CN115105861B - Oil-water separation method based on magnetic solid particle emulsifier - Google Patents
Oil-water separation method based on magnetic solid particle emulsifier Download PDFInfo
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- CN115105861B CN115105861B CN202110291228.0A CN202110291228A CN115105861B CN 115105861 B CN115105861 B CN 115105861B CN 202110291228 A CN202110291228 A CN 202110291228A CN 115105861 B CN115105861 B CN 115105861B
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- 150000003384 small molecules Chemical class 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an oil-water separation method based on a magnetic solid particle emulsifier, which comprises the following steps: dispersing magnetic solid particles into a solvent to obtain a magnetic solid particle dispersion; adding the magnetic solid particle dispersion liquid into a target treatment liquid to obtain a magnetic particle emulsion; and (3) magnetically reacting the magnetic particle emulsion to separate water and emulsified oil drops, enriching the emulsified oil drops to form magnetic dry liquid drops, demulsifying the magnetic dry liquid drops, respectively collecting oil and magnetic solid particles in the magnetic dry liquid drops, optionally leaching the collected magnetic solid particles with an organic solvent, and drying to obtain the recovered magnetic solid particles.
Description
Technical Field
The invention relates to an oil-water separation method based on a magnetic solid particle emulsifier.
Background
Petroleum is an extremely important resource and energy, and the comprehensive utilization way is wide, so that the human society depends on survival. With the consumption of petroleum by the development of human society, petroleum resources are increasingly reduced, and the progress of economy and society is severely restricted. Meanwhile, the consumption of petroleum and derived products by industry causes great pollution to the environment, and the unprecedented human beings face multiple environmental problems. The problems of oil slick caused by marine oil leakage accidents, oil-containing sewage generated by oil extraction and drilling, oil sludge formed on the inner wall of an oil storage tank, oil sand of a drilling platform and the like are all major oil pollution to be solved urgently. At present, no effective green treatment process is available worldwide, and effective treatment can be realized on the green treatment process without depending on chemical processes, so as to realize environmental protection and resource recycling.
The oil and water are typically immiscible two phases and emulsification is typically accomplished using small molecule surfactants, block polymers, biopeptides, and the like, to form a stable emulsion. Although the constraint of the oil can be realized through the process, the enrichment and separation of the oil cannot be realized, the control of the oil is almost impossible, most of the surfactants are biologically toxic, and the surfactants are high in price, difficult to separate and extremely easy to form secondary pollution. Therefore, the invention is an effective environment-friendly oil displacement technology. Among them, the emulsion emulsified based on the solid particle emulsifier can solve the above problems well. The emulsification process of the solid particle emulsifier is a physical process, the three-phase separation of water, oil and particles can be realized, the particles can be nontoxic and environment-friendly, and the particles can be recycled.
Disclosure of Invention
Problems to be solved by the invention
For oil-water separation technology based on solid particle emulsifiers, recycling of the solid particles remains a major bottleneck to achieve this technology.
Solution for solving the problem
The invention can well solve the problems by using the magnetic solid particle emulsifier, and has practical application value. The magnetic solid particles can concentrate various materials on one magnetic particle by a compound method, so that the particles have magnetism and various functions of corresponding materials. These magnetic particles can have different compositions and each part is precisely partitioned, enabling ton-scale production. The magnetic composite particles have excellent emulsifying property, the emulsified oil-water emulsion is very stable and limited by the assembled interface of the magnetic composite particles, the liquid drops can be controlled by an external magnetic field to realize the movement of the liquid drops, and the formed magnetic liquid drop model provides a new strategy for industrialized deep oil removal.
Specifically, the technical problems of the invention are solved by the following technical scheme.
[1] An oil-water separation method based on magnetic solid particle emulsifier comprises the following steps:
dispersing magnetic solid particles into water to obtain a magnetic solid particle dispersion liquid;
adding the magnetic solid particle dispersion liquid into a target treatment liquid to obtain a magnetic particle emulsion;
performing magnetic action on the magnetic particle emulsion to separate water and emulsified oil drops, and enriching the emulsified oil drops to form magnetic dry liquid drops;
demulsification is carried out on the magnetic dry liquid drops, and oil and magnetic solid particles in the magnetic dry liquid drops are respectively collected;
optionally leaching the collected magnetic solid particles by using an organic solvent, and drying to obtain the recovered magnetic solid particles.
[2] The method according to [1], wherein the magnetic solid particles are dispersed into water with the aid of a dispersion technique, which is a technique for achieving dispersion of the magnetic solid particles by mechanical equipment or ultrasound, including one of stirring paddle stirring, refiner shearing, vortex mixer mixing, magnetic stirrer stirring, ultrasonic disperser dispersion, ultrasonic breaker dispersion, or any combination thereof.
[3]According to [1]]Or [2]]The method is characterized in that the magnetic solid particles are Fe 3 O 4 Solid particles.
[4]According to [1]]Or [2]]The method is characterized in that the magnetic solid particles are SiO with a core-shell structure 2 @Fe 3 O 4 Composite magnetic solid particles, tiO 2 @Fe 3 O 4 Composite magnetic particles or Al 2 O 3 @Fe 3 O 4 Composite magnetic particles.
[5] The method according to [1] or [2], wherein the magnetic solid particles are amphiphilic modified inorganic magnetic solid particles, preferably amphiphilic magnetic Janus particles.
[6] The method according to [5], wherein the amphiphilically modified inorganic magnetic solid particles are one or more selected from the group consisting of magnetic snowman-like Janus particles, magnetic trilayer Janus nanoplatelets, polymer double-strand/magnetic nanoparticle composite Janus materials, and polymer single-strand/magnetic nanoparticle composite Janus materials;
the magnetic snowman-shaped Janus particle comprises a hydrophilic part and an oleophilic part which respectively form two spheres of the snowman-shaped particle, wherein the hydrophilic part comprises a polymer composite microsphere subjected to hydrophilic modification and magnetic nano particles attached to the surface of the polymer composite microsphere, and the oleophilic part comprises silicon dioxide subjected to hydrophobic modification;
The magnetic three-layer structure Janus nano sheet comprises a composite interlayer, a hydrophilic layer and a lipophilic layer, wherein the composite interlayer is an intermediate interlayer comprising inorganic magnetic solid particles and one or more substances selected from polymers and silicon dioxide; the hydrophilic layer is positioned on one side of the composite interlayer; the lipophilic layer is positioned on the other side of the composite interlayer;
the polymer double-chain/magnetic nanoparticle composite Janus material has a composite structure of a hydrophilic polymer single chain, an inorganic magnetic nanoparticle and a lipophilic polymer single chain, wherein the hydrophilic polymer single chain and the lipophilic polymer single chain are connected with the inorganic magnetic nanoparticle at the tail end of the chain through chemical bonds;
the polymer single strand/magnetic nanoparticle composite Janus material comprises a polymer single strand and inorganic nanoparticles, wherein the polymer single strand comprises an oleophilic end connected with the inorganic nanoparticles and a hydrophilic end far away from the inorganic nanoparticles, the oleophilic end comprises an oleophilic chain segment, and the hydrophilic end comprises a hydrophilic chain segment and/or a hydrophilic group.
[7]According to [6 ]]The method is characterized in that the magnetic snowman-shaped Janus particles are SiO 2 -C18@PS/PDVB/Fe 3 O 4 Magnetic snowman-like Janus particles; the Janus nano sheet with the magnetic three-layer structure is PS/PDVB@Fe 3 O 4 Janus nano-sheet with magnetic three-layer structure of PEO; the polymer double-chain/magnetic nanoparticle composite Janus material is PS@Fe 3 O 4 PEO magnetic double-stranded Janus particles; the polymer single-chain/magnetic nanoparticle composite Janus material is PS@Fe 3 O 4 Magnetic single-stranded Janus particles.
[8] The method according to [1] or [2], wherein the target treatment liquid is one or more of oily wastewater produced during crude oil extraction and post-treatment, oily wastewater discharged from food oil enterprises, and oily wastewater discharged from chemical plants.
[9] The method according to [8], wherein the oily wastewater produced during the crude oil extraction and post-treatment is enhanced oil recovery wastewater, oil tank cleaning wastewater, drilling platform cleaning wastewater.
[10] The method according to [1] or [2], wherein the magnetic particle emulsion is magnetically acted by placing it in a magnetic field, the magnetic field being applied by a magnetic assembly, the magnetic field strength being such that the emulsified oil droplets are attracted to migrate and concentrate by the magnetic assembly, and separation of water and emulsified oil droplets is achieved, but at the same time, further aggregation of the magnetic solid particles surrounding the emulsified oil droplets does not occur, resulting in demulsification.
[11] The method according to [1] or [2], wherein the magnetic dry droplets are demulsified by applying a magnetic field stronger than the magnetic action.
ADVANTAGEOUS EFFECTS OF INVENTION
The oil-water separation method based on the magnetic solid particle emulsifier has the following effects:
(1) The applicable particle size range is large, so that the universality is strong;
(2) The method is a physical process, so that the method is environment-friendly and does not produce secondary waste;
(3) The magnetic solid particles can be recovered and reused after treatment.
(4) Simple process, easily obtained raw materials and easy industrialized production.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
< terms and definitions >
In the present specification, for the composition of the parts of the magnetic solid particle emulsifier, only the substances therein relevant for achieving the effect of the invention are described, separated by @, other substances or structures may be contained in the parts than the composition explicitly indicated, e.g. ps @ fe 3 O 4 PEO magnetic double-stranded Janus particles, representing two polymer chains with PS and PEO segments, respectively, attached to a magnetic particle comprising Fe 3 O 4 Is a nanoparticle.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, the use of "optional" or "optional" means that certain substances, components, steps of performing, conditions of applying, etc. may or may not be used.
In the present specification, unit names used are international standard unit names, and "%" used represent weight or mass% unless otherwise specified.
As used herein, unless otherwise indicated, "particle size" refers to "average particle size" and may be measured by a commercial particle sizer or an electron scanning microscope.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
< magnetic solid particle emulsifier >
In the present specification, the "magnetic solid particles" refer to solid particles capable of responding to a magnetic field, and the shape of the magnetic solid particles is not particularly limited, and may be any suitable shape, for example, spherical, approximately spherical, snowman-like, parachute-like, or the like.
In the process of the present invention, the magnetic solid particle emulsifier has a saturation magnetization of 30 to 100emu/g and an average particle diameter of 10 to 2000nm, preferably 100 to 900nm, more preferably 300 to 600nm.
In the method of the invention, the magnetic solid particles are Fe 3 O 4 Particles, magnetic solid particles with core-shell structure orThe amphiphilic magnetic solid particles are preferably amphiphilic magnetic Janus particles, and more preferably amphiphilic magnetic organic/inorganic composite particles.
The magnetic solid particles having a core-shell structure therein may be, for example, siO 2 @Fe 3 O 4 Composite magnetic solid particles, tiO 2 @Fe 3 O 4 Composite magnetic solid particles and Al 2 O 3 @Fe 3 O 4 Composite magnetic solid particles, and the like.
The SiO is 2 @Fe 3 O 4 The composite magnetic solid particle has a core-shell structure, wherein the core is made of Fe 3 O 4 The shell is composed of SiO 2 Constructing; likewise, the above-listed TiO 2 @Fe 3 O 4 Composite magnetic solid particles and Al 2 O 3 @Fe 3 O 4 The composite magnetic solid particles also have a corresponding core-shell structure. In these magnetic solid particles having a core-shell structure, the diameter of the core is 100 to 300nm and the thickness of the shell is 10 to 50nm.
The SiO is 2 @Fe 3 O 4 The composite magnetic solid particles may be prepared, for example, by the following method:
firstly, synthesizing the core Fe by a coprecipitation method 3 O 4 Specifically, fe 2 SO 3 And FeCl 3 Dissolving in water, adding ammonia water, stirring for a period of time to obtain precipitated solid Fe 3 O 4 A nanoparticle; then Fe is added 3 O 4 Dispersing the particles into ethanol, adding Tetraethoxysilane (TEOS), fully hydrolyzing under stirring, washing and drying to obtain SiO 2 @Fe 3 O 4 Composite magnetic solid particles.
Other magnetic solid particles having a core-shell structure can be prepared accordingly by a similar method.
The preferred amphiphilic magnetic organic/inorganic composite particles are amphiphilic modified inorganic magnetic solid particles. The amphiphilic modification gives the inorganic magnetic solid particles both lipophilic and hydrophilic properties, either by hydrophilic and lipophilic modification methods known in the art or by the methods described below.
Specifically, the following amphiphilic modification method can be mentioned:
a. connecting hydrophilic chain segments and/or groups on the inorganic magnetic solid particles;
b. respectively connecting lipophilic and hydrophilic chain segments and/or groups on the inorganic magnetic solid particles;
c. attaching inorganic magnetic solid particles to other materials having amphiphilic properties;
d. Inorganic magnetic solid particles are embedded in other materials having amphiphilic properties.
Wherein the inorganic magnetic solid particles are formed of a magnetic material, and suitable magnetic materials may be selected from solid particles of one or more of cast alloy materials, sintered alloy materials, machinable alloy materials, ferrite-type materials, intermetallic compound materials, and derivatives thereof. Specifically, examples of cast alloy materials include, but are not limited to, alNi (Co), feCr (Co), feCrMo, feAlC, feCo (V) (W), and the like; examples of the sintered alloy material include, but are not limited to, re-Co (Re represents a rare earth element), re-Fe, alNi (Co), feCrCo, etc.; examples of machinable alloy materials include, but are not limited to FeCrCo, ptCo, mnAlC, cuNiFe and almngag, and the like; examples of ferrite-based materials include, but are not limited to, fe 2 O 3 、Fe 3 O 4 、BaO·6Fe 2 O 3 、SrO·6Fe 2 O 3 、PbO·6Fe 2 O 3 SrCa, laCa, etc.; examples of intermetallic materials include, but are not limited to MnBi, mnMo, mnLa and the like.
Specific amphiphilically modified inorganic magnetic solid particles include magnetic snowman-like Janus particles, janus nanosheets with a magnetic three-layer structure, polymer double-strand/magnetic nanoparticle composite Janus materials, polymer single-strand/magnetic nanoparticle composite Janus materials and the like.
These amphiphilically modified inorganic magnetic solid particles will be described in detail below.
A) Magnetic snowman-shaped Janus particles
The magnetic snowman-shaped Janus particle comprises a hydrophilic part and an oleophilic part which respectively form two spheres of the snowman-shaped particle, wherein the hydrophilic part comprises a polymer composite microsphere subjected to hydrophilic modification and magnetic nano particles attached to the surface of the polymer composite microsphere, and the oleophilic part comprises silicon dioxide subjected to hydrophobic modification.
The particle size of the magnetic snowman-shaped Janus particles is 450-1000nm; wherein the size ratio of the hydrophilic portion to the lipophilic portion is 10/1 to 10/10, and the particle size of the hydrophilic portion is 440 to 500nm.
The polymer forming the polymer composite microsphere is not particularly limited. In a preferred embodiment, the polymeric composite microsphere is a composite microsphere of polystyrene and other polymers, wherein the polystyrene and/or other polymers are optionally crosslinked, at least a portion of the molecular chains of the other polymers being interspersed between at least a portion of the molecular chains of the polystyrene, thereby forming a composite structural portion of the two polymers.
In one embodiment, the polymer composite microsphere has a substantially uniform polymer network structure formed by interpenetration of molecular chains of the polystyrene and the other polymer. In one embodiment, the polymer composite microsphere includes a polymer network structure layer formed by interpenetration of molecular chains of the polystyrene and the other polymer layer outside the layer. In one embodiment, the polymer composite microsphere comprises the polystyrene layer, a polymer network structure layer formed by interpenetration of molecular chains of the polystyrene and the other polymers and the other polymer layer from inside to outside.
The other polymer is formed by polymerizing a raw material composition containing one or more selected from olefin monomers, esters with double bonds and amide monomers with double bonds and optionally a cross-linking agent; the olefin monomer is preferably one or more selected from optionally halogenated alkenes, styrene and derivatives thereof, and acrylonitrile; the ester monomer with double bond is preferably one or more selected from vinyl acetate and alkyl (methyl) acrylate and derivatives thereof; the amide monomer having a double bond is preferably a monomer having a (meth) acrylamide group. In particular, the other polymer may also be an optionally crosslinked polystyrene.
Wherein the surface of the silica in the lipophilic portion is linked with hydrophobic groups and/or segments, and the linkage can be through covalent bonds, hydrogen bonds, coordination bonds and intermolecular forces, preferably through covalent bonds. Specific hydrophobic groups and/or segments are not particularly limited and include, but are not limited to, one or more of unsubstituted or optionally halogenated alkyl, alkoxy, alkenyl, aryl, arylalkyl groups. The alkyl moiety in the alkyl group and the alkoxy and arylalkyl groups is preferably a linear, branched or cyclic alkyl group having 1 to 30C atoms, the alkenyl group is preferably a linear or branched alkenyl group having 2 to 30C atoms, and the aryl group is preferably a monocyclic or fused ring aryl group having 6 to 40C atoms.
For specific magnetic snowman-like Janus particles, siO may be mentioned 2 -C18@PS/PDVB/Fe 3 O 4 Magnetic snowman-shaped Janus particles, PS/PDVB-Fe 3 O 4 @SiO 2 -C8 magnetic snowman-like Janus particles, PS/PDVB/PVBC-Fe 3 O 4 @SiO 2 -C18 magnetic snowman-like Janus particles, PS/PDVB/PVBC-Fe 3 O 4 @SiO 2 -C8 magnetic snowman-like Janus particles, PS/PMMA/PEGDMA-Fe 3 O 4 @SiO 2 -C18。
In the present invention, the magnetic snowman-like Janus particles can be prepared, for example, by the following method:
preparing seed emulsion: adding an oil/water emulsion containing a monomer, a cross-linking agent and an initiator into a dispersion liquid of a Polystyrene (PS) hollow sphere template, and heating and polymerizing to obtain a polymer composite seed emulsion;
snowman-like Janus particles were prepared: adding emulsion containing double bond-containing silane coupling agent monomer and surfactant into the polymer composite seed emulsion for swelling, and then heating for polymerization to induce phase separation to prepare snowman-shaped Janus particles;
and (3) hydrophobic modification: performing hydrophobic modification on the silicon dioxide part of the snowman-shaped Janus particles;
hydrophilic modification: carrying out hydrophilic modification on the snowman-shaped Janus particles subjected to hydrophobic modification to obtain amphiphilic snowman-shaped Janus particles;
magnetization: and attaching the magnetic nano particles to the surfaces of the amphiphilic snowman-shaped Janus particles to obtain the magnetic snowman-shaped Janus particles.
The silane coupling agent containing a double bond to be used is not particularly limited as long as it can undergo polymerization reaction with seeds in the polymer composite seed emulsion, polymerization-induced phase separation occurs, and the polymerized silane coupling agent undergoes hydrolysis, thereby forming a silica moiety. Those skilled in the art may appropriately select as desired, and specific examples thereof include, but are not limited to, one of 3- (methacryloxy) propyltrimethoxysilane, 3- (methacryloxy) propyltriethoxysilane, 3- (methacryloxy) propyltrichlorosilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, 3-allylbutyltrimethoxysilane, 3-allylbutyltriethoxysilane, 3-allylbutyltrichlorosilane, or any combination thereof.
The hydrophobic modification is performed by reacting the silica surface with a silane coupling agent, for example, by dispersing or dissolving the obtained snowman-like Janus particles in a solvent simultaneously with the silane coupling agent. The silane coupling agent used in this step is a silane coupling agent having a hydrophobic group and/or a segment, and any silane coupling agent having a hydrophobic group and/or a segment and capable of reacting with a silicon hydroxyl group on the surface of silica can be used in the present invention.
The hydrophilic modification may be performed, for example, by treating the hydrophobically modified snowman-like Janus particles with a solvent, for example, dispersing the hydrophobically modified snowman-like Janus particles in a solvent, and treating with a solvent to obtain hydrophilic groups, thereby obtaining hydrophilically modified amphiphilic snowman-like Janus particles.
The magnetization is performed by attaching magnetic nanoparticles to the surface of amphiphilic snowman-like Janus particles, for example, dispersing the amphiphilic snowman-like Janus particles in an aqueous solution in which divalent iron ions and trivalent iron ions are dissolved, coordinating, adding ammonia water, forming ferroferric oxide nanoparticles, and attaching the ferroferric oxide nanoparticles to the polymer composite microsphere side of the amphiphilic snowman-like Janus particles, thereby obtaining the magnetic snowman-like Janus particles.
B) Magnetic Janus nano sheet with three-layer structure
The magnetic three-layer structure Janus nano sheet used in the invention comprises a composite interlayer, a hydrophilic layer and a lipophilic layer, wherein the composite interlayer is an intermediate interlayer comprising inorganic magnetic solid particles and one or more substances selected from polymers and silicon dioxide; the hydrophilic layer is positioned on one side of the composite interlayer; the lipophilic layer is positioned on the other side of the composite interlayer.
The major axis diameter of the magnetic three-layer structure Janus nanoplatelets is in the range of 10 to 300nm, preferably in the range of 30 to 250nm, more preferably in the range of 50 to 200nm, still more preferably in the range of 80 to 180nm, and most preferably in the range of 100 to 150 nm. The thickness ratio of the hydrophilic layer, the composite interlayer and the lipophilic layer is 1-3:8-12:1-3, preferably 1-2:9-11:1-2, more preferably 1:10:1 or 2:10:1.
For the composite interlayers in which the inorganic magnetic solid particles are in a dispersed phase, the polymer and/or silica form a continuous phase. The polymer in the composite interlayer is not particularly limited and may be specifically selected as desired by those skilled in the art, and may be, for example, selected from polymers formed by polymerizing one or more monomers including olefins, acrylamides, and (meth) acrylic esters with an optional crosslinking agent.
The hydrophilic layer may be a hydrophilic polymer layer on one side of the composite interlayer or a hydrophilic group-carrying structure or a grafted hydrophilic segment introduced on one side of the composite interlayer, wherein the hydrophilic polymer layer and the composite interlayer are bonded together by intermolecular forces, and the hydrophilic group-carrying structure and the hydrophilic segment are connected to components in the composite interlayer, such as polymers in the composite interlayer, by chemical bonds. The monomer forming the hydrophilic polymer or the hydrophilic chain segment is one or more selected from acrylamide, (methyl) acrylic acid and polyethylene glycol methacrylate; the hydrophilic group is one or more selected from carboxyl, amino, hydroxyl and sulfonic acid groups.
The lipophilic layer may be a lipophilic polymer layer on one side of the composite interlayer or a structure with a lipophilic group introduced on one side of the composite interlayer or a grafted lipophilic segment, wherein the lipophilic polymer layer and the composite interlayer are bonded together by intermolecular forces, and the structure with a lipophilic group and the lipophilic segment are connected to components in the composite interlayer, such as polymers in the composite interlayer, by chemical bonds. The monomer forming the lipophilic polymer or lipophilic segment is preferably one or more selected from the group consisting of olefin-based, (meth) acrylate-based and styrene-based monomers.
As specific magnetic three-layer Janus nanosheets, PS/PDVB@Fe may be mentioned 3 O 4 @PEO、PVBC@Fe 3 O 4 @POEGMA、PMMA@Fe 3 O 4 @PAA and PDVB@Fe 3 O 4 Janus nanosheets with a magnetic three-layer structure of @ PAM, and the like.
The magnetic trilayer Janus nanoplatelets used in the present invention can be prepared, for example, by a process comprising the steps of:
dissolving and dispersing oil-soluble monomers, a cross-linking agent, an oil-soluble oxidant and oil-dispersible inorganic magnetic solid particles in paraffin as an oil phase;
mixing water and a surfactant as an aqueous phase;
after mixing and emulsifying oil-water phases into emulsion, adding a water-soluble reducing agent into the emulsion, and obtaining stable particle emulsion through interfacial redox polymerization;
Adding hydrophilic monomers into the obtained particle emulsion for polymerization, or adding compounds with hydrophilic groups and/or hydrophilic chain segments for reaction, so as to obtain the organic/inorganic hybrid two-layer structure particle emulsion;
adding a monomer and an oil-soluble initiator into the obtained organic/inorganic hybrid two-layer structure particle emulsion, and polymerizing to obtain the organic/inorganic hybrid three-layer structure particle emulsion;
and (3) separating the organic/inorganic hybridization three-layer structure particles from the obtained emulsion, and then mechanically crushing to obtain the magnetic Janus nano sheet with the three-layer structure.
In the preparation method, an oil phase consisting of an oil-soluble monomer, a cross-linking agent, an oil-soluble initiator, oil-dispersible inorganic magnetic nano particles, paraffin wax and the like and an aqueous phase containing a surfactant form stable miniemulsion (50-500 nm) through emulsification. Under the action of the water phase hydrophilic initiator, oxidation-reduction polymerization reaction is realized at the emulsion interface to form a polymer capsule shell, namely a composite interlayer. The paraffin plays a supporting and protecting role on the inner side of the capsule shell, and the other side is exposed to the water phase. Further hydrophilic monomers or radical terminators are added to form a hydrophilic layer on the aqueous phase side. Further enters the capsule cavity through the adsorption monomer, and is polymerized at the inner side of the capsule wall, namely, the lipophilic layer is formed, and the three-layer structure particles can be obtained. Washing to remove paraffin and surfactant, and lyophilizing and crushing to obtain Janus nanosheets with magnetic three-layer structure.
For the above preparation method, a person skilled in the art may select and use an appropriate monomer, a crosslinking agent, an initiator, a surfactant, a solvent, and the like according to specific needs.
In addition, the magnetic three-layer structure Janus nanoplatelets used in the present invention can also be prepared, for example, by the following method: firstly, preparing a silicon dioxide hollow sphere by a sol-gel method, wherein Fe is wrapped in a sphere phase 3 O 4 A nanoparticle; then carrying out hydrophilic modification on the outer side of the silicon dioxide hollow sphere; the hydrophilically modified silica hollow spheres are crushed and the inner side thereof is subjected to oleophylic modification.
The preparation of the hollow silica spheres can be carried out as follows: silane coupling agent with alkoxy and Fe 3 O 4 Mixing the nano particles, adding toluene and water, emulsifying under the action of a surfactant to obtain an oil-in-water emulsion, and obtaining the silica hollow spheres through a sol-gel process. The silane coupling agent having an alkoxy group therein may be, for example, ethyl orthosilicate, ethyl trimethoxysilane, propyl triethoxysilane, or the like.
Hydrophilic modification of the outside of the silica hollow sphere can be performed by contacting the silica hollow sphere with a silane coupling agent having a hydrophilic segment. The silane coupling agent having a hydrophilic segment may be, for example, PEO silane coupling agent, POEGMA silane coupling agent, PAA silane coupling agent, PAM silane coupling agent, or the like.
The lipophilic modification may be performed by first modifying with a benzyl chlorosilane coupling agent and then terminating the polymer segment with the lipophilic segment prepared by anionic living polymerization to the benzyl chloride side. The polymer chain segment with the lipophilic chain segment can be, for example, a PS/PDVB chain segment, a PVBC chain segment, a PDVB chain segment, a PMMA chain segment and the like.
C) Polymer double-strand/magnetic nanoparticle composite Janus material
The polymer double-chain/magnetic nanoparticle composite Janus material used in the invention comprises a composite structure of a hydrophilic polymer single chain, inorganic magnetic nanoparticles and a lipophilic polymer single chain, wherein the hydrophilic polymer single chain and the lipophilic polymer single chain are connected with the inorganic magnetic nanoparticles at the tail end of the chain through chemical bonds.
The hydrophilic polymer single strand and the lipophilic polymer single strand are not particularly limited, and may include other segments as long as the polymer single strand includes a hydrophilic segment or a lipophilic segment, respectively, without affecting the hydrophilic and lipophilic properties of the whole. For a particular segment, one skilled in the art can choose as desired.
For example, the monomer forming the hydrophilic polymer single chain may be one or more selected from the group consisting of acrylamides, (meth) acrylic acids and polyethylene glycol (meth) acrylates; or the hydrophilic polymer single chain may be a polymer chain having a hydrophilic group as a side group, the hydrophilic group being one or more selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, and a sulfonic acid group. The monomer forming the lipophilic polymer chain may be one or more selected from olefins and styrenes.
For specific polymer double-strand/magnetic nanoparticle composite Janus materials, PS@Fe may be mentioned 3 O 4 @PEO、PVBC@Fe 3 O 4 @POEGMA、PMMA@Fe 3 O 4 @PAA and PDVB@Fe 3 O 4 Magnetic double-stranded Janus particles of PAM, etc.
The polymeric double-stranded/magnetic nanoparticle composite Janus material used in the present invention can be prepared, for example, by a method comprising the steps of:
introducing amino groups on the surfaces of the inorganic nano particles through modification, and dispersing the inorganic nano particles with the amino groups on the surfaces in a solvent to obtain inorganic nano particle dispersion liquid;
the monomer for forming the polymer single chain A is prepared into an active chain solution of the polymer single chain A with an active center at the tail end through cationic polymerization;
dropping the active chain solution of the single-chain polymer A into the inorganic nanoparticle dispersion liquid to obtain a dispersion liquid of the single-chain polymer A/inorganic nanoparticle composite;
the monomer for forming the single-chain polymer B is prepared into an active chain solution of the single-chain polymer B with an active center at the tail end through cationic polymerization;
and (3) dripping the active chain solution of the single-chain polymer B into the dispersion liquid of the single-chain polymer A/inorganic nanoparticle composite to obtain the single-chain polymer A-inorganic nanoparticle-single-chain polymer B composite Janus material.
Optionally carrying out hydrophilic modification or oleophylic modification on the polymers A and B to obtain the polymer double-chain/magnetic nanoparticle composite Janus material with a hydrophilic polymer single-chain-inorganic magnetic nanoparticle-oleophilic polymer single-chain structure.
Wherein the monomers forming the polymer strands A and B are preferably vinyl ethers containing styrene double bonds or vinyl ethers containing alkyl double bonds.
Hydrophilic and/or lipophilic modification may be performed by initiating cationic polymerization of other monomers from segments containing styrene double bonds on polymer single chains a and/or B, thereby providing the polymer single chains a and/or B with hydrophilic or lipophilic segments.
Hydrophilic and/or lipophilic modification can also be carried out by reacting the segments containing alkyl double bonds on the polymer single chains a and/or B with compounds capable of introducing hydrophilic and/or lipophilic segments and/or groups.
The monomers, initiators, solvents and other reagents used in the above preparation method can be appropriately selected by those skilled in the art as required.
In addition, after the polymer single-chain A/inorganic nanoparticle composite is obtained, an acidic aqueous solution is used for etching to obtain hydroxyl on the surface of the inorganic nanoparticle, and then a silane coupling agent with a hydrophilic chain segment is grafted to obtain the polymer double-chain/magnetic nanoparticle composite Janus material.
D) Polymer single-chain/magnetic nanoparticle composite Janus material
The polymer single strand/inorganic nanoparticle composite Janus material used in the present invention comprises a polymer single strand and inorganic nanoparticles, wherein the polymer single strand comprises an oleophilic end connected with the inorganic nanoparticles and a hydrophilic end far away from the inorganic nanoparticles, the oleophilic end comprises an oleophilic chain segment, and the hydrophilic end comprises a hydrophilic chain segment and/or a hydrophilic group.
Wherein the monomer forming the lipophilic chain segment comprises one or more monomers selected from styrene, (methyl) acrylic ester, isocyanate, (methyl) acrylonitrile and cyanoacrylate; the hydrophilic segment includes one or more selected from polyvinyl alcohol, polyalkyl glycol, polysiloxane, poly (meth) acrylic acid and poly (meth) acrylamide segments; the hydrophilic group comprises one or more selected from carboxyl, hydroxyl, amino and sulfonic groups.
The polymer single strand further comprises an intermediate segment intermediate the lipophilic end and the hydrophilic end; the hydrophilic segment is a side chain attached to the intermediate segment; the hydrophilic group is a pendant group on the intermediate segment; the monomer forming the intermediate segment comprises one or more selected from 4- (vinyl phenyl) -1-butene, isoprene, 1, 2-butadiene, 4-vinyl benzyl methacrylate and allyl isocyanate.
The polymeric single-chain/inorganic nanoparticle composite Janus material used in the present invention can be prepared, for example, by a method comprising the steps of:
introducing halogen groups on the surface of the inorganic nano particles through modification;
Dispersing the modified inorganic nano particles in a solvent to obtain an inorganic nano particle dispersion liquid;
monomers are added sequentially according to the anionic polymerization activity sequence, and an anionic active chain solution of the polymer single chain A is prepared through anionic active polymerization.
Adding the anionic active chain solution of the single-chain polymer A into the inorganic nanoparticle dispersion liquid to obtain a single-chain polymer A/nanoparticle composite;
and carrying out hydrophilic modification on the polymer single chain A in the polymer single chain A/nano particle composite to obtain the polymer single chain/inorganic nano particle composite Janus material.
The hydrophilic modification may be performed, for example, by: when the side chain or side group of the single-chain polymer A contains double bond or benzyl, the hydrophilic chain segment and/or hydrophilic group is introduced on the single-chain polymer A by utilizing the click reaction of the mercapto-double bond, or halogen is introduced on the single-chain polymer A and then the hydrophilic polymer is grafted. The sulfhydryl compound used in the clicking reaction of the sulfhydryl-double bond comprises one or more selected from thioglycollic acid, mercaptopropionic acid, mercaptoethanol, mercaptoethylamine hydrochloride and methoxy polyethylene glycol sulfhydryl. The method for introducing halogen comprises introducing halogen through addition reaction of double bond, or introducing halogen through reaction of benzyl and N-bromosuccinimide; the method of grafting hydrophilic polymers includes forming hydrophilic polymers by ATRP polymerization, reacting with amino-terminated hydrophilic polymers, or terminating reactions with hydrophilic anionic polymers.
The steps or operations not specifically mentioned in the method are carried out by means known in the art, and the person skilled in the art can appropriately select the monomers, initiators, solvents and other reagents used in the above-mentioned preparation method as required.
< method for separating oil from water >
One of the purposes of the invention is to provide an oil-water separation method based on magnetic solid particle emulsifier, which comprises the following steps:
(1) Dispersing magnetic solid particles into a solvent to obtain a magnetic solid particle dispersion;
(2) Adding the magnetic solid particle dispersion liquid into a target treatment liquid to obtain a magnetic particle emulsion;
(3) Performing magnetic action on the magnetic particle emulsion to separate water and emulsified oil drops, collecting a water phase, and enriching the emulsified oil drops to form magnetic dry liquid drops;
(4) Demulsification is carried out on the magnetic dry liquid drops, and oil and magnetic solid particles in the magnetic dry liquid drops are respectively collected;
(5) Optionally leaching the collected magnetic solid particles by using an organic solvent, and drying to obtain the recovered magnetic solid particles.
The respective steps of this embodiment are described in detail below.
In step (1), the magnetic solid particles are preferably dispersed in water with the aid of a dispersing technique to obtain a magnetic solid particle dispersion. The dispersing technology is preferably a technology for dispersing magnetic solid particles by mechanical equipment or ultrasound, and can be one of stirring paddle stirring, shearing by a refiner, mixing by an eddy current mixer, stirring by a magnetic stirrer, dispersing by an ultrasonic disperser and dispersing by an ultrasonic crusher or any combination of the stirring paddle stirring and the shearing by the refiner.
The mass ratio of the magnetic solid particles to the water is 1:100-1:1, preferably 1:20-1:5.
The target treatment fluid in step (2) may be oily wastewater generated in crude oil extraction and post-treatment processes, such as oil extraction, particularly enhanced oil extraction wastewater, oil tanks, particularly oil extraction tank cleaning wastewater, drilling platform cleaning wastewater, oily wastewater discharged by food oil enterprises, oily wastewater discharged by chemical plants, and the like.
After the magnetic solid particle dispersion is injected into the target treatment liquid, a shearing force is preferably applied, for example, stirring is performed at a certain speed, to obtain a magnetic particle emulsion. The stirring speed is 100-400rpm/min, preferably 150-300rmp/min.
Wherein the amount of the magnetic solid particles to be used is 0.01 to 20wt%, preferably 0.1 to 10wt%, with respect to the objective treatment liquid.
In step (3), the magnetic particle emulsion may be magnetically acted upon by subjecting it to a magnetic field. The magnetic field may be applied by a magnetic assembly. Magnetic materials of various shapes, such as bar-shaped, block-shaped, and sheet-shaped magnetic materials, can be cited as the magnetic component. The specific magnetic material may be selected from the materials listed above for the inorganic magnetic solid particles.
In this step, the oil droplets emulsified by the magnetic particles in the magnetic particle emulsion migrate and concentrate together with the magnetic solid particles due to the response of the magnetic solid particles to the magnetic field, forming magnetic dry droplets, whereby separation of water and emulsified oil droplets, i.e. separation of water and oil phases, occurs.
The present embodiment is not particularly limited to a specific magnetic field direction. The proper magnetic field strength can make the emulsified oil drop attracted, migrated and enriched by the magnetic component, so as to separate water from the emulsified oil drop, but at the same time, the magnetic solid particles wrapping the emulsified oil drop can not be further aggregated to cause demulsification. In some embodiments, the magnetic assembly used has a magnetic induction of 400-1000Gs, preferably 600-900Gs.
In one embodiment, the magnetic component is a block or sheet of magnetic material that is placed in a magnetic field by placing the magnetic component outside of a container containing a magnetic particle emulsion. In this case, the oil droplets emulsified by the magnetic particles are attracted to and enriched on the side of the container close to the magnetic assembly together with the magnetic particles.
In another embodiment, the magnetic component is a rod-shaped magnetic material that is placed in a magnetic field by placing the magnetic material in a magnetic particle emulsion. In this case, the oil droplets emulsified by the magnetic particles are attracted to the rod-like magnetic material together with the magnetic particles and are enriched. In this method, water and oil can be separated by extracting a rod-shaped magnetic material from a magnetic particle emulsion.
In step (4), the magnetic dry droplets may be demulsified by applying a magnetic field that is stronger than the magnetic action. The stronger magnetic field may be applied by a magnetic component with a higher magnetic induction, which may have a magnetic induction of 1000-20000Gs, preferably 1200-18000Gs.
In step (5), the mixture of the formed magnetic solid particles and oil may be rinsed with an organic solvent selected from one or more of aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, ethers, esters, ketones, glycol derivatives, and other organic solvents. Examples of the aromatic hydrocarbon solvent include, but are not limited to, benzene, toluene, xylene, etc.; examples of aliphatic hydrocarbon solvents include, but are not limited to, pentane, hexane, octane, and the like; examples of cycloaliphatic solvents include, but are not limited to, cyclohexane, cyclohexanone, toluene cyclohexanone, and the like; examples of halogenated hydrocarbon solvents include, but are not limited to, chlorobenzene, dichlorobenzene, methylene chloride, and the like; examples of alcoholic solvents include, but are not limited to, methanol, ethanol, isopropanol, and the like; examples of the ether-based solvents include, but are not limited to, diethyl ether, propylene oxide, and the like; examples of the ester solvents include, but are not limited to, methyl acetate, ethyl acetate, propyl acetate, and the like; examples of ketone solvents include, but are not limited to, acetone, methyl butanone, methyl isobutyl ketone, and the like; examples of glycol derivative solvents include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and the like; examples of other solvents include, but are not limited to, one or any combination of acetonitrile, pyridine, phenol, and the like.
In a preferred embodiment, the method of the invention comprises the steps of:
by mixing magnetic solid particles Fe 3 O 4 Dispersing into water with the aid of dispersion technology of an ultrasonic disperser to obtain magnetic solid particles Fe 3 O 4 An aqueous dispersion of (a);
the magnetic solid particles Fe 3 O 4 Injecting the aqueous dispersion of (2) into the oily wastewater of the cleaning oil tank, and stirring at a certain speed to obtain a mixed solution;
injecting the mixed solution into equipment loaded with a magnetic rod, enabling the magnetic rod to interact with oil drops emulsified by magnetic particles, adsorbing the oil drops near the magnetic rod, realizing separation of water and emulsified oil drops through equipment control, and enabling the emulsified oil drops to be migrated, adsorbed and enriched by the magnetic equipment to obtain magnetic dry oil drops;
stripping the obtained magnetic dry oil drops from the magnetic equipment by using a scraper stripping method, so that the magnetic dry oil drops are separated from the magnetic device, and after demulsification, part of the oil flows down in a stranding way and can be recovered, and a mixture of magnetic solid particles and oil is formed in a part of the oil drops;
and leaching the obtained mixture by using an organic solvent, separating the residual oil from the magnetic solid particles by total elution, and drying to obtain the recovered magnetic solid particles.
Examples
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. Further, it is understood that various changes and modifications of the invention will become apparent to those skilled in the art upon reading the description herein, and such equivalents are intended to fall within the scope of the invention as defined by the appended claims.
Example 1: magnetic Fe 3 O 4 Oil-water separation of solid particles on oil tank cleaning wastewater
10kg of magnetic Fe 3 O 4 Dispersing the solid particles into 100kg of water with the assistance of ultrasonic dispersion technology to obtain magnetic Fe 3 O 4 An aqueous dispersion of solid particles. The aqueous dispersion was poured into 10t of tank washing wastewater and stirred at a speed of 200rpm/min to obtain a magnetic particle emulsion. And (3) magnetically acting the emulsion by using a magnetic rod with magnetic induction of 800Gs, adsorbing for 5min, then extracting the magnetic rod and the adsorbed magnetic particle emulsion, realizing separation of water and emulsified oil drops by equipment control, and carrying out migration adsorption and enrichment on the emulsified oil drops by magnetic equipment to obtain magnetic dry liquid drops. And stripping and squeezing the magnetic dry liquid drops by using a magnetic rod with magnetic induction intensity of 1.5T, adsorbing magnetic solid particles on the magnetic rod, and separating oil. And leaching the stripped magnetic particles on the magnetic rod by using an organic solvent, and drying to obtain the recovered magnetic solid particles. The granules are subjected to a drying process to achieve recycling.
Example 2: siO (SiO) 2 @Fe 3 O 4 Oil-water separation of composite magnetic solid particles on oil tank cleaning wastewater
1)SiO 2 @Fe 3 O 4 Preparation of composite magnetic solid particles
1.0g of Fe 2 SO 3 And 0.9g FeCl 3 Dissolving in 2.0g of water, adding 1.0mL of ammonia water (25 wt%), and stirring for 1h to obtain precipitated solid Fe 3 O 4 And (3) nanoparticles. 1g of Fe 3 O 4 Dispersing the particles into 50mL of ethanol, adding 1mL of Tetraethoxysilane (TEOS), fully hydrolyzing for 24h under stirring at 500rpm/min, repeatedly washing with ethanol and magnet, adsorbing and separating, and drying to obtain SiO 2 @Fe 3 O 4 Composite magnetic solid particle dry powder.
2) Oil-water separation
10kg of SiO 2 @Fe 3 O 4 Dispersing the solid particles into 100kg of water with the assistance of ultrasonic dispersion technology to obtain magnetic SiO 2 @Fe 3 O 4 An aqueous dispersion of solid particles. The particle dispersion was poured into oil tank washing wastewater and stirred at a speed of 200rpm/min to obtain a magnetic particle emulsion. And (3) magnetically acting the emulsion by using a magnetic rod with magnetic induction of 800Gs, adsorbing for 5min, then extracting the magnetic rod and the adsorbed magnetic particle emulsion, realizing separation of water and emulsified oil drops by equipment control, and carrying out migration adsorption and enrichment on the emulsified oil drops by magnetic equipment to obtain magnetic dry liquid drops. And stripping and squeezing the magnetic dry liquid drops by using a magnetic rod with magnetic induction intensity of 1.5T, adsorbing magnetic solid particles on the magnetic rod, and separating oil. And leaching the stripped magnetic particles on the magnetic rod by using an organic solvent, and drying to obtain the recovered magnetic solid particles. The granules are subjected to a drying process to achieve recycling.
Example 3: siO (SiO) 2 -C18@PS/PDVB/Fe 3 O 4 Oil-water separation of magnetic snowman-shaped Janus particles on oil tank cleaning wastewater
1)SiO 2 -C18@PS/PDVB/Fe 3 O 4 Preparation of magnetic snowman-shaped Janus particles
0.6g of divinylbenzene, 1g of styrene, 0.05g of sodium dodecyl sulfonate, 0.02g of azobisisobutyronitrile and 10mL of water were emulsified at a high speed to obtain an emulsion. Mixing the emulsion with 1g of polystyrene hollow sphere dispersion liquid for swelling, and carrying out polymerization reaction for 8 hours at 70 ℃ under the stirring speed of 300rpm/min to prepare the seed emulsion. 1.2g of 3- (methacryloyloxy) propyltrimethoxysilane, 0.04g of sodium dodecyl sulfate, 0.01g of potassium persulfate and 10mL of water were emulsified into an emulsion, and the seed emulsion was dropped into the emulsion and stirred for 5 hours. Under the stirring of 300rpm/min, the polymerization is carried out for 24 hours at 70 ℃ to prepare the PDVB/PS@SiO 2 Composite snowman-shaped Janus particle emulsion. The solids content was 15% and the snowman-like Janus particle size was 600nm.
The snowman-like Janus particles obtained above were dispersed in ethanol, and 0.1g of n-octadecyltriethoxysilane was added to carry out hydrophobic modification. The hydrophobically modified particles were dispersed in 10ml of concentrated sulfuric acid and sulfonated for 30min to hydrophilically modify the polymer fraction. Dispersing the obtained amphiphilic snowman-like Janus particles into 20ml of dissolved Fe 2+ And Fe (Fe) 3+ Adding ammonia water into the water solution with the total concentration of 0.5mol/L after adsorption to obtain magnetic Fe 3 O 4 Particle-composite SiO 2 -C18@PS/PDVB/Fe 3 O 4 Magnetic snowman-like Janus particles.
2) Oil-water separation
10kg of SiO 2 -C18@PS/PDVB/Fe 3 O 4 Dispersing magnetic snowman-shaped asymmetric Janus particles into 100kg of water with the assistance of an ultrasonic dispersion technology to obtain SiO 2 -C18@PS/PDVB/Fe 3 O 4 An aqueous dispersion of magnetic snowman-like asymmetric Janus particles. The particle dispersion was poured into oil tank washing wastewater and stirred at a speed of 200rpm/min to obtain a magnetic particle emulsion. And (3) magnetically acting the emulsion by using a magnetic rod with magnetic induction of 800Gs, adsorbing for 5min, then extracting the magnetic rod and the adsorbed magnetic particle emulsion, realizing separation of water and emulsified oil drops by equipment control, and carrying out migration adsorption and enrichment on the emulsified oil drops by magnetic equipment to obtain magnetic dry liquid drops. The magnetic dry liquid is dropped into the magnetic liquid by a magnetic rod with magnetic induction intensity of 1.5TAnd stripping and squeezing, wherein the magnetic solid particles are adsorbed on a magnetic rod, and oil is separated. And leaching the stripped magnetic particles on the magnetic rod by using an organic solvent, and drying to obtain the recovered magnetic solid particles. The granules are subjected to a drying process to achieve recycling.
Example 4: PS/PDVB@Fe 3 O 4 Oil-water separation of Janus nano sheet with magnetic three-layer structure at@PEO on oil tank cleaning wastewater
1)PS/PDVB@Fe 3 O 4 Preparation of Janus nanosheets with magnetic three-layer structure of @ PEO
Ethyl orthosilicate 1g (TEOS) and 0.1g Fe 3 O 4 Mixing the nano particles, emulsifying 5g toluene and 10g water under the action of 0.005g Sodium Dodecyl Sulfate (SDS), emulsifying the two phases to obtain an oil-in-water emulsion, obtaining the silicon dioxide hollow spheres through a sol-gel process, and wrapping Fe in the spherical phase shells 3 O 4 And (3) nanoparticles. Further, 0.1mL of PEO silane coupling agent is dissolved in 1mL of glacial acetic acid, the mixture is dropwise added into the emulsion, and the mixture is stirred for 3 hours at room temperature, so that the outer side of a silicon dioxide spherical shell is grafted with PEO through hydrolysis, then the silicon dioxide spherical shell is ultrasonically crushed, the inner side of the silicon dioxide spherical shell is modified by 0.1g of benzyl chlorosilane coupling agent, and meanwhile, about 0.05g of PS/PDVB polymer is prepared by anionic living polymerization and is terminated to one side of benzyl chloride, thus obtaining PS/PDVB@Fe 3 O 4 Janus nanosheets of magnetic trilayer structure @ PEO.
2) Oil-water separation
10kg PS/PDVB@Fe 3 O 4 Dispersing Janus nano-sheets with a magnetic three-layer structure of @ PEO into 100kg of water with the assistance of an ultrasonic dispersion technology to obtain PS/PDVB @ Fe 3 O 4 Aqueous dispersion of Janus nanoplatelets of magnetic three-layer structure @ PEO. The particle dispersion was poured into oil tank washing wastewater and stirred at a speed of 200rpm/min to obtain a magnetic particle emulsion. And (3) magnetically acting the emulsion by using a magnetic rod with magnetic induction of 800Gs, adsorbing for 5min, then extracting the magnetic rod and the adsorbed magnetic particle emulsion, realizing separation of water and emulsified oil drops by equipment control, and carrying out migration adsorption and enrichment on the emulsified oil drops by magnetic equipment to obtain magnetic dry liquid drops. Stripping and separating the magnetic dry liquid drop by using a magnetic rod with magnetic induction intensity of 1.5T Squeezing, adsorbing magnetic solid particles on a magnetic rod, and separating oil. And leaching the stripped magnetic particles on the magnetic rod by using an organic solvent, and drying to obtain the recovered magnetic solid particles. The granules are subjected to a drying process to achieve recycling.
Example 5: PS@Fe 3 O 4 Oil-water separation of oil extraction wastewater by PEO magnetic double-chain Janus particles
1)PS@Fe 3 O 4 Preparation of PEO magnetic double-strand Janus particles
1g of Fe 3 O 4 Dispersing the nano-particles into 20mL of tetrahydrofuran solvent, adding 0.01g of benzyl chlorosilane coupling agent into the dispersion, and performing ultrasonic treatment for 3 hours at room temperature to obtain benzyl chloride modified ferroferric oxide nano-particles. 2mL of styrene monomer was dissolved in 10mL of tetrahydrofuran solvent, 20. Mu.L of n-butyllithium initiator was added, and the mixture was sonicated for 10min to obtain PS polymer chains. The PS chain dispersion liquid is poured into the ferroferric oxide dispersion liquid to obtain PS@Fe 3 O 4 VBC nanoparticles. Repeatedly washing the above particles with ethanol and water, lyophilizing, etching with 0.1mol/L ammonium fluoride aqueous solution for 10min, washing, and drying to obtain PS@Fe 3 O 4 -OH nanoparticles. Dispersing the nano particles into absolute ethyl alcohol, adding 0.1g of PEO silane coupling agent, and carrying out ultrasonic treatment at room temperature for 3 hours to obtain particle dispersion liquid. Finally, the PS@Fe is obtained after repeated washing by ethanol and water and drying 3 O 4 @ PEO nanoparticles.
2) Oil-water separation
10kg PS@Fe 3 O 4 Dispersing PEO magnetic double-chain Janus particles into 100kg of water with the assistance of an ultrasonic dispersion technology to obtain PS@Fe 3 O 4 Aqueous dispersion of PEO magnetic double-stranded Janus particles. The particle dispersion is injected into oil extraction wastewater and stirred at the speed of 200rpm/min to obtain magnetic particle emulsion. And (3) magnetically acting the emulsion by using a magnetic rod with magnetic induction of 800Gs, adsorbing for 5min, then extracting the magnetic rod and the adsorbed magnetic particle emulsion, realizing separation of water and emulsified oil drops by equipment control, and carrying out migration adsorption and enrichment on the emulsified oil drops by magnetic equipment to obtain magnetic dry liquid drops. Using magnetic inductionThe magnetic dry liquid drops are stripped and pressed by a magnetic rod with the strength of 1.5T, magnetic solid particles are adsorbed on the magnetic rod, and oil is separated. And leaching the stripped magnetic particles on the magnetic rod by using an organic solvent, and drying to obtain the recovered magnetic solid particles. The granules are subjected to a drying process to achieve recycling.
Industrial applicability
The oil-water separation based on the magnetic solid particle emulsifier can be used for industrial deep oil removal.
Claims (7)
1. An oil-water separation method based on magnetic solid particle emulsifier comprises the following steps:
Dispersing magnetic solid particles into water to obtain a magnetic solid particle dispersion liquid;
adding the magnetic solid particle dispersion liquid into a target treatment liquid to obtain a magnetic particle emulsion;
performing magnetic action on the magnetic particle emulsion to separate water and emulsified oil drops, and enriching the emulsified oil drops to form magnetic dry liquid drops;
demulsification is carried out on the magnetic dry liquid drops, and oil and magnetic solid particles in the magnetic dry liquid drops are respectively collected;
optionally leaching the collected magnetic solid particles with an organic solvent, and drying to obtain recovered magnetic solid particles;
wherein the magnetic solid particles are Fe 3 O 4 Solid particles; or alternatively
The magnetic solid particles are SiO with core-shell structure 2 @Fe 3 O 4 Composite magnetic solid particles, tiO 2 @Fe 3 O 4 Composite magnetic particles or Al 2 O 3 @Fe 3 O 4 Composite magnetic particles; or alternatively
The magnetic solid particles are amphiphilic modified inorganic magnetic solid particles, and the amphiphilic modified inorganic magnetic solid particles are one or more selected from magnetic snowman-shaped Janus particles, janus nano sheets with a magnetic three-layer structure, polymer double chains/magnetic nano particle composite Janus materials and polymer single chains/magnetic nano particle composite Janus materials;
Wherein the magnetic snowman-shaped Janus particle comprises a hydrophilic part and an oleophilic part which respectively form two spheres of the snowman-shaped particle, wherein the hydrophilic part comprises a polymer composite microsphere subjected to hydrophilic modification and magnetic nano particles attached to the surface of the polymer composite microsphere, and the oleophilic part comprises silicon dioxide subjected to hydrophobic modification;
the magnetic three-layer structure Janus nano sheet comprises a composite interlayer, a hydrophilic layer and a lipophilic layer, wherein the composite interlayer is an intermediate interlayer comprising inorganic magnetic solid particles and one or more substances selected from polymers and silicon dioxide; the hydrophilic layer is positioned on one side of the composite interlayer; the lipophilic layer is positioned on the other side of the composite interlayer;
the polymer double-chain/magnetic nanoparticle composite Janus material has a composite structure of a hydrophilic polymer single chain, an inorganic magnetic nanoparticle and a lipophilic polymer single chain, wherein the hydrophilic polymer single chain and the lipophilic polymer single chain are connected with the inorganic magnetic nanoparticle at the tail end of the chain through chemical bonds;
the polymer single strand/magnetic nanoparticle composite Janus material comprises a polymer single strand and inorganic nanoparticles, wherein the polymer single strand comprises an oleophilic end connected with the inorganic nanoparticles and a hydrophilic end far away from the inorganic nanoparticles, the oleophilic end comprises an oleophilic chain segment, and the hydrophilic end comprises a hydrophilic chain segment and/or a hydrophilic group.
2. The method of claim 1, wherein the magnetic solid particles are dispersed into water with the aid of a dispersion technique that is a technique that achieves dispersion of magnetic solid particles by mechanical means or ultrasound, including one of paddle stirring, refiner shearing, vortex mixer mixing, magnetic stirrer stirring, ultrasonic disperser dispersion, ultrasonic breaker dispersion, or any combination thereof.
3. According to claim 1 or 2The method is characterized in that the magnetic snowman-shaped Janus particles are SiO 2 -C18@PS/PDVB/Fe 3 O 4 Magnetic snowman-like Janus particles; the Janus nano sheet with the magnetic three-layer structure is PS/PDVB@Fe 3 O 4 Janus nano-sheet with magnetic three-layer structure of PEO; the polymer double-chain/magnetic nanoparticle composite Janus material is PS@Fe 3 O 4 PEO magnetic double-stranded Janus particles; the polymer single-chain/magnetic nanoparticle composite Janus material is PS@Fe 3 O 4 Magnetic single-stranded Janus particles.
4. The method according to claim 1 or 2, wherein the target treatment liquid is one or more of oily wastewater produced during crude oil extraction and post-treatment, oily wastewater discharged from a food oil company, and oily wastewater discharged from a chemical plant.
5. The method of claim 4, wherein the oily wastewater produced during crude oil recovery and post-treatment is enhanced oil recovery wastewater, tank wash wastewater, drilling platform wash wastewater.
6. A method according to claim 1 or 2, characterized in that the emulsion of magnetic particles is magnetically acted upon by subjecting the emulsion to a magnetic field applied by a magnetic assembly, the strength of the magnetic field being such that the emulsion droplets are attracted to migrate and concentrate by the magnetic assembly, effecting separation of water and emulsion droplets, but without further aggregation of the magnetic solid particles surrounding the emulsion droplets resulting in emulsion breaking.
7. A method according to claim 1 or 2, characterized in that the magnetic dry droplets are demulsified by applying a magnetic field that is stronger than the magnetic action.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735367A (en) * | 2008-11-24 | 2010-06-16 | 中国石油天然气股份有限公司 | Method for preparing nano magnetic polymer composite microspheres |
| WO2015044450A1 (en) * | 2013-09-30 | 2015-04-02 | Mærsk Olie Og Gas A/S | Depletion of water from oil using magnetic hydrophilic nanoparticles |
| WO2016026464A1 (en) * | 2014-08-22 | 2016-02-25 | 中国科学院化学研究所 | Organic/inorganic hybrid janus particle and preparation method and modification method, and modified janus particle and use thereof |
| CN109052596A (en) * | 2018-08-21 | 2018-12-21 | 杭州电子科技大学 | The preparation method and application of magnetic Nano flocculant suitable for emulsifiable oil waste water processing |
| CN110373171A (en) * | 2019-07-10 | 2019-10-25 | 浙江海洋大学 | A kind of displacement of reservoir oil emulsion stable by magnetic nanoparticle |
| CN110613960A (en) * | 2019-09-17 | 2019-12-27 | 杭州电子科技大学 | Preparation method and application of magnetic demulsifier capable of simultaneously realizing efficient oil-water separation of O/W and W/O emulsions |
| CN111632405A (en) * | 2020-05-28 | 2020-09-08 | 清华大学 | Oil-water separation method based on magnetic Janus particles |
| CN111643926A (en) * | 2020-05-28 | 2020-09-11 | 清华大学 | Extraction method based on magnetic Janus particles |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015044450A1 (en) * | 2013-09-30 | 2015-04-02 | Mærsk Olie Og Gas A/S | Depletion of water from oil using magnetic hydrophilic nanoparticles |
| WO2016026464A1 (en) * | 2014-08-22 | 2016-02-25 | 中国科学院化学研究所 | Organic/inorganic hybrid janus particle and preparation method and modification method, and modified janus particle and use thereof |
| CN109052596A (en) * | 2018-08-21 | 2018-12-21 | 杭州电子科技大学 | The preparation method and application of magnetic Nano flocculant suitable for emulsifiable oil waste water processing |
| CN110373171A (en) * | 2019-07-10 | 2019-10-25 | 浙江海洋大学 | A kind of displacement of reservoir oil emulsion stable by magnetic nanoparticle |
| CN110613960A (en) * | 2019-09-17 | 2019-12-27 | 杭州电子科技大学 | Preparation method and application of magnetic demulsifier capable of simultaneously realizing efficient oil-water separation of O/W and W/O emulsions |
| CN111632405A (en) * | 2020-05-28 | 2020-09-08 | 清华大学 | Oil-water separation method based on magnetic Janus particles |
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