PREPARATION METHOD AND APPLICATION OF CLAY/TANNIC ACID/METAL ION COMPOSITE MATERIAL FOR EFFICIENT ADSORPTION OF ANTIBIOTICS

Abstract

A preparation method and an application of a clay/tannic acid/metal ion composite material for efficient adsorption of antibiotics are provided, which relate to the field of water environment treatments. A clay/tannic acid/metal ion composite adsorbent is prepared, preparation method and operation process are simple, synthesis time is short, and yield is large. A raw material used is tannic acid, which has a wide range of sources, is non-toxic, biodegradable, and has no risk of secondary pollution, due to abundant phenolic hydroxyl groups in tannic acid, the tannic acid can not only chelate with the metal ions, but also adsorb pollutants from water, when combined with the clay and the metal ions, a composite body is formed, which has a rougher surface, and adsorption active sites are increased, thereby effectively increasing adsorption, and improving an adsorption performance for pollutants. The clay/tannic acid/metal ion composite adsorbent has good adsorption effect for antibiotics.

Claims

1. A preparation method of a clay/tannic acid/metal ion composite material for adsorbing antibiotics, wherein the clay/tannic acid/metal ion composite material is a composite adsorbent obtained by mixing a polymer material, a clay mineral material and metal ions; the polymer material is tannic acid, the clay mineral material is kaolin, and the metal ions are titanium ions; a molar ratio of the tannic acid and the mental ions is 1:4; and a weight ratio of the tannic acid and the kaolin is 1:1, and the preparation method comprises: step 1, adding 2 grams (g) of the kaolin into a tri hydroxymethyl aminomethane (C.sub.4H.sub.11NO.sub.3) buffer solution or a 3-morpholinopropanesulfonic acid (C.sub.7H.sub.15NO.sub.4S) buffer solution to obtain a solution, and performing an ultrasonic dispersion on the solution to obtain a kaolin dispersion liquid; and step 2, adding a tannic acid solution with a concentration of 10 millimoles per liter (mmol/L) and a titanium ion solution with a concentration of 40 mmol/L into the kaolin dispersion liquid to obtain a mixed solution, adjusting a potential of hydrogen (pH) of the mixed solution to 7.5 to obtain an alkaline mixed solution, obtaining a reacted solution after the alkaline mixed solution reacts at a room temperature for 1 minute (min), and sequentially filtering, washing and drying the reacted solution to obtain the kaolin/tannic acid/titanium ion composite material with a feed molar ratio of 1:4 between the tannic acid and the mental ions.

2. The preparation method of the clay/tannic acid/metal ion composite material for adsorbing antibiotics as claimed in claim 1, wherein a method for drying the reacted solution is a room temperature drying method or a freeze-drying method.

3. An application method of the clay/tannic acid/metal ion composite material for adsorbing antibiotics prepared by the method as claimed in claim 1, comprising: applying the clay/tannic acid/metal ion composite material in sewage to adsorb antibiotics.

4. The application method of the clay/tannic acid/metal ion composite material for adsorbing antibiotics prepared by the method as claimed in claim 1, wherein the antibiotics comprise sulfonamides, fluoroquinolones, tetracyclines, -lactams and macrolides.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0027] FIG. 1 illustrates an infrared spectrogram of kaolin, tannic acid, a tannic acid/metal ion complex and a kaolin/tannic acid/metal ion composite adsorbent according to an embodiment of the disclosure.

[0028] FIG. 2 illustrates a scanning electron microscopy diagram of the kaolin, the tannic acid, the tannic acid/metal ion complex and the kaolin/tannic acid/metal ion composite adsorbent according to an embodiment of the disclosure.

[0029] FIG. 3 illustrates a schematic diagram of adsorption capacities of the kaolin, the tannic acid, the tannic acid/metal ion complex and the kaolin/tannic acid/metal ion composite adsorbent for a fluoroquinolone antibiotic: ofloxacin according to an embodiment of the disclosure.

[0030] FIG. 4 illustrates an adsorption kinetics diagram of a kaolin/tannic acid/iron ion composite adsorbent for the fluoroquinolone antibiotic: ofloxacin according to an embodiment of the disclosure.

DETAILED DESCRIPTION OF EMBODIMENTS

[0031] The disclosure is described by the following embodiments.

Embodiment 1

[0032] A preparation method of a clay/tannic acid/metal ion composite adsorbent is provided, and the method includes the following steps 1-2.

[0033] In step 1, 2 grams (g) of kaolin is added into a 3-morpholinopropanesulfonic acid (MOPS) buffer solution to obtain a solution, and an ultrasonic dispersion is performed on the solution to obtain a kaolin dispersion liquid.

[0034] In step 2, a tannic acid solution with a concentration of 10 millimoles per liter (mmol/L) and an iron ion solution with a concentration of 40 mmol/L are added into the kaolin dispersion liquid to obtain a mixed solution, a weight ratio of the tannic acid and the kaolin is 1:1, a potential of hydrogen (pH) of the mixed solution is adjusted to 7.5 to obtain an alkaline mixed solution, a reacted solution is obtained after the alkaline mixed solution reacts at a room temperature for 1 minute (min), and the reacted solution is sequentially filtered, washed and dried at the room temperature to obtain a kaolin/tannic acid/iron ion composite adsorbent with a feed molar ratio of 1:4 between the tannic acid and the metal ions. FIG. 1 illustrates an infrared spectrogram of the kaolin/tannic acid/metal ion composite adsorbent, the infrared spectrogram of the kaolin/tannic acid/metal ion composite adsorbent includes infrared characteristic peaks of a clay (i.e., kaolin) and the tannic acid compared to the clay, the tannic acid and a tannic acid/metal ion complex; moreover, after compounding the tannic acid with the kaolin, a carbonyl (CO) telescopic vibration peak of the tannic acid at 1720 centimeters.sup.1 (cm.sup.1) is shifted to 1714 cm.sup.1 and a CO bending vibration peak of the tannic acid at 1325 cm.sup.1 is shifted to 1350 cm.sup.1, which means that an electron transfer process occurs in the reaction after compounding the tannic acid with the kaolin, a chelating bond is formed between the iron ion and a phenolic hydroxyl group of the tannic acid, and a new composite body with a unique structure is formed. The scanning electron microscopy diagram in FIG. 2 also shows that the kaolin/tannic acid/metal ion composite adsorbent has a rougher surface and a larger specific surface area.

[0035] A preparation method of another clay/tannic acid/metal ion composite adsorbent is basically the same as that of the kaolin/tannic acid/iron ion composite adsorbent, except that the step 2 is changed to the following content: the tannic acid solution with the concentration of 10 mmol/L and a titanium ion solution with a concentration of 40 mmol/L are added into the kaolin dispersion liquid to obtain a mixed solution, a pH of the mixed solution is adjusted to 7.5 to obtain an alkaline mixed solution, a reacted solution is obtained after the alkaline mixed solution reacts at the room temperature for 1 min, and the reacted solution is sequentially filtered, washed and dried at the room temperature to obtain a kaolin/tannic acid/titanium ion composite adsorbent.

[0036] A preparation method of another clay/tannic acid/metal ion composite adsorbent is basically the same as that of the kaolin/tannic acid/iron ion composite adsorbent, except that the step 2 is changed to the following content: the tannic acid solution with the concentration of 10 mmol/L and a copper ion solution with a concentration of 40 mmol/L are added into the kaolin dispersion liquid to obtain a mixed solution, a pH of the mixed solution is adjusted to 7.5 to obtain an alkaline mixed solution, a reacted solution is obtained after the alkaline mixed solution reacts at the room temperature for 1 min, and the reacted solution is sequentially filtered, washed and dried at the room temperature to obtain a kaolin/tannic acid/copper ion composite adsorbent.

[0037] FIG. 3 illustrates a comparison diagram of adsorption effects by using wastewater including a fluoroquinolone antibiotic ofloxacin as a laboratory simulated water sample. FIG. 4 illustrates an adsorption kinetics diagram of the kaolin/tannic acid/iron ion composite adsorbent for adsorbing the fluoroquinolone antibiotic ofloxacin. An initial concentration of the ofloxacin in the wastewater is simulated as 0.2 mmol/L, and 10 mg of the composite adsorbent is added into 30 milliliters (mL) of ofloxacin solution to adsorb for 12 hours (h). A liquid chromatograph is used by the method to detect an actual adsorption capacity of products for adsorbing the ofloxacin. As shown in FIG. 3, adsorption effects of the above three composite adsorbents compared to adsorption effects of single kaolin and tannic acid/metal ion complex are significantly improved, this is mainly due to a compound of the kaolin with the tannic acid and the metal ions, a new composite body with a unique structure is formed, and the new composite body has a rougher surface and an increase in adsorption active sites. Meanwhile, it can be seen from Table 1 and FIG. 3 that adsorption capacities of the kaolin/tannic acid/titanium ion composite adsorbent, the kaolin/tannic acid/iron ion composite adsorbent and the kaolin/tannic acid/copper ion composite adsorbent gradually decrease, since metal ions with higher valence states have a stronger chelation with the ofloxacin, which greatly improve an adsorption capacity for the ofloxacin. As shown in FIG. 4, the adsorption capacity of the kaolin/tannic acid/iron ion composite adsorbent for the ofloxacin can basically reach adsorption saturation when adsorbing for 6 h, and a maximum adsorption effect can be reached when adsorbing for 12 h.

TABLE-US-00001 TABLE 1 A comparison of adsorption capacities of the above three types of composite adsorbents in the embodiment 1 Composite adsorbent Kaolin/tannic Kaolin/tannic Kaolin/tannic acid/copper ion acid/iron ion acid/titanium composite composite ion composite adsorbent adsorbent adsorbent Adsorption capacity 0.261 0.377 0.422 (mmol/L)

Embodiment 2

[0038] A preparation method of a clay/tannic acid/metal ion composite adsorbent is provided, and the method includes the following steps 1-2.

[0039] In step 1, 2 g of the kaolin is added into the MOPS solution to obtain a solution, and the ultrasonic dispersion is performed on the solution to obtain a kaolin dispersion liquid.

[0040] In step 2, iron ion solutions with concentrations of 20, 30, 40, 50 and 60 mmol/L are respectively added into the kaolin dispersion liquid together with a tannic acid solution with a concentration of 10 mmol/L to obtain mixed solutions, the weight ratio of the tannic acid and the kaolin is 1:1, pH of the mixed solutions are adjusted to 7.5 to obtain alkaline mixed solutions, reacted solutions are obtained after the alkaline mixed solutions react at the room temperature for 1 min, and the reacted solutions are sequentially filtered, washed and dried at the room temperature to obtain kaolin/tannic acid/iron ion composite adsorbents with feed molar ratios of 1:2, 1:3, 1:4, 1:5 and 1:6 between the tannic acid and the metal ions, respectively.

[0041] Wastewater with enrofloxacin antibiotics is used as the laboratory simulated water sample, an initial concentration of the enrofloxacin antibiotics in the wastewater is simulated as 0.2 mmol/L, and 10 mg of the composite adsorbents are added into the wastewater to adsorb for 12 h. The liquid chromatograph is used by the method to detect an actual adsorption effect of products for adsorbing the enrofloxacin antibiotics, adsorption capacities of the composite adsorbents are compared to the adsorption capacity of the kaolin/tannic acid/iron ion composite adsorbent with the feed molar ratio of 1:4 (i.e., Table 2), with an increase of the feed molar ratio, the adsorption capacity of the kaolin/tannic acid/iron ion composite adsorbents for the enrofloxacin antibiotics first increases and then slightly decreases, and the adsorption capacity achieves an optimal effect when the feed molar ratio is 1:4.

TABLE-US-00002 TABLE 2 a comparison of adsorption capacities of the kaolin/tannic acid/iron ion composite adsorbents with different feed molar ratios in the embodiment 2 Feed molar ratio (tannic acid:iron ions) 1:2 1:3 1:4 1:5 1:6 Adsorption capacity 0.183 0.261 0.381 0.364 0.355 (mmol/L)

Embodiment 3

[0042] A preparation method of a clay/tannic acid/metal ion composite adsorbent is provided, and the method includes the following steps 1-2.

[0043] In step 1, 10 g of attapulgite is added into a tri hydroxymethyl aminomethane (Tris) buffer solution to obtain a solution, and the ultrasonic dispersion is performed on the solution to obtain an attapulgite dispersion liquid.

[0044] In step 2, a tannic acid solution with a concentration of 1 mmol/L and a cooper ion solution with a concentration of 80 mmol/L are added into the attapulgite dispersion liquid to obtain a mixed solution, and a weight ratio of the tannic acid and the attapulgite is 1:1, a pH of the mixed solution is adjusted to 7 to obtain a neutral mixed solution, a reacted solution is obtained after the neutral mixed solution reacts at the room temperature for 1 min, and the reacted solution is sequentially filtered, washed and freeze dried to obtain a composite adsorbent.

[0045] Wastewater with tetracycline antibiotics is used as the laboratory simulated water sample, an initial concentration of the tetracycline antibiotics in the wastewater is simulated as 0.2 mmol/L, and 10 g of the composite adsorbent is added into the wastewater to adsorb for 12 h. The liquid chromatograph is used by the method to detect an actual adsorption effect of the product for adsorbing the tetracycline antibiotics.

Embodiment 4

[0046] A preparation method of a clay/tannic acid/metal ion composite adsorbent is provided, and the method includes the following steps 1-2.

[0047] In step 1, 1 g of bentonite is added into the MOPS buffer solution to obtain a solution, and the ultrasonic dispersion is performed on the solution to obtain a bentonite dispersion liquid.

[0048] In step 2, a tannic acid solution with a concentration of 100 mmol/L and a titanium ion solution with a concentration of 160 mmol/L are added into the bentonite dispersion liquid to obtain a mixed solution, and a weight ratio of the tannic acid and the bentonite is 1:1, a pH of the mixed solution is adjusted to 6.5 to obtain an acidic mixed solution, a reacted solution is obtained after the acidic mixed solution reacts at the room temperature for 1 min, and the reacted solution is sequentially filtered, washed and freeze dried to obtain a composite adsorbent.

[0049] Wastewater with sulfonamide antibiotics is used as the laboratory simulated water sample, an initial concentration of the sulfonamide antibiotics in the wastewater is simulated as 0.2 mmol/L, and 10 g of the composite adsorbent is added into the wastewater to adsorb for 12 h. The liquid chromatograph is used by the method to detect an actual adsorption effect of the product for adsorbing the sulfonamide antibiotics.

Embodiment 5

[0050] A preparation method of a clay/tannic acid/metal ion composite adsorbent is provided, and the method includes the following steps 1-2.

[0051] In step 1, 7 g of montmorillonite is added into the MOPS buffer solution to obtain a solution, and the ultrasonic dispersion is performed on the solution to obtain a montmorillonite dispersion liquid.

[0052] In step 2, a tannic acid solution with a concentration of 80 mmol/L and an aluminum ion solution with a concentration of 60 mmol/L are added into the montmorillonite dispersion liquid to obtain a mixed solution, and a weight ratio of the tannic acid and the montmorillonite is 1:1, a pH of the mixed solution is adjusted to 7 to obtain a neutral mixed solution, a reacted solution is obtained after the neutral mixed solution reacts at the room temperature for 1 min, and the reacted solution is sequentially filtered, washed and dried at the room temperature to obtain a composite adsorbent.

[0053] Wastewater with macrolide antibiotics is used as the laboratory simulated water sample, an initial concentration of the sulfonamide antibiotics in the wastewater is simulated as 0.2 mmol/L, and 10 g of the composite adsorbent is added into the wastewater to adsorb for 12 h. The liquid chromatograph is used by the method to detect an actual adsorption effect of the product for adsorbing the macrolide antibiotics.

Embodiment 6

[0054] A preparation method of a clay/tannic acid/metal ion composite adsorbent is provided, and the method includes the following steps 1-2.

[0055] In step 1, 5 g of illite is added into the Tris buffer solution to obtain a solution, and the ultrasonic dispersion is performed on the solution to obtain an illite dispersion liquid.

[0056] In step 2, a tannic acid solution with a concentration of 50 mmol/L and an magnesium ion solution with a concentration of 120 mmol/L are added into the illite dispersion liquid to obtain a mixed solution, and a weight ratio of the tannic acid and the illite is 1:1, a pH of the mixed solution is adjusted to 7.5 to obtain an alkaline mixed solution, a reacted solution is obtained after the alkaline mixed solution reacts at the room temperature for 1 min, and the reacted solution is sequentially filtered, washed and dried at the room temperature to obtain a composite adsorbent.

[0057] Wastewater with -lactam antibiotics is used as the laboratory simulated water sample, an initial concentration of the -lactam antibiotics in the wastewater is simulated as 0.2 mmol/L, and 10 g of the composite adsorbent is added into the wastewater to adsorb for 12 h. The liquid chromatograph is used by the method to detect an actual adsorption effect of the product for adsorbing the -lactam antibiotics.