CN104548667A - Net film applied to oil-in-water emulsion separation, preparation method and application of net film - Google Patents
Net film applied to oil-in-water emulsion separation, preparation method and application of net film Download PDFInfo
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- CN104548667A CN104548667A CN201410836247.7A CN201410836247A CN104548667A CN 104548667 A CN104548667 A CN 104548667A CN 201410836247 A CN201410836247 A CN 201410836247A CN 104548667 A CN104548667 A CN 104548667A
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- 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
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/10—Filter screens essentially made of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1241—Particle diameter
Abstract
The invention relates to a net film applied to oil-in-water emulsion separation, a preparation method and application of the net film. The net film is a composite net film formed by loading metal oxide layers of micro-nano composite structures on net holes and net wires of a metal net, wherein the metal oxide layers of the micro-nano composite structures are formed by clustering nano-zinc oxide and nano-cobalt oxide. The preparation method of the net film comprises the following steps: (1) dissolving an alkaline medium and dissolvable zinc salt in water and uniformly stirring to prepare a mixed solution A; (2) dipping a metal net in the mixed solution A and carrying out hydrothermal reaction to prepare a nano-zinc oxide loaded metal net; (3) dissolving carbamide and dissolvable cobalt salt in water and uniformly stirring the mixture to prepare a mixed solution B; and (4) taking out the metal net in the step (2), washing the metal net and dipping the metal net in the mixed solution B, carrying out hydrothermal reaction, and burning the metal net to prepare the net film. The net film can be widely applied to oil-water separation.
Description
Technical field
The invention belongs to chemical, technical field of function materials, be specifically related to a kind of nethike embrane for oil hydrosol separation and preparation method thereof and application.
Background technology
Surface wettability (also known as wetability) is a kind of important attribute of solid material.Material Field develops rapidly in recent years, has special infiltrating nano material and also obtains extensive concern.Special wellability basic to super hydrophilic, super-hydrophobic, super oleophylic, super oleophobic these four kinds is carried out multiplexed combination, the intelligent nano boundary material of Various Functions can be prepared.These materials have broad application prospects in the productive life of the mankind.
Along with socioeconomic development, environmental problem also highlights increasingly, the improvement of especially water pollution, more becomes global problem.Rely on the development of special wellability material, oily water separation technique starts to be applied to water treatment field.Such as publication number is the Chinese patent application of CN1721030A, CN101518695A, successfully prepares the nethike embrane be separated for oil water mixture.But for oil mixing with water emulsion, the emulsion especially containing surfactant, because it is compared with general oil water mixture, intermolecular interaction is more complicated, there is not the sharp interface between water-oil phase, is therefore difficult to process with general separation nethike embrane.
Document ADV.Mater.2014,26 (18): 2943-2948; Angew.Chem.Int.Ed.2014,53 (3): 856-860; J.Mater.Chem.A.2013,1 (45): 14071-14074 reports the nethike embrane with certain separation of emulsions function.Wherein, most of nethike embrane can only be separated a certain emulsion, and can not apply widely.The manufacturing process of these nethike embranes is comparatively complicated in addition, and step is more and condition is difficult to control, also for practical application brings restriction.
Summary of the invention
The object of the present invention is to provide a kind of nethike embrane for oil hydrosol separation and preparation method thereof.
The nethike embrane be separated for oil hydrosol provided by the present invention is that load has the metal oxide layer of micron-nanometer composite construction and the compound nethike embrane that formed on the mesh and netting twine of wire netting, wherein, the metal oxide layer described in micron-nanometer composite construction is formed by nano zine oxide and nanometer cobalt oxide cluster.
In above-mentioned nethike embrane, described wire netting be selected from following any one: stainless (steel) wire, copper mesh, iron net or aluminium net, the order number of described wire netting can be 100 ~ 1000 orders.
Described micron-nanometer composite construction is the micro-meter scale crystal flower-like structure of nanoneedle and nanometer sheet composition, and the diameter of described micro-meter scale crystal flower-like structure is 1 ~ 30 μm, is specially 6 ~ 25 μm.
The shape of described nano zine oxide is nanoneedle and/or nanometer sheet.
The shape of described nanometer cobalt oxide is nanoneedle and/or nanometer sheet.
The diameter of described nanoneedle is 50 ~ 600nm, specifically can be 100nm-500nm; The length of described nanoneedle is 2 ~ 16 μm.
The thickness of described nanometer sheet is 50 ~ 600nm, specifically can be 100nm-500nm; Described nanometer sheet is of a size of 2 ~ 16 μm.
The aperture of described nethike embrane can be 1 ~ 100 μm, is specially 2 ~ 10 μm.
The described nethike embrane for oil hydrosol separation is prepared by following preparation method.
The preparation method of the nethike embrane for oil hydrosol separation provided by the present invention, comprises following steps:
(1) by alkaline matter and soluble zinc salt soluble in water and stir, obtain mixed solution A;
(2) wire netting be impregnated in described mixed solution A, carry out hydro-thermal reaction, obtain the wire netting of supported nano zinc oxide;
(3) by urea and soluble cobalt soluble in water and stir, obtain mixed solution B;
(4) take out the wire netting in step (2), after cleaning, described wire netting be impregnated in described mixed solution B, carry out hydro-thermal reaction, after hydro-thermal reaction terminates, take out wire netting flushing to dry, and carry out calcination processing, obtain the described nethike embrane be separated for oil hydrosol.
In above-mentioned preparation method, in step (1), described alkaline matter is specifically selected from following at least one: lithium hydroxide, NaOH and potassium hydroxide etc.
In described mixed solution A, the molar concentration of described alkaline matter can be 0.01 ~ 0.20mol/L, is 0.030-0.035mol/L further, specifically can be 0.025mol/L, 0.030mol/L, 0.035mol/L or 0.045mol/L.
Described soluble zinc salt is specifically selected from following at least one: zinc acetate, zinc nitrate, zinc sulfate and zinc chloride etc., described soluble zinc salt can its form containing the crystallization water exist.
In described mixed solution A, the molar concentration of described soluble zinc salt can be 0.2 ~ 2.0mol/L, can be 0.5 ~ 0.6mol/L further, specifically can be: 0.45mol/L, 0.5mol/L, 0.55mol/L, 0.6mol/L or 0.65mol/L.
In above-mentioned preparation method, before described step (2), described method also comprises the step of to clean wire netting and rinsing, specifically described wire netting can be dipped in ethanol and/or acetone and carry out ultrasonic cleaning, then by described wire netting ethanol and/or acetone and/or deionized water rinsing.
In above-mentioned preparation method, in step (2), described wire netting be selected from following any one: stainless (steel) wire, copper mesh, iron net or aluminium net, the order number of described wire netting can be 100 ~ 1000 orders, is specially 300 ~ 400 orders.
The temperature of described hydro-thermal reaction can be 70 DEG C ~ 120 DEG C, can be 80 DEG C ~ 90 DEG C further, specifically can be 80 DEG C, 90 DEG C or 95 DEG C.
The time of described hydro-thermal reaction can be 8h ~ 56h, can be 24h-48h further, specifically can be 20h, 24h or 48h.
In above-mentioned preparation method, in step (3), in described mixed solution B, the molar concentration of described urea can be 0.2 ~ 1.0mol/L, specifically can be 0.3mol/L, 0.4mol/L or 0.5mol/L.
Described soluble cobalt is specifically selected from following at least one: cobalt nitrate, cobalt chloride, cobalt acetate and cobaltous sulfate etc., described soluble cobalt can its form containing the crystallization water exist.
The molar concentration of described solvable cobalt salt can be 0.2 ~ 2.0mol/L, specifically can be 0.8mol/L, 0.10mol/L or 1.0mol/L.
In above-mentioned preparation method, in step (4), the temperature of described hydro-thermal reaction can be 70 DEG C ~ 110 DEG C, specifically can be 80 DEG C, 85 DEG C or 90 DEG C.
The time of described hydro-thermal reaction can be 8 ~ 36h, can be 10-24h further, specifically can be 12h, 18h or 24h.
The temperature of described calcination processing can be 150 ~ 500 DEG C, can be 200 ~ 400 DEG C further, specifically can be 180 DEG C, 200 DEG C, 250 DEG C or 400 DEG C.
The time of described calcination processing can be 0.5 ~ 10h, can be 1.5 ~ 2h further.
The application of nethike embrane in water-oil separating for oil hydrosol separation provided by the present invention also belongs to protection scope of the present invention.
Described water-oil separating can be oil water mixture (as: oil-polluted water etc.) separation and/or oil hydrosol separation etc.
Oil during described oil water mixture is separated can be toluene, dichloroethanes, n-hexane, gasoline or diesel oil etc.
When described oil water mixture is separated, first with nethike embrane described in water retting, more described oil water mixture can be passed through described nethike embrane, the water in described oil water mixture is by nethike embrane, and oil is trapped within nethike embrane, thus reaches the object of water-oil separating; Equally, when described oil water mixture is separated, first with nethike embrane described in corresponding oil-impregnated, more described oil water mixture can be passed through described nethike embrane, the oil in described oil water mixture is by nethike embrane, and water is trapped within nethike embrane, thus reaches the object of water-oil separating; Certainly, also can not nethike embrane described in water in advance or oil-impregnated, only oil water mixture need be passed through nethike embrane, if the water in oil water mixture first contacts nethike embrane, then water passes through, and oil is trapped within nethike embrane, if the oil in oil water mixture first contacts nethike embrane, then oil passes through, and water is trapped within nethike embrane.
Described oil hydrosol is separated and can be not containing the oil hydrosol (as water-in-oil emulsion and O/w emulsion) of surfactant or being separated of oil hydrosol (as: emulsion containing sorbester p17 and/or polysorbas20 etc.) containing surfactant.
When oil hydrosol is water-in-oil emulsion, when being passed through nethike embrane, emulsion is by breakdown of emulsion, and oil is by nethike embrane, and water is trapped within nethike embrane; When oil hydrosol is O/w emulsion, when being passed through nethike embrane, emulsion is by breakdown of emulsion, and water is by nethike embrane, and oil is trapped within nethike embrane.
The nethike embrane be separated for oil hydrosol provided by the present invention has super hydrophilic super oleophylic in atmosphere (in atmosphere with the contact angle of water and oil close to 0 °), super oleophobic (being greater than 150 ° with the contact angle of oil droplet under water) under water, the character of oil lower super-hydrophobic (being greater than 150 ° with the contact angle of water droplet under oil), specifically can be used for oil-polluted water (as containing toluene, n-hexane, dichloroethanes, gasoline or diesel oil etc.) water-oil separating, do not contain surface active agent emulsions (as water-in-oil emulsion and O/w emulsion) and contain surface active agent emulsions (as contained sorbester p17, the emulsion of polysorbas20 etc.) separation.
Nethike embrane raw material provided by the present invention is easy to get, with low cost, and preparation method and technique simply, can be used for preparing on a large scale.Nethike embrane provided by the present invention has the advantages such as separating rate is fast, good separating effect, be suitable for the separating treatment of general oil water mixture and polytype oil hydrosol, all can be separated with miscella aqueous emulsion the oil water mixture containing oil such as n-hexane, dichloroethanes, toluene, gasoline or diesel oil.Nethike embrane provided by the invention is easy to cleaning, good stability, and can be recycled.
Accompanying drawing explanation
Fig. 1 is the surface topography stereoscan photograph of the nethike embrane of preparation in embodiment 1, and wherein, Fig. 1 a is large-area scanning electromicroscopic photograph, and Fig. 1 b is the enlarged photograph of Fig. 1 a cover surface ESEM.
Fig. 2 is the shape picture of the retinal surface that measurement water droplet or oil droplet are prepared in embodiment 1, wherein, Fig. 2 a measures the shape picture of water (2 μ L) at retinal surface in atmosphere, Fig. 2 b measures the shape picture of carrene (2 μ L) at retinal surface in water, Fig. 2 c measures the shape picture of carrene (2 μ L) at retinal surface in atmosphere, and Fig. 2 d measures the shape picture of water (2 μ L) at retinal surface in carrene.
Fig. 3 is that the nethike embrane of preparation in embodiment 1 is for separating of the experimental provision of oil water mixture and oil hydrosol and experiment effect figure.Wherein, 1 representative is separated nethike embrane; 2 represent oil hydrosol; 3 representatives are by the toluene of nethike embrane.
Detailed description of the invention
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, for the preparation of oil hydrosol be separated nethike embrane and oil hydrosol separating effect
One) for the preparation of the nethike embrane that oil hydrosol is separated
(1) 300 object copper mesh immerses in ethanol and acetone successively, each ultrasonic cleaning 15 minutes, (impurity that wire netting may exist is removed with after salt acid soak 1h, to facilitate the carrying out of subsequent reactions), (be specially: above-mentioned copper mesh is placed in 0.5mol/L copper-bath by electrochemical deposition method deposited copper particle, utilize electrochemical workstation to carry out electrodeposition process, response voltage 1.5V, reaction time 1min), increase its roughness, dry under room temperature;
(2) under room temperature, in 250ml beaker, add 6.38g zinc acetate, 0.14g NaOH and 100ml water, stir and obtain mixed solution, in this mixed solution, the molar concentration of zinc acetate is 0.55mol/L, and the molar concentration of NaOH is 0.035mol/L;
(3) mixed solution obtained in step (2) is transferred in hydrothermal reaction kettle, and the copper mesh obtained in step (1) is also inserted in reactor, make its thorough impregnation in mixed solution, carry out hydro-thermal reaction 48h at 90 DEG C, obtain the wire netting of supported nano zinc oxide;
(4) under room temperature, add 3.00g urea, 1.21g cobalt nitrate and 100ml water, stir and obtain mixed solution in 250ml beaker, in this mixed solution, the molar concentration of urea is 0.50mol/L, and the molar concentration of cobalt nitrate is 0.10mol/L;
(5) be transferred in hydrothermal reaction kettle by obtaining mixed solution in step (4), and the wire netting deionized water rinsing of supported nano zinc oxide will obtained in step (3), dry under room temperature, insert again in reactor, make its thorough impregnation in mixed solution, carry out hydro-thermal reaction 12h at 90 DEG C;
(6) the copper mesh deionized water rinsing after step (5) being processed, dries under room temperature, calcine 2h at 200 DEG C after.Obtain load and there is the metal oxide layer of micron-nanometer composite construction and the compound nethike embrane (as shown in Figure 1) formed.Be dispersed with that countless length is 4 ~ 12 μm on the net, nanoneedle or nanometer sheet that diameter or thickness are 200 ~ 500nm, and the diameter to be made up of both is the crystal flower-like structure (as shown in Figure 1 b) of 10 ~ 15 μm, obtain the nethike embrane of the nano-metal-oxide load be separated for oil hydrosol, the mesh aperture of the nethike embrane obtained is at about 2 ~ 5 μm.
Two) oil hydrosol separating effect
Measure the contact angle of the nethike embrane that obtains of the present embodiment and 2 μ L water droplets in atmosphere close to 0 ° (as shown in Figure 2 a); The nethike embrane obtained by the present embodiment soaks 10 minutes in water, and the contact angle measuring this nethike embrane and 2 μ L carrene is under water greater than 150 ° (as shown in Figure 2 b); Measure contact angle that the nethike embrane that obtains of the present embodiment and 2 μ L carrene drip in atmosphere close to 0 ° (as shown in Figure 2 c); The nethike embrane obtained by the present embodiment soaks 10 minutes in carrene, and the contact angle measuring this nethike embrane and 2 μ L water droplets under oil is greater than 150 ° (as shown in Figure 2 d).
The experimental provision shown in Fig. 3 is utilized to carry out oil hydrosol separating experiment to the nethike embrane that the present embodiment obtains.This nethike embrane is fixed in the middle of two fixtures, upper and lower access feed glass pipe and discharging glass tube respectively, by water-in-oil emulsion (the volume ratio 100:1 of toluene and water, containing 2.0mg sorbester p17, magnetic agitation 120 minutes, oil droplet size 5 ~ 20 μm) feed glass pipe through top is poured on this nethike embrane, emulsion is through nethike embrane breakdown of emulsion, oil through nethike embrane and discharging glass tube from below flow down, water is blocked in top by nethike embrane simultaneously, realize the object being separated water-in-oil emulsion, obtain the oil after being separated.
Embodiment 2, for the preparation of oil hydrosol be separated nethike embrane and oil hydrosol separating effect
One) for the preparation of the nethike embrane that oil hydrosol is separated
(1) 400 object copper mesh immerses in ethanol and acetone successively, each ultrasonic cleaning 15 minutes, with salt acid soak 1h, dries under room temperature;
(2) under room temperature, in 250ml beaker, add 5.80g zinc acetate, 0.168g potassium hydroxide and 100ml water, stir and obtain mixed solution, in this mixed solution, the molar concentration of zinc acetate is 0.50mol/L, and the molar concentration of potassium hydroxide is 0.030mol/L;
(3) mixed solution obtained in step (2) is transferred in hydrothermal reaction kettle, and the copper mesh obtained in step (1) is also inserted in reactor, make its thorough impregnation in mixed solution, carry out hydro-thermal reaction 48h at 80 DEG C, obtain the wire netting of supported nano zinc oxide;
(4) under room temperature, add 3.00g urea, 1.21g cobalt nitrate and 100ml water, stir and obtain mixed solution in 250ml beaker, in this mixed solution, the molar concentration of urea is 0.50mol/L, and the molar concentration of cobalt nitrate is 0.10mol/L;
(5) be transferred in hydrothermal reaction kettle by obtaining mixed solution in step (4), and the wire netting deionized water rinsing of supported nano zinc oxide will obtained in step (3), dry under room temperature, insert again in reactor, make its thorough impregnation in mixed solution, carry out hydro-thermal reaction 10h at 90 DEG C;
(6) the copper mesh deionized water rinsing after step (5) being processed, dries under room temperature, after calcining 2h, obtains load and has the metal oxide layer of micron-nanometer composite construction and the compound nethike embrane that formed at 250 DEG C.Be dispersed with that countless length is 2 ~ 10 μm on the net, nanoneedle or nanometer sheet that diameter or thickness are 100 ~ 400nm, and the diameter of its composition is the crystal flower-like structure of 6 ~ 12 μm, obtain the nethike embrane be separated for oil hydrosol, the mesh aperture of the nethike embrane obtained is at about 4 ~ 9 μm.
Two) oil hydrosol separating effect
Measure the contact angle of the nethike embrane that obtains of the present embodiment and 2 μ L water droplets in atmosphere close to 0 °; The separation nethike embrane obtained by the present embodiment soaks 10 minutes in water, and the contact angle measuring this nethike embrane and 2 μ L carrene is under water greater than 150 °; Measure contact angle that the nethike embrane that obtains of the present embodiment and 2 μ L carrene drip in atmosphere close to 0 °; The nethike embrane obtained by the present embodiment soaks 10 minutes in carrene, and the contact angle measuring this nethike embrane and 2 μ L water droplets under oil is greater than 150 °.
The experimental provision shown in Fig. 3 is utilized to carry out separation of emulsions experiment to the separation nethike embrane that the present embodiment obtains.This nethike embrane is fixed in the middle of two fixtures, upper and lower access feed glass pipe and discharging glass tube respectively, by O/w emulsion (the volume ratio 1:100 of diesel oil and water, magnetic agitation 120 minutes, oil droplet size 4 ~ 30 μm) feed glass pipe through top is poured on this nethike embrane, and oil hydrosol is through nethike embrane breakdown of emulsion, water through nethike embrane and discharging glass tube from below flow down, oil is blocked in top by nethike embrane simultaneously, realizes the object being separated O/w emulsion, obtains the water after being separated.
The nethike embrane that embodiment 3 is separated for the preparation of oil hydrosol and oil hydrosol separating effect thereof
One) for the preparation of the nethike embrane that oil hydrosol is separated
(1) 400 object stainless steel immerses in ethanol and acetone successively, each ultrasonic cleaning 15 minutes, with salt acid soak 1h, dries under room temperature;
(2) under room temperature, in 250ml beaker, add 6.96g zinc acetate, 0.084g potassium hydroxide and 100ml water, stir and obtain mixed solution, in this mixed solution, the molar concentration of zinc acetate is 0.60mol/L, and the molar concentration of lithium hydroxide is 0.035mol/L;
(3) mixed solution obtained in step (2) is transferred in hydrothermal reaction kettle, and the stainless (steel) wire obtained in step (1) is also inserted in reactor, make its thorough impregnation in mixed solution, carry out hydro-thermal reaction 24h at 90 DEG C, obtain the stainless (steel) wire of supported nano zinc oxide;
(4) under room temperature, in 250ml beaker, add 3.00g urea, 2.29g cabaltous nitrate hexahydrate and 100ml water, stir and obtain mixed solution, in this mixed solution, the molar concentration of urea is 0.50mol/L, and the molar concentration of cobalt nitrate is 0.10mol/L;
(5) be transferred in hydrothermal reaction kettle by obtaining mixed solution in step (4), and the stainless (steel) wire deionized water rinsing of supported nano zinc oxide will obtained in step (3), dry under room temperature, insert again in reactor, make its thorough impregnation in mixed solution, carry out hydro-thermal reaction 24h at 90 DEG C;
(6) the stainless (steel) wire deionized water rinsing after step (5) being processed, dries under room temperature, at 400 DEG C, calcines 1.5h.Obtain load and there is the metal oxide layer of micron-nanometer composite construction and the compound nethike embrane formed.Be dispersed with that countless length is 8 ~ 16 μm on the net, nanoneedle or nanometer sheet that diameter or thickness are 220 ~ 500nm, and the diameter of its composition is the crystal flower-like structure of 15 ~ 25 μm, obtain the nethike embrane be separated for oil hydrosol, the mesh aperture of the nethike embrane obtained is at about 2 ~ 10 μm.
Two) oil hydrosol separating effect
Measure the contact angle of the nethike embrane that obtains of the present embodiment and 2 μ L water droplets in atmosphere close to 0 °.The nethike embrane obtained by the present embodiment soaks 10 minutes in water, and the contact angle measuring this nethike embrane and 2 μ L carrene is under water greater than 150 °; Measure contact angle that the nethike embrane that obtains of the present embodiment and 2 μ L carrene drip in atmosphere close to 0 °; The nethike embrane obtained by the present embodiment soaks 10 minutes in carrene, and the contact angle measuring this nethike embrane and 2 μ L water droplets under oil is greater than 150 °.
The experimental provision shown in Fig. 3 is utilized to carry out separation of emulsions experiment to the nethike embrane that the present embodiment obtains.This nethike embrane is fixed in the middle of two fixtures, upper and lower access feed glass pipe and discharging glass tube respectively, by O/w emulsion (the volume ratio 1:100 of gasoline and water, containing 0.50mg polysorbas20, magnetic agitation 120 minutes, oil droplet size 1 ~ 40 μm) feed glass pipe through top is poured on this nethike embrane, emulsion is through nethike embrane breakdown of emulsion, water through nethike embrane and discharging glass tube from below flow down, oil is blocked in top by nethike embrane simultaneously, realize the object being separated O/w emulsion, obtain the water after being separated.
Claims (10)
1. the nethike embrane be separated for oil hydrosol, that load has the metal oxide layer of micron-nanometer composite construction and the compound nethike embrane formed on the mesh and netting twine of wire netting, wherein, the metal oxide layer described in micron-nanometer composite construction is formed by nano zine oxide and nanometer cobalt oxide cluster.
2. nethike embrane according to claim 1, is characterized in that: described wire netting be selected from following any one: stainless (steel) wire, copper mesh, iron net or aluminium net;
The order number of described wire netting is 100 ~ 1000 orders.
3. nethike embrane according to claim 1 and 2, is characterized in that: described micron-nanometer composite construction is the micro-meter scale crystal flower-like structure of nanoneedle and nanometer sheet composition, and the diameter of described micro-meter scale crystal flower-like structure is 1 ~ 30 μm;
The shape of described nano zine oxide is nanoneedle and/or nanometer sheet;
The shape of described nanometer cobalt oxide is nanoneedle and/or nanometer sheet;
The diameter of described nanoneedle is 50 ~ 600nm, and length is 2 ~ 16 μm;
The thickness of described nanometer sheet is 50 ~ 600nm, is of a size of 2 ~ 16 μm;
The aperture of described nethike embrane is 1 ~ 100 μm.
4. the nethike embrane according to any one of claim 1-3, is characterized in that: described nethike embrane is the preparation method according to any one of claim 5-8 prepare.
5. the preparation method of the nethike embrane according to any one of claim 1-4, comprises following steps:
(1) by alkaline matter and soluble zinc salt soluble in water and stir, obtain mixed solution A;
(2) wire netting be impregnated in described mixed solution A, carry out hydro-thermal reaction, obtain the wire netting of supported nano zinc oxide;
(3) by urea and soluble cobalt soluble in water and stir, obtain mixed solution B;
(4) take out the wire netting in step (2), after cleaning, described wire netting be impregnated in described mixed solution B, carry out hydro-thermal reaction, after hydro-thermal reaction terminates, take out wire netting flushing to dry, and carry out calcination processing, obtain the described nethike embrane be separated for oil hydrosol.
6. preparation method according to claim 5, is characterized in that: in step (1), in described mixed solution A, and the molar concentration of described alkaline matter is 0.01 ~ 0.20mol/L;
In described mixed solution A, the molar concentration of described soluble zinc salt is 0.2 ~ 2.0mol/L.
7. the preparation method according to claim 5 or 6, is characterized in that: before described step (2), and described preparation method also comprises the step of to clean wire netting and rinsing;
In step (2), described wire netting be selected from following any one: stainless (steel) wire, copper mesh, iron net or aluminium net;
The order number of described wire netting is 100 ~ 1000 orders;
The temperature of described hydro-thermal reaction is 70 DEG C ~ 120 DEG C;
The time of described hydro-thermal reaction is 8h ~ 56h.
8. the preparation method according to any one of claim 5-7, is characterized in that: in step (3), and in described mixed solution B, the molar concentration of described urea is 0.2 ~ 1.0mol/L;
The molar concentration of described soluble cobalt is 0.2 ~ 2.0mol/L;
In step (4), the temperature of described hydro-thermal reaction is 70 DEG C ~ 110 DEG C;
The time of described hydro-thermal reaction is 8 ~ 36h;
The temperature of described calcination processing is 150 ~ 500 DEG C;
The time of described calcination processing is 0.5 ~ 10h.
9. the application of the nethike embrane according to any one of claim 1-4 in water-oil separating.
10. application according to claim 9, is characterized in that: described water-oil separating is that oil water mixture is separated and/or oil hydrosol is separated;
Grease separation during described oil water mixture is separated descends at least one freely: toluene, dichloroethanes, n-hexane, gasoline and diesel oil;
Described oil hydrosol is separated into the separation not containing the oil hydrosol of surfactant or the oil hydrosol containing surfactant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104857742A (en) * | 2015-05-28 | 2015-08-26 | 重庆理工大学 | Water removal method of dichloromethane |
| CN105327526A (en) * | 2015-11-30 | 2016-02-17 | 东南大学 | Metal fiber felt used for separating emulsifying oil and modification method and application thereof |
| CN105617871A (en) * | 2015-12-23 | 2016-06-01 | 北京航空航天大学 | Preparation of super-wettability cobalt oxide nano-needle porous membrane and application of super-wettability cobalt oxide nano-needle porous membrane to emulsion separation |
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| CN106310718A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院宁波材料技术与工程研究所 | Superhydrophobic-superolephilic porous material as well as preparation method and application thereof |
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| CN105327526A (en) * | 2015-11-30 | 2016-02-17 | 东南大学 | Metal fiber felt used for separating emulsifying oil and modification method and application thereof |
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| CN108992971A (en) * | 2018-07-03 | 2018-12-14 | 福建师范大学 | The preparation method of polyimides water-oil separationg film |
| CN108992971B (en) * | 2018-07-03 | 2021-03-02 | 福建师范大学 | Preparation method of polyimide oil-water separation membrane |
| CN110075570A (en) * | 2019-05-05 | 2019-08-02 | 四川农业大学 | One-step method prepares super hydrophilic/underwater superoleophobic oil-water separation mesh film and method |
| CN112156813A (en) * | 2020-08-21 | 2021-01-01 | 成都理工大学 | Co of double-layer structure2+ZnO material and preparation method thereof |
| CN112494997A (en) * | 2020-10-23 | 2021-03-16 | 浙江海洋大学 | Porous super-hydrophilic oleophobic material |
| CN112494997B (en) * | 2020-10-23 | 2022-03-25 | 浙江海洋大学 | Porous super-hydrophilic oleophobic material |
| CN113304507A (en) * | 2021-06-03 | 2021-08-27 | 黄铭 | The separation of the molecular clusters in the solution realizes the enrichment and separation of different substances |
| CN115069096A (en) * | 2022-07-08 | 2022-09-20 | 辽宁工程技术大学 | Inorganic membrane and preparation method and application thereof |
| CN115069096B (en) * | 2022-07-08 | 2023-03-31 | 辽宁工程技术大学 | Inorganic membrane and preparation method and application thereof |
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