CN113198428B - Method for preparing three-dimensional multifunctional adsorbing material in situ by using corn pith and application thereof - Google Patents

Method for preparing three-dimensional multifunctional adsorbing material in situ by using corn pith and application thereof Download PDF

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CN113198428B
CN113198428B CN202110479334.1A CN202110479334A CN113198428B CN 113198428 B CN113198428 B CN 113198428B CN 202110479334 A CN202110479334 A CN 202110479334A CN 113198428 B CN113198428 B CN 113198428B
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corn pith
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CN113198428A (en
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彭丹
许泽杨
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Shenzhen Institute of Information Technology
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    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention relates to the technical field of wastewater adsorbing materials, in particular to a method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith and application thereof, wherein the preparation method comprises the following steps: firstly, obtaining corn pith; secondly, mixing choline chloride and p-toluenesulfonic acid monohydrate, heating to melt the choline chloride and the p-toluenesulfonic acid monohydrate, and uniformly mixing the melt with distilled water; thirdly, adding corn pith into the mixed solution, washing the corn pith to be neutral after the reaction is finished, and drying after freezing; fourthly, mixing the sodium phosphate solution and the tetramethylpiperidine oxide, adding sodium chlorite, adding the mixed solution of sodium hypochlorite and sodium phosphate, finally adding corn pith, putting the mixed solution on a shaking table for reaction after the mixture stays overnight, and finally cleaning the corn pith, freezing and drying the corn pith; and fifthly, spraying hydrophobic substances on the surface of the dried corn pith, and placing the corn pith in a fume hood for a period of time to prepare the three-dimensional multifunctional adsorbing material. Simple process, high production efficiency and good purification effect on waste water.

Description

Method for preparing three-dimensional multifunctional adsorbing material in situ by using corn pith and application thereof
Technical Field
The invention relates to the technical field of wastewater adsorbing materials, in particular to a method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith and application thereof.
Background
The oily wastewater is a common industrial wastewater, mainly comes from the processes of oil extraction, oil refining, oil storage, transportation, petrochemical production and the like in the petroleum industry, has various pollutants, high concentration, difficult biodegradation and high residue, and after oil enters a water body, a water film is formed on the surface layer of the oil to prevent oxygen from dissolving into the water body, so that the water body is anoxic, the organism dies, serious environmental pollution is caused, and especially, the generated odor seriously pollutes the environment and harms human health.
At present, the commonly used methods for treating the oily wastewater include an electrochemical method, a membrane separation method, an air floatation method, a chemical coagulation method and the like, but the methods have respective defects in the aspects of energy consumption, medicament addition, operation cost, sludge dehydration and the like. The adsorption method for treating the oily wastewater is to adsorb oil and organic matters in the wastewater by utilizing the porosity and the high specific surface area of the adsorbent so as to achieve the purpose of oil-water separation. In recent decades, the research and application of oil-absorbing materials have been rapidly developed, and traditional oil-absorbing materials, such as porous substances like activated carbon and clay, are widely used, and due to the structural properties of the materials, the oil-absorbing materials have small oil-absorbing amount and short service life, and are not beneficial to recovery. The synthetic high molecular polymer is widely used as a new oil absorption material, such as polyurethane, polyethylene, polypropylene and the like, and the high molecular oil absorption material has the advantages of large oil absorption amount and good oil absorption effect, however, most of the materials are toxic and harmful petrochemical materials, are not easy to degrade after oil absorption, have high comprehensive cost for treating wastes, are poor in reusability, and bring about the problems of secondary pollution to the environment and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the first purpose of the invention is to provide the method for preparing the three-dimensional multifunctional adsorbing material in situ by using corn pith, which has the advantages of simple process, high production efficiency, good wastewater purification effect, regeneration and reutilization, natural degradation and low raw material cost.
The second purpose of the invention is to provide the application of the three-dimensional multifunctional adsorbing material, which can be used for repairing industrial sewage.
The first purpose of the invention is realized by the following technical scheme:
a method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith comprises the following steps:
step one, drying waste corn straws, and removing leaves, outer-layer epidermis and stem nodes to obtain corn piths for later use;
step two, mixing choline chloride and p-toluenesulfonic acid monohydrate, heating to completely melt the mixture, mixing the melted mixture with distilled water, and uniformly stirring to form a eutectic mixed solution;
adding corn pith into the mixed solution for reaction, fully cleaning the corn pith to be neutral after the reaction is finished, and then freezing and drying the corn pith;
step four, mixing a sodium phosphate solution and tetramethylpiperidine oxide, adding sodium chlorite, adding a mixed solution of sodium hypochlorite and sodium phosphate, adding the corn pith dried in the step three for overnight, placing the mixed solution on a shaking table for reaction after the overnight, and finally taking out and cleaning the corn pith, and sequentially freezing and drying the corn pith;
and step five, spraying hydrophobic substances on the surface of the corn pith dried in the step four, and placing the corn pith in a fume hood for a period of time to prepare the three-dimensional multifunctional adsorbing material.
Specifically, in the step one, the obtained corn pith is cut to 1-3 cm.
In the first step, the drying is natural air drying or drying at 50-60 ℃, and the obtained corn pith does not contain other impurities.
Wherein, in the second step, the heating temperature is 80-180 ℃.
Wherein, in the third step, the reaction temperature is 60-100 ℃.
Wherein, in the third step, the reaction time is 1-3 h.
In the third step, when the corn pith is cleaned, the corn pith is firstly put into an ultrasonic cleaning instrument for cleaning, the power of the ultrasonic cleaning instrument is 60-240W, the cleaning time is 15-30 minutes, and the corn pith is fully washed to be neutral after ultrasonic cleaning.
Wherein, in the third step and the fourth step, the freezing temperature is between 18 ℃ below zero and 22 ℃ below zero, the freezing time is at least 6 hours, and the drying temperature is 24 to 48 hours.
Wherein, in the fourth step, the concentration of the sodium phosphate solution is 0.1mol/L, and the pH value is 6.5-6.9.
Wherein, in the fourth step, the concentration of the mixed solution of sodium hypochlorite and sodium phosphate is 0.1 mol/L.
Wherein, in the fourth step, the reaction temperature of the mixed solution on the shaking table is 55-65 ℃, and the rotation speed of the shaking table is 145-155 r/min.
Specifically, the hydrophobic substances are an octadecylamine ethanol solution, beeswax and silicon-containing hydrophobic substances, and the mass concentration of the octadecylamine ethanol solution is 1%.
Placing corn pith sprayed with hydrophobic substance in a fume hood for 6-12 h.
Corn straw pith possesses a natural nanocomposite structure, which is composed of highly crystalline cellulose-based fibrils and interfiber compounds, i.e., hemicellulose and lignin, bound together. Among these, lignin acts as a binder, covalently linking the hemicellulose molecules. The removal of lignin in corn straw pith is an effective way to improve the porosity of the material. Meanwhile, the corn straw pith has low density and a natural honeycomb structure, and is a good three-dimensional aerogel raw material. The invention partially extracts and depolymerizes lignin in corn straw pith by a eutectic solvent of p-toluenesulfonic acid monohydrate/choline chloride; meanwhile, because lignin is extracted and not dissolved, a compact tissue structure is loosened, and hemicellulose is also depolymerized, the corn straw pith after treatment mainly comprises cellulose. The main mechanism of delignification by the alkaline sodium chlorite method and the sodium sulfite method is to extract lignin after dissolution, and simultaneously hydrolyze a straw cellulose chain in the delignification process, however, the lignin is not obviously dissolved while the delignification is performed by using a eutectic solvent of p-toluenesulfonic acid monohydrate/choline chloride, and meanwhile, a large amount of acid-base wastewater is generated by the alkaline sodium chlorite method and the sodium sulfite method, and a large amount of black liquor with high toxicity is also generated due to dissolution of lignin. By the invention, the residual cellulose in the delignified corn straw pulp can help to maintain the skeleton structure of the material. Subsequent TEMPO/NaClO2/NaClO/Na3PO4The corn pith cellulose nano-fibrosis is realized, and the cellulose hydroxyl is converted into carboxyl and aldehyde, so that the activation of the corn pith surface is facilitated. The subsequent hydrophobization can change the hydrophilicity of the corn straw pith material into the hydrophobicity, thereby being beneficial to industrial water treatment. Meanwhile, compared with the traditional ionic liquid treatment method, the reaction system disclosed by the invention has the advantages of simplicity in preparation, rich raw materials, low price, environmental friendliness, biodegradability and the like.
Because the lignin and partial hemicellulose are removed and the hydrophobic substance is grafted, the corn straw pith has loose structure, further reduced density, reduced crystallinity and reduced hydrophilicity, and the hydrophobicity is increased, so that the oil absorption of the material in an oil-water system is obviously improved, and the dye adsorption capacity is increased.
The second purpose of the invention is realized by the following technical scheme:
the three-dimensional multifunctional adsorption material is prepared by the preparation method and used for adsorbing pollutants in industrial sewage, and the pollutants comprise oil substances, metal ions and dye ions.
The invention has the beneficial effects that:
the method for preparing the aerogel-like adsorption material in situ from the corn straw pith is safe, the prepared modified corn pith-like aerogel adsorption material is low in crystallinity, good in BET specific surface area, good in surface hydrophobicity, low in density and good in adsorptivity, can be processed in a reproducible manner, is not easy to pulverize, can be recycled, can solve the problems in the actual industrial process, is simple to operate and easy to amplify, and can be used for actively promoting the application and upgrading of the adsorption material in industrial wastewater.
The modified corn pith aerogel straw-based adsorption material can realize the purification of industrial wastewater, and is specifically represented as follows: the removal amount of the modified corn pith adsorbing material to the engine oil is more than 47.31g/g within 1 hour; the removal amount of soybean oil is more than 45.24 g/g; the removal amount of diesel oil is more than 42.64 g/g; the removal rate of methylene blue can reach 300.2 mg/g; the removal rate of the crystal violet can reach 340.7 mg/g.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a graph comparing the oil absorption of modified corn pith of example 1 of the present invention with that of unmodified corn pith of comparative example 1;
FIG. 2 is an XRD pattern of corn pith adsorbent materials of example 1, comparative example 2, and comparative example 3 of the present invention;
FIG. 3 is a graph comparing oil absorption of engine oil, soybean oil and diesel oil by modified corn pith of example 1 of the present invention;
FIG. 4 is a diagram of corn pith before and after modification according to the invention.
Detailed Description
The conception, the specific structure, and the technical effects produced by the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, the features, and the effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. In addition, all the connection/connection relations referred to in the patent do not mean that the components are directly connected, but mean that a better connection structure can be formed by adding or reducing connection auxiliary components according to specific implementation conditions. All technical characteristics in the invention can be interactively combined on the premise of not conflicting with each other.
Example 1
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith comprises the following steps:
the method comprises the following steps of firstly, recovering waste corn straws in crops, drying the corn straws, removing leaves, outer-layer epidermis and stem nodes to obtain corn piths, and cutting the corn piths to 2cm for later use;
step two, putting 69.8g of choline chloride and 95g of water-p-toluenesulfonic acid into the same beaker for mixing, then putting the beaker into an oven at 130 ℃ for heating to completely melt the mixture, then mixing the melted mixture with 270g of distilled water, and uniformly stirring by using a glass rod to form a eutectic mixed solution;
step three, taking 100mL of mixed solution, adding 3 corn piths into the mixed solution, reacting for 2 hours at 100 ℃, putting the corn piths into an ultrasonic cleaning instrument for cleaning after the reaction is finished, wherein the cleaning power of the ultrasonic cleaning instrument is 150W, cleaning for 22.5 minutes, fully cleaning the corn piths to be neutral after ultrasonic cleaning, then putting the corn piths into a refrigerator at minus 20 ℃ for freezing for at least 6 hours, finally putting the corn piths into a freeze dryer for drying for 36 hours, and taking out the dried corn piths for later use;
step four, preparing 200mL of 0.1mol/L sodium phosphate solution, adjusting the pH value of the solution to 6.8, mixing the sodium phosphate solution with 0.032g of tetramethylpiperidine oxide, then adding 2.26g of sodium chlorite, then adding 20mL of 0.1mol/L sodium hypochlorite and sodium phosphate mixed solution, finally adding the corn pith dried in the step three for overnight, placing the mixed solution on a shaker at 60 ℃ for reaction for 24 hours after the overnight, finally taking out and cleaning the corn pith, placing the corn pith in a refrigerator at-20 ℃ for freezing for at least 6 hours, and placing the corn pith in a freeze dryer for drying for 36 hours after freezing;
and fifthly, spraying a hydrophobic substance on the surface of the corn pith dried in the step four, wherein the hydrophobic substance is an octadecylamine ethanol solution with the mass concentration of 1%, putting the corn pith in a fume hood for 9 hours after spraying the hydrophobic substance, and finally taking out the corn pith to prepare the three-dimensional multifunctional adsorbing material.
Example 2
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith, wherein example 2 is different from example 1 in that the corn pith is reacted at 60 ℃ in the third step, and other preparation steps of the preparation method of example 2 are the same as those of example 1.
Example 3
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith, wherein example 3 is different from example 1 in that the corn pith is reacted at 70 ℃ in the third step, and other preparation steps of the preparation method of example 3 are the same as those of example 1.
Example 4
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith, wherein example 4 is different from example 1 in that the corn pith is reacted at 80 ℃ in the third step, and other preparation steps of the preparation method of example 4 are the same as those of example 1.
Example 5
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith, wherein example 5 is different from example 1 in that the corn pith is reacted at 90 ℃ in the third step, and other preparation steps of the preparation method of example 5 are the same as those of example 1.
Example 6
A method for preparing a three-dimensional multifunctional adsorbent material in situ using corn pith, example 6 is different from example 1 in that the molten mixture is mixed with 0g of distilled water in the second step, and other preparation steps of the preparation method of example 6 are the same as those of example 1.
Example 7
A method for preparing a three-dimensional multifunctional adsorbent material in situ using corn pith, example 7 is different from example 1 in that the molten mixture is mixed with 90g of distilled water in the second step, and other preparation steps of the preparation method of example 7 are the same as those of example 1.
Example 8
A method for preparing a three-dimensional multifunctional adsorbent material in situ using corn pith, example 8 is different from example 1 in that the molten mixture is mixed with 180g of distilled water in the second step, and other preparation steps of the preparation method of example 8 are the same as those of example 1.
Example 9
A method for preparing a three-dimensional multifunctional adsorbent material in situ using corn pith, example 9 is different from example 1 in that in the second step, the molten mixture is mixed with 360g of distilled water, and other preparation steps of the preparation method of example 9 are the same as those of example 1.
Example 10
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith, wherein example 10 is different from example 1 in that the reaction time of the corn pith and a mixed solution is 1h in the third step, and other preparation steps of the preparation method of example 10 are the same as those of example 1.
Example 11
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith, wherein example 11 is different from example 1 in that the reaction time of the corn pith and a mixed solution is 1.5h in the third step, and other preparation steps of the preparation method of example 11 are the same as those of example 1.
Example 12
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith, wherein example 12 is different from example 1 in that the reaction time of the corn pith and the mixed solution is 2.5h in the third step, and other preparation steps of the preparation method of example 12 are the same as those of example 1.
Example 13
A method for preparing a three-dimensional multifunctional adsorbent material in situ using corn pith, example 13 is different from example 1 in that the reaction time of the corn pith and the mixed solution is 3 hours in the third step, and other preparation steps of the preparation method of example 13 are the same as those of example 1.
Comparative example 1
Comparative example 1 is unmodified corn pith.
Comparative example 2
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith, wherein a comparative example 2 is different from an example 1 in that the preparation method of the comparative example 2 only comprises a step one, a step two and a step three, and does not comprise a step four and a step five, and the operation method of the step one, the step two and the step three of the comparative example 2 is the same as that of the step one, the step two and the step three of the example 1.
Comparative example 3
A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith, wherein a comparative example 3 is different from an example 1 in that the preparation method of the comparative example 3 comprises a step one, a step two, a step three and a step four, but does not comprise a step five, and the operation methods of the step one, the step two, the step three and the step four of the comparative example 3 are the same as those of the step one, the step two, the step three and the step four of the example 1.
Performance testing
1. Oil absorption test
1.1 oil absorption Experimental method
The oil absorption of the adsorbent was measured by gravimetric method, and the dried adsorbent was immersed in the oil body at room temperature. After a given period of time, the material was removed from the oil, dropped for 3 minutes to remove residual oil, and then weighed quickly. The oil absorption is calculated according to the following formula:
Q＝(m1-m0)/m0
wherein Q is the oil absorption (dry weight of oil divided by the weight of the sample), m0And m1The weights of the samples before and after oil absorption, respectively.
1.2 oil absorption comparison
The oil absorption of the unmodified corn pith of comparative example 1 and the oil absorption of the modified adsorbent of example 1 were measured using the oil absorption test method described above, and the oil absorption of the unmodified corn pith (a) and the oil absorption of the modified corn pith (B) of example 1 were compared, and the oil absorption is shown in fig. 1.
2. Test for influence of water on single factor of methylbenzenesulfonic acid modified corn pith
2.1 Effect of reaction temperature
The oil absorption of the corn pith modified by the methods of examples 1, 2, 3, 4 and 5 was measured by the oil absorption test method, and the effect of different reaction temperatures on the oil absorption of the modified corn pith was further measured, and the oil absorption of each group of modified corn pith was shown in table 1 below.
TABLE 1 oil absorption of modified corn pith obtained at different reaction temperatures
Group of Reaction temperature/. degree.C Subsequent oil absorption/(g/g)
Example 2 60 7.407
Example 3 70 15.706
Example 4 80 16.372
Example 5 90 17.514
Example 1 100 26.736
2.2 Effect of Water addition
The oil absorption of the corn pith modified by the methods of examples 1, 6, 7, 8 and 9 was measured by the oil absorption test method described above, and the effect of different amounts of distilled water on the oil absorption of the modified corn pith was further measured, and the oil absorption of each group of modified corn pith is shown in table 2 below.
TABLE 2 oil absorption of modified corn pith made at different water addition levels
Group of Different water addition/g Oil absorption/(g/g)
Example 6 0 22.989
Example 7 90 22.953
Example 8 180 23.85
Example 1 270 26.736
Example 9 360 24.457
2.3 Effect of reaction time
The oil absorption of the corn pith modified by the methods of examples 1, 10, 11, 12 and 13 was measured by the oil absorption test method described above, and the effect of different reaction times on the oil absorption of the modified corn pith was further measured, and the oil absorption of each group of modified corn pith was not shown in table 3 below.
TABLE 3 oil absorption of modified corn pith produced at different reaction times
Group of Reaction time/h Oil absorption/(g/g)
Example 10 1 26.74
Example 11 1.5 27.758
Example 1 2 26.736
Example 12 2.5 26.146
Example 13 3 47.314
3. XRD analysis of the adsorbent Material
The crystallinity index (CrI) is used to explain the structure of cellulose and is one of the most important characteristics of physical, chemical and mechanical properties. In order to explore the influence of the modification of the methylbenzenesulfonic acid/choline chloride by the monohydrate on the CrI of the material, the calculation can be carried out according to the Segal formula[52]：
Figure GDA0003105024700000101
Wherein I002Is the diffraction peak intensity of the crystalline region in cellulose; i isamDiffraction peak intensity of amorphous region.
FIG. 2 is an XRD pattern of comparative example 1, comparative example 2, comparative example 3 and example 13, specifically, an XRD pattern of unmodified corn pith of comparative example 1 labeled "original", an XRD pattern of modified corn pith material of comparative example 2 labeled "A", an XRD pattern of modified corn pith material of comparative example 3 labeled "B", an XRD pattern of modified corn pith material of example 13 labeled "C", and CrI of modified corn pith material of comparative example 3 and CrI of modified corn pith material of example 1, respectively calculated according to Segal formula (1) for investigating the effect of water on the crystallinity of the material by the methylbenzenesulfonic acid/choline system, the CrI of unmodified raw corn pith material of comparative example 1, the CrI of modified corn pith material of comparative example 2, the CrI of modified corn pith material of comparative example 3 and the CrI of modified corn pith material of example 1, the CrI of unmodified raw corn pith material of comparative example 1 was calculated to be 50.15%, the CrI of the modified corn pith material of comparative example 2 was 36.79%, the CrI of the modified corn pith material of comparative example 3 was 38.90%, and the CrI of the modified corn pith material of example 13 was 39.18%.
It can be seen that the crystallinity of the material is reduced after modification. The original corn pith fiber has high crystallinity, which shows that the crystallization area is large, the molecular structure is arranged tightly, the modification destroys the regular tight structure among molecules, the amorphous area of the material is increased, which is beneficial to the oil molecules and other pollutants to enter the internal structure of the material, and provides more adsorption space for the material, thereby improving the adsorption performance. And after the octadecylamine is sprayed on the basis of the modified corn pith, the crystallinity of the material has no obvious difference, namely, the hydrophobic modification experiment does not influence the crystallization characteristic of the material.
4. Measuring the adsorption capacity of the modified corn pith adsorption material to different types of oil
The test method comprises the steps of respectively filling 3 250mL beakers with 100mL of engine oil, 100mL of soybean oil and 100mL of diesel oil, then respectively adding 1 adsorbing material prepared by the method in example 13 into the 3 beakers, then oscillating the materials at a constant temperature of 25 ℃ for 30min, finally taking out the adsorbing materials, and measuring the adsorption capacity of the adsorbing materials on the three oils by adopting the oil absorption test method.
The adsorption performance of the adsorption material on engine oil, soybean oil and diesel oil is shown in fig. 3. The adsorbing material prepared by the invention has larger adsorption to 3 kinds of oil, wherein the adsorption capacity to machine oil and soybean oil is larger, and the adsorption capacity is 47.31g/g and 45.24g/g respectively.
5. Determination of adsorption Properties after regeneration of modified corn pith
The test method is as follows:
(1) 50mL of engine oil and 50mL of soybean oil are respectively filled in two 250mL beakers, 100mL of brine with the mass concentration of 0.1% is respectively added into the beakers, then 1 adsorbing material prepared by the method of example 13 is respectively added into the two beakers, and then the two beakers are vibrated for 30min at the temperature of 25 ℃, and the adsorbing capacity of the adsorbing material on the engine oil and the soybean oil is measured by adopting the oil absorption test method, namely a gravimetric method;
(2) extruding the adsorbing material adsorbing the engine oil and the soybean oil in the step (1) by using tweezers, and soaking the extruded adsorbing material in n-hexane for 24 hours to complete the regeneration of the adsorbing material;
(3) and (3) adsorbing the regenerated adsorbing material again by adopting the method in the step (1) to the machine oil and the soybean oil, and measuring the oil absorption of the adsorbing material at the moment.
Wherein the first oil absorption and the regenerated oil absorption of the adsorbent are shown in table 4 below.
TABLE 4 first oil absorption and oil absorption after regeneration of the adsorbent
Group of First oil absorption Oil absorption after regeneration
Engine oil (g/g) 47.31 45.07
Soybean oil (g/g) 45.24 43.82
As can be seen from the above table, the adsorption capacity after regeneration can still be kept above 95% by performing aerogel-like modification on corn pith by adopting the preparation method of the invention.
6. Dye testing method
6.1 drawing of methylene blue Standard Curve
Preparing a methylene blue standard stock solution: weighing 1.0000g of methylene blue, dissolving in pure water, and metering to 1000mL (1000 mg/L);
respectively putting 0.10mL, 0.20mL, 0.30mL, 0.40mL and 0.50mL of methylene blue standard stock solution into a 100mL volumetric flask, and performing constant volume to obtain solutions with the concentrations of 1.00mg/L, 2.00mg/L, 3.00mg/L, 4.00mg/L and 5.00 mg/L;
the absorbance of the above methylene blue solutions of different concentrations was measured using an ultraviolet spectrophotometer at 665nm with pure water as a reference, and a concentration-absorbance curve was plotted (degree of fitting R2>0.9990 was required).
6.2 methylene blue dye wastewater adsorption experiment
a. Preparing a methylene blue standard use solution: taking 100mL of methylene blue standard stock solution into a volumetric flask, fixing the volume to 1000mL, and preparing a methylene blue standard use solution with the concentration of 100 mg/L;
b. adding 1 adsorbing material into a 50mL polyethylene centrifuge tube, adding 40mL methylene blue standard use solution, placing into a shaking table, and adsorbing for 2 hours at 25 ℃ and 150 r/min;
c. taking 0.50mL of the adsorbed solution, adding the solution into a 10mL colorimetric tube, adding water to the scale 10, shaking up, measuring the absorbance at 665nm, and calculating the corresponding concentration from a standard curve;
the adsorption amount is calculated by the following formula:
Figure GDA0003105024700000131
in the formula: qe-amount of adsorption of dye wastewater by the adsorption material (mg/g);
c1-concentration of solution before adsorption (mg/L);
c2-concentration of solution after adsorption (mg/L);
n is dilution multiple;
v-volume of solution added (mL);
m-weight of material (g)
6.3 test of the adsorption quantity of the crystal violet dye wastewater, when the adsorption quantity of the adsorption material on the crystal violet dye wastewater is measured, only a crystal violet standard curve needs to be drawn, and the methylene blue dye wastewater is replaced by the crystal violet dye wastewater, and the other method steps are the same as those of the methylene blue dye wastewater adsorption test method. Wherein the dye has a pH of 9.
6.4 Using methylene blue dye wastewater adsorption test method and crystal violet dye wastewater adsorption test method, the adsorption amounts of the corn pith modified in example 1 to the two dyes and the adsorption amounts of the corn pith unmodified in proportion 1 to the two dyes were measured, respectively, and the adsorption amounts of the corn pith before and after modification to the dyes are shown in the following table.
TABLE 5 adsorption of dye by corn pith before and after modification
Group of Comparative example 1 Example 1
Methylene blue (mg/g) 13.03 300.2
Crystal violet (mg/g) 16.29 340.7
According to the table, the adsorption capacity of the modified corn pith exceeds 300mg/g and is larger than that of the unmodified corn pith in the comparative example 1, the preparation method disclosed by the invention is used for performing aerogel-like modification on the corn pith, and the adsorption effect of the modified corn pith on the dye is greatly improved compared with that of the unmodified corn pith, so that the preparation method disclosed by the invention can improve the adsorption performance of the adsorbent on the dye wastewater; the adsorption capacity of the modified corn pith dye is about 21-23 times of that of unmodified corn pith, and the improvement effect is obvious.
7. Analysis of oil and water contact angles of corn pith before and after modification
Typically materials with water contact angles greater than 90 degrees are non-wetting and materials greater than 150 degrees exhibit superhydrophobicity. From the following table, it can be seen that the surface water contact angle (152.8 degrees) of the modified corn pith is much larger than that (42.1 degrees) of the unmodified corn pith raw material, and the oil contact angle (0 degrees) is smaller than that (58.8 degrees) of the unmodified corn pith raw material, showing excellent superhydrophobicity.
TABLE 6 corn pith contact angles with oil and water before and after modification
Group of Comparative example 1 Example 1
Water contact angle (degree) 42.1 152.8
Oil contact angle (degree) 58.8 0
8. The specific surface area, pore volume and pore size of the corn pith before and after modification are shown in table 7.
TABLE 7 specific surface area, pore volume and pore size of corn pith before and after modification
Group of Comparative example 1 Example 1
Specific surface area (m)2/g) 3.1558 25.370
Pore volume (cm)3/g) 0.003829 0.01626
Pore size (nm) 4.03108 12.0738
As can be seen from Table 7, the specific surface area of the modified corn pith was 25.370m2Per g, the specific surface area of unmodified corn pith was 3.1558m2The volume of the modified pores is increased by 324.7 percent, the diameter of the pores is also increased,is favorable for adsorbing oil macromolecules.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A method for preparing a three-dimensional multifunctional adsorbing material in situ by using corn pith is characterized by comprising the following steps: the method comprises the following steps:
step one, drying waste corn straws, and removing leaves, outer-layer epidermis and stem nodes to obtain corn piths for later use;
step two, mixing choline chloride and p-toluenesulfonic acid monohydrate, heating to completely melt the mixture, mixing the melted mixture with distilled water, and uniformly stirring to form a eutectic mixed solution;
adding corn pith into the mixed solution for reaction, fully cleaning the corn pith to be neutral after the reaction is finished, and then freezing and drying the corn pith;
step four, mixing a sodium phosphate solution and tetramethylpiperidine oxide, adding sodium chlorite, adding a mixed solution of sodium hypochlorite and sodium phosphate, adding the corn pith dried in the step three for overnight, placing the mixed solution on a shaking table for reaction after the overnight, and finally taking out and cleaning the corn pith, and sequentially freezing and drying the corn pith;
and fifthly, spraying hydrophobic substances on the surfaces of the corn piths dried in the step four, and placing the corn piths in a fume hood for a period of time to prepare the three-dimensional multifunctional adsorbing material.
2. The method for preparing the three-dimensional multifunctional adsorbing material in situ by using the corn pith according to claim 1, wherein the method comprises the following steps: in the second step, the heating temperature is 80-180 ℃.
3. The method for preparing the three-dimensional multifunctional adsorbing material in situ by using the corn pith according to claim 1, wherein the method comprises the following steps: in the third step, the reaction temperature is 60-100 ℃.
4. The method for preparing the three-dimensional multifunctional adsorbing material in situ by using the corn pith according to claim 1, wherein the method comprises the following steps: in the third step, the reaction time is 1-3 h.
5. The method for preparing the three-dimensional multifunctional adsorbing material in situ by using the corn pith according to claim 1, wherein the method comprises the following steps: and in the third step, when the corn pith is cleaned, the corn pith is firstly put into an ultrasonic cleaning instrument for cleaning, the power of the ultrasonic cleaning instrument is 60-240W, the cleaning time is 15-30 minutes, and the corn pith is fully washed to be neutral after ultrasonic cleaning.
6. The method for preparing the three-dimensional multifunctional adsorbing material in situ by using the corn pith according to claim 1, wherein the method comprises the following steps: in the third step and the fourth step, the freezing temperature is between 18 ℃ below zero and 22 ℃ below zero, the freezing time is at least 6 hours, and the drying temperature is 24 to 48 hours.
7. The method for preparing the three-dimensional multifunctional adsorbing material in situ by using the corn pith according to claim 1, wherein the method comprises the following steps: in the fourth step, the concentration of the sodium phosphate solution is 0.1mol/L, and the pH value is 6.5-6.9.
8. The method for preparing the three-dimensional multifunctional adsorbing material in situ by using the corn pith according to claim 1, wherein the method comprises the following steps: in the fourth step, the concentration of the mixed solution of sodium hypochlorite and sodium phosphate is 0.1 mol/L.
9. The method for preparing the three-dimensional multifunctional adsorbing material in situ by using the corn pith according to claim 1, wherein the method comprises the following steps: in the fourth step, the reaction temperature of the mixed solution on the shaking table is 55-65 ℃.
10. The application of the three-dimensional multifunctional adsorbing material is characterized in that: the three-dimensional multifunctional adsorption material is prepared by the preparation method of any one of claims 1 to 9 and is used for adsorbing pollutants in industrial sewage, wherein the pollutants comprise oil substances, metal ions and dye ions.
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