CN111001397B - Method for synthesizing beta-cyclodextrin conjugated biochar by microwave-assisted one-pot method and application thereof - Google Patents
Method for synthesizing beta-cyclodextrin conjugated biochar by microwave-assisted one-pot method and application thereof Download PDFInfo
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Abstract
A method for synthesizing beta-cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof, and relates to a method for synthesizing beta-cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof. The invention provides a method for synthesizing beta-cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof. The method comprises the following steps: placing the rice hull powder in a sulfuric acid solution, uniformly mixing, standing, washing with distilled water to be neutral, and drying to obtain dried rice hull powder; heating and pyrolyzing the dried rice hull powder to obtain rice hull biochar; adding sodium hydroxide powder and beta-cyclodextrin into distilled water, adding rice hull biochar and glutaraldehyde, mixing uniformly, placing in a microwave reactor, and stirring for reaction to obtain the beta-cyclodextrin conjugated biochar. The invention can obtain a method for synthesizing beta-cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof.
Description
Technical Field
The invention relates to a method for synthesizing beta-cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof.
Background
Nowadays, the metal materials and the estrogen are increasingly widely used, so that a large amount of heavy metal ions and estrogen pollutants are discharged into wastewater to cause harm to human health and ecological safety, and thus, the metal materials and the estrogen are increasingly concerned. Bisphenol A [2, 2-bis (4-hydroxyphenyl) propane, BPA ] is a common environmental estrogen, is widely applied to the production of polycarbonate as an important monomer, and causes adverse health effects such as reproductive failure, early puberty and the like even at a low level. Lead, as a metal contaminant of estrogen, has extremely high toxicity and harmfulness, and can cause a plurality of diseases such as anemia, renal dysfunction, permanent brain injury and the like. In recent years, researchers have successively proposed some methods for eliminating such contaminants (such as chemical precipitation, photodegradation, and membrane filtration), however, most of the research has focused on the removal of a single type of contaminant (estrogen contaminant or metal ion), which makes the research unsuitable for practical use because Pb (II) and bisphenol a are practically coexistent in industrial wastewater. In addition, the two contaminants differ in their physicochemical properties, making it more difficult to remove Pb (II) and BPA simultaneously.
The adsorption method for removing Pb (II) and BPA has the advantages of convenient operation, strong adaptability, low cost and the like, and is considered to be one of the most effective methods at present. In addition, agricultural waste-based Adsorbents (AWBs) have received much attention in their abundant environmental properties, and among the numerous types of AWBs, biochar has received much attention in recent years as an economically efficient adsorbent, mainly derived from the thermal decomposition of agricultural residues under oxygen-limited conditions, due to its unique physicochemical properties, such as high porosity and good aromatic structure. Although recent research has highlighted the advantages of biochar in environmental remediation, biochar prepared using biomass has difficulty in removing Pb (II) and BPA from wastewater simultaneously, because biochar has a hydrophobic surface with fewer high affinity groups. In this case, it is considered that the surface functionalization technique can enhance the affinity of the biochar for the target contaminant, thereby improving the adsorption property thereof. Among the various modifiers (e.g., aminocarboxylates), beta-cyclodextrin polymers (beta-CD), a harmless cyclic oligosaccharide polymer that forms a non-toxic compound with some organic contaminants and metal ions, is considered a good choice. beta-CD is a substance with hydrophilic and hydrophobic inner cavities on the outer surface, contributes to forming an encapsulated compound with unique properties through the interaction of a host and an object and organic pollutants, and is gradually applied to the research on heavy metal enrichment and quantification. However, native β -CD is a contaminant that is difficult to capture from water due to its water solubility, and therefore should be grafted onto some insoluble material to increase its stability. Obviously, the coupling of the beta-CD and the biochar can solve the problem of low adsorption affinity of the original biochar, thereby improving the removal efficiency of pollutants. However, there have been few research results showing that Pb (II) and BPA can be simultaneously removed using β -CD functionalized biochar.
In many previous studies, the conventional process of heating the adsorbent usually takes hours or even days, which severely limits the wide application of the adsorbent. Microwave radiation can be considered as an effective alternative due to the particular advantages of microwaves (e.g., non-contact heating, high automation and rapid start/stop), the time to complete the process being a few seconds to a few minutes. However, there has been limited research on modifying raw biochar with microwave assistance to remove heavy metal ions and estrogen contaminants.
Disclosure of Invention
The invention provides a method for synthesizing beta-cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof.
The method for synthesizing the beta-cyclodextrin conjugated biochar by a microwave-assisted one-pot method comprises the following steps of:
1. placing the rice hull powder in a sulfuric acid solution, uniformly mixing, standing for 10-12 h, washing with distilled water to be neutral after standing, and drying to obtain dried rice hull powder, wherein the mass ratio of the rice hull powder to the volume of the sulfuric acid solution is (0.8-1.2 g): (2 mL-4 mL); heating the dried rice hull powder to 290-310 ℃ at a heating rate of 10 ℃/min in a nitrogen environment, and pyrolyzing the rice hull powder at 290-310 ℃ for 110-130 min to obtain rice hull biochar;
2. adding sodium hydroxide powder and beta cyclodextrin into distilled water, fully mixing, then adding rice hull biochar and glutaraldehyde, uniformly mixing, placing into a microwave reactor, and stirring and reacting for 10-15 min at a microwave power of 340-360W to obtain beta cyclodextrin conjugated biochar; the mass ratio of the sodium hydroxide powder to the beta cyclodextrin is (3.3-3.7): (1.8-2.2), the ratio of the mass of the sodium hydroxide powder to the volume of the distilled water is (3 g-4 g): (45-55 mL), the mass ratio of the beta cyclodextrin to the rice hull biochar is (1.8-2.2): (0.2-0.4), the ratio of the mass of the rice hull biochar to the volume of the glutaraldehyde is (0.2 g-0.4 g): (0.8 mL-1.2 mL).
The invention has the beneficial effects that:
the method for synthesizing the beta-cyclodextrin conjugated biochar by the microwave-assisted one-pot method and the application thereof adopt the one-pot method for synthesis, realize material modification by microwave radiation, and have quick and simple preparation process; the prepared beta-cyclodextrin conjugated biochar has high-efficiency adsorption performance and good reusability, can simultaneously adsorb BPA and Pb (II) in industrial wastewater, and promotes the development and application of the adsorbent for coexistence of heavy metals and organic pollutants in the wastewater.
The invention can obtain a method for synthesizing beta-cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof.
Drawings
FIG. 1 is a diagram of an experimental desorption experiment of beta-cyclodextrin conjugated biochar of an example, wherein 1 represents Pb (II), 2 represents BPA, \\ 9632; represents Pb (II), and a tangle-solidup represents BPA;
FIG. 2 is a graph of a kinetic experiment of a beta-cyclodextrin conjugated biochar of the example, wherein 1 represents a kinetic second-order model fitting Pb (II), 2 represents a kinetic first-order model fitting Pb (II), 3 represents a kinetic first-order model fitting BPA,4 represents a kinetic second-order model fitting BPA, \ 9632; represents Pb (II), \9679; and represents BPA;
FIG. 3 is an isotherm experimental plot of Pb (II) at v 9679a representing 5 ℃,. Tangle-solidup representing 20 ℃,. Diamond-solid representing 35 ℃,1 representing a Langmuir model fit, 2 representing a Freundlich model fit, 3 representing a Sims model fit, 4 representing a Langmuir model fit, 5 representing a Freundlich model fit, 6 representing a Sims model fit, 7 representing a Langmuir model fit, 8 representing a Freundlich model fit, and 9 representing a Sims model fit in example I;
FIG. 4 is an isotherm experimental plot of BPA in example one, \\9632 ℃; representing 5 ℃,. Tangle-solidup for 20 ℃, \9679representing35 ℃,1 for Freundlich model fitting, 2 for Langmuir model fitting, 3 for Sims model fitting, 4 for Freundlich model fitting, 5 for Langmuir model fitting, 6 for Sims model fitting, 7 for Freundlich model fitting, 8 for Langmuir model fitting, 9 for Sims model fitting;
FIG. 5 is a graph showing an adsorption experiment based on Pb (II) in the first example;
FIG. 6 is a graph of an adsorption experiment based on BPA in example I.
Detailed Description
The first specific implementation way is as follows: the method for synthesizing the beta-cyclodextrin conjugated biochar by the microwave-assisted one-pot method comprises the following steps:
1. placing the rice hull powder in a sulfuric acid solution, uniformly mixing, standing for 10-12 h, washing with distilled water to be neutral after standing, and drying to obtain dried rice hull powder, wherein the mass ratio of the rice hull powder to the volume of the sulfuric acid solution is (0.8-1.2 g): (2 mL-4 mL); heating the dried rice hull powder to 290-310 ℃ at a heating rate of 10 ℃/min in a nitrogen environment, and pyrolyzing the rice hull powder at 290-310 ℃ for 110-130 min to obtain rice hull biochar;
2. adding sodium hydroxide powder and beta-cyclodextrin into distilled water, fully mixing, then adding rice hull biochar and glutaraldehyde, uniformly mixing, placing in a microwave reactor, and stirring and reacting for 10-15 min at the microwave power of 340-360W to obtain beta-cyclodextrin conjugated biochar; the mass ratio of the sodium hydroxide powder to the beta cyclodextrin is (3.3-3.7): (1.8-2.2), the ratio of the mass of the sodium hydroxide powder to the volume of the distilled water is (3 g-4 g): (45-55 mL), the mass ratio of the beta cyclodextrin to the rice hull biochar is (1.8-2.2): (0.2-0.4), the ratio of the mass of the rice hull biochar to the volume of the glutaraldehyde is (0.2 g-0.4 g): (0.8 mL-1.2 mL).
The beneficial effects of the embodiment are as follows:
the method for synthesizing the beta-cyclodextrin conjugated biochar by the microwave-assisted one-pot method and the application thereof adopt the one-pot method for synthesis, realize material modification by microwave radiation, and have quick and simple preparation process; the prepared beta-cyclodextrin conjugated biochar has high-efficiency adsorption performance and good reusability, can adsorb BPA and Pb (II) in wastewater simultaneously, and promotes development and application of a heavy metal and organic pollutant coexisting adsorbent in the wastewater.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the rice hull powder in the first step is prepared according to the following steps: firstly washing rice hulls with distilled water for 3-5 times, then drying at 60-80 ℃, grinding after drying, and then sieving with a 100-mesh sieve to obtain rice hull powder.
Other steps are the same as in the first embodiment.
The third concrete implementation mode: the first or second difference between the present embodiment and the second embodiment is: the concentration of the sulfuric acid solution in the step one is 18.4mol/L, and H in the sulfuric acid solution 2 SO 4 The mass fraction of (2) is 98%.
The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is: and in the step one, drying is carried out at the temperature of 60-80 ℃.
The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode is as follows: the difference between this embodiment and one of the first to fourth embodiments is: the ratio of the mass of the rice hull powder to the volume of the sulfuric acid solution in the first step is 1g:3mL.
The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is as follows: in the first step, the dried rice hull powder is heated to 300 ℃ at a heating rate of 10 ℃/min in a nitrogen environment, and is pyrolyzed at 300 ℃ for 120min to obtain the rice hull biochar.
The other steps are the same as those in the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and the first to sixth embodiments is: stirring and reacting for 15min at the microwave power of 350W to obtain the beta-cyclodextrin conjugated biochar.
The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode eight: the difference between this embodiment and one of the first to seventh embodiments is: in the second step, the mass ratio of the sodium hydroxide powder to the beta cyclodextrin is 3.5:2, the ratio of the mass of the sodium hydroxide powder to the volume of the distilled water was 3.5g:50mL, wherein the mass ratio of the beta cyclodextrin to the rice hull biochar is 2:0.3, the ratio of the mass of the rice hull biochar to the volume of the glutaraldehyde is 0.3g:1mL.
The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the present embodiment relates to the use of beta-cyclodextrin conjugated biochar for the simultaneous adsorption of BPA and Pb (II) in industrial wastewater.
The following examples were employed to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the microwave-assisted one-pot method for synthesizing the beta-cyclodextrin conjugated biochar is completed by the following steps:
1. placing rice hull powder in a sulfuric acid solution, uniformly mixing, standing for 12h, washing with distilled water to be neutral after standing, and drying to obtain dried rice hull powder, wherein the ratio of the mass of the rice hull powder to the volume of the sulfuric acid solution is 1g:3mL; and (3) placing the dried rice hull powder in a tubular furnace, heating to 300 ℃ at a heating rate of 10 ℃/min in a nitrogen environment, and pyrolyzing at 300 ℃ for 120min to obtain the rice hull biochar, which is named as BC.
The concentration of the sulfuric acid solution in the step one is 18.4mol/L, and H in the sulfuric acid solution 2 SO 4 The mass fraction of (2) is 98%.
2. Adding 3.5g of sodium hydroxide powder and 2g of beta-cyclodextrin into 50mL of distilled water, fully mixing, adding 0.3g of rice hull biochar and 1mL of glutaraldehyde, uniformly mixing, placing in a microwave reactor, and stirring and reacting for 15min at the microwave power of 350W to obtain beta-cyclodextrin conjugated biochar, abbreviated as BC MW -β-CD。
The beta-cyclodextrin conjugated biochar prepared by the embodiment is used for carrying out desorption, dynamics, isotherms, BPA and Pb (II) simultaneous adsorption and various adsorbent adsorption effect comparison experiments, and the specific conclusion is as follows:
1. desorption:
first step, washing BC with absolute ethanol MW beta-CD to remove BPA, and BPA desorbed from the eluted BPA-ethanol solution can be further recovered by anhydrous ethanol evaporation. In the second desorption stage, the remainder is adsorbed on BC MW Pb (II) of-beta-CD can remove BC using hydrochloric acid and electrolysis MW beta-CD adsorbed Pb (II), thereby achieving BC MW -regeneration of beta-CD.
The absorbent was soaked in absolute ethanol for 60 minutes, then eluted with 1M HCl solution for 60 minutes, and washed with distilled water to neutrality. And drying the mixture in an oven at 60 ℃ overnight to obtain the regenerated material.
As shown in FIG. 1, BC MW beta-CD adsorbs Pb (II) and BPA binary system solution, the desorption efficiency is respectively kept at about 86.60 percent and 84.43 percent after 4 rounds of desorption, and in addition, anhydrous ethanol and hydrochloric acid can be found to effectively wash BC MW The desorption efficiency of Pb (II) and BPA adsorbed by β -CD decreased by 13.31% (Pb (II)) and 20.31% (BPA), respectively, clearly indicating BC MW beta-CD has excellent recoverability.
2. Kinetics:
the adsorption process is as follows: initial concentration of solution 100mg/L, pH =5.5, temperature: at 20 ℃, the dosage of the beta-cyclodextrin conjugated biochar material prepared in the embodiment is 0.5g/L, the material is added into 100mL of pollutant solution, and the pollutant solution is placed in a water area shaking table for adsorption for 2 hours at 20 ℃;
as shown in fig. 2, the adsorption rates of Pb (II) and BPA increased dramatically over the first 10 minutes by 92.91% and 95.56%, respectively, and the adsorption of Pb (II) and BPA tended to increase slowly and approach equilibrium around 20min and 30min, respectively.
BC MW The kinetic studies exploring the adsorption behavior for the removal of Pb (II) and BPA were carried out on β -CD. It was suggested that the adsorption rates for Pb (II) and BPA rose dramatically within the first 10 minutes due to the large amount of β -CD at the adsorbent surface. However, due to the increased repulsive forces between the adsorbents, the adsorption of Pb (II) and BPA showed a tendency to slowly increase and approach equilibrium within about 20 and 30 minutes.
R for BPA adsorption by a first order kinetic model 2 Higher value, which indicates that the first order-like kinetic model is more suitable for tracingThe kinetic data. However, the pseudo-second order kinetic model proved to be more suitable for describing the adsorption of BPA, showing that the binding between Pb (II) and polar functional groups is involved in BC MW -chemistry of adsorption of Pb (II) by β -CD.
3. Isotherm:
isotherm conditions: lead solution concentration range: 10 mg/L-300 mg/L, BPA solution concentration range: 5mg/L to 200mg/L, pH =5.5, and the dosage of the beta-cyclodextrin conjugated biochar material prepared in this example is 0.5g/L; 0.05g of the material was added to 100mL of contaminant solutions of different concentrations and adsorbed for 2 hours in a shaker in a water bath at pH 5.5 at 5 deg.C, 20 deg.C and 35 deg.C, respectively.
As shown in fig. 3 to 4, when the temperature is increased from 5 ℃ to 35 ℃, the adsorption amount of Pb (II) tends to increase, indicating that the adsorption exothermic reaction of Pb (II) is endothermic and the adsorption exothermic reaction of BPA is exothermic.
With increasing initial concentration, BC MW The uptake of Pb (II) and BPA by β -CD is gradually increased because relatively high concentration gradients in the initial stages can increase adsorption efficacy, but can also stimulate competition for limited adsorption sites for the same class of contaminants (e.g., pb (II) or BPA). When the water temperature is increased from 5 ℃ to 35 ℃, the endothermicity of Pb (II) tends to increase, indicating that the adsorption of Pb (II) is an endothermic reaction.
Langmuir isotherm (R) 2 >0.97 And sip model (R) 2 >0.93 Pb (II) absorption data that can better meet, suggesting BC MW The adsorption of Pb (II) by β -CD is more likely a monolayer adsorption. However, BC MW Comparison of the adsorption data of beta-CD to BPA in accordance with the Frededrich model (R) 2 >0.98 And sip model (R) 2 >0.98 Indicating that adsorption of BPA is a process that occurs in heterogeneous surface polymolecular layer adsorption.
4. Simultaneous adsorption of BPA and Pb (II):
adsorption conditions: the concentration of BPA and Pb (II) coexisting solution is 25 mg/L-100 mg/L, the concentration of Pb (II) ranges 50 mg/L-200 mg/L, the temperature is 20 ℃, the pH is =5.5, the beta-cyclodextrin conjugated biochar material prepared by the embodiment is added in an amount of 0.5g/L, 0.05g of the material is added into 100mL of mixed solution, and the mixed solution is adsorbed in a water bath shaker for 2 hours at the temperature of 20 ℃.
As shown in FIGS. 5 to 6, R is for the binary system Pb (II) -BPA qPb(II) Its value is between 0.93 and 1.02, R qBPA The value is between 0.94 and 1.03. Apparently, both values are almost close to 1, indicating BC MW The two-system solution of beta-CD adsorbing Pb (II) and BPA is not interfered mutually, and the phenomenon is mainly due to BC MW Different adsorption mechanisms of β -CD for Pb (II) and BPA. First, the beta-CD on the adsorbent may trap the organic substance BPA into the cavity through host-guest supramolecular interactions, BC MW The aromatic backbone of the-beta-CD can provide a potential pi-pi overlap to interact with BPA, increasing adsorption effectiveness. BC MW The adsorption of Pb (II) by β -CD may be associated with electrostatic attraction, the Pb (II) complexing with oxygen-containing functional groups on the adsorbent.
5. Comparison experiment of adsorption effect of various adsorbents:
table 2 shows comparison of adsorption effects of various adsorbents;
compared with the conventional heating method for preparing the adsorbent, the beta-cyclodextrin conjugated biochar material prepared by the embodiment has shorter preparation time and better adsorption effect; compared with other substance modified biochar, the beta-cyclodextrin conjugated biochar material prepared by the embodiment has better B-CD modified biochar adsorption capacity.
TABLE 2
Claims (5)
1. The microwave-assisted one-pot method for synthesizing the beta-cyclodextrin conjugated biochar is characterized by comprising the following steps of:
1. placing the rice hull powder in a sulfuric acid solution, uniformly mixing, standing for 10h to 12h, washing with distilled water to be neutral after standing, and drying to obtain dried rice hull powder, wherein the ratio of the mass of the rice hull powder to the volume of the sulfuric acid solution is (0.8g to 1.2g): (2mL to 4mL); heating the dried rice hull powder to 290-310 ℃ at a heating rate of 10 ℃/min in a nitrogen environment, and pyrolyzing for 110min-130min at 290-310 ℃ to obtain rice hull biochar;
the rice hull powder in the first step is prepared according to the following steps: washing rice hulls with distilled water for 3-5 times, drying at 60-80 ℃, grinding after drying, and sieving with a 100-mesh sieve to obtain rice hull powder;
2. adding sodium hydroxide powder and beta-cyclodextrin into distilled water, fully mixing, adding rice hull biochar and glutaraldehyde, uniformly mixing, placing into a microwave reactor, stirring and reacting for 15min at the microwave power of 350W to obtain beta-cyclodextrin conjugated biochar, wherein the beta-cyclodextrin conjugated biochar is used for simultaneously adsorbing BPA and Pb in industrial wastewater; the mass ratio of the sodium hydroxide powder to the beta cyclodextrin is 3.5:2, the ratio of the mass of sodium hydroxide powder to the volume of distilled water was 3.5g:50mL, wherein the mass ratio of the beta cyclodextrin to the rice hull biochar is 2:0.3, the ratio of the mass of the rice hull biochar to the volume of the glutaraldehyde is 0.3g:1mL.
2. The microwave-assisted one-pot method for synthesizing beta-cyclodextrin conjugated biochar according to claim 1, wherein the concentration of the sulfuric acid solution in the first step is 18.4mol/L, and H in the sulfuric acid solution 2 SO 4 The mass fraction of (2) is 98%.
3. The microwave-assisted one-pot method for synthesizing beta-cyclodextrin conjugated biochar according to claim 1, wherein the drying in the first step is performed at 60-80 ℃.
4. The microwave-assisted one-pot method for synthesizing beta-cyclodextrin conjugated biochar according to claim 1, wherein the ratio of the mass of the rice hull powder to the volume of the sulfuric acid solution in the first step is 1g:3mL.
5. The microwave-assisted one-pot method for synthesizing beta-cyclodextrin conjugated biochar according to claim 1, characterized in that in the first step, dried rice hull powder is heated to 300 ℃ at a heating rate of 10 ℃/min in a nitrogen environment and is pyrolyzed at 300 ℃ for 120min to obtain rice hull biochar.
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| CN105236507B (en) * | 2015-09-15 | 2017-09-26 | 湖南大学 | The method that the adsorbent being combined using beta cyclodextrin chitosan and walnut shell charcoal removes the Cr VI in waste water |
| CN105688812B (en) * | 2016-03-01 | 2018-01-02 | 湖南大学 | The preparation method and applications for the charcoal that a kind of beta cyclodextrin/polyglutamic acid is modified |
| US11014830B2 (en) * | 2016-12-15 | 2021-05-25 | Ada Carbon Solutions, Llc | Sorbent compositions for the removal of boron from aqueous mediums |
| CN107262039B (en) * | 2017-08-10 | 2019-05-10 | 福州大学 | A kind of high-molecular biologic charcoal ball immobilized microalgae compound adsorbent and its preparation and application |
| CN109289787A (en) * | 2018-10-31 | 2019-02-01 | 山东大学 | A kind of preparation method of the co-modified biological carbon composite of iron, cyclodextrin |
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