CN111420637B - Porous magnetic hydrophobic material, preparation method thereof and application thereof in oil stain treatment - Google Patents
Porous magnetic hydrophobic material, preparation method thereof and application thereof in oil stain treatment Download PDFInfo
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- CN111420637B CN111420637B CN202010096546.7A CN202010096546A CN111420637B CN 111420637 B CN111420637 B CN 111420637B CN 202010096546 A CN202010096546 A CN 202010096546A CN 111420637 B CN111420637 B CN 111420637B
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- 239000000463 material Substances 0.000 title claims abstract description 165
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 150
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- 239000000243 solution Substances 0.000 claims abstract description 31
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- 239000000696 magnetic material Substances 0.000 claims abstract description 23
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims abstract description 21
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 perfluorooctyl triethoxysilane ethanol Chemical compound 0.000 claims abstract description 18
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- 238000000034 method Methods 0.000 claims description 17
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 239000012452 mother liquor Substances 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 description 2
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- 229920000747 poly(lactic acid) Polymers 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
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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
- B01J20/28054—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 surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a porous magnetic hydrophobic material, a preparation method thereof and application thereof in oil stain treatment, wherein the preparation method comprises the following steps: preparation of Fe 3 O 4 Nano magnetic beads; pretreating water hyacinth, and carbonizing the pretreated water hyacinth in a vacuum tube furnace to obtain a porous carbon material; the Fe is 3 O 4 Dispersing the nano magnetic beads in a solvent to form a mixed solution, dripping the mixed solution on the surface of the porous carbon material, and vacuum drying to obtain the porous magnetic material; and carrying out hydrophobic treatment on the porous magnetic material by utilizing a perfluorooctyl triethoxysilane ethanol solution, and cleaning and drying to obtain the porous magnetic hydrophobic material. The invention prepares the water hyacinth into the biological carbon material, and then self-assembles Fe 3 O 4 The magnetic beads and the perfluorooctyl triethoxysilane are modified on the surface of the water hyacinth biochar to form a porous magnetic hydrophobic biochar material, so that water hyacinth resources are fully utilized, and the economic added value of the water hyacinth biochar is improved.
Description
Technical Field
The invention relates to the technical field of biological carbon materials, in particular to a porous magnetic hydrophobic material, a preparation method thereof and application thereof in oil stain treatment.
Background
Oil water pollution refers to pollution of oil entering a water body and products thereof causing water quality to be reduced or deteriorated. Such water pollution greatly reduces the utilization of water resources, severely threatening the health of humans and other organisms. There are various causes of pollution of the oil water, such as oil leakage during transportation and storage, oil discharge during machine manufacturing and service, edible fat and grease waste in domestic sewage, etc. Currently, methods for eliminating oil pollution are mainly combustion, filtration and collection, however combustion may cause another environmental pollution such as smoke and toxic gases, and thus filtration and collection are considered to be the most efficient and economical treatment methods.
The ideal oil adsorbent needs to have a strong adsorption capacity and a high adsorption efficiency, and also has a high separation efficiency and a high flux. Currently, many researchers have focused on the manufacture of various types of air-condensing, such as: DZ et al dissolve polylactic acid in dimethylformamide and dichloromethane mixed solution, prepare a PLA membrane through the electrostatic spinning technology; CY et al prepare an F-TiO2@PPS film by a self-assembly method, and PLA films and the F-TiO2@PPS film have the characteristics of good oil absorption capacity, low density and high porosity, but the preparation process is complicated, the cost is high, and the environment is polluted by byproducts.
The water hyacinth (Eichhornia crassipes) is also called eichhornia crassipes, is a floating plant, has rapid growth and strong reproductive capacity, can be used for treating the pollution problem of eutrophication nitrogen and phosphorus in water, and has extremely strong adaptability, so that the growth of the water hyacinth is easily out of control and floods into disasters, and a series of hazards are caused: such as influence on channel transportation, blockage of river channels, pollution of water bodies, influence on quality of aquatic products, destruction of balance of water ecology, and the like, and have adverse effects on water quality and aquaculture. In addition to the high salvaging cost, how to treat huge amount of water hyacinth waste is a troublesome problem in the physical salvaging process; the existing landfill method or composting organic fertilizer, soil conditioner and other technologies are rough, and the utilization added value is low.
But from another point of view, water hyacinth is a typical aquatic fiber biomass, and huge biomass resources are reserved in a huge number of water hyacinth. If the water hyacinth can be utilized for oil-water separation and sewage treatment, the treatment problem of the water hyacinth can be solved, waste can be changed into valuable, and the water hyacinth is converted into a high added value product.
Disclosure of Invention
The invention aims to solve the problem of how to use the water hyacinth in oil-water separation and sewage treatment to a certain extent.
In order to solve the problems, the invention provides a preparation method of a porous magnetic hydrophobic material, which comprises the following steps:
preparation of Fe 3 O 4 Nano magnetic beads; pretreating water hyacinth, and carbonizing the pretreated water hyacinth in a vacuum tube furnace to obtain a porous carbon material; the Fe is 3 O 4 Dispersing the nano magnetic beads in a solvent to form a mixed solution, dripping the mixed solution on the surface of the porous carbon material, and vacuum drying to obtain the porous magnetic material; and carrying out hydrophobic treatment on the porous magnetic material by utilizing a perfluorooctyl triethoxysilane ethanol solution, and cleaning and drying to obtain the porous magnetic hydrophobic material.
Optionally, the preparing Fe 3 O 4 A nanomagnetic bead, comprising: dissolving ferric chloride and sodium acetate in glycol, and performing hydrothermal reaction at 180-220 ℃ to obtain Fe 3 O 4 A nanometer magnetic bead.
Optionally, the Fe 3 O 4 The particle size of the nanometer magnetic beads is 780-820nm.
Optionally, the pretreatment of the water hyacinth and the carbonization of the pretreated water hyacinth in a vacuum tube furnace comprise: and (3) cleaning the stem of the water hyacinth, performing vacuum freeze drying, and then placing the dried sample in a high-temperature vacuum tube furnace, and carbonizing for 2-3h at 850-950 ℃ to obtain the porous carbon material.
Alternatively, the pores on the porous carbon material have an average diameter of 25 μm.
Optionally, the porous magnetic material is subjected to hydrophobic treatment by using perfluorooctyl triethoxysilane ethanol solution, and the porous magnetic hydrophobic material is obtained after cleaning and drying, and comprises the following steps: soaking the porous magnetic material in 2.5% perfluorooctyl triethoxysilane ethanol solution for 7.5-8.5h at room temperature to obtain Fe 3 O 4 And (3) replacing ethyl on the perfluorooctyl triethoxysilane by using the nano magnetic beads, washing off unreacted perfluorooctyl triethoxysilane by using absolute ethyl alcohol, and finally, drying in vacuum to obtain the porous magnetic hydrophobic material.
Optionally, the porous magnetic hydrophobic material has a porosity of 80.19+ -4.37% and a density of 13.44+ -1.11 mg/c 3 。
Optionally, the adsorption capacity of the porous magnetic hydrophobic material to oil and organic reagents is 50-140g/g; wherein the oil comprises one or more of engine oil, soybean oil and rapeseed oil; the organic reagent comprises one or more of chloroform, dichloromethane, n-hexane, diethyl ether and cyclohexane.
Compared with the prior art, the preparation method of the porous magnetic hydrophobic material provided by the invention has the following advantages:
(1) The invention prepares the water hyacinth into the biological carbon material by carbonizing in a tube furnace, and then self-assembles Fe 3 O 4 The magnetic beads and the perfluoro octyl triethoxysilane are modified on the surface of the water hyacinth biochar to form a porous magnetic hydrophobic biochar material; the preparation method has simple process and low production cost, changes waste into valuable, fully utilizes water hyacinth resources, improves the economic added value of the water hyacinth resources, and can repeat byproducts in the preparation process through simple treatmentThe utilization of the water-soluble paint can not cause pollution to the environment.
(2) The porous magnetic hydrophobic material prepared by the invention has high porosity and smaller density, has higher adsorption capacity to oil and organic reagents, can collect oil on the bottom and the surface of water on one hand, and can separate oil-water mixture on the other hand; on the other hand, after the target object is adsorbed, the target object is quickly separated from the mother liquor through an external magnetic field, so that the problem that the solid-liquid separation of the common nano adsorbent is difficult is well solved.
The invention further aims to provide a porous magnetic hydrophobic material so as to solve the problem of how to use the water hyacinth in oil-water separation and sewage treatment.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a porous magnetic hydrophobic material prepared according to the preparation method of the porous magnetic hydrophobic material of any one of claims 1-8, wherein a matrix of the porous magnetic hydrophobic material is a porous carbon material, and Fe after chemical bonding with perfluorooctyl triethoxysilane 3 O 4 The nanometer magnetic beads are loaded on the surface and in the pore canal of the porous carbon material.
The third purpose of the invention is to provide the application of the porous magnetic hydrophobic material, so as to solve the problem of how to apply the water hyacinth to oil-water separation and sewage treatment.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the application of the porous magnetic hydrophobic material in oil-water separation and sewage treatment.
The porous magnetic hydrophobic material and the application of the porous magnetic hydrophobic material are the same as the preparation method of the porous magnetic hydrophobic material in the prior art, and are not described herein.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a porous magnetic hydrophobic material according to an embodiment of the present invention;
FIG. 2 (a) is Fe 3 O 4 Nano SEM images of magnetic beads; FIG. 2 (b) is an SEM image of a porous magnetic hydrophobic material; FIG. 2 (c) is a SEM image of a porous magnetic hydrophobic material; FIG. 2 (d) is a schematic structural diagram of a porous magnetic hydrophobic material;
FIG. 3 is an EDS spectrum of a porous magnetic hydrophobic material according to an embodiment of the present invention;
FIG. 4 is a FT-IR spectrum of a porous magnetic hydrophobic material according to an embodiment of the invention;
FIG. 5 (a) is the superhydrophobic capability of a porous magnetic hydrophobic material under water; FIG. 5 (b) is a comparison of the adsorption properties of porous magnetic hydrophobic material to water and cyclohexane;
FIG. 6 shows the adsorption capacities of porous magnetic hydrophobic materials for different oils and organic reagents according to embodiments of the present invention;
FIG. 7 is a graph showing adsorption kinetics of porous magnetic hydrophobic materials according to embodiments of the present invention for various oils and organic reagents.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
In addition, the terms "comprising," "including," "containing," "having" and their derivatives are not limiting, as other steps and other ingredients not affecting the result may be added. Materials, equipment, reagents are commercially available unless otherwise specified.
In addition, although the steps in the preparation are described in the forms of S1, S2, S3, etc., the description is only for the convenience of understanding, and the forms of S1, S2, S3, etc. do not represent a limitation of the sequence of the steps.
Research on the treatment of eutrophic water plants at home and abroad shows that large-sized aquatic plants such as aquatic vascular plants, higher algae, water hyacinth and the like have great application prospects in the field of water pollution prevention and control. However, aquatic plants such as water hyacinth and the like have high propagation speed, and particularly as foreign species, ecological invasion is easy to cause, so that the water eutrophication treatment method cannot be widely applied. If the water hyacinth can be used as an oil absorption material for oil-water separation and sewage treatment, plant materials can be effectively utilized while water eutrophication is treated, and secondary pollution is avoided. In the prior art, after the water hyacinth is crushed and dried directly, the oil stain is adsorbed by utilizing a porous structure of the water hyacinth, however, the water can be absorbed while the oil is absorbed by the porous structure, so that the oil stain treatment capacity of the water hyacinth is greatly influenced, and meanwhile, the water hyacinth is inconvenient to separate and recycle.
In order to solve the problems, the invention provides a porous magnetic hydrophobic material and a preparation method thereof, wherein water hyacinth is used as a porous carbon source, is combined with magnetic nano particles, and is subjected to hydrophobic treatment to synthesize the porous magnetic hydrophobic material. The material has higher adsorption capacity to oil and organic reagents, on one hand, can collect oil on the bottom and the surface of water and can separate oil-water mixture; on the other hand, after the target object is adsorbed, the target object is quickly separated from the mother liquor through an external magnetic field, so that the problem that the solid-liquid separation of the common nano adsorbent is difficult is well solved; in addition, the waste biomass water hyacinth is converted into the active carbon material with rich pore structure, and an effective way is provided for the resource conversion and utilization of the water hyacinth.
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Referring to fig. 1, the embodiment of the invention provides a preparation method of a porous magnetic hydrophobic material, which specifically includes the following steps:
s1, preparing Fe 3 O 4 Nano magnetic beads;
s2, pretreating the water hyacinth, and carbonizing the pretreated water hyacinth in a vacuum tube furnace to obtain a porous carbon material;
s3, fe 3 O 4 Dispersing the nano magnetic beads in a solvent to form a mixed solution, dripping the mixed solution on the surface of a porous carbon material, and vacuum drying to obtain the porous magnetic material;
s4, performing hydrophobic treatment on the porous magnetic material by utilizing a perfluorooctyl triethoxysilane ethanol solution, and cleaning and drying to obtain the porous magnetic hydrophobic material.
From this, carbonization in a tube furnace prepares the water hyacinth into a biochar material, and self-assembling Fe 3 O 4 The magnetic beads and perfluoro octyl triethoxysilane (waterproof oleophobic agent) are modified on the surface of the water hyacinth biochar to form the porous magnetic hydrophobic biochar material. The preparation method has the advantages of simple process and low production cost, changes waste into valuable, fully utilizes water hyacinth resources, improves the economic added value of the water hyacinth resources, can recycle byproducts in the preparation process through simple treatment, and does not pollute the environment; in addition, the prepared porous magnetic hydrophobic material has high porosity (80.19%) and smaller density (13.44 mg/c) 3 ) Has higher adsorption capacity to organic reagents and oil, has a certain effect on the separation of oil-water emulsion, and provides a new route for the fields of oil-water separation and sewage treatment.
Specifically, in step S1, fe is prepared 3 O 4 A nano magnetic bead comprising the steps of:
dissolving ferric chloride and sodium acetate in glycol, and performing hydrothermal reaction at 180-220 ℃ to obtain Fe 3 O 4 A nanometer magnetic bead.
Specifically, 5.2g FeCl 3 ·6H 2 Dissolving O and 11.5g of sodium acetate in 100mL of ethylene glycol, vigorously stirring at 600rpm for 30min at 25 ℃, transferring the stirred solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing and placing in a hydrothermal oven, and preserving heat for 7-9h at 180-220 ℃; after the reaction was cooled to room temperature (25 ℃ C.), the black Fe in the reaction solution was repeatedly washed with absolute ethanol 3 O 4 Nano magnetic beads until Fe is cleaned 3 O 4 Absolute ethyl alcohol of the nano magnetic beads is colorless, and the prepared black Fe is prepared 3 O 4 The nano magnetic beads are dried in vacuum at 60 ℃ for standby.
Wherein Fe is 3 O 4 The particle size of the nanometer magnetic beads is 780-820nm.
As shown in FIG. 2, FIG. 2 (a) shows Fe 3 O 4 Nano SEM image of magnetic beads, from which it can be seen that Fe 3 O 4 The magnetic beads are spherical nano particles with the diameter of about 800nm, and can increase the magnetism of the materialSex.
Fe 3 O 4 The nanometer magnetic beads have magnetism, and can disperse Fe only through a magnet 3 O 4 The adsorption material of the nano magnetic beads and the recovery of the adsorbed oily substances avoid the problem of difficult solid-liquid separation of the common adsorbent, and have stronger operability and development prospect.
In step S2, the water hyacinth is pretreated, and the pretreated water hyacinth is carbonized in a vacuum tube furnace, comprising the steps of:
and (3) cleaning the stem of the water hyacinth, performing vacuum freeze drying, and then placing the dried sample in a high-temperature vacuum tube furnace, and carbonizing for 2-3h at 850-950 ℃ to obtain the porous carbon material.
Specifically, cleaning water hyacinth, peeling stem, cutting into sections with length of 2cm, freezing in refrigerator (-76 deg.C) for 24 hr, and freeze vacuum drying at 6 Pa-48 deg.C for 48 hr; the freeze-dried sample is placed into a high-temperature vacuum tube furnace for carbonization, the tube furnace is vacuumized for multiple times to thoroughly remove air in the tube furnace and the water hyacinth sample, argon is filled into the tube furnace at the speed of 9ccm/s until the experiment is finished, the tube furnace is heated at the speed of 5 ℃/min to ensure that the gas in the tube furnace does not participate in the carbonization process of the water hyacinth, the temperature of the tube furnace is kept for 2-3 hours at 850-950 ℃, the carbonized water hyacinth is taken out after being cooled to the room temperature, and the water hyacinth is sealed, dried and stored for standby.
The average diameter of the pores on the porous carbon material was 25 μm. The porous structure provides a storage space for adsorption experiments, and improves the adsorption capacity of the material. Fe (Fe) 3 O 4 The nano magnetic beads are distributed on the surface of the material and the inner wall of the porous structure through Van der Waals force, so that the mechanical strength of the material is increased, and the hydrophobicity of the material is improved through increasing the roughness of the material.
It is understood that water hyacinth belongs to fibrous biomass, which is mainly composed of cellulose, hemicellulose and lignin; the cellulose is a fiber bundle-shaped substance formed by twisting chain-shaped macromolecular polymers formed by the dehydration condensation of glucose, hemicellulose and other polysaccharides are wound around the cellulose, lignin covers and condenses various substances, and the special structure causes high stability of biomass, so that the material yield after heat treatment is better. Being hydrophilic due to the presence of a large number of hydroxyl groups in the cellulose and hemicellulose structures; lignin is a hydrophobic substance due to the hydrogen bonding action between lignin-polysaccharide (mainly cellulose and hemicellulose) complexes, so that simple smashing, grinding and pressurizing of water hyacinth can not change the hydrophobicity of materials, and therefore, the lignin needs to be modified by high-temperature heat treatment, and dehydration condensation reaction occurs among hydroxyl groups in fibers in the high-temperature process, so that the hydrophobicity of plant fibers is increased; and after high-temperature heat treatment, the porous structure generated in the plant material can also increase the capillary action of the material, so that the oil absorption rate of the plant fiber is increased, and the oil absorption capacity of the plant fiber is further improved.
Therefore, the waste biomass water hyacinth is converted into the biological carbon material with the rich pore structure, so that the problem of treatment and disposal of the water hyacinth is solved, the additional yield of the water hyacinth can be increased, and a new thought is provided for realizing large-scale recycling of the water hyacinth.
In step S3, the porous structure of the carbonized material (porous carbon material) and the carbon structure skeleton (Fe 3 O 4 Nano magnetic beads) have a certain adsorption capacity, and therefore, fe 3 O 4 The nano magnetic beads and carbonized water hyacinth can be mutually adsorbed together by Van der Waals force to form a stable magnetic material. During the mutual adsorption process, fe 3 O 4 The nano magnetic beads can enter the pore canal of the porous structure, and in the embodiment of the invention, fe is adopted in the experimental method 3 O 4 Dripping the nano magnetic bead ethanol solution on the surface of the material to perform self-assembly adsorption; because the material is porous structure, fe is dripped on the surface 3 O 4 After the nano magnetic bead ethanol solution, the solution enters the inside of the material along the hole, so that Fe 3 O 4 The magnetic beads are adsorbed on the surface of the porous carbon material and can adsorb the interior of the multi-cavity channel.
Specifically, 30-50mg of Fe is weighed 3 O 4 Adding the nanometer magnetic beads into 100mL absolute ethyl alcohol, and performing ultrasonic treatment for 10min to uniformly disperse the nanometer magnetic beads in the absolute ethyl alcoholEthanol. And (3) dripping the dispersed solution onto the carbonized material, and drying the carbonized material in vacuum at 45 ℃ for 8 hours to obtain a sample, namely the porous magnetic material.
In step S4, performing hydrophobic treatment on the porous magnetic material with a perfluorooctyl triethoxysilane ethanol solution, and cleaning and drying to obtain the porous magnetic hydrophobic material, which comprises the following steps:
soaking the porous magnetic material in 2.5% perfluoro octyl triethoxy silane ethanol solution for 7.5-8.5h at room temperature to make the Fe 3 O 4 And (3) replacing ethyl on the perfluorooctyl triethoxysilane by using the nano magnetic beads, washing off unreacted perfluorooctyl triethoxysilane by using absolute ethyl alcohol, and finally, drying in vacuum to obtain the porous magnetic hydrophobic material.
Therefore, the perfluor octyl triethoxysilane self-assembly method is adopted to carry out hydrophobic modification on the magnetic material, the hydrophobic performance is realized, and the ethyl in the perfluor octyl triethoxysilane is Fe in the reaction process 3 O 4 Magnetic bead substitution, so perfluorooctyl triethoxysilane and Fe 3 O 4 The magnetic beads are combined together through chemical reaction; from the above, fe 3 O 4 The magnetic beads are adsorbed on the surface of the porous carbon material and can adsorb the inside of the porous channel, so that the hydrophobic agent perfluorooctyl triethoxysilane exists on the surface of the porous carbon material and in the pore channel, the capillary action between the oil molecules and the fibers is further enhanced, and the oil absorption hydrophobicity of the implanted porous magnetic hydrophobic material is further improved.
Referring to fig. 2 (b) - (d), fig. 2 (b) shows an SEM of a porous magnetic hydrophobic material, and it can be seen from the drawing that the porous magnetic hydrophobic material has a porous three-dimensional structure, and a large number of holes exist on the surface and/or inside of the surface material of the three-dimensional porous structure, and a large number of gaps exist between fibers, which provides enough space for oil absorption capacity, and shows that the porous magnetic hydrophobic material prepared by the embodiment of the invention has better oil absorption capacity to a certain extent. FIG. 2 (c) is a microscopic SEM of a porous magnetic hydrophobic material, from which it can be seen that Fe 3 O 4 The nanometer magnetic beads are uniformly distributed on the surface of the material, so that the roughness of the surface of the material is increased, and the material is advancedThe hydrophobicity of the material is improved; FIG. 2 (d) is a schematic structural diagram of a porous magnetic hydrophobic material showing the overall morphology of the porous magnetic hydrophobic material, the high porosity of the material being 80.19.+ -. 4.37% and the ultralight density being 13.44.+ -. 1.11mg/c 3 As can be seen from the above analysis, the porous magnetic hydrophobic material is Fe chemically bonded with perfluorooctyl triethoxysilane by using porous carbon material as matrix 3 O 4 The nanometer magnetic beads are loaded on the surface and in the pore canal of the porous carbon material.
Referring to FIG. 3, FIG. 3 shows an EDS spectrum of a porous magnetic hydrophobic material, and from the graph, it can be seen that the prepared porous magnetic hydrophobic material has three elements of Fe, F and Si, indicating Fe 3 O 4 And superhydrophobic modification of perfluorooctyl triethoxysilane.
Referring to FIG. 4, FIG. 4 is a Fourier infrared spectrum FT-IR diagram of a porous magnetic hydrophobic material showing the transition from carbonized water hyacinth to porous magnetic hydrophobic material, the carbonized water hyacinth (EC) being 3328cm -1 Having a characteristic absorption peak of hydroxyl (-OH), fe 3 O 4 The characteristic absorption peak of the magnetic beads is 600cm -1 Perfluorooctyl triethoxysilane (PFOS) has C-H (2890 cm) respectively -1 )、C-F(1200cm -1 )、Si-O(1003cm -1 ) The equicharacteristic absorption peaks, as can be seen in FIG. 4, are seen in the porous magnetic hydrophobic material (E.C/Fe 3 O 4 PFOS) has all characteristic peaks of the three samples at the same time, and the porous magnetic hydrophobic material is successfully prepared by the preparation method disclosed by the embodiment of the invention.
The embodiment of the invention also provides a porous magnetic hydrophobic material, which is prepared according to the preparation method of the porous magnetic hydrophobic material. The porous magnetic hydrophobic material has better high porosity, low density and super-hydrophobic performance, has stronger adsorption capacity to engine oil, chloroform, methylene dichloride, normal hexane, diethyl ether, cyclohexane, soybean oil and rapeseed oil, can remove oil under water and water surface through adsorption, can separate oil-water mixed solution through gravity, has certain separation capacity to oil-water emulsion, and can provide potential possibility for solving the problem of oil-water pollution.
The invention also provides application of the porous magnetic hydrophobic material, and the porous magnetic hydrophobic material can be applied to the fields of oil-water separation and sewage treatment and has wide application prospect.
In order to illustrate the application of the porous magnetic hydrophobic material provided by the invention in the aspect of oil stain treatment, the following characterization of the adsorption performance of the porous magnetic hydrophobic material is provided:
characterization of oil absorption Properties of porous magnetic hydrophobic Material
The performance of a hydrophobic oleophilic material is primarily dependent on its adsorption capacity for oil or organic agents. The adsorption mechanism of the porous magnetic hydrophobic material is mainly physical adsorption, and when the magnetic hydrophobic material contacts oil or an organic reagent, the magnetic hydrophobic material fixes the oil to the inside of the porous magnetic hydrophobic material through hydrophobic interaction and magnetic siphoning.
In addition, the wettability of the porous magnetic hydrophobic material has an important meaning for the selective separation of the oil-water mixture, and as shown in FIG. 5 (a), the porous magnetic hydrophobic material has a relatively light density of 13.44mg/c 3 When the porous magnetic hydrophobic material is forced into the water, the water is blocked outside the magnetic hydrophobic material due to the hydrophobic nature. FIG. 5 (b) is a graph showing the comparison of the adsorption properties of water and cyclohexane by the porous magnetic hydrophobic material, and it can be seen from the graph that after water drops are added to the porous magnetic hydrophobic material, the water drops are only attached to the surface of the material and are not immersed; after cyclohexane is dripped on the porous magnetic hydrophobic material, liquid drops on the surface of the material rapidly enter the interior of the material, which proves the hydrophobic and oleophilic characteristics of the porous magnetic hydrophobic material.
Testing the adsorption capacity of the magnetic hydrophobic material to different oils and organic reagents by a test, wherein the oil comprises one or more of engine oil, soybean oil and rapeseed oil; the organic reagent comprises one or more of chloroform, dichloromethane, n-hexane, diethyl ether and cyclohexane. The testing steps comprise: the initial mass of the porous magnetic hydrophobic material is marked as W1, the porous magnetic hydrophobic material is put into an organic reagent or oil, the porous magnetic hydrophobic material is taken out after 1min, the surface liquid is wiped off, and the mass of the porous magnetic hydrophobic material is weighted again and marked as W2; adsorption capacity q1= (W2-W1)/W1.
FIG. 6 shows the adsorption capacity of the porous magnetic hydrophobic material for different oils and organic reagents, and as can be seen from FIG. 6, the adsorption capacity of the porous magnetic hydrophobic material is mainly related to the density, viscosity and surface tension of the reagents, and the mass ratio of the porous magnetic hydrophobic material to the adsorption reagent is measured to determine that the adsorption capacity of the porous magnetic hydrophobic material for the oils and the organic reagents is 50-140g/g, wherein the adsorption capacity of the porous magnetic hydrophobic material for chloroform is the highest (the adsorption capacity is about 140 g/g), and the adsorption capacity of the porous magnetic hydrophobic material for engine oil is the lowest (the adsorption capacity is about 50 g/g).
The adsorption rate is one of the key factors determining the quality of the adsorption material, and the adsorption saturation time of the adsorption material can be judged through adsorption kinetics. The test steps are as follows: firstly, weighing 7 pieces of porous magnetic hydrophobic material, namely Wa-g 1, wherein the porous magnetic hydrophobic material is adsorbed for 1s, 3s, 5s, 7s, 10s, 20s and 30s respectively. And calculating the adsorption capacity of different adsorption times through an adsorption capacity formula to obtain an adsorption kinetic curve.
Fig. 7 is a graph showing adsorption kinetics of the porous magnetic hydrophobic material on different oils and organic reagents, and as can be seen from fig. 7, the porous magnetic hydrophobic material has the fastest adsorption on dichloromethane, the adsorption capacity reaches saturation at 3s, and the adsorption capacity of the remaining oil and organic reagents can reach saturation at 7s, which indicates that the adsorption speed of the porous magnetic hydrophobic material prepared by the embodiment of the invention on greasy dirt and organic reagents is faster.
Characterization of the oil-Water separation Capacity of the porous magnetic hydrophobic Material
The porous magnetic hydrophobic material has stronger hydrophobic property and higher adsorption capacity to oil or organic reagents, so that the porous magnetic hydrophobic material has better performance in the aspect of oil-water separation. According to the test of the embodiment of the invention, the chloroform after dyeing is removed by using the porous magnetic hydrophobic material, so that the oil-water separation capability of the chloroform is demonstrated. Specifically, the density of chloroform dyed by Sudan III is higher than that of water, the chloroform is mixed with the water and then is sunk in the water, and the porous magnetic hydrophobic material can rapidly adsorb and remove the chloroform after entering the water, so that the water-oil separation capability of the porous magnetic hydrophobic material is higher.
In addition, oil-water separation can be realized by gravity separation under the condition of large oil-water proportion, and specifically: the porous magnetic hydrophobic material is fixed on the neck of the funnel, the mixed solution of chloroform and water is poured into the funnel, the chloroform in the mixed solution flows out from the lower layer through the magnetic hydrophobic material due to different densities, and the water on the upper layer is trapped in the funnel, so that the oil-water separation is realized.
Meanwhile, the porous magnetic hydrophobic material can remove cyclohexane on the surface of water, in particular: the density of cyclohexane dyed by sudan III is small, the cyclohexane floats on the surface of water, and the magnetism of the porous magnetic hydrophobic material is utilized, and the magnet is used as driving force to control the magnetic hydrophobic material so as to remove cyclohexane on the water surface; the porous magnetic hydrophobic material can be contacted with cyclohexane under the control of a magnet, and can quickly absorb the cyclohexane into the pores of the material, so that the cleaning effect is obvious.
Further, the adsorption effect of the porous magnetic hydrophobic material on the mixed oil-water emulsion can be tested, the cyclohexane/water emulsion is milky white, the turbidity is opaque, and tiny oil drops can be seen under an optical microscope. The emulsion was added to a beaker containing a porous magnetic hydrophobic material and after 30s the remaining liquid was collected. The appearance of the residual liquid is observed by an optical microscope, and most oil drops are adsorbed by the porous magnetic hydrophobic material, so that the magnetic hydrophobic material has a good effect on oil-water separation and has a certain separation capacity on oil-water emulsion.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, which do not address specific conditions in the following examples, are generally in accordance with the conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Example 1
The embodiment provides a preparation method of a porous magnetic hydrophobic material, which comprises the following specific steps:
5.2g FeCl3.6H2O and 11.5g sodium acetate are dissolved in 100mL ethylene glycol, the mixture is vigorously stirred at 600rpm for 30min at 25 ℃, the stirred solution is transferred into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, the mixture is placed in a hydrothermal oven in a sealing way, and the mixture is kept for 9H at 180 ℃; cooling the reaction solution to room temperature, repeatedly flushing black Fe in the reaction solution with absolute ethyl alcohol 3 O 4 Nano magnetic beads until Fe is cleaned 3 O 4 Absolute ethyl alcohol of the nano magnetic beads is colorless, and the prepared black Fe is prepared 3 O 4 The nano magnetic beads are dried in vacuum at 60 ℃ for standby.
Cleaning water hyacinth, peeling stem, cutting into sections with length of 2cm, freezing in refrigerator (-76 deg.C) for 24 hr, and vacuum freeze drying at 6 Pa-48 deg.C for 48 hr; the freeze-dried sample is placed into a high-temperature vacuum tube furnace for carbonization, argon is filled into the tube furnace at the speed of 9ccm/s, the tube furnace is heated at the speed of 5 ℃/min, the temperature is kept at 850 ℃ for 3 hours, and the carbonized water hyacinth is taken out after being cooled to room temperature, sealed, dried and stored for standby.
30mg of Fe is weighed 3 O 4 Adding the nano magnetic beads into 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 10min to uniformly disperse the nano magnetic beads in the absolute ethyl alcohol, dripping the dispersed solution onto a carbonized material, and carrying out vacuum drying at 45 ℃ for 8h to obtain a sample, namely the porous magnetic material.
Soaking the porous magnetic material in 2.5% perfluorooctyl triethoxysilane ethanol solution for 7.5h, washing off unreacted perfluorooctyl triethoxysilane by using absolute ethanol, and vacuum drying to obtain the porous magnetic hydrophobic material.
Example 2
5.2g FeCl3.6H2O and 11.5g sodium acetate are dissolved in 100mL ethylene glycol, the mixture is vigorously stirred at 600rpm for 30min at 25 ℃, the stirred solution is transferred into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, the mixture is placed in a hydrothermal oven in a sealing way, and the mixture is kept at 220 ℃ for 7H; cooling the reaction solution to room temperature, repeatedly flushing black Fe in the reaction solution with absolute ethyl alcohol 3 O 4 Nano magnetic beads until Fe is cleaned 3 O 4 Absolute ethyl alcohol of the nano magnetic beads is colorless, and the prepared black Fe is prepared 3 O 4 The nano magnetic beads are dried in vacuum at 60 ℃ for standby.
Cleaning water hyacinth, peeling stem, cutting into sections with length of 2cm, freezing in refrigerator (-76 deg.C) for 24 hr, and vacuum freeze drying at 6 Pa-48 deg.C for 48 hr; the freeze-dried sample is placed into a high-temperature vacuum tube furnace for carbonization, argon is filled into the tube furnace at the speed of 9ccm/s, the tube furnace is heated at the speed of 5 ℃/min, the temperature is kept at 950 ℃ for 2 hours, the carbonized material is taken out after being cooled to room temperature, and the carbonized material is sealed, dried and stored for standby.
40mg of Fe is weighed out 3 O 4 Adding the nano magnetic beads into 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 10min to uniformly disperse the nano magnetic beads in the absolute ethyl alcohol, dripping the dispersed solution onto a carbonized material, and carrying out vacuum drying at 45 ℃ for 8h to obtain a sample, namely the porous magnetic material.
Soaking the porous magnetic material in 2.5% perfluorooctyl triethoxysilane ethanol solution for 8 hours, then washing off unreacted perfluorooctyl triethoxysilane by using absolute ethanol, and drying in vacuum to obtain the porous magnetic hydrophobic material.
Example 3
5.2g FeCl3.6H2O and 11.5g sodium acetate are dissolved in 100mL ethylene glycol, the mixture is vigorously stirred at 600rpm for 30min at 25 ℃, the stirred solution is transferred into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, the mixture is placed in a hydrothermal oven in a sealing way, and the mixture is kept at 200 ℃ for 8H; cooling the reaction solution to room temperature, repeatedly flushing black Fe in the reaction solution with absolute ethyl alcohol 3 O 4 Nano magnetic beads until Fe is cleaned 3 O 4 Absolute ethyl alcohol of the nano magnetic beads is colorless, and the prepared black Fe is prepared 3 O 4 The nano magnetic beads are dried in vacuum at 60 ℃ for standby.
Cleaning water hyacinth, peeling stem, cutting into sections with length of 2cm, freezing in refrigerator (-76 deg.C) for 24 hr, and vacuum freeze drying at 6 Pa-48 deg.C for 48 hr; the freeze-dried sample is placed into a high-temperature vacuum tube furnace for carbonization, argon is filled into the tube furnace at the speed of 9ccm/s, the tube furnace is heated at the speed of 5 ℃/min, the temperature is kept at 900 ℃ for 2.5 hours, and the carbonized water hyacinth is taken out after being cooled to room temperature, sealed, dried and stored for standby.
50mg of Fe is weighed 3 O 4 Adding the nano magnetic beads into 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 10min to uniformly disperse the nano magnetic beads in the absolute ethyl alcohol, dripping the dispersed solution onto a carbonized material, and carrying out vacuum drying at 45 ℃ for 8h to obtain a sample, namely the porous magnetic material.
Soaking the porous magnetic material in 2.5% perfluorooctyl triethoxysilane ethanol solution for 8.5h, washing off unreacted perfluorooctyl triethoxysilane by using absolute ethanol, and vacuum drying to obtain the porous magnetic hydrophobic material.
In conclusion, the porous magnetic hydrophobic material prepared by the preparation method of the porous magnetic hydrophobic material provided by the embodiment of the invention has the advantages of high porosity, low density and superhydrophobic performance; the material has strong adsorption capacity to engine oil, chloroform, methylene dichloride, normal hexane, diethyl ether, cyclohexane, soybean oil and rapeseed oil, the adsorption capacity can reach 50-140g/g, and the adsorption saturation can be reached in 7 s; the porous magnetic hydrophobic material can remove oil under water and on the surface of water through adsorption, can separate oil-water mixed solution through gravity, and has certain separation capability on oil-water emulsion; therefore, the porous magnetic hydrophobic material provides potential possibility for solving the problem of oil water pollution, and has wide application prospect and better economic value.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.
Claims (8)
1. A method for preparing a porous magnetic hydrophobic material, comprising:
preparation of Fe 3 O 4 Nano magnetic beads;
pretreating water hyacinth, and carbonizing the pretreated water hyacinth in a vacuum tube furnace to obtain a porous carbon material;
the Fe is 3 O 4 Dispersing the nano magnetic beads in a solvent to form a mixed solution, dripping the mixed solution on the surface of the porous carbon material, and vacuum drying to obtain the porous magnetic material;
carrying out hydrophobic treatment on the porous magnetic material by utilizing a perfluorooctyl triethoxysilane ethanol solution, and cleaning and drying to obtain the porous magnetic hydrophobic material;
the pretreatment of the water hyacinth is carried out, and the pretreated water hyacinth is placed in a vacuum tube furnace for carbonization, and the pretreatment method comprises the following steps: washing the stem of the water hyacinth, performing vacuum freeze drying, then placing the dried sample in a high-temperature vacuum tube furnace, and carbonizing for 2-3h at 850-950 ℃ to obtain the porous carbon material;
the porous magnetic material is subjected to hydrophobic treatment by utilizing perfluorooctyl triethoxysilane ethanol solution, and the porous magnetic hydrophobic material is obtained after cleaning and drying, and comprises the following steps: soaking the porous magnetic material in 2.5% perfluorooctyl triethoxysilane ethanol solution for 7.5-8.5h at room temperature to obtain Fe 3 O 4 And (3) replacing ethyl on the perfluorooctyl triethoxysilane by using nano magnetic beads, washing off unreacted perfluorooctyl triethoxysilane by using absolute ethyl alcohol, and finally, drying in vacuum to obtain the porous magnetic hydrophobic material.
2. The method for producing a porous magnetic hydrophobic material according to claim 1, wherein Fe is produced 3 O 4 A nanomagnetic bead, comprising:
dissolving ferric chloride and sodium acetate in glycol, and performing hydrothermal reaction at 180-220 ℃ to obtain Fe 3 O 4 A nanometer magnetic bead.
3. The method for producing a porous magnetic hydrophobic material according to claim 2, wherein the Fe 3 O 4 The particle size of the nanometer magnetic beads is 780-820nm.
4. The method for preparing a porous magnetic hydrophobic material according to claim 1, wherein the average diameter of the pores on the porous carbon material is 25 μm.
5. The method for preparing a porous magnetic hydrophobic material according to claim 4, wherein the porous magnetic hydrophobic material has a porosity of 80.19+ -4.37% and a density of 13.44+ -1.11 mg/c 3 。
6. The method for preparing a porous magnetic hydrophobic material according to claim 5, wherein the adsorption capacity of the porous magnetic hydrophobic material to oil and organic reagents is 50-140g/g;
wherein the oil comprises one or more of engine oil, soybean oil and rapeseed oil; the organic reagent comprises one or more of chloroform, dichloromethane, n-hexane, diethyl ether and cyclohexane.
7. A porous magnetic hydrophobic material, characterized in that the porous magnetic hydrophobic material is prepared according to the preparation method of the porous magnetic hydrophobic material as claimed in any one of claims 1-6, wherein a matrix of the porous magnetic hydrophobic material is a porous carbon material, and Fe after chemical bonding with perfluorooctyl triethoxysilane 3 O 4 The nanometer magnetic beads are loaded on the surface and in the pore canal of the porous carbon material.
8. The use of the porous magnetic hydrophobic material according to claim 7, wherein the porous magnetic hydrophobic material is used in oil-water separation and sewage treatment.
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