CN113582317A - Cation functionalized beta-cyclodextrin/chitosan composite material and preparation method and application thereof - Google Patents
Cation functionalized beta-cyclodextrin/chitosan composite material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/02—Separating microorganisms from their culture media
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- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/12—Unicellular algae; Culture media therefor
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Abstract
The invention provides a cation functionalized beta-cyclodextrin/chitosan composite material and a preparation method and application thereof, wherein the method comprises the following steps: adding an initiator into beta-cyclodextrin and chitosan to generate free radicals, and introducing 3- (methacrylamide) propyl trimethyl ammonium chloride to generate graft copolymerization reaction to obtain the cationic functionalized beta-cyclodextrin/chitosan composite material. The invention adds initiator to generate free radical, and introduces 3- (methacrylamide) propyl trimethyl ammonium chloride for graft copolymerization to form cationized beta-cyclodextrin/chitosan composite material. The beta-cyclodextrin has an excellent cavity structure, the surface of the chitosan has positive charges and abundant amino groups, and the two high polymer materials are strongly combined to form a synergistic effect and exert excellent flocculation capacity. And quaternary ammonium groups are introduced, and chlorella is efficiently flocculated through mechanisms such as charge neutralization and adsorption bridging, so that the harvesting efficiency of chlorella is further increased.
Description
Technical Field
The invention relates to the technical field of microalgae harvesting, in particular to a cation functionalized beta-cyclodextrin/chitosan composite material and a preparation method and application thereof.
Background
The significant deterioration of global climate has been caused by the continuous rapid development of industrialization and the massive development and utilization of fossil energy by human since the 21 st century. The idea of biofuels to replace fossil fuels has received a great deal of attention. The microalgae is considered as a raw material of the third-generation biofuel and has good development prospect. Microalgae are simple, autotrophic or heterotrophic, photosynthetic microorganisms that can efficiently utilize carbon dioxide and light energy to synthesize cellular material such as starch, proteins, nucleic acids, lipids, etc., wherein lipids can be converted into biodiesel through transesterification reactions. The microalgae is used as an important raw material for synthesizing the biofuel, and has the great advantages of higher yield than crops, high growth rate and high oil yield; does not compete with crops for cultivated land, needs less water and can realize low-cost cultivation. At present, microalgae have application research in food additives, animal feeds, cosmetics industries and the like, and have the potential of gradually realizing industrialization. However, the cost of microalgae cultivation and harvesting is too high, and the economic law for making cheap biodiesel is not met. In addition, microalgae cells are negatively charged and small in size, only 2-20 μm, stably suspended in the growth medium, and these characteristics make the process of harvesting microalgae very expensive. Microalgae are harvested by high energy consumption techniques such as centrifugation, filtration, flotation and the like, and the harvesting method has high energy demand and low efficiency. Among the various methods for harvesting microalgae, flocculation is a very promising technique, which is a process of aggregating algal cells into clumps by using different types of flocculants through mechanisms such as charge neutralization, sweeping, net-capturing bridging and the like, thereby precipitating.
The chitosan is aThe efficient and non-toxic biological flocculant is a cation weak electrolyte. The chitosan has amino (-NH)2) And hydroxyl (-OH) groups. It is a natural cationic carbohydrate bioflocculant, which is generated by deacetylation reaction of chitin. The chitin is mainly from shrimp and crab shells, and the chitosan prepared by the chitin can realize value-added recovery of shell wastes and efficient flocculation of microalgae biomass at the same time. However, when the chitosan is applied to microalgae collection, the required dosage is high, and the cost is also high. In addition, the traditional chitosan only shows good harvesting performance on partial microalgae species, and the harvesting performance on chlorella vulgaris is not high. Cyclodextrins (CDs) are a general term for a series of cyclic oligosaccharides produced from amylose by the action of Cyclodextrin glucosyltransferases secreted by Bacillus. It is a cyclic oligosaccharide consisting of six, seven and eight nonalkyl sugarless units, defined as alpha-cyclodextrin (alpha-CD), beta-cyclodextrin (beta-CD), gamma-cyclodextrin (gamma-CD), respectively. In recent years, beta-cyclodextrin has been widely used in the fields of chemistry, pharmacy, and environmental protection due to its low production cost and unique structural characteristics; however, there is no report that beta-cyclodextrin can be used for microalgae recovery.
Therefore, in combination with the above analysis, it is necessary to develop a flocculant with high recovery performance for chlorella vulgaris.
Disclosure of Invention
The invention aims to provide a cationic functionalized beta-cyclodextrin/chitosan composite material and a preparation method and application thereof. The cation functionalized chitosan/beta-cyclodextrin composite material has excellent harvesting performance on chlorella vulgaris, is biodegradable, and has little influence on the downstream biomass utilization process.
In a first aspect of the present invention, there is provided a method for preparing a cationically functionalized β -cyclodextrin/chitosan composite, the method comprising: adding an initiator into beta-cyclodextrin and chitosan macromolecules to generate free radicals, and introducing 3- (methacrylamide) propyl trimethyl ammonium chloride to generate graft copolymerization reaction to obtain the cationic functionalized beta-cyclodextrin/chitosan composite material.
Further, the method comprises:
dissolving beta-cyclodextrin powder in deionized water to obtain a beta-cyclodextrin aqueous solution;
dissolving chitosan powder in an acetic acid solution to obtain a chitosan acetic acid solution;
uniformly mixing the beta-cyclodextrin aqueous solution and the chitosan acetic acid solution, adding an initiator to perform a free radical generation reaction, and then adding 3- (methacrylamide) propyl trimethyl ammonium chloride to perform a graft copolymerization reaction to obtain a reaction mixture;
and adding the reaction mixture into a sodium hydroxide solution for neutralization reaction, then adding an absolute ethanol solution to obtain a precipitate, and washing and drying to obtain the cation functionalized beta-cyclodextrin/chitosan composite material.
Further, the mass ratio of the beta-cyclodextrin powder to the chitosan powder is (0.9-1.1): (0.9-1.1). More preferably, the mass ratio is 1: 1.
further, the volume fraction of the acetic acid solution is 0.8-1.2%.
Further, the initiator is cerium ammonium nitrate.
Further, the temperature of the free radical generating reaction is 75-80 ℃, and the time of the free radical generating reaction is 10-60 min; the temperature of the graft copolymerization reaction is 75-80 ℃, and the time of the graft copolymerization reaction is 30-120 min.
Further, the concentration of the sodium hydroxide solution is 0.05-0.2 mol/L.
Further, the ethanol solution is an anhydrous ethanol solution.
In a second aspect of the invention, the cation functionalized beta-cyclodextrin/chitosan composite material prepared by the method is provided.
In a third aspect of the invention, the application of the cation functionalized beta-cyclodextrin/chitosan composite material in microalgae recovery is provided.
Further, the method for recovering microalgae by using the cation functionalized beta-cyclodextrin/chitosan composite material comprises the following steps:
adjusting the pH value of the algae liquid to 6-8 respectively, adding 45-150mg/L of cation functionalized CTS/beta-CD composite flocculant, and uniformly mixing the flocculant and the algae liquid through magnetic stirring.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the invention provides a cationic functionalized beta-cyclodextrin/chitosan composite material and a preparation method and application thereof, wherein an initiator is added to generate free radicals, 3- (methacrylamide) propyl trimethyl ammonium chloride is introduced for graft copolymerization to form the cationic functionalized beta-cyclodextrin/chitosan composite material, and the cationic functionalized beta-cyclodextrin/chitosan composite material has high efficiency for harvesting chlorella, and specifically comprises the following steps:
(1) the beta-cyclodextrin/chitosan composite material is non-toxic and biodegradable, is a green environment-friendly bioflocculant, can reduce the influence on the natural ecological environment and avoid secondary pollution. The chitosan/beta-cyclodextrin composite material contains rich amino (-NH)3) And hydroxyl (-OH), and a large number of quaternary ammonium groups are introduced, so that the surface of the chlorella is positively charged, and the chlorella is beneficial to harvesting.
(2) The beta-cyclodextrin and chitosan composite material generates free radicals through an initiator, 3- (methacrylamide) propyl trimethyl ammonium chloride is introduced to carry out graft copolymerization, quaternary ammonium groups are introduced, the molecular weight and surface cationic charges of the composite material are increased, the charge neutralization and adsorption bridging effects between the chitosan/beta-cyclodextrin composite material and microalgae cells are enhanced, the harvesting efficiency of chlorella is increased, and the dosage of chitosan used alone is reduced.
(3) The beta-cyclodextrin can effectively overcome the defect that the chitosan is insoluble in water, and the modified beta-cyclodextrin and chitosan composite material is prepared by introducing a hydrophilic group-N+-(CH3)3Can be dissolved in water. And, the beta-cyclodextrin is composed of glucose, and has no toxicity or toxicityNo side effect, and no toxic effect on the utilization and processing of downstream microalgae biomass.
(4) The harvesting efficiency of the cationic functionalized chitosan/beta-cyclodextrin composite material to chlorella vulgaris of 60mg/L can reach more than 90.80% in 2 min. Greatly improves the harvesting efficiency and reduces the time required for harvesting compared to the original chitosan alone.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a cationic functionalized beta-cyclodextrin/chitosan composite material according to an embodiment of the present invention;
FIG. 2 is an infrared spectroscopy (FTIR) spectrum of a cationically functionalized β -cyclodextrin/chitosan composite prepared in an example of the present invention;
FIG. 3 is an X-ray diffraction (XRD) pattern of a cationically functionalized β -cyclodextrin/chitosan composite material prepared in accordance with an embodiment of the present invention;
FIG. 4 shows the harvesting efficiency of the cation functionalized beta-cyclodextrin/chitosan composite material for Chlorella vulgaris at different addition concentrations according to the embodiment of the present invention;
FIG. 5 shows the harvesting efficiency of the cation functionalized beta-cyclodextrin/chitosan composite material for Chlorella vulgaris under different pH conditions, according to the embodiment of the present invention;
FIG. 6 shows the effect of different dosages of cation-functionalized beta-cyclodextrin/chitosan composite material prepared by the embodiment of the invention on the recovery efficiency of Chlorella vulgaris.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, 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 invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be obtained by an existing method.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
the invention adds initiator to generate free radical, and introduces 3- (methacrylamide) propyl trimethyl ammonium chloride for graft copolymerization to form cationized beta-cyclodextrin/chitosan composite material. The beta-cyclodextrin has an excellent cavity structure, the surface of the chitosan has positive charges and abundant amino groups, and the two high polymer materials are strongly combined to form a synergistic effect and exert excellent flocculation capacity. Simultaneously, quaternary ammonium groups are introduced, and the cation functionalized beta-cyclodextrin/chitosan composite material can efficiently flocculate chlorella through mechanisms such as charge neutralization, adsorption bridging and the like, so that the harvesting efficiency of the chlorella is further increased; simultaneously introducing hydrophilic group-N+-(CH3)3Can be dissolved in water. The invention prepares the cation functionalized beta-cyclodextrin/chitosan composite material, has high efficiency of harvesting chlorella, and has simple and easy preparation method, rapidness and convenience.
The specific preparation steps, as shown in fig. 1, include:
step S1, dissolving beta-cyclodextrin powder in deionized water to obtain a beta-cyclodextrin aqueous solution;
in the technical scheme, the concentration range of the beta-cyclodextrin aqueous solution is preferably 5-10 g/L. Better dissolution in this range;
in the above technical solution, the β -cyclodextrin powder is preferably (2-hydroxypropyl) - β -cyclodextrin, and the β -cyclodextrin is (2-hydroxypropyl) - β -cyclodextrin, and the molecular weight of the β -cyclodextrin is between 973 and 2163; the beta-cyclodextrin structure is a toroidal cone or a hollow cone, and the interior of the ring is hydrophobic. The interior of the torus is formed by electron-rich glycosidic oxygen atoms. The exterior of the torus is hydrophilic and is capable of interacting with aqueous media during solvation. The molecular structural formula of the beta-cyclodextrin is shown as follows.
Step S2, dissolving chitosan powder in an acetic acid solution to obtain a chitosan acetic acid solution;
the chitosan has deacetylation degree of 70-80%, and is a compound obtained by deacetylating chitin, and has molecular formula of (C)6H11-NO4) n, the structural formula is shown as follows. The chitosan has biodegradability, no toxicity and good adsorption characteristic, and is a potential flocculant for microalgae harvesting.
In the technical scheme, the volume fraction of the acetic acid solution is 0.8-1.2%. If the volume fraction of the acetic acid solution is too large, the solubility, conductivity and viscosity of the chitosan are adversely affected; increase in acid concentration, -NH3 +Acid anions gathered around the ions are increased, and the content of-NH in macromolecules is reduced3 +The charged macromolecules tend to curl, and the viscosity of the solution is reduced. Preferably, the volume fraction of the acetic acid solution is 1%; chitosan is insoluble in water and readily soluble in organic acid solutions. Because the acetic acid has low cost and no pollution, the acetic acid solution is used as a solvent to dissolve the chitosan. Weighing a certain amount of chitosan powder, suspending the chitosan powder in an acetic acid solution, and fully stirring and dissolving to obtain a chitosan acetic acid solution.
In the technical scheme, the ratio of the mass of the chitosan powder to the volume of the acetic acid solution is (0.5-1) mg: (50-100) mL. To allow the chitosan powder to be well dissolved in the acetic acid solution.
Step S3, uniformly mixing the beta-cyclodextrin aqueous solution and the chitosan acetic acid solution, adding an initiator to perform a free radical generation reaction, and then adding 3- (methacrylamide) propyl trimethyl ammonium chloride to perform a graft copolymerization reaction to obtain a reaction mixture;
in the above technical scheme, the mass ratio of the beta-cyclodextrin powder to the chitosan powder is (0.9-1.1): (0.9-1.1). Preferably 1: 1; the mass ratio is favorable for the complete graft copolymerization reaction;
in the technical scheme, the initiator is ammonium ceric nitrate, and is a good initiator due to high initiation capability and wide adaptability.
According to the invention, the initiator is added to carry out free radical generation reaction, and then 3- (methacrylamide) propyl trimethyl ammonium chloride is added to carry out graft copolymerization reaction, so that the reaction efficiency is high, and the cationized beta-cyclodextrin/chitosan composite material is formed, and the chlorella harvesting efficiency is high; the method solves the problems of low efficiency and complicated steps of the traditional method (particularly adding a catalyst and a crosslinking agent) graft copolymerization reaction.
In the technical scheme, the structural formula of the 3- (methacrylamide) propyl trimethyl ammonium chloride is as follows:
3- (methacrylamide) propyl trimethyl ammonium chloride is adopted to introduce quaternary ammonium groups, so that a large number of quaternary ammonium groups are introduced, positive charges are carried on the surface, and the harvesting of chlorella is facilitated; and a hydrophilic group-N is introduced+-(CH3)3The modified beta-cyclodextrin and chitosan composite material is prepared by introducing hydrophilic group-N+-(CH3)3Can be dissolved in water.
In the technical scheme, the addition amount of the initiator is usually 0.1-0.3 mL. And may be increased or decreased as appropriate in other embodiments.
The temperature of the free radical generating reaction is 75-80 ℃, and the time of the free radical generating reaction is 10-60 min; under the condition, more free radicals can be generated;
the temperature of the graft copolymerization reaction is 75-80 ℃, and the time of the graft copolymerization reaction is 30-120 min. Under the condition, the graft copolymerization reaction is complete;
and step S4, adding the reaction mixture into a sodium hydroxide solution for neutralization reaction, then adding an absolute ethanol solution to obtain a precipitate, and washing and drying to obtain the cation functionalized beta-cyclodextrin/chitosan composite material.
In the step S4, in the above step,
the concentration of the sodium hydroxide solution is 0.05-0.2 mol/L. Preferably 0.1mol/L, and adding sodium hydroxide solution to carry out neutralization reaction to adjust the pH.
The ethanol solution is an absolute ethanol solution. The adoption of absolute ethyl alcohol solution is easier to generate precipitate;
in conclusion, the embodiment of the invention can generate a synergistic effect by uniformly mixing the beta-cyclodextrin/chitosan, thereby improving the harvesting effect of microalgae. And quaternary ammonium groups are introduced, so that the harvesting efficiency of the chlorella is further increased. Simultaneously introducing hydrophilic group-N+-(CH3)3Can be dissolved in water;
the following describes a cationic functionalized β -cyclodextrin/chitosan composite material, a preparation method and applications thereof in detail with reference to examples and experimental data.
EXAMPLE 1 preparation of cationic functionalized beta-cyclodextrin/chitosan composite flocculant (CTS/beta-CD)
Preparation of cation functionalized beta-cyclodextrin/chitosan flocculant
Weighing 1-2g of beta-cyclodextrin powder, and dissolving in 100-200mL of deionized water to obtain a beta-cyclodextrin aqueous solution for later use. Chitosan is insoluble in water and readily soluble in organic acid solutions. Because the acetic acid has low cost and no pollution, the acetic acid solution is used as a solvent to dissolve the chitosan.
Weighing 1-2g of chitosan powder, suspending the chitosan powder in 100-200mL of 1% acetic acid solution, and fully stirring and dissolving to obtain chitosan acetic acid solution for later use.
The two solutions are mixed well, and 0.01-0.05g of initiator Cerium Ammonium Nitrate (CAN) is slowly added to generate free radicals. To the above mixed solution, 5 to 15mL of 3- (methacrylamide) propyltrimethylammonium chloride was added to effect graft copolymerization.
Adding 50-100mL of 0.1mol/L sodium hydroxide into the mixed solution obtained in the step for neutralization, and then adding 50-200 mL of absolute ethanol solution to obtain a precipitate. Finally, repeated washing with absolute ethyl alcohol and deionized water for 3 times, and vacuum drying to obtain the target product, abbreviated as CTS/beta-CD.
(II) detection
FIG. 2 is an infrared spectrum of Chitosan (CTS) and CTS/β -CD alone. Wherein, 1574cm-1Is the in-plane bending vibration peak of N-H in primary amine, 3465cm-1is-NH of chitosan2Absorption Peak, 2960cm-11310cm is the stretching vibration peak of C-H-1The absorption peak of alcoholic hydroxyl group is shown. As can be seen from the infrared spectrogram of CTS/beta-CD, 3200-3500 cm-1Has stronger absorption vibration peak, which is caused by the absorption peak change caused by the increase of O-H groups introduced into beta-cyclodextrin. At the same time, 1300--1The peak of vibration of (2) is weakened due to an absorption peak caused by stretching vibration of-COOH. For the infrared spectrum of CTS/beta-CD at 1750 and 1650cm-1And the peaks in the vicinity are relatively weakened, the strong change of the peaks can be attributed to the stretching vibration peak of a small amount of acetyl in the chitosan, and the beta-cyclodextrin is added and reacts with the functional group of the chitosan. In addition, the infrared spectrogram of CTS/beta-CD has more-C ═ O, N+-(CH3)3and-CH3,-CH2The vibration peak of the flocculant is the characteristic peak of the introduced cationic group, and the deformation vibration peak of the quaternary ammonium group and the methylene group shows that the cationic functionalized CTS/beta-CD composite flocculant is successfully prepared. As can be seen from the infrared image, the chitosan/beta-cyclodextrin composite flocculant (CTS/beta-CD) is successfully prepared.
FIG. 3 is an XRD pattern of Chitosan (CTS) and CTS/β -CD alone. Wherein, the chitosan has stronger characteristic absorption peaks at about 10 ℃ and 20 ℃, which indicates that the chitosan has higher crystallinity because of the existence of a large amount of amino (-NH) in the chitosan molecule3) And hydroxyl (-OH) to form strong intramolecular and intermolecular hydrogen bonds, so that the chitosan molecular structure has certain regularity and a crystalline region exists. From the XRD pattern of CTS/beta-CD, it can be seen that the intensity of the diffraction absorption peak at 2 theta equal to around 20 ℃ is reduced, which indicates that a reaction between chitosan and beta-cyclodextrin occurs and the molecular structure exhibits a high degree of asymmetry, resulting in a reduction in the crystallinity of the CTS/beta-CD polymer.
Example 2 recovery efficiency of cationic functionalized CTS/beta-CD composite flocculant on Chlorella vulgaris at different dosages
The method comprises the following steps: adding CTS/beta-CD composite flocculating agents (30,45,60,90,120,150 and 210mg/L) with different concentrations into 100mL of chlorella algae liquid, wherein the concentration of chlorella is 0.978g/L, quickly stirring at 200rpm for 2min and then at 50rpm for 10min in a magnetic stirrer, and uniformly mixing the flocculating agents and the algae liquid for 30 min. In order to better study the harvesting efficiency of the CTS/beta-CD composite flocculant on chlorella, the harvesting efficiency of the CTS/beta-CD composite flocculant on chlorella is calculated according to the following formula 1, and the results are shown in FIG. 4.
The dosage of the flocculant plays a crucial role in evaluating the sustainable application and economic development of the microalgae flocculant. As can be seen from FIG. 3, the CTS/beta-CD complex flocculant exhibited a tendency of increasing and then slightly decreasing efficiency to Chlorella as the dosage was increased. Experiments show that when the concentration of the flocculant is 60mg/L, the harvesting efficiency of the chlorella can reach 99.56%, the content of the composite flocculant is continuously increased, and the harvesting efficiency of the chlorella is reduced to 74.41%. This is because excess flocculant can cause destabilization of flocs formed and thus reduced recovery efficiency. The addition amount of the flocculant is mainly influenced by the properties of microalgae cells, biomass concentration and the harvesting operation conditions.
Example 3 recovery efficiency of cationic functionalized CTS/beta-CD composite flocculant on Chlorella vulgaris at different acidity
The method comprises the following steps: the pH of the algal solution was adjusted to 2, 4, 6, 8 and 10 by 0.1mol/L HCl and NaOH solutions, respectively. And then adding 60mg/L cation functionalized CTS/beta-CD composite flocculant, quickly stirring for 2min at 200rpm in a magnetic stirrer, then stirring for 10min at 50rpm, and uniformly mixing the flocculant and the algae liquid, wherein the separation time is 30 min. After 30min, the OD was determined680nmThe recovery efficiency was determined according to equation 1. The recovery efficiency of the cation functionalized CTS/beta-CD composite flocculant on chlorella vulgaris under different acidity is shown in figure 5.
The pH value is an important factor influencing the protonation balance and microalgae properties of the chitosan-based flocculant in an aqueous solution. As can be seen from fig. 5, the harvesting efficiency of the composite flocculant on chlorella is 36.44%, 74.49%, 98.80%, 98.43% and 89.66% at pH 2, 4, 6, 8 and 10, respectively. Therefore, the chlorella is harvested with the highest efficiency when the pH is 6-8, because the cationic functionalized CTS/beta-CD composite flocculant is positively charged on the surface and is tightly connected with the microalgae cells with negative charges under the pH condition. In addition, the long molecular chain structure of the chitosan can play a role of bridging, microalgae cells are wound together, so that larger flocs are formed, and the microalgae cells are precipitated. Due to-NH in an acidic environment2and-NH3+Repulsive force exists among groups, and the CTS/beta-CD flocculant exists in a linear chain form and shows the characteristic of maintaining dispersion, so that electrostatic repulsion exists between the composite flocculant and microalgae cells, and the flocculation efficiency is reduced. And at pH 10, the CTS/beta-CD surface is negatively charged with-OH and-NH under alkaline conditions2The groups (a) are weakened, and under alkaline conditions, a part of negative ions in beta-cyclodextrin molecules are ionized. Under the action of coulomb force, when the distance between two atoms is close to a certain degree, electrostatic repulsion effect can occur, thereby influencing the harvesting effect of chlorella. It is worth mentioning that the chlorella is generally neutral, so that when the cation functionalized CTS/beta-CD composite flocculant is applied, higher harvesting efficiency can be obtained without additionally adjusting the pH of chlorella solution.
Example 4 efficiency of harvesting Chlorella vulgaris at different resting time with cationic functionalized CTS/beta-CD composite flocculant
The method comprises the following steps: adding 60mg/L of composite flocculant into 50mL of algae liquid, quickly stirring at 200rpm for 2min in a magnetic stirrer, then stirring at 50rpm for 10min, uniformly mixing the flocculant and the algae liquid, measuring absorbance at 2min, 4min,6min,8min,10min,20min and 30min respectively, and calculating flocculation efficiency according to formula 1. the result is shown in FIG. 6.
As can be seen from FIG. 6, when the pH value is 6, the recovery efficiency of the composite flocculant reaches 90.80% in 2min, gradually becomes stable along with the increase of time, and reaches 98.80% in 30 min. The chitosan recovery and separation time alone is reported in the literature to be 60 min. Under the condition of lower standing time, the harvesting efficiency is lower. The cation functionalized CTS/beta-CD composite flocculant can form stronger connection with the surface of microalgae cells, so that the connection of flocculants is tighter. Thus, the time required for flocculation is reduced. At 2min, the harvesting efficiency has reached 90.80%. For the recovery of the cationic functionalized CTS/beta-CD composite flocculant on microalgae, the particle size of flocs is increased, and the flocculation sedimentation rate is improved, so that the sedimentation time is shortened, and the time cost required for recovering the microalgae is reduced to a certain extent.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method for preparing a cationically functionalized β -cyclodextrin/chitosan composite, the method comprising: adding an initiator into beta-cyclodextrin and chitosan to generate free radicals, and introducing 3- (methacrylamide) propyl trimethyl ammonium chloride to generate graft copolymerization reaction to obtain the cationic functionalized beta-cyclodextrin/chitosan composite material.
2. The method for preparing the cation functionalized beta-cyclodextrin/chitosan composite material according to claim 1, wherein the method comprises the following steps:
dissolving beta-cyclodextrin powder in deionized water to obtain a beta-cyclodextrin aqueous solution;
dissolving chitosan powder in an acetic acid solution to obtain a chitosan acetic acid solution;
uniformly mixing the beta-cyclodextrin aqueous solution and the chitosan acetic acid solution, adding an initiator to perform a free radical generation reaction, and then adding 3- (methacrylamide) propyl trimethyl ammonium chloride to perform a graft copolymerization reaction to obtain a reaction mixture;
and adding the reaction mixture into a sodium hydroxide solution for neutralization reaction, then adding an absolute ethanol solution to obtain a precipitate, and washing and drying to obtain the cation functionalized beta-cyclodextrin/chitosan composite material.
3. The method for preparing the cation functionalized beta-cyclodextrin/chitosan composite material according to claim 2, wherein the mass ratio of the beta-cyclodextrin powder to the chitosan powder is (0.9-1.1): (0.9-1.1).
4. The method for preparing the cation functionalized beta-cyclodextrin/chitosan composite material according to claim 2, wherein the volume fraction of the acetic acid solution is 0.8-1.2%.
5. The method for preparing the cation functionalized beta-cyclodextrin/chitosan composite material according to claim 2, wherein the initiator is cerium ammonium nitrate.
6. The method for preparing the cation functionalized beta-cyclodextrin/chitosan composite material as claimed in claim 2, wherein the temperature of the free radical generating reaction is 75-80 ℃, and the time of the free radical generating reaction is 10-60 min; the temperature of the graft copolymerization reaction is 75-80 ℃, and the time of the graft copolymerization reaction is 30-120 min.
7. The method for preparing the cation functionalized beta-cyclodextrin/chitosan composite material as claimed in claim 2, wherein the concentration of the sodium hydroxide solution is 0.05-0.2 mol/L; the ethanol solution is an absolute ethanol solution.
8. A cationically functionalized β -cyclodextrin/chitosan composite material prepared according to the method of any one of claims 1 to 7.
9. Use of the cationically functionalized β -cyclodextrin/chitosan composite material of claim 8 in harvesting microalgae.
10. The use of claim 9, wherein the method for recovering microalgae using the cationically functionalized β -cyclodextrin/chitosan composite comprises:
respectively adjusting the pH value of the algae liquid to 6-8, then adding 45-150mg/L of cation functionalized CTS/beta-CD composite flocculant, and uniformly mixing the flocculant and the algae liquid by magnetic stirring and rapid stirring and then slow stirring.
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