CN115090264B - Super-hydrophobic/super-oleophylic adsorbent prepared from coal gas slag as raw material, and preparation method and application thereof - Google Patents
Super-hydrophobic/super-oleophylic adsorbent prepared from coal gas slag as raw material, and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a super-hydrophobic/super-oleophylic adsorbent prepared by taking coal gas slag as a raw material, a preparation method thereof and application thereof in selectively separating oil in oil-in-water emulsion. The preparation method comprises the following steps: crushing and screening the gas slag, washing with water and drying, soaking in hydrochloric acid solution, washing with water to be neutral, and drying to obtain treated gas slag; mixing the treated gas slag with an alkaline activator, adding water to prepare a saturated solution, stirring at room temperature, drying, placing in a nitrogen atmosphere for microwave activation, washing with water to neutrality, and drying to obtain chemically activated gas slag; immersing chemically activated gas slag in a nitric acid solution, adding hydrogen peroxide for ultrasonic etching treatment, and washing and drying to obtain a porous active adsorbent; adding the porous active adsorbent into acetone solution of low-surface-energy substance, soaking at room temperature, solid-liquid separating, washing, and drying to obtain the super-hydrophobic/super-oleophylic adsorbent.
Description
Technical Field
The application relates to the field of adsorption materials, in particular to a super-hydrophobic/super-oleophylic adsorbent prepared by taking gas slag as a raw material, and a preparation method and application thereof.
Background
Oil leakage and industrial production produce tens of millions of tons of oily wastewater each year, which not only causes serious harm to the ecological environment, but also brings great influence to human production and life. The complex composition of oily wastewater, how to efficiently separate oily wastewater, especially the efficient separation of stable oil-water emulsion, has attracted great attention.
Conventional oil-water separation techniques include gravity separation, centrifugal separation and air-flotation separation. The former two are based on oil-water relative density difference and realize the separation under the action of gravity or centrifugal force, are mainly used for the separation of large-size oil-water mixture, can not separate the emulsion and dissolved oil with smaller size, and have poor separation effect on the oil/water mixture with similar density. The air floatation method is to inject highly dispersed gas into the oily wastewater to contact with oil drops to form a copolymer, float on the water surface under the action of buoyancy force, and realize the separation of oil and water; the method can be used to separate emulsified oil-water mixtures. However, the air floatation method cannot be used for treating oily wastewater with high toxicity and high volatility, and toxic and harmful substances in the water body are easily brought into the air, so that the health of human beings is threatened.
The adsorption method is a relatively promising separation technology at present, and mainly utilizes the inherent characteristics of porous and large specific surface area of the solid adsorbent to adsorb oil pollutants and organic pollutants in the wastewater so as to realize the effective separation of the oil and the water.
The adsorbent material with special wettability can be prepared by carrying out surface modification on the adsorbent, so that the oil-water separation effect of the adsorbent is further improved. These adsorbents with special wettability can be used not only to separate insoluble oil-water mixtures, but also have higher separation efficiency for emulsions with smaller particle sizes.
The super-hydrophobic/super-oleophylic adsorbent has a repulsive action on water and extremely strong affinity on oil, is a typical oil removing adsorbent, can selectively separate various oil-water mixtures and adsorb floating oil on water surface, and shows ultrahigh separation efficiency.
The coal gasification slag is a product obtained by quenching coal through high-temperature gasification, and is a coal-based solid waste formed by converting inorganic mineral components and incompletely oxidized carbonaceous components in raw coal in the coal gasification process, and the annual yield is up to tens of millions of tons.
The gas slag has the excellent characteristics of fine and loose structure, rich amorphous carbon content, higher reactivity of siliceous components, rich pore structure and the like, and has the potential of being prepared into an adsorbent. The affinity of the coal gas slag to oil can be improved and the coal gas slag is used for treating oily wastewater by carrying out oleophylic/hydrophobic modification on the surface of the coal gas slag, so that the recycling utilization of the coal gas slag is realized.
Therefore, the coal gas slag is an ideal raw material for preparing the super-hydrophobic/super-oleophylic adsorbent, and the key point is how to prepare the coal gas slag into the super-hydrophobic/super-oleophylic adsorbent.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the application provides a method for preparing a super-hydrophobic/super-oleophylic adsorbent by taking coal gas slag as a raw material, and the obtained adsorbent has a repulsive action on water and extremely strong affinity on oil, and can selectively separate oil in oil-in-water emulsion.
The specific technical scheme is as follows:
a method for preparing super-hydrophobic/super-oleophylic adsorbent by taking gas-ized slag as raw material, as shown in figure 1, comprises the following steps:
(1) Crushing and screening the gas slag, washing with water and drying, fully soaking in hydrochloric acid solution, washing with water to be neutral, and drying to obtain treated gas slag;
(2) Mixing the treated gas slag with an alkaline activator, adding water to prepare a saturated solution, stirring at room temperature, drying to obtain gas slag impregnated with the alkaline activator, placing the gas slag in a nitrogen atmosphere for microwave activation, washing with water to neutrality, and drying to obtain chemically activated gas slag;
the alkaline activator is Na 2 CO 3 、K 2 CO 3 、Na 2 O 2 At least one of NaOH and KOH;
(3) Immersing chemically activated gas slag in a nitric acid solution, adding hydrogen peroxide for ultrasonic etching treatment, and washing and drying to obtain a porous active adsorbent;
(4) Adding the porous active adsorbent into an acetone solution of a low-surface-energy substance, soaking the porous active adsorbent fully at room temperature, and performing solid-liquid separation, washing and drying to obtain the super-hydrophobic/super-oleophylic adsorbent.
The method of the application is characterized in that:
firstly, hydrochloric acid is used for modifying the gas slag, so that impurities in the gas slag pore canal are dissolved, and the pore canal is smoother;
then, a specific type of saturated alkaline activator solution is adopted for impregnation, so that the saturated alkaline activator can be fully absorbed into the inner pore canal of the coal gasification slag, and the subsequent microwave activation effect is improved;
then, nitric acid is combined with hydrogen peroxide to carry out surface etching on the gas slag under the ultrasonic condition, so that the surface activity of the gas slag is improved, the combination capacity of the gas slag and low-surface-energy substances in the next step is stronger, the combination is firmer, and the hydrophobicity and lipophilicity of the product are further improved;
and finally, modifying the surface of the gas slag by using low-surface energy substances to form a super-hydrophobic/super-oleophylic surface, and improving the affinity and adsorption capacity for oil in the oily wastewater.
The method comprises the following steps:
the microwave chemical activation can directly penetrate through the gas slag, microwave energy is continuously accumulated and is transferred outwards after being converted into heat energy in particles, the purpose of quickly and uniformly activating the gas slag is achieved, and uniform pore size distribution is formed in the gas slag;
nitric acid has strong corrosiveness, hydrogen peroxide is decomposed to release oxygen under the catalysis of gas slag, and the size of micro bubbles is kept under the action of ultrasound; meanwhile, the cavitation effect of the ultrasonic wave enables the micro-bubbles to generate strong impact force in the collapse process, so that the local corrosion rate of the gas slag is enhanced; the etching effect increases the surface roughness of the gas slag, obtains more active sites, enhances the surface affinity of the gas slag and low surface energy substances, and further improves the hydrophobicity and lipophilicity of the final product.
In a preferred embodiment, in the step (1), the gas-slag is crushed and sieved to a size fraction of less than 0.25mm.
The application washes the broken coal gas slag, washes off dust and soluble attachments on the surface of the coal gas slag particles, and dries the coal gas slag in a constant temperature drying oven at 105 ℃ to obtain clean coal gas slag.
In a preferred example, in the step (1), the concentration of the hydrochloric acid solution is 0.5-5 mol/L, and the solid-liquid mass ratio of the gas slag to the hydrochloric acid solution is 1: (0.5-3.0).
After the gas slag is immersed in the saturated solution of the alkaline activator and dried, the alkaline activator can be uniformly dispersed in the inner pore canal of the gas slag, so that the combination effect which cannot be realized by common mechanical mixing is achieved.
The pore size distribution of the gas slag can be regulated and controlled by regulating the proportion of the alkaline activator and the gas slag and the microwave activation time, so that better hydrophobic/oleophylic performance can be obtained.
In a preferred embodiment, in the step (2), the mass ratio of the treated gas slag to the alkaline activator is 1: (1-4).
In a preferred embodiment, in the step (2), the microwave power for microwave activation is 500-700W, and the microwave activation time is 20-40 min.
In a preferred embodiment, in the step (3), the solid-liquid mass ratio of the chemically activated gas slag to the nitric acid solution is 1: (0.5-2.0).
In a preferred example, in the step (3), the concentration of the nitric acid solution is 1.0-6.0 mol/L, the mass concentration of the hydrogen peroxide is 20-30%, and the volume ratio of the hydrogen peroxide to the nitric acid solution is (0.1-1): 1.
in a preferred embodiment, in the step (3), the temperature of the ultrasonic etching is room temperature, and the time is 5-20 min.
In a preferred embodiment, in the step (4), the low surface energy material is at least one of stearic acid, lauric acid, perfluorodecanoic acid, perfluorooctanoic acid, dodecyl mercaptan, stearyl mercaptan, octadecyl trichlorosilane, tetraethoxysilane, polydimethylsiloxane, and perfluorooctyltriethoxysilane.
The hydrophilic end in the low surface energy substance is tightly combined with the hydrophilic group on the surface of the gas-stripping slag, the ultrasonic etching treatment in the step (3) enables the surface combination energy of the gas-stripping slag to be further enhanced, and the lipophilic end in the low surface energy substance faces outwards, so that a super-hydrophobic/super-lipophilic interface is formed on the surface of the gas-stripping slag, and the adsorption capacity of oil in the oil-containing wastewater is improved.
In a preferred embodiment, in the step (4), the mass concentration of the low surface energy substance in the acetone solution of the low surface energy substance is 2% -8%.
In a preferred embodiment, in the step (4), the solid-liquid mass ratio of the porous active adsorbent to the acetone solution of the low-surface-energy substance is 1: (0.5-3.0).
In a preferred embodiment, in step (4), the solvent used for the washing is acetone.
In a preferred embodiment, in the step (4), the drying temperature is 60-80 ℃ and the drying time is 10-20 min.
The application also provides the super-hydrophobic/super-oleophylic adsorbent prepared by the method.
The super-hydrophobic/super-oleophylic adsorbent has a contact angle of not less than 145 DEG with water and a contact angle of 0 DEG with oil.
The application also provides application of the super-hydrophobic/super-oleophylic adsorbent in selectively separating oil in oil-in-water emulsion.
The beneficial effects of the application are as follows:
1. according to the application, holes are formed and layered in the gas slag in a mode of impregnating an alkaline activator and microwave chemical activation, high-temperature calcination is not needed, high energy consumption is avoided, and meanwhile, the activation efficiency is improved.
2. The application enhances the surface activity of the gas slag by ultrasonic etching of nitric acid-hydrogen peroxide solution, so that the gas slag is firmly combined with the low surface energy modifier, the modifier is not easy to run off, and the hydrophobicity and the lipophilicity of the adsorbent are better.
3. The raw material gas slag used in the application is one of solid wastes in large coal-based industry in China, and has wide sources, low cost and easy obtainment.
Drawings
FIG. 1 is a flow chart of the adsorbent preparation process of the present application;
fig. 2 is a Scanning Electron Microscope (SEM) image of the gas slag of example 1 as it is.
Detailed Description
The application will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
Example 1
(1) Crushing and screening the gas slag (the morphology is shown in figure 2) until the granularity is less than 0.25mm, washing the gas slag by tap water, and then placing the gas slag in a constant-temperature drying oven for drying at 105 ℃. 1.0kg of the cleaned gas slag was immersed in 1.0L of hydrochloric acid solution having a concentration of 0.5mol/L for 24 hours, then washed with tap water to neutrality, and dried in a blow drying oven at 105 ℃.
(2) 1.0kg of treated gas slag was admixed with 1.0kg of Na 2 CO 3 After mixing the powders, tap water is added to Na 2 CO 3 After being just dissolved completely and stirred for 2 hours at room temperature, the mixture is placed in a 105 ℃ blast drying oven for drying, and the Na is fully and uniformly impregnated 2 CO 3 And (3) carrying out microwave activation on the coal gas slag of the activating agent for 40min in a nitrogen atmosphere, wherein the microwave power is 500W, washing with tap water to be neutral, and drying in a blast drying oven at 105 ℃ to obtain the chemically activated coal gas slag.
(3) Immersing the gas slag obtained in the step (2) in 0.8L nitric acid solution with the concentration of 1.0mol/L, adding 0.2L hydrogen peroxide with the mass fraction of 20%, carrying out ultrasonic treatment for 5min, washing to be neutral by tap water, and drying in a blast drying oven at 105 ℃ to obtain the porous active adsorbent subjected to ultrasonic etching.
(4) And (3) adding the porous active adsorbent obtained in the step (3) into 1.0L of acetone solution with the dodecyl mercaptan concentration of 2wt%, soaking for 24 hours at room temperature, filtering, washing by the acetone solution, and drying in a blast drying oven at 60 ℃ for 20 minutes to finally obtain the adsorbent with a large number of micropores and super-hydrophobic/super-oleophylic surfaces. The specific surface area of the super-hydrophobic/super-oleophylic adsorbent is 1680m 2 Per gram, pore volume of 0.958cm 3 Per gram, the volume ratio of the adsorbent is 54.8 percent, and the micropore volume is 0.568cm 3 And/g, the pore volume ratio is 58.3%. The contact angles of the super-hydrophobic/super-oleophilic adsorbent to water and oil are 145.2 degrees and 0 degrees respectively.
Example 2
(1) Crushing and screening the gas slag until the granularity is less than 0.25mm, washing the gas slag by tap water, and drying the gas slag in a constant-temperature drying oven at 105 ℃. 1.0kg of the cleaned gas slag was immersed in 1.2L of 1.0mol/L hydrochloric acid solution for 24 hours, then washed with tap water to neutrality, and dried in a blow drying oven at 105 ℃.
(2) 1.0kg of treated gas slag is mixed with 1.5kg of K 2 CO 3 After mixing the powder, tap water is added to K 2 CO 3 After being just dissolved completely and stirred for 2 hours at room temperature, the mixture is placed in a 105 ℃ blast drying oven for drying, and the fully and uniformly impregnated K is obtained 2 CO 3 And (3) carrying out microwave activation on the coal gas slag of the activating agent for 35min under the nitrogen atmosphere, wherein the microwave power is 550W, washing with tap water to be neutral, and drying in a blast drying oven at 105 ℃ to obtain the chemically activated coal gas slag.
(3) Immersing the gas slag obtained in the step (2) in 1.0L nitric acid solution with the concentration of 2.0mol/L, adding 0.4L hydrogen peroxide with the mass fraction of 22%, carrying out ultrasonic treatment for 5min, washing to be neutral by tap water, and drying in a blast drying oven at the temperature of 105 ℃ to obtain the porous active adsorbent subjected to ultrasonic etching.
(4) And (3) adding the porous active adsorbent obtained in the step (3) into 1.0L of acetone solution with the perfluoro caprylic acid concentration of 4wt%, filtering after soaking for 24 hours at room temperature, washing by the acetone solution, and drying in a blowing drying oven at 65 ℃ for 18 minutes to finally obtain the super-hydrophobic/super-oleophilic adsorbent with a large number of micropores on the surface. The specific surface area of the super-hydrophobic/super-oleophylic adsorbent is 1750m 2 Per gram, pore volume of 0.972cm 3 Per gram, the volume ratio of the adsorbent is 55.6 percent, and the micropore volume is 0.689cm 3 And/g, the pore volume ratio is 59.8%. The super-hydrophobic/super-oleophilic adsorbent has contact angles of 148.9 degrees and 0 degrees for water and oil respectively.
Example 3
(1) Crushing and screening the gas slag until the granularity is less than 0.25mm, washing the gas slag by tap water, and drying the gas slag in a constant-temperature drying oven at 105 ℃. 1.5kg of the cleaned gas slag was immersed in 2.0L of 1.6mol/L hydrochloric acid solution for 24 hours, then washed with tap water to neutrality, and dried in a blow drying oven at 105 ℃.
(2) 1.5kg of treated gas slag was admixed with 2.0kg of Na 2 O 2 After mixing the powders, tap water is added to Na 2 O 2 After being just dissolved completely and stirred for 2 hours at room temperature, the mixture is placed in a 105 ℃ blast drying oven for drying, and the Na is fully and uniformly impregnated 2 O 2 And (3) carrying out microwave activation on the coal gasification slag of the activating agent for 30min under the nitrogen atmosphere, wherein the microwave power is 600W, washing with tap water to be neutral, and drying in a blast drying oven at 105 ℃ to obtain the chemically activated coal gasification slag.
(3) Immersing the gas slag obtained in the step (2) in 1.5L of nitric acid solution with the concentration of 3.0mol/L, adding 0.6L of 25% hydrogen peroxide by mass fraction, carrying out ultrasonic treatment for 5min, washing to be neutral by tap water, and drying in a blast drying oven at 105 ℃ to obtain the porous active adsorbent subjected to ultrasonic etching.
(4) Adding the porous active adsorbent obtained in the step (3) into 1.5L of acetone solution with octadecyl trichlorosilane concentration of 5wt%, soaking at room temperature for 24 hr, filtering, washing with acetone solution, and drying in 70 deg.C air drying oven for 15min to obtain the final productA plurality of microporous and super-hydrophobic/super-oleophilic adsorbents on the surfaces. The specific surface area of the super-hydrophobic/super-oleophylic adsorbent is 1860m 2 Per gram, pore volume of 0.984cm 3 Per gram, the volume ratio of the adsorbent is 56.4 percent, and the micropore volume is 0.709cm 3 And/g, the pore volume ratio is 61.8%. The contact angles of the super-hydrophobic/super-oleophilic adsorbent to water and oil are 152.4 degrees and 0 degrees respectively.
Example 4
(1) Crushing and screening the gas slag until the granularity is less than 0.25mm, washing the gas slag by tap water, and drying the gas slag in a constant-temperature drying oven at 105 ℃. 2.0kg of the cleaned gas slag was immersed in 2.5L of hydrochloric acid solution having a concentration of 2.0mol/L for 24 hours, then washed with tap water to neutrality, and dried in a blow drying oven at 105 ℃.
(2) 2.0kg of treated gas slag was admixed with 1.0kg of Na 2 CO 3 Mixing with 2.0kg NaOH powder, adding tap water to Na 2 CO 3 Completely dissolved with NaOH, stirred for 2 hours at room temperature, and then dried in a blast drying oven at 105 ℃ to obtain the fully and uniformly impregnated Na 2 CO 3 And (3) carrying out microwave activation on the gas slag with a NaOH activating agent for 25min under a nitrogen atmosphere, wherein the microwave power is 650W, washing with tap water to be neutral, and drying in a blast drying oven at 105 ℃ to obtain the chemically activated gas slag.
(3) Immersing the gas slag obtained in the step (2) in 2.5L of nitric acid solution with the concentration of 4.0mol/L, adding 0.9L of 25% hydrogen peroxide by mass fraction, carrying out ultrasonic treatment for 5min, washing to be neutral by tap water, and drying in a blast drying oven at 105 ℃ to obtain the porous active adsorbent subjected to ultrasonic etching. The specific surface area of the porous active adsorbent is 1890m 2 Per gram, pore volume of 0.998cm 3 Per gram, the volume ratio of the adsorbent is 57.3 percent, and the micropore volume is 0.783cm 3 And/g, the pore volume ratio is 62.6%. The contact angles of the porous active adsorbent to water and oil were 55.2 ° and 58.4 °, respectively.
(4) Adding the porous active adsorbent obtained in the step (3) into 2.5L of acetone solution with tetraethoxysilane concentration of 6.5wt%, soaking for 24 hours at room temperature, filtering, washing with acetone solution, and drying at 60 ℃ by blowingDrying in a box for 20min to finally obtain the adsorbent with a large number of micropores and super-hydrophobic/super-oleophilic surface. The specific surface area of the super-hydrophobic/super-oleophylic adsorbent is 1910m 2 Per gram, pore volume of 0.998cm 3 Per gram, the volume ratio of the adsorbent is 60.3 percent, and the micropore volume is 0.783cm 3 And/g, the pore volume ratio is 62.6%. The contact angles of the super-hydrophobic/super-oleophilic adsorbent to water and oil are 157.2 degrees and 0 degrees respectively.
Example 5
(1) Crushing and screening the gas slag until the granularity is less than 0.25mm, washing the gas slag by tap water, and drying the gas slag in a constant-temperature drying oven at 105 ℃. 2.0kg of the cleaned gas slag was immersed in 3.0L of hydrochloric acid solution having a concentration of 3.0mol/L for 24 hours, then washed with tap water to neutrality, and dried in a blow drying oven at 105 ℃.
(2) 2.0kg of treated gas slag are mixed with 1.5kg of K 2 CO 3 Mixing with 2.0kg KOH powder, adding tap water to K 2 CO 3 Completely dissolving with KOH, stirring at room temperature for 2 hr, and oven drying in 105 deg.C air drying oven to obtain fully and uniformly impregnated K 2 CO 3 And (3) carrying out microwave activation on the gas slag with the KOH activating agent for 20min in a nitrogen atmosphere, wherein the microwave power is 700W, then washing with tap water to be neutral, and drying in a blast drying oven at 105 ℃ to obtain the chemically activated gas slag.
(3) Immersing the gas slag obtained in the step (2) in 3.0L of nitric acid solution with the concentration of 5.0mol/L, adding 0.9L of 25% hydrogen peroxide by mass fraction, carrying out ultrasonic treatment for 5min, washing to be neutral by tap water, and drying in a blast drying oven at 105 ℃ to obtain the porous active adsorbent subjected to ultrasonic etching.
(4) And (3) adding the porous active adsorbent obtained in the step (3) into an acetone solution with 3.0L of stearic acid and 4.0wt% of lauric acid, respectively, soaking for 24 hours at room temperature, filtering, washing by the acetone solution, and drying in a blast drying oven at 60 ℃ for 20 minutes to finally obtain the adsorbent with a large number of micropores and super-hydrophobic/super-oleophylic surfaces. The specific surface area of the super-hydrophobic/super-oleophylic adsorbent is 2021m 2 Per gram, pore volume of 1.024cm 3 Per gram, the volume ratio of the adsorbent is63.9% and a micropore volume of 0.803cm 3 And/g, the pore volume ratio is 61.4%. The super-hydrophobic/super-oleophilic adsorbent has contact angles of 159.8 DEG and 0 DEG for water and oil respectively.
Example 6
(1) Crushing and screening the gas slag until the granularity is less than 0.25mm, washing the gas slag by tap water, and drying the gas slag in a constant-temperature drying oven at 105 ℃. 2.5kg of the cleaned gas slag were immersed for 24 hours in 3.0L of 4.0mol/L hydrochloric acid solution, then washed with tap water to neutrality and dried in a blow-drying oven at 105 ℃.
(2) 2.5kg of treated gas slag and 2.5kg of Na 2 CO 3 3.0kg Na 2 O 2 After mixing the powders, tap water is added to Na 2 CO 3 With Na and Na 2 O 2 After being just dissolved completely and stirred for 2 hours at room temperature, the mixture is placed in a 105 ℃ blast drying oven for drying, and the Na is fully and uniformly impregnated 2 CO 3 With Na and Na 2 O 2 And (3) carrying out microwave activation on the coal gas slag of the activating agent for 20min in a nitrogen atmosphere, washing with tap water to be neutral, and drying in a blast drying oven at 105 ℃ to obtain the chemically activated coal gas slag.
(3) Immersing the gas slag obtained in the step (2) in 4.0L nitric acid solution with the concentration of 6.0mol/L, adding 2.4L hydrogen peroxide with the mass fraction of 30%, carrying out ultrasonic treatment for 5min, washing to be neutral by tap water, and drying in a blast drying oven at the temperature of 105 ℃ to obtain the porous active adsorbent subjected to ultrasonic etching.
(4) Adding the porous active adsorbent obtained in the step (3) into 4.0L of acetone solution with the polydimethylsiloxane concentration of 6.0wt%, soaking for 24 hours at room temperature, filtering, washing by the acetone solution, and drying in a blast drying oven at 60 ℃ for 20 minutes to finally obtain the adsorbent with a large number of micropores and super-hydrophobic/super-oleophilic surfaces. The specific surface area of the super-hydrophobic/super-oleophylic adsorbent is 2046m 2 Per gram, pore volume of 1.148cm 3 Per gram, the volume ratio of the adsorbent is 68.4 percent, and the micropore volume is 0.846cm 3 And/g, the pore volume ratio is 62.6%. The contact angles of the super-hydrophobic/super-oleophilic adsorbent to water and oil are 168.6 degrees and 0 degrees respectively.
Comparative example 1
The difference from example 1 is only that step (3) is absent, the chemically activated gas-gasified slag obtained in step (2) is directly used for replacing the porous active adsorbent to carry out step (4), the rest are the same, and the specific surface area of the finally obtained adsorbent is 1605m 2 Per gram, pore volume of 0.942cm 3 Per gram, the volume ratio of the adsorbent is 52.4 percent, and the micropore volume is 0.552cm 3 And/g, the pore volume ratio is 56.2%. The contact angles of the adsorbent to water and oil were 138.2 ° and 0 °, respectively.
Comparative example 2
The difference from example 1 is only that in step (2), the gas slag is mixed with Na 2 CO 3 The powder is mechanically and uniformly mixed and then subjected to microwave activation, and the steps of dissolving by adding water, dipping and drying are omitted; subsequent nitrogen microwave activation, the same steps (3) and (4), and the specific surface area of the finally obtained adsorbent is 1215m 2 Per gram, pore volume of 0.628cm 3 Per gram, the volume ratio of the adsorbent is 42.4 percent, and the micropore volume is 0.372cm 3 And/g, the ratio of the pore volume is 35.6%. The contact angles of the adsorbent to water and oil were 136.4 ° and 0 °, respectively.
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (9)
1. The method for preparing the super-hydrophobic/super-oleophylic adsorbent by taking the gas slag as the raw material is characterized by comprising the following steps:
(1) Crushing and screening the gas slag, washing with water and drying, fully soaking in hydrochloric acid solution, washing with water to be neutral, and drying to obtain treated gas slag;
(2) Mixing the treated gas slag with an alkaline activator, adding water to prepare a saturated solution, stirring at room temperature, drying to obtain gas slag impregnated with the alkaline activator, placing the gas slag in a nitrogen atmosphere for microwave activation, washing with water to neutrality, and drying to obtain chemically activated gas slag;
the alkaline activator is Na 2 CO 3 、K 2 CO 3 、Na 2 O 2 At least one of NaOH and KOH;
(3) Immersing chemically activated gas slag in a nitric acid solution, adding hydrogen peroxide for ultrasonic etching treatment, and washing and drying to obtain a porous active adsorbent; the solid-liquid mass ratio of the chemically activated gas slag to the nitric acid solution is 1: (0.5-2.0); the concentration of the nitric acid solution is 1.0-6.0 mol/L, the mass concentration of the hydrogen peroxide is 20-30%, and the volume ratio of the hydrogen peroxide to the nitric acid solution is (0.1-1): 1, a step of; the temperature of the ultrasonic etching is room temperature and the time is 5-20 min;
(4) Adding the porous active adsorbent into an acetone solution of a low-surface-energy substance, soaking the porous active adsorbent fully at room temperature, and performing solid-liquid separation, washing and drying to obtain the super-hydrophobic/super-oleophylic adsorbent; the low surface energy substance is at least one of stearic acid, lauric acid, perfluorodecanoic acid, perfluorooctanoic acid, dodecyl mercaptan, octadecyl trichlorosilane, tetraethoxysilane, polydimethylsiloxane and perfluorooctyl triethoxysilane.
2. The method of claim 1, wherein in step (1), the gas-gasified slag is crushed and sieved to a size fraction of less than 0.25mm.
3. The method according to claim 1, wherein in the step (1), the concentration of the hydrochloric acid solution is 0.5-5 mol/L, and the solid-liquid mass ratio of the gas slag to the hydrochloric acid solution is 1: (0.5-3.0).
4. The method of claim 1, wherein in step (2), the mass ratio of the treated gas-slag to the alkaline activator is 1: (1-4).
5. The method according to claim 1, wherein in the step (2), the microwave power for the microwave activation is 500-700W, and the microwave activation time is 20-40 min.
6. The method of claim 1, wherein in step (4):
in the acetone solution of the low-surface-energy substance, the mass concentration of the low-surface-energy substance is 2% -8%;
the solid-liquid mass ratio of the porous active adsorbent to the acetone solution of the low-surface-energy substance is 1: (0.5-3.0).
7. The method of claim 1, wherein in step (4):
the solvent adopted in the washing is acetone;
the drying temperature is 60-80 ℃ and the drying time is 10-20 min.
8. The superhydrophobic/superoleophilic adsorbent prepared according to the method of any one of claims 1-7.
9. Use of the superhydrophobic/superoleophilic adsorbent of claim 8 for selectively separating oil in an oil-in-water emulsion.
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