CN112121771A - A kind of biomass adsorbent for removing refractory organic pollutants, its preparation method and its use method - Google Patents

Abstract

The invention relates to a biomass adsorbent for removing refractory organic pollutants, a preparation method and a use method thereof, and belongs to the field of sewage treatment in environmental protection. The invention provides a method for preparing a biomass adsorbent for removing refractory organic pollutants. The agricultural waste corn husk is used as a raw material, and the corn husk powder is acidified and then loaded with metal ions. The present invention uses agricultural wastes as raw materials, and utilizes corn husk leaves to prepare a modified biomass material adsorbent through acidification or alkalization and loading metal ions; the adsorbent can adsorb levofloxacin, tetracycline hydrochloride and other refractory organic pollutants in water, thereby The purpose of controlling drug pollution is achieved; the invention has the characteristics of waste reuse, wide source of raw materials, simple preparation, strong adsorption capacity of the adsorbent and the like.

Description

A kind of biomass adsorbent for removing refractory organic pollutants, and preparation method thereof law and how to use it

technical field

The invention relates to a biomass adsorbent for removing refractory organic pollutants, a preparation method and a use method thereof, and belongs to the field of sewage treatment in environmental protection.

Background technique

Levofloxacin and tetracycline hydrochloride are widely used antibiotics with the characteristics of broad antibacterial spectrum, strong antibacterial activity, good curative effect and few adverse reactions. However, due to the abuse of antibiotics and the unreasonable treatment of wastewater, they accumulate in the water environment, and their refractory biodegradation characteristics will not only affect the normal growth and metabolism of microorganisms, but also have certain harm to aquatic organisms and humans. At the same time, it may also cause the bacteria to develop drug resistance, posing a huge threat to the ecosystem and human health. Therefore, the development of antibacterial drug treatment technology in water is of great significance and urgent need for environmental protection and alleviation of the accumulation of antibiotics in the water environment.

At present, the common methods of removing antibiotics in water mainly include biological methods, chemical methods, and physicochemical methods. Biological method can greatly reduce COD and improve biodegradability. However, due to the complex composition of drug-containing wastewater, refractory substances and biotoxic substances, it is difficult to achieve industry standards through biological treatment. The Fenton oxidation method in the chemical method is a traditional water treatment method that is easy to handle and simple to operate. However, the applicable pH range of the Fenton oxidation method is narrow, and a large amount of iron sludge is produced, the reagent cost is high, and the device is easily corroded. Photocatalytic oxidation treatment of pollutants has the characteristics of easy operation and control, the use of solar energy for catalytic degradation, strong oxidation ability, and no secondary pollution. However, the photocatalytic quantum efficiency of this method is low, the utilization rate of solar energy is low, and the powdered photocatalyst has problems such as difficulty in recycling.

The adsorption method uses porous solids or flocs to adsorb the drugs in the wastewater to the surface or internal micropores, so as to achieve the purpose of effectively separating pollutants in the environment. The adsorption method has the advantages of simple operation, no highly toxic metabolites, wide source of adsorbents, and recyclability, but the adsorbents have the problems of low removal rate or high cost. Therefore, how to improve the removal rate of adsorbents and find economical and easily available adsorbents is the key to using adsorbents to remove drugs in wastewater.

SUMMARY OF THE INVENTION

1. The problem to be solved

Aiming at the problem of poor adsorption effect of adsorbents in the prior art, the present invention provides a method for preparing a biomass adsorbent for removing refractory organic pollutants. The leaf powder is acidified and then loaded with metal ions, the pore area and active adsorption sites of the adsorbent are increased, the adsorption capacity is increased, and the problem of poor adsorption effect of the adsorbent is solved.

Further, the present invention also provides a biomass adsorbent prepared by the above method for removing refractory organic pollutants, and an adsorbent prepared from acidified corn husk leaves, which has a remarkable adsorption effect.

Further, the present invention provides a method for adsorbing levofloxacin or tetracycline hydrochloride using the above adsorbent, which not only solves the problem of agricultural waste treatment and disposal, realizes secondary utilization, but also reduces drug pollution in water bodies.

2. Technical solutions

In order to solve the above problems, the technical scheme adopted in the present invention is as follows:

The present invention provides a preparation method of a biomass adsorbent for removing refractory organic pollutants. The specific preparation steps are as follows:

S100, after the plant leaves are washed and dried, pulverized and sieved to obtain powder to be treated; the plant leaves are corn husks;

S200, adding 0.1 mol/L sulfuric acid solution to the powder to be treated according to the ratio of 1 g: 25 ml, and stirring and reacting for 24 h to obtain acidified powder;

S300, the above acidified powder is taken out and washed to pH=6～8 of the supernatant, and dried to obtain the powder to be loaded;

S400, putting the above-mentioned powder to be loaded into the metal ion solution according to the ratio of 1g:20ml, stirring and reacting for 4h, and standing for 20h to obtain a mixed solution;

S500, slowly add sodium hydroxide solution dropwise to the above mixed solution to pH=5～7, stir and react for 1h, and let stand for 24h to obtain the loaded product;

S600, after filtering the loaded product, drying to obtain a biomass adsorbent.

Preferably, the drying temperature in S100 is 60°C.

Preferably, the stirring rate of the stirring reaction in S200 is 180 r/min.

Preferably, the concentration of the metal ion solution in S400 is 0.1-1.5 mol/L.

Preferably, the metal ions contained in the metal ion solution in S400 are one or both of zirconium ions and aluminum ions.

Preferably, the reaction temperature of the stirring reaction in S400 is 30° C., and the stirring rate is 180 r/min.

Preferably, the reaction temperature of the stirring reaction in S500 is 30° C., and the stirring rate is 120 r/min.

Preferably, the drying temperature in S600 is 40°C.

The present invention also provides a biomass adsorbent prepared by the above-mentioned preparation method for a biomass adsorbent for removing refractory organic pollutants.

The present invention also provides an application of the above-mentioned biomass adsorbent in removing refractory organic pollutants, wherein the refractory organic pollutants are antibiotics such as levofloxacin or tetracycline hydrochloride.

3. Beneficial effects

Compared with the prior art, the beneficial effects of the present invention are:

(1) a preparation method of a biomass adsorbent for removing refractory organic pollutants of the present invention, using agricultural waste corn husks as raw materials, the adsorbent preparation raw materials are easily available, and waste recycling is realized; The bract leaf powder is acidified and then loaded with metal ions, the adsorbent preparation process is simple, and the operating cost is low; acidification treatment increases the pore area and active adsorption sites of the adsorbent, and the adsorption capacity increases, which solves the problem of poor adsorption effect of the adsorbent. .

(2) A preparation method of a biomass adsorbent for removing refractory organic pollutants of the present invention, the drying temperature is 40°C or 60°C, the reaction temperature is 30°C, the treatment process conditions are mild, and it is suitable for popularization and use.

(3) A kind of biomass adsorbent for removing refractory organic pollutants of the present invention, the present invention uses agricultural wastes as raw materials, and utilizes corn husk leaves to prepare modified biomass by acidification or alkalization and loading metal ions The material adsorbent can adsorb a variety of drugs in the water body, has low cost, is economical and environmentally friendly, and has a wide range of applications; the adsorbent can adsorb levofloxacin and tetracycline hydrochloride, so as to achieve the purpose of controlling drug pollution; the invention has the advantages of waste reuse, It has the characteristics of wide source of raw materials, simple preparation and strong adsorption capacity of the adsorbent.

Detailed ways

The present invention is described in detail below with reference to specific exemplary embodiments. However, it should be understood that various modifications and variations can be made without departing from the scope of the present invention as defined by the appended claims. The detailed description is to be regarded as illustrative only and not restrictive, and if any such modifications and variations exist, they will fall within the scope of the invention described herein. In addition, the background art is intended to illustrate the research and development status and significance of the present technology, and is not intended to limit the present invention or the application and application fields of the present invention.

Example 1

A preparation method of a biomass adsorbent for removing refractory organic pollutants of the present invention, the specific steps are as follows,

S100, after washing and drying the plant leaves, pulverizing and sieving to obtain the powder to be treated; the plant leaves are corn husk leaves; and the drying temperature is 60°C;

S200, adding the to-be-treated powder into a 0.1 mol/L sulfuric acid solution according to a ratio of 1 g:25 ml, and stirring the reaction for 24 h at a stirring rate of 180 r/min to obtain acidified powder;

S300, the above acidified powder is taken out and washed to pH=6～8 of the supernatant, and dried to obtain the powder to be loaded;

S400, put the above-mentioned powder to be loaded into the metal ion solution according to the ratio of 1g:20ml, the reaction temperature is 30°C, the stirring rate is 180r/min, the stirring reaction is 4h, and the mixed solution is obtained by standing for 20h; The concentration of the metal ion solution is 0.1～1.5mol/L, and the metal ion contained in the metal ion solution is one or both of zirconium ion and aluminum ion;

S500. Slowly add sodium hydroxide solution dropwise to the above mixed solution to pH=5～7, the reaction temperature is 30°C, the stirring rate is 120r/min, the reaction is stirred for 1h, and left to stand for 24h to obtain the loaded product;

S600 , after filtering the loaded product, drying is performed at a drying temperature of 40° C. to obtain a biomass adsorbent.

The invention adopts the treatment method of acid, which destroys the structure of corn husk, reduces the polymerization degree and crystallinity of cellulose, can form a swollen porous structure, and increases the pore area and active adsorption site of the adsorbent. , the adsorption capacity increased. It is worth noting that the present invention adopts sulfuric acid for acidification treatment, which is more conducive to the hydrolysis of cellulose and hemicellulose, destroys the structure of corn husks, reduces the degree of polymerization and crystallinity of cellulose, and can form swollen cellulose. The porous structure increases the pore area and active adsorption sites of the adsorbent, resulting in a significant increase in the adsorption capacity.

The present invention also provides a biomass adsorbent prepared by the above method, an adsorbent prepared from acidified corn husk leaves, and the adsorption effect is remarkable. The invention uses agricultural waste as raw material, and utilizes corn husk leaves to prepare a modified biomass material adsorbent through acidification or alkalization and loading metal ions, which can adsorb a variety of drugs in water, has low cost, is economical and environmentally friendly, and is suitable for Wide. Using the biomass adsorbent of the present invention to remove organic pollutants in water, such as levofloxacin or tetracycline hydrochloride, not only solves the problem of agricultural waste treatment and disposal, realizes secondary utilization, but also reduces drug pollution in water.

In this embodiment, the specific preparation steps are as follows,

S100, after washing the corn husk leaves, drying at 60°C, and crushing through an 80-mesh sieve to obtain powder to be treated;

S200, adding the to-be-treated powder into a 0.1 mol/L sulfuric acid solution according to a ratio of 1 g:25 ml, and stirring the reaction for 24 h at a stirring rate of 180 r/min to obtain acidified powder;

S300, the above acidified powder is taken out and washed to pH=6～8 of the supernatant, and dried to obtain the powder to be loaded;

S400, put the above-mentioned powder to be loaded into a 0.5mol/L zirconium ion solution according to the ratio of 1g:20ml, the reaction temperature is 30°C, the stirring rate is 180r/min, the stirring reaction is 4h, and the mixture is left for 20h to obtain a mixed solution;

S500, slowly add sodium hydroxide solution dropwise to the above mixed solution to pH=6, the reaction temperature is 30° C., the stirring rate is 120 r/min, the reaction is stirred for 1 h, and left to stand for 24 h to obtain the loaded product;

S600 , after filtering the loaded product, drying is performed at a drying temperature of 40° C. to obtain a biomass adsorbent.

Put 0.1g of the above biomass adsorbent into 50ml, 100mg/L, pH 3 levofloxacin solution, after 24h adsorption reaction at 30℃, the adsorption capacity can reach 35mg/g. Put 0.1g of the above biomass adsorbent into 50ml, 200mg/L, pH 7 tetracycline hydrochloride solution, after 24h adsorption reaction at 30℃, the adsorption capacity can reach 100mg/g.

More particularly, although exemplary embodiments of the present invention have been described herein, the present invention is not limited to these embodiments, but includes modifications, omissions, Any and all embodiments such as combinations, adaptations and/or substitutions between the various embodiments. The definitions in the claims are to be construed broadly according to the language used in the claims, and are not limited to the examples described in the foregoing detailed description or during the practice of this application, which examples are to be considered non-exclusive. Any steps recited in any method or process claims may be performed in any order and are not limited to the order presented in the claims. Accordingly, the scope of the invention should be determined only by the appended claims and their legal equivalents, rather than by the description and examples given above.

Claims (10)

1. A preparation method of a biomass adsorbent for removing refractory organic pollutants is characterized by comprising the following steps: the preparation method comprises the following specific steps of,

s100, cleaning and drying plant leaves, and crushing and sieving to obtain powder to be treated; the plant leaves are corn bracts;

s200, mixing the powder to be treated according to the weight ratio of 1 g: adding 0.1mol/L sulfuric acid solution into 25ml of the mixture, and stirring the mixture to react for 24 hours to obtain acidified powder;

s300, taking the acidified powder out, washing the acidified powder to obtain supernatant, wherein the pH value of the supernatant is 6-8, and drying to obtain powder to be loaded;

s400, mixing the powder to be loaded according to the weight ratio of 1 g: 20ml of the solution is put into the metal ion solution, stirred and reacted for 4 hours, and kept stand for 20 hours to obtain a mixed solution;

s500, dropwise and slowly adding a sodium hydroxide solution into the mixed solution until the pH value is 5-7, stirring for reaction for 1 hour, and standing for 24 hours to obtain a load product;

s600, filtering the load product, and drying to obtain the biomass adsorbent.

2. The preparation method of the biomass adsorbent for removing the refractory organic pollutants as claimed in claim 1, wherein the preparation method comprises the following steps: the drying temperature in S100 is 60 ℃.

3. The preparation method of the biomass adsorbent for removing the refractory organic pollutants as claimed in claim 1, wherein the preparation method comprises the following steps: the stirring rate of the stirring reaction in S200 is 180 r/min.

4. The preparation method of the biomass adsorbent for removing the refractory organic pollutants as claimed in claim 1, wherein the preparation method comprises the following steps: the concentration of the metal ion solution in S400 is 0.1-1.5 mol/L.

5. The preparation method of the biomass adsorbent for removing the refractory organic pollutants as claimed in claim 1, wherein the preparation method comprises the following steps: the metal ions contained in the metal ion solution in S400 are one or both of zirconium ions and aluminum ions.

6. The preparation method of the biomass adsorbent for removing the refractory organic pollutants as claimed in claim 1, wherein the preparation method comprises the following steps: the reaction temperature of the stirring reaction in S400 was 30 ℃ and the stirring rate was 180 r/min.

7. The preparation method of the biomass adsorbent for removing the refractory organic pollutants as claimed in claim 1, wherein the preparation method comprises the following steps: the reaction temperature of the stirring reaction in S500 was 30 ℃ and the stirring rate was 120 r/min.

8. The preparation method of the biomass adsorbent for removing the refractory organic pollutants as claimed in claim 1, wherein the preparation method comprises the following steps: the drying temperature in S600 is 40 ℃.

9. The biomass adsorbent prepared by the preparation method of the biomass adsorbent for removing the refractory organic pollutants in any one of claims 1 to 8.

10. Use of the biomass adsorbent of any one of claim 9 for removing refractory organic pollutants, said refractory organic pollutants being levofloxacin or tetracycline hydrochloride.