CN110639477A - Preparation method of porous starch-metal organic framework composite material - Google Patents
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Abstract
The invention discloses a preparation method of a porous starch-metal organic framework composite material. Dispersing starch in a citric acid buffer solution, and adding a complex enzyme to prepare porous starch; synthesizing a metal organic framework material; performing ultrasonic reaction on chitosan and a metal organic framework material under the condition of pH 4.5-5.5; and dripping the obtained suspension into a porous starch suspension with the concentration of 5-8 wt%, drying and crushing to obtain the porous starch-metal organic framework composite material. The MOF loading rate of the invention can reach 10.76%, the adsorption capacity of the composite material in adsorbing sulfanilamide in a water body is tested, the adsorption capacity in a 40mg/L solution with a lower sulfanilamide concentration is 46.46mg/g, and the adsorption capacity is 31.11mg/g after the composite material is repeatedly used for four times. The method for adsorbing the medicinal chemical substances in the water body has the characteristics of simple process and low cost, and realizes the immobilization and the reutilization of the nano MOF material.
Description
Technical Field
The invention relates to a metal organic framework material, in particular to a porous starch-metal organic framework composite material for adsorbing sulfanilamide and a preparation method thereof; belongs to the field of pharmaceutical wastewater treatment, and is used for removing pharmaceutical chemicals in an environmental water body.
Background
In the pharmaceutical industry, natural or artificially synthesized pharmaceutical chemicals and their secondary products are inevitably migrated from industrial sewage and domestic water to environmental water, and some chemicals with allergenicity, teratogenicity and even mutagenicity are not sufficient, thus greatly threatening the safety of domestic water, agricultural products and aquatic products. It is understood that over 200 different medicinal chemicals have been detected in rivers, lakes and oceans. The broad-spectrum antibiotic sulfanilamide has strong allergenicity and certain psychotoxicity, and related industrial wastewater of the broad-spectrum antibiotic sulfanilamide potentially threatens human health. The development of a novel efficient, convenient and environment-friendly drug wastewater treatment technology is urgent.
The commonly used treatment means of the pharmaceutical wastewater mainly comprise adsorption, flocculation, membrane filtration, photocatalysis, electrochemical oxidation and the like. Among the methods, the adsorption separation method is one of the methods with the most application prospect, and compared with the flocculation sedimentation method, the adsorption method does not need to add a flocculating agent, so that secondary chemical pollution is avoided; compared with the catalytic and electrochemical oxidation methods, the adsorption method does not produce harmful secondary products in the process of environmental treatment. In addition, the adsorption separation also has the advantages of high efficiency, convenience, easy operation, low cost, low energy consumption and the like.
The prior commonly used adsorbents comprise macroporous resin, porous starch, biochar, argil, montmorillonite, diatomite and the like. The adsorbents have the advantages of low cost, convenient operation and the like, and alleviate the problem of environmental pollution to a certain extent. However, most of the existing adsorbents are disposable materials, the low adsorption capacity results in large use amount, and the adsorbents are difficult to recycle, so that the adsorbents do not accord with the green chemical principle, and can cause secondary pollution to the environment. The reported modified fly ash has the characteristics of low cost and waste treatment by waste, but the sulfonamide adsorption amount is lower and is only 4.1mg/g (Lingqi, Sunxiang, Wuchang, Huanghuai, Lixiong).
Metal-Organic Framework (MOF) materials, which have a high specific surface area, flexible and adjustable radical sites, controllable pore size, excellent mechanical strength and stability, have emerged in the nineties of the 20 th century, and are currently one of the most promising recyclable adsorbent materials. However, the MOF material is a powdery crystal, and the size of the MOF material is mostly in the nanometer level, which greatly limits the application of the MOF material. The key point of the method is to design an environment-friendly composite material which has high chemical accessibility, relatively stable physicochemical properties and can immobilize the MOF for realizing the efficient sustainable utilization of the MOF adsorption material.
Disclosure of Invention
The invention aims to provide an environment-friendly porous starch-metal organic framework composite material for adsorbing sulfanilamide, which has the advantages of low cost, strong adsorption performance and reusability, and a preparation method thereof.
The MOF material is immobilized through a porous starch frame and chitosan nodes by utilizing a pore diameter adjusting technology, and sulfanilamide adsorption is realized; firstly, the granular porous starch with a macroporous structure (>50nm) is prepared by an enzymatic hydrolysis method, so that the specific surface area of the starch granules is greatly increased, more hydroxyl action sites are exposed, and a structure which is easy to generate strong hydrogen bond action with carbohydrate is generated. Chitosan is used as an adhesive, amino is used as a node, and the carboxylated MOF nano material UiO-66-COOH is adhered to the inner surface and the outer surface of the porous starch by utilizing the electrostatic effect, so that the MOF material is immobilized. The UiO-66-COOH has extremely high specific surface area and micro-mesoporous structure and extremely high affinity to benzene ring-containing chemical substances, so that the composite material can realize the adsorption of drug chemical substances such as sulfanilamide and the like. The invention uses the porous starch-metal organic framework composite material to adsorb medicinal chemical substances in water, has the characteristics of simple process and lower cost, and particularly realizes the immobilization and the reutilization of the nano MOF material. The invention provides a new choice for the technology of treating the environment harmful substances, and is an improvement and development of the existing sewage treatment technology.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a porous starch-metal organic framework composite material comprises the following steps and process conditions:
1) preparing porous starch: dispersing starch in a citric acid buffer solution, adding a complex enzyme, reacting for 3-6 h at 45-55 ℃, inactivating enzyme, drying, and sieving to obtain porous starch; the complex enzyme is alpha-amylase and glucoamylase complex enzyme;
2) synthesis of metal organic framework material: dispersing zirconium chloride and phthalic acid in deionized water, and treating for 18-30 h at 90-120 ℃ by using a reflux method; redispersing the washed material in deionized water, and carrying out secondary reflux for 10-20 h; centrifuging, freeze-drying and crushing to obtain a metal organic framework material UiO-66-COOH; the mass ratio of the zirconium chloride to the phthalic acid is 2.4-7.2: 2.2-6.6; the mass volume ratio of the phthalic acid to the deionized water is 2.2-6.6: 50-150; wherein the mass unit is g, and the volume unit is mL;
3) and (3) porous starch-metal organic framework composite material immobilization: performing ultrasonic reaction on chitosan and a metal organic framework material under the condition of pH 4.5-5.5; dripping the obtained suspension into a porous starch suspension with the concentration of 5-8 wt%, stirring, carrying out suction filtration, and filtering to remove non-immobilized metal organic framework particles; drying and crushing to obtain the porous starch-metal organic framework composite material.
To further achieve the object of the present invention, preferably, in step 1), the starch is one or more of corn starch, tapioca starch and potato starch; the pH value of the citric acid buffer solution is 5.0-5.5, the mesh number of the screen is 80-100 meshes, and the mass-volume ratio of the starch to the citric acid buffer solution is 5-15: 20-100, wherein the mass unit is g, and the volume unit is mL.
Preferably, the volume ratio of the alpha-amylase to the glucoamylase is 1: 2-1: 5, and the addition amount of the complex enzyme is 0.01-0.03 mL per gram of starch.
Preferably, the chitosan is low-viscosity chitosan with the concentration of 50-100 KDa.
Preferably, in the step 3), the chitosan is heated and dissolved by using 0.01-0.05 mol/L hydrochloric acid solution, and then the pH value is adjusted to 4.5-5.5 by using distilled water; the time of the ultrasonic reaction is 5-15 min; the frequency of the ultrasonic wave is 30-50 KHZ.
Preferably, the time of the secondary reflux is 10-20 h.
Preferably, the suspension is dripped into the porous starch suspension with the concentration of 5-8 wt% by a constant flow pump, and the flow rate of the constant flow pump is 40-60 rpm;
preferably, the stirring speed in the step 3) is 300-600 rpm; the drying is carried out in an oven at the temperature of 30-40 ℃ for 9-12 h.
The filtration in step 3) is carried out through a 0.45 μm filter membrane.
Preferably, the mass ratio of the chitosan to the metal organic framework material in the step 3) is 1: 1-3: 1
Compared with the prior art, the invention has the advantages that:
1) the method realizes the immobilization of the nano MOF material, constructs the reusable MOF composite adsorbing material, and compared with porous starch, argil, diatomite and the like, the method realizes the reutilization of the adsorbing material and embodies the environmental management concept of sustainable development.
2) The invention has stronger sulfanilamide adsorption capacity, can realize the equilibrium adsorption rate of 46.46mg/g in sulfanilamide solution with lower concentration (40mg/L), has faster adsorption rate, and can reach the adsorption equilibrium within 5 h.
3) The adsorbing material of the method uses an environment-friendly synthesis means, and the required equipment and preparation process are simple and convenient and have low cost.
Drawings
FIG. 1 is an X-ray diffraction pattern of the porous starch-metal organic framework composite of example 1.
FIG. 2 is a scanning electron microscope and an energy spectrometer imaging chart of the porous starch-metal organic framework composite material of example 1.
FIG. 3 is a nitrogen adsorption and desorption curve of the porous starch-metal organic framework composite material of example 1.
FIG. 4 shows the sulfonamide adsorptive capacity test of the porous starch-metal organic framework composite of example 1.
Fig. 5 is a repeat sulfonamide adsorption test of the porous starch-metal organic framework composite of example 1.
Detailed Description
The invention will be further described with reference to the following examples for better understanding, but the scope of the invention as claimed is not limited to the examples.
In the examples, the adsorption method of sulfanilamide: 20mg of porous starch-metal organic framework composite was placed in a 0.45 μm filter cloth bag and immersed in 40mg/L of sulfanilamide solution. Taking 2mL of sulfanilamide solution in different adsorption reaction time, measuring the absorbance of sulfanilamide at the absorption wavelength lambda-243 by using a spectrophotometer, and comparing with a sulfanilamide standard curve to obtain the sulfanilamide concentration of the solution in different time periods. The adsorption capacity of the material is calculated by the following formula:
in the formula, qtIs the adsorption capacity of the material at different points in time, C0And CtRespectively representing the initial concentration of the sulfanilamide solution and the concentration of different time points, wherein V represents the volume of the sulfanilamide solution and is a unit L; m represents the adsorbent usage unit g; t represents a time point. And (3) soaking the adsorbed porous starch-metal organic framework composite material and the filter cloth bag in 50mL of 0.02mol/L hydrochloric acid solution for 10min, washing the filter cloth bag by using absolute ethyl alcohol, drying, and repeating the steps to determine the recycling performance of the material.
Comparative example 1
Porous starch adsorbent material was used as comparative example: 20mg of porous starch was placed in a 0.45 μm filter cloth bag and immersed in 40mg/L of a sulfanilamide solution. Taking 2mL of sulfanilamide solution in different adsorption reaction time, measuring the absorbance of sulfanilamide at the absorption wavelength lambda-243 by using a spectrophotometer, and comparing with a sulfanilamide standard curve to obtain the sulfanilamide concentration of the solution in different time periods. The sulfonamide adsorption capacity was calculated according to formula (1).
The sulfonamide adsorption capacity of the sample was tested to be 8.30 mg/g.
Example 1
(1) Preparation of the starting Material
a) Preparing porous starch: dispersing 10g corn starch in citric acid buffer solution (50mL) with pH of 5.0, adding 0.10mL alpha-amylase and glucoamylase complex enzyme (1:3, v/v), reacting at 50 deg.C for 5 hr, inactivating enzyme, drying, and sieving with 100 mesh sieve to obtain porous starch.
b) Synthesis of metal organic framework material: 4.8g of zirconium chloride and 4.4g of phthalic acid were dispersed in 100mL of deionized water and treated at 100 ℃ for 24 hours by the reflux method. The sample obtained after refluxing was further washed with deionized water and added with 80mL of deionized water for a second reflux for 16 h. And centrifuging, freeze-drying and crushing the sample to obtain the metal organic framework material.
(2) Porous starch-metal organic framework composite material immobilization
a) Electrostatic adsorption: first, 0.2g of low viscosity chitosan was dissolved by heating with 0.01mol/L hydrochloric acid solution (20mL), and then the pH was adjusted to 5.5 with distilled water and 0.1g of a metal organic framework material was added and reacted under ultrasonic conditions of 40kHz for 10 min.
b) Immobilization: the suspension obtained in a) was added dropwise by means of a constant flow pump at 60rpm to 100mL of a 6% strength porous starch suspension, the stirring speed of which was 500 rpm.
c) Washing: suction-filtering the suspension obtained in step b), and removing the non-immobilized metal organic framework particles through a 0.45 mu m filter membrane.
d) And (3) drying: and c), drying the composite material obtained in the step c) in an oven at 40 ℃ for 12h, and crushing to obtain the porous starch-metal organic framework composite material.
Through tests, the sulfanilamide adsorption rate of the sample is 46.46mg/g, and the sulfanilamide adsorption rate after the sample is recycled for four times is 31.11 mg/g.
FIG. 1 is an X-ray diffraction pattern of the porous starch-metal organic framework composite and the porous starch of example 1. The composite material exhibited diffraction peaks of MOF material at 7.2 ° and 8.4 ° compared to porous starch, indicating that MOF material was immobilized on porous starch.
FIG. 2 is a scanning electron microscope image of the porous starch-metal organic framework composite material and imaging images of different sizes of four elements of carbon, nitrogen, oxygen and zirconium in the porous starch-metal organic framework composite material in example 1. The characteristic zirconium elements of the metal organic framework are uniformly distributed on the inner surface and the outer surface of the porous starch, and the MOF material is uniformly distributed on the surface of the porous starch.
FIG. 3 is a nitrogen adsorption/desorption curve and a pore size distribution diagram of the porous starch-metal organic framework composite material of example 1. The adsorption-desorption curve of the composite material shows a hysteresis loop of H4 type, which indicates that the composite material is a mixed pore material. The pore size distribution diagram shows that the composite material is a multi-layer pore material with micropores (2 microns) and mesopores (2-50 microns), and the chemical accessibility of the MOF material and the liquidity of sulfanilamide molecules are guaranteed.
FIG. 4 is a sulfanilamide adsorption capacity test of the porous starch-metal organic framework composite material of example 1, and the result shows that the sulfanilamide equilibrium adsorption rate of the porous starch-metal organic framework composite material is 46.46mg/g, which is much higher than the sulfanilamide equilibrium adsorption value of the porous starch 8.30 mg/g. The composite material reached adsorption equilibrium in a shorter time and exhibited a stronger adsorption capacity, indicating that the accessibility of the MOF material was not affected by the support.
Fig. 5 shows the repeated sulfanilamide adsorption test of the porous starch-metal organic framework composite material of example 1, and the sulfanilamide adsorption rate of the porous starch-metal organic framework composite material after being recycled for four times is 31.11mg/g, and the higher adsorption level is still maintained.
In the comparative example, the adsorption capacity of the porous starch to sulfanilamide is weak because there are few micro-mesopores in the porous starch and there is no interaction force to sulfanilamide, which makes it difficult to capture sulfanilamide molecules. In the embodiment, the affinity of the material and sulfanilamide molecules is enhanced by immobilizing the MOF material, the micro mesoporous volume is increased, the specific surface area of the porous starch is increased, and the sulfanilamide adsorption capacity is greatly enhanced.
Example 2
(1) Preparation of the starting Material
a) Preparing porous starch: dispersing 12g corn starch in citric acid buffer solution (60mL) with pH of 5.0, adding 0.15mL alpha-amylase and glucoamylase complex enzyme (1:2, v/v), reacting at 55 deg.C for 6h, inactivating enzyme, drying, and sieving with 100 mesh sieve to obtain porous starch.
b) Synthesis of metal organic framework material: 2.4g of zirconium chloride and 2.2g of phthalic acid were dispersed in 50mL of deionized water and treated at 110 ℃ for 20h using the reflux method. The sample obtained after refluxing was further washed with deionized water and added with 90mL of deionized water for a second reflux for 15 h. And centrifuging, freeze-drying and crushing the sample to obtain the metal organic framework material.
(2) Porous starch-metal organic framework composite material immobilization
a) Electrostatic adsorption: first, 0.3g of low viscosity chitosan was dissolved by heating using 0.01mol/L hydrochloric acid solution (30mL), and then pH was adjusted to 5.5 with distilled water and 0.1g of a metal organic framework material was added and reacted under ultrasonic conditions of 50kHz for 15 min.
b) Immobilization: the suspension obtained in a) was added dropwise by means of a constant flow pump at 60rpm to 100mL of a 5% strength porous starch suspension, the stirring speed of which was 600 rpm.
c) Washing: suction-filtering the suspension obtained in step b), and removing the non-immobilized metal organic framework particles through a 0.45 mu m filter membrane.
d) And (3) drying: and c), drying the composite material obtained in the step c) in an oven at 30 ℃ for 12h, and crushing to obtain the porous starch-metal organic framework composite material.
The sulfanilamide adsorption rate of the sample is 44.70 mg/g.
Example 3
(1) Preparation of the starting Material
a) Preparing porous starch: dispersing 9g corn starch in citric acid buffer solution (55mL) with pH of 5.2, adding 0.10mL alpha-amylase and glucoamylase complex enzyme (1:3, v/v), reacting at 55 deg.C for 5h, inactivating enzyme, drying, and sieving with 80 mesh sieve to obtain porous starch.
b) Synthesis of metal organic framework material: 4.8g of zirconium chloride and 4.4g of phthalic acid were dispersed in 100mL of deionized water and treated at 95 ℃ for 30 hours by the reflux method. The sample obtained after refluxing was further washed with deionized water and added with 80mL of deionized water for a second reflux for 20 h. And centrifuging, freeze-drying and crushing the sample to obtain the metal organic framework material.
(2) Porous starch-metal organic framework composite material immobilization
a) Electrostatic adsorption: first, 0.1g of a low viscosity was dissolved by heating using a 0.01mol/L hydrochloric acid solution (10mL), followed by adjusting the pH to 5.0 with distilled water and adding 0.1g of a metal organic framework material, and reacted under ultrasonic conditions of 35kHz for 15 min.
b) Immobilization: the suspension obtained in a) was added dropwise by means of a constant flow pump at 60rpm to 100mL of a 8% strength porous starch suspension, the stirring speed of which was 400 rpm.
c) Washing: suction-filtering the suspension obtained in step b), and removing the non-immobilized metal organic framework particles through a 0.45 mu m filter membrane.
d) And (3) drying: and c), drying the composite material obtained in the step c) for 12 hours in an oven at the temperature of 35 ℃, and crushing to obtain the porous starch-metal organic framework composite material.
The sulfanilamide adsorption rate of the sample is tested to be 42.01 mg/g.
It should be noted that those skilled in the art to which the invention pertains will appreciate that alternative or obvious modifications of the embodiments described herein may be made without departing from the spirit of the invention, and such modifications are to be considered as falling within the scope of the invention.
Claims (10)
1. A preparation method of a porous starch-metal organic framework composite material is characterized by comprising the following steps and process conditions:
1) preparing porous starch: dispersing starch in a citric acid buffer solution, adding a complex enzyme, reacting for 3-6 h at 45-55 ℃, inactivating enzyme, drying, and sieving to obtain porous starch; the complex enzyme is alpha-amylase and glucoamylase complex enzyme;
2) synthesis of metal organic framework material: dispersing zirconium chloride and phthalic acid in deionized water, and treating for 18-30 h at 90-120 ℃ by using a reflux method; redispersing the washed material in deionized water, and carrying out secondary reflux for 10-20 h; centrifuging, freeze-drying and crushing to obtain a metal organic framework material UiO-66-COOH; the mass ratio of the zirconium chloride to the phthalic acid is 2.4-7.2: 2.2 to 6.6; the mass volume ratio of the phthalic acid to the deionized water is 2.2-6.6: 50-150; wherein the mass unit is g, and the volume unit is mL;
3) and (3) porous starch-metal organic framework composite material immobilization: performing ultrasonic reaction on chitosan and a metal organic framework material under the condition of pH 4.5-5.5; dripping the obtained suspension into a porous starch suspension with the concentration of 5-8 wt%, stirring, carrying out suction filtration, and filtering to remove non-immobilized metal organic framework particles; drying and crushing to obtain the porous starch-metal organic framework composite material.
2. The method for preparing a porous starch-metal organic framework composite material according to claim 1, wherein in step 1), the starch is one or more of corn starch, tapioca starch and potato starch; the pH value of the citric acid buffer solution is 5.0-5.5, the mesh number of the screen is 80-100 meshes, the mass-volume ratio of the starch to the citric acid buffer solution is 5-15: 20-100, wherein the mass unit is g, and the volume unit is mL.
3. The method for preparing the porous starch-metal organic framework composite material according to claim 1, wherein the volume ratio of the alpha-amylase to the glucoamylase is 1: 2-1: 5, the addition amount of the complex enzyme is 0.01-0.03 mL per gram of starch, and the activities of the alpha-amylase and the glucoamylase are 480U/g and 1850U/g respectively.
4. The method for preparing the porous starch-metal organic framework composite material as claimed in claim 1, wherein the chitosan is low viscosity chitosan of 50-100 KDa.
5. The method for preparing the porous starch-metal organic framework composite material according to the claims 1 and 5, wherein in the step 3), the chitosan is dissolved by heating with 0.01-0.05 mol/L hydrochloric acid solution, and then is adjusted to pH 4.5-5.5 by distilled water; the time of the ultrasonic reaction is 5-15 min; the frequency of the ultrasonic wave is 30-50 KHZ.
6. The preparation method of the porous starch-metal organic framework composite material according to claim 1, wherein the time of the secondary reflux is 10-20 h.
7. The preparation method of the porous starch-metal organic framework composite material according to claim 1, wherein the suspension is dripped into the porous starch suspension with the concentration of 5-8 wt% by a constant flow pump with the flow rate of 40-60 rpm.
8. The preparation method of the porous starch-metal organic framework composite material as claimed in claim 1, wherein the stirring speed in the step 3) is 300-600 rpm; the drying is carried out in an oven at the temperature of 30-40 ℃ for 9-12 h.
9. The method for preparing a porous starch-metal organic framework composite material as claimed in claim 1, wherein the filtration in step 3) is a 0.45 μm filtration membrane.
10. The preparation method of the porous starch-metal organic framework composite material as claimed in claim 1, wherein the mass ratio of the chitosan to the metal organic framework material in the step 3) is 1: 1-3: 1.
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| CN112759473A (en) * | 2021-02-26 | 2021-05-07 | 汤雨 | Cultivation fertilizer for promoting growth of plant root system and processing method thereof |
| CN113845701A (en) * | 2021-09-13 | 2021-12-28 | 桂林理工大学 | Copper metal organic framework modified starch-based composite film and preparation method thereof |
| CN114534691A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院大连化学物理研究所 | Magnetic modified zeolite-like imidazole ester framework material and preparation and application thereof |
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