CN112619613A - Powdery vanillin modified chitosan schiff base decolorant and preparation method thereof - Google Patents
Powdery vanillin modified chitosan schiff base decolorant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a powdery vanillin-modified chitosan schiff base decolorant, belonging to the field of chemical industry. The preparation method of the powdery vanillin-modified chitosan Schiff base decolorant adopts nontoxic chitosan and vanillin as raw materials, takes nucleophilic addition reaction between amino in chitosan and aldehyde in vanillin under the catalysis of glacial acetic acid, and directly prepares a powdery decolorant product by a one-step method. According to the method, the addition ratio of the chitosan and the vanillin is limited, so that the obtained powdery vanillin modified chitosan Schiff base decolorant is high in purity and excellent in adsorption performance, and is high in adsorption rate and large in adsorption capacity when used for methyl orange adsorption. The invention also discloses the powdery vanillin-modified chitosan schiff base decolorant prepared by the preparation method of the powdery vanillin-modified chitosan schiff base decolorant and application of the powdery vanillin-modified chitosan schiff base decolorant in methyl orange adsorption.
Description
Technical Field
The invention relates to the field of chemical industry, and in particular relates to a powdery vanillin-modified chitosan schiff base decolorant and a preparation method thereof.
Background
The problem of serious industrial wastewater pollution is caused by insufficient monitoring strength of industrial wastewater discharge in China at present. In the printing and dyeing industry, the proportion of the azo dye wastewater is more than 50%, and the azo dye wastewater has carcinogenic effect on human and animals, wherein methyl orange is the most common azo dye. Adsorption is one of the main methods for treating azo dye wastewater, and decolorants which can be used for adsorbing methyl orange are reported to be modified bentonite, metal oxide nanoparticles, a cross-linked chitosan/cyclodextrin compound and the like. However, the preparation of these adsorbents is relatively complicated. For example, metal oxide nanoparticles require fine control of reaction conditions and use a wide variety of types of solvents. Thus, in contrast, if a decolorizer with a simple preparation process were available, it would have a greater market potential.
Chitosan, a naturally occurring linear polysaccharide, is prepared from chitosan deacetylation, which may be extracted from biological materials such as shells, shrimp shells, crab shells, and the like. The chitosan has important physiological characteristics of biocompatibility, biodegradability, non-sensitization and the like. Chitosan Schiff bases have been reported in a few as depigmenting agents, and have also been shown to have the ability to adsorb dyes. However, if the decolorant product is obtained by preparing the chitosan schiff base hydrogel and drying the chitosan schiff base hydrogel in vacuum, the powdery decolorant cannot be directly obtained; if the solid chitosan Schiff base decolorant is directly prepared, solvents harmful to human health, such as Tetrahydrofuran (THF), acetone and the like, are involved in the preparation process.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide the preparation method of the powdery vanillin-modified chitosan schiff base decolorant, the preparation process of the method has no harmful solvent, the powdery decolorant product can be directly prepared, and the operation steps are simple.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a powdery vanillin-modified chitosan Schiff base decolorant comprises the following steps:
(1) sequentially adding chitosan and vanillin into ethanol to obtain a mixture A; the molar ratio of amino groups on the chitosan to the vanillin is 1: 1-1.5;
(2) adding glacial acetic acid into the mixture A obtained in the step (1), heating and continuously stirring, standing and cooling to room temperature after complete reaction, and removing supernatant to obtain a mixture B;
(3) adding ethanol into the mixture B obtained in the step (2), uniformly mixing, standing, and removing a supernatant;
(4) and (4) repeating the step (3) for 3 times, filtering the obtained mixture, washing the filtered mixture with ethanol, and drying to obtain the powdery vanillin-modified chitosan schiff base decolorant.
The preparation method of the powdery vanillin-modified chitosan Schiff base decolorant adopts nontoxic chitosan and vanillin as raw materials, takes nucleophilic addition reaction between amino in chitosan and aldehyde in vanillin under the catalysis of glacial acetic acid, and directly prepares a powdery decolorant product by a one-step method. According to the method, the addition ratio of the chitosan and the vanillin is limited, so that the obtained powdery vanillin modified chitosan Schiff base decolorant is high in purity and excellent in adsorption performance, and is high in adsorption rate and large in adsorption capacity when used for methyl orange adsorption.
Preferably, the molar amount of the amino groups on the chitosan is calculated by the formula: n (-NH)2) 1/161.2 × DD × m. Wherein 161.2 is the monomer relative mass of chitosan; the DD is the deacetylation degree of chitosan; and m is the mass of the chitosan. The method can be used for measuring the molar weight of the amino groups of the chitosan more accurately.
Preferably, the molar ratio of the amino groups on the chitosan to the vanillin is 1: 1.5. The molar ratio of amino groups on the chitosan to vanillin is 1:1.5, the prepared powdery vanillin modified chitosan schiff base decolorant has high methyl orange adsorption efficiency and proper adsorption cost.
Preferably, the ratio of the volume of the glacial acetic acid to the mass of the chitosan in the step (2) is as follows: volume of glacial acetic acid: the mass of the chitosan is 1-3 mL:1 g. The grafting of vanillin on chitosan can be effectively promoted by adding glacial acetic acid with specific content, and the methyl orange adsorption amount of the finally prepared product when the decolorant with different dosages is used can be effectively regulated and controlled by controlling the using amount of the catalyst. More preferably, the ratio of the volume of glacial acetic acid to the mass of chitosan in step (2) is: volume of glacial acetic acid: the mass of chitosan is 1mL to 1 g.
Preferably, the heating temperature in the step (2) is 50-70 ℃, and the stirring time is 5-7 h. The vanillin can be efficiently grafted with the chitosan under the reaction condition.
The invention also aims to provide the powdery vanillin-modified chitosan schiff base decolorant prepared by the preparation method of the powdery vanillin-modified chitosan schiff base decolorant. The product is nontoxic and harmless, has high grafting rate of vanillin, can be effectively used for adsorbing methyl orange dye, and has high adsorption efficiency.
The invention also aims to provide application of the powdery vanillin modified chitosan schiff base decolorant to azo dye adsorption. Preferably, the azo dye includes methyl orange and methyl red.
The invention has the beneficial effects that the invention provides a preparation method of a powdery vanillin-modified chitosan Schiff base decolorant, which adopts nontoxic chitosan and vanillin as raw materials, and adopts glacial acetic acid to catalyze amino in chitosan and aldehyde group in vanillin to carry out nucleophilic addition reaction, so that a powdery decolorant product is directly prepared by a one-step method. According to the method, the addition ratio of the chitosan and the vanillin is limited, so that the obtained powdery vanillin modified chitosan Schiff base decolorant is high in purity and excellent in adsorption performance, and is high in adsorption rate and large in adsorption capacity when used for methyl orange adsorption. The invention also provides the powdery vanillin-modified chitosan schiff base decolorant prepared by the preparation method of the powdery vanillin-modified chitosan schiff base decolorant and application of the powdery vanillin-modified chitosan schiff base decolorant in methyl orange adsorption.
Drawings
FIG. 1 is a graph of the results of infrared spectroscopy (FTIR) tests on powdered vanillin-modified chitosan Schiff base decolorant of the present invention;
FIG. 2 shows the nuclear magnetic resonance of the powdered vanillin-modified chitosan schiff base decolorant of the invention (1HNMR) test result graph; wherein the left picture is a test picture of powdery vanillin modified chitosan schiff base decolorant; the right figure is a test chart of the chitosan control sample;
FIG. 3 is a graph of the results of a Thermogravimetric (TGA) test of a powdered vanillin-modified chitosan Schiff base decolorizer of the present invention; wherein the left panel is a TGA test analysis of the sample; the right panel is a DTG test analysis chart of the sample;
FIG. 4 is a test chart of the methyl orange adsorption effect of the product in the embodiment of the present invention, which is obtained by examining the molar ratio of the amino group on chitosan to vanillin;
fig. 5 is a test chart of the absorption effect of methyl orange of the product according to the amount of glacial acetic acid added in the preparation process of the product in the embodiment of the invention.
Detailed Description
For better illustrating the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples, which are intended to be understood in detail, but not intended to limit the present invention.
The reagents and raw materials used in the examples of the present invention and comparative examples were purchased from the market, unless otherwise specified.
The used reagents and raw materials comprise:
and (3) chitosan: biological purity, degree of deacetylation 90%, provided by Shanghai-source leaf Biotechnology Co., Ltd. (Shanghai, China);
vanillin: analytical grade purity, provided by Shanghai Michelin Biochemical technology, Inc. (Shanghai, China);
glacial acetic acid: 99.5% (w/w) analytical grade purity, provided by Tianjin Yongda chemical reagents, Inc. (Tianjin, China);
ethanol, potassium bromide: analytical grade purity, provided by Tianjin Dalochi chemical reagents, Inc. (Tianjin, China);
methyl orange: analytical grade purity, provided by Tianjin Tianxin Fine chemical development center (Tianjin, China).
Example 1
The embodiment of the preparation method of the powdery vanillin modified chitosan schiff base decolorant comprises the following steps:
(1) sequentially adding 1g of chitosan into 50mL of ethanol, and after 30min, adding 1.276g of vanillin to obtain a mixture A; the molar ratio of the amino groups on the chitosan to the vanillin is 1: 1.5;
(2) adding 3mL of glacial acetic acid into the mixture A obtained in the step (1), heating to 60 ℃ in an oil bath, continuously stirring, standing and cooling to room temperature after complete reaction, and removing supernatant to obtain a mixture B;
(3) adding 30mL of ethanol into the mixture B obtained in the step (2), uniformly mixing, standing, and removing a supernatant;
(4) and (4) repeating the step (3) for 3 times, filtering the obtained mixture, washing the filtered mixture with ethanol for 5 times to obtain yellow filter residue, and drying the yellow filter residue in vacuum at the temperature of 60 ℃ for 24 hours to obtain the powdery vanillin-modified chitosan Schiff base decolorant.
Example 2
This example differs from example 1 only in that the molar ratio of amino groups on the chitosan to the vanillin was 1:1(0.851g of vanillin).
Example 3
The difference between this example and example 1 is only that the amount of glacial acetic acid added is 1 mL.
Example 4
The difference between this example and example 1 is only that the amount of glacial acetic acid added is 2 mL.
Comparative example 1
The comparative example differs from example 1 only in that the molar ratio of amino groups on the chitosan to the vanillin was 1:0.5(0.425g of vanillin).
Comparative example 2
The comparative example differs from example 1 only in that the amount of glacial acetic acid added was 5 mL.
To verify the powdery vanillin modified chitosan Schiff base of the inventionThe decolorizer was successfully prepared by subjecting the product of example 1 to characterization tests including infrared spectroscopy (FTIR) test, nuclear magnetic resonance (R) ((R))1HNMR) test and Thermogravimetric (TGA) test with chitosan as a control sample. Wherein, the FTIR test is carried out on a KBr mixed sample which is tabletted at 450-4000 cm–1Measurements were made within the range. The infrared tester is model number Spectrum 100, Perkin Elmer Inc., USA; the above-mentioned1HNMR was tested using 1% HCl/D2Solvent O, wherein the HCl concentration is 36%, tested on a nuclear magnetic resonance spectrometer operating at 400MHz, the model of which is Ascend 400, Bruker, Switzerland; the TGA test measures the thermal stability of a sample under a nitrogen atmosphere at a flow rate of 50mL/min at 40 ℃ to 600 ℃ at a rate of 10 ℃/min. The thermogravimetric analyzer was a model TGA2, Mettler Toledo, switzerland (Mettler Toledo, switzerland)).
The test results are shown in FIG. 1, and the infrared test curves of chitosan as the control sample include hydroxyl (-OH) and amino (-NH)2) The characteristic peak of the superimposed tensile vibration was 3368cm-1The carbon-hydrogen bond (-CH) appears at 2878cm-1Here, the stretching vibration of the amide group and the bending vibration of the amino group were 1657cm-1And 1596cm-1Has characteristic peaks. The product of example 1 is at 3400cm-1The characteristic peak of the stretching vibration of the hydroxyl group and the amino group overlapping appears, and 1643cm-1The compound has a characteristic peak of Schiff base imine structure (C ═ N). As can be seen from the figure, the amino group on the product of example 1 is 1657cm higher than that on chitosan-1The characteristic peak is red-shifted, which indicates that the raw material vanillin is successfully grafted with the chitosan, and the powdery vanillin modified chitosan Schiff base decolorant is successfully prepared.
The nuclear magnetic resonance test dissolves a sample to be tested in 1% HCl/D2In O, test solvent D2The chemical shift of O was 4.790ppm, which was used as a calibration peak. The test results are shown in FIG. 2, the chemical shift of the control sample chitosan H1 is 4.58ppm, the chemical shift of H2 is 3.08ppm, the chemical shifts of H3-H6 are 3.59-3.94 ppm, and the chemical shift of H7 is 2.05 ppm. Practice ofThe product of example 1 is clearly different from the above sample. First, methyl (-CH) at 3.94ppm3) The peak is stronger than chitosan due to the methoxy (-OCH) group on vanillin3) H12 enhances the methyl peak, and in addition, a peak is obvious at 7.07-7.55 ppm, the peak in the range is a characteristic peak of H9-H11 on the benzene ring of vanillin, and a peak at 9.72ppm is a characteristic peak of H8 in (HC ═ N), and the peak appears after 7ppm, so that the vanillin is grafted on the chitosan, and the powdery vanillin-modified chitosan Schiff base decolorant is successfully prepared. The spectrogram does not have other impurity characteristic peaks, which indicates that the powdery vanillin modified chitosan schiff base decolorant prepared by the invention has high purity.
The thermogravimetric analysis test results are shown in fig. 3. Both chitosan of a control sample and the product obtained in example 1 have weight loss peaks at about 48-126 ℃, which are caused by the weight loss of the bound water in the chitosan and the powdery vanillin modified chitosan schiff base decolorant, and the weight loss rates are 8.51% and 6.28% respectively; meanwhile, the two substances also have weight loss peaks at about 225-404 ℃, which are weight loss peaks of the chitosan polysaccharide long chain segment, wherein the maximum weight loss peak of the chitosan of the control sample is at 301 ℃, and the product of the example 1 has a weight loss peak of 299 ℃, which is caused by that most of amino groups on the chitosan are replaced by vanillin, and the thermal stability of the polysaccharide chain segment is reduced due to the reduction of free amino groups; in addition, the product of example 1 shows an additional weight loss peak at approximately 174 ℃ compared to chitosan, which is caused by the weight loss of vanillin grafted onto chitosan. Thermogravimetric analysis proves that vanillin is successfully grafted on the chitosan, and the powdery vanillin-modified chitosan Schiff base decolorant is successfully prepared.
In order to verify the service performance of the vanillin-modified chitosan schiff base decolorant, the products obtained in examples 1-4 and comparative examples 1-2 are subjected to a methyl orange adsorption test, and the test method comprises the following steps: 10, 20, 40, 80 and 160mg of each example/comparative example product and 10 parts of chitosan are weighed, placed in 20mL of 10mg/mL methyl orange solution respectively, stirred for 10 minutes, filtered, and the filtrate is taken and the absorbance of the filtrate is measured by an ultraviolet spectrophotometer at the wavelength of 463 nm.
First, chitosan control samples, examples 1-2 and comparative example 1 were tested to examine the effect of vanillin addition on the adsorption performance of the product. The concentration of the methyl orange solution before and after adsorption is measured by an ultraviolet spectrophotometer, and the standard curve is that A is 0.0668c-0.0042, R20.9991. Methyl orange adsorption results test as shown in fig. 4, the adsorption capacity of the chitosan control sample and the product obtained by the implementation/comparison example to methyl orange increases with the amount of the used chitosan control sample, but obviously, the rate of increase of the product obtained by the implementation/comparison example is much greater than that of the chitosan control sample. The results of the specific data of the test are shown in Table 1, when the amount of chitosan is 160mg, the removal rate of methyl orange at 10mg/mL is 34.82%, while examples 1 and 2 reach 46.98% and 44.93%, and the adsorption capacity is much higher than that of chitosan. The adsorption rate of the chitosan is increased along with the increase of the molar ratio of the amino group on the chitosan to the vanillin, and when the product is used in an amount of 160mg, the adsorption rates of the products obtained in the comparative example 1, the example 2 and the example 1 to methyl orange are 87.30%, 93.34% and 96.07% respectively.
TABLE 1
Next, examples 1, 3 to 4 and comparative example 2 were tested to examine the influence of the amount of glacial acetic acid catalyst added on the adsorption performance of the product. The test results are shown in fig. 5. As can be seen from the figure, the methyl orange adsorption rate of the product is obviously different under different use amounts. The adsorption efficiency of the products of examples 4 and 5 was higher when the amount used was less than 80mg, while the adsorption efficiency of the product of example 1 was slightly higher when the amount used was 160 mg. In consideration of the raw material cost, the dosage range and the methyl orange adsorption effect of the product, the use effect of the product prepared when the addition amount of the glacial acetic acid is 1mL is the best.
In addition, the product of example 3 was used in the methyl red adsorption test at a usage amount of 80mg, and the removal rate of the product to 10mg/mL methyl red is 94.35% as described above, which proves that the product of the invention also has the adsorption effect to similar methyl red dyes.
TABLE 2
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A preparation method of a powdery vanillin-modified chitosan Schiff base decolorant is characterized by comprising the following steps:
(1) sequentially adding chitosan and vanillin into ethanol to obtain a mixture A; the molar ratio of amino groups on the chitosan to the vanillin is 1: 1-1.5;
(2) adding glacial acetic acid into the mixture A obtained in the step (1), heating and continuously stirring, standing and cooling to room temperature after complete reaction, and removing supernatant to obtain a mixture B;
(3) adding ethanol into the mixture B obtained in the step (2), uniformly mixing, standing, and removing a supernatant;
(4) and (4) repeating the step (3) for 3 times, filtering the obtained mixture, washing the filtered mixture with ethanol, and drying to obtain the powdery vanillin-modified chitosan schiff base decolorant.
2. The method of preparing a powdered vanillin-modified chitosan schiff base decolorant of claim 1, wherein the molar ratio of amino groups on the chitosan to the vanillin is 1: 1.5.
3. The method of preparing a powdered vanillin-modified chitosan schiff base decolorant of claim 1, wherein the ratio of the volume of glacial acetic acid to the mass of chitosan in step (2) is: volume of glacial acetic acid: the mass of the chitosan is 1-3 mL:1 g.
4. The method of preparing a powdered vanillin-modified chitosan schiff base decolorant of claim 3, wherein the ratio of the volume of glacial acetic acid to the mass of chitosan in step (2) is: volume of glacial acetic acid: the mass of chitosan is 1mL to 1 g.
5. The method for preparing the powdery vanillin-modified chitosan schiff base decolorant of claim 1, wherein the heating temperature in the step (2) is 50-70 ℃.
6. The method for preparing the powdery vanillin-modified chitosan schiff base decolorant of claim 1, wherein the stirring time in the step (2) is 5-7 hours.
7. The powdery vanillin-modified chitosan schiff base decolorant prepared by the method for preparing the powdery vanillin-modified chitosan schiff base decolorant according to any one of claims 1 to 6.
8. Use of a powdery vanillin-modified chitosan schiff base decolorant of claim 7 for azo dye adsorption.
9. Use of a powdered vanillin-modified chitosan schiff base decolorant of claim 8, wherein the azo dyes comprise methyl orange and methyl red for azo fuel adsorption.
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