepared in the step S1, 7-12 parts by weight of modified MgO deposition magnetic halloysite prepared in the step S4, 2-4 parts by weight of vitamin composition and 1-3 parts by weight of inorganic salt into 100-120 parts by weight of water, and carrying out ultraviolet sterilization to prepare a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 3-5:2;
s6, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture for 12-18 hours under the micro-anoxic condition at 36-38 ℃ and 50-70r/min to obtain strain seed liquid;
the micro-anoxic condition is that the oxygen content is 3-7v/v%, the carbon dioxide content is 3-5v/v%, and the balance is nitrogen;
s7, fermenting: inoculating the bacillus subtilis and bacillus coagulans strain seed liquid prepared in the step S6 into the fermentation substrate prepared in the step S5, wherein the inoculum sizes of the bacillus subtilis and bacillus coagulans strain seed liquid are respectively 2-4% and 1-3%, the temperature is 36-38 ℃, the speed is 50-70r/min, fermentation culture is carried out for 24-36h under a micro-anoxic condition, the modified MgO deposition magnetic halloysite prepared in the step S4 is supplemented, the additive amount is 3-5g/L, fermentation culture is continued for 12-18h, filtering, filtrate concentration and drying are carried out, and a fermented product is prepared;
The micro-anoxic condition is that the oxygen content is 3-7v/v%, the carbon dioxide content is 3-5v/v%, and the balance is nitrogen;
s8, preparing a metal-containing lamellar compound: dissolving 2 molar equivalents of aluminum salt and 3 molar equivalents of calcium salt in 50 parts by weight of water, adding 3-5 molar equivalents of sodium carboxymethyl cellulose under the protection of inert gas, adjusting the pH value of the solution to 8.5-8.8, heating to 70-80 ℃, stirring for 3-5 hours, cooling, centrifuging, washing, drying and grinding to obtain a metal-containing lamellar compound;
s9, preparing embedding liquid: 10-12 parts by weight of polyvinyl alcohol and 15-20 parts by weight of sodium alginate are dissolved in 100 parts by weight of water to obtain embedding liquid;
s10, preparing a biological composite carbon source by using blue algae: adding 5-10 parts by weight of the metal-containing layered compound prepared in the step S8 and 7-12 parts by weight of the fermentation product prepared in the step S7 into 50-60 parts by weight of the embedding liquid prepared in the step S9, uniformly mixing, emulsifying for 3-5min at 10000-12000r/min, dropwise adding 10-15wt% of calcium chloride solution, curing for 20-30min at normal temperature, centrifuging, washing, and drying to prepare the biological composite carbon source prepared by using blue algae.
The invention further protects the biological composite carbon source prepared by the preparation method and prepared by using the blue algae.
Preferably, the inert gas is at least one selected from nitrogen, neon, helium and argon.
The invention has the following beneficial effects: the method disclosed by the invention is characterized in that the cell wall of the blue algae is destroyed by adopting a repeated freeze thawing method, so that substances such as glycoprotein, polysaccharide and the like which are rich in nutrition in the blue algae are dissolved out, and after homogenization, a relatively uniform blue algae wall-breaking liquid is prepared, which is used as one of main substances of a fermentation matrix, contains rich carbon sources and nitrogen sources, provides sufficient raw materials for fermentation, greatly improves the yield of short-chain fatty acids, small-molecule sugar, carbohydrates and the like produced by fermentation, and improves the recycling effect of the blue algae, thereby realizing the effect of treating waste by waste.
The organic matters in the blue algae have complex components and low biodegradation and bioconversion efficiency, and the hydrolytic acidification of the blue algae in the fermentation process can be limited to generate carbon source substances.
The invention adds and prepares the modified MgO deposition magnetic halloysite, takes porous and cheap halloysite powder as a framework, and deposits ferromagnetic Fe on the surface 3 O 4 And MgO, and further carrying a polydopamine layer on the surface. The metal oxide includes Fe 3 O 4 And MgO, wherein ferromagnetic Fe 3 O 4 Has the characteristics of strong magnetism, good adsorptivity, good electric conductivity and the like, can be used as a carrier for electron transfer between anaerobic microorganisms with an extracellular electron transfer function, thereby strengthening the inter-species electron transfer between the anaerobic microorganisms, improving the acid production efficiency and the yield of zymobacteria because a direct inter-species electron transfer is established in a reaction system, the transfer is located above magnetite particles, and mediates electron transfer between Bacillus subtilis and Bacillus coagulans, and the iron oxide can promote fermentation bacteria to utilize various substrates and participate in the decomposition of complex organic matters by reduction of iron oxide, and improve phase of hydrolysis acidificationThe activity of the related enzyme is enhanced, the activities of alpha-glucokinase, protease and acetate kinase are enhanced, the relative abundance of the fermenting bacteria is improved, and the yield of short-chain fat is improved.
However, in the fermentation process of the fermenting bacteria, a certain amount of N, P and other elements are inevitably released, and if the element is directly used as an additional carbon source for biological denitrification and dephosphorization of sewage, N, P load of the system can be increased, and the original ecological system is impacted. Therefore, N, P in the fermentation broth needs to be recovered to improve the purity as a carbon source.
The modified MgO-deposited magnetic halloysite prepared by the invention has another important function, wherein MgO can improve NH in fermentation broth 4 + Phosphate (PO) 4 3- 、HPO 4 2- 、H 2 PO 4 - ) The deposition of the polymer is carried out so as to efficiently adsorb N, P impurities in the fermentation broth, in addition, the polydopamine layer on the surface layer contains rich amino, hydroxyl, carboxyl and other groups, and has good hydrogen bond adsorption capacity for nitrate ions, phosphate ions and ammonium ions, so that the content of N, P in the fermentation broth is greatly reduced, N, P in the fermentation broth is removed by adopting an adsorption precipitation method, and the adsorbed modified MgO deposition magnetic halloysite can be separated by magnetism, and the product can be used as a slow release fertilizer. Compared with the traditional fertilizer, the fertilizer can ensure the growth of crops, and the low solubility of the fertilizer ensures that the fertilizer is slowly dissolved in the environment, so that the nutrient release rate is suitable for the absorption of crops, and the recycling of intermediate products is further realized.
The added vitamin composition comprises a mixture of vitamin B1 and vitamin D3, and is added into a fermentation substrate, so that the resistance of zymobacteria can be obviously improved, the acid production capacity of the zymobacteria can be improved, the time of a stable period can be prolonged, the acid production yield can be improved, and the fermentation product contains rich short-chain fatty acid and other carbohydrates.
In addition, modified MgO deposited magnetic halloysite is also added in the fermentation process, the stress resistance of the fermentation bacteria is further improved by the released metal ions, the stable period of the fermentation bacteria is prolonged, the acid production efficiency is further improved, the fixation of N, P in the fermentation liquid is improved to a certain extent, and the N, P content in the fermentation product is extremely small.
The invention also prepares the metal-containing lamellar compound which is a lamellar structure containing bimetal, negative ions are combined between layers, hydrogen bonds exist between the layers, the metal-containing lamellar compound is tightly combined, the structure is stable, and the metal-containing lamellar compound has good mechanical property and slow release property. According to the invention, the metal-containing layered compound and the ferment are mixed, and the metal-containing layered compound can fix the ferment through hydrogen bonds, so that the slow release effect of the carbon source is further improved. Meanwhile, the metal-containing layered compound can also slowly release metal ions aluminum and calcium, so that the biological denitrification rate is improved, the microbial denitrification performance is improved, and the organic matter sodium hydroxymethyl cellulose has the advantages of adhesiveness and low cost, and can be used as a carbon source to promote the reaction of nitrifying bacteria or denitrifying bacteria.
The invention adopts the mixture of the polyvinyl alcohol and the sodium alginate as an embedding shell layer, embeds the metal-containing lamellar compound and the ferment, realizes the slow release function of the carbon source, prolongs the action time of the carbon source, is also a biodegradable polymer material, can be degraded in organisms or is subjected to enzymolysis by extracellular enzymes released by microorganisms to generate micromolecular organic matters, is utilized by organisms, and has the characteristics of good biodegradability and stable carbon release performance as the carbon source, environmental friendliness, high mechanical strength, good water stability and high biocompatibility.
The preparation method of the biological composite carbon source by using blue algae takes blue algae as a main raw material, realizes 'waste' treatment by 'waste', has the advantages of simple preparation process, good slow release effect, long acting time, low investment cost and low operation cost, and has high nitrification rate, good denitrification and phosphorus effect and wide application prospect after the prepared composite carbon source is put into use.
Description of the embodiments
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Blue algae powder is purchased from Jiangsu national information and co-energy limited company, and is subjected to deep dehydration and drying until the solid content is more than 90%, and is ground into powder to obtain the blue algae powder.
Halloysite powder with a particle size of 300 meshes, white or pink, and a refractoriness of 1730-1750 ℃ is purchased from a mineral product processing plant in the Ministry of life.
Bacillus subtilis, 200 hundred million cfu/g, purchased from Jinan Qinghai chemical Co., ltd; bacillus coagulans, BCN-019, 100 hundred million cfu/g, purchased from Jia Yi bioengineering Co., ltd., shandong,
Example 1
The embodiment provides a preparation process for preparing a biological composite carbon source by using blue algae, which specifically comprises the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:5g/mL, repeatedly freezing and thawing, homogenizing for 15min at 12000r/min, and preparing blue algae wall-breaking liquid;
the repeated freezing and thawing method comprises the steps of placing the suspension in a temperature of minus 20 ℃ for 2 hours, dissolving at room temperature, and repeating the operation for 1 time;
s2, preprocessing halloysite: immersing halloysite powder in a 7wt% NaOH solution for 30min, wherein the solid-to-liquid ratio of the halloysite powder to the 7wt% NaOH solution is 1:3g/mL, filtering, washing with clear water, and drying at 105 ℃ for 1h to obtain pretreated halloysite;
s3, preparing MgO deposition magnetic halloysite: dissolving 3 parts by weight of magnesium sulfate, 4.1 parts by weight of ferric chloride and 3.2 parts by weight of ferrous chloride in 50 parts by weight of water, adding 10 parts by weight of the pretreated halloysite powder prepared in the step S2, dropwise adding 10 parts by weight of 22wt% ammonia water under the protection of argon, heating to 40 ℃, stirring for reacting for 1h, filtering, washing with clear water, and calcining at 300 ℃ for 2h to prepare MgO deposition magnetic halloysite;
s4, modifying polydopamine: uniformly dispersing 10 parts by weight of the MgO deposition magnetic halloysite prepared in the step S3 in 100 parts by weight of water, adding 12 parts by weight of dopamine hydrochloride and 0.2 part by weight of catalyst, heating to 45 ℃, stirring and reacting for 30min, separating the magnet, washing with clear water, and drying at 105 ℃ for 1h to prepare the modified MgO deposition magnetic halloysite;
The catalyst was a catalyst containing 3wt% Co (NO 3 ) 2 Tris-HCl solution at ph=5.5;
s5, preparing a fermentation substrate: adding 20 parts by weight of blue algae wall breaking liquid prepared in the step S1, 7 parts by weight of modified MgO deposition magnetic halloysite prepared in the step S4, 2 parts by weight of vitamin composition, 0.5 part by weight of sodium chloride, 0.2 part by weight of zinc sulfate, 0.1 part by weight of copper sulfate and 0.2 part by weight of manganese sulfate into 100 parts by weight of water, and carrying out ultraviolet sterilization to obtain a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 3:2;
s6, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture for 12 hours under the micro-anoxic condition at 36 ℃ and 50r/min to obtain strain seed liquid;
the micro-anoxic condition is that the oxygen content is 3v/v%, the carbon dioxide content is 3v/v%, and the balance is nitrogen;
s7, fermenting: inoculating the bacillus subtilis and bacillus coagulans strain seed liquid prepared in the step S6 into the fermentation substrate prepared in the step S5, wherein the inoculum size of the bacillus subtilis and bacillus coagulans strain seed liquid is 2% and 1%, respectively, at 36 ℃, at 50r/min, fermenting and culturing for 24 hours under a micro-anoxic condition, supplementing the modified MgO deposition magnetic halloysite prepared in the step S4, adding the additive amount of 3g/L, continuing fermenting and culturing for 12 hours, filtering, concentrating filtrate, and freeze-drying to obtain a fermented product;
The micro-anoxic condition is that the oxygen content is 3v/v%, the carbon dioxide content is 3v/v%, and the balance is nitrogen;
s8, preparing a metal-containing lamellar compound: dissolving 2mol of aluminum chloride and 3mol of calcium chloride in 50 parts by weight of water, adding 3mol of sodium carboxymethylcellulose under the protection of argon, adjusting the pH value of the solution to 8.5, heating to 70 ℃, stirring for 3 hours, cooling, centrifuging at 3000r/min for 15 minutes, washing with clear water, drying at 105 ℃ for 1 hour, grinding, and sieving with a 100-mesh sieve to obtain a metal-containing lamellar compound;
s9, preparing embedding liquid: 10 parts by weight of polyvinyl alcohol and 15 parts by weight of sodium alginate are dissolved in 100 parts by weight of water to obtain embedding liquid;
s10, preparing a biological composite carbon source by using blue algae: adding 5 parts by weight of the metal-containing layered compound prepared in the step S8 and 7 parts by weight of the fermentation product prepared in the step S7 into 50 parts by weight of the embedding liquid prepared in the step S9, uniformly mixing, emulsifying for 3min at 10000r/min, dropwise adding 10wt% of calcium chloride solution, solidifying for 20min at normal temperature, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 1h at 105 ℃ to prepare the biological composite carbon source by using blue algae.
Example 2
The embodiment provides a preparation process for preparing a biological composite carbon source by using blue algae, which specifically comprises the following steps:
S1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:10g/mL, repeatedly freezing and thawing, homogenizing for 20min at 15000r/min, and preparing blue algae wall-breaking liquid;
the repeated freezing and thawing method comprises the steps of placing the suspension in a temperature of minus 25 ℃ for 4 hours, dissolving at room temperature, and repeating the operation for 2 times;
s2, preprocessing halloysite: immersing halloysite powder in a 10wt% KOH solution for 50min, wherein the solid-to-liquid ratio of the halloysite powder to the 10wt% KOH solution is 1:5g/mL, filtering, washing with clear water, and drying at 105 ℃ for 1h to obtain pretreated halloysite;
s3, preparing MgO deposition magnetic halloysite: dissolving 5 parts by weight of magnesium nitrate, 5.5 parts by weight of ferric chloride and 4.3 parts by weight of ferrous chloride in 50 parts by weight of water, adding 10 parts by weight of the pretreated halloysite powder prepared in the step S2, dropwise adding 12 parts by weight of 25wt% ammonia water under the protection of helium, heating to 50 ℃, stirring for reacting for 2 hours, filtering, washing with clear water, and calcining at 500 ℃ for 3 hours to prepare MgO deposition magnetic halloysite;
s4, modifying polydopamine: uniformly dispersing 10 parts by weight of the MgO deposition magnetic halloysite prepared in the step S3 in 100 parts by weight of water, adding 15 parts by weight of dopamine hydrochloride and 0.4 part by weight of catalyst, heating to 50 ℃, stirring and reacting for 50min, separating the magnet, washing with clear water, and drying at 105 ℃ for 1h to prepare the modified MgO deposition magnetic halloysite;
The catalyst was a catalyst containing 5wt% Co (NO 3 ) 2 Tris-HCl solution at ph=6;
s5, preparing a fermentation substrate: adding 30 parts by weight of blue algae wall breaking liquid prepared in the step S1, 12 parts by weight of modified MgO deposition magnetic halloysite prepared in the step S4, 4 parts by weight of vitamin composition, 2 parts by weight of sodium chloride, 0.2 part by weight of zinc chloride, 0.1 part by weight of copper chloride, 0.2 part by weight of manganese chloride, 0.3 part by weight of calcium chloride and 0.2 part by weight of magnesium sulfate into 120 parts by weight of water, and carrying out ultraviolet sterilization to obtain a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 5:2;
s6, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture for 18 hours under the micro-anoxic condition at 38 ℃ and 70r/min to obtain strain seed liquid;
the micro-anoxic condition is that the oxygen content is 7v/v%, the carbon dioxide content is 5v/v%, and the balance is nitrogen;
s7, fermenting: inoculating the bacillus subtilis and bacillus coagulans strain seed liquid prepared in the step S6 into the fermentation substrate prepared in the step S5, wherein the inoculum size of the bacillus subtilis and bacillus coagulans strain seed liquid is 4% and 3%, respectively, at 38 ℃, at 70r/min, fermenting and culturing for 36h under a micro-anoxic condition, supplementing the modified MgO deposition magnetic halloysite prepared in the step S4, adding 5g/L, continuing fermenting and culturing for 18h, filtering, concentrating filtrate, and freeze-drying to obtain a fermented product;
The micro-anoxic condition is that the oxygen content is 7v/v%, the carbon dioxide content is 5v/v%, and the balance is nitrogen;
s8, preparing a metal-containing lamellar compound: dissolving 2mol of aluminum chloride and 3mol of calcium chloride in 50 parts by weight of water, adding 5mol of sodium carboxymethylcellulose under the protection of helium, adjusting the pH value of the solution to 8.8, heating to 80 ℃, stirring for 5 hours, cooling, centrifuging at 3000r/min for 15 minutes, washing with clear water, drying at 105 ℃ for 1 hour, grinding, and sieving with a 100-mesh sieve to obtain a metal-containing lamellar compound;
s9, preparing embedding liquid: 12 parts by weight of polyvinyl alcohol and 20 parts by weight of sodium alginate are dissolved in 100 parts by weight of water to obtain embedding liquid;
s10, preparing a biological composite carbon source by using blue algae: adding 10 parts by weight of the metal-containing layered compound prepared in the step S8 and 12 parts by weight of the fermentation product prepared in the step S7 into 60 parts by weight of the embedding liquid prepared in the step S9, uniformly mixing, emulsifying for 5min at 12000r/min, dropwise adding 15wt% of calcium chloride solution, solidifying for 30min at normal temperature, centrifuging for 15min at 3000r/min, washing with clear water, drying at 105 ℃ for 1h, and preparing the biological composite carbon source by using blue algae.
Example 3
The embodiment provides a preparation process for preparing a biological composite carbon source by using blue algae, which specifically comprises the following steps:
S1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:7g/mL, repeatedly freezing and thawing, homogenizing for 17min at 13500r/min, and preparing blue algae wall-breaking liquid;
the repeated freezing and thawing method comprises the steps of placing the suspension in a temperature of-22 ℃ for 3 hours, dissolving at room temperature, and repeating the operation for 2 times;
s2, preprocessing halloysite: immersing halloysite powder in an 8.5wt% NaOH solution for 40min, wherein the solid-to-liquid ratio of the halloysite powder to the 8.5wt% NaOH solution is 1:4g/mL, filtering, washing with clear water, and drying at 105 ℃ for 1h to obtain pretreated halloysite;
s3, preparing MgO deposition magnetic halloysite: dissolving 4 parts by weight of magnesium chloride, 6.8 parts by weight of ferric chloride and 5.3 parts by weight of ferrous chloride in 50 parts by weight of water, adding 10 parts by weight of the pretreated halloysite powder prepared in the step S2, dropwise adding 11 parts by weight of 23.5wt% ammonia water under the protection of nitrogen, heating to 45 ℃, stirring and reacting for 1.5 hours, filtering, washing with clear water, and calcining at 400 ℃ for 2.5 hours to prepare MgO-deposited magnetic halloysite;
s4, modifying polydopamine: uniformly dispersing 10 parts by weight of the MgO deposition magnetic halloysite prepared in the step S3 in 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 0.3 part by weight of catalyst, heating to 47 ℃, stirring and reacting for 40min, separating the magnet, washing with clear water, and drying at 105 ℃ for 1h to prepare the modified MgO deposition magnetic halloysite;
The catalyst was a catalyst containing 4wt% Co (NO 3 ) 2 Tris-HCl solution at ph=5.7;
s5, preparing a fermentation substrate: adding 25 parts by weight of blue algae wall breaking liquid prepared in the step S1, 10 parts by weight of modified MgO deposition magnetic halloysite prepared in the step S4, 3 parts by weight of vitamin composition, 1 part by weight of sodium chloride, 0.6 part by weight of potassium chloride, 0.2 part by weight of calcium chloride, 0.1 part by weight of magnesium sulfate and 0.1 part by weight of zinc chloride into 110 parts by weight of water, and carrying out ultraviolet sterilization to obtain a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 4:2;
s6, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture for 16 hours under the micro-anoxic condition at 37 ℃ and 60r/min to obtain strain seed liquid;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen;
s7, fermenting: inoculating the bacillus subtilis and bacillus coagulans strain seed liquid prepared in the step S6 into the fermentation substrate prepared in the step S5, wherein the inoculum size of the bacillus subtilis and bacillus coagulans strain seed liquid is 3% and 2%, respectively, at 37 ℃ and 60r/min, fermenting and culturing for 30h under a micro-anoxic condition, supplementing the modified MgO deposition magnetic halloysite prepared in the step S4, adding the additive amount of 4g/L, continuing fermenting and culturing for 16h, filtering, concentrating filtrate, and freeze-drying to obtain a fermented product;
The micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen;
s8, preparing a metal-containing lamellar compound: dissolving 2mol of aluminum chloride and 3mol of calcium chloride in 50 parts by weight of water, adding 4mol of sodium carboxymethylcellulose under the protection of nitrogen, adjusting the pH value of the solution to 8.6, heating to 75 ℃, stirring for 4 hours, cooling, centrifuging at 3000r/min for 15 minutes, washing with clear water, drying at 105 ℃ for 1 hour, grinding, and sieving with a 100-mesh screen to obtain a metal-containing lamellar compound;
s9, preparing embedding liquid: 11 parts by weight of polyvinyl alcohol and 17 parts by weight of sodium alginate are dissolved in 100 parts by weight of water to obtain embedding liquid;
s10, preparing a biological composite carbon source by using blue algae: adding 7 parts by weight of the metal-containing layered compound prepared in the step S8 and 10 parts by weight of the fermentation product prepared in the step S7 into 55 parts by weight of the embedding liquid prepared in the step S9, uniformly mixing, emulsifying for 4min at 11000r/min, dropwise adding 12wt% of calcium chloride solution, solidifying for 25min at normal temperature, centrifuging for 15min at 3000r/min, washing with clear water, drying at 105 ℃ for 1h, and preparing the biological composite carbon source by using blue algae.
Example 4
The difference compared to example 3 is that the vitamin composition is a single vitamin B1.
Example 5
The difference compared to example 3 is that the vitamin composition is a single vitamin D3.
Comparative example 1
In comparison with example 3, the difference is that step S1 is not repeated freeze thawing.
The method comprises the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:7g/mL, and homogenizing for 17min at 13500r/min to obtain blue algae wall breaking liquid.
Comparative example 2
In comparison with example 3, the difference is that step S2 is not performed.
The method comprises the following steps:
the method specifically comprises the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:7g/mL, repeatedly freezing and thawing, homogenizing for 17min at 13500r/min, and preparing blue algae wall-breaking liquid;
the repeated freezing and thawing method comprises the steps of placing the suspension in a temperature of-22 ℃ for 3 hours, dissolving at room temperature, and repeating the operation for 2 times;
s2, preparation of MgO deposition magnetic halloysite: dissolving 4 parts by weight of magnesium chloride, 6.8 parts by weight of ferric chloride and 5.3 parts by weight of ferrous chloride in 50 parts by weight of water, adding 10 parts by weight of halloysite powder, dropwise adding 11 parts by weight of 23.5wt% ammonia water under the protection of nitrogen, heating to 45 ℃, stirring for reacting for 1.5 hours, filtering, washing with clear water, and calcining at 400 ℃ for 2.5 hours to prepare MgO deposition magnetic halloysite;
S3, modifying polydopamine: uniformly dispersing 10 parts by weight of the MgO deposition magnetic halloysite prepared in the step S2 in 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 0.3 part by weight of catalyst, heating to 47 ℃, stirring and reacting for 40min, separating the magnet, washing with clear water, and drying at 105 ℃ for 1h to prepare the modified MgO deposition magnetic halloysite;
the catalyst was a catalyst containing 4wt% Co (NO 3 ) 2 Tris-HCl solution at ph=5.7;
s4, preparation of a fermentation substrate: adding 25 parts by weight of blue algae wall breaking liquid prepared in the step S1, 10 parts by weight of modified MgO deposition magnetic halloysite prepared in the step S3, 3 parts by weight of vitamin composition, 1 part by weight of sodium chloride, 0.6 part by weight of potassium chloride, 0.2 part by weight of calcium chloride, 0.1 part by weight of magnesium sulfate and 0.1 part by weight of zinc chloride into 110 parts by weight of water, and carrying out ultraviolet sterilization to obtain a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 4:2;
s5, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture for 16 hours under the micro-anoxic condition at 37 ℃ and 60r/min to obtain strain seed liquid;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen;
S6, fermenting: inoculating the bacillus subtilis and bacillus coagulans strain seed liquid prepared in the step S5 into the fermentation substrate prepared in the step S5, wherein the inoculum size of the bacillus subtilis and bacillus coagulans strain seed liquid is 3% and 2%, respectively, at 37 ℃ and 60r/min, fermenting and culturing for 30h under a micro-anoxic condition, supplementing the modified MgO deposition magnetic halloysite prepared in the step S3, adding the additive amount of 4g/L, continuing fermenting and culturing for 16h, filtering, concentrating filtrate, and freeze-drying to obtain a fermented product;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen;
s7, preparing a metal-containing lamellar compound: dissolving 2mol of aluminum chloride and 3mol of calcium chloride in 50 parts by weight of water, adding 4mol of sodium carboxymethylcellulose under the protection of nitrogen, adjusting the pH value of the solution to 8.6, heating to 75 ℃, stirring for 4 hours, cooling, centrifuging at 3000r/min for 15 minutes, washing with clear water, drying at 105 ℃ for 1 hour, grinding, and sieving with a 100-mesh screen to obtain a metal-containing lamellar compound;
s8, preparing embedding liquid: 11 parts by weight of polyvinyl alcohol and 17 parts by weight of sodium alginate are dissolved in 100 parts by weight of water to obtain embedding liquid;
s9, preparing a biological composite carbon source by using blue algae: adding 7 parts by weight of the metal-containing layered compound prepared in the step S7 and 10 parts by weight of the fermentation product prepared in the step S6 into 55 parts by weight of the embedding liquid prepared in the step S8, uniformly mixing, emulsifying for 4min at 11000r/min, dropwise adding 12wt% of calcium chloride solution, solidifying for 25min at normal temperature, centrifuging for 15min at 3000r/min, washing with clear water, drying at 105 ℃ for 1h, and preparing the biological composite carbon source by using blue algae.
Comparative example 3
In comparison with example 3, the difference is that no magnesium chloride was added in step S3.
The method comprises the following steps:
s3, preparing MgO deposition magnetic halloysite: 9.6 parts by weight of ferric chloride and 7.5 parts by weight of ferrous chloride are dissolved in 50 parts by weight of water, 10 parts by weight of the pretreated halloysite powder prepared in the step S2 is added, 11 parts by weight of 23.5wt% ammonia water is dropwise added under the protection of nitrogen, the mixture is heated to 45 ℃, the mixture is stirred and reacted for 1.5 hours, the mixture is filtered, washed by clear water and calcined for 2.5 hours at 400 ℃, and the MgO deposition magnetic halloysite is prepared.
Comparative example 4
In comparison with example 3, the difference is that ferric chloride and ferrous chloride are not added in step S3.
The method comprises the following steps:
s3, preparing MgO deposition magnetic halloysite: dissolving 16.1 parts by weight of magnesium chloride in 50 parts by weight of water, adding 10 parts by weight of the pretreated halloysite powder prepared in the step S2, dropwise adding 11 parts by weight of 23.5wt% ammonia water under the protection of nitrogen, heating to 45 ℃, stirring and reacting for 1.5 hours, filtering, washing with clear water, and calcining at 400 ℃ for 2.5 hours to prepare the MgO-deposited magnetic halloysite.
Comparative example 5
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
the method specifically comprises the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:7g/mL, repeatedly freezing and thawing, homogenizing for 17min at 13500r/min, and preparing blue algae wall-breaking liquid;
The repeated freezing and thawing method comprises the steps of placing the suspension in a temperature of-22 ℃ for 3 hours, dissolving at room temperature, and repeating the operation for 2 times;
s2, preprocessing halloysite: immersing halloysite powder in an 8.5wt% NaOH solution for 40min, wherein the solid-to-liquid ratio of the halloysite powder to the 8.5wt% NaOH solution is 1:4g/mL, filtering, washing with clear water, and drying at 105 ℃ for 1h to obtain pretreated halloysite;
s3, modifying polydopamine: uniformly dispersing 10 parts by weight of the pretreated halloysite prepared in the step S2 in 100 parts by weight of water, adding 13.5 parts by weight of dopamine hydrochloride and 0.3 part by weight of catalyst, heating to 47 ℃, stirring and reacting for 40min, separating a magnet, washing with clear water, and drying at 105 ℃ for 1h to prepare the modified halloysite;
the catalyst was a catalyst containing 4wt% Co (NO 3 ) 2 Tris-HCl solution at ph=5.7;
s4, preparation of a fermentation substrate: adding 25 parts by weight of blue algae wall breaking liquid prepared in the step S1, 10 parts by weight of modified halloysite prepared in the step S3, 3 parts by weight of vitamin composition, 1 part by weight of sodium chloride, 0.6 part by weight of potassium chloride, 0.2 part by weight of calcium chloride, 0.1 part by weight of magnesium sulfate and 0.1 part by weight of zinc chloride into 110 parts by weight of water, and sterilizing by ultraviolet rays to prepare a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 4:2;
S5, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture for 16 hours under the micro-anoxic condition at 37 ℃ and 60r/min to obtain strain seed liquid;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen;
s6, fermenting: inoculating the bacillus subtilis and bacillus coagulans strain seed liquid prepared in the step S5 into the fermentation substrate prepared in the step S5, wherein the inoculum size of the bacillus subtilis and bacillus coagulans strain seed liquid is 3% and 2%, respectively, at 37 ℃ and 60r/min, fermenting and culturing for 30h under a micro-anoxic condition, supplementing the modified halloysite prepared in the step S3, and continuously fermenting and culturing for 16h with the additive size of 4g/L, filtering, concentrating the filtrate, and freeze-drying to obtain a fermented product;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen;
s7, preparing a metal-containing lamellar compound: dissolving 2mol of aluminum chloride and 3mol of calcium chloride in 50 parts by weight of water, adding 4mol of sodium carboxymethylcellulose under the protection of nitrogen, adjusting the pH value of the solution to 8.6, heating to 75 ℃, stirring for 4 hours, cooling, centrifuging at 3000r/min for 15 minutes, washing with clear water, drying at 105 ℃ for 1 hour, grinding, and sieving with a 100-mesh screen to obtain a metal-containing lamellar compound;
S8, preparing embedding liquid: 11 parts by weight of polyvinyl alcohol and 17 parts by weight of sodium alginate are dissolved in 100 parts by weight of water to obtain embedding liquid;
s9, preparing a biological composite carbon source by using blue algae: adding 7 parts by weight of the metal-containing layered compound prepared in the step S7 and 10 parts by weight of the fermentation product prepared in the step S6 into 55 parts by weight of the embedding liquid prepared in the step S8, uniformly mixing, emulsifying for 4min at 11000r/min, dropwise adding 12wt% of calcium chloride solution, solidifying for 25min at normal temperature, centrifuging for 15min at 3000r/min, washing with clear water, drying at 105 ℃ for 1h, and preparing the biological composite carbon source by using blue algae.
Comparative example 6
In comparison with example 3, the difference is that step S4 is not performed.
The method specifically comprises the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:7g/mL, repeatedly freezing and thawing, homogenizing for 17min at 13500r/min, and preparing blue algae wall-breaking liquid;
the repeated freezing and thawing method comprises the steps of placing the suspension in a temperature of-22 ℃ for 3 hours, dissolving at room temperature, and repeating the operation for 2 times;
s2, preprocessing halloysite: immersing halloysite powder in an 8.5wt% NaOH solution for 40min, wherein the solid-to-liquid ratio of the halloysite powder to the 8.5wt% NaOH solution is 1:4g/mL, filtering, washing with clear water, and drying at 105 ℃ for 1h to obtain pretreated halloysite;
S3, preparing MgO deposition magnetic halloysite: dissolving 4 parts by weight of magnesium chloride, 6.8 parts by weight of ferric chloride and 5.3 parts by weight of ferrous chloride in 50 parts by weight of water, adding 10 parts by weight of the pretreated halloysite powder prepared in the step S2, dropwise adding 11 parts by weight of 23.5wt% ammonia water under the protection of nitrogen, heating to 45 ℃, stirring and reacting for 1.5 hours, filtering, washing with clear water, and calcining at 400 ℃ for 2.5 hours to prepare MgO-deposited magnetic halloysite;
s4, preparation of a fermentation substrate: adding 25 parts by weight of blue algae wall breaking liquid prepared in the step S1, 10 parts by weight of MgO deposition magnetic halloysite prepared in the step S3, 3 parts by weight of vitamin composition, 1 part by weight of sodium chloride, 0.6 part by weight of potassium chloride, 0.2 part by weight of calcium chloride, 0.1 part by weight of magnesium sulfate and 0.1 part by weight of zinc chloride into 110 parts by weight of water, and carrying out ultraviolet sterilization to obtain a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 4:2;
s5, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture for 16 hours under the micro-anoxic condition at 37 ℃ and 60r/min to obtain strain seed liquid;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen;
S6, fermenting: inoculating the bacillus subtilis and bacillus coagulans strain seed liquid prepared in the step S6 into the fermentation substrate prepared in the step S5, wherein the inoculum size of the bacillus subtilis and bacillus coagulans strain seed liquid is 3% and 2%, respectively, under the condition of micro-hypoxia, fermenting and culturing for 30h at 37 ℃ and 60r/min, supplementing the MgO deposition magnetic halloysite prepared in the step S3, adding the additive amount of 4g/L, continuing fermenting and culturing for 16h, filtering, concentrating filtrate, and freeze-drying to obtain a fermented product;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen;
s7, preparing a metal-containing lamellar compound: dissolving 2mol of aluminum chloride and 3mol of calcium chloride in 50 parts by weight of water, adding 4mol of sodium carboxymethylcellulose under the protection of nitrogen, adjusting the pH value of the solution to 8.6, heating to 75 ℃, stirring for 4 hours, cooling, centrifuging at 3000r/min for 15 minutes, washing with clear water, drying at 105 ℃ for 1 hour, grinding, and sieving with a 100-mesh screen to obtain a metal-containing lamellar compound;
s8, preparing embedding liquid: 11 parts by weight of polyvinyl alcohol and 17 parts by weight of sodium alginate are dissolved in 100 parts by weight of water to obtain embedding liquid;
s9, preparing a biological composite carbon source by using blue algae: adding 7 parts by weight of the metal-containing layered compound prepared in the step S7 and 10 parts by weight of the fermentation product prepared in the step S6 into 55 parts by weight of the embedding liquid prepared in the step S8, uniformly mixing, emulsifying for 4min at 11000r/min, dropwise adding 12wt% of calcium chloride solution, solidifying for 25min at normal temperature, centrifuging for 15min at 3000r/min, washing with clear water, drying at 105 ℃ for 1h, and preparing the biological composite carbon source by using blue algae.
Comparative example 7
The difference compared with example 3 is that the modified MgO is not added in step S5 to deposit magnetic halloysite.
The method comprises the following steps:
s5, preparing a fermentation substrate: adding 35 parts by weight of blue algae wall breaking liquid prepared in the step S1, 3 parts by weight of vitamin composition, 1 part by weight of sodium chloride, 0.6 part by weight of potassium chloride, 0.2 part by weight of calcium chloride, 0.1 part by weight of magnesium sulfate and 0.1 part by weight of zinc chloride into 110 parts by weight of water, and sterilizing by ultraviolet rays to prepare a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 4:2.
Comparative example 8
Compared with example 3, the difference is that the blue algae wall breaking liquid in the step S5 is replaced by the same amount of glucose.
The method comprises the following steps:
s5, preparing a fermentation substrate: adding 25 parts by weight of glucose, 10 parts by weight of the modified MgO deposition magnetic halloysite prepared in the step S4, 3 parts by weight of a vitamin composition, 1 part by weight of sodium chloride, 0.6 part by weight of potassium chloride, 0.2 part by weight of calcium chloride, 0.1 part by weight of magnesium sulfate and 0.1 part by weight of zinc chloride into 110 parts by weight of water, and sterilizing by ultraviolet rays to prepare a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 4:2.
Comparative example 9
The difference compared to example 3 is that no vitamin composition is added in step S5.
The method comprises the following steps:
s5, preparing a fermentation substrate: 28 parts by weight of blue algae wall breaking liquid prepared in the step S1, 10 parts by weight of modified MgO deposition magnetic halloysite prepared in the step S4, 1 part by weight of sodium chloride, 0.6 part by weight of potassium chloride, 0.2 part by weight of calcium chloride, 0.1 part by weight of magnesium sulfate and 0.1 part by weight of zinc chloride are added into 110 parts by weight of water, and ultraviolet sterilization is carried out to prepare the fermentation substrate.
Comparative example 10
The difference compared with example 3 is that bacillus subtilis is not inoculated in step S7.
The method comprises the following steps:
s7, fermenting: inoculating the bacillus coagulans strain seed liquid prepared in the step S6 into the fermentation substrate prepared in the step S5, wherein the inoculum size of the bacillus coagulans strain seed liquid is 5%, fermenting and culturing for 30 hours at 37 ℃ under the micro-anoxic condition, adding the modified MgO deposited magnetic halloysite prepared in the step S4, the additive size is 4g/L, continuing fermenting and culturing for 16 hours, filtering, concentrating the filtrate, and freeze-drying to obtain a fermented product;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen.
Comparative example 11
The difference compared with example 3 is that Bacillus coagulans was not inoculated in step S7.
The method comprises the following steps:
s7, fermenting: inoculating the bacillus coagulans strain seed liquid prepared in the step S6 into the fermentation substrate prepared in the step S5, wherein the inoculum size of the bacillus coagulans strain seed liquid is 5%, fermenting and culturing for 30 hours at 37 ℃ under the micro-anoxic condition, adding the modified MgO deposited magnetic halloysite prepared in the step S4, the additive size is 4g/L, continuing fermenting and culturing for 16 hours, filtering, concentrating the filtrate, and freeze-drying to obtain a fermented product;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen.
Comparative example 12
The difference compared with example 3 is that the modified MgO deposition magnetic halloysite is not supplemented in step S7.
The method comprises the following steps:
s7, fermenting: inoculating the bacillus subtilis and bacillus coagulans strain seed liquid prepared in the step S6 to the fermentation substrate prepared in the step S5, wherein the inoculum size of the bacillus subtilis and bacillus coagulans strain seed liquid is 3% and 2%, respectively, at 37 ℃ and 60r/min, fermenting and culturing for 46h under a micro-anoxic condition, filtering, concentrating the filtrate, and freeze-drying to obtain a fermented product;
the micro-anoxic condition is that the oxygen content is 5v/v%, the carbon dioxide content is 4v/v%, and the balance is nitrogen.
Comparative example 13
In comparison with example 3, the difference is that steps S2 to S7 are not performed.
The method comprises the following steps:
the method specifically comprises the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:7g/mL, repeatedly freezing and thawing, homogenizing for 17min at 13500r/min, and preparing blue algae wall-breaking liquid;
the repeated freezing and thawing method comprises the steps of placing the suspension in a temperature of-22 ℃ for 3 hours, dissolving at room temperature, and repeating the operation for 2 times;
s2, preparing a metal-containing lamellar compound: dissolving 2mol of aluminum chloride and 3mol of calcium chloride in 50 parts by weight of water, adding 4mol of sodium carboxymethylcellulose under the protection of nitrogen, adjusting the pH value of the solution to 8.6, heating to 75 ℃, stirring for 4 hours, cooling, centrifuging at 3000r/min for 15 minutes, washing with clear water, drying at 105 ℃ for 1 hour, grinding, and sieving with a 100-mesh screen to obtain a metal-containing lamellar compound;
s3, preparing embedding liquid: 11 parts by weight of polyvinyl alcohol and 17 parts by weight of sodium alginate are dissolved in 100 parts by weight of water to obtain embedding liquid;
s4, preparing a biological composite carbon source by using blue algae: adding 7 parts by weight of the metal-containing layered compound prepared in the step S2 and 10 parts by weight of the metal-containing layered compound prepared in the step S1 into 55 parts by weight of the embedding liquid prepared in the step S3, uniformly mixing, emulsifying for 4min at 11000r/min, dropwise adding 12wt% of calcium chloride solution, solidifying for 25min at normal temperature, centrifuging for 15min at 3000r/min, washing with clear water, drying at 105 ℃ for 1h, and preparing the biological composite carbon source by using blue algae.
Comparative example 14
The difference from example 3 is that no polyvinyl alcohol is added in step S9.
The method comprises the following steps:
s9, preparing embedding liquid: 28 parts by weight of sodium alginate was dissolved in 100 parts by weight of water to obtain an embedding liquid.
Comparative example 15
In comparison with example 3, the difference is that no metal-containing layered compound was added in step S10.
The method comprises the following steps:
s10, preparing a biological composite carbon source by using blue algae: adding 17 parts by weight of the fermented product prepared in the step S7 into 55 parts by weight of the embedding liquid prepared in the step S9, uniformly mixing, emulsifying for 4min at 11000r/min, dripping 12wt% calcium chloride solution, solidifying for 25min at normal temperature, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 1h at 105 ℃ to prepare the biological composite carbon source prepared by using the blue algae.
Comparative example 16
The difference from example 3 is that no fermented product was added in step S10.
The method comprises the following steps:
s10, preparing a biological composite carbon source by using blue algae: adding 17 parts by weight of the metal-containing lamellar compound prepared in the step S8 into 55 parts by weight of the embedding liquid prepared in the step S9, uniformly mixing, emulsifying for 4min at 11000r/min, dripping a 12wt% calcium chloride solution, solidifying for 25min at normal temperature, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 105 ℃ for 1h to prepare the biological composite carbon source by using blue algae.
Comparative example 17
The difference from example 3 is that embedding is not performed in step S10.
The method comprises the following steps:
s10, preparing a biological composite carbon source by using blue algae: and (3) uniformly mixing 7 parts by weight of the metal-containing layered compound prepared in the step (S8) and 10 parts by weight of the fermented product prepared in the step (S7), and drying at 105 ℃ for 1h to prepare the biological composite carbon source by using blue algae.
Test example 1 sustained release Performance test
1g of the biocomposite carbon source prepared by using blue algae prepared in examples 1 to 5 and comparative examples 1 to 17 was added to 1L of ultrapure water, sampled at 1, 2, 4, 6, 8, 10, 12, 24, 48, 72, 96, 120, 144, 168 h, COD value was measured, a carbon release curve was drawn, and then the carbon release coefficient was calculated by the following formula:
K=c m /t 1/2
wherein K is a carbon release coefficient, and represents the resistance to the carbon source release process, and the lower the K value is, the better the carbon release performance of the carbon source release filter material is, c m The saturated COD value, t, of the unit slow-release carbon source filter material released in the solution is 1/2 The time for the COD released by the unit slow-release carbon source filter material in the solution to reach half of the saturation concentration is taken.
The results are shown in Table 1.
As can be seen from the above table, the biological composite carbon source prepared by using the blue algae prepared in the embodiments 1-3 of the invention has good property of slowly releasing the carbon source.
Test example 2
Through artificially synthesizing wastewater, COD (chemical oxygen demand) in the influent water is 220mg/L, nitrate nitrogen is 85mg/L, the concentration of potassium hydrogen phosphate is 32mg/L, calcium chloride is 22mg/L, magnesium chloride is 19mg/L, zinc sulfate is 0.2mg/L, manganese chloride is 0.3mg/L, pH is 8.2, inoculated sludge is taken from an anoxic section of an oxidation ditch process of a municipal sewage treatment plant in Nanjing city, suspended solid concentration of mixed liquor is about 3200 mg/L, activated sludge is poured into a denitrification filter tank until a filter material is submerged, after 24 hours of exposure, the inoculated activated sludge is completely discharged and continuously introduced into artificially synthesized wastewater, 2g/L of the biological composite carbon source prepared by using blue algae and prepared in examples 1-5 and comparative examples 1-17 is added into the wastewater, dissolved oxygen concentration of experimental influent water is 0.3-0.35 mg/L, during the operation of a reactor, effluent of the reactor is collected in 5d, and water quality index is measured. NO (NO) 3 - -N、NO 2 - N, determination methods reference water and wastewater monitoring and analysis methods, TOC (total organic matter) and TN (total nitrogen) are determined by using a total organic carbon determination instrument, and denitrification load is calculated.
The results are shown in Table 2.
TABLE 2
As can be seen from the table, the preparation of the biological composite carbon source by using the blue algae prepared in the embodiment 1-3 of the invention is beneficial to improving the nitrogen load, improving the denitrification efficiency, obviously reducing the TOC and TN contents of effluent, promoting the activity of heterotrophic denitrifying bacteria and improving the denitrification performance of the system.
Test example 3
Municipal sewage from a municipal sewage plant is selected, and specific indexes are shown in table 3 below.
TABLE 3 Table 3
Activated sludge from an oxidation ditch of a municipal sewage treatment plant in Nanjing city is added into municipal sewage, the addition amount is 10wt%, the activated sludge is subjected to SBR domestication for 72 hours, water with equal mass is added into a blank group, and the biological composite carbon source prepared by using blue algae and prepared by adding in the examples 1-5 and the comparative examples 1-17 is added with the addition amount of 0.2wt%.
The results are shown in Table 4.
TABLE 4 Table 4
From the above table, the biological composite carbon source prepared by using the blue algae in the embodiments 1-3 of the invention is helpful to obviously improve the denitrification effect in the municipal sewage treatment process.
Examples 4 and 5 compare with example 3 in that the vitamin composition is a single vitamin B1 or vitamin D3. Comparative example 9 in contrast to example 3, no vitamin composition was added in step S5. The denitrification load is reduced, and the total nitrogen degradation rate is reduced. The added vitamin composition comprises a mixture of vitamin B1 and vitamin D3, and is added into a fermentation substrate, so that the resistance of zymobacteria can be obviously improved, the acid production capacity of the zymobacteria can be improved, the time of a stable period can be prolonged, the acid production yield can be improved, and the fermentation product contains rich short-chain fatty acid and other carbohydrates.
Comparative example 1 in comparison with example 3, step S1 was not subjected to repeated freeze thawing. The sewage treatment effect is reduced, the denitrification load is reduced, and the total nitrogen degradation rate is reduced. The method disclosed by the invention is characterized in that the cell wall of the blue algae is destroyed by adopting a repeated freeze thawing method, so that substances such as glycoprotein, polysaccharide and the like which are rich in nutrition in the blue algae are dissolved out, and after homogenization, a relatively uniform blue algae wall-breaking liquid is prepared, which is used as one of main substances of a fermentation matrix, contains rich carbon sources and nitrogen sources, provides sufficient raw materials for fermentation, greatly improves the yield of short-chain fatty acids, small-molecule sugar, carbohydrates and the like produced by fermentation, and improves the recycling effect of the blue algae, thereby realizing the effect of treating waste by waste.
Comparative example 2 compared to example 3, step S2 was not performed. In comparative examples 3 and 4, as compared with example 3, magnesium chloride, or iron chloride and ferrous chloride, was not added in step S3. Comparative example 5 compared to example 3, step S3 was not performed. Comparative example 6 compared to example 3, step S4 was not performed. Comparative example 7 in comparison with example 3, the magnetic halloysite was deposited without adding modified MgO in step S5. The sewage treatment effect is reduced, and the total nitrogen degradation rate is reduced because N is further doped. The invention adds and prepares a modified MgO deposition magnetic halloysite, takes porous and cheap halloysite nano-tubes as a framework, and deposits ferromagnetic Fe on the surface 3 O 4 And MgO, and further carrying a polydopamine layer on the surface. The metal oxide includes Fe 3 O 4 And MgO, wherein ferromagnetic Fe 3 O 4 The magnetic material has the characteristics of strong magnetism, good adsorptivity, good electric conduction performance and the like, can be used as a carrier for electron transfer between anaerobic microorganisms with extracellular electron transfer function, so as to strengthen the inter-species electron transfer between the anaerobic microorganisms, thereby improving the acid production efficiency and yield of zymobacteria, because a direct inter-species electron transfer is established in a reaction system, and the transfer is positioned above magnetite particles to mediate the acid productionIn addition, the iron oxide can promote zymobacteria to utilize various substrates and participate in the decomposition of complex organic matters through reduction of iron dissimilate, so that the activity of enzymes related to hydrolytic acidification is improved, the activities of alpha-glucokinase, protease and acetate kinase are enhanced, the relative abundance of the zymobacteria is improved, and the yield of short-chain fat is improved. The modified MgO-deposited magnetic halloysite prepared by the invention has another important function, wherein MgO can improve NH in fermentation broth 4 + Phosphate (PO) 4 3- 、HPO 4 2- 、H 2 PO 4 - ) The deposition of the polymer is carried out so as to efficiently adsorb N, P impurities in the fermentation broth, in addition, the polydopamine layer on the surface layer contains rich amino, hydroxyl, carboxyl and other groups, and has good hydrogen bond adsorption capacity for nitrate ions, phosphate ions and ammonium ions, so that the content of N, P in the fermentation broth is greatly reduced, N, P in the fermentation broth is removed by adopting an adsorption precipitation method, and the adsorbed modified MgO deposition magnetic halloysite can be separated by magnetism, and the product can be used as a slow release fertilizer. Compared with the traditional fertilizer, the fertilizer can ensure the growth of crops, and the low solubility of the fertilizer ensures that the fertilizer is slowly dissolved in the environment, so that the nutrient release rate is suitable for the absorption of crops, and the recycling of intermediate products is further realized.
Comparative example 8 compared with example 3, the blue algae wall breaking liquid in step S5 was replaced with an equal amount of glucose. In comparative example 16, no fermented product was added in step S10, compared with example 3. The sewage treatment effect is reduced, the denitrification load is reduced, and the total nitrogen degradation rate is reduced. The blue algae wall-breaking liquid contains rich carbon source and nitrogen source as one of the main matters of the fermentation matrix, provides sufficient raw materials for fermentation, greatly improves the yield of short chain fatty acid, small molecular sugar, carbohydrate and the like produced by fermentation, and improves the recycling effect of blue algae, thereby realizing the effect of treating waste with waste.
Comparative examples 10 and 11 in comparison with example 3, in step S7, bacillus subtilis or Bacillus coagulans was not inoculated. Comparative example 13 in comparison with example 3, steps S2 to S7 were not performed. The sewage treatment effect is obviously reduced, the denitrification load is obviously reduced, and the total nitrogen degradation rate is obviously reduced. The organic matters in the blue algae have complex components and low biodegradation and bioconversion efficiency, and the hydrolytic acidification of the blue algae in the fermentation process can be limited to generate carbon source substances.
Comparative example 12 in comparison with example 3, the modified MgO-deposited magnetic halloysite was not supplemented in step S7. The denitrification load is reduced, and the total nitrogen degradation rate is reduced. The modified MgO deposited magnetic halloysite is also added in the fermentation process, the stress resistance of the fermentation bacteria is further improved by the released metal ions, the stable period of the fermentation bacteria is prolonged, the acid production efficiency is further improved, the fixation of N, P in the fermentation liquid is improved to a certain extent, and the N, P content in the fermentation product is extremely low.
Comparative example 14 in contrast to example 3, no polyvinyl alcohol was added in step S9. Comparative example 17 compared with example 3, no embedding was performed in step S10. The carbon release coefficient is obviously improved, the sewage treatment effect is reduced, the denitrification load is reduced, and the total nitrogen degradation rate is reduced for a long time. The invention adopts the mixture of the polyvinyl alcohol and the sodium alginate as an embedding shell layer, embeds the metal-containing lamellar compound and the ferment, realizes the slow release function of the carbon source, prolongs the action time of the carbon source, is also a biodegradable polymer material, can be degraded in organisms or is subjected to enzymolysis by extracellular enzymes released by microorganisms to generate micromolecular organic matters, is utilized by organisms, and has the characteristics of good biodegradability and stable carbon release performance as the carbon source, environmental friendliness, high mechanical strength, good water stability and high biocompatibility.
In comparative example 15, in contrast to example 3, no metal-containing layered compound was added in step S10. The carbon release coefficient is obviously improved, the sewage treatment effect is reduced, the denitrification load is reduced, and the total nitrogen degradation rate is reduced for a long time. The invention also prepares the metal-containing lamellar compound which is a lamellar structure containing bimetal, negative ions are combined between layers, hydrogen bonds exist between the layers, the metal-containing lamellar compound is tightly combined, the structure is stable, and the metal-containing lamellar compound has good mechanical property and slow release property. According to the invention, the metal-containing layered compound and the ferment are mixed, and the metal-containing layered compound can fix the ferment through hydrogen bonds, so that the slow release effect of the carbon source is further improved. Meanwhile, the metal-containing layered compound can also slowly release metal ions aluminum and calcium, so that the biological denitrification rate is improved, the microbial denitrification performance is improved, and the organic matter sodium hydroxymethyl cellulose has the advantages of adhesiveness and low cost, and can be used as a carbon source to promote the reaction of nitrifying bacteria or denitrifying bacteria.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation process for preparing a biological composite carbon source by using blue algae is characterized in that blue algae powder is added into water and repeatedly frozen and thawed to obtain blue algae wall breaking liquid; soaking halloysite in alkali solution, and depositing MgO and Fe on the surface 3 O 4 Further depositing a polydopamine layer on the surface to prepare modified MgO deposited magnetic halloysite, adding the modified MgO deposited magnetic halloysite, blue algae liquid, a vitamin composition and inorganic salt into water to prepare a fermentation substrate, inoculating bacillus subtilis and bacillus coagulans strain seed liquid, and fermenting and culturing to prepare a fermentation product; adding aluminum salt, calcium salt and sodium carboxymethyl cellulose into water, reacting to obtain metal-containing lamellar compound, embedding the compound and fermented product into polyvinyl alcohol and sodium alginate shell, and preparing biological composite carbon source by blue algae.
2. The preparation process according to claim 1, characterized by comprising the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, repeatedly freezing and thawing, and homogenizing to obtain blue algae wall breaking liquid;
s2, preprocessing halloysite: soaking halloysite powder in alkali liquor, filtering, washing and drying to obtain pretreated halloysite;
s3, preparing MgO deposition magnetic halloysite: dissolving magnesium salt, ferric chloride and ferrous chloride in water, adding the pretreated halloysite powder prepared in the step S2, dropwise adding ammonia water under the protection of inert gas, heating and stirring for reaction, filtering, washing and calcining to prepare MgO-deposited magnetic halloysite;
S4, modifying polydopamine: uniformly dispersing the MgO deposition magnetic halloysite prepared in the step S3 in water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, separating a magnet, washing and drying to prepare the modified MgO deposition magnetic halloysite;
s5, preparing a fermentation substrate: adding the blue algae wall-breaking liquid prepared in the step S1, the modified MgO deposition magnetic halloysite prepared in the step S4, the vitamin composition and the inorganic salt into water, and sterilizing to prepare a fermentation substrate;
s6, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture to obtain strain seed liquid;
s7, fermenting: inoculating the bacillus subtilis strain seed liquid and the bacillus coagulans strain seed liquid prepared in the step S6 to the fermentation substrate prepared in the step S5 for fermentation culture for a first time period, supplementing the modified MgO deposited magnetic halloysite prepared in the step S4, continuing fermentation culture for a second time period, filtering, concentrating the filtrate, and drying to obtain a fermented product;
s8, preparing a metal-containing lamellar compound: dissolving aluminum salt and calcium salt in water, adding sodium carboxymethylcellulose under the protection of inert gas, regulating the pH value of the solution, heating and stirring, cooling, centrifuging, washing, drying and grinding to obtain a metal-containing lamellar compound;
S9, preparing embedding liquid: dissolving polyvinyl alcohol and sodium alginate in water to obtain embedding liquid;
s10, preparing a biological composite carbon source by using blue algae: adding the metal-containing layered compound prepared in the step S8 and the fermented product prepared in the step S7 into the embedding liquid prepared in the step S9, uniformly mixing, emulsifying, dropwise adding a calcium chloride solution, solidifying at normal temperature, centrifuging, washing, and drying to prepare the biological composite carbon source by using blue algae.
3. The preparation process according to claim 2, wherein in the step S1, the solid-to-liquid ratio of the blue algae powder to the water is 1:5-10g/mL, the repeated freezing and thawing method is that the suspension is frozen for 2-4 hours at-20-25 ℃ and then dissolved at room temperature, and then the operation is repeated for 1-2 times, the rotation speed of the homogenate is 12000-15000r/min, and the time is 15-20min; the solid-to-liquid ratio of the halloysite powder to the alkali liquor in the step S2 is 1:3-5g/mL, the alkali liquor is 7-10wt% NaOH or KOH solution, and the soaking time is 30-50min.
4. The preparation process according to claim 2, wherein in step S3, the magnesium salt is at least one of magnesium chloride, magnesium nitrate and magnesium sulfate, the molar ratio of the magnesium salt to the ferric chloride to the ferrous chloride is 2-3:1:1, the mass ratio of the magnesium salt to the pretreated halloysite powder is 3-5:10, the concentration of the ammonia water is 22-25wt%, the temperature of the heating and stirring reaction is 40-50 ℃, the time is 1-2h, the calcining temperature is 300-500 ℃ and the time is 2-3h; in the step S4, the mass ratio of the MgO deposition magnetic halloysite to the dopamine hydrochloride to the catalyst is 10:12-15:0.2-0.4, and the catalyst contains 3-5wt% of Co (NO 3 ) 2 The temperature of the heating and stirring reaction is 45-50 ℃ and the time is 30-50min.
5. The preparation process according to claim 2, wherein in the step S5, the mass ratio of the blue algae wall breaking liquid to the modified MgO deposited magnetic halloysite to the vitamin composition to the inorganic salt to the water is 20-30:7-12:2-4:1-3:100-120, and the vitamin composition is at least two selected from vitamin a, vitamin B1, vitamin B2, vitamin B3, vitamin B6, vitamin B12, vitamin C, vitamin D1, vitamin D3, vitamin K, vitamin E, and folic acid, and the inorganic salt is at least one selected from sodium chloride, potassium chloride, calcium chloride, magnesium sulfate, ferric chloride, zinc sulfate, copper sulfate, manganese sulfate, zinc chloride, copper chloride, manganese chloride, ferric sulfate, copper nitrate, magnesium nitrate, copper nitrate, and manganese nitrate; and step S6, the condition of the activation culture is that the activation culture is carried out for 12-18 hours under the micro-anoxic condition at the temperature of 36-38 ℃ and at the speed of 50-70r/min, wherein the micro-anoxic condition is that the oxygen content is 3-7v/v%, the carbon dioxide content is 3-5v/v%, and the balance is nitrogen.
6. The preparation process according to claim 5, wherein the vitamin composition is a mixture of vitamin B1 and vitamin D3 in a mass ratio of 3-5:2.
7. The preparation process according to claim 2, wherein in step S7, the seed liquids of bacillus subtilis and bacillus coagulans are respectively inoculated in an amount of 2-4% and 1-3%, the conditions of fermentation culture are that under the conditions of 36-38 ℃ and 50-70r/min, and under the condition of micro-hypoxia, the conditions of micro-hypoxia are that the oxygen content is 3-7v/v%, the carbon dioxide content is 3-5v/v%, and the balance is nitrogen, the first time period is 24-36h, the second time period is 12-18h, and the addition amount of the additional modified MgO deposited magnetic halloysite is 3-5g/L; in the step S8, the aluminum salt is selected from at least one of aluminum chloride, aluminum nitrate and aluminum sulfate, the calcium salt is selected from at least one of calcium chloride, calcium sulfate and calcium nitrate, the molar ratio of the aluminum salt to the calcium salt to the sodium carboxymethyl cellulose is 2:3:3-5, the pH is adjusted to 8.5-8.8, the temperature of heating and stirring is 70-80 ℃, and the time is 3-5h.
8. The preparation process according to claim 2, wherein the mass ratio of the polyvinyl alcohol, sodium alginate and water in the step S9 is 10-12:15-20:100; in the step S10, the mass ratio of the metal-containing layered compound to the fermentation product to the embedding liquid is 5-10:7-12:50-60, the emulsification condition is 10000-12000r/min, the time is 3-5min, the concentration of the calcium chloride solution is 10-15wt%, and the normal-temperature solidification time is 20-30min.
9. The preparation process according to claim 2, characterized by comprising the following steps:
s1, breaking the wall of blue algae: adding blue algae powder into water, wherein the solid-to-liquid ratio of the blue algae powder to the water is 1:5-10g/mL, repeatedly freezing and thawing, homogenizing for 15-20min at 12000-15000r/min, and obtaining blue algae wall-breaking liquid;
the repeated freezing and thawing method comprises the steps of placing the suspension in a temperature range of-20 to-25 ℃ for freezing for 2-4 hours, dissolving at room temperature, and repeating the operation for 1-2 times;
s2, preprocessing halloysite: immersing halloysite powder in 7-10wt% NaOH or KOH solution for 30-50min, wherein the solid-to-liquid ratio of the halloysite powder to alkali liquor is 1:3-5g/mL, filtering, washing and drying to obtain pretreated halloysite;
s3, preparing MgO deposition magnetic halloysite: dissolving 3-5 parts by weight of magnesium salt, ferric chloride and ferrous chloride in 50 parts by weight of water, wherein the molar ratio of the magnesium salt to the ferric chloride to the ferrous chloride is 2-3:1:1, adding 10 parts by weight of the pretreated halloysite powder prepared in the step S2, dropwise adding 10-12 parts by weight of 22-25wt% ammonia water under the protection of inert gas, heating to 40-50 ℃, stirring for reacting for 1-2 hours, filtering, washing, and calcining at 300-500 ℃ for 2-3 hours to prepare MgO-deposited magnetic halloysite;
s4, modifying polydopamine: uniformly dispersing 10 parts by weight of the MgO deposition magnetic halloysite prepared in the step S3 in 100 parts by weight of water, adding 12-15 parts by weight of dopamine hydrochloride and 0.2-0.4 part by weight of catalyst, heating to 45-50 ℃, stirring and reacting for 30-50min, separating by a magnet, washing and drying to prepare the modified MgO deposition magnetic halloysite;
The catalyst contains 3-5wt% Co (NO) 3 ) 2 Tris-HCl solution at ph=5.5-6;
s5, preparing a fermentation substrate: adding 20-30 parts by weight of blue algae wall-breaking liquid prepared in the step S1, 7-12 parts by weight of modified MgO deposition magnetic halloysite prepared in the step S4, 2-4 parts by weight of vitamin composition and 1-3 parts by weight of inorganic salt into 100-120 parts by weight of water, and carrying out ultraviolet sterilization to prepare a fermentation substrate;
the vitamin composition is a mixture of vitamin B1 and vitamin D3, and the mass ratio is 3-5:2;
s6, activating zymophyte: inoculating bacillus subtilis and bacillus coagulans into a Gao's culture medium, and performing activation culture for 12-18 hours under the micro-anoxic condition at 36-38 ℃ and 50-70r/min to obtain strain seed liquid;
the micro-anoxic condition is that the oxygen content is 3-7v/v%, the carbon dioxide content is 3-5v/v%, and the balance is nitrogen;
s7, fermenting: inoculating the bacillus subtilis and bacillus coagulans strain seed liquid prepared in the step S6 into the fermentation substrate prepared in the step S5, wherein the inoculum sizes of the bacillus subtilis and bacillus coagulans strain seed liquid are respectively 2-4% and 1-3%, the temperature is 36-38 ℃, the speed is 50-70r/min, fermentation culture is carried out for 24-36h under a micro-anoxic condition, the modified MgO deposition magnetic halloysite prepared in the step S4 is supplemented, the additive amount is 3-5g/L, fermentation culture is continued for 12-18h, filtering, filtrate concentration and drying are carried out, and a fermented product is prepared;
The micro-anoxic condition is that the oxygen content is 3-7v/v%, the carbon dioxide content is 3-5v/v%, and the balance is nitrogen;
s8, preparing a metal-containing lamellar compound: dissolving 2 molar equivalents of aluminum salt and 3 molar equivalents of calcium salt in 50 parts by weight of water, adding 3-5 molar equivalents of sodium carboxymethyl cellulose under the protection of inert gas, adjusting the pH value of the solution to 8.5-8.8, heating to 70-80 ℃, stirring for 3-5 hours, cooling, centrifuging, washing, drying and grinding to obtain a metal-containing lamellar compound;
s9, preparing embedding liquid: 10-12 parts by weight of polyvinyl alcohol and 15-20 parts by weight of sodium alginate are dissolved in 100 parts by weight of water to obtain embedding liquid;
s10, preparing a biological composite carbon source by using blue algae: adding 5-10 parts by weight of the metal-containing layered compound prepared in the step S8 and 7-12 parts by weight of the fermentation product prepared in the step S7 into 50-60 parts by weight of the embedding liquid prepared in the step S9, uniformly mixing, emulsifying for 3-5min at 10000-12000r/min, dropwise adding 10-15wt% of calcium chloride solution, curing for 20-30min at normal temperature, centrifuging, washing, and drying to prepare the biological composite carbon source prepared by using blue algae.
10. A biocomposite carbon source produced by the process of any one of claims 1-9 using blue algae.
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