CN108568289B - Method for preparing carbon-copper coated ferroferric oxide composite magnetic oil removal particles - Google Patents

Method for preparing carbon-copper coated ferroferric oxide composite magnetic oil removal particles Download PDF

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CN108568289B
CN108568289B CN201810366392.1A CN201810366392A CN108568289B CN 108568289 B CN108568289 B CN 108568289B CN 201810366392 A CN201810366392 A CN 201810366392A CN 108568289 B CN108568289 B CN 108568289B
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ferroferric oxide
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CN108568289A (en
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刘泰奇
李志杰
史桂梅
陈旭
陈鑫力
李懿霖
王晓燕
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Shenyang University of Technology
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Abstract

The invention discloses a method for preparing carbon-copper coated ferroferric oxide composite magnetic oil removal particles, which comprises the steps of modifying ferroferric oxide, introducing a carbon source, adding a lubricant, an emulsifying agent, a thickening agent and a stabilizing agent, and performing heat treatment to prepare Fe3O4@ C/Cu composite magnetic degreasing particles. The invention solves the technical problems of complicated preparation process, incapability of mass production and the like of the floating oil cleaning technology. The particle prepared by the method has high surface carbonization degree and stable carbon layer, and can be produced in large batch to provide a good particle preparation method for solving the problem of oil slick on the water surface.

Description

Method for preparing carbon-copper coated ferroferric oxide composite magnetic oil removal particles
The technical field is as follows:
the invention belongs to the field of nanometer preparation, and particularly relates to a method for preparing carbon-copper coated ferroferric oxide composite magnetic oil removal particles.
Background art:
petroleum causes environmental pollution, especially water pollution, in the processes of production, transportation, storage, refining and use. With the stricter and stricter water quality standards and regulations, the technology for cleaning the floating oil on the water surface is more and more comprehensive, but the technology for effectively solving the large-area oil layer with the thickness of less than 50 mu m is still a technical problem. Nano iron oxide materials, which have high hydrophobicity, high lipophilicity through surface modification or combination with functional materials and can be recovered from water surface under an external magnetic field against viscous resistance, surface tension and gravity, have become the first choice for dealing with the above problems. The nano iron oxide material for treating the water surface thin oil layer mainly comprises magnetic oil absorption foam, magnetic oil absorption sponge and magnetic oil absorption particles. The magnetic oil absorption foam and the magnetic oil absorption sponge depend on an oil removal device and cannot be used for oil removal operation on a wide sea surface. Magnetic oil-absorbing particles become the best choice. For coating Fe3O4The nano-particle material mainly comprises inorganic oxide and high molecular polymer, and the carbon shell has higher stability in a special environment, so that the nano-particle material not only can effectively shield the interaction of dipoles, but also can well interact with metal ions. However, most of the auxiliary materials for synthesizing the compounds are high-molecular compounds, and the preparation process is complicated, the temperature resistance is poor, and the mass production cannot be realized.
The invention content is as follows:
the purpose of the invention is as follows:
the invention provides a method for preparing carbon-copper coated ferroferric oxide (Fe)3O4@ C/Cu) composite magnetic oil removing particle method, which aims to solve the technical problem of recovery treatment of floating oil on water surface. The invention mainly prepares the carbon-copper coated ferroferric oxide composite magnetic oil removal particles by a hydrothermal method and a high-temperature carbonization method, and commercially available pure Fe is used3O4The nano-particles are used as an inner core; modifying with citric acid solution to make it easy to introduce functional group on the surface; dispersing and emulsifying the particles by using easily available, cheap and environment-friendly span-60 as a dispersing agent; preparing a shell by anaerobic decomposition and carbonization of edible glucose at 450 ℃; adding basic carbon easy to high-temp. decompositionThe acid copper helps the adsorption and reutilization of the acid copper on oil. The preparation process is simple and suitable for large-scale production, and the material has high hydrophobicity, lipophilicity and temperature resistance, and is a novel nano material for cleaning floating oil pollution on water surface.
The technical scheme is as follows:
a method for preparing carbon-copper coated ferroferric oxide composite magnetic oil removal particles comprises the following specific steps:
the method comprises the following steps: preparing 0.1mol/L citric acid modified solution: preparing distilled water and absolute ethyl alcohol according to a volume ratio of 4:1 as a solvent, heating in a water bath at 50-70 ℃ for 5-10 min, and stirring until the distilled water and the absolute ethyl alcohol are completely dissolved to obtain 0.1mol/L citric acid modified solution;
step two: preparing a saturated glucose solution;
step three: preparing a span-60 solution: preparing a span-60 solution with the concentration of 0.4-0.5 g/mL, heating in a water bath at 50-70 ℃ for 5-10 min, and stirring until the span-60 solution is completely dissolved to obtain the span-60 solution with the concentration of 0.4-0.5 g/mL;
step four: modified ferroferric oxide: putting the ferroferric oxide nano particles into 0.1mol/L citric acid modified solution, wherein the ratio of ferroferric oxide to citric acid is (4-5): 2-3, heating in a water bath for 50-70 ℃, heating for 7-9 hours, stirring or ultrasonically treating for 5 minutes every 1 hour, sucking the bottom of the container by using a magnet after heating, so that the ferroferric oxide nanoparticles cannot be lost along with water flow, pouring out a beaker to remove supernatant, heating in the water bath at the temperature of 50-70 ℃ during cleaning by using excessive distilled water, stirring for 5-10 minutes, pouring out the supernatant, repeating the method for 2-3 times in the same way as the method for pouring out the supernatant to obtain a modified ferroferric oxide sticky matter;
step five: introducing a carbon source: pouring a saturated glucose solution into the modified ferroferric oxide sticky matter, wherein the molar ratio of the ferroferric oxide to the glucose is 1: 1.16-1.25, heating in a water bath at 50-70 ℃, and stirring for 20-40 min to obtain a glucose suspension coated with the ferroferric oxide;
step six: introducing a lubricant: adding basic copper carbonate into a ferroferric oxide-coated glucose suspension, wherein the molar ratio of the ferroferric oxide-coated glucose to the basic copper carbonate is 10-12: 1, heating in a water bath at 50-70 ℃, and stirring for 8-15 minutes to obtain a mixed suspension solution;
step seven: adding emulsifying and thickening agents: adding span-60 solution into the mixed suspension solution, wherein the volume ratio of the mixed suspension solution to the span-60 solution is 8-10: 1, heating in a water bath at 50-70 ℃, and stirring for 8-15 minutes to obtain low-viscosity suspension;
step eight: adding a stabilizer: adding sodium chloride into the viscous suspension, wherein the mass ratio of the sodium chloride to the added glucose is 2-3: 100, heating in a water bath at 50-70 ℃, and stirring for 120 minutes to obtain high-viscosity suspension;
step nine: drying the high-viscosity suspension at 50-70 ℃ for 10-15 h, and grinding into powder to obtain powder;
step ten: and (3) heat treatment: the first stage of heat treatment: (1) heating from room temperature to 200 ℃ at 2 ℃/min, (2) heating from 200 ℃ to 300 ℃ at 1 ℃/min, (3) heating from 300 ℃ to 400 ℃ at 2 ℃/min;
and (3) a second stage of heat treatment: (4) heating from 400 ℃ to 450 ℃ at the speed of 2 ℃/min, (5) keeping the temperature of 450 ℃ for 30min to obtain high-temperature carbonized aggregates,
in the heat treatment stage, high-purity nitrogen is kept introduced to prevent ferroferric oxide from being oxidized, and the ventilation volume is 1-1.5L/min;
step eleven: crushing the high-temperature carbonized aggregate: treating the high-temperature carbonized aggregate for 1-2 min under a 3000-3500 r/min pulverizer to obtain powder;
step twelve: fe3O4@ C/Cu composite magnetic oil removal particles: washing the powder with excessive water for 2-5 times to remove floating substances on the water surface, rinsing with absolute ethyl alcohol for 1-2 times to remove liquid, putting the powder into a blast drying oven, drying at 50-70 ℃ for 5-7 hours, and screening the powder with a 400-mesh sieve to obtain Fe3O4@ C/Cu composite magnetic degreasing particles.
The method for preparing the carbon-copper coated ferroferric oxide composite magnetic oil removing particles and the prepared Fe3O4The @ C/Cu composite magnetic oil removal particles can be suspended on the water surface and are nearly positiveHexahedral shape.
The method for preparing the carbon-copper coated ferroferric oxide composite magnetic oil removal particles comprises the following specific preparation method of a saturated glucose solution in the step two: weighing 15.0-20.0 g of glucose at room temperature, putting the glucose into a beaker, adding 15-20 ml of distilled water, heating in a water bath at 50-70 ℃, and stirring to completely dissolve the glucose until the solution is clear to obtain a saturated glucose solution.
The advantages and effects are as follows:
the particle prepared by the method has high surface carbonization degree and stable carbon layer, and has the protection effect of nitrogen during sintering, so that the ferroferric oxide is not damaged by oxidation, the particles still have strong magnetic response, and the method can be used for mass production and provides a good particle preparation method for solving the problem of oil slick on the water surface.
Solves the dependence of the conventional treatment method on treatment equipment, and the particles produced by the method can be operated on a wide sea surface and can be recovered by an external magnetic field, so the method is simple, has strong controllability and can be used for preparing Fe in an industrialized production manner3O4A method for @ C/Cu composite magnetic oil removing particles.
Fe prepared by the invention3O4Compared with the existing foam, sponge and the like for treating the floating oil, the @ C/Cu composite magnetic oil removing particle is not limited by a device, is not limited by regions and water areas when used, can be used in a large area, can effectively solve the problem of large-area floating oil with the oil layer thickness of less than 50 microns, and still retains higher magnetic response, so that simple, quick and efficient recovery can be achieved by adopting simple magnetic equipment.
Description of the drawings:
FIG. 1 is Fe3O4A preparation flow chart of @ C/Cu composite magnetic oil removing particles;
FIG. 2 is Fe3O4An XRD (X-ray diffraction analysis) pattern of @ C/Cu composite magnetic degreasing particles;
FIG. 3 is Fe3O4FT-IR spectrogram of @ C/Cu composite magnetic oil removing particles and pure ferroferric oxide;
FIG. 4 is Fe3O4@ C/Cu compositeVSM (vibration sample magnetic strength analysis) plot of resultant magnetic degreasing particles;
FIG. 5 is Fe3O4A low resolution SEM (scanning electron microscope) picture of @ C/Cu composite magnetic degreasing particles;
FIG. 6 is Fe3O4A high resolution SEM (scanning electron microscope) picture of @ C/Cu composite magnetic degreasing particles;
FIG. 7 is Fe3O4The differential thermal analysis curve chart of the @ C/Cu composite magnetic oil removing particles and diesel oil, kerosene and engine oil adsorbed by the particles.
The specific implementation mode is as follows:
the invention is further described below with reference to the accompanying drawings:
the invention provides a method for preparing carbon-copper shell layer coated Fe3O4The high-temperature carbonization method of the magnetic oil removing particles on the suspended water surface is an effective method for preparing the coated nano particles, can carbonize glucose into a carbon shell layer, is a simple and controllable method for preparing the magnetic oil removing particles, and belongs to the field of nano preparation.
Example 1
As shown in FIG. 1, FIG. 1 is Fe3O4A preparation flow chart of @ C/Cu composite magnetic oil removing particles.
In the preparation of 0.1mol/L citric acid modified solution, 0.600g of citric acid is weighed by an electronic balance and put into a beaker, 20ml of distilled water and 4ml of absolute ethyl alcohol are added, the beaker is put into a water bath heating pot and heated for 5-10 min at the water temperature of 60 ℃, and the solution is stirred until the solution is completely dissolved, so that 0.1mol/L citric acid modified solution is obtained.
When preparing a saturated glucose solution, firstly weighing 15.0-20.0 g of glucose by using an electronic balance, putting the weighed glucose into another beaker, then adding 15-20 ml of distilled water, putting the beaker into a water bath heating pot, heating the beaker at the temperature of 60 ℃, and stirring the beaker to completely dissolve the glucose until the solution is clear, thus obtaining the saturated glucose solution.
When preparing the span-60 solution, firstly weighing 0.8-1.0 g of span-60 by using an electronic balance, putting the weighed span-60 into a third beaker, adding 2-4 ml of absolute ethyl alcohol, putting the beaker into a water bath heating pot, heating the beaker at the temperature of 60 ℃, and stirring the beaker to completely dissolve the absolute ethyl alcohol until the solution is clear, thus obtaining the span-60 solution.
When the ferroferric oxide is modified, firstly, 10.0g of ferroferric oxide nanoparticles are weighed and then added into 0.1mol/L citric acid modified solution, a beaker is placed into a water bath heating pot to be heated for 8 hours at the water temperature of 60 ℃, stirring or ultrasonic treatment is carried out for 5 minutes every 1 hour in the process, after 8 hours, the bottom of the beaker is attracted by a magnet, so that the ferroferric oxide nanoparticles cannot be lost along with water flow, the beaker is poured to remove supernatant, the beaker is washed by excessive distilled water, the beaker is placed into the water bath heating pot to be heated and stirred for 5 minutes at the water temperature of 60 ℃, the method of pouring the supernatant is repeated for 2-3 times in the same way as the method, and the modified ferroferric oxide sticky matter is obtained.
Pouring the beaker filled with the saturated glucose solution into the beaker filled with the modified ferroferric oxide sticky matter, then putting the beaker into a water bath heating pot, heating at the water temperature of 60 ℃, and stirring for 30 minutes to obtain the suspension of the ferroferric oxide @ glucose.
Adding 0.3-0.4 g of basic copper carbonate into a beaker filled with ferroferric oxide @ glucose turbid liquid, then putting the beaker into a water bath heating pot, heating at the water temperature of 60 ℃, and stirring for 10 minutes to obtain a mixed suspension solution. The basic copper carbonate is added to facilitate the treatment effect on the engine oil and has a lubricating effect.
Pouring the beaker filled with the span-60 solution into the beaker filled with the mixed suspension solution, then putting the beaker into a water bath heating pot, heating at the water temperature of 60 ℃ and stirring for 10 minutes to obtain a low-viscosity suspension. Adding span-60 mesh to change the mixed solution into emulsion so as to ensure that the ferroferric oxide is fully contacted with glucose.
And adding 0.30-0.50 g of sodium chloride into the beaker filled with the low-viscosity suspension, then putting the beaker into a water bath heating pot, heating at the water temperature of 60 ℃, and stirring for 120 minutes to obtain the high-viscosity suspension. Sodium chloride is added to make the carbon shell coated with ferroferric oxide more stable.
The beaker after heating in a water bath for 2 hours is placed in a forced air oven to dry at 60 ℃ for 12 hours, and the dried granules are poured out (possibly hard and requiring sharp instruments such as a flat screwdriver) and put into powder with a mill pulverizer.
Putting the powder into a tubular sintering furnace for high-temperature carbonization heat treatment: the first stage of heat treatment: (1) heating from room temperature (23 ℃) to 200 ℃ at 2 ℃/min; (2) heating from 200 deg.C to 300 deg.C at 1 deg.C/min; (3) heating from 300 ℃ to 400 ℃ at 2 ℃/min. And (3) a second stage of heat treatment: (1) heating from 400 deg.C to 450 deg.C at 2 deg.C/min; (2) keeping the temperature at 450 ℃ for 30 min. During the period, high-purity nitrogen is required to be introduced to prevent the ferroferric oxide from being oxidized, and the ventilation volume is 1.5L/min. The effect of the heat treatment is to facilitate the formation of the main phase; the first stage of heat treatment is to further dry the powder; the second stage of heat treatment is mainly to accelerate the carbonization of the powder by volatile organic compounds.
And taking the high-temperature carbonized aggregate out of the tubular sintering furnace, and treating the aggregate for 2 minutes at 3400r/min by using a high-speed pulverizer to obtain powder.
Pouring the powder into a clean beaker, washing twice with excessive water, sucking the bottom of the beaker by a magnet during the washing so that the ferroferric oxide nano particles cannot be lost along with water flow, pouring the beaker to remove supernatant, removing floating matters on the water surface, and rinsing once with absolute ethyl alcohol. Finally, the beaker is put into an air-blast drying oven to be dried for 6 hours at the temperature of 60 ℃, and then the powder is screened by a 400-mesh sieve to obtain the final Fe3O4@ C/Cu composite magnetic degreasing particles. The water washing and the alcohol washing are carried out for effectively removing organic impurities which are not coated on the ferroferric oxide after the glucose is carbonized.
For Fe prepared in example 13O4A series of performance tests were carried out on the @ C/Cu composite magnetic oil removal particles, and the results were as follows:
as shown in FIG. 2, core-shell nanoparticles are mixed with pure Fe3O4The diffraction peaks corresponding to the nanoparticles are weak, but the pure copper peaks at (200) and (111) confirm that basic copper carbonate decomposes to copper attached to the carbon layer during high temperature carbonization.
As shown in fig. 3, the FT-IR spectrum reveals the nature of the bonds formed between the atoms. At 3425cm-1The peak at (A) shows the presence of-COOH and-OH groups at 2359cm-1The nearby peak is the vibration of C ≡ C, and the existence of alkyne proves that the ferroferric oxide surface contains functional groups easy to carbonize in the heat treatment because hydrogen atoms in the alkyne are very active and are easily replaced by metal to form an acetylide, 1626cm-1The peak at (A) corresponds to the shaking of C ═ C, which reflects the carbonization of glucose at 1181cm-1And 1135cm-1The peak at (B) is shifted to the right into 1148cm-1And 1110cm-1Indicating the original Fe3O4The functional groups on the surface of the particles are coordinated and interacted and successfully modified, and the length of the functional groups is 1024cm-1The nearby C-C peak is attributed to the residue of partial alcohol compounds, and it is worth mentioning that C ≡ C, C ═ C, C-C is nonpolar functional group, and they are attached on the surface of the particle to make the particle contact with water molecules, break the ordered structure of the surrounding water molecules to increase entropy and obtain thermodynamic stability to achieve hydrophobic or hydrophobic effect, and finally, the particles are mixed with pure Fe3O4In comparison, 563cm-1The vibration peak in the vicinity is Fe3O4Moderate Fe-O vibration, but the vibration peak is obviously weakened and slightly shifted to the right, which indicates that Fe3O4The surface produces a coating effect. Also describes the Fe prepared3O4The @ C/Cu composite magnetic oil removal particles can suspend the water surface.
As shown in FIG. 4, core-shell nanoparticles are mixed with pure Fe3O4Compared with the nano-particles, the maximum magnetic energy level is reduced by 27.6%, which shows that the carbon layer has influence on the magnetic performance, but the remanence, the coercive force and the magnetic conductivity have little influence, and the particles can still keep high magnetic response to an external magnetic field, which shows that the particles still have stronger adsorption capacity. Fe produced by the method3O4The @ C/Cu composite magnetic oil removal particles can be used for large-area oil removal operation on wide sea and can be recovered through an external magnetic field, so that the method is simple, strong in controllability and capable of industrially producing the prepared Fe3O4A method for @ C/Cu composite magnetic oil removing particles.
As can be seen from FIGS. 5 and 6, Fe is present at low resolution3O4The @ C/Cu composite magnetic oil removing particles have good dispersibility, and Fe is prepared under high resolution3O4The @ C/Cu composite magnetic oil removal particles are close to a regular hexahedron shape, and it can be seen that the particles have rough surfaces and large specific surface areas, so that the adsorption effect of the particles on oil in water is promoted.
As shown in fig. 7, the weight loss of the particles is the largest when the particles are adsorbed on kerosene at 163.4 ℃, which reaches 20.11%, the particles show stronger adsorption capacity on kerosene, the second phase of the weight loss is not ended at 454.5 ℃, which increases the temperature resistance of 54.5 ℃ compared with the initial particles, and the weight loss of the particles is a continuous process when the particles are adsorbed on engine oil, until 423.8 ℃, the weight loss is stabilized to 50.71%, which shows that the engine oil has better penetration effect on the particles, and in contrast, the particles also have a certain adsorption effect on diesel oil, and the weight loss is 10.08% at 213.2 ℃, but compared with the initial sample, the particles start the second phase when the temperature of the particles is 303.06 ℃, which shows that the oil product is subjected to weight loss secondary coating at the time of carbonization and aromatization, the weight loss of the particles is promoted, and the weight loss reaches stability at 430.6 ℃, and the temperature resistance is improved by 7.7% compared with the original particles. Fe can be seen from the differential thermal analysis curve of FIG. 63O4The @ C/Cu composite magnetic oil removal particles have good adsorption capacity for diesel oil, kerosene and engine oil, especially for engine oil and kerosene. The marine pollution is mainly petroleum, so the three oils are selected as representatives, and Fe is used for adsorbing the three oils3O4The @ C/Cu composite magnetic degreasing particles can also adsorb other pollutants, such as domestic oil stains, mineral oil and the like.
Example 2
A method for preparing carbon-copper coated ferroferric oxide composite magnetic oil removal particles is characterized by comprising the following steps: the method comprises the following specific steps:
the method comprises the following steps: preparing 0.1mol/L citric acid modified solution: preparing distilled water and absolute ethyl alcohol according to a volume ratio of 4:1 as a solvent, heating in a water bath at 50 ℃ for 5min, and stirring until the distilled water and the absolute ethyl alcohol are completely dissolved to obtain a 0.1mol/L citric acid modified solution;
step two: preparing a saturated glucose solution: weighing 15.0g of glucose at room temperature, putting the glucose into a beaker, adding 15ml of distilled water, heating in a water bath at 50 ℃, and stirring to completely dissolve the glucose until the solution is clear to obtain a saturated glucose solution;
step three: preparing a span-60 solution: preparing a span-60 solution with the concentration of 0.4g/mL, heating for 5min in a water bath at 50 ℃, and stirring until the span-60 solution is completely dissolved to obtain the span-60 solution with the concentration of 0.4 g/mL;
step four: modified ferroferric oxide: putting 10.0g of ferroferric oxide nano particles into 0.1mol/L citric acid modified solution, wherein the ratio of ferroferric oxide to citric acid is 4:3 according to the molar ratio, heating the mixture in a water bath at 50 ℃ for 7 hours, stirring or ultrasonically treating the mixture every 1 hour for 5 minutes, sucking the bottom of a container by using a magnet after heating to ensure that the ferroferric oxide nano particles are not lost along with water flow, pouring a beaker to remove supernatant, heating the mixture in the water bath at the water temperature of 50 ℃ during washing by using excessive distilled water, stirring the mixture for 5 minutes, pouring the supernatant, repeating the method for 2 times as the method for obtaining the modified ferroferric oxide;
step five: introducing a carbon source: pouring a saturated glucose solution into the modified ferroferric oxide viscous substance, wherein the molar ratio of the ferroferric oxide to the glucose is 1:1.16, heating in a water bath at 50 ℃, and stirring for 20min to obtain a glucose suspension coated with ferroferric oxide;
step six: introducing a lubricant: adding basic copper carbonate into a ferroferric oxide-coated glucose suspension, wherein the molar ratio of the ferroferric oxide-coated glucose to the basic copper carbonate is 10:1, heating in a water bath at 50 ℃, and stirring for 8 minutes to obtain a mixed suspension solution;
wherein, the basic copper carbonate precipitates when more basic copper carbonate is added, and EDS (electron-discharge spectroscopy) shows that the addition amount of the basic copper carbonate is about 10 percent of the mass of the ferroferric oxide and is uniformly distributed;
step seven: adding emulsifying and thickening agents: adding span-60 solution into the mixed suspension solution, wherein the volume ratio of the mixed suspension solution to the span-60 solution is 6:1.6, heating in a water bath at 50 ℃ and stirring for 8 minutes to obtain low-viscosity suspension;
step eight: adding a stabilizer: adding sodium chloride into the viscous suspension, wherein the mass ratio of the sodium chloride to the added glucose is 2:100, heating in a water bath at 50-70 ℃, and stirring for 120 minutes to obtain high-viscosity suspension;
wherein the sodium chloride is used for stabilizing the carbon shell, and the added mass of the sodium chloride is preferably 2-3% of the added mass of glucose in the added saturated glucose solution;
step nine: drying the high-viscosity thick suspension at 50 ℃ for 10h, and grinding into powder to obtain powder;
step ten: and (3) heat treatment: the first stage of heat treatment: (1) heating from room temperature to 200 ℃ at 2 ℃/min, (2) heating from 200 ℃ to 300 ℃ at 1 ℃/min, (3) heating from 300 ℃ to 400 ℃ at 2 ℃/min;
and (3) a second stage of heat treatment: (4) heating from 400 ℃ to 450 ℃ at the speed of 2 ℃/min, and (5) keeping the temperature of 450 ℃ for 30min to obtain high-temperature carbonized aggregates;
in the heat treatment stage, high-purity nitrogen is kept introduced to prevent ferroferric oxide from being oxidized, and the ventilation volume is 1L/min;
step eleven: crushing the high-temperature carbonized aggregate: treating the high-temperature carbonized aggregate with a pulverizer at 3000r/min for 2min to obtain powder;
step twelve: fe3O4@ C/Cu composite magnetic oil removal particles: washing the powder with excessive water for 2 times to remove floating substances on water surface, rinsing with anhydrous ethanol for 1 time to remove liquid, drying in a forced air drying oven at 50 deg.C for 5 hr, and sieving with 400 mesh sieve to obtain Fe3O4@ C/Cu composite magnetic degreasing particles.
Example 3
A method for preparing carbon-copper coated ferroferric oxide composite magnetic oil removal particles is characterized by comprising the following steps: the method comprises the following specific steps:
the method comprises the following steps: preparing 0.1mol/L citric acid modified solution: preparing distilled water and absolute ethyl alcohol according to a volume ratio of 4:1 as a solvent, heating in a water bath at 70 ℃ for 10min, and stirring until the distilled water and the absolute ethyl alcohol are completely dissolved to obtain a 0.1mol/L citric acid modified solution;
step two: preparing a saturated glucose solution: weighing 20.0g of glucose at room temperature, putting the glucose into a beaker, adding 20ml of distilled water, heating in a water bath at 70 ℃, and stirring to completely dissolve the glucose until the solution is clear to obtain a saturated glucose solution;
step three: preparing a span-60 solution: preparing a span-60 solution with the concentration of 0.5g/mL, heating for 10min in a water bath at 70 ℃, and stirring until the span-60 solution is completely dissolved to obtain the span-60 solution with the concentration of 0.5 g/mL;
step four: modified ferroferric oxide: putting the ferroferric oxide nano particles into 0.1mol/L citric acid modified solution, wherein the ratio of ferroferric oxide to citric acid is 5:2 according to the molar ratio, heating the ferroferric oxide nano particles in a water bath at 70 ℃ for 9 hours, stirring or ultrasonically treating the ferroferric oxide nano particles every 1 hour for 5 minutes, sucking the bottom of a container by a magnet after heating to ensure that the ferroferric oxide nano particles cannot be lost along with water flow, pouring a beaker to remove supernatant, heating the ferroferric oxide nano particles in the water bath at 70 ℃ during washing by using excessive distilled water, stirring the heated ferroferric oxide nano particles for 10 minutes, pouring the supernatant, repeating the method for 3 times to obtain modified ferroferric oxide sticky matter;
step five: introducing a carbon source: pouring a saturated glucose solution into the modified ferroferric oxide viscous substance, wherein the molar ratio of the ferroferric oxide to the glucose is 1:1.25, heating in a water bath at 70 ℃, and stirring for 40min to obtain a glucose suspension coated with ferroferric oxide;
step six: introducing a lubricant: adding basic copper carbonate into a ferroferric oxide-coated glucose suspension, wherein the molar ratio of the ferroferric oxide-coated glucose to the basic copper carbonate is 12:1, heating in a 70 ℃ water bath, and stirring for 15 minutes to obtain a mixed suspension solution;
wherein, the basic copper carbonate precipitates when more basic copper carbonate is added, and EDS (electron-discharge spectroscopy) shows that the addition amount of the basic copper carbonate is about 10 percent of the mass of the ferroferric oxide and is uniformly distributed;
step seven: adding emulsifying and thickening agents: adding span-60 solution into the mixed suspension solution, wherein the volume ratio of the mixed suspension solution to the span-60 solution is 10:1, heating in a water bath at 70 ℃, and stirring for 15 minutes to obtain low-concentration suspension;
step eight: adding a stabilizer: adding sodium chloride into the low-concentration suspension, wherein the mass ratio of the sodium chloride to the added glucose is 3:100, heating in a water bath at 70 ℃, and stirring for 120 minutes to obtain high-viscosity suspension;
wherein the sodium chloride is used for stabilizing the carbon shell, and the addition amount of the sodium chloride is preferably 2-3% of the addition amount of the glucose;
step nine: drying the high-concentration suspension at 70 ℃ for 15h, and grinding into powder to obtain powder;
step ten: and (3) heat treatment: the first stage of heat treatment: (1) heating from room temperature to 200 ℃ at 2 ℃/min, (2) heating from 200 ℃ to 300 ℃ at 1 ℃/min, (3) heating from 300 ℃ to 400 ℃ at 2 ℃/min;
and (3) a second stage of heat treatment: (4) heating from 400 ℃ to 450 ℃ at the speed of 2 ℃/min, and (5) keeping the temperature of 450 ℃ for 30min to obtain high-temperature carbonized aggregates;
in the heat treatment stage, high-purity nitrogen is kept introduced to prevent ferroferric oxide from being oxidized, and the ventilation volume is 1.5L/min;
step eleven: crushing the high-temperature carbonized aggregate: treating the high-temperature carbonized aggregate with a pulverizer at 3500r/min for 1min to obtain powder;
step twelve: fe3O4@ C/Cu composite magnetic oil removal particles: washing the powder with excessive water for 5 times to remove floating substances on water surface, rinsing with anhydrous ethanol for 2 times to remove liquid, drying in air-blast drying oven at 70 deg.C for 7 hr, and sieving with 400 mesh sieve to obtain Fe3O4@ C/Cu composite magnetic degreasing particles.
Example 4
Preparing span-60 with the concentration of 0.45g/L, wherein the molar ratio of ferroferric oxide to citric acid in the modified ferroferric oxide is 9:5, the volume ratio of the added span-60 solution to the mixed suspension solution is 6:0.8, and the other conditions are the same as those in the example 2.

Claims (3)

1. A method for preparing carbon-copper coated ferroferric oxide composite magnetic oil removal particles is characterized by comprising the following steps: the method comprises the following specific steps:
the method comprises the following steps: preparing 0.1mol/L citric acid modified solution: preparing distilled water and absolute ethyl alcohol according to a volume ratio of 4:1 as a solvent, heating in a water bath at 50-70 ℃ for 5-10 min, and stirring until the distilled water and the absolute ethyl alcohol are completely dissolved to obtain 0.1mol/L citric acid modified solution;
step two: preparing a saturated glucose solution;
step three: preparing a span-60 solution: preparing a span-60 solution with the concentration of 0.4-0.5 g/mL, heating in a water bath at 50-70 ℃ for 5-10 min, and stirring until the span-60 solution is completely dissolved to obtain the span-60 solution with the concentration of 0.4-0.5 g/mL;
step four: modified ferroferric oxide: putting the ferroferric oxide nano particles into 0.1mol/L citric acid modified solution, wherein the ratio of ferroferric oxide to citric acid is (4-5): 2-3, heating in a water bath for 50-70 ℃, heating for 7-9 hours, stirring or ultrasonically treating for 5 minutes every 1 hour, sucking the bottom of the container by using a magnet after heating, so that the ferroferric oxide nanoparticles cannot be lost along with water flow, pouring out a beaker to remove supernatant, heating in the water bath at the temperature of 50-70 ℃ during cleaning by using excessive distilled water, stirring for 5-10 minutes, pouring out the supernatant, repeating the method for 2-3 times in the same way as the method for pouring out the supernatant to obtain a modified ferroferric oxide sticky matter;
step five: introducing a carbon source: pouring a saturated glucose solution into the modified ferroferric oxide sticky matter, wherein the molar ratio of the ferroferric oxide to the glucose is 1: 1.16-1.25, heating in a water bath at 50-70 ℃, and stirring for 20-40 min to obtain a glucose suspension coated with the ferroferric oxide;
step six: introducing a lubricant: adding basic copper carbonate into a ferroferric oxide-coated glucose suspension, wherein the molar ratio of the ferroferric oxide-coated glucose to the basic copper carbonate is 10-12: 1, heating in a water bath at 50-70 ℃, and stirring for 8-15 minutes to obtain a mixed suspension solution;
step seven: adding emulsifying and thickening agents: adding span-60 solution into the mixed suspension solution, wherein the volume ratio of the mixed suspension solution to the span-60 solution is 8-10: 1, heating in a water bath at 50-70 ℃, and stirring for 8-15 minutes to obtain low-viscosity suspension;
step eight: adding a stabilizer: adding sodium chloride into the low-viscosity suspension, wherein the mass ratio of the sodium chloride to the added glucose is 2-3: 100, heating in a water bath at 50-70 ℃, and stirring for 120 minutes to obtain high-viscosity suspension;
step nine: drying the high-viscosity suspension at 50-70 ℃ for 10-15 h, and grinding into powder to obtain powder;
step ten: and (3) heat treatment: the first stage of heat treatment: (1) heating from room temperature to 200 ℃ at 2 ℃/min, (2) heating from 200 ℃ to 300 ℃ at 1 ℃/min, (3) heating from 300 ℃ to 400 ℃ at 2 ℃/min;
and (3) a second stage of heat treatment: (4) heating from 400 ℃ to 450 ℃ at the speed of 2 ℃/min, (5) keeping the temperature of 450 ℃ for 30min to obtain high-temperature carbonized aggregates,
in the heat treatment stage, high-purity nitrogen is kept introduced to prevent ferroferric oxide from being oxidized, and the ventilation volume is 1-1.5L/min;
step eleven: crushing the high-temperature carbonized aggregate: treating the high-temperature carbonized aggregate for 1-2 min under a 3000-3500 r/min pulverizer to obtain powder;
step twelve: fe3O4@ C/Cu composite magnetic oil removal particles: washing the powder with excessive water for 2-5 times to remove floating substances on the water surface, rinsing with absolute ethyl alcohol for 1-2 times to remove liquid, putting the powder into a blast drying oven, drying at 50-70 ℃ for 5-7 hours, and screening the powder with a 400-mesh sieve to obtain Fe3O4@ C/Cu composite magnetic degreasing particles.
2. The method for preparing the carbon-copper coated ferroferric oxide composite magnetic oil removal particle according to claim 1, wherein the method comprises the following steps: prepared Fe3O4The @ C/Cu composite magnetic oil removal particles can be suspended on the water surface and are in a nearly regular hexahedron shape.
3. The method for preparing the carbon-copper coated ferroferric oxide composite magnetic oil removal particle according to claim 1, wherein the method comprises the following steps: the specific preparation method of the saturated glucose solution in the second step comprises the following steps: weighing 15.0-20.0 g of glucose at room temperature, putting the glucose into a beaker, adding 15-20 ml of distilled water, heating in a water bath at 50-70 ℃, and stirring to completely dissolve the glucose until the solution is clear to obtain a saturated glucose solution.
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