CN114849657B - Preparation of efficient amphiphilic chitosan-loaded bentonite adsorbent and application of efficient amphiphilic chitosan-loaded bentonite adsorbent in coking wastewater - Google Patents

Preparation of efficient amphiphilic chitosan-loaded bentonite adsorbent and application of efficient amphiphilic chitosan-loaded bentonite adsorbent in coking wastewater Download PDF

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CN114849657B
CN114849657B CN202210452845.9A CN202210452845A CN114849657B CN 114849657 B CN114849657 B CN 114849657B CN 202210452845 A CN202210452845 A CN 202210452845A CN 114849657 B CN114849657 B CN 114849657B
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chitosan
adsorbent
efficient
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CN114849657A (en
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麦荣
朱洲
王林平
寇海群
周瑜昌
兰新典
余美莹
陈浩南
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Yu Zhang Teachers College
Nanchang Guochang Environmental Protection Technology Co ltd
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Nanchang Guochang Environmental Protection Technology Co ltd
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Abstract

The application belongs to the field of preparation of industrial wastewater treatment adsorbents, and relates to preparation of an efficient amphiphilic chitosan loaded bentonite adsorbent and application thereof in coking wastewater, wherein the amino on chitosan is protected by Schiff base reaction by utilizing the characteristic that active amino and hydroxyl in a chitosan molecular structure are easy to modify, long-chain alkane with strong hydrophobic effect is introduced on secondary hydroxyl by alkylation reaction on the basis, so that amphiphilic chitosan O-octadecyl-chitosan (C18 CS) is prepared, and is loaded to bentonite under the microwave auxiliary condition by cation exchange, so that the amphiphilic chitosan loaded bentonite adsorbent (C18 CS-BT) is prepared. The adsorbent disclosed by the application has larger interlayer spacing in coking wastewater treatment and stronger enrichment capacity for organic matters in coking wastewater, so that the adsorption capacity of the adsorbent for the organic matters in the coking wastewater is enhanced, and the adsorbent has great application potential.

Description

Preparation of efficient amphiphilic chitosan-loaded bentonite adsorbent and application of efficient amphiphilic chitosan-loaded bentonite adsorbent in coking wastewater
Technical Field
The application belongs to the field of preparation of industrial wastewater treatment adsorbents, and particularly relates to an amphiphilic chitosan-loaded bentonite adsorbent.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the application and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The coking wastewater is industrial organic wastewater generated in the process of preparing coke from bituminous coal in the coking industry, and has the characteristics of large discharge, high toxicity, difficult degradation, complex components and the like. The organic matters in the coking wastewater are mainly phenol, quinoline, polycyclic aromatic hydrocarbon, indole, furan, long-chain alkane and homologues or derivatives thereof, wherein the phenol, quinoline and polycyclic aromatic hydrocarbon organic matters become characteristic pollutants in the coking wastewater due to high concentration, high toxicity and special structure, and the phenol, quinoline and polycyclic aromatic hydrocarbon organic matters must be treated. At present, coking wastewater is usually treated by adopting a combined process of pretreatment, biochemical treatment and advanced treatment, and the treated wastewater can reach the discharge standard. The biochemical treatment is the core of the coking wastewater treatment process, and the removal and conversion of polluted/inorganic matters in the coking wastewater are realized through the combination of anaerobic, anoxic, aerobic and other biological treatment units. Due to poor biodegradability of coking wastewater (BOD 5 The COD value of the effluent after biochemical treatment is still higher than 150mg/L (the discharge standard is lower than 80 mg/L), and the biochemical effluent must be further processed to meet the discharge requirement.
The advanced treatment technology of the coking wastewater mainly comprises advanced oxidation, coagulation, adsorption, membrane treatment technology and the like. Aiming at the water quality condition after biochemical treatment, a mode of coupling one or more technologies can be adopted to achieve the purpose. The adsorption method has the advantages of simple process, recoverability and regeneration, high adsorption rate, no secondary pollution and the like, and becomes a research hot spot in the field. The adsorbents commonly used in the water treatment field are mainly activated carbon, activated alumina, molecular sieve, silica gel and the like, and the adsorbents have the advantages of large specific surface area, abundant mesopores, renewable utilization and the like, but the inventor discovers that: because the coking wastewater has large water yield and high price, the application of the adsorbents is limited, and the development of the adsorbent which has low cost, environment protection, no secondary pollution and high efficiency becomes a research hot spot in the field.
Disclosure of Invention
In order to overcome the defects, the application provides a high-efficiency amphiphilic chitosan-loaded bentonite adsorbent for coking wastewater treatment. The Bentonite (BT) used as a main raw material of the adsorbent has abundant mineral resources, is a porous adsorption material taking montmorillonite as a main mineral component, and has the advantages of large specific surface area, excellent adsorptivity, easiness in modification through cation exchange and the like. Chitosan (CS) is a product of deacetylation of chitin, and the raw material chitin is widely distributed in nature and is a second largest natural polymer polysaccharide, and has the advantages of abundant and easily available raw materials, safety, environmental protection, no secondary pollution, abundant functional groups, easy modification and the like.
In order to achieve the technical purpose, the application adopts the following technical scheme:
the application provides a preparation method of a high-efficiency amphiphilic chitosan-loaded bentonite adsorbent, which comprises the following steps:
preparing amphipathic chitosan O-octadecyl-chitosan C18CS;
adding the amphipathic chitosan O-octadecyl-chitosan C18CS into glacial acetic acid solution to dissolve the amphipathic chitosan O-octadecyl-chitosan C18CS, adding bentonite, reacting under microwave, taking out the product, drying, grinding and sieving to obtain the amphipathic chitosan.
Aiming at the characteristic that the coking wastewater biochemical treatment effluent still contains refractory organic matters such as long-chain alkane, aromatic hydrocarbon, heterocyclic compound and the like, from the molecular structure design, the amino on chitosan is protected by Schiff base reaction firstly by utilizing the characteristic that active amino and hydroxyl in the molecular structure of chitosan are easy to modify, on the basis, long-chain alkane with strong hydrophobic effect is introduced on secondary hydroxyl by alkylation reaction to prepare amphiphilic chitosan O-octadecyl-chitosan (C18 CS), and the amphiphilic chitosan O-octadecyl-chitosan is loaded on bentonite under the microwave auxiliary condition by cation exchange to prepare the amphiphilic chitosan loaded bentonite adsorbent (C18 CS-BT).
In a second aspect, the application provides the high-efficiency amphiphilic chitosan loaded bentonite adsorbent and application thereof in coking wastewater treatment.
Currently, there are related literature reports: the chitosan modified bentonite adsorbent has excellent removal rate on COD of coking wastewater, and the treatment effect is obviously better than that of single bentonite and chitosan. The main action mechanism is that chitosan is intercalated in the crystal layer of bentonite, the interlayer spacing of the bentonite is increased, and the adsorption performance of the bentonite is enhanced. In the application, long-chain alkyl with strong hydrophobic effect is introduced into the molecular structure of chitosan to prepare an amphiphilic chitosan natural high molecular polymer, and then the amphiphilic chitosan natural high molecular polymer is loaded to bentonite through cation exchange. Compared with the non-hydrophobically modified chitosan-loaded bentonite adsorbent, the introduction of the amphiphilic chitosan can bring about two unique effects: (1) Because the space volume occupied by the hydrophobically modified chitosan molecules is larger, the interlayer spacing of the bentonite is further increased, so that the adsorption capacity of the adsorbent is further increased; (2) Because of the introduction of the strong hydrophobic group of the long-chain alkyl, the adsorbent C18CS-BT forms a hydrophobic micro-region in the wastewater, and hydrophobic organic matters in the coking wastewater are more easily enriched around the adsorbent through the hydrophobic effect, so that the removal performance of the adsorbent C18CS-BT on the organic matters in the coking wastewater is enhanced. The synergistic effect of the two aspects ensures that the adsorbent C18CS-BT has high-efficiency adsorption performance on organic matters in coking wastewater.
The application has the beneficial effects that:
(1) The application provides a high-efficiency amphiphilic chitosan-loaded bentonite adsorbent which has larger interlayer spacing in coking wastewater treatment and stronger enrichment capacity for organic matters in coking wastewater, so that the adsorption capacity of the high-efficiency amphiphilic chitosan-loaded bentonite adsorbent for the organic matters in the coking wastewater is enhanced, and the high-efficiency amphiphilic chitosan-loaded bentonite adsorbent has great application potential.
(2) The application discloses a high-efficiency adsorbent suitable for coking wastewater treatment through effective design of various raw materials in the aspects of molecular structure, addition proportion, preparation process and the like, and has larger adsorption capacity and enrichment performance on organic matters in wastewater.
(3) The preparation method is simple, high in adsorption efficiency on organic matters in the wastewater, high in practicability and easy to popularize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application.
FIG. 1C18CS is a preparation roadmap;
FIG. 2 infrared spectra of adsorbents BT, CS-BT and C18 CS-BT;
FIG. 3X-ray diffraction patterns of adsorbents BT, CS-BT and C18 CS-BT;
FIG. 4 is a scanning electron microscope image of adsorbents BT, CS-BT and C18 CS-BT;
fig. 5 effect of adsorbent amount on adsorption performance (ph=7, adsorption time 2 h);
FIG. 6 influence of pH on adsorption performance (adsorbent amount 1.5g/L, adsorption time 2 h);
FIG. 7 effect of adsorption time on adsorption performance (adsorbent amount 1.5g/L, pH=7);
FIG. 8 is a GC-MS diagram of distilled wastewater raw water;
FIG. 9C18 GC-MS of the water sample after CS-BT treatment;
FIG. 10 is a GC-MS diagram of secondary sedimentation tank raw water;
FIG. 11C18 GC-MS of the water sample after CS-BT treatment.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The application provides a preparation method of a high-efficiency amphiphilic chitosan-loaded bentonite adsorbent.
The first step: an amphipathic chitosan O-octadecyl-chitosan (C18 CS) is prepared, and the preparation route is shown in figure 1:
and a second step of: the preparation method of the efficient amphiphilic chitosan-loaded bentonite adsorbent (C18 CS-BT) comprises the following steps:
a certain mass of C18CS is weighed and added into 100mL of glacial acetic acid solution with the volume percentage of 1%, and the mixture is fully stirred to be completely dissolved. Adding bentonite with a certain mass, stirring at a certain temperature, and forming into paste. Placing in a microwave reactor, setting a certain power, and heating for a certain time. And taking out the product, drying, grinding and sieving to obtain the amphiphilic chitosan-loaded bentonite adsorbent (C18 CS-BT).
In some embodiments, the mass ratio of the amphiphilic chitosan O-octadecyl-chitosan C18CS to bentonite is 1:10-30, preferably 1:25.
In some embodiments, the microwave has a power of 100W to 800W and a heating time of 5 minutes to 20 minutes.
The application provides a preparation method of a high-efficiency amphiphilic chitosan-loaded bentonite adsorbent, which is prepared by taking chitosan and bentonite which are rich in sources and low in cost as raw materials, firstly carrying out hydrophobic modification on chitosan through alkylation reaction, and then loading amphiphilic chitosan to bentonite under the assistance of microwaves.
The preparation method is simple, high in adsorption efficiency on organic matters in the wastewater, high in practicability and easy to popularize.
The application provides an application of a high-efficiency amphiphilic chitosan loaded bentonite adsorbent in coking wastewater treatment.
Currently, there are related literature reports: the chitosan modified bentonite adsorbent has excellent removal rate on COD of coking wastewater, and the treatment effect is obviously better than that of single bentonite and chitosan. The main action mechanism is that chitosan is intercalated in the crystal layer of bentonite, the interlayer spacing of the bentonite is increased, and the adsorption performance of the bentonite is enhanced. In the application, long-chain alkyl with strong hydrophobic effect is introduced into the molecular structure of chitosan to prepare an amphiphilic chitosan natural high molecular polymer, and then the amphiphilic chitosan natural high molecular polymer is loaded to bentonite through cation exchange. Compared with the non-hydrophobically modified chitosan-loaded bentonite adsorbent, the introduction of the amphiphilic chitosan can bring about two unique effects: (1) Because the space volume occupied by the hydrophobically modified chitosan molecules is larger, the interlayer spacing of the bentonite is further increased, so that the adsorption capacity of the adsorbent is further increased; (2) Because of the introduction of the strong hydrophobic group of the long-chain alkyl, the adsorbent C18CS-BT forms a hydrophobic micro-region in the wastewater, and organic matters in the coking wastewater are more easily enriched around the adsorbent through the hydrophobic effect, so that the removal performance of the adsorbent C18CS-BT on the organic matters in the coking wastewater is enhanced. The synergistic effect of the two aspects ensures that the adsorbent C18CS-BT has high-efficiency adsorption performance on organic matters in coking wastewater.
The application provides a high-efficiency amphiphilic chitosan-loaded bentonite adsorbent which has larger interlayer spacing in coking wastewater treatment and stronger enrichment capacity for organic matters in coking wastewater, so that the adsorption capacity of the high-efficiency amphiphilic chitosan-loaded bentonite adsorbent for the organic matters in the coking wastewater is enhanced, and the high-efficiency amphiphilic chitosan-loaded bentonite adsorbent has great application potential.
The application will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
In the following examples, the preparation method of O-octadecyl-chitosan is as follows: chitosan (1.0 g) was added to 50mL of 1% (w/v) aqueous acetic acid and the suspension was mixed with a magnetic stirrer for more than 4 hours until a homogeneous, transparent and viscous solution was obtained. Absolute ethanol (50 mL) was added with continuous stirring for 2 hours. Then, a homogeneous mixed solution of ethanol (30 mL) and benzaldehyde (30 mmol) was added dropwise to the chitosan solution with continuous stirring, and reacted at 70℃for 6 hours. After the reaction, all the residual products were dried with a constant temperature oven to give chitosan-schiff base benzaldehyde solid (B-CS).
2-g B-CS,4g of sodium hydroxide and 24mL of isopropyl alcohol were placed in a 100mL three-necked flask, and the temperature of the water bath was set at 40℃and then the temperature was kept constant for 1 hour to alkalize the B-CS. After the temperature is raised to 60 ℃, 6mL of bromooctadecane is added dropwise, stirring is continued and the reaction is carried out at constant temperature for 8h. And after the reaction is finished, carrying out suction filtration on the product, repeatedly washing with absolute ethyl alcohol and ultrapure water, and drying to obtain the hydrophobically modified O-octadecyl-benzaldehyde chitosan (B-C18 CS) product. And (3) soaking the B-C18CS in dilute hydrochloric acid, stirring for 2 hours, and extracting the product for 12 hours by using absolute ethyl alcohol as a solvent by using a Soxhlet extractor to finally obtain the refined product O-octadecyl-chitosan (C18 CS).
Example 1
A preparation method of a high-efficiency amphiphilic chitosan-loaded bentonite adsorbent.
The first step: an amphipathic chitosan O-octadecyl-chitosan (C18 CS) is prepared, and the preparation route is shown in figure 1:
and a second step of: the preparation method of the efficient amphiphilic chitosan-loaded bentonite adsorbent (C18 CS-BT) comprises the following steps:
1g of the prepared C18CS was weighed and added to 100mL of 1% by volume glacial acetic acid solution, followed by stirring to dissolve it completely. 25g of bentonite was added and stirred at 45℃for 1h to give a paste. Placing in a microwave reactor, setting the power at 300W and heating for 10min. And taking out the product, drying, grinding and sieving to obtain the amphiphilic chitosan-loaded bentonite adsorbent (C18 CS-BT).
The experiment adopts coking wastewater as the COD removal rate of the adsorbent for evaluating the effluent of a secondary sedimentation tank after biochemical treatment of a coking plant in Jiangxi province, the pH value of the water quality condition is 7.2, the chemical oxygen demand (CODcr) is 342mg/L, and the ammonia Nitrogen (NH) 3 -N) 8.82mg/L, total Nitrogen (TN) 100.6mg/L and Total Phosphorus (TP) 1.73mg/L. The optimized treatment process is that the dosage of the adsorbent is 1.5 g.L -1 Adsorption time is 60min, and pH value of the system is 7.2. Under the condition, CODcr after the adsorbent treatment is changed from 342 mg.L -1 Reduce to 146 mg.L -1 The COD removal rate in the corresponding wastewater is 57.31%.
Example 2
A preparation method of a high-efficiency amphiphilic chitosan-loaded bentonite adsorbent.
The first step: an amphipathic chitosan O-octadecyl-chitosan (C18 CS) is prepared, and the preparation route is shown in figure 1:
and a second step of: the preparation method of the efficient amphiphilic chitosan-loaded bentonite adsorbent (C18 CS-BT) comprises the following steps:
1g of the prepared C18CS was weighed and added to 100mL of 1% by volume glacial acetic acid solution, followed by stirring to dissolve it completely. 10g of bentonite was added and stirred at 45℃for 1h to give a paste. Placing in a microwave reactor, setting the power at 800W and heating for 5min. And taking out the product, drying, grinding and sieving to obtain the amphiphilic chitosan-loaded bentonite adsorbent (C18 CS-BT).
The experiment adopts coking wastewater as the COD removal rate of the adsorbent for evaluating the effluent of a secondary sedimentation tank after biochemical treatment of a coking plant in Jiangxi province, the pH value of the water quality condition is 7.2, the chemical oxygen demand (CODcr) is 342mg/L, and the ammonia Nitrogen (NH) 3 -N) 8.82mg/L, total Nitrogen (TN) 100.6mg/L and Total Phosphorus (TP) 1.73mg/L. The optimized treatment process is that the dosage of the adsorbent is 1.5 g.L -1 Adsorption time is 60min, and pH value of the system is 7.2. Under the condition, CODcr after the adsorbent treatment is changed from 342 mg.L -1 Reduce to 196 mg.L -1 The COD removal rate in the corresponding wastewater is 42.69%.
Example 3
A preparation method of a high-efficiency amphiphilic chitosan-loaded bentonite adsorbent.
The first step: an amphipathic chitosan O-octadecyl-chitosan (C18 CS) is prepared, and the preparation route is shown in figure 1:
and a second step of: the preparation method of the efficient amphiphilic chitosan-loaded bentonite adsorbent (C18 CS-BT) comprises the following steps:
1g of the prepared C18CS was weighed and added to 100mL of 1% by volume glacial acetic acid solution, followed by stirring to dissolve it completely. 20g of bentonite was added and stirred at 45℃for 1h to give a paste. Placing in a microwave reactor, setting the power to be 100W and heating for 20min. And taking out the product, drying, grinding and sieving to obtain the amphiphilic chitosan-loaded bentonite adsorbent (C18 CS-BT).
The experiment adopts coking wastewater as the COD removal rate of the adsorbent for evaluating the effluent of a secondary sedimentation tank after biochemical treatment of a coking plant in Jiangxi province, the pH value of the water quality condition is 7.2, the chemical oxygen demand (CODcr) is 342mg/L, and the ammonia Nitrogen (NH) 3 -N) 8.82mg/L, total Nitrogen (TN) 100.6mg/L and Total Phosphorus (TP) 1.73mg/L. The optimized treatment process is that the dosage of the adsorbent is 1.5 g.L -1 Adsorption time is 60min, and pH value of the system is 7.2. Under the condition, CODcr after the adsorbent treatment is changed from 342 mg.L -1 Reduced to 173 mg.L -1 The COD removal rate in the corresponding wastewater is 49.42%.
Example 4
1. Characterization of materials
The preparation of the non-hydrophobic modified chitosan-loaded bentonite adsorbent (CS-BT) and the bentonite adsorbent (BT) by the method of the example 1 are convenient for comparison and research.
FT-IR analysis
The functional groups of the adsorbent molecular structure were characterized by fourier infrared spectroscopy (FT-IR, nicolet 6700, thermo, usa). FIG. 2 is an infrared spectrum of three different adsorbents. For adsorbent BT,3625.57cm -1 The telescopic vibration absorption peak of Al-O-H is positioned; 3423.08cm -1 And 1635.36cm -1 The positions are respectively the absorption peaks of the stretching vibration and the bending vibration of the water molecules O-H between the crystal layers; 1037.53cm -1 And 792.61cm -1 The position is Si-O-Si antisymmetric telescopic vibration absorption peak in the adsorbent BT; 522.62cm -1 And 466.69cm -1 The absorption peak at this point is related to the coupled vibration of Si-O-M (metal ion) and M-O in BT. For adsorbent CS-BT,3260cm -1 ～3500cm -1 The broader absorption peak is-NH 2 And a telescopic vibration overlap absorption peak of-OH; 1731.58cm -1 And 1646.94cm -1 The C=O stretching vibration and N-H bending vibration absorption peaks are respectively shown, and are characteristic absorption peaks of amide groups, which are caused by incomplete deacetylation degree of Chitosan (CS), and also indicate that the preparation of the adsorbent CS-BT is successful. For adsorbent C18CS-BT, its infrared spectrum is similar to that of adsorbent CS-BT, except at 2877.318cm -1 The C-H telescopic vibration absorption peak at the position is obviously enhanced, and 1087.82cm -1 At 1162.53cm -1 And 1031.06cm -1 The two shoulder peaks are characteristic absorption peaks caused by bending vibration of-OH and stretching vibration of C-O-C; 663.41cm -1 The characteristic absorption peak of long-chain alkyl is shown, which indicates that the adsorbent C18CS-BT is successfully prepared.
XRD analysis
The phase characteristics of the material were analyzed by an X-ray diffractometer (Ultimate IV, rigaku, japan), cu target Ka-rays (wavelength 0.15418 nm), scanning speed 5 °/min. As can be seen from fig. 3, the XRD patterns of the three different adsorbents correspond to different diffraction peaks at different diffraction angles, and the interlayer spacing is generally calculated as the diffraction angle corresponding to the first peak. For adsorbents BT, CS-BT and C18CS-BT, the diffraction angles corresponding to the first peaks in their diffraction patterns were 7.08, 6.38 and 6.32, respectively. The layer spacing of the adsorbents BT, CS-BT and C18CS-BT were calculated to be 1.2485nm, 1.3853nm and 1.3985nm, respectively, according to Bragg's formula. The results show that: the interlayer spacing of the adsorbents CS-BT and C18CS-BT is obviously larger than that of the unmodified adsorbent BT, which means that positively charged amino groups in CS or C18CS are effectively intercalated into the crystal layer of BT through cation exchange, so that the interlayer spacing is expanded, and the interlayer spacing after the intercalation of the C18CS into BT is the largest. As can also be seen from fig. 3, the XRD patterns of the three different adsorbents are about the same in the diffraction peaks corresponding to the different diffraction angles, indicating that the modification has no effect on the basic structure of the adsorbent BT, but the interlayer spacing is changed.
Sem analysis
The surface topography of the material was analyzed by scanning electron microscopy (SEM, JSM-7900F, JEOL, japan). As can be seen from fig. 4 (a) and (b), the surface of the unmodified BT has some "wrinkles" and channels, and thus has a certain adsorption capacity. From FIGS. 4 (c) and (d), it can be seen that the surface of the adsorbent CS-BT is significantly rougher and the number of channels is significantly increased, since chitosan is loaded onto bentonite through cation exchange. FIGS. 4 (e) and (f) show that the adsorbent C18CS-BT surface also exhibits a rugged and fluffy-like structure. Through SEM analysis, the surface of BT becomes rough obviously through CS or C18CS loading on BT, and the number of pore channels is increased obviously, which is helpful to improve the adsorption performance.
2. Adsorption performance
The coking wastewater used in the experiment is the effluent of a secondary sedimentation tank after biochemical treatment of a coking plant in Jiangxi province, the pH value of the water quality condition is 7.2, the Chemical Oxygen Demand (COD) is 342mg/L, and ammonia Nitrogen (NH) 3 -N) 8.82mg/L, total Nitrogen (TN) 100.6mg/L and Total Phosphorus (TP) 1.73mg/L.
1. Influence of the amount of adsorbent
The corresponding relation between the adsorbent dosage and the adsorption capacity is one of important factors influencing the adsorption performance of the adsorbent, and has important reference significance on the operation cost of the adsorbent in practical application to wastewater treatment. Fig. 5 shows the effect of the amount of the adsorbent on the adsorption performance, and it can be seen that as the amount of the adsorbent increases, the removal rate of the organic matters in the coking wastewater by the three adsorbents all show a tendency of rapidly increasing and then slowly increasing. As the amount of the adsorbent increases, the adsorption sites increase, and the adsorption capacity of the adsorbent increases, so that the adsorption removal rate of the adsorbent for organic matters in coking wastewater increases remarkably. However, on the premise that the concentration of organic matters in coking wastewater is limited, as the amount of the adsorbent is increased, the mass concentration of the adsorbent in the system is increased, adsorption sites on the surface of the adsorbent are overlapped, the effective adsorption area and adsorption functional groups of the adsorbent per unit mass are correspondingly reduced, and the increase of the adsorption removal rate of the organic matters in the coking wastewater by the adsorbent is not obvious. Under the same adsorbent addition, the removal rate of organic matters in the coking wastewater is compared with that of the three adsorbents, and after modification, CS-BT and C18CS-BT are higher than BT, which indicates that after CS is loaded with BT, the adsorption performance of the adsorbent on the organic matters in the wastewater is obviously improved. Further comparison finds that: the adsorption performance of the amphiphilic C18CS-BT is further improved after the hydrophobic modification, which indicates that the adsorption performance is enhanced by the hydrophobic modification.
Influence of pH
The pH in the system is a very important factor affecting the adsorption performance of the adsorbent, and is mainly expressed in the following two aspects: (1) a change in the form of the presence of an adsorbate in the wastewater; (2) The change in the surface charge distribution of the adsorbent affects its adsorption performance essentially by affecting the electrostatic forces between the adsorbent and the adsorbate. FIG. 6 is a graph showing the effect of pH on three different sorbent removal rates. When the pH value of the system is changed within the range of 4.5-9.0, the removal rates of BT, CS-BT and C18CS-BT are the lowest and are respectively 12.72%, 16.45% and 48.34% when the pH value is 4.5. As the pH increases, the removal rates of BT, CS-BT and C18CS-BT are highest at pH 7.0, at 27.48%, 38.55% and 57.43%, respectively. Under alkaline conditions, the removal rates of the three adsorbents all showed a tendency to decrease. At pH 9.0, the removal rates of BT, CS-BT and C18CS-BT were 22.51%, 34.68% and 52.61%, respectively. This is because under acidic conditions H in solution + The adsorption sites of the adsorbent are occupied by electrostatic interactions, and the phenomenon of 'competitive adsorption' leads to the reduction of the removal rate of organic matters in the coking wastewater by the adsorbent. Under alkaline conditions, the existence form of organic matters in the coking wastewater is changed, for example, some polyphenols which are difficult to biodegrade exist in an anion form, the surface of an adsorbent taking bentonite as a base material is negatively charged, and the removal rate of the organic matters is reduced due to electrostatic repulsive interaction.
Further analysis found that: for C18CS-BT, the effect of system pH on removal rate was less pronounced relative to other adsorbents, indicating a broader pH application range. When the pH value is in the range of 4.5-9.0, the removal rate fluctuates in the range of 48.34-57.43%. Because of the introduction of the strong hydrophobic group, the surface of the C18CS-BT in the system forms a hydrophobic micro-area, which prevents the acid system from being easy to be mixed with water to a certain extentMolecular bound H + Approaching the surface thereof, thereby weakening H in the system + Is "competitive adsorption" of (a). Under alkaline conditions, the removal rate is reduced due to the change of the existence form of the adsorbate in the coking wastewater. In addition, under different pH values, the removal rate of the C18CS-BT in the coking wastewater is higher than that of other two adsorbents. This is because after hydrophobic modification, some hydrophobic organics (such as long-chain alkyl, polycyclic aromatic hydrocarbon, etc.) in the coking wastewater preferentially approach the surface of the C18CS-BT through hydrophobic action, thereby strengthening the adsorption performance of the coking wastewater on organics.
3. Influence of adsorption time
The adsorption time is an important influence factor influencing the adsorption efficiency, and is one of important process parameters for the practical application of the adsorbent. FIG. 7 is a graph showing the relationship between the removal rate of organic matters in coking wastewater and the adsorption time of three different adsorbents. From the graph, the removal rate of the three adsorbents shows the characteristic of rapid increase in 0-30 min, the removal rate of the adsorbents increases slowly in 30-100 min along with the increase of the adsorption time, and the removal rate of the adsorbents basically tends to be stable after the adsorption time exceeds 100 min. This is because there are a large number of adsorption sites on the surface of the adsorbent in the initial stage, and organic matters in the coking wastewater are diffused to the surface of the adsorbent by concentration, and the adsorption rate in this stage is relatively large through surface adsorption and internal pore adsorption. As the adsorption time is prolonged, the adsorption rate at this stage is reduced due to the gradual decrease of adsorption sites on the adsorbent surface. When the adsorption of the surface and the internal pore canal of the adsorbent is saturated, the adsorption rate and the desorption rate are equivalent, the adsorption is in a dynamic balance, and the removal rate tends to be stable. As can be seen from FIG. 7, the adsorption equilibrium time of BT and CS-BT is about 100min, while the adsorption equilibrium time of C18CS-BT is shortened to 60min, and the adsorption efficiency is greatly improved.
In summary, C18CS-BT has the performance advantages of lower loading, wider pH application range, and less adsorption equilibration time relative to BT and CS-BT.
3. Practical application
1. Application in pretreatment of coking wastewater
The coking wastewater is distilled ammonia water of a coking plant in Jiangxi province, the pH of the water quality condition is 8.6, the Chemical Oxygen Demand (COD) is 4981mg/L, and ammonia Nitrogen (NH) 4 + -N) 22.27mg/L, total Nitrogen (TN) 810.5mg/L and Total Phosphorus (TP) 5.42mg/L.
Oscillating in a constant temperature shaking table at 25deg.C and 200rpm for a certain time, filtering the wastewater with 0.45 μm microporous filter membrane, collecting filtrate, and measuring CODcr and NH of coking wastewater before and after treatment by a multiparameter water quality tester 4 + N, TN and TP values.
The concentration of the used adsorbents is 2.5g/L, and the water quality data after the adsorbent treatment are shown in Table 1:
TABLE 1 Water quality after adsorbent treatment (unit: mg/L)
As can be seen from Table 1, the various water quality indexes of the wastewater are improved after the wastewater is treated by three different adsorbents. The bentonite BT reduces the CODcr of the wastewater by 17.21 percent and the NH 4 + 39.82% reduction in N, 18.27% reduction in TP, 22.59% reduction in TN. The chitosan-supported bentonite CS-BT reduces the CODcr of wastewater by 26.28 percent and NH 4 + 44.59% reduction in N, 23.43% reduction in TP, 35.60% reduction in TN. The amphiphilic chitosan loaded bentonite C18CS-BT reduces the CODcr of wastewater by 52.90 percent and NH 4 + 56.13% reduction in N, 29.52% reduction in TP, 57.21% reduction in TN. The above results indicate that: the treatment effect of the amphiphilic chitosan loaded bentonite C18CS-BT on the raw water of the ammonia distillation wastewater is optimal on various water quality indexes, and the advantages of the hydrophobically modified chitosan loaded bentonite adsorbent in the coking wastewater treatment are reflected.
Further analysis of adsorption effect of amphiphilic chitosan-loaded bentonite C18CS-BT on organic matters in ammonia distillation wastewater raw water by GC-MS is carried out, FIG. 8 is a GC-MS diagram of the ammonia distillation wastewater raw water, and FIG. 9 is a GC-MS diagram of a water sample after the amphiphilic chitosan-loaded bentonite C18CS-BT treatment.
The GC-MS diagram in FIG. 8 detects 76 characteristic peaks at different flow times, corresponding to 76 different organics. The GC-MS plot in FIG. 9 detects a total of 50 characteristic peaks at different flow times, corresponding to 50 different organics. Comparing peaks corresponding to different flow time in the figures 8 and 9, the characteristic peaks of the water sample after the C18CS-BT treatment are obviously reduced, which indicates that organic matters in raw water are removed by the adsorbent C18CS-BT, and the CODcr value of the water sample is greatly reduced.
2. Application in deep treatment of coking wastewater
The coking wastewater is discharged from a secondary sedimentation tank after biochemical treatment in a coking plant of Jiangxi province, the pH of the water quality condition is 7.2, the Chemical Oxygen Demand (COD) is 342mg/L, and ammonia Nitrogen (NH) 3 -N) 8.82mg/L, total Nitrogen (TN) 100.6mg/L and Total Phosphorus (TP) 1.73mg/L.
Oscillating in a constant temperature shaking table at 25deg.C and 200rpm for a certain time, filtering the wastewater with 0.45 μm microporous filter membrane, collecting filtrate, and measuring CODcr and NH of coking wastewater before and after treatment by a multiparameter water quality tester 4 + N, TN and TP values.
The concentration of the used adsorbents is 1.5g/L, and the water quality data after the adsorbent treatment are shown in Table 2:
TABLE 2 Water quality after adsorbent treatment (unit: mg/L)
CODcr NH 4 + -N TP TN
Raw water of secondary sedimentation tank 342 8.82 1.73 100.6
BT 256 5.86 1.21 62.3
CS-BT 210 4.55 0.92 48.6
C18CS-BT 152 3.84 0.75 40.2
As can be seen from Table 2, the various water quality indexes of the wastewater are improved after the wastewater is treated by three different adsorbents. Bentonite BT reduces CODcr of wastewater by 25.15 percent and NH 3 -33.56% decrease in N, 30.06% decrease in TP, 38.07% decrease in TN. The chitosan-supported bentonite CS-BT reduces the CODcr of wastewater by 38.60 percent and NH 3 48.41% reduction in N, 46.82% reduction in TP, 51.69% reduction in TN. The amphiphilic chitosan loaded bentonite C18CS-BT reduces the CODcr of wastewater by 55.56 percent and NH 3 -56.46% decrease in N, 56.65% decrease in TP, 60.04% decrease in TN. The above results indicate that: treatment of biochemical treatment-treated secondary sedimentation tank raw water by amphiphilic chitosan-loaded bentonite C18CS-BTThe effect is optimal on various water quality indexes, and the advantages of the hydrophobically modified chitosan-loaded bentonite adsorbent in coking wastewater treatment are reflected.
Further analyzing the adsorption effect of the amphiphilic chitosan-loaded bentonite C18CS-BT on the organic matters in the raw water of the secondary sedimentation tank after biochemical treatment by GC-MS, wherein FIG. 10 is a GC-MS diagram of the raw water of the secondary sedimentation tank, and FIG. 11 is a GC-MS diagram of a water sample after the amphiphilic chitosan-loaded bentonite C18CS-BT treatment. The GC-MS plot in FIG. 10 detected a total of 93 characteristic peaks at different flow times, corresponding to 93 different organics. The GC-MS diagram in FIG. 11 detects 41 characteristic peaks at different flow times, corresponding to 41 different organics. Comparing peaks corresponding to different flow time in the figures 10 and 11, the characteristic peaks of the water sample after the C18CS-BT treatment are obviously reduced, which indicates that organic matters in raw water are removed by the adsorbent C18CS-BT, and the CODcr value of the water sample is greatly reduced.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present application, and the present application is not limited to the above-mentioned embodiments, but may be modified or substituted for some of them by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application. While the foregoing description of the embodiments of the present application has been presented in conjunction with the drawings, it should be understood that it is not intended to limit the scope of the application, but rather, it is intended to cover all modifications or variations within the scope of the application as defined by the claims of the present application.

Claims (9)

1. The preparation method of the efficient amphiphilic chitosan-loaded bentonite adsorbent is characterized by comprising the following steps of:
firstly protecting amino groups on chitosan through Schiff base reaction, grafting octadecyl on secondary hydroxyl groups of the chitosan through alkylation reaction, and then soaking in dilute hydrochloric acid to remove Schiff base, so as to prepare amphipathic chitosan O-octadecyl-chitosan C18CS;
adding the amphipathic chitosan O-octadecyl-chitosan C18CS into glacial acetic acid solution to dissolve the amphipathic chitosan O-octadecyl-chitosan C18CS, adding bentonite, reacting under microwave, taking out the product, drying, grinding and sieving to obtain the amphipathic chitosan.
2. The preparation method of the efficient amphiphilic chitosan-loaded bentonite adsorbent disclosed in claim 1, wherein the mass ratio of the amphiphilic chitosan O-octadecyl-chitosan C18CS to bentonite is 1:10-30.
3. The method for preparing the efficient amphiphilic chitosan-loaded bentonite adsorbent according to claim 1, wherein the power of microwaves is 100-800W, and the heating time is 5-20 min.
4. The method for preparing the efficient amphiphilic chitosan-loaded bentonite adsorbent according to claim 1, wherein the volume percentage of the glacial acetic acid solution is 1% -1.5%.
5. The efficient amphiphilic chitosan-loaded bentonite adsorbent prepared by the method of any one of claims 1-4.
6. The efficient amphiphilic chitosan loaded bentonite adsorbent of claim 5, wherein the efficient amphiphilic chitosan loaded bentonite adsorbent is used for coking wastewater treatment.
7. The efficient amphiphilic chitosan-loaded bentonite adsorbent of claim 6, wherein the coking wastewater is secondary sedimentation tank effluent after biochemical treatment of a coking plant or coking plant ammonia distillation effluent.
8. The efficient amphiphilic chitosan-loaded bentonite adsorbent of claim 6, wherein the pH value of the coking wastewater is 4.5-9.
9. The efficient amphiphilic chitosan loaded bentonite adsorbent of claim 6, wherein the efficient amphiphilic chitosan loaded bentonite adsorbent is used for adsorbing organic matters in wastewater.
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