CN116850959A - Electropositive magnetic filler and preparation method thereof - Google Patents
Electropositive magnetic filler and preparation method thereof Download PDFInfo
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- CN116850959A CN116850959A CN202310718105.XA CN202310718105A CN116850959A CN 116850959 A CN116850959 A CN 116850959A CN 202310718105 A CN202310718105 A CN 202310718105A CN 116850959 A CN116850959 A CN 116850959A
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- electropositive
- magnetic
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- 239000012762 magnetic filler Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 37
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 26
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 229960002089 ferrous chloride Drugs 0.000 claims description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 241000894006 Bacteria Species 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 244000005700 microbiome Species 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 4
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- 239000000696 magnetic material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 3
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- 210000002381 plasma Anatomy 0.000 description 3
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000006727 cell loss Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000001450 methanotrophic effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
- B01D53/85—Biological processes with gas-solid contact
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3014—Kneading
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/95—Specific microorganisms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Chemical & Material Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses an electropositive magnetic filler and a preparation method thereof, and belongs to the technical field of biology. The technical proposal is as follows: positively charged magnetic nanoparticle coated biochar filler PSt-DMC-BA@Fe 3 O 4 The preparation method comprises the following steps: 1) Nanoparticle DTAB@Fe 3 O 4 Is prepared by the steps of (1); 2) Positively charged nanoparticle PDMC@Fe 3 O 4 Is prepared by the steps of (1); 3) Electropositive magnetic filler PSt-BA@PDMC@Fe 3 O 4 Preparation of @ BC. The invention takes vinasse biogas residue biochar as a raw material, adopts a nanoparticle adsorption-film forming coating method, and greatly positively charges a large amount of the biological carbonQuaternary ammonium radical of charge group (-NC) 3 + ) Modified magnetic nanoparticle Fe 3 O 4 Film forming and coating on the surface of biogas residue biochar to obtain the core, -NC by taking the biochar as the core 3 + &Fe 3 O 4 And (3) coating the surface of the electropositive magnetic biochar material.
Description
Technical Field
The invention belongs to the technical field of biological fillers, and particularly relates to an electropositive magnetic filler and a preparation method thereof.
Background
Methane is the global second largest greenhouse gas, the warming potential of the methane is about 20-30 times of that of the carbon dioxide with the same mass, and the exacerbation effect on climate change is not neglected. The methane biological filter mediated by the methanotrophic bacteria is a high-efficiency, safe, economic and environment-friendly low-concentration methane removal method, has the advantages of mild operation conditions, high safety, high removal rate, low cost, few byproducts and the like, and in actual operation, however, the problems that the filter operation performance and the methane removal efficiency cannot be kept high and stable for a long time due to the adverse factors of slow cell growth, difficult culture, low activity and poor stability are often faced.
In order to improve the growth strength, metabolic activity and bacterial stability of the methane-oxidizing bacteria in the filter, porous fillers with lower cost can be used for attaching and immobilizing the bacteria, and the pores rich in the fillers can provide a large number of attachment sites for the methane-oxidizing bacteria to form a biomembrane coated on the surface of the filler, so that compared with free microbial cells, the immobilized biomembrane has higher cell density and stronger metabolic activity; meanwhile, the pores have a shielding effect, so that cell loss and damage caused by external force are avoided, and the stability and tolerance of microorganisms are stronger. The invention discloses a novel magnetic material for sewage treatment and application thereof, and discloses a novel magnetic material for sewage treatment, wherein the magnetic nano particles are functionally modified by food waste banana peel, and the molecular formula of the novel magnetic material contains a large number of hydroxyl functional groups because of the enrichment of lignin, hemicellulose and cellulose, so that the adsorption effect of the novel magnetic material on metal ions in sewage can be effectively increased. Meanwhile, the magnetic particles subjected to oleic acid surface modification have good sedimentation stability and effectively avoid the aggregation phenomenon. The Chinese patent No. CN110745965A discloses a magnetic filler for sewage treatment, which is prepared by firstly carrying out acidic modification on biochar, then adsorbing iron ions and heavy metal ions to obtain biochar for adsorbing heavy metal, and placing the biochar in a strong alkali solution for reaction to obtain the magnetic filler for sewage treatment; the preparation process of the magnetic filler is simple, the operation is convenient, and the prepared magnetic filler biological film forming effect based on the treatment of heavy metal wastewater by using biochar is good. The Chinese patent No. 103641233B discloses a method for preparing magnetic filler by using waste plastic bottles, which comprises the steps of cutting plastic bottles, modifying low-temperature plasmas and spraying fine ferrite powder. The specific preparation process is as follows: firstly cutting waste plastic bottles into thin strip-shaped plastic, and then adopting a medium resistorThe low-temperature plasma generated by the discharge-blocking plasma generator is used for modifying the fine strip-shaped plastic, and finally, the air flow is used for spraying the fine ferrite powder on the surface of the fine strip-shaped plastic to form the plastic magnetic filler. The magnetic filler is prepared from waste plastic bottles and a heavy metal ion wastewater treatment product magnetic ferrite, so that the cost is low, and the recycling of solid wastes is realized; the magnetic filler has higher biological affinity on the surface, is easy to form a film, and has high sewage treatment efficiency. The polyurethane sponge filler modified by the Chinese invention patent CN114181429B, the preparation method and the application thereof adopt polyurethane sponge with larger porosity and specific surface area as a main body, and firstly, the polyurethane sponge filler is soaked and corroded in potassium permanganate sulfuric acid solution to obviously improve the surface roughness of the filler; then loading the powder activated carbon on the surface of the filler, increasing the specific surface area and having a certain adsorption capacity on pollutants; then soaking in ferric trichloride chitosan solution to make the surface of the filler have positive charges, and attracting the modified polyurethane sponge and bacteria with opposite charges due to electrostatic interaction to promote adhesion and film formation of microorganisms; and washing and drying to obtain the modified polyurethane sponge filler. The modified polyurethane sponge filler prepared by the invention has strong adsorptivity to waste gas and bacteria, solves the problems of low mass transfer rate, long film forming time and the like in the existing waste gas biological treatment while ensuring the treatment efficiency, and improves the waste gas treatment effect. The invention patent CN103420490B is prepared from (by weight parts) polymer base 100-250, electrophilic functional material 2-15, adjuvant 1, adjuvant 2 and adjuvant 3 2-20, 2-20 and 1-10. Mixing the above materials, granulating, extruding with screw, cooling, cutting, and shaping. The biological carrier provided by the invention is convenient to prepare, and the density is 0.91-0.97g/cm 3 Controllable; according to the characteristic that microorganisms have negative charges in water, positively charged functional materials are mixed in the carrier to make the surface of the carrier have positive charges so as to enhance the affinity between the microorganisms and the carrier. The biological carrier is favorable for microorganism adhesion growth, easy film formation and short period; the biomass is large, the ammonia nitrogen removal efficiency is high, and the quality of the effluent water is good; the sludge sedimentation performance is good, and the equipment runs without sludge blockage; service life of biological carrierLong and does not require manual replacement and maintenance. However, the current filler modification technology still has the following problems: firstly, the microorganism adhesion efficiency and the growth metabolism activity of the existing modified filler need to be further improved; secondly, few filler modification technologies suitable for improving the methane-oxidizing bacteria immobilization efficiency and improving the methane biological filter removal efficiency are provided; thirdly, most of the existing magnetic modified fillers are simple physical adsorption of the porous materials to the magnetic nano particles, acting force between the porous materials and the magnetic nano particles is weak and unstable, so that the formed compound fillers are difficult to maintain stable performance for a long time in the actual use process.
Disclosure of Invention
The invention provides an electropositive magnetic filler and a preparation method thereof, which takes vinasse biogas residue biochar as a raw material and adopts a nanoparticle adsorption-film forming coating method to carry out the preparation of a large number of positively charged groups-NC 3 + Modified magnetic nanoparticle Fe 3 O 4 Film forming and coating on the surface of biogas residue biochar to obtain the core, -NC by taking the biochar as the core 3 + And Fe (Fe) 3 O 4 And (3) coating the surface of the electropositive magnetic biochar material.
The technical scheme of the invention is as follows:
in a first aspect, a method for preparing an electropositive magnetic filler is disclosed, comprising the steps of:
1) Nanoparticle DTAB@Fe 3 O 4 Is prepared from the following steps: adding distilled water, ferrous chloride and ferric chloride into a reactor in sequence under the constant-speed stirring condition in a nitrogen atmosphere, stirring until the ferrous chloride and the ferric chloride are dissolved, heating to 80-90 ℃, adding ammonia water to adjust the pH value to 9-12, adding dodecyl trimethyl ammonium bromide after the solution turns black, and reacting for 0.5-1h at the constant temperature of 80-90 ℃ to prepare the stable dispersion DTAB@Fe 3 O 4 Washing the nanoparticle dispersion to obtain DTAB@Fe 3 O 4 A nanoparticle;
2) Positively charged nanoparticle PDMC@Fe 3 O 4 Is prepared from the following steps: DTAB@Fe prepared in step 1) 3 O 4 Dispersing the nano particles into distilled water, and sequentially adding styrene and methacryloyl under constant stirringStirring oxyethyl trimethyl ammonium chloride and butyl acrylate until the oxyethyl trimethyl ammonium chloride and butyl acrylate are dissolved, heating to 70-90 ℃, dropwise adding an initiator to initiate polymerization reaction, and continuing the reaction for 2-4h to obtain PDMC@Fe with positive charges 3 O 4 Collecting the nano particles and strong magnets to obtain the PDMC@Fe 3 O 4 Washing and drying;
3) Electropositive magnetic filler PSt-BA@PDMC@Fe 3 O 4 Preparation of @ BC: pdmc@fe prepared in step 2) 3 O 4 Dispersing in distilled water, adding biogas residue biochar, fully adsorbing for 1-2h under constant speed stirring, sequentially adding styrene and butyl acrylate, stirring to dissolve, heating to 80-90 ℃, dropwise adding initiator to initiate copolymerization of styrene and butyl acrylate, continuing to react for 2-4h, stopping reaction, filtering, taking solid filter residues, drying at 100-105 ℃ for 24-48h, taking out, cooling at room temperature, and finally coating the biochar filler PSt-BA@PDMC@Fe with positively charged magnetic nano particles 3 O 4 @BC。
Preferably, the medium stirring speed in both step 1) and step 2) is 300-400rpm.
Preferably, the total mass of the ferrous chloride, the ferric chloride and the dodecyl trimethyl ammonium bromide in the step 1) is 15-20% of the mass of distilled water, the mass ratio of the ferrous chloride to the ferric chloride is 1:2-3, and the addition amount of the dodecyl trimethyl ammonium bromide is 20-30% of the total mass of the ferrous chloride and the ferric chloride.
Preferably, the amount of methacryloyloxyethyl trimethyl ammonium chloride added in step 2) is the DTAB@Fe prepared 3 O 4 20-40% of the dry weight of the nanoparticles.
Preferably, in the step 2), the initiator is potassium persulfate or ammonium persulfate, and the addition amount of the initiator is 5-15% of the mass of the methacryloyloxyethyl trimethyl ammonium chloride.
Preferably, the addition of styrene and butyl acrylate in step 3) is calculated by the formula so that the glass transition temperature of the copolymer is between 70 and 80 ℃, the formula is as follows:wherein T is g Glass transition temperature (K), (T) of the copolymer g ) A 、(T g ) B Glass transition temperatures (K), W for homopolymer styrene and butyl acrylate, respectively A 、W B The weight fractions of homopolymer styrene and butyl acrylate in the copolymer are respectively.
Preferably, in the step 3), the initiator is potassium persulfate or ammonium persulfate, and the addition amount of the initiator is 5-15% of the total mass of the styrene and the butyl acrylate.
In the second aspect, the positively charged magnetic nanoparticle coated biochar filler PSt-BA@PDMC@Fe prepared by the preparation method is disclosed 3 O 4 @BC。
The preparation principle is as follows: first, the surfactant dodecyltrimethylammonium bromide (DTAB) is added to Fe 3 O 4 In the coprecipitation reaction of magnetic nano particles, magnetic nano particles DTAB@Fe with good dispersibility are prepared 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Then, DTAB@Fe 3 O 4 In the soap-free emulsion polymerization process of dispersing methacryloxyethyl trimethyl ammonium chloride (DMC), macromolecular chain PDMC formed by polymerization is wound and wrapped in DTAB@Fe 3 O 4 The surface of the magnetic nanoparticle forms positive charge groups-NC 3 + Surrounded magnetic nanoparticles PDMC@Fe 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Next, negatively charged biochar particles of porous material are added to PDMC@Fe 3 O 4 In the dispersion, the mixture is fully and evenly mixed and stirred for a period of time, and the positively charged PDMC@Fe is caused by the action of electrostatic adsorption 3 O 4 Adsorbing particles on the surface of negatively charged biochar, fully adsorbing, then adding styrene (St) and Butyl Acrylate (BA), coating copolymer PSt-BA on the surface of biochar in the copolymerization process of St and BA, taking out adsorbed biochar particles, placing in a 105 ℃ oven to enable the copolymer PSt-BA to be fully fused into a high-elastic state and be adhered on the surface of biochar, then placing the biochar in room temperature to enable the copolymer film to be converted into a hard glassy state, enabling the nano particles to be firmly coated on the surface of the biochar, and finally obtaining the magnetic nano particle coated biochar filler with positively charged surface。
Compared with the prior art, the invention has the following beneficial effects:
the invention can effectively change electronegativity of the biochar surface into electropositivity, is favorable for the attachment of methane-oxidizing bacteria cells with negative charges, and is favorable for the growth of membrane hanging and microbial biomass of microorganisms on the porous filler surface; meanwhile, the surface of the biochar has paramagnetism, which is favorable for improving the intracellular metabolic strength of methane-oxidizing bacteria, so that the absorption and conversion efficiency of the bacteria on methane molecules are improved, and the methane removal efficiency of the biological filter is obviously improved. In addition, compared with the traditional acid-base modification, the reaction condition is mild, the pore structure of the biochar is not damaged, and meanwhile, the film forming effect of the butyl acrylate is strong and firm, so that the magnetic nano particles are not easy to fall off, and the magnetic nano particles are stable in performance and durable in use.
Drawings
FIG. 1 shows electropositive magnetic nanoparticle PSt-BA@PDMC@Fe according to example 1 of the present invention 3 O 4 @ BC preparation flow chart.
FIG. 2 shows electropositive magnetic nanoparticle PSt-BA@PDMC@Fe according to example 1 of the present invention 3 O 4 Schematic diagram of the @ BC preparation principle.
FIG. 3 shows the biogas residue charcoal (A) of example 1 and the positively charged nanoparticle-coated charcoal filler PSt-BA@PDMC@Fe prepared in example 1 of the present invention 3 O 4 Scanning electron microscope contrast map of @ BC (B).
Detailed Description
Example 1
(1) Nanoparticle DTAB@Fe 3 O 4 Is prepared from the following steps: 4.05g FeCl 2 And 10.92g FeCl 3 Then, 100mL of distilled water was added thereto, dissolved under stirring at 300rpm, the temperature was raised to 90℃under nitrogen protection, and 20mL of aqueous ammonia was added thereto to adjust the pH to 10. When the color of the solution turns black, 3mL of Dodecyl Trimethyl Ammonium Bromide (DTAB) solution is added, and after half an hour, stable dispersion of DTAB@Fe is obtained 3 O 4 Nanoparticle dispersion. Collecting the prepared DTAB@Fe under a magnetic field 3 O 4 Magnetic nanoparticles, washing;
(2) Positively charged nano-meterRice particle PDMC@Fe 3 O 4 Is prepared from the following steps: the DTAB@Fe prepared by the steps is used for preparing 3 O 4 Dispersing into 100mL distilled water, adding 4g methacryloyloxyethyl trimethyl ammonium chloride (DMC) at 300rpm, stirring to dissolve, heating to 75deg.C, and dropwise adding 5mL potassium persulfate solution (50g.L) -1 ) The reaction was initiated. The polymer chain PDMC coated PDMC@Fe with positive charges is obtained through 2h polymerization 3 O 4 Collecting the nano particles and strong magnets to obtain the PDMC@Fe 3 O 4 Washing and drying the nano particles;
(3) Electropositive magnetic filler PSt-BA@PDMC@Fe 3 O 4 Preparation of @ BC: pdmc@fe prepared by the above steps 3 O 4 Dispersing into 100mL water, adding 10g biogas residue biochar, stirring at 300rpm for adsorption, and making the surface of biochar negatively charged and positively charged PDMC@Fe under the action of electrostatic attraction 3 O 4 The nano particles are fully adsorbed on the surface of the biochar and fully stirred for 2 hours; then, 5.2g of styrene (St) and 3g of polybutyl acrylate (BA) were successively added to the flask, the glass transition temperature of the PSt-BA copolymer was set to 70℃to calculate the addition amounts of styrene (St) and polybutyl acrylate (BA), the temperature was raised to 80℃and 5mL of potassium persulfate solution (150 g.L) -1 ) Initiating copolymerization of styrene and polybutyl acrylate, stopping the reaction after 4 hr, filtering and collecting solid residue. Drying at 105 ℃ for 24 hours at a temperature higher than the glass transition temperature (70 ℃) of the PSt-BA copolymer, and at the same time, fully converting the PSt-BA copolymer into a high-elastic state, tightly wrapping and adhering the PSt-BA copolymer on the surface of a filler to form a flexible high-elastic state coating film, taking out, cooling at room temperature, converting the coating film of the PSt-BA copolymer into a hard glass state, and firmly converting positively charged magnetic particles PDMC@Fe 3 O 4 Fixing on the surface of the filler to finally obtain the magnetic nano particle coated biochar filler PSt-BA@PDMC@Fe with positive charges 3 O 4 @BC。
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions for embodiments of the invention may be made by those skilled in the art without departing from the spirit and scope of the invention, and these modifications and substitutions are intended to be within the scope of the invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (8)
1. A method for preparing an electropositive magnetic filler, comprising the steps of:
1) Nanoparticle DTAB@Fe 3 O 4 Is prepared from the following steps: adding distilled water, ferrous chloride and ferric chloride into a reactor in sequence under the constant-speed stirring condition in a nitrogen atmosphere, stirring until the ferrous chloride and the ferric chloride are dissolved, heating to 80-90 ℃, adding ammonia water to adjust the pH value to 9-12, adding dodecyl trimethyl ammonium bromide after the solution turns black, and reacting for 0.5-1h at the constant temperature of 80-90 ℃ to prepare the stable dispersion DTAB@Fe 3 O 4 Washing the nanoparticle dispersion to obtain DTAB@Fe 3 O 4 A nanoparticle;
2) Positively charged nanoparticle PDMC@Fe 3 O 4 Is prepared from the following steps: DTAB@Fe prepared in step 1) 3 O 4 Dispersing the nano particles into distilled water, adding methacryloxyethyl trimethyl ammonium chloride under constant stirring, stirring until the nano particles are dissolved, heating to 70-90 ℃, adding an initiator dropwise to initiate polymerization reaction, and continuing to react for 2-4h to obtain PDMC@Fe with positive charges 3 O 4 Collecting the nano particles and strong magnets to obtain the PDMC@Fe 3 O 4 Washing and drying;
3) Electropositive magnetic filler PSt-BA@PDMC@Fe 3 O 4 Preparation of @ BC: pdmc@fe prepared in step 2) 3 O 4 Dispersing in distilled water, adding biogas residue charcoal, fully adsorbing for 1-2 hr under constant speed stirring, sequentially adding styrene and butyl acrylate, stirring to dissolve, heating to 80-90deg.C, dropwise adding initiator to initiate copolymerization of styrene and butyl acrylate, continuing to react for 2-4 hr, stopping reaction, filtering, collecting solid residue, oven drying at 100-105deg.C for 24-48 hr, taking out, cooling at room temperature, and finally preparing magnetic nanoparticle coated with positive chargesBiochar filler PSt-BA@PDMC@Fe 3 O 4 @BC。
2. The method for producing an electropositive magnetic filler according to claim 1 wherein the stirring speed in each of step 1), step 2) and step 3) is 300 to 400rpm.
3. The method for preparing an electropositive magnetic filler according to claim 1, wherein the total mass of the ferrous chloride, the ferric chloride and the dodecyl trimethyl ammonium bromide added in the step 1) is 15-20% of the mass of distilled water, the mass ratio of the ferrous chloride to the ferric chloride is 1:2-3, and the addition amount of the dodecyl trimethyl ammonium bromide is 20-30% of the total mass of the ferrous chloride and the ferric chloride.
4. The method for preparing an electropositive magnetic filler according to claim 1, wherein the amount of methacryloyloxyethyl trimethyl ammonium chloride added in step 2) is dtab@fe prepared 3 O 4 20-40% of the dry weight of the nanoparticles.
5. The method for preparing an electropositive magnetic filler according to claim 1, wherein in the step 2), the initiator is potassium persulfate or ammonium persulfate, and the addition amount of the initiator is 5-15% of the mass of the methacryloyloxyethyl trimethyl ammonium chloride.
6. The method for preparing an electropositive magnetic filler according to claim 1, wherein the addition of styrene and butyl acrylate in step 3) is calculated by the formula to obtain a copolymer having a glass transition temperature of 70-80 ℃, wherein the formula is as follows:
wherein T is g Glass transition temperature (K), (T) of the copolymer g ) A 、(T g ) B Glass transition temperatures (K), W for homopolymer styrene and butyl acrylate, respectively A 、W B The weight fractions of homopolymer styrene and butyl acrylate in the copolymer are respectively.
7. The method for preparing an electropositive magnetic filler according to claim 1, wherein the initiator in the step 3) is potassium persulfate or ammonium persulfate, and the addition amount of the initiator is 5% -15% of the total mass of styrene and butyl acrylate.
8. The positively charged magnetic nanoparticle coated biochar filler PSt-BA@PDMC@Fe prepared by the preparation method according to any one of claims 1 to 7 3 O 4 @BC。
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