CN111001397A - Method for synthesizing β cyclodextrin conjugated biochar by microwave-assisted one-pot method and application thereof - Google Patents
Method for synthesizing β cyclodextrin conjugated biochar by microwave-assisted one-pot method and application thereof Download PDFInfo
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Abstract
The invention provides a method for synthesizing β cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof, and relates to a method for synthesizing β cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof.
Description
Technical Field
The invention relates to a method for synthesizing β cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof.
Background
Nowadays, the metal materials and the estrogen are increasingly widely applied, so that a large amount of heavy metal ions and estrogen pollutants are discharged into waste water to cause harm to human health and ecological safety, and therefore, 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 even a very low level can cause reproductive failure, premature adolescence and other adverse health effects. 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 of eliminating such contaminants (such as chemical precipitation, photodegradation, and membrane filtration), however, most of the research has focused on the removal of a single class of contaminants (estrogen contaminants or metal ions), 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.
In addition, agricultural waste-based Adsorbents (AWBs) have received a great deal of attention in view of their abundant environmental protection properties, and among the numerous types of AWBs, biochar has received a great deal of 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, among which there has been a recent wide range of interest in recent years, although studies have highlighted the advantages of biochar in terms of environmental remediation, biochar prepared using biomass has difficulty in simultaneously removing pb (ii) and BPA in wastewater due to its hydrophobic surface, its high affinity groups are few, in this case, surface functionalization techniques are believed to enhance the affinity of biochar for target contaminants, thereby improving its adsorption properties, such as aminocarboxylates, β cyclodextrin polymers (β -CD), a non-cyclic polymer and BPA low-ionic and non-toxic, and therefore, it is considered as a non-toxic and non-toxic, and it is considered as a problem that the removal of biological contaminants from the bulk water by the interaction of organic contaminants with the modified carbon, such as CD 34-CD 54 cyclodextrin polymers, β -CD, CD 54, CD-c, and CD-c, thus, a non-c, which is considered a non-c, and a non-c, which is a non-c, and a non-c, which are highly toxic, and a non-c.
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 β cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof, wherein β cyclodextrin conjugated biochar is synthesized by the microwave-assisted one-pot method, and β cyclodextrin conjugated biochar is used for simultaneously adsorbing BPA and Pb (II) in industrial wastewater.
The microwave-assisted one-pot method for synthesizing β cyclodextrin conjugated biochar is completed according to the following steps:
firstly, placing 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 then 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;
adding sodium hydroxide powder and β 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 β cyclodextrin conjugated biochar, wherein the mass ratio of the sodium hydroxide powder to β cyclodextrin is (3.3-3.7) to (1.8-2.2), the mass ratio of the sodium hydroxide powder to the volume of the distilled water is (3-4 g) to (45-55 mL), the mass ratio of β cyclodextrin to the rice hull biochar is (1.8-2.2) to (0.2-0.4), and the mass ratio of the rice hull biochar to the volume of the glutaraldehyde is (0.2-0.4 g) to (0.8-1.2 mL).
The invention has the beneficial effects that:
the invention relates to a method for synthesizing β cyclodextrin conjugated biochar by a microwave-assisted one-pot method and application thereof, wherein the one-pot method is adopted for synthesis, material modification is realized by microwave radiation, the preparation process is rapid and simple, the prepared β cyclodextrin conjugated biochar has high-efficiency adsorption performance and good reusability, BPA and Pb (II) in industrial wastewater can be adsorbed simultaneously, and the development and application of a heavy metal and organic pollutant coexistence adsorbent in the wastewater are promoted.
The invention can obtain a method for synthesizing β 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 β cyclodextrin conjugated biochar of example, wherein 1 represents Pb (II), 2 represents BPA, &lTtT transfer = 9632 & gTt represents Pb (II), ▲ represents BPA;
FIG. 2 is a diagram of kinetic experiments of β cyclodextrin conjugated biochar of example, 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, &lTtTtransformation = 9632, "&gTt 9632 &lTt/T &gTtrepresents Pb (II), ● represents BPA;
FIG. 3 is an experimental isotherm of Pb (II) in example one, wherein ● represents 5 ℃, ▲ represents 20 ℃, ◆ represents 35 ℃, 1 represents Langmuir model fitting, 2 represents Freundlich model fitting, 3 represents Sims model fitting, 4 represents Langmuir model fitting, 5 represents Freundlich model fitting, 6 represents Sims model fitting, 7 represents Langmuir model fitting, 8 represents Freundlich model fitting, and 9 represents Sims model fitting;
FIG. 4 is an experimental isotherm of BPA in example I, ■ for 5 deg.C, ▲ for 20 deg.C, ● for 35 deg.C, 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, and 9 for Sims model fitting;
FIG. 5 is a graph of 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 embodiment is a method for synthesizing β cyclodextrin conjugated biochar by a microwave-assisted one-pot method, which comprises the following steps:
firstly, placing 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 then 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;
adding sodium hydroxide powder and β 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 β cyclodextrin conjugated biochar, wherein the mass ratio of the sodium hydroxide powder to β cyclodextrin is (3.3-3.7) to (1.8-2.2), the mass ratio of the sodium hydroxide powder to the volume of the distilled water is (3-4 g) to (45-55 mL), the mass ratio of β cyclodextrin to the rice hull biochar is (1.8-2.2) to (0.2-0.4), and the mass ratio of the rice hull biochar to the volume of the glutaraldehyde is (0.2-0.4 g) to (0.8-1.2 mL).
The beneficial effects of the embodiment are as follows:
the method for synthesizing β cyclodextrin conjugated biochar by using the microwave-assisted one-pot method and the application thereof have the advantages that the one-pot method is adopted for synthesis, material modification is realized through microwave radiation, the preparation process is quick and simple, the prepared β cyclodextrin conjugated biochar has high-efficiency adsorption performance and good reusability, BPA and Pb (II) in wastewater can be adsorbed simultaneously, and development and application of a heavy metal and organic pollutant coexistence adsorbent in the wastewater are promoted.
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 those in the first embodiment.
The third concrete implementation mode: the first or second differences from the present embodiment are as follows: the concentration of the sulfuric acid solution in the step one is 18.4mol/L, and H in the sulfuric acid solution2SO4The 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 as follows: 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: 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 1 g: 3 mL.
The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: 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.
Seventh embodiment mode, the difference between this embodiment mode and one of the first to sixth embodiment modes is that the microwave power of 350W is used for stirring and reacting for 15min in the second step, so as to obtain β cyclodextrin conjugated biochar.
The other steps are the same as those in the first to sixth embodiments.
The eighth embodiment is different from the first to seventh embodiments in that the mass ratio of the sodium hydroxide powder to the β cyclodextrin in the second step is 3.5: 2, the mass ratio of the sodium hydroxide powder to the distilled water is 3.5 g: 50mL, the mass ratio of β cyclodextrin to the rice hull biochar is 2: 0.3, and the mass ratio of the rice hull biochar to the glutaraldehyde is 0.3 g: 1 mL.
The other steps are the same as those in the first to seventh embodiments.
Ninth embodiment mode β application of the cyclodextrin conjugated biochar β for simultaneously adsorbing BPA and pb (ii) in industrial wastewater.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is a method for synthesizing β cyclodextrin conjugated biochar by a microwave-assisted one-pot method, which comprises the following steps:
firstly, placing rice hull powder in a sulfuric acid solution, uniformly mixing, standing for 12 hours, washing the rice hull powder to be neutral by using distilled water after standing, and then 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 1 g: 3 mL; 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 solution2SO4The mass fraction of (2) is 98%.
Adding 3.5g of sodium hydroxide powder and 2g of β g of 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 β cyclodextrin conjugated biochar, abbreviated as BCMW-β-CD。
The β cyclodextrin conjugated biochar prepared by the embodiment is used for carrying out desorption, kinetics, isotherm, BPA and Pb (II) simultaneous adsorption and various adsorbent adsorption effect comparison experiments, and specific conclusions are as follows:
1. desorption:
first step, washing BC with absolute ethanolMWβ -CD to remove BPA, BPA desorbed from the eluted BPA-ethanol solution can be further recovered by anhydrous ethanol evaporationMWPb (II) of- β -CD BC can be removed using hydrochloric acid and electrolysisMWβ -adsorption of Pb (II) by CD, thereby achieving BCMW- β -regeneration of 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, BCMWβ -CD adsorbs Pb (II) and BPA binary system solution, the desorption efficiency is respectively kept at 86.60% and 84.43% after 4 times of desorption, and in addition, anhydrous ethanol and hydrochloric acid can be found to effectively wash BCMWβ -CD adsorbed Pb (II) and BPA, the desorption efficiency decreased by 13.31% (Pb (II)) and 20.31% (BPA), respectively, clearly indicating that BC was adsorbed by CDMW- β -CD is superiorThe recoverability of the show.
2. Kinetics:
the adsorption process is that the initial concentration of the solution is 100mg/L, the pH value is 5.5, the temperature is 20 ℃, the adding amount of the β 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 the temperature of 20 ℃;
as shown in FIG. 2, in the first 10 minutes, the adsorption rates for Pb (II) and BPA increased dramatically 92.91% and 95.56%, respectively, and the adsorption rates for Pb (II) and BPA showed a slow increase and equilibrium trend at around 20min and 30min, respectively.
BCMWIt was proposed that the adsorption rate of Pb (II) and BPA rose dramatically 10 minutes before the adsorption rate of Pb (II) and BPA, due to the large amount of β -CD on the adsorbent surface, however, due to the increased repulsive forces between the adsorbents, the adsorption of Pb (II) and BPA tended to increase slowly and approach equilibrium within about 20 and 30 minutes.
R for BPA adsorption by a first order kinetic model2The value is higher, which indicates that the first-order dynamics simulation model is more suitable for describing dynamics 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 BCMW- β -chemical process of adsorption of CD to Pb (II).
3. Isotherm:
the isothermal line conditions include that the concentration range of a lead solution is 10mg/L to 300mg/L, the concentration range of a BPA solution is 5mg/L to 200mg/L, the pH value is 5.5, the adding amount of the β cyclodextrin conjugated biochar material prepared in the embodiment is 0.5g/L, 0.05g of the material is added into 100mL of pollutant solutions with different concentrations, and the pollutant solutions are respectively adsorbed in a water bath shaking table with the pH value of 5.5 at 5 ℃, 20 ℃ and 35 ℃ for 2 hours.
As shown in FIGS. 3 to 4, when the temperature is raised 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, BCMWStepwise increase in the uptake of Pb (II) and BPA by- β -CDThis is because a relatively high concentration gradient at the initial stage may increase the adsorption efficacy, but may also stimulate the competition of the same class of contaminants for limited adsorption sites (e.g. pb (ii) or BPA). When the water temperature is increased from 5 ℃ to 35 ℃, the endothermicity of Pb (II) is increased, which indicates that the absorption of Pb (II) is an endothermic reaction.
Langmuir isotherm (R)2>0.97) and sip model (R)2>0.93) better fitting Pb (II) absorption data, suggesting BCMWThe adsorption of Pb (II) by- β -CD is more likely to be monolayer adsorption, however, BCMWComparison of the adsorption data of- β -CD on BPA in accordance with the Friedrichs 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 monolayer adsorption.
4. Simultaneous adsorption of BPA and pb (ii):
adsorption conditions of a coexisting solution of BPA and Pb (II), the concentration of BPA ranged from 25mg/L to 100mg/L, the concentration of Pb (II) ranged from 50mg/L to 200mg/L, the temperature was 20 ℃, the pH was 5.5, the amount of β cyclodextrin conjugated biochar material added was 0.5g/L, 0.05g of the material was added to 100mL of the mixed solution, and the mixture was adsorbed for 2 hours in a water bath shaker at 20 ℃.
As shown in FIGS. 5 to 6, R is for the binary system Pb (II) -BPAqPb(II)Its value is between 0.93 and 1.02, RqBPAThe value is between 0.94 and 1.03. Apparently, both values are almost close to 1, indicating BCMWThe binary system solution of- β -CD adsorbing Pb (II) and BPA is not interfered with each other, and the phenomenon is mainly due to BCMWFirst, β -CD on the adsorbent may trap organic substances BPA into the cavity through host-guest supramolecular interactions, BCMWThe aromatic backbone of- β -CD can provide a potential pi-pi overlap with BPA interaction, increasing adsorption efficiencyMWThe adsorption of Pb (II) by- β -CD may be associated with electrostatic attraction, and the complexation of Pb (II) 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 β cyclodextrin conjugated biochar material prepared by the embodiment has shorter preparation time and better adsorption effect, and compared with other substance modified biochar, the β cyclodextrin conjugated biochar material prepared by the embodiment has better B-CD modified biochar adsorption capacity.
TABLE 2
Claims (9)
1. The microwave-assisted one-pot method for synthesizing β cyclodextrin conjugated biochar is characterized by comprising the following steps:
firstly, placing 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 then 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;
adding sodium hydroxide powder and β 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 β cyclodextrin conjugated biochar, wherein the mass ratio of the sodium hydroxide powder to β cyclodextrin is (3.3-3.7) to (1.8-2.2), the mass ratio of the sodium hydroxide powder to the volume of the distilled water is (3-4 g) to (45-55 mL), the mass ratio of β cyclodextrin to the rice hull biochar is (1.8-2.2) to (0.2-0.4), and the mass ratio of the rice hull biochar to the volume of the glutaraldehyde is (0.2-0.4 g) to (0.8-1.2 mL).
2. The microwave-assisted one-pot method for synthesizing β cyclodextrin conjugated biochar according to claim 1, wherein the rice hull powder in the first step is prepared by 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 the rice hull powder.
3. The microwave-assisted one-pot method for synthesizing β 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 solution2SO4The mass fraction of (2) is 98%.
4. The microwave-assisted one-pot method for synthesizing β cyclodextrin conjugated biochar according to claim 1, wherein the drying is performed at 60-80 ℃ in step one.
5. The microwave-assisted one-pot method for synthesizing β 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 1 g: 3 mL.
6. The microwave-assisted one-pot method for synthesizing β cyclodextrin conjugated biochar according to claim 1, wherein in the step one, 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.
7. The microwave-assisted one-pot method for synthesizing β cyclodextrin conjugated biochar according to claim 1, wherein the microwave power of 350W is used for stirring and reacting for 15min in the second step to obtain β cyclodextrin conjugated biochar.
8. The microwave-assisted one-pot method for synthesizing β cyclodextrin conjugated biochar according to claim 1, wherein in step two, the mass ratio of sodium hydroxide powder to β cyclodextrin is 3.5: 2, the mass ratio of sodium hydroxide powder to distilled water is 3.5 g: 50mL, the mass ratio of β cyclodextrin to rice hull biochar is 2: 0.3, and the mass ratio of rice hull biochar to glutaraldehyde is 0.3 g: 1 mL.
9. The use of β cyclodextrin-conjugated biochar as claimed in claim 1, wherein β cyclodextrin-conjugated biochar is used to adsorb BPA and Pb simultaneously in industrial wastewater.
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| CN111729654A (en) * | 2020-07-06 | 2020-10-02 | 浙江豪宇生态科技有限公司 | Preparation method and application of modified pagodatree leaf biochar |
| CN115254041A (en) * | 2022-07-20 | 2022-11-01 | 东北农业大学 | Preparation method and application of beta-CD functionalized magnetic sodium alginate microspheres |
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| CN115254041B (en) * | 2022-07-20 | 2023-09-08 | 东北农业大学 | Preparation method and application of beta-CD functionalized magnetic sodium alginate microspheres |
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