CN106830431B - Method for treating waste emulsion by combining magnetic nanoparticles and ultrafiltration membrane - Google Patents
Method for treating waste emulsion by combining magnetic nanoparticles and ultrafiltration membrane Download PDFInfo
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Abstract
The invention relates to a method for treating waste emulsion by combining magnetic nanoparticles and an ultrafiltration membrane, which comprises the following specific steps: (1) preparation of functionalized magnetic Fe3O4Nanoparticles; (2) magnetic Fe to functionalize3O4Preparing the nano particles into suspension, mixing the suspension with the waste emulsion, and stirring to obtain a particle-emulsion mixture; (3) performing ultrafiltration demulsification on the particle-emulsion mixture through an ultrafiltration membrane; (4) after demulsification is carried out to realize oil-water separation, separated water and functional magnetic Fe are treated3O4And (4) recovering the nano particles. Compared with the prior art, the flux of the ultrafiltration membrane is improved by 5-22.5 times after the magnetic nanoparticles are mixed with the waste emulsion by adopting the method; the time of the ultrafiltration membrane of the mixed solution of the magnetic nanoparticles and the waste emulsion with the same volume is shortened to 6.7-23%; water after oil-water separation can flow back to the front end to dilute the waste emulsion, so that the waste water utilization is realized; the magnetic nano particles and the oil are separated and then recycled, so that the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of hazardous waste and wastewater and waste liquid treatment, and particularly relates to a method for treating waste emulsion by combining magnetic nanoparticles and an ultrafiltration membrane.
Background
In the machining processes of turning, grinding, cutting, rolling and the like of metallurgy, coking and various machining factories, emulsion is generally used for cooling, lubricating, cleaning and preventing rust so as to improve the quality of products and prolong the service life of machine tools. Due to the action of the surfactant and various auxiliaries in the emulsion, oil drops are dispersed into stable, uniform and fine oil drops, and the formed waste emulsion is extremely difficult to treat, belongs to dangerous waste, and is an unavoidable challenge to treatment at present. At present, the waste emulsion is treated by a multi-stage treatment process mainly by adopting methods such as gravity separation, flocculation, air flotation, advanced oxidation, electrolysis and the like or a combination of a plurality of methods.
Wherein, demulsification, namely the realization of oil-water separation, is the key for treating the waste emulsion. In recent years, the advantages of simple operation, short flow, thorough separation, stable effect, no need of chemical additives, small occupied area, low energy consumption and the like are obvious in the treatment of waste emulsion due to the membrane demulsification for oil-water separation. However, severe membrane fouling not only reduces the efficiency of membrane treatment of emulsion wastewater, but also reduces the membrane lifetime, thereby restricting the widespread use of membrane technology in the field of waste emulsion treatment.
Membrane fouling is often caused by membrane pore clogging due to oil phase formation, solute adsorption, gel layer due to concentration polarization, and the like. Some researchers have been working on solving this problem by modifying the membrane, using changes in surface properties such as membrane wettability, chargeability, etc. to effect waste emulsion treatment; there are also some researchers that use membrane technology in combination with other methods/processes to achieve treatment of waste emulsions, such as membrane technology in combination with electric field, photocatalytic systems, ozone treatment, etc.
Among them, the process research on the combination of nanoparticles and films is in the trend. The existing research focuses on mixing nano particles or depositing the nano particles on the surface of a membrane to treat the waste emulsion in the membrane preparation process, and the method changes the properties of the original membrane through the mixing or deposition of the nano particles, so that a membrane layer formed by the nano particles can play the roles of protection and filtration, and the treatment of the waste emulsion is realized. However, studies indicate that the method of mixing the nanoparticles with the waste emulsion before membrane passing can reduce the membrane flux and increase membrane pollution, and studies have not been satisfactory in effect because the method of mixing the nanoparticles with the waste emulsion before membrane passing is combined with the method of membrane modification to achieve better treatment of the waste emulsion.
Chinese patent CN 104261617A discloses a method for treating waste emulsion, which comprises the following process steps: step one, demulsifying and precipitating; step two, MBR membrane bioreaction; and step three, activated carbon adsorption and UV disinfection. According to the invention, the high-efficiency demulsifier and the flocculant are adopted to effectively remove oil in the waste emulsion, the oil and the water are separated by precipitation, biological treatment is carried out through an anoxic tank and an aerobic zone of an MBR membrane biological treatment system, nitrogen and soluble organic matters in the waste emulsion are effectively removed, solid-liquid separation is carried out through an MBR membrane component, UV ultraviolet disinfection is carried out, and the effluent can be directly discharged, but the problem of membrane pollution still exists in the invention.
Disclosure of Invention
The invention aims to solve the problems, and provides a method for treating waste emulsion by combining magnetic nanoparticles and an ultrafiltration membrane, which improves the membrane flux and shortens the filtration time, practically solves the problem of membrane pollution, realizes the recycling of the magnetic nanoparticles and provides a way for researching the demulsification mechanism of the combination of the magnetic nanoparticles and the ultrafiltration membrane.
The purpose of the invention is realized by the following technical scheme:
a method for treating waste emulsion by combining magnetic nanoparticles and an ultrafiltration membrane specifically comprises the following steps:
(1) preparation of functionalized magnetic Fe3O4Nanoparticles;
(2) magnetic Fe to functionalize3O4Preparing the nano particles into suspension, mixing the suspension with the waste emulsion, and stirring to obtain a particle-emulsion mixture;
(3) performing ultrafiltration demulsification on the particle-emulsion mixture through an ultrafiltration membrane;
(4) after demulsification is carried out to realize oil-water separation, separated water and functional magnetic Fe are treated3O4The nanoparticles are recovered.
The functionalized magnetic Fe in the step (1)3O4The nano particles are prepared by a chemical coprecipitation method, and the surface of the particles is modified with SiO2And NH2The Zeta potential value of the functional group and the particle is 22-30 mv.
The functional magnetic Fe3O4The nanoparticles are prepared by the following steps:
(a) in N2Under the atmosphere, FeSO4·7H2O and FeCl3·6H2Dissolving O in water, heating and stirring, adding ammonia water and stirring when the temperature is 75-85 ℃, separating the precipitate by a magnetic field, and washing by water to obtain Fe3O4；
(b) Mixing Fe3O4Dispersing in the mixed solution of ethanol, water and ammonia water, adding tetraethyl orthosilicate, ultrasonically dispersing, stirring, separating the precipitate by a magnetic field, washing by ethanol, and drying to obtain Fe3O4@SiO2；
(c) Mixing Fe3O4@SiO2Dispersing in toluene solution containing KH-560, ultrasonic dispersing, reacting at 85-95 deg.C for 5-7h, cooling to room temperature, separating precipitate with magnetic field, washing with toluene, dispersing in toluene solution containing excessive triethylene tetramine, stirring, reacting at 45-55 deg.C for 5-7h, washing with ethanol, washing with water, and cold drying to obtain Fe3O4@SiO2@NH2I.e. functionalised magnetic Fe3O4Nanoparticles, designated as MNPs.
FeSO as described in step (a)4·7H2O、FeCl3·6H2The mass ratio of O, water and ammonia water is 1: 1-3: 60-65: 3-4.
Fe described in step (b)3O4And the proportion of the mixed solution to tetraethyl orthosilicate is 1 g: 30-32 ml: 0.5-1.0mL, wherein the volume ratio of ethanol to water to ammonia water in the mixed solution is 60: 15: 1.
fe described in step (c)3O4@SiO2The ratio of the toluene solution containing KH-560 to the toluene solution containing triethylene tetramine is 1 g: 50-55 ml: 50-55ml, wherein the volume ratio of KH-560 to the toluene solution is 1: 50, the volume ratio of triethylene tetramine to toluene solution is 1: 25.
the functionalized magnetic Fe in the step (2)3O4The concentration of the suspension prepared from the nano particles is 5-20g/L, and the functionalized magnetic Fe3O4The volume ratio of the nanoparticle suspension to the waste emulsion is 1:1, the concentration range of the magnetic nanoparticles to the waste emulsion oil drops is 1-4 g/mL.
The volume percentage of the emulsion oil of the waste emulsion in the step (2) is 0.5-5%, the particle size range is 400-5700nm, and the Zeta potential value is-20 to-55 mv.
The pores of the ultrafiltration membrane in the step (3)The diameter is 100-300kDa, and is selected from inorganic Ceramic Membrane (CM) or organic polyether sulfone membrane (PES), and the pressure filtration membrane of the particle-emulsion mixture is N of 1bar2And (4) performing filter pressing, and monitoring the flux of the filtrate in real time by using an electronic balance and a computer.
Refluxing the water obtained after the oil-water separation in the step (4) for diluting the waste emulsion to functionalize the magnetic Fe3O4The nano particles are washed by n-hexane and ethanol, and recovered under the action of an external magnetic field, so that the nano particles can be recycled.
The invention firstly mixes the magnetic nanoparticles with the waste emulsion, the amino-modified positively charged nanoparticles and the negatively charged waste emulsion generate electrostatic interaction, and the nanoparticles reach an oil-water interface. When the concentration range of the magnetic nanoparticles to the waste emulsion oil drops is 1-4g/mL, the nanoparticles can effectively wrap the oil drops, and direct contact between an oil phase and the membrane can be reduced through the organic/inorganic membrane, so that pollution of oil to the membrane is relieved. The method can realize the improvement of the membrane flux and the shortening of the filtration time, does not modify the used organic/inorganic membrane and saves the cost. The pre-mixed magnetic nanoparticles and the waste emulsion are subjected to membrane demulsification, oil and water are separated under the action of an external magnetic field after oil-water separation is realized, the magnetic nanoparticles are recycled, and the cost is reduced.
The invention has the advantages that:
1. compared with a waste emulsion direct ultrafiltration membrane, the magnetic nanoparticles with opposite charges and the waste emulsion can reach an oil-water interface under the action of electrostatic force, when the concentration range of the nanoparticles to oil drops of the waste emulsion is 1-4g/mL, the nanoparticles can effectively wrap the oil drops, the contact between the oil drops and the membrane is reduced, the membrane pollution is reduced, and the flux of the ultrafiltration membrane after the magnetic nanoparticles are mixed with the waste emulsion can be improved by 5-22.5 times; the time of the ultrafiltration membrane of the mixed solution of the magnetic nanoparticles and the waste emulsion with the same volume is shortened to 6.7-23%;
2. the magnetic nanoparticles and the waste emulsion are mixed and then are subjected to ultrafiltration membrane, water after oil-water separation can flow back to the front end to dilute the waste emulsion, the membrane filtration treatment effect is improved, and the concentration range of the magnetic nanoparticles to oil drops of the waste emulsion is controlled to be 1-4g/mL, so that wastewater utilization is realized; the magnetic nano particles are separated from the oil under the action of the external magnetic field and then recycled, so that the cost is reduced;
3. the method for treating the waste emulsion by combining the magnetic nanoparticles with the membrane is suitable for membranes of different types (organic/inorganic) and different pore diameters (100-300kDa), has wide application range, and can effectively intercept the waste emulsion with the average particle size of a dispersed phase of more than 400 nm; meanwhile, the magnetic nano particles do not pass through the membrane, and the COD of the effluent cannot be influenced.
Drawings
FIG. 1 is a schematic flow diagram of the waste emulsion treatment of an embodiment;
FIG. 2 is a graph comparing the flux of PES300kDa and MNP + PES300kDa treated waste emulsion of example 2;
FIG. 3 is a graph showing the comparison of the time taken for equal volumes of waste emulsion of example 2 with and without MNP to pass through PES300 kDa;
FIG. 4 is a graph comparing the flux of PES100kDa versus MNP + PES100kDa treated waste emulsion of example 3;
FIG. 5 is a graph comparing the time elapsed for equal volumes of waste emulsion of example 3 with and without MNP addition to PES100 kDa;
FIG. 6 is a graph comparing the flux of the waste emulsion of the CM150kDa and MNP + CM150kDa treatment of example 4;
FIG. 7 is a graph comparing the time taken for equal volumes of waste emulsion to pass through CM150kDa with and without MNP in example 4;
FIG. 8 is a graph comparing the flux of PES100kDa versus MNP + PES100kDa treatment laboratory formulated emulsions of example 5;
FIG. 9 is a graph comparing the time elapsed for equal volumes of laboratory formulated emulsion of example 5 with and without MNP addition over PES100 kDa;
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The invention treats the waste emulsion by combining magnetic nano particles with an ultrafiltration membrane, and the flow schematic diagram is shown in figure 1, wherein, the functional magnetic Fe3O4The specific preparation method of the nanoparticles (MNP) is as follows:
5.56g of FeSO were weighed out separately4·7H2O and 11.6g FeCl3·6H2O, in N2Dissolved in 350mL of distilled water under stripping, heated in a water bath and vigorously stirred (500rpm), 20mL of aqueous ammonia was added rapidly as the temperature rose to 80 ℃ and the solution was stirred under N2Stirring for 20min under atmosphere, and stopping N2Stirring for 2h, cooling, separating by magnetic field, washing for five times by deionized water to obtain Fe3O4(ii) a Mixing Fe3O4Re-dispersing in a mixed solution of 120mL of ethanol, 30mL of distilled water and 2mL of ammonia water, and performing ultrasonic treatment for 5 min; continuously adding 4mL tetraethyl orthosilicate (TEOS), performing ultrasonic treatment for 5min, mechanically stirring for 6h (500rpm), performing magnetic separation, washing with ethanol for five times, and drying to obtain Fe3O4@SiO2Weighing 2g of Fe3O4@SiO2Dispersing in toluene solution containing 2mL of KH-560, performing ultrasonic dispersion for 30min, then reacting for 6 hours at 90 ℃, cooling to room temperature, performing magnetic separation, washing with toluene for four times, dispersing the obtained product in toluene solution containing 4mL of excessive triethylene tetramine again, mechanically stirring, reacting for 6 hours at 50 ℃, washing with ethanol for three times, washing with deionized water for five times, and freeze-drying the obtained product for 24 hours to obtain the MNP with high amino content.
The prepared magnetic nano particles Fe3O4@SiO2@NH2Dissolving in water by ultrasonic wave to prepare 20g/L suspension, and marking as solution A; diluting the waste emulsion with reflux liquid of water after oil-water separation until the oil concentration is in the range of 0.5-5% (v/v), marking as liquid B, continuously and dropwise adding the liquid A into the liquid B, and enabling the volume ratio of the liquid A to the liquid B to be 1:1, then the mixture was shaken 50 times and stirred with a paddle for 1h (350 rpm).
The target waste emulsion comprises waste emulsion generated by actual machining and emulsion prepared in a laboratory, the waste emulsion generated by the actual machining is obtained by diluting stock solution purchased in the market according to the ratio of 1:19, the main components of the waste emulsion are shown in Table 1, and the particle size of the waste emulsion is about 428 nm; the preparation method of the emulsion prepared in the laboratory comprises the following steps: preparing oil-in-water (O/W) emulsion with paraffin and water, adding 95ml of water solution dissolved with 0.5g of emulsifier Tween 80 into a 250ml high-leg beaker, then adding 5ml of paraffin, stirring for 10min by a high-speed stirrer at the rotating speed of 12000rpm, wherein the particle size is about 5700nm, and the oil concentration range of the target waste emulsion is 0.5-5% (v/v).
TABLE 1 chemical composition Table of commercial semisynthetic emulsions
Example 1
Firstly, preparing synthetic magnetic nano-particles Fe3O4@SiO2@NH2Ultrasonically dissolving the prepared magnetic nanoparticles in water to prepare 20g/L suspension, and marking as solution A; diluting the waste emulsion with a reflux of water after oil-water separation until the oil concentration is 1%, marking as liquid B, continuously dropwise adding the liquid A into the liquid B to mix the liquid A and the liquid B at a ratio of 1:1(v/v), then oscillating the mixed liquid for 50 hours, stirring for 1 hour (350rpm) in a slurry manner, performing ultrafiltration demulsification on the mixed liquid through a membrane of a filtering device, wherein the water after oil-water separation can reflux and dilute the waste emulsion, and further realizing wastewater utilization; on the other hand, the mixture of the magnetic nanoparticles and the oil is washed by normal hexane and ethanol, and the nanoparticles are recovered by magnetic separation, so that the recycling is realized.
Example 2
Selecting a Polyethersulfone (PES) membrane with the diameter of 76mm and the pore diameter of 300kDa and the effective area of 39.57cm2. Putting the mixed solution of MNP and waste emulsion into a pressure tank, and adding the mixed solution into a reactor under the condition of N of 1bar2And filtering the mixed hydraulic pressure through a membrane under a pressure filtration condition, and monitoring the flux of the filtrate in real time by using an electronic balance and a computer. The waste emulsion without MNP was run through a membrane for comparison under the same conditions. The flux of MNP mixed with waste emulsion passing through the membrane is stabilized at 90 L.m-2·h-1·bar-1The time required for filtering 60mL of mixed solution is about 4min, and the emulsions without MNP are respectively 4 L.m-2·h-1·bar-1And 60min, the PES300kDa stable flux after MNP addition is 22.5 times that of MNP, the time for filtering the emulsion with the same volume is about 6.7 percent, the COD removal rate of the waste emulsion directly passing through the membrane is 91.9 percent, and the COD removal rate of MNP and waste emulsion mixed passing through the membrane is 90.7 percent, and the results are shown in figures 2 and 3.
Example 3
Selecting a Polyethersulfone (PES) membrane with the diameter of 76mm and the pore diameter of 100kDa and the effective area of 39.57cm2. Putting the mixed solution of MNP and waste emulsion into a pressure tank, and adding the mixed solution into a reactor under the condition of N of 1bar2And filtering the mixed hydraulic pressure through a membrane under a pressure filtration condition, and monitoring the flux of the filtrate in real time by using an electronic balance and a computer. The waste emulsion without MNP was passed through the membrane under the same conditions, and the flux of MNP mixed with the waste emulsion through the membrane was stabilized at 41 L.m-2·h-1·bar-1The time required for filtering 60mL of mixed solution is about 21min, and the emulsions without MNP are respectively 4 L.m-2·h-1·bar-1And 149min, the PES100kDa stable flux after MNP addition is 10.25 times that without MNP, and the time for filtering the emulsion with the same volume is about 14.1 percent. The COD removal rate of the waste emulsion directly passing through the membrane was 91.2%, and the COD removal rate of the MNP mixed with the waste emulsion passing through the membrane was 90.6%, and the results are shown in FIGS. 4 and 5.
Example 4
Ceramic Membrane (CM) with diameter of 47mm and aperture of 150kDa is selected, and effective area is 10.17CM2. Putting the mixed solution of MNP and waste emulsion into a pressure tank, and adding the mixed solution into a reactor under the condition of N of 1bar2And filtering the mixed hydraulic pressure through a membrane under a pressure filtration condition, and monitoring the flux of the filtrate in real time by using an electronic balance and a computer. Under the same conditions, waste emulsion without MNP is filtered, and the flux of MNP mixed with waste emulsion and filtered by the membrane is stabilized at 16 L.m-2·h-1·bar-1The time required for filtering 30mL of mixed solution is about 68min, and the respective emulsion without MNP is 3.2 L.m-2·h-1·bar-1And 289 min. After MNP is added, the 150kDa stable flux of the ceramic membrane is 5 times that of the ceramic membrane without MNP, the time for filtering the emulsion with the same volume is about 23 percent, and the emulsion is discardedThe COD removal rate of the membrane directly passed through the membrane was 92.2%, and the COD removal rate of the membrane mixed with MNP and waste emulsion was 90.6%, and the results are shown in FIGS. 6 and 7.
Example 5
Selecting a Polyethersulfone (PES) membrane with the diameter of 76mm and the pore diameter of 100kDa and the effective area of 39.57cm2. Putting mixed solution of MNP and laboratory prepared emulsion into a pressure tank, and adding the mixed solution into a reactor under the condition of N of 1bar2Filtering the mixed hydraulic pressure through a membrane under the condition of filter pressing, monitoring the flux of the filtrate in real time by using an electronic balance and a computer, comparing the flux of the mixed emulsion without MNP through the membrane under the same condition, and stabilizing the flux of the mixed emulsion of MNP and the mixed emulsion prepared in the laboratory through the membrane at 66 L.m.-2·h-1·bar-1The time required for filtering 60mL of mixed solution is about 12.4min, and the emulsions without MNP are 10 L.m-2·h-1·bar-1And 64.7 min. PES100kDa stable flux after MNP addition was 6.6 times that without MNP, and the time taken to filter an equal volume of emulsion was about 19%. The COD removal rate of the membrane directly passed through the emulsion prepared in the laboratory was 93%, and the COD removal rate of the membrane mixed with MNP and the emulsion prepared in the laboratory was 96.4%, and the results are shown in FIGS. 8 and 9.
Example 6
A method for treating waste emulsion by combining magnetic nanoparticles and an ultrafiltration membrane comprises the following specific steps:
(1) preparation of functional magnetic Fe by chemical coprecipitation method3O4Nano particle, particle surface modified SiO2And NH2The Zeta potential value of the functional group and the particle is 22-30mv, and the specific steps are as follows:
(a) in N2Under the atmosphere, FeSO4·7H2O and FeCl3·6H2Dissolving O in water, heating and stirring, adding ammonia water and stirring when the temperature is 75 ℃, separating and washing a precipitate magnetic field to obtain Fe3O4Wherein, FeSO4·7H2O、FeCl3·6H2The mass ratio of O, water and ammonia water is 1: 1: 60: 3.
(b) mixing Fe3O4Dispersing in mixture of ethanol, water and ammonia waterAdding tetraethyl orthosilicate into the mixed solution, performing ultrasonic dispersion and stirring, separating the precipitate by a magnetic field, washing by ethanol, and drying to obtain Fe3O4@SiO2Wherein, Fe3O4And the proportion of the mixed solution to tetraethyl orthosilicate is 1 g: 30 ml: 0.5mL, wherein the volume ratio of ethanol to water to ammonia water in the mixed solution is 60: 15: 1.
(c) mixing Fe3O4@SiO2Dispersing in toluene solution containing KH-560, ultrasonic dispersing, reacting at 85 deg.C for 5h, cooling to room temperature, separating precipitate with magnetic field, washing with toluene, dispersing in toluene solution containing excessive triethylene tetramine, stirring, reacting at 45 deg.C for 5h, washing with ethanol, washing with water, and cold drying to obtain MNP, wherein Fe3O4@SiO2The ratio of the toluene solution containing KH-560 to the toluene solution containing triethylene tetramine is 1 g: 50 ml: 50ml, volume ratio of KH-560 to toluene solution 1: 50, the volume ratio of triethylene tetramine to toluene solution is 1: 25.
(2) magnetic Fe to functionalize3O4Preparing nanoparticles into suspension, mixing with waste emulsion, stirring to obtain particle-emulsion mixture, and functionalizing magnetic Fe3O4The concentration of the nano particles prepared into suspension is 5g/L, and the magnetic Fe is functionalized3O4The volume ratio of the nanoparticle suspension to the waste emulsion is 1:1, the concentration range of the magnetic nano particles to the waste emulsion oil drops is 1g/mL, the volume percentage of the waste emulsion oil is 0.5 percent, the particle size range is 400-5700nm, and the Zeta potential value is-20 to-55 mv.
(3) Subjecting the particle-emulsion mixture to ultrafiltration demulsification by ultrafiltration membrane with aperture of 100kDa, and adopting organic polyether sulfone (PES) membrane, and subjecting the particle-emulsion mixture to pressure filtration by membrane filtration with N of 1bar2And (4) performing filter pressing, and monitoring the flux of the filtrate in real time by using an electronic balance and a computer.
(4) After demulsification is carried out to realize oil-water separation, separated water and functional magnetic Fe are treated3O4Recovering nano particles, refluxing water after oil-water separation for diluting waste emulsion, and functionalizing magnetic Fe3O4The nano particles are washed by n-hexane and ethanol and are recovered under the action of an external magnetic field.
Example 7
A method for treating waste emulsion by combining magnetic nanoparticles and an ultrafiltration membrane comprises the following specific steps:
(1) preparation of functional magnetic Fe by chemical coprecipitation method3O4Nano particle, particle surface modified SiO2And NH2The Zeta potential value of the functional group and the particle is 25mv, and the method comprises the following steps:
(a) in N2Under the atmosphere, FeSO4·7H2O and FeCl3·6H2Dissolving O in water, heating and stirring, adding ammonia water and stirring when the temperature is 80 ℃, separating the precipitate by a magnetic field, and washing by water to obtain Fe3O4Wherein, FeSO4·7H2O、FeCl3·6H2The mass ratio of O, water and ammonia water is 1: 2: 62: 3.5.
(b) mixing Fe3O4Dispersing in the mixed solution of ethanol, water and ammonia water, adding tetraethyl orthosilicate, ultrasonically dispersing, stirring, separating the precipitate by a magnetic field, washing by ethanol, and drying to obtain Fe3O4@SiO2Wherein, Fe3O4And the proportion of the mixed solution to tetraethyl orthosilicate is 1 g: 31 ml: 0.6mL, wherein the volume ratio of ethanol to water to ammonia water in the mixed solution is 60: 15: 1.
(c) mixing Fe3O4@SiO2Dispersing in toluene solution containing KH-560, ultrasonic dispersing, reacting at 90 deg.C for 6h, cooling to room temperature, separating precipitate with magnetic field, washing with toluene, dispersing in toluene solution containing excessive triethylene tetramine, stirring, reacting at 50 deg.C for 6h, washing with ethanol, washing with water, and cold drying to obtain MNP, wherein Fe3O4@SiO2The ratio of the toluene solution containing KH-560 to the toluene solution containing triethylene tetramine is 1 g: 50 ml: 51ml, volume ratio of KH-560 to toluene solution 1: 50, the volume ratio of triethylene tetramine to toluene solution is 1: 25.
(2) magnetic Fe to functionalize3O4Preparing nanoparticles into suspension, mixing with waste emulsion, stirring to obtain particle-emulsion mixture, and functionalizing magnetic Fe3O4The concentration of the nano particles prepared into suspension is 10g/L, and the magnetic Fe is functionalized3O4The volume ratio of the nanoparticle suspension to the waste emulsion is 1:1, the volume percentage of the emulsion oil of the waste emulsion is 3 percent, the particle size range is 400-5700nm, and the Zeta potential value is-20 to-55 mv.
(3) Subjecting the particle-emulsion mixture to ultrafiltration demulsification by ultrafiltration membrane with pore diameter of 150kDa, and filtering with inorganic Ceramic Membrane (CM) under pressure of 1bar N2And (4) performing filter pressing, and monitoring the flux of the filtrate in real time by using an electronic balance and a computer.
(4) After demulsification is carried out to realize oil-water separation, separated water and functional magnetic Fe are treated3O4Recovering nano particles, refluxing water after oil-water separation for diluting waste emulsion, and functionalizing magnetic Fe3O4The nano particles are washed by n-hexane and ethanol and are recovered under the action of an external magnetic field.
Example 8
A method for treating waste emulsion by combining magnetic nanoparticles and an ultrafiltration membrane comprises the following specific steps:
(1) preparation of functional magnetic Fe by chemical coprecipitation method3O4Nano particle, particle surface modified SiO2And NH2The Zeta potential value of the functional group and the particle is 30mv, and the method comprises the following steps:
(a) in N2Under the atmosphere, FeSO4·7H2O and FeCl3·6H2Dissolving O in water, heating and stirring, adding ammonia water and stirring when the temperature is 85 ℃, separating a precipitate magnetic field, and washing to obtain Fe3O4Wherein, FeSO4·7H2O、FeCl3·6H2The mass ratio of O, water and ammonia water is 1: 3: 65: 4.
(b) mixing Fe3O4Dispersing in the mixture of alcohol, water and ammonia water, adding tetraethyl orthosilicate, and addingDispersing by sound, stirring, separating the precipitate by magnetic field, washing with ethanol, and oven drying to obtain Fe3O4@SiO2Wherein, Fe3O4And the proportion of the mixed solution to tetraethyl orthosilicate is 1 g: 32 ml: 1.0mL, wherein the volume ratio of ethanol to water to ammonia water in the mixed solution is 60: 15: 1.
(c) mixing Fe3O4@SiO2Dispersing in toluene solution containing KH-560, ultrasonic dispersing, reacting at 95 deg.C for 7h, cooling to room temperature, separating precipitate with magnetic field, washing with toluene, dispersing in toluene solution containing excessive triethylene tetramine, stirring, reacting at 55 deg.C for 7h, washing with ethanol, washing with water, and cold drying to obtain MNP, wherein Fe3O4@SiO2The ratio of the toluene solution containing KH-560 to the toluene solution containing triethylene tetramine is 1 g: 55 ml: 55ml, and the volume ratio of KH-560 to the toluene solution is 1: 50, the volume ratio of triethylene tetramine to toluene solution is 1: 25.
(2) magnetic Fe to functionalize3O4Preparing nanoparticles into suspension, mixing with waste emulsion, stirring to obtain particle-emulsion mixture, and functionalizing magnetic Fe3O4The concentration of the nano particles prepared into suspension is 20g/L, and the magnetic Fe is functionalized3O4The volume ratio of the nanoparticle suspension to the waste emulsion is 1:1, the volume percentage of the emulsion oil of the waste emulsion is 5 percent, the particle size range is 400-5700nm, and the Zeta potential value is-20 to-55 mv.
(3) Subjecting the particle-emulsion mixture to ultrafiltration demulsification by ultrafiltration membrane with aperture of 300kDa, and adopting inorganic Ceramic Membrane (CM) with pressure filtration of 1bar N2And (4) performing filter pressing, and monitoring the flux of the filtrate in real time by using an electronic balance and a computer.
(4) After demulsification is carried out to realize oil-water separation, separated water and functional magnetic Fe are treated3O4Recovering nano particles, refluxing water after oil-water separation for diluting waste emulsion, and functionalizing magnetic Fe3O4The nano particles are washed by n-hexane and ethanol and are recovered under the action of an external magnetic field.
Claims (8)
1. A method for treating waste emulsion by combining magnetic nanoparticles and an ultrafiltration membrane is characterized by comprising the following steps:
(1) preparation of functionalized magnetic Fe3O4Nanoparticles of said functionalized magnetic Fe3O4The nano particles are prepared by a chemical coprecipitation method, and the surface of the particles is modified with SiO2And NH2The Zeta potential value of the particle is 22-30 mv;
(2) magnetic Fe to functionalize3O4Preparing nano particles into suspension, mixing with waste emulsion, stirring to obtain particle-emulsion mixture, and adding the functional magnetic Fe3O4The concentration of the suspension prepared from the nano particles is 5-20g/L, and the functionalized magnetic Fe3O4The volume ratio of the nanoparticle suspension to the waste emulsion is 1:1, enabling the concentration range of the magnetic nanoparticles to waste emulsion oil drops to be 1-4 g/mL;
(3) performing ultrafiltration demulsification on the particle-emulsion mixture through an ultrafiltration membrane;
(4) after demulsification is carried out to realize oil-water separation, separated water and functional magnetic Fe are treated3O4The nanoparticles are recovered.
2. The method for treating the waste emulsion by combining the magnetic nanoparticles with the ultrafiltration membrane according to claim 1, wherein the functionalized magnetic Fe is3O4The nanoparticles are prepared by the following steps:
(a) in N2Under the atmosphere, FeSO4·7H2O and FeCl3·6H2Dissolving O in water, heating and stirring, adding ammonia water and stirring when the temperature is 75-85 ℃, separating the precipitate by a magnetic field, and washing by water to obtain Fe3O4；
(b) Mixing Fe3O4Dispersing in the mixed solution of ethanol, water and ammonia water, adding tetraethyl orthosilicate, ultrasonically dispersing, stirring, separating the precipitate by a magnetic field, washing by ethanol, and drying to obtain Fe3O4@SiO2；
(c) Mixing Fe3O4@SiO2Dispersing in toluene solution containing KH-560, ultrasonic dispersing, reacting at 85-95 deg.C for 5-7h, cooling to room temperature, separating precipitate with magnetic field, washing with toluene, dispersing in toluene solution containing excessive triethylene tetramine, stirring, reacting at 45-55 deg.C for 5-7h, washing with ethanol, washing with water, and cold drying to obtain Fe3O4@SiO2@NH2I.e. functionalised magnetic Fe3O4Nanoparticles.
3. The method for treating the waste emulsion by combining the magnetic nanoparticles with the ultrafiltration membrane according to claim 2, wherein the FeSO obtained in the step (a)4·7H2O、FeCl3·6H2The mass ratio of O, water and ammonia water is 1: 1-3: 60-65: 3-4.
4. The method of claim 2, wherein the Fe in step (b) is used as the Fe component in the waste emulsion treatment process3O4And the proportion of the mixed solution to tetraethyl orthosilicate is 1 g: 30-32 ml: 0.5-1.0mL, wherein the volume ratio of ethanol to water to ammonia water in the mixed solution is 60: 15: 1.
5. the method of claim 2, wherein the Fe in step (c) is used for treating the waste emulsion by combining the magnetic nanoparticles with the ultrafiltration membrane3O4@SiO2The ratio of the toluene solution containing KH-560 to the toluene solution containing triethylene tetramine is 1 g: 50-55 ml: 50-55ml, wherein the volume ratio of KH-560 to the toluene solution is 1: 50, the volume ratio of triethylene tetramine to toluene solution is 1: 25.
6. the method for treating the waste emulsion by combining the magnetic nanoparticles and the ultrafiltration membrane as claimed in claim 1, wherein the volume percentage of the emulsion oil of the waste emulsion in the step (2) is 0.5-5%, the particle size range is 400-5700nm, and the Zeta potential value is-20-55 mv.
7. The method for treating the waste emulsion by combining the magnetic nanoparticles with the ultrafiltration membrane as claimed in claim 1, wherein the ultrafiltration membrane in the step (3) has a pore size of 100kDa and 300kDa, and is selected from an inorganic ceramic membrane or an organic polyethersulfone membrane, and the filter-pressed membrane of the particle-emulsion mixture is N at 1bar2Under the condition of filter pressing.
8. The method for treating the waste emulsion by combining the magnetic nanoparticles and the ultrafiltration membrane according to claim 1, wherein the water reflux obtained after the oil-water separation in the step (4) is used for diluting the waste emulsion to functionalize the magnetic Fe3O4The nano particles are washed by n-hexane and ethanol and are recovered under the action of an external magnetic field.
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| CN112138430B (en) * | 2020-09-07 | 2022-04-15 | 同济大学 | Magnetic nanorod demulsifier, preparation method thereof and method for treating nanoemulsion by using magnetic nanorod demulsifier |
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