CN110917661B - Method for treating oil-in-water emulsion by using positive electricity enhanced oleophylic hydrophobic three-dimensional porous material - Google Patents
Method for treating oil-in-water emulsion by using positive electricity enhanced oleophylic hydrophobic three-dimensional porous material Download PDFInfo
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Abstract
The invention relates to a method for treating oil-in-water emulsion by using a positive electricity reinforced oleophylic hydrophobic three-dimensional porous material, which comprises the following specific steps: preparing a three-dimensional porous material with the surface rich in positive charge groups and oleophylic and hydrophobic properties, compressing the material into a water-filtering and oil-absorbing device, and treating oil-in-water emulsions with different oil phases, oil-in-water emulsions without emulsifiers and stable oil-in-water emulsions with different charged emulsifiers. The invention aims at that the adsorption capacity of various oils is above 68g/g, and the COD and the oil concentration of various emulsion wastewater can be reduced by more than 80%. The invention can realize the water purification of the emulsion wastewater and the recovery of oil resources at the same time; the application range of the oil-in-water emulsion is wide; the operation is convenient and fast, the operation condition is mild, and the method has the potential of treating the actual waste emulsion.
Description
Technical Field
The invention belongs to the technical field of oily wastewater treatment, and particularly relates to a method for treating oil-in-water emulsion by using a positive electricity reinforced oleophylic hydrophobic three-dimensional porous material.
Background
With the acceleration of the industrialization process, the production amount of the oily wastewater is increasing day by day. Oil pollutants discharged in industrial processes such as machining and the like, particularly waste emulsion, aggravate the pollution problem of oily wastewater and cause serious harm to the environment, economy and human health. Oily wastewater can be divided into floating oil, dispersed oil, emulsified oil and dissolved oil according to the existence state of oil drops in the wastewater. The treatment links of the floating oil and the dispersed oil are relatively easy; the content of the dissolved oil is less, and the dissolved oil can be treated by a biochemical method; the emulsified oily wastewater is difficult to treat due to small droplet particle size and strong stability, and a large amount of emulsifying agents (mostly surfactants) are usually added into the emulsified liquid, and are wrapped on the surfaces of the droplets, so that the surface tension of the system is further reduced, aggregation and coalescence among the droplets are hindered, the stability of the emulsified liquid is enhanced, and the difficulty of oil-water separation is further improved. In the existing industrial application process, the commonly used emulsion treatment method comprises the steps of adding a large amount of flocculating agent, acid precipitation, salting out and the like, and although the method has a certain oil-water separation effect, the problems of large dosage of the agent, poor effluent quality (higher COD value), possibility of secondary pollution and the like still exist. Therefore, research in the field of oily wastewater treatment focuses on finding a simpler and more convenient environment-friendly way for realizing oil-water separation of emulsion.
In recent years, porous materials having oil-water selectivity by wettability modification have been receiving attention from researchers. The three-dimensional porous material has rich pore channel structures and larger specific surface area, increases the contact area with the oily wastewater, and avoids the problem that pore channels are easy to block; meanwhile, due to good elasticity, the oil-water separator can be repeatedly extruded and recycled, and the circulation and the continuity of the oil-water separation process are ensured. Therefore, the application advantages are shown in the field of oil slick adsorption (CN201610123661.2, CN 201610178715.5). In the process, oleophylic and hydrophobic three-dimensional porous materials are mostly adopted, oil drops are firstly attracted by the capillary action of porous channels, and then the oleophylic and hydrophobic properties of the surface and the inner wall are utilized to selectively absorb the oil drops and repel and block the water drops, so that the oil drops are enriched in a porous structure. And after the material is saturated with oil, taking out the material and extruding the material again, separating an oil phase from a material framework under the action of external force, and re-exposing adsorption sites and an oil-rich space of the material to realize recycling.
The oleophylic and hydrophobic three-dimensional porous material can realize good adsorption on floating oil, but aiming at oil-in-water emulsion, the oleophylic and hydrophobic three-dimensional material cannot be well soaked in the emulsion due to a continuous water phase, and forced immersion and other modes are needed; the contact probability between the emulsion dispersed in the continuous water phase and the materials is very limited, which is a great difficulty in the treatment process. Further, for the oil-in-water emulsion containing the emulsifier, the emulsifier layer coated on the outer layer of the oil drops reduces the probability of coalescence among the oil drops and enhances the stability of the system; the emulsifier is usually connected with oil drops in a lipophilic group, and the hydrophilic group is exposed, so that the hydrophilic and hydrophobic effects between the material and the oil drops are weakened, and the treatment difficulty is further improved.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a method for treating an oil-in-water emulsion by using a positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material, which is capable of improving the contact probability of the oil-in-water emulsion and a porous material and preventing a water phase from being adhered to the surface of the porous material, increasing the adsorption of the porous material surface with an anionic emulsion and reducing the stability of an oil-in-water emulsion system.
The technical scheme of the invention is as follows:
a method for treating oil-in-water emulsion by using a positive electricity reinforced oleophylic hydrophobic three-dimensional porous material specifically comprises the following steps:
(1) selecting a three-dimensional material with the pore diameter distributed between 150 and 250 microns, adopting catechol compound to perform oxidative polymerization assembly on the surface of the material to form a polymer coating, and only using polyethyleneimine as a modifier to connect a reactive group on the surface of the coating to form a positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material;
(2) filling the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material obtained in the step (1) into a water and oil absorption device, and compressing the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material to 1/2-1/5 of the original volume for later use;
(3) injecting an oil-in-water emulsion to be treated into the water-filtering oil-absorbing device, and performing suction filtration operation on the oil-in-water emulsion, wherein an oil phase of the oil-in-water emulsion is retained in the porous material, and a water phase in the oil-in-water emulsion is subjected to suction filtration and is collected through a port below the device;
(4) and after the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material is saturated in oil absorption, eluting the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material by using n-butane or ethanol, collecting the eluted oil to realize resource recovery, and reloading the eluted positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material into the device for utilization.
Further, the specific manufacturing method of the positive electricity reinforced oleophylic and hydrophobic three-dimensional porous material in the step (1) comprises the following steps:
(a) soaking the three-dimensional material in an ethanol solution, ultrasonically cleaning for 10-20 min, washing with water, and vacuum drying at 40-60 ℃ for 4-8 h to constant weight to obtain a pretreated three-dimensional material;
(b) adding the catechol compound and polyethyleneimine into a Tris-HCl buffer solution, and ultrasonically dispersing for 2-5 min to prepare a mixed modification solution;
(c) and (b) adding the pretreated three-dimensional material obtained in the step (a) into the mixed modification liquid obtained in the step (b), mechanically stirring at 200-300 rpm for 18-24 h, washing with water, and then drying in vacuum at 40-60 ℃ for 4-8 h until the weight is constant, thereby obtaining the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material.
Further, when the volume of the positive electricity reinforced oleophylic and hydrophobic three-dimensional porous material monolith is 1 multiplied by 1cm3～1×1×3cm3Within the range, the using amount of the catechol compound is 0.2 g-0.4 g, the using amount of the polyethyleneimine is 0.4 g-0.7 g, and the pH value of the Tris-HCl buffer solution is 8-8.5.
Further, the water filtering and oil absorbing process in the step (3) adopts gravity or a low negative pressure driving environment of 0kPa to 5kPa, and the step (2) is carried out under the vacuum condition of-0.8 kPa to-1.2 kPa.
Further, the solid surface Zeta potential isoelectric point of the positive electricity reinforced type oleophylic and hydrophobic three-dimensional porous material is larger than 6.
Further, the water static contact angle of the positive electricity reinforced oleophylic and hydrophobic three-dimensional porous material is larger than 130 degrees, and the oil static contact angle is smaller than 5 degrees.
Further, the three-dimensional material in the step (1) is one or more of melamine sponge, polyurethane or methyl methacrylate-methacrylic acid copolymer.
Further, the catechol compound in the step (1) is one or more of dopamine or dihydroxyphenylpropionic acid.
Further, the oil phase of the oil-in-water emulsion to be treated by the method comprises one or more of liquid paraffin, N-hexane, N-heptane, dichloromethane, chloroform, acetone, methanol, petroleum ether, vacuum pump oil, toluene, N-dimethylformamide or oil slick.
The treatment object using the liquid paraffin as the oil phase includes an emulsifier-free oil-in-water emulsion, an anionic emulsifier-stabilized oil-in-water emulsion, a cationic emulsifier-stabilized oil-in-water emulsion, or a nonionic emulsifier-stabilized oil-in-water emulsion.
The beneficial technical effects of the invention are as follows:
the method designs and prepares a positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material, adopts a water and oil filtering and absorbing operation device with the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material, and promotes an oil-in-water emulsion to flow through pore channels of the hydrophobic oleophylic and positively charged porous material in an accelerated mode through external auxiliary pressurization or by means of gravity action only, wherein in the operation process, charged liquid drops in the oil-in-water emulsion and positively charged groups on the surface of the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material generate electrostatic interaction, and the method specifically comprises the following steps: 1) in emulsifier-free emulsion, oil drops with negative charges are electrostatically attracted by positive groups on the surface of a material 2) in emulsion with stable anionic emulsifier, and the anionic emulsifier on the surface of the emulsified liquid drops is negatively charged and is electrostatically attracted by positive groups on the surface of the material; 3) in the emulsion with stable cationic emulsifier, the cationic emulsifier on the surface of the emulsion drop is charged with positive electricity and is electrostatically repelled by the positive electricity groups on the surface of the material;
through the electrostatic action of the different principles, oil phase in the oil-in-water emulsion is trapped and gathered by the hydrophobic framework of the material to form oil drops, the oil drops are retained in the porous material, water phase in the oil-in-water emulsion is forced to pass through the pore channel of the material to be separated from the emulsion, and then is filtered out in a suction mode, and the oil drops are collected through the interface below the device
The positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material provided by the invention can generate electrostatic action aiming at oil phases of oil-in-water emulsions stabilized by different charged emulsifiers, so that water is forced to pass through pore channels of the material and not to adhere to the surface of the material, and the effective contact probability between the material and oil drops is improved under the drive of the water phase;
the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material ensures effective adsorption of oil drops and repulsion of water phase by using the oleophylic and hydrophobic properties of the material, so that the oil drops are gradually enriched on the surface of the framework and are retained in the pore structure of the material;
particularly, the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material provided by the invention utilizes the action of the positive electricity groups on the surface of the material and the negative electrostatic attraction between anionic emulsifiers to pull liquid drops, so that the stability of an emulsifier layer is damaged, the oil-water separation effect on the oil-in-water emulsion containing the emulsifiers is further enhanced, and a new thought and method are provided for expanding the application field of the three-dimensional porous material from floating oil adsorption to emulsion treatment.
The method utilizes a positive electricity reinforced oleophylic hydrophobic three-dimensional porous material to realize the adsorption of emulsified oil in oil-in-water emulsion through a water filtering and oil absorbing treatment process. Not only reduces the concentration of the effluent oil and the COD value, but also exerts the advantages of high capacity and high enrichment rate of the three-dimensional porous material and realizes the recovery of oil resources.
The method for treating the oil-in-water emulsion by adopting the positive electricity enhanced oleophylic hydrophobic three-dimensional porous material can treat various oil-in-water emulsions with different oil phases, the adsorption capacity is above 68g/g, the reduction of COD (chemical oxygen demand) and oil concentration by more than 80% is realized, and the oil phase after oil-water separation can be enriched in the material, so that the subsequent treatment and recovery are facilitated. Compared with the prior art, the method has the advantages that the water purification of the emulsion wastewater and the recovery of oil resources are realized simultaneously; can treat various oily wastewater containing emulsifier, oil-in-water emulsion, etc.; the operation is convenient, the effective treatment process can be ensured only by external pressure of about-1 kPa, the operation is only required under the normal temperature condition, the advantage of mild operation condition is realized, and the potential of treating the actual waste emulsion is realized.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a positive electricity enhanced oleophilic and hydrophobic three-dimensional porous material designed in example 1 of the present invention;
FIG. 2 is a flow chart of oil-in-water emulsions treated by positively-charged enhanced oleophilic and hydrophobic three-dimensional porous materials according to examples 1, 3 and 5-6 of the present invention;
FIG. 3 is a comparison graph of the solid surface electrification of the positive electricity reinforced oleophilic and hydrophobic three-dimensional porous material prepared in example 1 of the present invention and an unmodified porous material;
FIG. 4 is a graph showing the adsorption effect of the positive electricity-enhanced oleophilic hydrophobic three-dimensional porous material on different oils in example 1 of the present invention;
FIG. 5 is a graph showing the effect of water contact angle and oil contact angle between the positive electric enhanced oleophilic and hydrophobic three-dimensional porous material prepared by the method of the present invention and an unmodified three-dimensional porous material in example 1 of the present invention;
FIG. 6 is a graph comparing the effect of the method of example 2 of the present invention on treating emulsifier-free emulsions with unmodified materials;
FIG. 7 is a solid surface electrification characteristic of the positive electricity enhanced oleophilic hydrophobic three-dimensional porous material prepared by different polyethyleneimine application amounts in example 3 of the present invention;
FIG. 8 is a graph showing the effect of using the method of example 3 to treat oil-in-water emulsions stabilized by different charged emulsifiers;
FIG. 9 is a graph showing the oil concentration reduction ratio of different stable emulsions of charged emulsifiers processed by the method of the present invention in example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The treatment object is oil-in-water emulsion prepared in a laboratory, and the specific preparation method comprises the following steps:
(a) emulsifier-free oil-in-water emulsion: adding 2g of liquid paraffin into a 250ml high-leg beaker, then adding 198ml of aqueous solution, stirring for 4min by a high-speed stirrer at 13000rpm to obtain emulsified liquid with oil concentration of about 9900mg/L, particle size of 6-100 mu m and Zeta potential value of-15-17 mv.
(b) Oil-in-water emulsions stabilized with different charged emulsifiers: in a 250ml high-end beaker, 2g of liquid paraffin in which 0.2g of Sodium Dodecylbenzenesulfonate (SDBS) is dissolved is added, then 198ml of aqueous solution is added, and stirred for 4min by a high-speed stirrer at 13000rpm to obtain the oil-in-water emulsion with stable anionic emulsifier. And respectively replacing the emulsifier SDBS with a cationic emulsifier-cetyltrimethylammonium bromide (CTAB), a nonionic emulsifier-Brij 35 and a nonionic emulsifier-Span 80, wherein the other operation methods and the material dosage are not changed, so that the stable oil-in-water emulsions of different charged emulsifiers are obtained. The respective oil concentration, Zeta potential and particle size parameters are shown in table 1.
TABLE 1 Stable O/W type emulsions of different charged emulsifiers characteristic parameters
(c) Oil-in-water emulsions of different oil phases: the oil-in-water emulsion takes floating oil such as liquid paraffin, N-hexane, N-heptane, dichloromethane, chloroform, acetone, methanol, petroleum ether, vacuum pump oil, toluene, N-Dimethylformamide (DMF), crude oil and the like as an oil phase.
Example 1
Referring to fig. 1-fig. 5, the method for treating oil-in-water emulsion by using positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material and the comparison of the electrification effect of the three-dimensional porous material provided by the invention are as follows: the volume is 1 x 3cm3Soaking Melamine Sponge (MS) with the aperture of 160 mu m in ethanol solution, ultrasonically cleaning for 20min, washing with water, and vacuum drying at 60 ℃ for 4h to constant weight to obtain pretreated melamine sponge; respectively weighing 0.4g of dopamine (PDA) and 0.5g of Polyethyleneimine (PEI), dissolving in 200mL of Tris-HCl buffer solution with the pH value of 8.5, and ultrasonically dispersing for 5min to prepare a mixed modification solution; the pretreated MSAdding into the mixed modifying solution, mechanically stirring at 200rpm for 18h, washing with water, vacuum drying at 60 deg.C for 4h to constant weight to obtain positive electricity reinforced oleophylic hydrophobic three-dimensional porous material, and recording as MSA. The surface electrification of the prepared MSA and the surface electrification of the MS prepared by the method not provided by the invention are respectively measured, the measurement results are shown in figure 3, and as can be seen from figure 3, the surface electropositivity of the positive electricity reinforced type oleophylic hydrophobic three-dimensional porous material prepared for treating the oil-in-water emulsion is obviously higher than that of the MS not treated, so that the positive electricity reinforced type oleophylic hydrophobic three-dimensional porous material has good electrostatic adsorption capacity with an anionic emulsifier. As can be seen from fig. 5, the oil contact angle of the positive electrical enhanced oleophylic and hydrophobic three-dimensional porous Material (MSA) prepared for treating the oil-in-water emulsion is 0 °, the water contact angle is 133 °, the oil contact angle of the unmodified MS is 0 °, and the water contact angle is 0 °, which proves that the positive electrical enhanced oleophylic and hydrophobic three-dimensional porous material prepared for treating the oil-in-water emulsion has good oleophylic and hydrophobic effects, while the porous material not modified by the method of the present invention has no oleophylic property and cannot perform good oil phase adsorption and aggregation effects.
The MSA synthesized as described above was weighed 3 times on a balance and the initial mass m recorded0. Using a 25mL beaker to contain 20mL of oil-in-water emulsion with different oil phases prepared by the method (c), adding a 1cm oil-in-water emulsion3Sponge, fully adsorbing for 30s, taking out and weighing, and recording mass m1. Calculating the unit mass oil absorption of the MSA as (m)1-m0)/m0. Each set of experiments was repeated 3 times and the average was taken as the final result. As a result, as shown in FIG. 4, the MSA adsorbed more than 68g/g of various oils, and the adsorption treatment effect was good.
Example 2
The emulsifier-free oil-in-water emulsion prepared by the method (a) was treated with the MSA prepared in example 1 and the MS which was not subjected to the surface modification treatment in the treatment method provided by the present invention, and the COD value and the oil concentration reduction effect of the filtrate were compared. The specific treatment method comprises the following steps: the synthetic MSA prepared in example 1 was filled into a water-filtered oil-pumping unit and compressed to 1/3 of original volume for use. Preparing the oil-in-water emulsion prepared by the method (a), measuring and recording the COD of the initial emulsionValue and oil concentration. The emulsion was filter-pressed through the material under a low negative pressure drive environment of 0kPa, under a pressure of-1 kPa, 10mL of the filtrate was connected down using a beaker or plastic graduated tube, and the COD value and oil concentration of the filtrate were measured. Using 1 x 3cm3The MSA was replaced with Melamine Sponge (MS), and the above operation was repeated to measure the COD value and oil concentration of the filtrate. As shown in FIG. 6, the COD removal rate and the oil concentration reduction rate were 99.6% and 93.2% respectively by the treatment of the present method; the emulsifier-free oil-in-water emulsion is treated by an unmodified MS material, and the COD removal rate and the oil concentration reduction rate are only about 30 percent.
Therefore, the treatment effect of the three-dimensional porous material subjected to positive electricity strengthening modification and oleophylic and hydrophobic modification on emulsifier-free oil-in-water emulsion is obviously higher than that of the porous material which is not modified by the preparation method for preparing the three-dimensional porous material in the treatment method.
Example 3
Preparing 0 g-0.7 g of positive electricity reinforced three-dimensional porous materials with different PEI application amounts, measuring the surface electrification condition of the materials, treating the emulsions with different electrification emulsifying agents prepared by the (b) method by using the porous materials modified by different PEI, and comparing the oil concentration reduction effects of the emulsions.
The specific operation method comprises the following steps: the positive electricity reinforced three-dimensional porous material prepared in the embodiment is different from the MSA prepared in the embodiment 1 only in that the added PEI has different masses and is respectively provided with gradients of 0g, 0.1g, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g and 0.7g, the porous materials with different positive electricity intensities are prepared, the chargeability of the porous materials is represented, and the result is shown in FIG. 7, and the isoelectric point of the Zeta potential on the surface of the material moves forward along with the increase of the PEI modification amount; when the addition amount of PEI is 0.5g or more, the isoelectric point of the Zeta potential on the surface of the material is more than 6, which shows that the prepared MSA has good anion electrostatic adsorption capacity when the addition amount of PEI is more than or equal to 0.5 g.
MSA prepared from PEI with different mass gradients as described above was filled into the handling device and compressed to 1/3 of the original volume for use. Oil-in-water emulsions stabilized with different charged emulsifiers as described in method (b) were formulated and the oil concentration of the initial emulsion was measured and recorded. The emulsion was filter-pressed through the material under a low negative pressure drive environment of 0kPa, a pressure of-0.8 kPa, 10mL of the filtrate was removed using a beaker or plastic graduated tube, and the oil concentration of the filtrate was measured. The results are shown in FIG. 8, where the treatment effect on the emulsion stabilized with the anionic emulsifier was the best, and the oil concentration reduction rate was 82.1%; the treatment effect on the emulsion stabilized with the cationic emulsifier was the weakest, and the oil concentration reduction rate was 14.5%. Therefore, the positive electricity reinforced oleophylic and hydrophobic three-dimensional porous material prepared by the invention has a better treatment effect on the oil-in-water emulsion with stable anionic emulsifier.
Example 4
The oil concentration reduction was measured using the anionic emulsifier stabilized oil-in-water emulsions prepared by the MSA treatment (b) method prepared with different mass gradients of PEI prepared in example 2 and the results are shown in FIG. 9. As shown in fig. 9, as the PEI modification amount was increased, the oil concentration reduction rate was increased; when the amount of PEI added was 0.5g or more, the reduction of the oil concentration was stabilized at 80% or more. It can be seen that the MSA-treated anionic emulsifier stabilized oil-in-water emulsion prepared when the PEI addition level is 0.5g or more has a good oil-reducing effect.
Example 5
This example differs from example 1 only in that the positively charged reinforcing type oleophilic and hydrophobic three-dimensional porous material used for treating the oil-in-water emulsion is selected from polyurethane with a pore size of 200 μm and a volume of 1X 2cm3Soaking in ethanol solution, ultrasonically cleaning for 10min, washing with water, and vacuum drying at 40 deg.C for 6h to constant weight to obtain pretreated polyurethane; respectively weighing 0.2g of dihydroxyphenylpropionic acid and 0.4g of Polyethyleneimine (PEI), dissolving in 200mL of Tris-HCl buffer solution with the pH value of 8, and ultrasonically dispersing for 2min to prepare a mixed modification solution; and adding the pretreated polyurethane into the mixed modification liquid, mechanically stirring at 250rpm for 24 hours, washing with water, and vacuum drying at 40 ℃ for 6 hours until the weight is constant to obtain the positive electricity reinforced oleophylic and hydrophobic three-dimensional porous material. When the oil-in-water emulsion is treated by using the positively-charged reinforced oleophilic and hydrophobic porous material obtained in the embodiment, the emulsion is subjected to filter pressing through the material under the low negative pressure driving environment of 5kPa and the pressure of-1.2 kPa, so that the porous material is compressed to 1/2 of the original volume.
Example 6
This example differs from example 1 only in that the positively charged reinforcing type oleophilic and hydrophobic three-dimensional porous material used for treating the oil-in-water emulsion is a methyl methacrylate-methacrylic acid copolymer with a pore size of 250 μm and a volume of 1X 1cm3Soaking in ethanol solution, ultrasonically cleaning for 15min, washing with water, and vacuum drying at 40 deg.C for 8h to constant weight to obtain pretreated methyl methacrylate-methacrylic acid copolymer; respectively weighing 0.3g of dopamine (PDA) and 0.7g of Polyethyleneimine (PEI), dissolving in 200mL of Tris-HCl buffer solution with the pH value of 8.25, and ultrasonically dispersing for 4min to prepare a mixed modification solution; and adding the pretreated methyl methacrylate-methacrylic acid copolymer into the mixed modification liquid, mechanically stirring at 300rpm for 20 hours, washing with water, and vacuum drying at 50 ℃ for 8 hours until the weight is constant to obtain the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material. When the oil-in-water emulsion is treated by using the positively charged reinforced oleophilic and hydrophobic porous material obtained in the embodiment, the emulsion is subjected to pressure filtration through the material under the gravity environment and the pressure of-0.9 kPa, so that the porous material is compressed to 1/5 of the original volume.
While the invention has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the embodiments can be combined in any way as long as there is no structural conflict. It is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (7)
1. A method for treating oil-in-water emulsion by using a positive electricity reinforced oleophylic hydrophobic three-dimensional porous material is characterized by comprising the following steps:
(1) selecting a three-dimensional material with the pore diameter distributed between 150 and 250 microns, adopting catechol compound to perform oxidative polymerization assembly on the surface of the material to form a polymer coating, and only using polyethyleneimine as a modifier to connect a reactive group on the surface of the coating to form a positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material;
(2) filling the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material obtained in the step (1) into a water and oil absorption device, and compressing the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material to 1/2-1/5 of the original volume for later use;
(3) injecting an oil-in-water emulsion to be treated into the water-filtering oil-absorbing device, and performing suction filtration operation on the oil-in-water emulsion, wherein an oil phase of the oil-in-water emulsion is retained in the porous material, and a water phase in the oil-in-water emulsion is subjected to suction filtration and is collected through a port below the device;
(4) after the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material is saturated in oil absorption, eluting the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material by using n-butane or ethanol, collecting the eluted oil to realize resource recovery, and reloading the eluted positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material into the device for utilization;
the specific manufacturing method of the positive electricity reinforced oleophylic and hydrophobic three-dimensional porous material in the step (1) comprises the following steps:
(a) soaking the three-dimensional material in an ethanol solution, ultrasonically cleaning for 10-20 min, washing with water, and vacuum drying at 40-60 ℃ for 4-8 h to constant weight to obtain a pretreated three-dimensional material;
(b) adding the catechol compound and polyethyleneimine into a Tris-HCl buffer solution, and ultrasonically dispersing for 2-5 min to prepare a mixed modification solution;
(c) adding the pretreated three-dimensional material obtained in the step (a) into the mixed modification liquid obtained in the step (b), mechanically stirring at 200-300 rpm for 18-24 h, washing with water, and then vacuum drying at 40-60 ℃ for 4-8 h to constant weight to obtain the positive electricity enhanced oleophylic and hydrophobic three-dimensional porous material;
when the volume of the positive electricity reinforced oleophylic hydrophobic three-dimensional porous material monolith is 1 multiplied by 1cm3～1×1×3cm3When the concentration is within the range, the using amount of the catechol compound is 0.2 g-0.4 g, the using amount of the polyethyleneimine is 0.4 g-0.7 g, and the pH value of a Tris-HCl buffer solution is 8-8.5;
the water and oil filtering process of the step (3) adopts gravity or a low negative pressure driving environment of 0kPa to 5kPa, and the step (2) is carried out under the vacuum condition of-0.8 kPa to-1.2 kPa.
2. The method for treating oil-in-water emulsion with the positively charged reinforced lipophilic and hydrophobic three-dimensional porous material of claim 1, wherein the solid surface Zeta potential isoelectric point of the positively charged reinforced lipophilic and hydrophobic three-dimensional porous material is greater than 6.
3. The method of claim 1, wherein the positive electric strengthening type oleophilic and hydrophobic three-dimensional porous material has a water static contact angle of more than 130 ° and an oil static contact angle of less than 5 °.
4. The method for treating oil-in-water emulsion by using the positively charged reinforced lipophilic and hydrophobic three-dimensional porous material according to claim 1, wherein the three-dimensional material in the step (1) is one or more of melamine sponge, polyurethane or methyl methacrylate-methacrylic acid copolymer.
5. The method for treating the oil-in-water emulsion by using the positively charged enhanced lipophilic hydrophobic three-dimensional porous material according to claim 1, wherein the catechol compound in the step (1) is one or more of dopamine or dihydroxyphenylpropionic acid.
6. The method for treating the oil-in-water emulsion with the positive electricity-enhanced lipophilic and hydrophobic three-dimensional porous material, according to claim 1, wherein the oil phase of the oil-in-water emulsion comprises one or more of liquid paraffin, N-hexane, N-heptane, dichloromethane, chloroform, acetone, methanol, petroleum ether, vacuum pump oil, toluene and N, N-dimethylformamide.
7. The method of claim 6, wherein the oil-in-water emulsion with liquid paraffin as an oil phase comprises an emulsifier-free oil-in-water emulsion, an anionic emulsifier-stabilized oil-in-water emulsion, a cationic emulsifier-stabilized oil-in-water emulsion, or a nonionic emulsifier-stabilized oil-in-water emulsion.
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