CN117326702B - Citric acid composition biomass carbon source and preparation method thereof - Google Patents
Citric acid composition biomass carbon source and preparation method thereof Download PDFInfo
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- CN117326702B CN117326702B CN202311501329.1A CN202311501329A CN117326702B CN 117326702 B CN117326702 B CN 117326702B CN 202311501329 A CN202311501329 A CN 202311501329A CN 117326702 B CN117326702 B CN 117326702B
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 239000002028 Biomass Substances 0.000 title claims abstract description 30
- 239000010802 sludge Substances 0.000 claims abstract description 167
- 238000001914 filtration Methods 0.000 claims abstract description 63
- 238000000855 fermentation Methods 0.000 claims abstract description 52
- 238000001035 drying Methods 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 50
- 241000894006 Bacteria Species 0.000 claims abstract description 46
- 239000010902 straw Substances 0.000 claims abstract description 46
- 230000004151 fermentation Effects 0.000 claims abstract description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000002244 precipitate Substances 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000010865 sewage Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000002699 waste material Substances 0.000 claims abstract description 17
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 15
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 15
- 235000005822 corn Nutrition 0.000 claims abstract description 15
- 235000013379 molasses Nutrition 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 239000004005 microsphere Substances 0.000 claims description 48
- 238000005406 washing Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 241000194108 Bacillus licheniformis Species 0.000 claims description 20
- 244000063299 Bacillus subtilis Species 0.000 claims description 20
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- 229960000892 attapulgite Drugs 0.000 claims description 17
- 229910052625 palygorskite Inorganic materials 0.000 claims description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 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 13
- 239000000661 sodium alginate Substances 0.000 claims description 13
- 235000010413 sodium alginate Nutrition 0.000 claims description 13
- 229940005550 sodium alginate Drugs 0.000 claims description 13
- -1 alkyl orthosilicate Chemical compound 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 10
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 235000021323 fish oil Nutrition 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical group Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 229920001690 polydopamine Polymers 0.000 claims description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 8
- 229920000053 polysorbate 80 Polymers 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- 239000003337 fertilizer Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 230000001580 bacterial effect Effects 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- MXXDSLLVYZMTFA-UHFFFAOYSA-N octadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 MXXDSLLVYZMTFA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- KBAFDSIZQYCDPK-UHFFFAOYSA-M sodium;octadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O KBAFDSIZQYCDPK-UHFFFAOYSA-M 0.000 claims description 2
- AYFACLKQYVTXNS-UHFFFAOYSA-M sodium;tetradecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCS([O-])(=O)=O AYFACLKQYVTXNS-UHFFFAOYSA-M 0.000 claims description 2
- ORLPWCUCEDVJNN-UHFFFAOYSA-N sodium;tetradecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 ORLPWCUCEDVJNN-UHFFFAOYSA-N 0.000 claims description 2
- 241000209149 Zea Species 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 229910000859 α-Fe Inorganic materials 0.000 claims 1
- 240000008042 Zea mays Species 0.000 abstract description 13
- 230000002053 acidogenic effect Effects 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 230000002503 metabolic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 238000001132 ultrasonic dispersion Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000001546 nitrifying effect Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 150000004666 short chain fatty acids Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000009360 aquaculture Methods 0.000 description 2
- 244000144974 aquaculture Species 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 241000192700 Cyanobacteria Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000009835 boiling Methods 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biological Treatment Of Waste Water (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention provides a citric acid composition biomass carbon source and a preparation method thereof, and belongs to the technical field of biomass carbon sources. The preparation method comprises the steps of carrying out alkali treatment and acid high-temperature heating treatment on corn straws to obtain pretreated straws, mixing the pretreated straws with molasses waste liquid, biochemical treated residual sludge and a surfactant to obtain a mixture, carrying out fermentation, filtering, adding calcium salt into filtrate, precipitating, adding the obtained mixed precipitate into dilute sulfuric acid, stirring for reaction, filtering, taking filter residues as calcium sulfate precipitate, recycling, and drying the filtrate to obtain the citric acid composition biomass carbon source. The biomass carbon source of the citric acid composition can obviously improve the biodegradability in sewage treatment, improves the denitrification efficiency of a treatment unit, has high propagation speed of hydrolysis and acidogenic bacteria, high metabolic strength, short domestication time, high safety, convenient transportation and convenient operation control.
Description
Technical Field
The invention relates to the technical field of biomass carbon sources, in particular to a citric acid composition biomass carbon source and a preparation method thereof.
Background
Total nitrogen (including ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and the like) is a common pollutant in water, has an important influence on water quality safety, is an important participant in water eutrophication, and is strictly controlled. The total nitrogen content is high to promote the growth of aquatic algae plants, and planktonic algae such as blue-green algae and the like overgrow to deteriorate water quality. Ammonia nitrogen inhibits oxygen transfer in fish, which causes increased aquaculture cost and even causes loss of the whole dead pond when serious. Therefore, the denitrification technology has wide demands in aspects of water treatment, landscape water maintenance, aquaculture and the like. The main method for denitrification in the sewage treatment plant at present is biological denitrification, and has the advantages of good removal effect, mature process, low cost and the like.
Biological denitrification is a core process for removing nitrogen, nitrogen in a water body is converted into gaseous nitrogen to be removed by utilizing the nitrification and denitrification process of microorganisms, when organic matters in the water are insufficient, living activity is reduced, the denitrification process is blocked, and the denitrification effect is poor. The problem can be effectively solved by adopting an external carbon source to improve the carbon nitrogen ratio (C/N) and strengthening the denitrification process.
In water plants, soluble carbon sources such as methanol, ethanol, acetic acid, glucose and the like are usually added to supplement the shortage of the carbon sources and improve the denitrification effect. Although the traditional soluble carbon source has quick effect and good effect, the traditional soluble carbon source has the defects of large water fluctuation, complex adding mode, high cost, energy consumption, certain toxicity of part of external carbon sources, transportation and safety problems and the like. Natural solid carbon sources (such as branches, straws and the like) can also be used for denitrification, and the denitrification effect is poor and unstable although the price is low and the materials are wide. Therefore, the research and development of biomass carbon sources for improving denitrification capability has important significance for effectively controlling total nitrogen in sewage and surface water treatment.
Straw is the general term for the stem and leaf parts of mature crops, including the rest of wheat, rice, corn, potato, rape and other crops after harvesting seeds. The straw consists of three components of cellulose, hemicellulose and lignin, wherein the cellulose and the hemicellulose can be degraded and converted into sugar, and then converted into reducing sugar which can be utilized by microorganisms. In the fermentation process of straw, molasses waste liquid, excrement and the like, a large amount of citric acid which is a byproduct is generated, and if the citric acid is not utilized, the citric acid is directly discarded, so that environmental substances are caused, and huge waste is caused. If the biomass carbon source is recycled, the treatment cost of byproducts is reduced, the environment is protected, and the biomass carbon source with economic value can be prepared, so that the biomass carbon source is applied to sewage treatment and has profound practical significance.
Disclosure of Invention
The invention aims to provide a biomass carbon source of a citric acid composition and a preparation method thereof, which can obviously improve the biodegradability in sewage treatment, improve the denitrification efficiency of a treatment unit, and have the advantages of high propagation speed, high metabolic strength, short domestication time, high safety, convenience in transportation and convenience in operation control of hydrolysis and acidogenic bacteria.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a citric acid composition biomass carbon source, which comprises the steps of carrying out alkali treatment and acid high-temperature heating treatment on corn straws to obtain pretreated straws, mixing the pretreated straws with molasses waste liquid, biochemical treatment residual sludge and a surfactant to obtain a mixture, fermenting, filtering, adding calcium salt into filtrate, precipitating, adding the obtained mixed precipitate into dilute sulfuric acid, stirring for reaction, filtering, recovering and utilizing filter residues which are calcium sulfate precipitate, and drying the filtrate to obtain the citric acid composition biomass carbon source.
As a further improvement of the invention, the method comprises the following steps:
s1, pretreatment of straws: crushing corn straw, adding into alkali liquor for soaking treatment, filtering, adding into acid liquor, heating at high temperature, filtering, washing, and drying to obtain pretreated straw;
s2, preparing a mixture: uniformly mixing the pretreated straw, molasses waste liquid, biochemically treated residual sludge and surfactant which are prepared in the step S1 to prepare a mixture;
s3, fermenting: adding magnetic embedded sludge zymocyte microspheres into the mixture prepared in the step S2, performing anaerobic fermentation treatment firstly, performing micro-anoxic fermentation treatment secondly, separating the magnetic embedded sludge zymocyte microspheres by a magnet, fixing heavy metal ions by using the separated magnetic embedded sludge zymocyte microspheres for sewage treatment, filtering, reserving filtrate, and using filter residues as fertilizers;
s4, precipitation: adding calcium salt into the filtrate obtained in the step S3, precipitating, filtering, washing and drying to obtain a mixed precipitate;
s5, replacement: and (3) adding the mixed precipitate obtained in the step (S4) into dilute sulfuric acid, stirring for reaction, filtering, recovering and utilizing the filter residue which is calcium sulfate precipitate, and drying the filtrate to obtain the citric acid composition biomass carbon source.
As a further improvement of the invention, the concentration of the alkali liquor in the step S1 is 1-2wt%, the alkali is NaOH or KOH, the soaking treatment time is 0.5-1h, the acid liquor is 1-1.5wt% sulfuric acid solution, the high-temperature heating treatment temperature is 120-130 ℃, and the high-temperature heating treatment is carried out in an autoclave for 1-2h.
As a further improvement of the invention, the mass ratio of the pretreated straw, molasses waste liquid, biochemically treated residual sludge and surfactant in the step S2 is 15-20:100-120:7-12:0.5-1, and the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium tetradecyl benzene sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl benzene sulfonate, sodium octadecyl benzene sulfonate and sodium octadecyl sulfonate.
As a further improvement of the invention, the mass ratio of the mixture to the magnetic embedded sludge zymocyte microspheres in the step S3 is 1000:12-15, the anaerobic fermentation treatment condition is 100-120r/min under anaerobic condition, 22-27 ℃ and fermentation treatment is 24-48h, the micro-anoxic fermentation treatment condition is 100-120r/min under micro-anoxic condition, 25-30 ℃ and fermentation treatment is 24-36h, and the micro-anoxic condition is 3-5% O 2 ％、7-10％CO 2 The balance being nitrogen, wherein% is by volume.
As a further improvement of the invention, the preparation method of the magnetic embedded sludge fermentation bacteria microsphere comprises the following steps:
t1, preparation of magnetic anaerobic sludge: adding the dried sludge powder into an aqueous solution containing ferrous salt, stirring and mixing uniformly, then dropwise adding ammonia water, stirring and reacting, aging, filtering, washing and drying to obtain magnetic anaerobic sludge;
T2.SiO 2 coating: adding the magnetic anaerobic sludge prepared in the step T1 into water, dispersing uniformly, adding the alkyl orthosilicate, the pore-forming agent and the ammonia water, stirring for reaction, filtering, washing and drying to obtain porous SiO 2 Coating magnetic anaerobic sludge;
t3. fixing strains: uniformly mixing seed solution of bacillus subtilis and bacillus licheniformis strains, and adding porous SiO prepared in the step T2 2 Coating magnetic anaerobic sludge, dispersing uniformly, volatilizing solvent to obtain immobilized bacteria porous SiO 2 Coating magnetic anaerobic sludge;
t4. modification of polydopamine: the immobilized bacteria porous SiO prepared in the step T3 is treated 2 Adding water into the coated magnetic anaerobic sludge, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, filtering, washing and drying to obtain modified sludge;
and T5, preparing the magnetic embedded sludge fermentation bacteria microsphere: and (3) uniformly mixing the modified sludge and the attapulgite powder prepared in the step (T4), adding the mixture into water, adding sodium alginate and an emulsifying agent, uniformly dispersing, adding the mixture into fish oil, emulsifying, dropwise adding a calcium chloride solution, curing at normal temperature, filtering, washing and drying to obtain the magnetic embedded sludge fermentation bacteria microsphere.
As a further improvement of the invention, the concentration of the ferrous salt-containing aqueous solution in the step T1 is 0.1-0.2mol/L, the ferrous salt is at least one of ferrous chloride, ferrous sulfate and ferrous nitrate, the concentration of the ammonia water is 15-20wt%, the stirring reaction time is 1-3h, and the aging time is 20-24h; in the step T2, the mass ratio of the magnetic anaerobic sludge to the alkyl orthosilicate to the pore-forming agent to the ammonia water is 10-12:15-20:0.1-0.2:2-4, the concentration of the ammonia water is 15-20wt%, the pore-forming agent is at least one of an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and a PEO106-PPO70-PEO106, the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate, and the stirring reaction time is 10-12h; the seed solution of the bacillus subtilis and the bacillus licheniformis strains in the step T3 has the bacterial content of 10 8 -10 9 cfu/mL, the bacillus subtilis and bacillus licheniformis strain seed solution and porous SiO 2 The mass ratio of the coated magnetic anaerobic sludge is 20-30:15-17:10.
As a further improvement of the present invention, the immobilized bacteria porous SiO in step T4 2 The mass ratio of the coated magnetic anaerobic sludge to the dopamine hydrochloride to the catalyst is 10-12:13-15:0.1-0.2, the catalyst is Tris-HCl solution with pH value of 8.5-9, the temperature of the heating and stirring reaction is 35-40 ℃, and the time is 2-4 hours; in the step T5, the mass ratio of the modified sludge to the attapulgite powder to the sodium alginate to the emulsifier is 12-15:7-10:25-30:1-2, the emulsifier is at least one of Tween-20, tween-40, tween-60 and Tween-80, the concentration of the calcium chloride solution is 5-7wt%, and the normal-temperature curing time is 20-40min.
As a further improvement of the present invention, the immobilized bacteria porous SiO in step T4 2 The mass ratio of the coated magnetic anaerobic sludge to the dopamine hydrochloride to the catalyst is 10-12:13-15:0.1-0.2, the catalyst is Tris-HCl solution with pH value of 8.5-9, the temperature of the heating and stirring reaction is 35-40 ℃, and the time is 2-4 hours; in the step T5, the mass ratio of the modified sludge, the attapulgite powder, the sodium alginate and the emulsifier is 12-15:7-10:25-30:1-2, and the emulsifier is selected from Tween-20 and vomitingAt least one of temperature-40, tween-60 and Tween-80, wherein the concentration of the calcium chloride solution is 5-7wt%, and the curing time at normal temperature is 20-40min.
The invention further protects the citric acid composition biomass carbon source prepared by the preparation method.
The invention has the following beneficial effects:
corn straw is an effective and low-cost sewage treatment denitrification carbon source, contains abundant cellulose, hemicellulose and lignin, and can destroy the lattice structures of a lignin protective layer and cellulose and promote the decomposition of cellulose, lignin and the like through pretreatment (including alkali, acid and high-temperature treatment), so that the subsequent strains can quickly and efficiently utilize the carbon source to generate rich mixtures of citric acid, short-chain fatty acid and the like.
The molasses waste liquid contains a large amount of carbon, and can produce a large amount of organic acids such as citric acid, lactic acid and the like under the anaerobic fermentation action of nitrifying bacteria and denitrifying bacteria and the fermentation action of bacillus subtilis and bacillus licheniformis.
In the sewage treatment process, the residual activated sludge is rich in rich organic matters, volatile fatty acid can be generated through anaerobic fermentation, the residual activated sludge is used as an organic carbon source, the residual activated sludge can be recycled under the anaerobic fermentation action of nitrifying bacteria and denitrifying bacteria and the fermentation action of bacillus subtilis and bacillus licheniformis, meanwhile, the organic matters adsorbed on the surface of the sludge are separated from sludge particles through the addition of a surfactant and are further utilized by acidogenic bacteria, so that the hydrolysis rate and efficiency of the sludge are improved, and the anaerobic fermentation rapidly enters an acidogenic stage, so that the acidogenic rate and acidogenic acid are improved.
After the mixture is subjected to fermentation treatment of magnetic embedded sludge zymophyte microspheres, a large amount of short-chain fatty acid, citric acid, lactic acid and other organic acids are generated in fermentation liquor, calcium salt precipitation is added to prepare calcium citrate, calcium lactate and other precipitates, the precipitates are replaced by sulfuric acid to generate calcium sulfate precipitation and a composition containing rich short-chain fatty acid, citric acid, lactic acid and other organic acids, and the composition is dried to obtain a citric acid composition biomass carbon source.
In the preparation process of the citric acid composition biomass carbon source, the generated solid waste residue can be used for plant fertilizers, the generated byproduct calcium sulfate can be further recycled, and the magnetic embedded sludge fermentation bacteria microsphere after fermentation treatment can be continuously used in sewage treatment, and the surface and interlayer structure of the attapulgite contains abundant complexing groups (amino, carboxyl and the like), and acid center sites such as Bronsted acid, lewis acid and the like and abundant active bacteria, so that the immobilized adsorption of organic matters and heavy metal ions is facilitated, and a good sewage treatment effect is achieved.
The magnetic embedded sludge zymocyte microsphere is magnetic and convenient to separate, and the microsphere is fixedly coated with a layer of porous silicon dioxide on the surface of dried sludge powder, so that the specific surface area of a carrier material is greatly improved, rich fixing sites are provided for the subsequent fixation of bacillus subtilis and bacillus licheniformis, and the prepared immobilized bacterium porous SiO is promoted by modifying polydopamine 2 The magnetic anaerobic sludge and attapulgite powder coated adhesive effect is further embedded by sodium alginate, so that the immobilized magnetic embedded sludge zymocyte microsphere is prepared, has the advantages of high microorganism density, high reaction speed, easiness in product separation, easiness in reaction process control and the like, is loaded with abundant strains including nitrifying bacteria, denitrifying bacteria and the like carried by the sludge powder, and bacillus subtilis and bacillus licheniformis which are fixed subsequently, so that fermentation and acid production of a mixture are facilitated, the fermented product can still be used for sewage treatment, waste production is reduced, and the recycling utilization rate of materials is improved.
Detailed Description
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.
The sludge powder is activated sludge of an aerobic tank of a municipal sewage treatment plant in tin-free city, an SBR reaction device is used for culture and domestication, and after drying, the obtained activated sludge powder has a water content of less than 2%.
Bacillus subtilis, bacillus licheniformis, 1000 hundred million cfu/g, purchased from Guangzhou true microbiological technologies, inc.
Attapulgite powder, 2000 mesh, purchased from Yu Mingguang City Star Attapulgite Inc.
The molasses waste liquid is waste liquid produced by Hebei molasses Feng agricultural technology Co-Ltd, and COD is 8-12 ten thousand mg/L.
The residual sludge after biochemical treatment is residual sludge after biochemical treatment after sewage treatment in the southeast industrial sewage treatment plant in Changzhou, and is dried, crushed and screened by a 100-mesh screen, and the organic matter content is 52-55%.
The preparation method of the bacillus subtilis and bacillus licheniformis strain seed solution comprises the following steps: inoculating Bacillus subtilis and Bacillus licheniformis into slant culture medium respectively, fermenting at 25deg.C for 24 hr at 100r/min to obtain strain seed solution with a bacterial content of 10 8 -10 9 cfu/mL。
Preparation example 1 preparation of magnetic Encapsulated sludge fermentation tubes microsphere
The method comprises the following steps:
t1, preparation of magnetic anaerobic sludge: adding 20 parts by weight of dried sludge powder into 100 parts by weight of aqueous solution containing 0.1mol/L ferrous nitrate, stirring and mixing for 10min, then dropwise adding 15wt% ammonia water into 20 parts by weight, stirring and reacting for 1h, aging for 20h, filtering, washing and drying to obtain magnetic anaerobic sludge;
T2.SiO 2 coating: adding 10 parts by weight of the magnetic anaerobic sludge prepared in the step T1 into 200 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, and adding 15 parts by weight of methyl orthosilicate, 0.1 part by weight of PEO106-PPO70-PEO106 and 2 parts by weight of 15wt% ammonia waterStirring and reacting for 10h, filtering, washing and drying to obtain porous SiO 2 Coating magnetic anaerobic sludge;
t3. fixing strains: stirring and mixing 20 parts by weight of bacillus subtilis and 15 parts by weight of bacillus licheniformis strain seed solution for 10min, and adding 10 parts by weight of porous SiO prepared in the step T2 2 Coating magnetic anaerobic sludge, performing 1000W ultrasonic dispersion for 10min, volatilizing solvent to obtain immobilized bacteria porous SiO 2 Coating magnetic anaerobic sludge;
t4. modification of polydopamine: 10 parts by weight of immobilized bacteria porous SiO prepared in step T3 2 Adding 200 parts by weight of water into the coated magnetic anaerobic sludge, adding 13 parts by weight of dopamine hydrochloride and 0.1 part by weight of catalyst, heating to 35 ℃, stirring for reacting for 2 hours, filtering, washing and drying to obtain modified sludge;
the catalyst is Tris-HCl solution with pH=8.5;
and T5, preparing the magnetic embedded sludge fermentation bacteria microsphere: uniformly mixing 12 parts by weight of the modified sludge prepared in the step T4 and 7 parts by weight of attapulgite powder, adding 200 parts by weight of water, adding 25 parts by weight of sodium alginate and 1 part by weight of tween-20, performing 1000W ultrasonic dispersion for 10min, adding 500 parts by weight of fish oil, emulsifying for 10min at 7000r/min, dropwise adding 20 parts by weight of 5wt% calcium chloride solution, curing for 20min at normal temperature, filtering, washing and drying to obtain the magnetic embedded sludge fermentation tubes microsphere.
Preparation example 2 preparation of magnetic Encapsulated sludge fermentation tubes microsphere
The method comprises the following steps:
t1, preparation of magnetic anaerobic sludge: adding 20 parts by weight of dried sludge powder into 100 parts by weight of aqueous solution containing 0.2mol/L ferrous sulfate, stirring and mixing for 10min, then dropwise adding 20 parts by weight of 20wt% ammonia water, stirring and reacting for 3h, aging for 24h, filtering, washing and drying to obtain magnetic anaerobic sludge;
T2.SiO 2 coating: adding 12 parts by weight of the magnetic anaerobic sludge prepared in the step T1 into 200 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, adding 20 parts by weight of tetraethoxysilane, 0.2 part by weight of ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and 4 parts by weight of 20wt% ammonia water, and stirringStirring and reacting for 12h, filtering, washing and drying to obtain porous SiO 2 Coating magnetic anaerobic sludge;
t3. fixing strains: mixing 30 parts by weight of bacillus subtilis and 17 parts by weight of bacillus licheniformis strain seed solution by stirring for 10min, and adding 10 parts by weight of porous SiO prepared in the step T2 2 Coating magnetic anaerobic sludge, performing 1000W ultrasonic dispersion for 10min, volatilizing solvent to obtain immobilized bacteria porous SiO 2 Coating magnetic anaerobic sludge;
t4. modification of polydopamine: 12 parts by weight of immobilized bacteria porous SiO prepared in the step T3 2 Adding 200 parts by weight of water into the coated magnetic anaerobic sludge, adding 15 parts by weight of dopamine hydrochloride and 0.2 part by weight of catalyst, heating to 40 ℃, stirring for reacting for 4 hours, filtering, washing and drying to obtain modified sludge;
the catalyst is Tris-HCl solution with pH=9;
and T5, preparing the magnetic embedded sludge fermentation bacteria microsphere: uniformly mixing 15 parts by weight of the modified sludge prepared in the step T4 and 10 parts by weight of attapulgite powder, adding 200 parts by weight of water, adding 30 parts by weight of sodium alginate and 2 parts by weight of tween-40, performing ultrasonic dispersion for 10min at 1000W, adding 500 parts by weight of fish oil, emulsifying for 10min at 7000r/min, dropwise adding 20 parts by weight of 7wt% calcium chloride solution, curing for 40min at normal temperature, filtering, washing and drying to obtain the magnetic embedded sludge fermentation tubes microsphere.
Preparation example 3 preparation of magnetic Encapsulated sludge fermentation tubes microspheres
The method comprises the following steps:
t1, preparation of magnetic anaerobic sludge: adding 20 parts by weight of dried sludge powder into 100 parts by weight of aqueous solution containing 0.15mol/L ferrous chloride, stirring and mixing for 10min, then dropwise adding 17wt% ammonia water into 20 parts by weight, stirring and reacting for 2h, aging for 22h, filtering, washing and drying to obtain magnetic anaerobic sludge;
T2.SiO 2 coating: adding 11 parts by weight of the magnetic anaerobic sludge prepared in the step T1 into 200 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, adding 17 parts by weight of tetraethoxysilane, 0.15 part by weight of ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and 3 parts by weight of 17wt% ammonia water, and stirringReacting for 11h, filtering, washing and drying to obtain porous SiO 2 Coating magnetic anaerobic sludge;
t3. fixing strains: mixing 25 parts by weight of bacillus subtilis and 16 parts by weight of bacillus licheniformis strain seed solution by stirring for 10min, and adding 10 parts by weight of porous SiO prepared in the step T2 2 Coating magnetic anaerobic sludge, performing 1000W ultrasonic dispersion for 10min, volatilizing solvent to obtain immobilized bacteria porous SiO 2 Coating magnetic anaerobic sludge;
t4. modification of polydopamine: 11 parts by weight of immobilized bacteria porous SiO prepared in the step T3 2 Adding 200 parts by weight of water into the coated magnetic anaerobic sludge, adding 14 parts by weight of dopamine hydrochloride and 0.15 part by weight of catalyst, heating to 37 ℃, stirring for reaction for 3 hours, filtering, washing and drying to obtain modified sludge;
the catalyst is Tris-HCl solution with pH=8.7;
and T5, preparing the magnetic embedded sludge fermentation bacteria microsphere: uniformly mixing 13 parts by weight of the modified sludge prepared in the step T4 and 8 parts by weight of attapulgite powder, adding 200 parts by weight of water, adding 27 parts by weight of sodium alginate and 1.5 parts by weight of tween-80, performing 1000W ultrasonic dispersion for 10min, adding 500 parts by weight of fish oil, emulsifying for 10min at 7000r/min, dropwise adding 20 parts by weight of 6wt% calcium chloride solution, curing for 30min at normal temperature, filtering, washing and drying to obtain the magnetic embedded sludge fermentation tubes microsphere.
Comparative preparation example 1
In comparison with preparation example 3, the difference is that step T2 is not carried out.
The method comprises the following steps:
t1, preparation of magnetic anaerobic sludge: adding 20 parts by weight of dried sludge powder into 100 parts by weight of aqueous solution containing 0.15mol/L ferrous chloride, stirring and mixing for 10min, then dropwise adding 17wt% ammonia water into 20 parts by weight, stirring and reacting for 2h, aging for 22h, filtering, washing and drying to obtain magnetic anaerobic sludge;
t2. fixing strains: stirring and mixing 25 parts by weight of bacillus subtilis and 16 parts by weight of bacillus licheniformis strain seed liquid for 10min, adding 10 parts by weight of the magnetic anaerobic sludge prepared in the step T1, performing 1000W ultrasonic dispersion for 10min, and volatilizing a solvent to prepare fixed bacteria coated magnetic anaerobic sludge;
t3. modification of polydopamine: adding 11 parts by weight of the immobilized bacteria coated magnetic anaerobic sludge prepared in the step T2 into 200 parts by weight of water, adding 14 parts by weight of dopamine hydrochloride and 0.15 part by weight of catalyst, heating to 37 ℃, stirring and reacting for 3 hours, filtering, washing and drying to prepare modified sludge;
the catalyst is Tris-HCl solution with pH=8.7;
t4. preparation of magnetic embedded sludge fermentation bacteria microsphere: mixing 13 parts by weight of the modified sludge prepared in the step T3 and 8 parts by weight of attapulgite powder uniformly, adding 200 parts by weight of water, adding 27 parts by weight of sodium alginate and 1.5 parts by weight of tween-80, performing 1000W ultrasonic dispersion for 10min, adding 500 parts by weight of fish oil, emulsifying for 10min at 7000r/min, dropwise adding 20 parts by weight of 6wt% calcium chloride solution, curing for 30min at normal temperature, filtering, washing and drying to obtain the magnetic embedded sludge fermentation tubes microsphere.
Comparative preparation example 2
Compared with preparation example 3, the difference is that the bacillus subtilis strain seed liquid is not added in the step T3.
The method comprises the following steps:
t3. fixing strains: adding 41 parts by weight of bacillus licheniformis strain seed solution into 10 parts by weight of porous SiO prepared in the step T2 2 Coating magnetic anaerobic sludge, performing 1000W ultrasonic dispersion for 10min, volatilizing solvent to obtain immobilized bacteria porous SiO 2 Coating magnetic anaerobic sludge.
Comparative preparation example 3
The difference compared with preparation example 3 is that the seed solution of Bacillus licheniformis bacteria is not added in the step T3.
The method comprises the following steps:
t3. fixing strains: 41 weight parts of bacillus subtilis strain seed liquid is added into 10 weight parts of porous SiO prepared in the step T2 2 Coating magnetic anaerobic sludge, performing 1000W ultrasonic dispersion for 10min, volatilizing solvent to obtain immobilized bacteria porous SiO 2 Coating magnetic anaerobic sludge.
Comparative preparation example 4
In comparison with preparation example 3, the difference is that step T3 is not carried out.
The method comprises the following steps:
t1, preparation of magnetic anaerobic sludge: adding 20 parts by weight of dried sludge powder into 100 parts by weight of aqueous solution containing 0.15mol/L ferrous chloride, stirring and mixing for 10min, then dropwise adding 17wt% ammonia water into 20 parts by weight, stirring and reacting for 2h, aging for 22h, filtering, washing and drying to obtain magnetic anaerobic sludge;
T2.SiO 2 coating: adding 11 parts by weight of the magnetic anaerobic sludge prepared in the step T1 into 200 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, adding 17 parts by weight of tetraethoxysilane, 0.15 part by weight of ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and 3 parts by weight of 17wt% ammonia water, stirring and reacting for 11h, filtering, washing and drying to obtain porous SiO 2 Coating magnetic anaerobic sludge;
t3. modification of polydopamine: 11 parts by weight of porous SiO obtained in step T2 2 Adding 200 parts by weight of water into the coated magnetic anaerobic sludge, adding 14 parts by weight of dopamine hydrochloride and 0.15 part by weight of catalyst, heating to 37 ℃, stirring for reaction for 3 hours, filtering, washing and drying to obtain modified sludge;
the catalyst is Tris-HCl solution with pH=8.7;
t4. preparation of magnetic embedded sludge fermentation bacteria microsphere: mixing 13 parts by weight of the modified sludge prepared in the step T3 and 8 parts by weight of attapulgite powder uniformly, adding 200 parts by weight of water, adding 27 parts by weight of sodium alginate and 1.5 parts by weight of tween-80, performing 1000W ultrasonic dispersion for 10min, adding 500 parts by weight of fish oil, emulsifying for 10min at 7000r/min, dropwise adding 20 parts by weight of 6wt% calcium chloride solution, curing for 30min at normal temperature, filtering, washing and drying to obtain the magnetic embedded sludge fermentation tubes microsphere.
Comparative preparation example 5
In comparison with preparation example 3, the difference is that step T4 is not carried out.
The method comprises the following steps:
t1, preparation of magnetic anaerobic sludge: adding 20 parts by weight of dried sludge powder into 100 parts by weight of aqueous solution containing 0.15mol/L ferrous chloride, stirring and mixing for 10min, then dropwise adding 17wt% ammonia water into 20 parts by weight, stirring and reacting for 2h, aging for 22h, filtering, washing and drying to obtain magnetic anaerobic sludge;
T2.SiO 2 coating: adding 11 parts by weight of the magnetic anaerobic sludge prepared in the step T1 into 200 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, adding 17 parts by weight of tetraethoxysilane, 0.15 part by weight of ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and 3 parts by weight of 17wt% ammonia water, stirring and reacting for 11h, filtering, washing and drying to obtain porous SiO 2 Coating magnetic anaerobic sludge;
t3. fixing strains: mixing 25 parts by weight of bacillus subtilis and 16 parts by weight of bacillus licheniformis strain seed solution by stirring for 10min, and adding 10 parts by weight of porous SiO prepared in the step T2 2 Coating magnetic anaerobic sludge, performing 1000W ultrasonic dispersion for 10min, volatilizing solvent to obtain immobilized bacteria porous SiO 2 Coating magnetic anaerobic sludge;
t4. preparation of magnetic embedded sludge fermentation bacteria microsphere: 13 parts by weight of immobilized bacteria porous SiO prepared in the step T3 2 Uniformly mixing the coated magnetic anaerobic sludge and 8 parts by weight of attapulgite powder, adding 200 parts by weight of water, adding 27 parts by weight of sodium alginate and 1.5 parts by weight of tween-80, performing 1000W ultrasonic dispersion for 10min, adding 500 parts by weight of fish oil, emulsifying for 10min at 7000r/min, dropwise adding 20 parts by weight of 6wt% calcium chloride solution, curing for 30min at normal temperature, filtering, washing and drying to obtain the magnetic embedded sludge fermentation tubes microsphere.
Comparative preparation example 6
In comparison with preparation example 3, the difference is that no attapulgite powder was added in step T5.
The method comprises the following steps:
and T5, preparing the magnetic embedded sludge fermentation bacteria microsphere: adding 21 parts by weight of the modified sludge prepared in the step T4 into 200 parts by weight of water, adding 27 parts by weight of sodium alginate and 1.5 parts by weight of tween-80, performing 1000W ultrasonic dispersion for 10min, adding 500 parts by weight of fish oil, emulsifying for 10min at 7000r/min, dropwise adding 20 parts by weight of 6wt% calcium chloride solution, curing for 30min at normal temperature, filtering, washing and drying to obtain the magnetic embedded sludge zymocyte microsphere.
Comparative preparation example 7
In comparison with preparation example 3, the difference is that no embedding is carried out in step T5.
The method comprises the following steps:
t5. preparation of magnetic sludge fermentation bacteria: and (3) uniformly mixing 13 parts by weight of the modified sludge prepared in the step (T4) and 8 parts by weight of the attapulgite powder to prepare the magnetic sludge fermentation bacteria.
Example 1
The embodiment provides a preparation method of a citric acid composition biomass carbon source, which comprises the following steps:
s1, pretreatment of straws: crushing corn straw, adding into a NaOH solution with the concentration of 1wt% for soaking treatment for 0.5h, filtering, adding into a sulfuric acid solution with the concentration of 1wt%, steaming at 120 ℃ in an autoclave for 1h, filtering, washing and drying to obtain pretreated straw;
s2, preparing a mixture: stirring and mixing 15 parts by weight of the pretreated straw prepared in the step S1, 100 parts by weight of molasses waste liquid, 7 parts by weight of biochemically treated residual sludge and 0.5 part by weight of sodium hexadecyl benzene sulfonate for 20 minutes to prepare a mixture;
s3, fermenting: adding 12 parts by weight of the magnetic embedded sludge zymocyte microspheres prepared in the preparation example 1 into 1000 parts by weight of the mixture prepared in the step S2, fermenting for 24 hours at the temperature of 22 ℃ at 100r/min under the anaerobic condition, fermenting for 24 hours at the temperature of 25 ℃ at 100r/min under the micro-anoxic condition, separating the magnetic embedded sludge zymocyte microspheres by using a magnet, fixing heavy metal ions by using the separated magnetic embedded sludge zymocyte microspheres for sewage treatment, filtering, reserving filtrate, and using filter residues as fertilizers;
the micro-anoxic condition is 3O 2 ％、7％CO 2 The balance being nitrogen, wherein,% is by volume;
s4, precipitation: adding calcium nitrate into the filtrate obtained in the step S3, wherein the addition amount of the calcium nitrate is 10 weight percent of the total mass of the system, precipitating for 2 hours, filtering, washing and drying to obtain a mixed precipitate;
s5, replacement: adding 10 parts by weight of the mixed precipitate obtained in the step S4 into 300 parts by weight of 2wt% dilute sulfuric acid, stirring and reacting for 0.5h, filtering, recycling the filter residue which is calcium sulfate precipitate, and drying the filtrate to obtain the citric acid composition biomass carbon source.
Example 2
The embodiment provides a preparation method of a citric acid composition biomass carbon source, which comprises the following steps:
s1, pretreatment of straws: crushing corn straw, adding into 2wt% KOH solution for soaking treatment for 1h, filtering, adding into 1.5wt% sulfuric acid solution, steaming at 130 ℃ in an autoclave for 2h, filtering, washing and drying to obtain pretreated straw;
s2, preparing a mixture: stirring and mixing 20 parts by weight of the pretreated straw prepared in the step S1, 120 parts by weight of molasses waste liquid, 12 parts by weight of biochemically treated residual sludge and 1 part by weight of sodium dodecyl sulfate for 20 minutes to prepare a mixture;
s3, fermenting: adding 15 parts by weight of the magnetic embedded sludge zymocyte microspheres prepared in the preparation example 2 into 1000 parts by weight of the mixture prepared in the step S2, fermenting for 48 hours at the temperature of 27 ℃ at 120r/min under the anaerobic condition, fermenting for 36 hours at the temperature of 30 ℃ at 120r/min under the micro-anoxic condition, separating the magnetic embedded sludge zymocyte microspheres by using a magnet, fixing heavy metal ions by using the separated magnetic embedded sludge zymocyte microspheres for sewage treatment, filtering, reserving filtrate, and using filter residues as fertilizers;
the micro-anoxic condition is 5O 2 ％、10％CO 2 The balance being nitrogen, wherein,% is by volume;
s4, precipitation: adding calcium nitrate into the filtrate obtained in the step S3, wherein the addition amount of the calcium nitrate is 15wt% of the total mass of the system, precipitating for 4 hours, filtering, washing and drying to obtain a mixed precipitate;
s5, replacement: adding 10 parts by weight of the mixed precipitate obtained in the step S4 into 300 parts by weight of 3wt% dilute sulfuric acid, stirring and reacting for 1h, filtering, recycling the filter residue which is calcium sulfate precipitate, and drying the filtrate to obtain the citric acid composition biomass carbon source.
Example 3
The embodiment provides a preparation method of a citric acid composition biomass carbon source, which comprises the following steps:
s1, pretreatment of straws: crushing corn straw, adding into 1.2wt% NaOH solution for soaking treatment for 1h, filtering, adding into 1.2wt% sulfuric acid solution, steaming at 125 ℃ in an autoclave for 1.5h, filtering, washing and drying to obtain pretreated straw;
s2, preparing a mixture: mixing 17 parts by weight of the pretreated straw prepared in the step S1, 110 parts by weight of molasses waste liquid, 10 parts by weight of biochemically treated residual sludge and 0.7 part by weight of sodium dodecyl benzene sulfonate for 20 minutes to prepare a mixture;
s3, fermenting: adding 14 parts by weight of the magnetic embedded sludge zymocyte microspheres prepared in the preparation example 3 into 1000 parts by weight of the mixture prepared in the step S2, fermenting for 36 hours at the temperature of 25 ℃ at 110r/min under the anaerobic condition, fermenting for 30 hours at the temperature of 27 ℃ at 110r/min under the micro-anoxic condition, separating the magnetic embedded sludge zymocyte microspheres by using a magnet, fixing heavy metal ions by using the separated magnetic embedded sludge zymocyte microspheres for sewage treatment, filtering, reserving filtrate, and using filter residues as fertilizers;
the micro-anoxic condition is 4%O 2 、8％CO 2 The balance being nitrogen, wherein,% is by volume;
s4, precipitation: adding calcium chloride into the filtrate obtained in the step S3, wherein the addition amount of the calcium chloride is 12 weight percent of the total mass of the system, precipitating for 3 hours, filtering, washing and drying to obtain a mixed precipitate;
s5, replacement: adding 10 parts by weight of the mixed precipitate obtained in the step S4 into 300 parts by weight of 2.5wt% dilute sulfuric acid, stirring and reacting for 1h, filtering, recycling the filter residue which is calcium sulfate precipitate, and drying the filtrate to obtain the citric acid composition biomass carbon source.
Comparative examples 1 to 7 differ from example 3 in that magnetic sludge fermentation tubes microspheres were prepared from comparative preparation example 1.
Comparative example 8
The difference from example 3 is that no alkali treatment is performed in step S1.
The method comprises the following steps:
s1, pretreatment of straws: crushing corn straw, adding the crushed corn straw into a sulfuric acid solution with the concentration of 1.2wt%, steaming and boiling the crushed corn straw for 1.5 hours at the temperature of 125 ℃ in an autoclave, filtering, washing and drying the crushed corn straw to obtain pretreated straw.
Comparative example 9
The difference from example 3 is that the acid high temperature treatment is not performed in step S1.
The method comprises the following steps:
s1, pretreatment of straws: crushing corn straw, adding into 1.2wt% NaOH solution for soaking treatment for 1h, filtering, washing and drying to obtain pretreated straw.
Comparative example 10
In comparison with example 3, the difference is that sodium dodecylbenzenesulfonate is not added in step S2.
The method comprises the following steps:
s2, preparing a mixture: 17 parts by weight of the pretreated straw prepared in the step S1, 110 parts by weight of molasses waste liquid and 10 parts by weight of biochemically treated residual sludge are stirred and mixed for 20 minutes to prepare a mixture.
Test example 1
The magnetic embedded sludge fermentation microspheres obtained in examples 1-3 and comparative examples 1-7 are used for treating wastewater with serious exceeding of certain heavy metal, the addition amount is 1g/L, the wastewater is discharged after the treatment process, and various indexes of the wastewater are shown in table 1.
TABLE 1
As can be seen from the above table, the magnetic embedded sludge fermentation tubes microspheres obtained by separation in examples 1-3 and comparative examples 1-7 have good sewage treatment effect.
Test example 2
Taking a sludge mixed solution of a biochemical pool of a sewage plant, removing supernatant after precipitation, collecting activated sludge, mixing with inlet water (COD/TN=3), wherein the content of the activated sludge is 1g/L, and aerating a water sample for 12 hours to obtain a test solution; taking the stock solution to measure nitrate nitrogen after stopping aeration; the citric acid compositions prepared in examples 1 to 3 or comparative examples 1 to 10 of the present invention were added with a final concentration of 0.5g/L as a carbon source to a test solution, and stirred at room temperature for 0.5h, 1h, 2h, and 3h to obtain a nitrate nitrogen removal rate (%).
The results are shown in Table 2.
TABLE 2 removal of nitrate nitrogen at various times (%)
| Group of | 0.5h | 1h | 2h | 3h |
| Blank group | 0.42 | 1.54 | 4.21 | 7.04 |
| Glucose | 42.19 | 50.93 | 61.85 | 65.29 |
| Ethanol | 32.95 | 41.85 | 52.41 | 58.92 |
| Example 1 | 68.96 | 79.50 | 86.82 | 95.26 |
| Example 2 | 69.10 | 80.11 | 86.94 | 95.82 |
| Example 3 | 69.42 | 80.57 | 87.25 | 96.31 |
| Comparative example 1 | 62.35 | 73.15 | 79.58 | 89.23 |
| Comparative example 2 | 63.51 | 74.58 | 81.29 | 91.25 |
| Comparative example 3 | 63.22 | 74.21 | 81.05 | 90.58 |
| Comparative example 4 | 59.82 | 71.20 | 77.21 | 85.63 |
| Comparative example 5 | 64.25 | 75.92 | 82.24 | 91.24 |
| Comparative example 6 | 63.20 | 73.86 | 81.67 | 90.56 |
| Comparative example 7 | 62.09 | 72.58 | 80.11 | 89.85 |
| Comparative example 8 | 59.10 | 70.58 | 76.28 | 84.53 |
| Comparative example 9 | 57.85 | 69.29 | 75.38 | 83.95 |
| Comparative example 10 | 65.28 | 75.49 | 83.29 | 92.24 |
As can be seen from the table, after the biomass carbon source of the citric acid composition prepared in the embodiment 1-3 is added, the removal rate of nitrate nitrogen is high, the removal rate is high, the method is obviously higher than that of a single carbon source, the biodegradability can be obviously improved, the denitrification efficiency of a treatment unit is improved, the safety is high, the transportation is convenient, and the operation and the control are convenient.
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 (8)
1. A preparation method of a citric acid composition biomass carbon source is characterized in that corn straw is subjected to alkali treatment and acid high-temperature heating treatment to obtain pretreated straw, the pretreated straw is mixed with molasses waste liquid, biochemical treatment residual sludge and a surfactant to obtain a mixture, the mixture is fermented, filtered, calcium salt is added into filtrate to precipitate, the obtained mixed precipitate is added into dilute sulfuric acid to react under stirring, filtration is carried out, filter residues are calcium sulfate precipitate, recycling is carried out, and filtrate is dried to obtain the citric acid composition biomass carbon source;
the method comprises the following steps:
s1, pretreatment of straws: crushing corn straw, adding into alkali liquor for soaking treatment, filtering, adding into acid liquor, heating at high temperature, filtering, washing, and drying to obtain pretreated straw;
s2, preparing a mixture: uniformly mixing the pretreated straw, molasses waste liquid, biochemically treated residual sludge and surfactant which are prepared in the step S1 to prepare a mixture;
s3, fermenting: adding magnetic embedded sludge zymocyte microspheres into the mixture prepared in the step S2, performing anaerobic fermentation treatment firstly, performing micro-anoxic fermentation treatment secondly, separating the magnetic embedded sludge zymocyte microspheres by a magnet, fixing heavy metal ions by using the separated magnetic embedded sludge zymocyte microspheres for sewage treatment, filtering, reserving filtrate, and using filter residues as fertilizers;
s4, precipitation: adding calcium salt into the filtrate obtained in the step S3, precipitating, filtering, washing and drying to obtain a mixed precipitate;
s5, replacement: adding the mixed precipitate obtained in the step S4 into dilute sulfuric acid, stirring for reaction, filtering, wherein filter residues are calcium sulfate precipitates, recycling, and drying filtrate to obtain a citric acid composition biomass carbon source;
the concentration of the alkali liquor in the step S1 is 1-2wt%, the alkali is NaOH or KOH, the soaking treatment time is 0.5-1h, the acid liquor is 1-1.5wt% sulfuric acid solution, the high-temperature heating treatment temperature is 120-130 ℃, and the high-temperature heating treatment is carried out in an autoclave for 1-2h.
2. The preparation method according to claim 1, wherein the mass ratio of the pretreated straw, molasses waste liquid, biochemically treated residual sludge and surfactant in the step S2 is 15-20:100-120:7-12:0.5-1, and the surfactant is at least one selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium tetradecyl benzene sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl benzene sulfonate, sodium octadecyl benzene sulfonate and sodium octadecyl sulfonate.
3. The preparation method according to claim 2, wherein in the step S3, the mass ratio of the mixture to the magnetic embedded sludge zymocyte microspheres is 1000:12-15, the anaerobic fermentation treatment is performed under anaerobic conditions, the anaerobic fermentation treatment is performed at the temperature of between 100 and 120r/min and between 22 and 27 ℃ for 24 to 48 hours, and the micro-defects are formedThe condition of oxygen fermentation treatment is 100-120r/min under micro-anoxic condition, 25-30deg.C, fermentation treatment is 24-36h, said micro-anoxic condition is 3-5% O 2 %、7-10% CO 2 The balance being nitrogen, wherein% is by volume.
4. The preparation method of the magnetic embedded sludge fermentation bacteria microsphere according to claim 3, wherein the preparation method comprises the following steps:
t1, preparation of magnetic anaerobic sludge: adding the dried sludge powder into an aqueous solution containing ferrous salt, stirring and mixing uniformly, then dropwise adding ammonia water, stirring and reacting, aging, filtering, washing and drying to obtain magnetic anaerobic sludge;
T2.SiO 2 coating: adding the magnetic anaerobic sludge prepared in the step T1 into water, dispersing uniformly, adding the alkyl orthosilicate, the pore-forming agent and the ammonia water, stirring for reaction, filtering, washing and drying to obtain porous SiO 2 Coating magnetic anaerobic sludge;
t3. fixing strains: uniformly mixing seed solution of bacillus subtilis and bacillus licheniformis strains, and adding porous SiO prepared in the step T2 2 Coating magnetic anaerobic sludge, dispersing uniformly, volatilizing solvent to obtain immobilized bacteria porous SiO 2 Coating magnetic anaerobic sludge;
t4. modification of polydopamine: the immobilized bacteria porous SiO prepared in the step T3 is treated 2 Adding water into the coated magnetic anaerobic sludge, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, filtering, washing and drying to obtain modified sludge;
and T5, preparing the magnetic embedded sludge fermentation bacteria microsphere: and (3) uniformly mixing the modified sludge and the attapulgite powder prepared in the step (T4), adding the mixture into water, adding sodium alginate and an emulsifying agent, uniformly dispersing, adding the mixture into fish oil, emulsifying, dropwise adding a calcium chloride solution, curing at normal temperature, filtering, washing and drying to obtain the magnetic embedded sludge fermentation bacteria microsphere.
5. The process according to claim 4, wherein the concentration of the aqueous solution containing a ferrite salt in the step T1 is 0.1-0.2mol/L, wherein the ferrous salt is at least one of ferrous chloride, ferrous sulfate and ferrous nitrate, the concentration of ammonia water is 15-20wt%, the stirring reaction time is 1-3h, and the aging time is 20-24h; in the step T2, the mass ratio of the magnetic anaerobic sludge to the alkyl orthosilicate to the pore-forming agent to the ammonia water is 10-12:15-20:0.1-0.2:2-4, the concentration of the ammonia water is 15-20wt%, the pore-forming agent is at least one of an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and a PEO106-PPO70-PEO106, the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate, and the stirring reaction time is 10-12h; the seed solution of the bacillus subtilis and the bacillus licheniformis strains in the step T3 has the bacterial content of 10 8 -10 9 cfu/mL, the bacillus subtilis and bacillus licheniformis strain seed solution and porous SiO 2 The mass ratio of the coated magnetic anaerobic sludge is 20-30:15-17:10.
6. The method according to claim 5, wherein the immobilized bacteria porous SiO in step T4 2 The mass ratio of the coated magnetic anaerobic sludge to the dopamine hydrochloride to the catalyst is 10-12:13-15:0.1-0.2, the catalyst is Tris-HCl solution with pH value of 8.5-9, the temperature of the heating and stirring reaction is 35-40 ℃, and the time is 2-4 hours; in the step T5, the mass ratio of the modified sludge to the attapulgite powder to the sodium alginate to the emulsifier is 12-15:7-10:25-30:1-2, the emulsifier is at least one of Tween-20, tween-40, tween-60 and Tween-80, the concentration of the calcium chloride solution is 5-7wt%, and the normal-temperature curing time is 20-40min.
7. The preparation method according to claim 6, wherein the addition amount of the calcium salt in the step S4 is 10-15wt% of the total mass of the system, the calcium salt is at least one selected from calcium chloride and calcium nitrate, and the time for precipitation is 2-4h; the concentration of the dilute sulfuric acid in the step S5 is 2-3wt%, and the stirring reaction time is 0.5-1h.
8. A citric acid composition biomass carbon source produced by the method of any one of claims 1-7.
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| CA2212819A1 (en) * | 1995-02-13 | 1996-08-22 | W.R. Grace & Co.-Conn. | Composition and method for degradation of nitroaromatic contaminants |
| GB2599235A (en) * | 2020-09-23 | 2022-03-30 | Univ Jiangsu | Method for converting lignin-containing biomass to synthesize curcumin |
| CN114875105A (en) * | 2022-03-09 | 2022-08-09 | 益水源生物技术(西安)有限公司 | Biomass-based efficient carbon source and preparation method thereof |
| CN116371183A (en) * | 2023-04-06 | 2023-07-04 | 盐城工学院 | Method for removing odor generated by anaerobic fermentation of compost through biological filter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2212819A1 (en) * | 1995-02-13 | 1996-08-22 | W.R. Grace & Co.-Conn. | Composition and method for degradation of nitroaromatic contaminants |
| GB2599235A (en) * | 2020-09-23 | 2022-03-30 | Univ Jiangsu | Method for converting lignin-containing biomass to synthesize curcumin |
| CN114875105A (en) * | 2022-03-09 | 2022-08-09 | 益水源生物技术(西安)有限公司 | Biomass-based efficient carbon source and preparation method thereof |
| CN116371183A (en) * | 2023-04-06 | 2023-07-04 | 盐城工学院 | Method for removing odor generated by anaerobic fermentation of compost through biological filter |
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