CN114988734B - Preparation method and application of silica fume-based geopolymer composite hydrophobic microsphere - Google Patents

Preparation method and application of silica fume-based geopolymer composite hydrophobic microsphere Download PDF

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CN114988734B
CN114988734B CN202210690406.1A CN202210690406A CN114988734B CN 114988734 B CN114988734 B CN 114988734B CN 202210690406 A CN202210690406 A CN 202210690406A CN 114988734 B CN114988734 B CN 114988734B
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oil
silica fume
water
geopolymer composite
hydrophobic
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CN114988734A (en
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谢圆圆
薛兴勇
刘松洋
谭家宝
韩要丛
苏俏俏
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Guangxi University for Nationalities
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Guangxi University for Nationalities
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

The invention discloses a preparation method and application of silica fume based geopolymer composite hydrophobic microspheres, and belongs to the technical field of hydrophobic materials. The preparation method of the composite microsphere comprises the following steps: evenly mixing deionized water, water glass, powder (one or a mixture of metakaolin, fly ash and slag) and silica fume according to a certain proportion to obtain mixed slurry; dripping the mixed slurry into hot silicone oil in a stirring state to obtain a silicone oil slurry mixture; maintaining and filtering the silicone oil slurry mixture to obtain hydrophobic microspheres; washing the hydrophobic microspheres with boiled deionized water, drying, calcining and sieving to obtain the silica fume base geopolymer composite hydrophobic microspheres. The silica fume-based geopolymer composite hydrophobic microsphere disclosed by the invention meets the requirements of super-hydrophobic materials, has a good separation effect on oil-water mixtures, can quickly separate oil-water mixtures, has good acid resistance, alkali resistance and high temperature resistance, and can be applied to oil-water separation in various occasions.

Description

Preparation method and application of silica fume-based geopolymer composite hydrophobic microsphere
Technical Field
The invention relates to the technical field of hydrophobic materials, in particular to a preparation method and application of silica fume based geopolymer composite hydrophobic microspheres.
Background
In recent years, frequent marine crude oil extraction leakage not only seriously pollutes the marine environment, but also reduces crude oil mineral resources, and even seriously damages ecological balance of nature; in addition, the random discharge of industrial oily wastewater is also a problem of urgent need for treatment, and if the industrial oily wastewater cannot be effectively treated in time, serious harm can be caused to soil, crops, atmosphere, water body, natural landscape and the like. The traditional methods for treating the oily industrial wastewater mainly comprise an electrocoagulation method, an oxidation method, a chemical agent dispersion method, a filtration method, a centrifugal separation method, a microorganism restoration method and the like. However, the above methods have serious defects that on one hand, the mechanization is low and the method cannot be used on a large scale, and on the other hand, the performance is poor and secondary pollution is easy to form.
With the continuous development and progress of technology, the application range of metal materials is also becoming wider and wider, and metal corrosion is becoming a problem. The awareness of human being on environmental protection is stronger and the choice of metal corrosion-resistant materials is stricter, but the original metal corrosion-resistant methods such as metal plating layers, organic coatings and the like have serious defects, and some application materials not only pollute the environment, but also harm the physical health of human beings. Icing is a common phenomenon in nature, and is also an important influencing factor of safety accidents in winter, and the number of traffic accidents caused by icing is up to thousands each year. The harm of icing is mainly expressed in the aspects of aerospace, electric power systems, communication systems, ground traffic and the like. Over ten years ago, continuous ice disasters occur in the southeast of the united states and the south of China, so that communication cables are frozen and cannot be communicated, the daily life and production economy of people are seriously affected, and the direct economic loss is up to several trillion yuan.
Therefore, the material which can perform effective oil-water separation, can treat the problem of marine crude oil exploitation leakage, solves the problem of industrial oily wastewater discharge, is cheap, environment-friendly and effective in metal corrosion prevention, and can effectively remove ice and solve the influence of potential safety hazards in aerospace and the like is unprecedented.
In order to solve the above problems, researchers have developed hydrophobic materials, and methods and techniques for developing hydrophobic surfaces have tended to be mature, wherein hydrothermal methods, self-assembly methods, suspension methods, etching methods, electrochemical deposition methods, electrochemical methods, template methods, spray methods, dip coating methods, and the like are widely used. Some of these methods and techniques have significant drawbacks such as expensive materials to be used, limited in certain situations, etc., and thus cannot be used in real life on a large scale. Therefore, it becomes important to develop a superhydrophobic material with simple preparation process, low production cost and wide application.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a preparation method and application of the silica fume based geopolymer composite hydrophobic microsphere.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the silica fume-based geopolymer composite hydrophobic microsphere comprises the following steps:
(1) Regulating the modulus of industrial potash water glass to 1.0-1.5 by using solid KOH, sealing and naturally cooling to room temperature to obtain potash water glass for later use;
(2) Weighing deionized water, the potash water glass, the powder and the silica fume obtained in the step (1), and uniformly mixing the weighed silica fume, the weighed potash water glass, the weighed powder and the weighed deionized water to obtain mixed slurry; the deionized water is prepared according to H 2 O/Na 2 The O is added in the molar ratio of 17-23; the mass ratio of the potash water glass to the total solids is 0.9-1.3; the silica fume accounts for 5% -50% of the total solid mass; the total solid consists of the powder material and the silica fume; the powder is one or a combination of a plurality of metakaolin, fly ash and slag;
(3) Dripping the mixed slurry prepared in the step (2) into silicon oil at 60-90 ℃ and in a stirring state to obtain a silicon oil slurry mixture;
(4) Curing the silicone oil slurry mixture prepared in the step (3) for 2-6 hours at the temperature of 70-95 ℃ and filtering to obtain hydrophobic microspheres;
(5) Washing the hydrophobic microspheres prepared in the step (4) by boiled deionized water, then drying, calcining the dried hydrophobic microspheres, and sieving to obtain the silica fume based geopolymer composite hydrophobic microspheres.
Further, the silica fume is silica fume with a silica content of not less than 93%.
In the step (2), the weighed silica fume, water glass, powder and deionized water are mixed in a plastic beaker and stirred for 2 to 5 minutes at the rotating speed of 1000 to 1500 r/min.
Further, in the step (3), the stirring speed of the silicone oil is 300r/min-500r/min.
Further, in the step (5), the calcination temperature is 300-500 ℃ and the calcination time is 3-7 h.
Further, in the step (5), the sieving is through an 80 mesh sieve.
Further, in the step (2), the powder is used after being modified as follows: calcining the powder at 800-1000 ℃ for 3-6 hours, grinding, sieving to control the particle size to be less than 45 microns, drying the sieved powder at 105 ℃ for 2-5 hours, transferring into a ball mill, adding an aminosilane coupling agent accounting for 0.3-2% of the powder mass, mixing and ball milling for 6-10 hours to obtain the modified powder.
The invention also provides application of the silica fume based geopolymer composite hydrophobic microsphere prepared by the preparation method in treatment of oil-containing polluted water.
Further, the oil-containing polluted water comprises oil-containing sea water which is polluted by marine crude oil exploitation leakage, oil-containing industrial wastewater in petrochemical enterprises and oil-containing domestic wastewater in catering enterprises.
Further, when the silica fume based geopolymer composite hydrophobic microsphere is applied to treatment of oil-containing polluted water, the invention also provides a method for treating the oil-containing polluted water by adopting the silica fume based geopolymer composite hydrophobic microsphere, which specifically comprises the following steps: the silica fume based geopolymer composite hydrophobic microspheres are paved in various filtering containers as a filtering layer, such as a suction filtration sand core funnel, a columnar filter with an inlet and an outlet and the like, so that the hydrophobic materials are convenient to recycle, a layer of gauze or cotton balls are paved on a supporting plate of the filter, then the silica fume based geopolymer composite hydrophobic microspheres are paved on the gauze or cotton balls, and a layer of gauze or cotton balls (serving as a protective layer of the microspheres) are paved and fixed on the silica fume based geopolymer composite hydrophobic microspheres. For oil-water mixtures containing heavy oil, such as carbon tetrachloride oil-water mixtures, carbon disulfide oil-water mixtures, silicone oil-water mixtures and the like, the oil-containing sewage to be treated is introduced into the filter from the upper feed inlet, oil can quickly flow into the container below through the microsphere filter layer, and water is trapped above the filter layer and flows out from the water outlet above, so that the purpose of separating oil from water is achieved. For oil-water mixtures containing light oil, such as cyclohexane oil-water mixtures, vinyl acetate oil-water mixtures, oil-water mixtures of gasoline (or kerosene, diesel oil, naphtha and the like), edible oil-oil mixtures and the like, the oily water to be treated is introduced into the filter from the lower feed inlet under a certain pressure, oil can rapidly flow out from the upper part of the filter container through the microsphere filter layer, water is trapped below the filter layer and flows out from the water outlet below, and therefore the purpose of separating oil from water is achieved. The oil obtained by separation is recycled, the water obtained by separation can be recycled or directly discharged, and the silica fume-based geopolymer composite hydrophobic microspheres are continuously recycled.
The silica fume based geopolymer composite hydrophobic microsphere prepared by the preparation method can be used as a raw material to be added into metal piece coating or plating, including metal pieces of aerospace, electric power systems, communication systems and ground traffic, so as to enhance the hydrophobic effect.
The beneficial effects of the invention are as follows:
the surface of the silica fume base geopolymer composite hydrophobic microsphere material prepared by the invention is provided with a nanoscale porous structure, which provides a nanometer rough surface for the construction of the silica fume base geopolymer composite hydrophobic microsphere material, and the Si-O-Si structure on the surface of the microsphere material reduces the surface energy of the silica fume base geopolymer composite hydrophobic microsphere hydrophobic material.
The contact angle of the silica fume-based geopolymer composite hydrophobic microsphere prepared by the invention is up to 163 degrees, and the requirements of the super-hydrophobic material are met; the composite microsphere hydrophobic material has remarkable oil-water separation effect, and experiments prove that the composite microsphere hydrophobic material can be used for oil-water separation of carbon tetrachloride-water mixture, cyclohexane-water mixture, vinyl acetate-water mixture and the like, and can complete oil-water separation within one to two minutes, and the separation efficiency is as high as more than 92%.
The hydrophobic material of the silica fume based geopolymer composite hydrophobic microsphere prepared by the invention can still carry out oil-water separation with high efficiency after being soaked in seawater for 24 hours at pH=13, pH=3, which shows that the silica fume based geopolymer composite hydrophobic microsphere has strong acid and alkali resistance and still has oil-water separation performance in seawater. In addition, the composite microsphere hydrophobic material is generated by calcining at high temperature, and also has good high temperature resistance.
The silica fume-based geopolymer composite hydrophobic microsphere hydrophobic material has the advantages of low-cost and easily obtained raw materials, simple preparation method, low cost, excellent hydrophobic performance, corrosion resistance and high temperature resistance, can be applied to treatment of oil-containing industrial wastewater and seawater polluted by petroleum, and can be used as raw materials of coatings of metal parts such as aerospace, power systems, communication systems and ground traffic, for example, as anti-icing raw materials to be added into coatings of communication cables, and as anti-icing and anti-corrosion auxiliary materials to be added into coatings of aviation devices.
Drawings
FIG. 1 is an enlarged SEM image of the silica fume based geopolymer composite hydrophobic microsphere and its surface prepared in example 1;
FIG. 2 is a graph showing the contact angle of silica fume-based geopolymer composite hydrophobic microspheres prepared in example 1;
FIG. 3 is a graph showing the contact angle of silica fume based geopolymer composite hydrophobic microspheres prepared in example 2;
FIG. 4 is a graph showing the contact angle of silica fume-based geopolymer composite hydrophobic microspheres prepared in example 3;
FIG. 5 is a graph showing the contact angle of silica fume based geopolymer composite hydrophobic microspheres prepared in example 4;
FIG. 6 is a graph showing the contact angle of silica fume-based geopolymer composite hydrophobic microspheres prepared in example 5;
FIG. 7 is a graph showing the contact angle of silica fume-based geopolymer composite hydrophobic microspheres prepared in comparative example 1;
FIG. 8 is a graph showing the contact angle of silica fume-based geopolymer composite hydrophobic microspheres prepared in comparative example 2;
FIG. 9 is a graph showing the contact angle of silica fume-based geopolymer composite hydrophobic microspheres prepared in comparative example 3;
FIG. 10 shows the experimental results of the oil-water separation cycle of carbon tetrachloride by the microspheres of example 5;
fig. 11 is the results of the microsphere circulation experiment of example 5 immersed in a solution at ph=13 for 24 hours;
fig. 12 is the results of the microsphere circulation experiment of example 5 immersed in a solution at ph=3 for 24 hours;
FIG. 13 shows the results of the microsphere circulation test of example 5 immersed in a seawater solution for 24 hours.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific examples.
Example 1
The preparation method of the silica fume-based geopolymer composite hydrophobic microsphere comprises the following steps:
(1) The modulus of industrial potash water glass was adjusted to 1.3 with solid KOH in a beaker, and the beaker mouth was sealed with a preservative film (to prevent CO from being present in the air) 2 Reacting to generate silicic acid), and naturally cooling to room temperature for standby;
(2) Weighing deionized water, potash water glass with the modulus of 1.3 obtained in the step (1), metakaolin and silica fume containing 93% of silicon dioxide, mixing the weighed silica fume, potash water glass, metakaolin and deionized water in a plastic beaker, and stirring for 3min at the rotation speed of 1200r/min to obtain mixed slurry; the deionized water is prepared according to H 2 O/Na 2 The molar ratio of O is 19; the mass ratio of the potash water glass to the total solids is 1.1; the silica fume accounts for 5% of the total solid mass; the total solids consist of the metakaolin and the silica fume;
(3) Placing a beaker (reaching the lowest part of a bevel opening of the beaker) containing 900mL of silicone oil into an oven at 80 ℃, heating to 80 ℃, transferring the silicone oil onto a stirrer, adjusting the height of the stirrer to enable the stirrer to extend to a depth of about 2cm below the liquid level of the silicone oil, setting the rotating speed of the stirrer to 400r/min, taking a constant-pressure dropping funnel, pouring the mixed slurry stirred in the step (2) into the constant-pressure dropping funnel, uniformly dripping the silicone oil, closing the stirrer after dripping, adjusting the height of the stirrer to be above the liquid level of the silicone oil, starting the stirrer to rotate at a low speed to enable the silicone oil remained on a rotor to be thrown into the beaker, and closing the stirrer after finishing to obtain a silicone oil slurry mixture;
(4) Placing the silicone oil slurry mixture prepared in the step (3) back into an oven at 80 ℃ for curing for 3 hours, pouring the silicone oil slurry mixture into a Buchner funnel paved with 2000-mesh filter cloth, performing vacuum filtration, and performing suction drying to obtain hydrophobic microspheres, wherein the silicone oil is recycled;
(5) And (3) putting the hydrophobic microspheres obtained in the step (4) after suction filtration into a 1000mL beaker, washing 3 times with boiled deionized water, pouring the hydrophobic microspheres into a culture dish after washing, and putting into an oven for drying. And (3) placing the dried hydrophobic microspheres into a porcelain boat, transferring into a muffle furnace, calcining for 6 hours at 400 ℃, and sieving with a 80-mesh sieve after calcining to obtain the silica fume base geopolymer composite hydrophobic microspheres.
As shown in FIG. 1, the silica fume based geopolymer composite hydrophobic microsphere prepared in example 1 shows good spherical distribution, the diameter of the microsphere is concentrated to about 100 micrometers, and after the microsphere is magnified 20000 times by an electron microscope, the surface of the microsphere can be seen to have nano-scale protrusions and have a nano-scale microporous structure with a plurality of different pore diameters, which is beneficial to the structure of the hydrophobic surface.
The contact angle test is carried out on the silica fume based geopolymer composite hydrophobic microsphere prepared in the embodiment 1 by using a JY-PHB contact angle tester, a microsphere sample is uniformly adhered on a glass slide by using double-sided adhesive tape before the test, the glass slide with the adhered sample is placed on a tester, a trace (5.0 mu L) injector is used for dripping water on the microsphere sample, the image is stored after the stability is reached, and then the contact angle is measured. To reduce experimental error, 3 different positions were selected on the slide for drop analysis measurements, and the contact angle was averaged over three measurements. As shown in FIG. 2, the contact angle of the silica fume based geopolymer composite hydrophobic microsphere prepared in the embodiment reaches 155 degrees.
Example 2
The preparation method of the silica fume-based geopolymer composite hydrophobic microsphere comprises the following steps:
(1) Regulating the modulus of industrial potash water glass to 1.2 by using solid KOH, sealing and naturally cooling to room temperature for later use;
(2) Weighing deionized water, potash water glass with the modulus of 1.2 obtained in the step (1), fly ash and silica fume containing 93% of silicon dioxide, mixing the weighed silica fume, potash water glass, fly ash and deionized water in a plastic beaker, and stirring for 3min at the rotation speed of 1300r/min to obtain mixed slurry; the deionized water is prepared according to H 2 O/Na 2 The molar ratio of O is 20; the mass ratio of the potash water glass to the total solids is 1.2; the silica fume accounts for 10% of the total solid mass; the total solid consists of the fly ash and the silica fume;
(3) Placing a beaker containing 900mL of silicone oil into a 75 ℃ oven, heating the silicone oil to 75 ℃, transferring the silicone oil onto a stirrer, adjusting the height of the stirrer to enable the stirrer to extend to a depth of about 2cm below the liquid level of the silicone oil, setting the rotating speed of the stirrer to 400r/min, taking a constant-pressure dropping funnel, pouring the mixed slurry stirred in the step (2) into the constant-pressure dropping funnel, uniformly dropping the mixed slurry into the silicone oil, and closing the stirrer after dropping to obtain a silicone oil slurry mixture;
(4) Placing the silicone oil slurry mixture prepared in the step (3) back into a 75 ℃ oven, curing for 4 hours, pouring the silicone oil slurry mixture into a Buchner funnel paved with 2000-mesh filter cloth, performing vacuum filtration, and performing suction drying to obtain hydrophobic microspheres, wherein the silicone oil is recycled;
(5) And (3) putting the hydrophobic microspheres obtained in the step (4) after suction filtration into a 1000mL beaker, washing with boiled deionized water for 2 times, pouring the hydrophobic microspheres into a culture dish after washing, and putting into an oven for drying. And (3) placing the dried hydrophobic microspheres into a porcelain boat, transferring the porcelain boat into a muffle furnace, setting the temperature to 400 ℃, and calcining for 5 hours. And (3) sieving the mixture through a 80-mesh sieve after calcination to obtain the silica fume base geopolymer composite hydrophobic microspheres.
As shown in FIG. 3, the contact angle of the silica fume based geopolymer composite hydrophobic microsphere prepared in the embodiment reaches 157 degrees.
Example 3
The preparation method of the silica fume-based geopolymer composite hydrophobic microsphere comprises the following steps:
(1) Regulating the modulus of industrial potash water glass to 1.0 by using solid KOH, sealing and naturally cooling to room temperature for later use;
(2) Weighing deionized water, potash water glass with the modulus of 1.0 obtained in the step (1), granulated blast furnace slag and silica fume containing 94% of silicon dioxide, mixing the weighed silica fume, the potash water glass, the granulated blast furnace slag and the deionized water in a plastic beaker, and stirring for 5min at the rotating speed of 1000r/min to obtain mixed slurry; the deionized water is prepared according to H 2 O/Na 2 The O molar ratio is 17; the mass ratio of the potash water glass to the total solids is 1.3; the silica fume accounts for 25% of the total solid mass; the total solids consist of the granulated blast furnace slag and the silica fume;
(3) Placing a beaker containing 900mL of silicone oil into a 60 ℃ oven, heating the temperature of the silicone oil to 60 ℃, transferring the silicone oil onto a stirrer, adjusting the height of the stirrer to enable the stirrer to extend to a depth of about 2cm below the liquid level of the silicone oil, setting the rotating speed of the stirrer to 300r/min, taking a constant-pressure dropping funnel, pouring the mixed slurry stirred in the step (2) into the constant-pressure dropping funnel, uniformly dripping the mixed slurry into the silicone oil, and closing the stirrer after dripping is finished to obtain a silicone oil slurry mixture;
(4) Placing the silicone oil slurry mixture prepared in the step (3) back into a 70 ℃ oven, curing for 6 hours, pouring the silicone oil slurry mixture into a Buchner funnel paved with 2000-mesh filter cloth, performing vacuum filtration, and performing suction drying to obtain hydrophobic microspheres, wherein the silicone oil is recycled;
(5) And (3) putting the hydrophobic microspheres obtained in the step (4) after suction filtration into a 1000mL beaker, washing with boiled deionized water for 2 times, pouring the hydrophobic microspheres into a culture dish after washing, and putting into an oven for drying. And (3) placing the dried hydrophobic microspheres into a porcelain boat, transferring into a muffle furnace, setting the temperature to 300 ℃, calcining for 7 hours, and sieving with a 80-mesh sieve after calcining to obtain the silica fume base geopolymer composite hydrophobic microspheres.
As shown in fig. 4, the contact angle of the silica fume based geopolymer composite hydrophobic microsphere prepared in the embodiment reaches 154 °.
Example 4
The preparation method of the silica fume-based geopolymer composite hydrophobic microsphere comprises the following steps:
(1) Regulating the modulus of industrial potash water glass to 1.5 by using solid KOH, sealing and naturally cooling to room temperature for later use;
(2) Weighing deionized water, potassium water glass with the modulus of 1.5 obtained in the step (1), powder and silica fume containing 94% of silicon dioxide, mixing the weighed silica fume, potassium water glass, powder and deionized water in a plastic beaker, and stirring for 2min at the rotating speed of 1500r/min to obtain mixed slurry; the deionized water is prepared according to H 2 O/Na 2 The molar ratio of O is 23; the mass ratio of the potash water glass to the total solids is 0.9; the silica fume accounts for 50% of the total solid mass; the total solid consists of the powder and the silica fume, wherein the powder is a mixture of metakaolin and fly ash with the same mass;
(3) Placing a beaker containing 900mL of silicone oil into a 90 ℃ oven, heating the silicone oil to 90 ℃, transferring the silicone oil onto a stirrer, adjusting the height of the stirrer to enable the stirrer to penetrate into the depth of about 2cm below the liquid level of the silicone oil, setting the rotating speed of the stirrer to 500r/min, taking a constant-pressure dropping funnel, pouring the mixed slurry stirred in the step (2) into the constant-pressure dropping funnel, uniformly dropping the mixed slurry into the silicone oil, and closing the stirrer after dropping to obtain a silicone oil slurry mixture;
(4) Placing the silicone oil slurry mixture prepared in the step (3) back into a baking oven at 95 ℃, curing for 2 hours, pouring the silicone oil slurry mixture into a Buchner funnel paved with 2000-mesh filter cloth, performing vacuum filtration, and performing suction drying to obtain hydrophobic microspheres, wherein the silicone oil is recycled;
(5) And (3) putting the hydrophobic microspheres obtained in the step (4) after suction filtration into a 1000mL beaker, washing with boiled deionized water for 2 times, pouring the hydrophobic microspheres into a culture dish after washing, and putting into an oven for drying. And (3) placing the dried hydrophobic microspheres into a porcelain boat, then transferring the porcelain boat into a muffle furnace for calcination, wherein the calcination temperature is 500 ℃, the calcination time is 3 hours, and sieving the calcined hydrophobic microspheres with a 80-mesh sieve to obtain the silica fume base geopolymer composite hydrophobic microspheres.
As shown in FIG. 5, the contact angle of the silica fume based geopolymer composite hydrophobic microsphere prepared in the embodiment reaches 146 degrees.
Example 5
The preparation method of the silica fume-based geopolymer composite hydrophobic microsphere comprises the following steps:
(1) The modulus of industrial potash water glass was adjusted to 1.3 with solid KOH in a beaker, and the beaker mouth was sealed with a preservative film (to prevent CO from being present in the air) 2 Reacting to generate silicic acid), and naturally cooling to room temperature for standby;
(2) Modification of metakaolin: calcining metakaolin at 900 ℃ for 5 hours, grinding, sieving to control the particle size to be less than 45 microns, drying the sieved powder at 105 ℃ for 3 hours, transferring the powder into a ball mill, adding an amino functional silane coupling agent with the mass of 0.6% of that of the metakaolin, mixing and ball milling for 8 hours to obtain modified metakaolin;
weighing deionized water, the potassium water glass with the modulus of 1.3 obtained in the step (1), the modified metakaolin and the silica fume containing 93% of silicon dioxide, mixing the weighed silica fume, the potassium water glass, the modified metakaolin and the deionized water in a plastic beaker, and stirring for 3min at the rotation speed of 1200r/min to obtain mixed slurry; the deionized water is prepared according to H 2 O/Na 2 The molar ratio of O is 19; the mass ratio of the potash water glass to the total solids is 1.1; the silica fume accounts for 5% of the total solid mass; the total solids consist of the modified metakaolin and the silica fume;
(3) Placing a beaker (reaching the lowest part of a bevel opening of the beaker) containing 900mL of silicone oil into an oven at 80 ℃, heating to 80 ℃, transferring the silicone oil onto a stirrer, adjusting the height of the stirrer to enable the stirrer to extend to a depth of about 2cm below the liquid level of the silicone oil, setting the rotating speed of the stirrer to 400r/min, taking a constant-pressure dropping funnel, pouring the mixed slurry stirred in the step (2) into the constant-pressure dropping funnel, uniformly dripping the silicone oil, closing the stirrer after dripping, adjusting the height of the stirrer to be above the liquid level of the silicone oil, starting the stirrer to rotate at a low speed to enable the silicone oil remained on a rotor to be thrown into the beaker, and closing the stirrer after finishing to obtain a silicone oil slurry mixture;
(4) Placing the silicone oil slurry mixture prepared in the step (3) back into an oven at 80 ℃ for curing for 3 hours, pouring the silicone oil slurry mixture into a Buchner funnel paved with 2000-mesh filter cloth, performing vacuum filtration, and performing suction drying to obtain hydrophobic microspheres, wherein the silicone oil is recycled;
(5) And (3) putting the hydrophobic microspheres obtained in the step (4) after suction filtration into a 1000mL beaker, washing 3 times with boiled deionized water, pouring the hydrophobic microspheres into a culture dish after washing, and putting into an oven for drying. And (3) placing the dried hydrophobic microspheres into a porcelain boat, transferring into a muffle furnace, calcining for 6 hours at 400 ℃, and sieving with a 80-mesh sieve after calcining to obtain the silica fume base geopolymer composite hydrophobic microspheres.
As shown in fig. 6, the contact angle of the silica fume based geopolymer composite hydrophobic microsphere prepared in the embodiment reaches 163 °.
Comparative example 1
The silica fume based geopolymer composite hydrophobic microsphere was prepared by setting the silica fume content to 55% based on example 2. Through experiments, after the silica fume proportion is increased to 55%, the final product cannot be balled.
As shown in fig. 7, the contact angle of the silica fume based geopolymer composite hydrophobic microsphere prepared in this comparative example is only 131 °.
Comparative example 2
The silica fume based geopolymer composite hydrophobic microsphere was prepared by setting silica fume to be silica fume containing 90% silica based on example 2.
As shown in fig. 8, the contact angle of the silica fume based geopolymer composite hydrophobic microsphere prepared in this comparative example is only 136 °.
Comparative example 3
The preparation method of the silica fume-based geopolymer composite hydrophobic microsphere changes the calcination temperature to 200 ℃ on the basis of the example 2.
As shown in fig. 9, the contact angle of the silica fume based geopolymer composite hydrophobic microsphere prepared in this comparative example is only 138 °.
The microspheres of examples 1 to 5 and comparative examples 1 to 3 were subjected to oil-water separation test and analysis, and specifically as follows:
1、CCl 4 -water mixed liquor separation test and analysis
1g of microspheres was packed in a conical funnel, 50mg of cotton balls were then immobilized on the microspheres, and the beaker was placed under the conical funnel, accurately weighing 10.0g of methylene blue solution (25 mg/L) and 10.0g of oil (CCl) 4 Scarlet dyeing) and then pouring them together into a filter, the red oil will flow through the microspheres into the lower beaker, and the blue water will be trapped on top of the microspheres. Oil-water separation test was performed at room temperature, the reaction time was recorded, the mass of oil was collected, and the oil-water separation efficiency was calculated by the following formula.
η＝V Oil (oil) /V Total (S) X 100%; wherein η represents the oil-water separation efficiency; v (V) Oil (oil) Indicating the mass of oil collected after separation; v (V) Total (S) Indicating the total mass of oil added prior to separation.
Table 1 microsphere pairs CCl for each set 4 Separation data of the water mixture
Figure BDA0003699292630000101
As can be seen from Table 1, the microspheres of examples 1-5 all have an oil-water separation efficiency of carbon tetrachloride of over 90%, and example 5 is more than 95.6%. The separation efficiency of comparative examples 1 to 3 was lowered while there was a great difference in oil-water separation time, and example 5 separated the oil-water mixture having the same mass in about one minute, whereas comparative examples 1 to 3 required more than 3 minutes, and the separation speed was significantly lowered.
The microspheres of example 5 were selected for 11 times of circulating oil-water separation, as shown in fig. 10, except that the oil-water separation efficiency of carbon tetrachloride is only 62.4% because the microspheres and cotton absorb a part of carbon tetrachloride in the first separation, the other separation efficiencies are higher, and are above 94.9%. After 11 times of cyclic separation, the sample of the example 5 still has high separation efficiency, which indicates that the microsphere can be reused in oil-water separation and has strong durability.
2. Vinyl acetate-water and cyclohexane oil-water mixed liquid separation test
Taking the cone made of plastic bottle with the bottom removed as a filter, and arranging the filterAbove the beaker, 3.0g of microspheres were deposited into the conical mouth, 50mg of cotton balls were then laid and fixed on the microspheres, a mixture of 10.0g of methylene blue solution (25 mg/L) and 10.0g of oil (vinyl acetate or cyclohexane oil reddish dye) was poured into the filter, the red oil was allowed to pass through the microspheres into the lower beaker, and the blue water was trapped on top of the silica fume microspheres. Other steps are as same as CCl 4 -water mix separation test.
Table 2 data on cyclohexane-water mixture separation for each set of microspheres
Figure BDA0003699292630000111
As can be seen from Table 2, the oil-water separation efficiency of the microspheres of examples 1 to 5 on cyclohexane is over 90%, wherein the separation efficiency of example 5 is 93.2%. The microsphere of example 5 is selected to carry out 11 times of continuous oil-water separation experiments on cyclohexane oil-water mixture, and as the mass of the microsphere in the filter is increased to 3g, a large amount of microspheres and cotton absorb a part of cyclohexane, so that the first oil-water separation efficiency of cyclohexane is only 56.2%, the other separation efficiency is 96.3% -97.4%, and after 11 times of circulating separation, the microsphere of example 5 still has high separation efficiency, which indicates that the microsphere can be reused in oil-water separation and has strong durability.
TABLE 3 data on the separation of microspheres from vinyl acetate-water mixtures for each set
Figure BDA0003699292630000121
As can be seen from Table 3, the microspheres of examples 1 to 5 all have an oil-water separation efficiency of 88.2% or more with respect to vinyl acetate, wherein the microsphere of example 5 has a separation efficiency of 95.2%. The microspheres of example 5 are selected to carry out 11 continuous oil-water separation experiments on the vinyl acetate oil-water mixture, the first oil-water separation efficiency is only 57.1% in the same way as cyclohexane, the other separation efficiencies are 95.6% -97.6%, and after 11 times of circulation separation, the microspheres of example 5 still have high separation efficiency on the vinyl acetate oil-water mixture, so that the microspheres of example 5 can be recycled in oil-water separation and have high durability.
Corrosion resistance testing and analysis: the microspheres of example 5 were immersed in HCl (pH 3), naOH (pH 13) and seawater for 24 hours, respectively, and the oil-water separation effect of the immersed sample on CCl 4-water mixture was tested.
The test shows that the microsphere sample of the example 5 subjected to the pH=13, the pH=3 and the seawater soaking for 24 hours still floats on the surface of the solution, and does not absorb water to sink to the water bottom, so that the microsphere of the example 5 corroded by strong acid and strong alkali still has strong hydrophobic property.
In order to further confirm the performance of the microsphere sample of example 5 immersed in the seawater with ph=13 and ph=3, the immersed sample was subjected to carbon tetrachloride oil-water separation cycle experiment test to obtain fig. 11, 12 and 13, and it can be seen from the three graphs that the separation efficiency of the immersed microsphere of example 5 on the carbon tetrachloride-water mixed solution is still very high, more than 92.3%, and the separation efficiency can still reach 92.3%, 94.4% and 94.2% after multiple cycle separation. In conclusion, the hydrophobic microsphere prepared by the invention has strong acid and alkali resistance, can be used for efficiently separating oil from water in seawater, and can solve the long-standing problem of difficult treatment after marine crude oil extraction leakage.
Application examples
The method for treating the oil-containing polluted water by adopting the silica fume base geopolymer composite hydrophobic microsphere prepared in the embodiment 5 specifically comprises the following steps:
(1) The silica fume base geopolymer composite hydrophobic microspheres are used as a filter layer to be paved in a suction filtration sand core funnel, specifically, a layer of gauze is paved on a sand core filter plate of the suction filtration sand core funnel, then the silica fume base geopolymer composite hydrophobic microspheres with the thickness of 2-3cm are paved on the gauze, a layer of gauze is paved and fixed on the silica fume base geopolymer composite hydrophobic microspheres, and then the suction filtration sand core funnel and the suction filtration sand core funnel are assembled; respectively treating oily industrial wastewater of petrochemical enterprises and oily domestic wastewater of catering enterprises;
(2) For the oily industrial wastewater of petrochemical enterprises, the oily industrial wastewater to be treated is introduced into a suction filtration sand core funnel from an upper feed inlet, oil can quickly flow into a lower container of a suction filter through a microsphere filter layer, and water is trapped on the filter layer and flows out from a water outlet above the filter layer, so that the purpose of separating oil from water is achieved. Through detection, the oil-water separation efficiency of the embodiment on the oily chemical wastewater is 91.2%.
(3) For oily domestic wastewater of catering enterprises, the oily wastewater to be treated is introduced into the suction filter from the lower feed inlet under a certain pressure, oil can rapidly flow out from the upper part of a lower container of the suction filter through the microsphere filter layer, and water is trapped below the filter layer and flows out from a water outlet below, so that the purpose of separating oil and water is achieved. Through detection, the oil-water separation efficiency of the embodiment on oily domestic wastewater of catering enterprises is 89.3%.
(4) The oil obtained by separation is recycled, the water obtained by separation can be recycled or directly discharged, and the silica fume-based geopolymer composite hydrophobic microspheres are dried or continuously recycled.
While the invention has been described with reference to the preferred embodiments, it is not intended to limit the invention thereto, and it is to be understood that other modifications and improvements may be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (6)

1. The preparation method of the silica fume-based geopolymer composite hydrophobic microsphere is characterized by comprising the following steps of:
(1) Regulating the modulus of industrial potash water glass to 1.0-1.5 by using solid KOH, sealing and naturally cooling to room temperature to obtain potash water glass for later use;
(2) Weighing deionized water, the potash water glass, the powder and the silica fume obtained in the step (1), and uniformly mixing the weighed silica fume, the weighed potash water glass, the weighed powder and the weighed deionized water to obtain mixed slurry; the deionized water is prepared according to H 2 O/Na 2 The O is added in the molar ratio of 17-23; the quality of the potash water glass and the total solidThe weight ratio is 0.9-1.3; the silica fume accounts for 5% -50% of the total solid mass; the total solid consists of the powder material and the silica fume; the powder is one or a combination of a plurality of metakaolin, fly ash and slag; the silica fume is silica fume with the silica content not less than 93%; the powder is modified as follows and then used: calcining the powder at 800-1000 ℃ for 3h-6h, grinding, sieving to control the particle size to be less than 45 microns, drying the sieved powder at 105 ℃ for 2h-5h, transferring into a ball mill, adding an aminosilane coupling agent accounting for 0.3-2% of the powder mass, and mixing and ball milling for 6h-10h to obtain modified powder;
(3) Dripping the mixed slurry prepared in the step (2) into silicon oil at 60-90 ℃ and in a stirring state to obtain a silicon oil slurry mixture;
(4) Curing the silicone oil slurry mixture prepared in the step (3) at the temperature of 70-95 ℃ for 2h-6h, and filtering to obtain hydrophobic microspheres;
(5) Washing the hydrophobic microsphere prepared in the step (4) by boiled deionized water, drying, calcining the dried hydrophobic microsphere, wherein the calcining temperature is 300-500 ℃, the calcining time is 3h-7h, and sieving to obtain the silica fume base geopolymer composite hydrophobic microsphere.
2. The method for preparing the silica fume-based geopolymer composite hydrophobic microsphere according to claim 1, which is characterized by comprising the following steps: in the step (2), the weighed silica fume, water glass, powder and deionized water are mixed in a plastic beaker and stirred for 2min-5min at the rotating speed of 1000r/min-1500 r/min.
3. The method for preparing the silica fume-based geopolymer composite hydrophobic microsphere according to claim 1, which is characterized by comprising the following steps: in the step (3), the stirring speed of the silicone oil is 300r/min-500r/min.
4. Use of the silica fume based geopolymer composite hydrophobic microsphere prepared by the preparation method of any one of claims 1 to 3 in the treatment of oil-containing contaminated water; the oil-containing polluted water comprises oil-containing sea water which is polluted by marine crude oil exploitation leakage, oil-containing industrial wastewater of petrochemical enterprises and oil-containing domestic wastewater of catering enterprises.
5. The use according to claim 4, wherein: when the silica fume base geopolymer composite hydrophobic microsphere is applied to oil-containing polluted water treatment, a method for treating the oil-containing polluted water by adopting the silica fume base geopolymer composite hydrophobic microsphere is provided, and the method comprises the following steps of: laying the silica fume-based geopolymer composite hydrophobic microspheres as a filter layer in a filter, specifically laying a layer of gauze or cotton balls on a supporting plate of the filter, then laying the silica fume-based geopolymer composite hydrophobic microspheres as the filter layer on the gauze or cotton balls, and then laying and fixing a layer of gauze or cotton balls on the silica fume-based geopolymer composite hydrophobic microspheres; for the oil-water mixture containing heavy oil, the oil-containing sewage to be treated is introduced into the filter from the upper feed inlet, oil flows into the container below through the filter layer, and water is trapped on the filter layer and flows out from the water outlet above, so that the purpose of separating oil from water is achieved; for an oil-water mixture containing light oil, the oil-containing sewage to be treated is introduced into the filter from the lower feed inlet through pressure, oil flows out from the upper part of the filter container through the filter layer, and water is trapped below the filter layer and flows out from the lower water outlet, so that the purpose of separating oil from water is achieved; the oil obtained by separation is recycled, the water obtained by separation is recycled or directly discharged, and the silica fume-based geopolymer composite hydrophobic microspheres are recycled.
6. The silica fume based geopolymer composite hydrophobic microsphere prepared by the preparation method of any one of claims 1-3, which is used as a raw material for metal piece coating or plating, including aerospace, electric power system, communication system and ground traffic metal pieces.
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