WO2020097955A1 - Phosphorylation ultra-fast straw fiber adsorption material, preparation method and application thereof - Google Patents

Abstract

Provided are a green, environmentally-friendly, high-efficiency and low-cost phosphorylation ultra-fast straw fiber adsorption material, a preparation method and an application thereof, which relates to the field of adsorption material preparation and application. The phosphorylation ultra-fast straw fiber adsorption material is obtained by modifying straw powder with phosphorous acid, paraformaldehyde and hydrochloric acid, wherein the specific surface area of the adsorption material is 2.6-2.7m ²/g, and the pore volume is 0.005-0.006cm ³/g.

Description

Phosphonated ultra-fast straw fiber adsorption material, preparation method and application thereof Technical field

The invention relates to the field of preparation and application of adsorption materials, in particular to a phosphonated ultra-fast straw fiber adsorption material and its preparation method and application.

Background technique

In recent years, a new class of pollutants-medicines and personal care products (PPCPs) have been frequently detected in various water bodies and attracted more and more attention. Antibiotics are an important kind of PPCPs pollutants. Although they are present in trace amounts in the water environment, they are in a "persistent" state due to their refractory and continuous input properties, and their residues will flow into Groundwater or surface water even accumulates in the soil, enters animals, plants, and humans through the food chain, inhibits its function, and threatens human health. Sulfa drugs are synthetic antibacterial drugs that have been used in clinics for nearly 50 years. It has the advantages of a broad antibacterial spectrum, stable properties, and easy use. Therefore, the frequency of detection in water is high. The detection and pollution of antibiotic substances in surface water, drinking water and sewage surveyed by USGS (1999-2000) in the United States have the highest detection frequency of sulfonamides, and the residual concentration is generally less than 1 μg / L. There are also reports of sulfa antibiotics detected in water and soil in many places in China. Chang Hong et al. Investigated and investigated sulfa antibiotics in a Beijing urban sewage treatment plant, and detected sulfamethoxazole, sulfapyridine, sulfamethazine , Sulfadiazine and sulfamethoxazole five sulfonamide antibiotics, the effluent concentration is 0.008-1.4μg / L. The sulfonamide antibiotics remaining in the environment have become a potential source of environmental ecological hazards, causing adverse effects on soil, water, etc., as well as affecting the normal life activities of microorganisms, animals and plants, and ultimately human health.

For the removal of sulfonamide antibiotics in water, physical and chemical methods are mainly used. Conventional water treatment processes include coagulation, precipitation, quartz sand filtration, activated carbon adsorption, and disinfection. However, the conventional water treatment process often cannot completely remove the residual antibiotics in the water. Xu Weihai and other four types of antibiotics such as sulfonamides and quinolones have been monitored in the effluent of four sewage treatment plants, and their detection rates and contents are higher than those in the United States and European level. As a mature physical method, the adsorption method can effectively remove sulfonamide antibiotics in water and soil. It has low energy consumption, no by-products, high adsorption efficiency, and the adsorbent can be recycled and reused, and the treatment cost is low.

Corn stalk fiber is an adsorbent with low cost, low energy consumption, environmental friendliness and simple process. At the same time, it is a very rich and cheap resource as agricultural waste, but its specific surface area and pore volume are small, so the adsorption efficiency is low.

Summary of the invention

One of the objectives of the present invention is to provide a phosphonated ultra-fast straw fiber adsorbent material that is green, environmentally friendly, efficient, and inexpensive to remove sulfonamide antibiotics.

In order to achieve the above object, the technical solution provided by the present invention is as follows: a phosphonic acid ultra-fast straw fiber adsorbent material, which is obtained by modifying straw powder with phosphorous acid, paraformaldehyde and hydrochloric acid. The specific surface area is 2.6-2.7 m ² / g, and the pore volume is 0.005-0.006 cm ³ / g.

As an embodiment of the present invention, the specific surface area of the adsorbent material of the present invention is 2.61 m ² / g, and the pore volume is 0.0055 cm ³ / g.

The second object of the present invention is to provide a preparation method of the above-mentioned phosphonized ultra-fast straw fiber adsorbent.

In order to achieve the above object, the technical solution provided by the present invention is as follows: a method for preparing a phosphonated ultra-fast straw fiber adsorbent material, drying straw powder, mixing with phosphorous acid and paraformaldehyde, and dissolving with hydrochloric acid solution, Wash to neutrality and dry to get it.

Wherein, the concentration of the hydrochloric acid solution is 10-30%.

As a preferred solution of the present invention, the concentration of the hydrochloric acid solution is 25%.

Wherein, the mass mixing ratio of the straw powder, phosphorous acid and paraformaldehyde is 1: 0.5-10: 0.5-10.

As a preferred solution of the present invention, the mass mixing ratio of the straw powder, phosphorous acid and paraformaldehyde is 1: 5: 5.

Wherein, the dissolution temperature is 60-90 ° C, and the dissolution time is 3-8h.

As a preferred solution of the present invention, the dissolution temperature is 80 ° C and the dissolution time is 5 hours.

Wherein, the drying temperature is 50-70 ° C.

As a preferred solution of the present invention, the drying temperature is 60 ° C.

The third object of the present invention is to provide the application of the above-mentioned phosphonated ultra-fast straw fiber adsorbent material.

In order to achieve the above object, the technical solution provided by the present invention is as follows: a phosphonic acid ultra-fast straw fiber adsorbent material as described above is used for adsorbing antibiotics in water, especially sulfonamide antibiotics in water containing sulfonamide antibiotics .

Wherein, the adsorption temperature is 23-27 ° C, and the adsorption oscillation time is 24-96h.

The beneficial effects of the present invention are: the present invention selects agricultural straw corn stalk with huge biomass as raw material, and obtains phosphonic acid ultra-fast straw fiber adsorbent material after modifying it by a mixed solution of phosphorous acid, paraformaldehyde and hydrochloric acid , Significantly increased its specific surface area, from 1.44m ² / g of unmodified corn stalks to more than 2.6m ² / g; at the same time, the pore volume has also been improved, from 0.0024cm ³ / of unmodified corn stalks When g is increased to more than 0.005cm ³ / g, the adsorption capacity is improved and the adsorption efficiency is greater. In addition, the adsorption material provided by the invention is easily biodegradable and has no pollution to the environment.

BRIEF DESCRIPTION

Figure 1 is a scanning electron microscope image of unmodified corn stalk raw materials;

Figure 2 is a scanning electron micrograph of phosphonated ultra-fast straw fiber adsorbent material;

Figure 3 is a scanning electron micrograph of the phosphonated ultra-fast straw fiber adsorbent after adsorbing SPY;

Figure 4 is a scanning electron micrograph of the phosphonic ultrafast straw fiber adsorbent after adsorbing SMM;

Figure 5 is a scanning electron micrograph of the phosphonated ultra-fast straw fiber adsorbent after adsorbing SMZ;

6 is an analysis diagram of the influence of adsorption time on the adsorption effect of phosphonated ultra-fast straw fiber adsorbent material;

Figure 7 is a graph showing the change in the adsorption rate of SPY, SMZ and SMM with initial concentration of phosphonated ultra-fast straw fiber adsorbent material and unmodified corn stover raw material at pH = 1;

Figure 8 is a graph showing the change in the adsorption rate of SPY, SMZ and SMM with initial concentration of phosphonated ultra-fast straw fiber adsorbent material and unmodified corn stover raw material at pH = 3;

9 is a graph showing the change of the adsorption rate of SPY, SMZ and SMM with the initial concentration of phosphonized ultra-fast straw fiber adsorbent material and unmodified corn stover raw material at pH = 5;

Figure 10 is a graph showing the change in the adsorption rate of SPY, SMZ and SMM with initial concentration of phosphonated ultra-fast straw fiber adsorbent material and unmodified corn stover raw material at pH = 7;

FIG. 11 is a graph showing the change in the adsorption rate of SPY, SMZ and SMM with initial concentration of phosphonated ultra-fast straw fiber adsorbent material and unmodified corn stover raw material at pH = 9;

Fig. 12 is a graph showing the change of the adsorption rate of SPY, SMZ and SMM with the initial concentration of phosphonized ultra-fast straw fiber adsorbent material and unmodified corn stover raw material at pH = 11.

detailed description

The present invention will be described below with reference to specific embodiments: but it can be understood that these specific embodiments are only used to illustrate the present invention, rather than to limit the present invention. A person skilled in the art can fully improve the specific implementation or technical features of the present invention under the inspiration of the present invention, but these improved or replaced technical technical solutions still fall within the protection scope of the present invention.

Example 1

Crush the straw, pass through a 60-mesh sieve, wash it three times with water, and dry to constant weight at 60 ° C; mix with phosphorous acid and paraformaldehyde at a mass ratio of 1: 5: 5, and add to the concentration at 80 ° C Heat the reaction in 25% hydrochloric acid solution for 5h; wash to neutrality with water and dry to constant weight at 60 ℃ to obtain phosphonated ultra-fast straw fiber adsorbent material.

Example 2

Sulfapyridine (SPY), sulfamethoxine (SMM) and sulfamethoxazole (SMZ) at a concentration of 2 mg / l were added to 10ml glass bottles, respectively, and the phosphonated superoxide prepared in Example 1 was added respectively The fast straw fiber adsorption material is adsorbed, and three sets of parallel samples are prepared. The adsorption temperature is 25 ± 2 ℃, and the adsorption oscillation time is 72h.

The scanning electron micrograph of the unmodified corn stalk raw material is shown in Figure 1; the scanning electron micrograph of the phosphonated ultra-fast straw fiber adsorbent is shown in Figure 2; 3; the scanning electron micrograph of the phosphonated ultra-fast straw fiber adsorbent after adsorbing SMM is shown in Figure 4; the scanning electron micrograph of the phosphonated ultra-fast straw fiber adsorbent after adsorbing SMZ is shown in Figure 5.

The results show that the surface of the raw material of unmodified corn stalk is smooth, the pores are irregular blocks or flakes, and the pores are irregular and uneven in size both inside and outside. The surface of phosphonated ultra-fast straw fiber adsorption material is rough like corrosion, increasing the specific surface area. The phosphonated ultra-fast straw fiber adsorbent has little change after adsorption of SPY, SMZ, SMM and before adsorption, indicating that its mechanical strength is large and can be reused.

Example 3

Effect of adsorption time on adsorption effect

Add 0.05g of phosphonated ultra-fast straw fiber adsorbent material to the Erlenmeyer flask, 2 for each group, 3 groups in total. Add 10mL of SPY, SMM and SMZ to each Erlenmeyer flask, and put them into a shaker at 25 ℃ and 180r / min full temperature after sealing. After 24h, 48h, 72h, and 96h, one group was taken out, and each was put into a liquid vial after passing through the membrane and detected by high performance liquid chromatography. The results are shown in Figure 6.

The results show that the adsorption rate of SPY shows an upward trend before 72h with time, and then decreases. Therefore, the optimal adsorption time of SPY is 72h, and the adsorption rate can reach 91.90%; the optimal adsorption time of SMZ is At 48h, the adsorption rate was 93.96%; the optimal adsorption time of SMM was also 48h, and the adsorption rate was 88.61%.

Example 4

Effect of pH on adsorption effect

Configure SPY, SMM and SMZ with 0.3mg / L, 0.5mg / L, 1.0mg / L, 1.5mg / L and 2.0mg / L respectively, and adjust the pH to 1, 3, 5, 7, 9 and 11. Each 5mL of the above standard solution was added to a small conical flask containing 0.05g of unmodified corn stalk raw material and phosphonized ultra-fast straw fiber adsorbent material, and then sealed and placed at 25 ℃, 180r / min full temperature Take it out after shaking the shaker, put it into a liquid vial after passing through the membrane, and detect it by high performance liquid chromatography. Among them, the oscillation adsorption time of SPY is 72h, and the oscillation adsorption time of SMZ and SMM is 48h. Compare the effects of different pH values on the adsorption effect of SPY, SMM and SMZ. The results are shown in Figure 7-12. The original SPY refers to the adsorption effect of unmodified corn stover raw materials on SPY; the original SMZ refers to the unmodified The adsorption effect of raw corn stalk raw materials on SMZ; the original SMM refers to the adsorption effect of unmodified corn stalk raw materials on SMM; the change of SPY refers to the adsorption of SPY on the phosphonated ultra-fast straw fiber adsorbent; the change of SMZ is Refers to the adsorption effect of phosphonated ultra-fast straw fiber adsorbent on SMZ; change to SMM refers to the adsorption effect of phosphonated ultra-fast straw fiber adsorbent on SMM.

the result shows:

In addition to the adsorption rate of 50-70% at pH = 1, the adsorption rate of SPY is basically about 90% under other pH conditions, and the adsorption of SPY by phosphonated ultra-fast straw fiber adsorbent under extremely alkaline conditions is not affected.

The adsorption rate of SMZ at pH = 1 is basically about 80%. Compared with the adsorption rates of other pH values of 3, 5, 7, 9 at 85% -90%, the adsorption effect is slightly reduced. However, at pH = 11, the phosphonated ultra-fast straw fiber adsorbent may have a maximum adsorption rate of only 48% for SMZ due to extremely alkaline conditions.

The adsorption rate of SMM at pH 3, 5, 7, 9 is basically 90%, and the adsorption rate is about 60% under the condition of extremely acid pH = 1, and the highest adsorption rate is 0.3mg / L, which is 75.6%.

In summary, the adsorption effect of phosphonated ultra-fast straw fiber adsorbent on sulfonamide antibiotics in water is significantly better than that of unmodified corn straw raw materials, and the adsorption effect is better in mild acid-base environment.

Claims (10)

1. A phosphonated ultra-fast straw fiber adsorption material, characterized in that straw powder is modified by phosphorous acid, paraformaldehyde and hydrochloric acid, and the specific surface area of the adsorption material is 2.6-2.7m ² / g, The pore volume is 0.005-0.006 cm ³ / g.
2. A method for preparing a phosphonated ultra-fast straw fiber adsorbent material according to claim 1, wherein the straw powder is dried, mixed with phosphorous acid and paraformaldehyde, dissolved with hydrochloric acid solution, and washed with water until neutral. Dry, you get it.
3. The method for preparing a phosphonated ultra-fast straw fiber adsorbent material according to claim 2, wherein the concentration of the hydrochloric acid solution is 10-30%.
4. The method for preparing a phosphonated ultra-fast straw fiber adsorbent material according to claim 3, wherein the concentration of the hydrochloric acid solution is 25%.
5. The method for preparing a phosphonated ultra-fast straw fiber adsorbent material according to any one of claims 2-4, characterized in that the mass mixing ratio of the straw powder to phosphorous acid and paraformaldehyde is 1: 0.5-10: 0.5-10.
6. The method for preparing a phosphonated ultra-fast straw fiber adsorbent material according to claim 5, wherein the mass mixing ratio of the straw powder to phosphorous acid and paraformaldehyde is 1: 5: 5.
7. The method for preparing a phosphonated ultra-fast straw fiber adsorbent material according to claim 2 or 3 or 4 or 6, wherein the dissolution temperature is 60-90 ° C and the dissolution time is 3-8h.
8. The method for preparing a phosphonated ultra-fast straw fiber adsorbent material according to claim 7, wherein the dissolution temperature is 80 ° C and the dissolution time is 5 hours.
9. The method for preparing a phosphonated ultra-fast straw fiber adsorbent material according to claim 2 or 3 or 4 or 6 or 8, wherein the drying temperature is 50-70 ° C.
10. A phosphonated ultra-fast straw fiber adsorbent material according to any one of claims 1-9 is used for adsorbing antibiotics in water.

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