CN115090264A - Super-hydrophobic/super-oleophylic adsorbent prepared from coal gasification slag as raw material and preparation method and application thereof - Google Patents
Super-hydrophobic/super-oleophylic adsorbent prepared from coal gasification slag as raw material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a super-hydrophobic/super-oleophilic adsorbent prepared by taking gasified residues as a raw material, a preparation method thereof and application of the adsorbent in selective separation of oil in an oil-in-water emulsion. The preparation method comprises the following steps: crushing, screening, washing with water, drying, soaking in hydrochloric acid solution, washing with water to neutrality, and drying to obtain treated gasified slag; mixing the treated gasified slag with an alkaline activator, adding water to prepare a saturated solution, stirring at room temperature fully, drying, placing in a nitrogen atmosphere for microwave activation, washing with water to be neutral, and drying to obtain chemically activated gasified slag; soaking the chemically activated coal gasification 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 an acetone solution of a low-surface-energy substance, fully soaking at room temperature, and carrying out solid-liquid separation, washing and drying to obtain the super-hydrophobic/super-oleophylic adsorbent.
Description
Technical Field
The invention relates to the field of adsorption materials, in particular to a super-hydrophobic/super-oleophylic adsorbent prepared by taking gasified slag as a raw material, and a preparation method and application thereof.
Background
Oil leakage and industrial production generate thousands of tons of oily wastewater every year, which not only causes serious harm to the ecological environment, but also brings great influence to human production and life. The oily wastewater has complex components, and how to efficiently separate the oily wastewater, especially how to efficiently separate stable oil-water emulsion, has attracted extensive attention.
Conventional oil-water separation techniques include gravity separation, centrifugal separation, and air-flotation separation. The former two are based on the oil-water relative density difference to realize separation under the action of gravity or centrifugal force, and are mainly used for separating large-size oil-water mixture, and can not separate emulsion and dissolved oil with smaller size, and the separation effect on oil/water mixture with similar density is not good. The air floatation method is to inject highly dispersed gas into the oily wastewater to contact with oil drops to form a copolymer, and the copolymer floats on the water surface under the action of buoyancy force to realize the separation of oil and water; the method can be used for separating emulsified oil-water mixture. However, the air floatation method cannot be used for treating oily wastewater with high toxicity and strong volatility, and is easy to bring toxic and harmful substances in the water body into the air, thereby threatening the health of human beings.
The adsorption method is a separation technology which is relatively promising at present, and mainly utilizes the inherent characteristics of porosity and large specific surface area of a solid adsorbent to adsorb oil pollutants and organic pollutants in wastewater so as to realize effective separation of oil and water.
The adsorbent material with special wettability can be prepared by surface modification of the adsorbent, and the oil-water separation effect of the adsorbent is further improved. These adsorbents with specific wettability can be used not only to separate insoluble oil-water mixtures, but also to have a high separation efficiency for emulsions with a small particle size.
The super-hydrophobic/super-oleophylic adsorbent has a repulsive effect on water and a strong affinity for oil, is a typical oil-removing adsorbent, can selectively separate various oil-water mixtures and adsorb floating oil on the water surface, and shows ultra-high separation efficiency.
The coal gasification slag is a product of coal after high-temperature gasification and quenching, is coal-based solid waste formed by conversion of inorganic mineral components and carbon components which are not completely oxidized in raw coal in the coal gasification process, and has the annual output of thousands of tons.
The gasified slag has the excellent characteristics of fine and loose structure, rich amorphous carbon content, higher reaction activity of siliceous components, rich pore structure and the like, and has the potential of being prepared into an adsorbent. The oleophylic/hydrophobic modification is carried out on the surface of the gasified slag, so that the affinity of the gasified slag to oil can be improved, the gasified slag can be used for treating oily wastewater, and the resource utilization of the gasified slag can be further realized.
Therefore, the coal gasification slag is an ideal raw material for preparing the super-hydrophobic/super-oleophylic adsorbent, and the key point is how to prepare the coal gasification slag into the super-hydrophobic/super-oleophylic adsorbent.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides a method for preparing a super-hydrophobic/super-oleophylic adsorbent by taking coal gasification slag as a raw material, and the obtained adsorbent has a repulsive action on water and strong affinity on oil and can selectively separate the oil in an oil-in-water emulsion.
The specific technical scheme is as follows:
a method for preparing super-hydrophobic/super-oleophylic adsorbent by taking gasified slag as raw material is shown in figure 1 and comprises the following steps:
(1) crushing, screening, washing and drying the gasified slag, fully soaking the gasified slag in a hydrochloric acid solution, washing the gasified slag to be neutral, and drying the gasified slag to obtain treated gasified slag;
(2) mixing the treated gasified slag with an alkaline activator, adding water to prepare a saturated solution, stirring at room temperature fully, drying to obtain gasified slag impregnated with the alkaline activator, placing the gasified slag in a nitrogen atmosphere for microwave activation, washing with water to be neutral, and drying to obtain chemically activated gasified 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) soaking the chemically activated coal gasification 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, fully soaking at room temperature, and carrying out solid-liquid separation, washing and drying to obtain the super-hydrophobic/super-oleophylic adsorbent.
The method of the invention is characterized in that:
firstly, modifying the gasified slag by hydrochloric acid, and dissolving impurities in the pore channel of the gasified slag to ensure that the pore channel is smoother;
then, impregnating with a saturated alkaline activator solution of a specific type, so that the saturated alkaline activator can be fully adsorbed into the pore canal inside the gasified slag, thereby improving the subsequent microwave activation effect;
then, the surface of the gasified slag is etched by combining nitric acid and hydrogen peroxide under the ultrasonic condition, so that the surface activity of the gasified slag is improved, the next step has stronger binding capacity with low-surface-energy substances and firmer binding, and the hydrophobicity and lipophilicity of the product are further improved;
and finally, performing low surface energy substance modification on the coal gasification slag surface to form a super-hydrophobic/super-oleophylic surface, so as to improve 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 gasified slag, the microwave energy is converted into heat energy in particles and then continuously accumulated and transferred outwards, the purpose of quickly and uniformly activating the gasified slag is realized, and uniform pore size distribution is formed in the gasified slag;
the nitric acid has strong corrosivity, the hydrogen peroxide is decomposed to release oxygen under the catalytic action of the gasified slag, and the size of the micro bubbles is kept under the ultrasonic action; meanwhile, the cavitation effect of the ultrasonic wave enables the micro bubbles to generate strong impact force in the collapse process, and the local corrosion rate of the gasified slag is enhanced; the etching action increases the surface roughness of the gasified slag, obtains more active sites, enhances the surface affinity of the gasified slag and low-surface-energy substances, and further improves the hydrophobicity and lipophilicity of the final product.
In a preferable example, in the step (1), the gasified slag is crushed and sieved until the size fraction is less than 0.25 mm.
The crushed gasified slag is washed by water, the dust and soluble attachments on the surfaces of the gasified slag particles are washed off, and the cleaned gasified slag is obtained after the coal is placed in a constant-temperature drying oven and dried at the temperature of 105 ℃.
In a preferable example, in the step (1), the concentration of the hydrochloric acid solution is 0.5 to 5mol/L, and the solid-liquid mass ratio of the gasified slag to the hydrochloric acid solution is 1: (0.5 to 3.0).
After the gasified slag is soaked and dried in a saturated solution of an alkaline activator, the alkaline activator can be uniformly dispersed in the inner pore canal of the gasified slag, and the combination effect which can not be realized by common mechanical mixing is achieved.
The pore size distribution of the gasified slag can be regulated and controlled by adjusting the ratio of the alkaline activator to the gasified slag and the microwave activation time, so as to obtain better hydrophobic/oleophylic performance.
In a preferred example, in the step (2), the mass ratio of the treated gasified slag to the alkaline activator is 1: (1-4).
In a preferred embodiment, in the step (2), the microwave power of the microwave activation is 500-700W, and the microwave activation time is 20-40 min.
In a preferable example, in the step (3), a solid-liquid mass ratio of the chemically activated coal gasification slag to the nitric acid solution is 1: (0.5-2.0).
In a preferable 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 example, in the step (3), the ultrasonic etching temperature is room temperature, and the time is 5-20 min.
In a preferred example, in step (4), the low surface energy material is at least one of stearic acid, lauric acid, perfluorodecanoic acid, perfluorooctanoic acid, dodecylmercaptan, octadecylmercaptan, octadecyltrichlorosilane, 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 gasified slag, the ultrasonic etching treatment in the step (3) further enhances the surface combination energy of the gasified slag, and the oleophilic end in the low surface energy substance faces outwards, so that a super-hydrophobic/super-oleophilic interface is formed on the surface of the gasified slag, and the adsorption capacity to oil in the oily wastewater is improved.
In a preferred example, 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% to 8%.
In a preferred example, 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 to 3.0).
In a preferred embodiment, in the step (4), the solvent used for 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 invention also provides the super-hydrophobic/super-oleophylic adsorbent prepared by the method.
The contact angle of the super-hydrophobic/super-oleophylic adsorbent to water is not less than 145 degrees, and the contact angle to oil is 0 degree.
The invention also provides the application of the super-hydrophobic/super-oleophilic adsorbent in selectively separating oil in an oil-in-water emulsion.
The invention has the beneficial effects that:
1. according to the invention, pores are formed and layered in the gasified slag in a manner of impregnating an alkaline activator and microwave chemical activation, high-temperature calcination is not required, high energy consumption is avoided, and the activation efficiency is improved.
2. The invention enhances the surface activity of the gasified slag by ultrasonic etching of the nitric acid-hydrogen peroxide solution, so that the gasified slag and the low-surface-energy modifier are firmly combined, the modifier is not easy to run off, and the hydrophobicity and lipophilicity of the adsorbent are better.
3. The raw material gasified slag used in the invention is one of the bulk coal-based industrial solid wastes in China, and has wide sources, low price and easy obtainment.
Drawings
FIG. 1 is a flow diagram of the adsorbent preparation process of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the as-gasified slag of example 1.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
(1) Crushing and screening the coal gasification slag (the appearance is shown in figure 2) until the granularity is less than 0.25mm, washing the coal gasification slag by tap water, and drying the coal gasification slag in a constant-temperature drying oven at 105 ℃. 1.0kg of the cleaned gasified residue was immersed in 1.0L of a hydrochloric acid solution having a concentration of 0.5mol/L for 24 hours, then washed to neutrality with tap water, and dried in a 105 ℃ forced air drying oven.
(2) 1.0kg of treated gas slag was mixed with 1.0kg of Na 2 CO 3 Mixing the powders, adding tap water to Na 2 CO 3 Completely dissolving, stirring at room temperature for 2 hr, and drying in 105 deg.C forced air drying oven to obtain fully and uniformly impregnated Na 2 CO 3 Gasifying the activated coal to slag, performing microwave activation for 40min under the nitrogen atmosphere with the microwave power of 500W, and washing with tap water until the activated coal is completely dissolvedAnd (4) neutralizing, and drying in a 105 ℃ forced air drying oven to obtain the chemically activated coal gasification slag.
(3) And (3) soaking the gasified slag obtained in the step (2) in 0.8L of 1.0mol/L nitric acid solution, adding 0.2L of 20 mass percent hydrogen peroxide, carrying out ultrasonic treatment for 5min, washing the gasified slag to be neutral by using tap water, and drying the gasified slag in a 105 ℃ blast drying box to obtain the porous active adsorbent subjected to ultrasonic etching.
(4) And (4) adding the porous active adsorbent obtained in the step (3) into 1.0L of acetone solution with the dodecyl mercaptan concentration of 2 wt%, soaking for 24h at room temperature, filtering, washing with the acetone solution, and drying in a 60 ℃ forced air drying oven for 20min 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 1680m 2 Per g, pore volume 0.958cm 3 The volume ratio of the adsorbent is 54.8%, and the micropore volume is 0.568cm 3 In terms of pore volume, 58.3%. The contact angles of the super-hydrophobic/super-oleophilic adsorbent to water and oil were 145.2 ° and 0 °, respectively.
Example 2
(1) Crushing and screening the gasified slag until the granularity is less than 0.25mm, washing the crushed gasified slag by tap water, and drying the crushed gasified slag in a constant-temperature drying box at 105 ℃. 1.0kg of the cleaned gas slag was immersed in 1.2L of a 1.0mol/L hydrochloric acid solution for 24 hours, then washed to neutrality with tap water and dried in a 105 ℃ forced air drying oven.
(2) 1.0kg of treated coal gasification slag was mixed with 1.5kg of K 2 CO 3 Mixing the powders, adding tap water to K 2 CO 3 Dissolving completely, stirring at room temperature for 2 hr, and drying in 105 deg.C blast drying oven to obtain fully and uniformly impregnated K 2 CO 3 And (3) gasifying the activated coal gas slag, performing microwave activation for 35min under the nitrogen atmosphere, wherein the microwave power is 550W, then washing the activated coal gas slag to be neutral by using tap water, and drying the activated coal gas slag in a 105 ℃ blast drying oven to obtain the chemically activated coal gas slag.
(3) And (3) soaking the gasified slag obtained in the step (2) in 1.0L of 2.0mol/L nitric acid solution, adding 0.4L of 22% hydrogen peroxide by mass, ultrasonically treating for 5min, washing with tap water to be neutral, and drying in a 105 ℃ forced air drying oven to obtain the ultrasonically etched porous active adsorbent.
(4) And (3) adding the porous active adsorbent obtained in the step (3) into 1.0L of acetone solution with the concentration of 4 wt% of perfluorooctanoic acid, soaking for 24h at room temperature, filtering, washing by the acetone solution, and drying in a 65 ℃ forced air drying oven for 18min to finally obtain the surface superhydrophobic/superoleophilic adsorbent with a large number of micropores. The specific surface area of the super-hydrophobic/super-oleophylic adsorbent is 1750m 2 Per g, pore volume 0.972cm 3 The volume ratio of the adsorbent is 55.6%, and the micropore volume is 0.689cm 3 In terms of pore volume, 59.8%. The superhydrophobic/superoleophilic adsorbent has contact angles of 148.9 ° and 0 ° for water and oil, respectively.
Example 3
(1) Crushing and screening the gasified slag until the granularity is less than 0.25mm, washing the crushed gasified slag by tap water, and drying the crushed gasified slag in a constant-temperature drying box at 105 ℃. 1.5kg of the cleaned gasified residue was immersed in 2.0L of a 1.6mol/L hydrochloric acid solution for 24 hours, then washed to neutrality with tap water, and dried in a 105 ℃ forced air drying oven.
(2) 1.5kg of treated gas slag was mixed with 2.0kg of Na 2 O 2 Mixing the powders, adding tap water to Na 2 O 2 Dissolving completely, stirring at room temperature for 2 hr, and drying in 105 deg.C forced air drying oven to obtain fully and uniformly impregnated Na 2 O 2 And (3) gasifying the coal gasification slag of the activating agent, performing microwave activation for 30min under the nitrogen atmosphere, wherein the microwave power is 600W, then washing the coal gasification slag to be neutral by using tap water, and drying the coal gasification slag in a 105 ℃ blast drying oven to obtain the chemically activated coal gasification slag.
(3) And (3) soaking the gasified slag obtained in the step (2) in 1.5L of nitric acid solution with the concentration of 3.0mol/L, adding 0.6L of hydrogen peroxide with the mass fraction of 25%, ultrasonically treating for 5min, washing with tap water to be neutral, and drying in a 105 ℃ forced air drying oven to obtain the ultrasonically etched porous active adsorbent.
(4) Adding the porous active adsorbent obtained in the step (3) into 1.5L acetone solution with the octadecyl trichlorosilane concentration of 5 wt%, and keeping the temperature at room temperatureSoaking for 24h under the condition, filtering, washing by acetone solution, and drying in a 70 ℃ forced air drying oven for 15min to finally obtain the super-hydrophobic/super-oleophilic adsorbent with a large number of micropores. The specific surface area of the super-hydrophobic/super-oleophylic adsorbent is 1860m 2 Per g, pore volume 0.984cm 3 The volume ratio of the adsorbent is 56.4%, and the micropore volume is 0.709cm 3 In terms of pore volume, 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 gasified slag until the granularity is less than 0.25mm, washing the crushed gasified slag by tap water, and drying the crushed gasified slag in a constant-temperature drying box at 105 ℃. 2.0kg of the cleaned gasified residue were immersed in 2.5L of a 2.0mol/L hydrochloric acid solution for 24 hours, then washed to neutrality with tap water, and dried in a 105 ℃ forced air drying oven.
(2) 2.0kg of treated gas slag was mixed with 1.0kg of Na 2 CO 3 And 2.0kg of NaOH powder, and adding tap water to Na 2 CO 3 Dissolving with NaOH completely, stirring at room temperature for 2 hr, and drying in 105 deg.C forced air drying oven to obtain Na 2 CO 3 And (3) carrying out coal gasification slag treatment with NaOH activating agent, carrying out microwave activation for 25min under nitrogen atmosphere, wherein the microwave power is 650W, then washing with tap water to be neutral, and drying in a 105 ℃ blast drying oven to obtain the chemically activated coal gasification slag.
(3) And (3) soaking the gasified slag obtained in the step (2) in 2.5L of 4.0mol/L nitric acid solution, adding 0.9L of 25% hydrogen peroxide by mass, ultrasonically treating for 5min, washing with tap water to be neutral, and drying in a 105 ℃ forced air drying oven to obtain the ultrasonically etched porous active adsorbent. The specific surface area of the porous active adsorbent is 1890m 2 Per g, pore volume 0.998cm 3 The volume ratio of the adsorbent to the pore is 57.3%, and the pore volume is 0.783cm 3 In terms of pore volume, 62.6%. The contact angles of the porous active adsorbent to water and oil are 55.2 degrees and 58.4 degrees respectively.
(4) Adding the porous active adsorbent obtained in the step (3) into 2.5L of tetraethoxysilaneSoaking in 6.5 wt% acetone solution at room temperature for 24 hr, filtering, washing with acetone solution, and drying in 60 deg.C forced air drying oven for 20min to obtain super-hydrophobic/super-oleophilic adsorbent with large amount of micropores. The specific surface area of the super-hydrophobic/super-oleophilic adsorbent is 1910m 2 Per g, pore volume 0.998cm 3 The volume of the adsorbent is 60.3%, and the micropore volume is 0.783cm 3 In terms of pore volume, 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 gasified slag until the granularity is less than 0.25mm, washing the crushed gasified slag by tap water, and drying the crushed gasified slag in a constant-temperature drying box at 105 ℃. 2.0kg of the cleaned gas slag were immersed for 24 hours in 3.0L of a 3.0mol/L hydrochloric acid solution, washed to neutrality with tap water and dried in a 105 ℃ forced air drying cabinet.
(2) 2.0kg of treated gas slag were mixed with 1.5kg of K 2 CO 3 And 2.0kg of KOH powder, and adding tap water to K 2 CO 3 Completely dissolving with KOH, stirring at room temperature for 2h, and drying in 105 deg.C forced air drying oven to obtain fully and uniformly impregnated K 2 CO 3 And (3) carrying out gasification slag with a KOH activating agent, carrying out microwave activation for 20min under the nitrogen atmosphere, wherein the microwave power is 700W, then washing the coal gasification slag to be neutral by using tap water, and drying the coal gasification slag in a 105 ℃ blast drying box to obtain the chemically activated gasification slag.
(3) And (3) soaking the gasified slag obtained in the step (2) in 3.0L of 5.0mol/L nitric acid solution, adding 0.9L of 25% hydrogen peroxide by mass, ultrasonically treating for 5min, washing with tap water to be neutral, and drying in a 105 ℃ forced air drying oven to obtain the ultrasonically etched porous active adsorbent.
(4) And (4) adding the porous active adsorbent obtained in the step (3) into 3.0L of acetone solution with the stearic acid and lauric acid concentrations of 3.5 wt% and 4.0 wt%, soaking for 24 hours at room temperature, filtering, washing by the acetone solution, and drying in a 60 ℃ forced air drying oven for 20 minutes to finally obtain the adsorbent which has a large number of micropores and is super-hydrophobic/super-oleophylic in surface. The superhydrophobicThe specific surface area of the super-oleophilic adsorbent is 2021m 2 Per g, pore volume 1.024cm 3 (ii)/g, the volume ratio of the adsorbent is 63.9%, and the volume of the micropores is 0.803cm 3 In terms of pore volume, 61.4%. The contact angles of the super-hydrophobic/super-oleophilic adsorbent to water and oil were 159.8 ° and 0 °, respectively.
Example 6
(1) Crushing and screening the gasified slag until the granularity is less than 0.25mm, washing the crushed gasified slag by tap water, and drying the crushed gasified slag in a constant-temperature drying box at 105 ℃. 2.5kg of the cleaned gasified residue were immersed in 3.0L of a 4.0mol/L hydrochloric acid solution for 24 hours, then washed to neutrality with tap water, and dried in a 105 ℃ forced air drying oven.
(2) 2.5kg of treated gas slag was mixed with 2.5kg of Na 2 CO 3 And 3.0kg of Na 2 O 2 Mixing the powders, adding tap water to Na 2 CO 3 With Na 2 O 2 Dissolving completely, stirring at room temperature for 2 hr, and drying in 105 deg.C forced air drying oven to obtain fully and uniformly impregnated Na 2 CO 3 With Na 2 O 2 And (3) gasifying the coal gasification slag of the activating agent, performing microwave activation for 20min under the nitrogen atmosphere, wherein the microwave power is 700W, then washing the coal gasification slag to be neutral by using tap water, and drying the coal gasification slag in a 105 ℃ blast drying oven to obtain the chemically activated coal gasification slag.
(3) And (3) soaking the gasified slag obtained in the step (2) in 4.0L of 6.0mol/L nitric acid solution, adding 2.4L of 30% hydrogen peroxide by mass, ultrasonically treating for 5min, washing with tap water to be neutral, and drying in a 105 ℃ forced air drying oven to obtain the ultrasonically etched porous active adsorbent.
(4) And (3) adding the porous active adsorbent obtained in the step (3) into 4.0L of acetone solution with 6.0 wt% of polydimethylsiloxane concentration, soaking for 24h at room temperature, filtering, washing by the acetone solution, and drying in a 60 ℃ forced air drying oven for 20min to finally obtain the adsorbent with a large number of micropores and super-hydrophobic/super-oleophylic surface. The specific surface area of the super-hydrophobic/super-oleophylic adsorbent is 2046m 2 Per g, pore volume 1.148cm 3 The volume ratio of the adsorbent is 68.4%, and the micropore volume is 0.846cm 3 /g，The pore volume ratio was 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 the example 1 is only that the step (3) is lacked, the step (4) is directly carried out by replacing the porous active adsorbent with the chemically activated coal gasification slag obtained in the step (2), the rest is the same, and the specific surface area of the finally obtained adsorbent is 1605m 2 Per g, pore volume 0.942cm 3 The volume ratio of the adsorbent is 52.4%, and the micropore volume is 0.552cm 3 Per g, the pore volume ratio was 56.2%. The contact angles of the adsorbent for water and oil were 138.2 ° and 0 °, respectively.
Comparative example 2
The only difference from example 1 is that in step (2), the gas slag is gasified with Na 2 CO 3 The microwave activation is carried out after the powder is mechanically and uniformly mixed, and the steps of dissolving by adding water, dipping and drying are lacked; the subsequent nitrogen microwave activation and the steps (3) and (4) are the same, and the specific surface area of the finally obtained adsorbent is 1215m 2 Per g, pore volume 0.628cm 3 The volume ratio of the adsorbent is 42.4%, and the micropore volume is 0.372cm 3 In terms of pore volume, 35.6%. The contact angles of the adsorbent to water and oil were 136.4 ° and 0 °, respectively.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing super-hydrophobic/super-oleophylic adsorbent by taking gasified slag as raw material is characterized by comprising the following steps:
(1) crushing, screening, washing and drying the gasified slag, fully soaking the gasified slag in a hydrochloric acid solution, washing the gasified slag to be neutral, and drying the gasified slag to obtain treated gasified slag;
(2) mixing the treated gasified slag with an alkaline activator, adding water to prepare a saturated solution, stirring at room temperature fully, drying to obtain gasified slag impregnated with the alkaline activator, placing the gasified slag in a nitrogen atmosphere for microwave activation, washing with water to be neutral, and drying to obtain chemically activated gasified 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) soaking the chemically activated coal gasification 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, fully soaking at room temperature, and carrying out solid-liquid separation, washing and drying to obtain the super-hydrophobic/super-oleophylic adsorbent.
2. The method according to claim 1, wherein in the step (1), the gasified slag is crushed and sieved to a size fraction of less than 0.25 mm.
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 gasified slag to the hydrochloric acid solution is 1: (0.5-3.0).
4. The method according to claim 1, wherein in the step (2), the mass ratio of the treated gasified slag to the alkaline activator is 1: (1-4).
5. The method according to claim 1, wherein in the step (2), the microwave activation has a microwave power of 500-700W and a microwave activation time of 20-40 min.
6. The method of claim 1, wherein in step (3):
the solid-liquid mass ratio of the chemically activated coal gasification slag to the nitric acid solution is 1: (0.5 to 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;
the temperature of the ultrasonic etching is room temperature, and the time is 5-20 min.
7. The method of claim 1, wherein in step (4):
the low surface energy substance is at least one of stearic acid, lauric acid, perfluorodecanoic acid, perfluorooctanoic acid, dodecyl mercaptan, octadecanethiol, octadecyl trichlorosilane, tetraethoxysilane, polydimethylsiloxane and perfluorooctyl triethoxysilane;
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).
8. The method of claim 1, wherein in step (4):
the solvent adopted for washing is acetone;
the drying temperature is 60-80 ℃, and the drying time is 10-20 min.
9. The super-hydrophobic/super-oleophilic adsorbent prepared by the method according to any one of claims 1 to 8.
10. Use of the superhydrophobic/superoleophilic adsorbent of claim 9 for selectively separating oil in an oil-in-water emulsion.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115888673A (en) * | 2022-11-14 | 2023-04-04 | 陕西煤业新型能源科技股份有限公司 | Method for preparing adsorption material by utilizing coal gasification fine slag |
| CN116060065A (en) * | 2023-03-21 | 2023-05-05 | 重庆工商大学 | Novel supported composite photocatalyst and preparation method thereof |
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Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211753A (en) * | 2010-04-08 | 2011-10-12 | 中国科学院化学研究所 | Composite material having multiple characteristics in surface and preparation method thereof |
| CN102381705A (en) * | 2011-07-27 | 2012-03-21 | 西南科技大学 | Method for producing activated carbon by thermally activating coal tar dreg/ sludge fermentation body by using microwaves |
| CN102989414A (en) * | 2012-11-22 | 2013-03-27 | 中国石油大学(华东) | Preparation method of super-hydrophobic active carbon modified material |
| CN103021666A (en) * | 2012-12-03 | 2013-04-03 | 彩虹集团公司 | Method for preparing compound titanium dioxide film |
| CN103626175A (en) * | 2013-12-17 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Method for preparing activated carbon from coal tar residues and application thereof |
| CN104437444A (en) * | 2014-10-14 | 2015-03-25 | 天津理工大学 | Preparation method of hydrophobic activated carbon modified material |
| CN105056901A (en) * | 2015-07-31 | 2015-11-18 | 东北林业大学 | Superhydrophobic and super-oleophilic adsorbent with straw as raw material and preparation method thereof |
| CN106422423A (en) * | 2016-11-30 | 2017-02-22 | 天津大学 | Super-hydrophobic wire mesh and preparation method thereof |
| CN106693907A (en) * | 2017-01-13 | 2017-05-24 | 中国科学院合肥物质科学研究院 | Method for preparing oil absorption material of porous structure by utilizing ultrasonic method |
| CN107011534A (en) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | A kind of super-hydrophobic super-oleophylic melamine foamed plastic and preparation method and application |
| WO2017133312A1 (en) * | 2016-02-04 | 2017-08-10 | 苏州蓝锐纳米科技有限公司 | Ultrahydrophobic fabric and construction method thereof |
| CN107855103A (en) * | 2017-03-15 | 2018-03-30 | 吉林大学 | The method of sorbing material and obtained sorbing material are prepared using coal gasification fine slag |
| CN107855104A (en) * | 2017-03-16 | 2018-03-30 | 吉林大学 | The thick slag of coal gasification prepares the method for complex mesoporous material and obtained mesoporous material |
| CN109665523A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of preparation method and supercapacitor of graphene composite stone oil coke matrix activated carbon |
| CN109761236A (en) * | 2019-03-15 | 2019-05-17 | 武汉科技大学 | A kind of method that microwave-assisted re-activation prepares multistage mesoporous activated carbon |
| CN110117193A (en) * | 2019-05-20 | 2019-08-13 | 中国建筑材料科学研究总院有限公司 | The preparation method of hydrophobicity haydite light-weight aggregate, the hydrophobicity haydite light-weight aggregate by this method preparation and its application |
| CN110434034A (en) * | 2019-08-26 | 2019-11-12 | 青岛理工大学 | Preparation method of super-hydrophobic coating |
| CN112408390A (en) * | 2020-11-20 | 2021-02-26 | 西北化工研究院有限公司 | Method for preparing activated carbon adsorbent from kerosene co-refining residues |
| CN112409022A (en) * | 2020-11-20 | 2021-02-26 | 武汉科技大学 | Carbon nanotube/fiber modified self-heating porous hydrophobic/oleophylic ceramic and preparation method thereof |
| CN113019326A (en) * | 2021-03-15 | 2021-06-25 | 中南大学 | Iron-based-carboxyl modified biochar and preparation method and application thereof |
| CN113332751A (en) * | 2021-06-25 | 2021-09-03 | 太原理工大学 | Process for using dipropylamine as reversible extraction solvent |
| CN113333436A (en) * | 2021-05-21 | 2021-09-03 | 中国矿业大学 | All-component comprehensive utilization method of coal gasification fine slag |
| CN113351376A (en) * | 2021-05-28 | 2021-09-07 | 中国矿业大学 | Gasified slag flotation collector and preparation method thereof |
| CN114591677A (en) * | 2022-03-31 | 2022-06-07 | 陕西科技大学 | Basalt nanosheet-based super-hydrophobic coating material and preparation method thereof |
-
2022
- 2022-07-26 CN CN202210883700.4A patent/CN115090264B/en active Active
Patent Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211753A (en) * | 2010-04-08 | 2011-10-12 | 中国科学院化学研究所 | Composite material having multiple characteristics in surface and preparation method thereof |
| CN102381705A (en) * | 2011-07-27 | 2012-03-21 | 西南科技大学 | Method for producing activated carbon by thermally activating coal tar dreg/ sludge fermentation body by using microwaves |
| CN102989414A (en) * | 2012-11-22 | 2013-03-27 | 中国石油大学(华东) | Preparation method of super-hydrophobic active carbon modified material |
| CN103021666A (en) * | 2012-12-03 | 2013-04-03 | 彩虹集团公司 | Method for preparing compound titanium dioxide film |
| CN103626175A (en) * | 2013-12-17 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Method for preparing activated carbon from coal tar residues and application thereof |
| CN104437444A (en) * | 2014-10-14 | 2015-03-25 | 天津理工大学 | Preparation method of hydrophobic activated carbon modified material |
| CN105056901A (en) * | 2015-07-31 | 2015-11-18 | 东北林业大学 | Superhydrophobic and super-oleophilic adsorbent with straw as raw material and preparation method thereof |
| WO2017133312A1 (en) * | 2016-02-04 | 2017-08-10 | 苏州蓝锐纳米科技有限公司 | Ultrahydrophobic fabric and construction method thereof |
| CN106422423A (en) * | 2016-11-30 | 2017-02-22 | 天津大学 | Super-hydrophobic wire mesh and preparation method thereof |
| CN106693907A (en) * | 2017-01-13 | 2017-05-24 | 中国科学院合肥物质科学研究院 | Method for preparing oil absorption material of porous structure by utilizing ultrasonic method |
| CN107011534A (en) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | A kind of super-hydrophobic super-oleophylic melamine foamed plastic and preparation method and application |
| CN107855103A (en) * | 2017-03-15 | 2018-03-30 | 吉林大学 | The method of sorbing material and obtained sorbing material are prepared using coal gasification fine slag |
| CN107855104A (en) * | 2017-03-16 | 2018-03-30 | 吉林大学 | The thick slag of coal gasification prepares the method for complex mesoporous material and obtained mesoporous material |
| CN109665523A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of preparation method and supercapacitor of graphene composite stone oil coke matrix activated carbon |
| CN109761236A (en) * | 2019-03-15 | 2019-05-17 | 武汉科技大学 | A kind of method that microwave-assisted re-activation prepares multistage mesoporous activated carbon |
| CN110117193A (en) * | 2019-05-20 | 2019-08-13 | 中国建筑材料科学研究总院有限公司 | The preparation method of hydrophobicity haydite light-weight aggregate, the hydrophobicity haydite light-weight aggregate by this method preparation and its application |
| CN110434034A (en) * | 2019-08-26 | 2019-11-12 | 青岛理工大学 | Preparation method of super-hydrophobic coating |
| CN112408390A (en) * | 2020-11-20 | 2021-02-26 | 西北化工研究院有限公司 | Method for preparing activated carbon adsorbent from kerosene co-refining residues |
| CN112409022A (en) * | 2020-11-20 | 2021-02-26 | 武汉科技大学 | Carbon nanotube/fiber modified self-heating porous hydrophobic/oleophylic ceramic and preparation method thereof |
| CN113019326A (en) * | 2021-03-15 | 2021-06-25 | 中南大学 | Iron-based-carboxyl modified biochar and preparation method and application thereof |
| CN113333436A (en) * | 2021-05-21 | 2021-09-03 | 中国矿业大学 | All-component comprehensive utilization method of coal gasification fine slag |
| CN113351376A (en) * | 2021-05-28 | 2021-09-07 | 中国矿业大学 | Gasified slag flotation collector and preparation method thereof |
| CN113332751A (en) * | 2021-06-25 | 2021-09-03 | 太原理工大学 | Process for using dipropylamine as reversible extraction solvent |
| CN114591677A (en) * | 2022-03-31 | 2022-06-07 | 陕西科技大学 | Basalt nanosheet-based super-hydrophobic coating material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YU-YAN GU ET AL.: "A carbon silica composite prepared from water slurry coal gasification slag", 《MICROPOROUS AND MESOPOROUS MATERIALS》, no. 279, pages 303 - 307 * |
| 毛林: "煤气化细渣制备磁性炭硅复合材料及其吸附性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 02, pages 016 - 674 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143484A (en) * | 2022-11-11 | 2023-05-23 | 昆明理工大学 | Mine filling material based on coal gas slag, and preparation method and application thereof |
| CN116143484B (en) * | 2022-11-11 | 2024-08-23 | 昆明理工大学 | Mine filling material based on coal gas slag, and preparation method and application thereof |
| CN115888673A (en) * | 2022-11-14 | 2023-04-04 | 陕西煤业新型能源科技股份有限公司 | Method for preparing adsorption material by utilizing coal gasification fine slag |
| CN116060065A (en) * | 2023-03-21 | 2023-05-05 | 重庆工商大学 | Novel supported composite photocatalyst and preparation method thereof |
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