CN113845207A - Cellulose magnetic carrier and preparation method thereof, anaerobic granular sludge containing cellulose magnetic carrier and preparation method thereof - Google Patents
Cellulose magnetic carrier and preparation method thereof, anaerobic granular sludge containing cellulose magnetic carrier and preparation method thereof Download PDFInfo
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- CN113845207A CN113845207A CN202111359640.8A CN202111359640A CN113845207A CN 113845207 A CN113845207 A CN 113845207A CN 202111359640 A CN202111359640 A CN 202111359640A CN 113845207 A CN113845207 A CN 113845207A
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- 239000010802 sludge Substances 0.000 title claims abstract description 196
- 229920002678 cellulose Polymers 0.000 title claims abstract description 86
- 239000001913 cellulose Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 235000010980 cellulose Nutrition 0.000 claims abstract description 84
- 229920000168 Microcrystalline cellulose Chemical group 0.000 claims abstract description 26
- 239000008108 microcrystalline cellulose Chemical group 0.000 claims abstract description 26
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 26
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 97
- 239000000243 solution Substances 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 35
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 20
- 239000011790 ferrous sulphate Substances 0.000 claims description 20
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 20
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 20
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 20
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 230000007935 neutral effect Effects 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000008213 purified water Substances 0.000 claims description 16
- 239000000969 carrier Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 54
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000000975 bioactive effect Effects 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract 1
- 229960004099 azithromycin Drugs 0.000 description 39
- MQTOSJVFKKJCRP-BICOPXKESA-N azithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)N(C)C[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 MQTOSJVFKKJCRP-BICOPXKESA-N 0.000 description 39
- 238000002156 mixing Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000002351 wastewater Substances 0.000 description 17
- 238000007599 discharging Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- 230000001174 ascending effect Effects 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012452 mother liquor Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 244000005700 microbiome Species 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 239000007836 KH2PO4 Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- -1 sodium hydroxide Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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- 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
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/001—Upstream control, i.e. monitoring for predictive control
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/003—Downstream control, i.e. outlet monitoring, e.g. to check the treating agents, such as halogens or ozone, leaving the process
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention discloses a cellulose magnetic carrier and a preparation method thereof, and anaerobic granular sludge containing the cellulose magnetic carrier and a preparation method thereof, belonging to the technical field of wastewater treatment; according to the preparation method of the cellulose magnetic carrier, nano ferroferric oxide generated by ferric iron metal salt and ferrous iron metal salt and microcrystalline cellulose form a complex compound in the preparation process, the complex compound is tightly combined on the surface of the microcrystalline cellulose, and the ferroferric oxide is not easy to fall off, so that the stable structure of the prepared magnetic anaerobic granular sludge is ensured; according to the preparation method of the anaerobic granular sludge, the prepared anaerobic granular sludge is subjected to growth, wrapping and winding by taking cellulose nano ferroferric oxide as a parent nucleus, and finally, compact and compact bioactive granular sludge is formed.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a cellulose magnetic carrier and a preparation method thereof, and anaerobic granular sludge containing the carrier and a preparation method thereof.
Background
The anaerobic granular sludge has the characteristics of high settling rate, high organic load, high anaerobic gas production efficiency and the like, and is widely applied to novel anaerobic reactors such as IC (integrated Circuit), EGSB (expanded granular sludge), and the like, but the culture period of the anaerobic granular sludge is very long, stable biological granules can be formed in 3-6 months generally, and the anaerobic granular sludge formed in the natural state is fragile, and is easily disintegrated once entering severe environments such as high biological toxicity, high salt and the like, so that the treatment efficiency of the anaerobic reactor is greatly reduced. The antibiotic wastewater is industrial wastewater with high COD concentration and large biological toxicity, and people pay attention to how to rapidly prepare anaerobic granular sludge, improve the stability of the anaerobic granular sludge in the antibiotic wastewater and improve the treatment efficiency of an anaerobic reactor on the antibiotic wastewater.
Through retrieval, the patent application document with the publication number of CN105771918A discloses preparation and application of a magnetic anaerobic granular sludge-chitosan adsorbent, in the scheme, chitosan is dissolved in a mixed solution of water and glacial acetic acid, Fe3O4 is added and stirred for a period of time, then anaerobic granular sludge is added and continuously stirred, products are sequentially washed by petroleum ether, ethanol and deionized water until the pH value is neutral, the obtained black solid is dried in vacuum at 40-60 ℃, and finally the magnetic anaerobic granular sludge-chitosan adsorbent is prepared; the magnetic anaerobic granular sludge prepared by the scheme has adsorption performance, can adsorb pollutants such as heavy metals in water to a certain extent, is essentially biased to utilize physical adsorption, and has a relatively limited treatment effect on water; in addition, various organic solvents such as ethylene glycol, ethylenediamine, glutaraldehyde, petroleum ether, ethanol and the like are used in the preparation process of the scheme, and the preparation process is complex.
The porosity of the traditional magnetic anaerobic granular sludge is 40-50%, the volume of methane produced in a culture solution by each liter of granular sludge is 800-1300L, and the anaerobic organism gas production activity is low. Therefore, the anaerobic granular sludge with good stability and controllable production cost is needed at present.
Disclosure of Invention
Aiming at the technical problem of poor biological water treatment effect caused by poor stability of anaerobic granular sludge in the prior art, the invention provides a cellulose magnetic carrier and a preparation method thereof, and anaerobic granular sludge containing the cellulose magnetic carrier and a preparation method thereof.
In order to achieve the aim, the invention provides the technical scheme that
The invention relates to a preparation method of a cellulose magnetic carrier, which comprises the steps of dissolving microcrystalline cellulose, ferric iron metal salt and ferrous iron metal salt, and heating; then adding a volatile non-metallic alkaline substance, and adjusting the pH value to 9-10; preserving heat, stirring, cleaning solid substances in the mixture to be neutral, and finally drying to obtain the cellulose magnetic carrier; in the reaction process, microcrystalline cellulose is contained, and nano ferroferric oxide generated by ferric iron metal salt and ferrous iron metal salt and the microcrystalline cellulose form a complex compound which is tightly combined on the surface of the microcrystalline cellulose, so that the ferroferric oxide is not easy to fall off, and the stable structure of the prepared magnetic anaerobic granular sludge is ensured.
If the microcrystalline cellulose and the nano ferroferric oxide are directly and simply mixed and then solidified, the microcrystalline cellulose and the nano ferroferric oxide are combined only by Van der Waals force, the ferroferric oxide is easy to peel off and fall off, and the magnetic anaerobic granular sludge is easy to disintegrate and lose efficacy.
Preferably, the ferric metal salt and the ferrous metal salt are ferric chloride and ferrous sulfate, respectively.
Preferably, in the dissolving process, the microcrystalline cellulose, the ferric chloride, the ferrous sulfate and the purified water are mixed and dissolved according to the mass ratio of 20:2:1: 200.
Preferably, the volatile basic substance is ammonia or triethylamine. The use of metal salts such as sodium hydroxide or sodium carbonate is avoided, otherwise, other metal ion impurities can be mixed in the nano ferroferric oxide generated by the reaction. It is only used for adjusting and controlling the pH value of the reaction, and can be completely volatilized without generating residue after the reaction is finished and is dried. If the pH is adjusted by metal salt such as sodium hydroxide, residues may be generated after the reaction, and impurities are mixed in the nano ferroferric oxide.
The ferric chloride, the ferrous sulfate and the ammonia water are all conventional compounds which are easy to purchase and obtain, the cost of raw materials is low, and the preparation process is simple. Compared with the method that the nano ferroferric oxide sold in the market is sold after being prepared by manufacturers, the price is high, and the water treatment cost is increased suddenly when a large amount of nano ferroferric oxide is applied; the effect is otherwise inferior to the solution of the invention.
Preferably, in the heat preservation stirring process, the stirring speed is 5-10 rpm; the nano ferroferric oxide generated by the reaction cannot be uniformly complexed on the surface of the microcrystalline cellulose due to too high stirring speed, so that free ferroferric oxide is formed, and the free ferroferric oxide is eluted and discharged out of the system, so that the preparation efficiency is not high.
Preferably, the heat preservation temperature is kept at 70-75 ℃, and the yield of the nano ferroferric oxide generated by the chemical reaction is not high due to overhigh or overlow temperature.
The cellulose magnetic carrier is prepared by the preparation method.
The specific method for preparing the cellulose nano ferroferric oxide (cellulose magnetic carrier) comprises the following steps:
mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 70-75 ℃, adjusting the pH to 9-10 by using ammonia water, slowly stirring, controlling the stirring speed to be 5-10 rpm, keeping the reaction temperature for 1.5-2 h, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide.
The invention relates to a preparation method of anaerobic granular sludge, which comprises the steps of placing cellulose magnetic carriers into anaerobic flocculent sludge, mixing, placing the mixed anaerobic flocculent sludge containing the cellulose magnetic carriers into a container, introducing anaerobic granular sludge culture solution from the bottom in the container, and directly discharging the culture solution flowing through an anaerobic flocculent sludge layer out of the container to obtain the anaerobic granular sludge, wherein the cellulose magnetic carriers are the cellulose magnetic carriers; the anaerobic granular sludge is grown, wrapped and wound by taking cellulose nano ferroferric oxide as a parent nucleus to finally form compact and compact bioactive granular sludge. The culture solution is uniformly introduced from the bottom of the anaerobic sludge, a certain amount of upward shearing force and screening pressure can be provided, the anaerobic flocculent sludge which is not tightly combined is washed out of the system, only the tightly combined anaerobic sludge is reserved, and finally, the surfaces of the prepared magnetic anaerobic sludge can be tightly combined with anaerobic microorganisms.
Preferably, the flow speed of the anaerobic granular sludge culture solution introduced into the bottom is 0.3-0.5 m/h. The upflow rate is to provide a certain amount of upward shear and screening pressure to wash the loosely bound anaerobic flocculent sludge out of the system, leaving only the tightly bound anaerobic sludge. If the rising flow rate is too high, the scouring force is too high, anaerobic microorganisms are difficult to be planted on the surface of the cellulose nano ferroferric oxide, and even the cellulose nano ferroferric oxide can be directly flushed out of the system. If the upward flow rate is too small to provide sufficient shearing force and screening pressure, loose flocculent sludge may remain in the system, consuming nutrients in the culture broth, resulting in degradation of production efficiency.
Preferably, the anaerobic granular sludge culture solution is prepared from 3 mother solutions, and the formula of the anaerobic granular sludge culture solution is as follows:
mother liquor A: glucose solution 93.8g/L
Mother liquor B: k2HPO4·3H2O 22~28g/L
KH2PO4 8~12g/L
NH4Cl 28~32g/L
The anaerobic granular sludge is prepared by the preparation method.
In the scheme, the mother liquor A and the mother liquor B are used for providing a carbon source, a nitrogen source and a phosphorus source, and are conventional nutrients. The mother liquor C is very important for culturing the granular sludge, wherein Mg, Fe, Ca, Zn and Mn are key elements for growth and structure formation of the magnetic anaerobic granular sludge, can stimulate the rapid growth of anaerobic microorganisms, and if the magnetic anaerobic granular sludge is lacked, the anaerobic granular sludge can grow slowly, and the structure is easy to loosen and break. The composition and the proportion of the several metal salts of the mother liquor C are preferably combined.
The invention relates to a preparation method of anaerobic granular sludge, which comprises the following specific process flows:
firstly, preparing an anaerobic granular sludge culture solution:
the anaerobic granular sludge culture solution is prepared from 3 mother solutions, and the formula comprises:
mother liquor A: glucose solution 93.8g/L
Mother liquor B: k2HPO4·3H2O 22~28g/L
KH2PO4 8~12g/L
NH4Cl 28~32g/L
The anaerobic granular sludge culture solution is prepared at present, and the mother solution A25mL, the mother solution B10mL and the mother solution C10mL are respectively added into 1L of pure water and mixed to prepare the anaerobic granular sludge culture solution.
Then preparing magnetic anaerobic granular sludge:
and (3) taking commercially available anaerobic flocculent sludge with SS of 40-50 g/L, adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5-8%, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.3-0.5 m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After the continuous culture for 20 days, the anaerobic flocculent sludge in the container can be converted into cellulose magnetic anaerobic granular sludge.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the process of preparing the anaerobic granular sludge, the microcrystalline cellulose is added, the material has a stable structure and good biocompatibility, can provide physical support for nano ferroferric oxide generated by reaction, provides a carrier for growth and permanent planting of anaerobic microorganisms, and increases the structural stability of the anaerobic granular sludge.
(2) According to the invention, ferric chloride and ferrous sulfate are utilized to generate nano ferroferric oxide under a high-temperature alkaline condition, and the nano ferroferric oxide can mediate inter-species electron transfer in an anaerobic sludge system, so that the degradation efficiency of anaerobic microorganisms on complex organic matters (residual antibiotics) is enhanced, and the treatment capacity of the anaerobic reactor on antibiotic wastewater is improved.
(3) The invention takes the cellulose nano ferroferric oxide as the skeleton core, so that the anaerobic flocculent sludge is quickly attached to the surface for field planting growth, and the preparation culture period of the anaerobic granular sludge can be greatly shortened.
(4) The porosity of the cellulose magnetic anaerobic granular sludge is 60-70%, the volume of methane in a culture solution of each liter of granular sludge is 1400-2000L, and the anaerobic biological gas production activity is high.
Drawings
FIG. 1 is a flow chart of a process for preparing cellulose-based magnetic anaerobic granular sludge
Detailed Description
For a further understanding of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings and examples.
The structure, proportion, size and the like shown in the drawings are only used for matching with the content disclosed in the specification, so that the person skilled in the art can understand and read the description, and the description is not used for limiting the limit condition of the implementation of the invention, so the method has no technical essence, and any structural modification, proportion relation change or size adjustment still falls within the scope of the technical content disclosed by the invention without affecting the effect and the achievable purpose of the invention. Meanwhile, the terms such as "upper", "lower", "left", "right" and "middle" used in the present specification are for clarity of description only, and are not used to limit the implementable scope, and the relative relationship changes or adjustments may be considered to be within the implementable scope of the present invention without substantial technical changes; in addition, the embodiments of the present invention are not independent of each other, but may be combined.
Example 1
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 70 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After the continuous culture for 20 days, the cellulose magnetic anaerobic granular sludge is prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent water is 1120mg/L, and the azithromycin residual quantity is 2.5 mg/L. The anaerobic sludge loss rate was monitored to be 1.3% during the run.
Example 2
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 75 ℃, adjusting the pH to 10 by using ammonia water, slowly stirring, controlling the stirring speed to be 8rpm, keeping the reaction temperature for 1.5h, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) taking commercially available anaerobic flocculent sludge with SS of 40g/L, adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5%, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.3m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After the continuous culture for 20 days, the cellulose magnetic anaerobic granular sludge is prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent water is 1240mg/L, and the azithromycin residual quantity is 3.6 mg/L. The anaerobic sludge loss rate was monitored to be 1.9% during the run.
Comparative example 1
Mixing and dissolving ferric chloride, ferrous sulfate and purified water according to the mass ratio of 2:1:200, heating to 70 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the nano ferroferric oxide. And (3) taking commercially available anaerobic flocculent sludge with SS of 50g/L, adding nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5%, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After continuous culture for 20 days, magnetic anaerobic granular sludge is prepared.
Inoculating the magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent was 2180mg/L, and the azithromycin residual quantity was 7.3 mg/L. The anaerobic sludge loss rate was monitored to be 4.2% during the run.
Comparative example 2
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 60:5:1:200, heating to 50 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After the continuous culture for 20 days, the cellulose magnetic anaerobic granular sludge is prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent water is 1780mg/L, and the azithromycin residual quantity is 9.9 mg/L. The anaerobic sludge loss rate was monitored to be 3.7% during the run.
Comparative example 3
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 50 ℃, adjusting the pH to 11 by using ammonia water, slowly stirring, controlling the stirring speed to be 20rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After the continuous culture for 20 days, the cellulose magnetic anaerobic granular sludge is prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; the COD in the effluent is 2630mg/L, and the azithromycin residual quantity is 7.9 mg/L. The anaerobic sludge loss rate was monitored to be 5.4% during the run.
Comparative example 4
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 70 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 1% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After continuous culture for 40 days, preparing and obtaining the cellulose magnetic anaerobic granular sludge.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent water is 2950mg/L, and the azithromycin residual quantity is 15.3 mg/L. The anaerobic sludge loss rate monitored during the operation process is 8.8 percent.
Comparative example 5
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 70 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.1m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After continuous culture for 60 days, preparing and obtaining the cellulose magnetic anaerobic granular sludge.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent water is 2150mg/L, and the azithromycin residual quantity is 12.4 mg/L. The anaerobic sludge loss rate was monitored to be 6.3% during the run.
Comparative example 6
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 5:2:1:200, heating to 70 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After the continuous culture for 20 days, the cellulose magnetic anaerobic granular sludge is prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent is 2090mg/L, and the azithromycin residual quantity is 6.5 mg/L. The anaerobic sludge loss rate was monitored to be 3.8% during the run.
Comparative example 7
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 50 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After the continuous culture for 20 days, the cellulose magnetic anaerobic granular sludge is prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent water is 2530mg/L, and the azithromycin residual quantity is 8.6 mg/L. The anaerobic sludge loss rate was monitored to be 6.1% during the run.
Comparative example 8
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 70 ℃, adjusting the pH to 9 by using sodium hydroxide, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After the continuous culture for 20 days, the cellulose magnetic anaerobic granular sludge is prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent is 2740mg/L, and the azithromycin residual quantity is 7.2 mg/L. The anaerobic sludge loss rate was monitored to be 7.5% during the run.
Comparative example 9
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 70 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 50rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After the continuous culture for 20 days, the cellulose magnetic anaerobic granular sludge is prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent was 2910mg/L, and the azithromycin residual quantity was 6.9 mg/L. The anaerobic sludge loss rate was monitored to be 9.3% during the run.
Comparative example 10
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 70 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 1% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.5m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After continuous culture for 40 days, the cellulose magnetic anaerobic granular sludge can be prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent water is 2840mg/L, and the azithromycin residual quantity is 12.7 mg/L. The anaerobic sludge loss rate was monitored to be 7.7% during the run.
Comparative example 11
Mixing and dissolving microcrystalline cellulose, ferric chloride, ferrous sulfate and purified water according to the mass ratio of 20:2:1:200, heating to 70 ℃, adjusting the pH to 9 by using ammonia water, slowly stirring, controlling the stirring speed to be 5rpm, keeping the reaction temperature for 2 hours, washing solid substances to be neutral by using pure water, and drying in the shade to obtain the cellulose nano ferroferric oxide. And (3) adding cellulose nano ferroferric oxide into the anaerobic flocculent sludge according to the mass fraction of 5% from commercially available anaerobic flocculent sludge with the SS of 50g/L, and uniformly mixing. Placing the uniformly mixed anaerobic flocculent sludge into a container, uniformly introducing a fresh anaerobic granular sludge culture solution from the bottom of the anaerobic sludge, controlling the ascending flow rate of the culture solution to be 0.1m/h, and directly discharging the culture solution flowing through the anaerobic flocculent sludge layer out of the culture container. After continuous culture for 60 days, the cellulose magnetic anaerobic granular sludge can be prepared.
Inoculating cellulose magnetic anaerobic granular sludge into an anaerobic reactor, taking azithromycin wastewater as water inflow, continuously passing through the anaerobic reactor, and detecting the water inflow and the water outflow of the anaerobic reactor after running for 4 weeks: the COD of the inlet water is 6800mg/L, and the residual quantity of the azithromycin is 66 mg/L; COD in the effluent water is 2150mg/L, and the azithromycin residual quantity is 12.4 mg/L. The anaerobic sludge loss rate was monitored to be 6.3% during the run.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Claims (10)
1. A preparation method of a cellulose magnetic carrier is characterized in that microcrystalline cellulose, ferric iron metal salt and ferrous iron metal salt are dissolved and heated; then adding a volatile non-metallic alkaline substance, and adjusting the pH value to 9-10; keeping the temperature and stirring, then cleaning the solid matter in the mixture to be neutral, and finally drying the mixture to obtain the cellulose magnetic carrier.
2. The method according to claim 1, wherein the ferric metal salt and the ferrous metal salt are ferric chloride and ferrous sulfate, respectively.
3. The method for preparing the cellulose magnetic carrier according to claim 2, wherein in the dissolving process, the microcrystalline cellulose, the ferric chloride, the ferrous sulfate and the purified water are mixed and dissolved according to a mass ratio of 20:2:1: 200.
4. The method according to claim 1, wherein the volatile basic substance is ammonia or triethylamine.
5. The method for preparing the cellulose magnetic carrier according to claim 1, wherein the stirring speed is 5-10 rpm in the heat-preservation stirring process.
6. A cellulose magnetic carrier produced by the production method according to any one of claims 1 to 5.
7. A method for preparing anaerobic granular sludge, characterized in that cellulose magnetic carriers are placed in anaerobic flocculent sludge and mixed, the mixed anaerobic flocculent sludge containing the cellulose magnetic carriers is placed in a container, then anaerobic granular sludge culture solution is introduced from the bottom in the container, and the culture solution flowing through the anaerobic flocculent sludge layer is directly discharged out of the container, thereby preparing the anaerobic granular sludge, wherein the cellulose magnetic carriers are the cellulose magnetic carriers of claim 6.
8. The method for preparing anaerobic granular sludge according to claim 7, wherein the flow rate of the anaerobic granular sludge culture solution introduced into the bottom is 0.3-0.5 m/h.
10. an anaerobic granular sludge, which is prepared by the preparation method of any one of claims 6 to 9.
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CN105195112A (en) * | 2015-10-26 | 2015-12-30 | 福建农林大学 | Preparation method of melamine-modified chitosan-coated magnetic nanocellulose adsorbent and product thereof |
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