CN112023925A - Preparation method and application of livestock and poultry manure biochar loaded nano zero-valent iron composite material - Google Patents
Preparation method and application of livestock and poultry manure biochar loaded nano zero-valent iron composite material Download PDFInfo
- Publication number
- CN112023925A CN112023925A CN202010894905.3A CN202010894905A CN112023925A CN 112023925 A CN112023925 A CN 112023925A CN 202010894905 A CN202010894905 A CN 202010894905A CN 112023925 A CN112023925 A CN 112023925A
- Authority
- CN
- China
- Prior art keywords
- livestock
- composite material
- biochar
- valent iron
- nano zero
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the field of waste resource utilization and the technical field of water treatment, and discloses a preparation method of a livestock and poultry manure biochar loaded nano zero-valent iron composite material and application of the composite material in rapid removal of sulfamethoxazole. The preparation method of the livestock and poultry manure biochar loaded nano zero-valent iron composite material comprises the following steps: (1) drying livestock and poultry feces to constant weight, heating and cracking to obtain biochar, soaking the biochar in mixed acid of hydrochloric acid and hydrofluoric acid, washing with water to pH6.7-7.3, drying to constant weight, grinding, and sieving; (2) adding the biochar obtained by sieving into a ferrous sulfate solution, uniformly stirring, and slowly dropwise adding a sodium borohydride solution under the protection of nitrogen to obtain a suspension; (3) and (4) carrying out suction filtration on the suspension, washing, drying, and then grinding into powder. The biochar loaded nano zero-valent iron composite material prepared by the method has a good degradation effect on wastewater containing sulfamethoxazole and/or sulfisoxazole, is strong in stability and can be recycled.
Description
Technical Field
The invention relates to the field of waste resource utilization and the technical field of water treatment, in particular to a preparation method of a livestock and poultry manure biochar loaded nano zero-valent iron composite material and application thereof in quickly removing sulfamethoxazole and/or sulfisoxazole.
Background
In recent years, with the increase of antibiotic varieties, antibiotics are increasingly widely used, wherein Sulfamethoxazole (SMX) is one of common antibiotics and is frequently detected in water environment. The long-term residual SMX has great harm to the stability of a water body ecosystem and human health, however, the traditional sewage treatment technology is difficult to realize the effective removal of SMX antibiotics.
In the prior art, for example, patent CN104261504 discloses a method for removing sulfamethoxazole in water by using modified bamboo charcoal, which comprises the steps of sequentially crushing the bamboo charcoal, carrying iron oxide by ultrasonic treatment and impregnation, and freeze-drying to obtain the modified bamboo charcoal, and using the modified bamboo charcoal as a filler or an adsorbent to adsorb and remove the sulfamethoxazole in the water, but the method needs a large amount of adsorbent, has long adsorption time and is low in efficiency. For another example, patent CN106914216 discloses a method for preparing animal manure biochar and removing sulfonamide antibiotics in water, which comprises the following steps: (1) drying the livestock and poultry manure to constant weight, and preparing the dried livestock and poultry manure into biochar through high-temperature thermal cracking in a muffle furnace; (2) using the livestock and poultry manure biochar obtained in the step (1) in a ratio of 1:1, soaking in mixed acid of hydrochloric acid and hydrofluoric acid, washing with water to about neutral, drying to constant weight, grinding, and sieving; (3) and (3) putting the charcoal adsorbent obtained in the step (2) into a water body containing sulfonamide antibiotics to adsorb and remove the sulfonamide antibiotics, wherein the method also has the problem of low efficiency, and the maximum adsorption amount needs 24 hours.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provides a preparation method of a livestock and poultry manure biochar loaded nano zero-valent iron composite material and application of the composite material in quickly removing sulfamethoxazole and/or sulfisoxazole. According to the invention, the dried animal manure biochar is added into a ferrous sulfate solution, then sodium borohydride is added under a nitrogen environment, and the mixture is stirred and mixed uniformly, so that the biochar-loaded nano zero-valent iron composite material has a good degradation effect on wastewater containing sulfamethoxazole and/or sulfisoxazole, is strong in stability, and can be recycled.
In order to achieve the aim of the invention, the preparation method of the livestock and poultry manure biochar loaded nano zero-valent iron composite material comprises the following steps:
(1) drying the livestock and poultry manure to constant weight, heating and cracking the dried livestock and poultry manure to prepare biochar, and mixing the obtained livestock and poultry manure biochar with a raw material according to a volume ratio of 1: soaking in 0.8-1.2% mixed acid of hydrochloric acid and hydrofluoric acid, washing with water to pH6.7-7.3, oven drying to constant weight, grinding, and sieving;
(2) adding the biochar obtained by sieving in the step (1) into a ferrous sulfate solution, stirring and mixing uniformly, and slowly dropwise adding a sodium borohydride solution under the protection of nitrogen to obtain a suspension;
(3) and (3) carrying out suction filtration on the turbid liquid obtained in the step (2), cleaning, drying in a vacuum oven, and grinding into powder to obtain the livestock and poultry manure biochar loaded nano zero-valent iron composite material.
Preferably, in some embodiments of the present invention, the volume ratio of hydrochloric acid to hydrofluoric acid in the step (1) is 1: 1.
preferably, in some embodiments of the present invention, the livestock manure is cow manure.
Further, the cracking is to grind the livestock and poultry manure to 2-6cm, seal the manure with tin foil paper, and thermally crack the manure for 5-7 hours at the high temperature of 650 ℃ in the absence of oxygen at 550-.
Further, the concentration of hydrochloric acid in the step (1) is 0.9-1.1mol/L, and the concentration of hydrofluoric acid is 0.9-1.1 mol/L.
Further, the soaking time in the step (1) is 10-14h, the soaking process is accompanied by mechanical stirring, and the soaking process is repeated for 2-4 times.
Further, the drying is carried out for 22-26h at the temperature of 55-65 ℃ until the constant weight is achieved.
Further, the sieving is 60-mesh sieving.
Further, the concentration of the ferrous sulfate solution is 0.035-0.045 mol/L.
Further, the concentration of the sodium borohydride solution is 0.09-0.11mol/L, and the dropping speed is 12-14 mL/min.
Further, the molar ratio of the sodium borohydride solution to the ferrous sulfate solution is 2: 1.
Further, the washing in the step (3) is washing with water.
Further, the temperature of the oven in the step (3) is 55-65 ℃, and the drying time is 7-9 h.
Further, the mass ratio of carbon to iron in the livestock manure biochar loaded nano zero-valent iron composite material is 1/4-1/2, or 3.
Preferably, in some embodiments of the invention, the mass ratio of carbon to iron in the livestock and poultry manure biochar-loaded nano zero-valent iron composite is 1:4, 1:3, 1:2 or 3:1, and more preferably 1: 3.
On the other hand, the invention also provides application of the livestock and poultry manure biochar loaded nano zero-valent iron composite material, namely the livestock and poultry manure biochar loaded nano zero-valent iron composite material is added into a solution containing sulfamethoxazole and/or sulfisoxazole to remove the sulfamethoxazole.
Preferably, in the application of the livestock and poultry manure biochar loaded nano zero-valent iron composite material, the ratio of the initial concentration of sulfamethoxazole and sulfisoxazole in the solution containing sulfamethoxazole and/or sulfisoxazole to the mass of the livestock and poultry manure biochar loaded nano zero-valent iron composite material added is 0.9-1.2 g/L: 5g of the total weight.
Further, the pH of the sulfamethoxazole and/or sulfisoxazole-containing solution is 2 to 10, preferably 4 to 10, and more preferably 4 to 6.
Compared with the prior art, the invention has the following advantages:
(1) the biochar used in the invention is formed by converting livestock and poultry manure waste, so that the raw material cost is low, and the resource utilization of waste biomass is realized;
(2) the livestock and poultry manure biochar loaded nano zero-valent iron composite material prepared by the method has an excellent removal effect on sulfamethoxazole wastewater, the removal rate of the sulfamethoxazole can reach over 99% within 0.5 hour, and the livestock and poultry manure biochar can be repeatedly utilized for 5 times and still reach 75%. The material has excellent removal effect on the sulfisoxazole, the removal rate can reach 99% in 0.5 hour, and the material can be repeatedly used for 10 times and still reach over 75%.
Drawings
FIG. 1 is an XPS diagram of cow dung Biochar (BC), cow dung biochar loaded nano zero-valent iron composite (BC/nZVI);
FIG. 2 is a fragmentary detail view of Fe in the XPS plot of the cow dung biochar-supported nano zero-valent iron composite (BC/nZVI) of FIG. 1;
FIG. 3 is a comparison graph of the dynamics curve of removing sulfamethoxazole from the animal manure biochar loaded nano zero-valent iron composite material prepared by different mass ratios of C/Fe;
FIG. 4 is a comparative graph of cow dung charcoal-loaded nano zero-valent iron composite material of the present invention with C: Fe ═ 1:3, in which sulfamethoxazole is removed under different pH values.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
Furthermore, the description below of the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily for the same embodiment or example. Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
The preparation steps of the C/Fe-1: 1 biochar loaded nano zero-valent iron composite material are as follows:
(1) taking cow dung, drying to constant weight, carrying out high-temperature thermal cracking for 6 hours in a muffle furnace at 600 ℃ to prepare biochar, and carrying out thermal cracking on the biochar by using a raw material formula 1:1, soaking in mixed acid of hydrochloric acid and hydrofluoric acid (the concentration of the hydrochloric acid is 1mol/L and the concentration of the hydrofluoric acid is 1mol/L), washing with water to be about neutral, drying at 60 ℃ for 24 hours to constant weight, grinding, and sieving with a 60-mesh sieve;
(2)1.861g of ferrous sulfate heptahydrate is added into 250mL of water, 0.375g of cow dung biochar which is sieved by a 60-mesh sieve in the step (1) is added, and the mixture is stirred and mixed uniformly;
(3) under nitrogen (nitrogen flow rate 20mL/min), 0.5087g of NaBH was added4Slowly dripping the solution dissolved in 200mL of water into the solution obtained in the step (2) to obtain suspension;
(4) carrying out suction filtration on the suspension obtained in the step (3), cleaning for three times, and then drying for 8h at the temperature of 60 ℃ in vacuum;
(5) and (4) grinding the biochar-loaded nano zero-valent iron blocks obtained in the step (4) into powder to obtain the C/Fe-1: 1 biochar-loaded nano zero-valent iron composite material.
The experiment for degrading sulfamethoxazole by using the biochar-loaded nano zero-valent iron composite material is carried out in a 1L three-neck flask, the initial concentration Co of 250mL of simulated sulfamethoxazole in a reaction system is 100mg/L, and the adding amount of the biochar-loaded nano zero-valent iron composite material is 0.5 g. In the reaction process, the rotating speed of the magnetic stirrer is 200r/min, so that the biochar-loaded nano zero-valent iron composite material is fully and uniformly mixed with the solution, 250 mu L of supernatant fluid is extracted from the reaction system within a set time and filtered by a 45nm filter membrane, and the change of the sulfamethoxazole concentration along with the time is measured, and the result is shown in figure 3. The example has the same effect on removing the sulfamethoxazole as the sulfamethoxazole, and can be recycled at least 5 times.
Example 2
The preparation method of the catalytic material with Fe-1: 2 biochar loaded with nano zero-valent iron comprises the following steps:
(1) taking cow dung, drying to constant weight, carrying out high-temperature thermal cracking for 6 hours in a muffle furnace at 600 ℃ to prepare biochar, and carrying out thermal cracking on the biochar by using a raw material formula 1:1, soaking in mixed acid of hydrochloric acid and hydrofluoric acid (the concentration of the hydrochloric acid is 1mol/L and the concentration of the hydrofluoric acid is 1mol/L), washing with water to be about neutral, drying at 60 ℃ for 24 hours to constant weight, grinding, and sieving with a 60-mesh sieve;
(2)2.8421g of ferrous sulfate heptahydrate is added into 250mL of water, 0.25g of cow dung biochar which is sieved by a 60-mesh sieve in the step (1) is added, and the mixture is stirred and mixed uniformly;
(3) under nitrogen (nitrogen flow rate 40mL/min), 0.6786g of NaBH was added4Slowly dripping the solution dissolved in 200mL of water into the solution obtained in the step (2) to obtain suspension;
(4) carrying out suction filtration on the suspension obtained in the step (3), cleaning for three times, and then drying for 8h at the temperature of 60 ℃ in vacuum;
(5) and (4) grinding the biochar-loaded nano zero-valent iron blocks obtained in the step (4) into powder to obtain the biochar-loaded nano zero-valent iron composite material with the ratio of C/Fe to 1: 2.
The experiment for degrading sulfamethoxazole by using the biochar-loaded nano zero-valent iron composite material is carried out in a 1L three-neck flask, the initial concentration Co of 250mL of simulated sulfamethoxazole in a reaction system is 100mg/L, and the adding amount of the biochar-loaded nano zero-valent iron composite material is 0.5 g. In the reaction process, the rotating speed of the magnetic stirrer is 200r/min, so that the biochar-loaded nano zero-valent iron composite material is fully and uniformly mixed with the solution, 250 mu L of supernatant fluid is extracted from the reaction system within a set time and filtered by a 45nm filter membrane, and the change of the sulfamethoxazole concentration along with the time is measured, and the result is shown in figure 3. The example has the same effect on removing the sulfamethoxazole as the sulfamethoxazole, and can be recycled at least 5 times.
Example 3
The preparation method of the catalytic material with Fe-1: 3 biochar loaded with nano zero-valent iron comprises the following steps:
(1) taking cow dung, drying to constant weight, carrying out high-temperature thermal cracking for 6 hours in a muffle furnace at 600 ℃ to prepare biochar, and carrying out thermal cracking on the biochar by using a raw material formula 1:1, soaking in mixed acid of hydrochloric acid and hydrofluoric acid (the concentration of the hydrochloric acid is 1mol/L and the concentration of the hydrofluoric acid is 1mol/L), washing with water to be about neutral, drying at 60 ℃ for 24 hours to constant weight, grinding, and sieving with a 60-mesh sieve;
(2)2.7924g of ferrous sulfate heptahydrate is added into 250mL of water, 0.1875g of cow dung biochar which is sieved by a 60-mesh sieve in the step (1) is added, and the mixture is stirred and mixed uniformly;
(3) under nitrogen (nitrogen flow rate 30mL/min), 0.7633g of NaBH was added4Slowly dripping the solution dissolved in 200mL of water into the solution obtained in the step (2) to obtain suspension;
(4) carrying out suction filtration on the suspension obtained in the step (3), cleaning for three times, and then drying for 8h at the temperature of 60 ℃ in vacuum;
(5) and (4) grinding the biochar-loaded nano zero-valent iron blocks obtained in the step (4) into powder to obtain the biochar-loaded nano zero-valent iron composite material with the ratio of C/Fe to 1: 3.
The experiment for degrading sulfamethoxazole by using the biochar-loaded nano zero-valent iron composite material is carried out in a 1L three-neck flask, the initial concentration Co of 250mL of simulated sulfamethoxazole in a reaction system is 100mg/L, and the adding amount of the biochar-loaded nano zero-valent iron composite material is 0.5 g. In the reaction process, the rotating speed of the magnetic stirrer is 200r/min, so that the biochar-loaded nano zero-valent iron composite material is fully and uniformly mixed with the solution, 250 mu L of supernatant fluid is extracted from the reaction system within a set time and filtered by a 45nm filter membrane, and the change of the sulfamethoxazole concentration along with the time is measured, and the result is shown in figure 3. The example has the same effect on removing the sulfamethoxazole as the sulfamethoxazole, and can be recycled at least 5 times.
Example 4
The preparation method of the catalytic material with Fe-1: 4 biochar loaded with nano zero-valent iron comprises the following steps:
(1) taking cow dung, drying to constant weight, carrying out high-temperature thermal cracking for 6 hours in a muffle furnace at 600 ℃ to prepare biochar, and carrying out thermal cracking on the biochar by using a raw material formula 1:1, soaking in mixed acid of hydrochloric acid and hydrofluoric acid (the concentration of the hydrochloric acid is 1mol/L and the concentration of the hydrofluoric acid is 1mol/L), washing with water to be about neutral, drying at 60 ℃ for 24 hours to constant weight, grinding, and sieving with a 60-mesh sieve;
(2)2.9786g of ferrous sulfate heptahydrate is added into 250mL of water, 0.15g of cow dung biochar which is sieved by a 60-mesh sieve in the step (1) is added, and the mixture is stirred and mixed uniformly;
(3) under nitrogen (nitrogen flow rate 30mL/min), 0.8143g of NaBH was added4Slowly dripping the solution dissolved in 200mL of water into the solution obtained in the step (2) to obtain suspension;
(4) carrying out suction filtration on the suspension obtained in the step (3), cleaning for three times, and then drying for 8h at the temperature of 60 ℃ in vacuum;
(5) and (4) grinding the biochar-loaded nano zero-valent iron blocks obtained in the step (4) into powder to obtain the biochar-loaded nano zero-valent iron composite material with the ratio of C/Fe to 1: 4.
The experiment for degrading sulfamethoxazole by using the biochar-loaded nano zero-valent iron composite material is carried out in a 1L three-neck flask, the initial concentration Co of 250mL of simulated sulfamethoxazole in a reaction system is 100mg/L, and the adding amount of the biochar-loaded nano zero-valent iron composite material is 0.5 g. In the reaction process, the rotating speed of the magnetic stirrer is 200r/min, so that the biochar-loaded nano zero-valent iron composite material is fully and uniformly mixed with the solution, 250 mu L of supernatant fluid is extracted from the reaction system within a set time and filtered by a 45nm filter membrane, and the change of the sulfamethoxazole concentration along with the time is measured, and the result is shown in figure 3. The example has the same effect on removing the sulfamethoxazole as the sulfamethoxazole, and can be recycled at least 5 times.
Example 5
The preparation steps of the composite material of the charcoal-loaded nano zero-valent iron with Fe being 2:1 are as follows:
(1) taking cow dung, drying to constant weight, carrying out high-temperature thermal cracking for 6 hours in a muffle furnace at 600 ℃ to prepare biochar, and carrying out thermal cracking on the biochar by using a raw material formula 1:1, soaking in mixed acid of hydrochloric acid and hydrofluoric acid (the concentration of the hydrochloric acid is 1mol/L and the concentration of the hydrofluoric acid is 1mol/L), washing with water to be about neutral, drying at 60 ℃ for 24 hours to constant weight, grinding, and sieving with a 60-mesh sieve;
(2)1.2411g of ferrous sulfate heptahydrate is added into 250mL of water, 0.5g of cow dung biochar which is sieved by a 60-mesh sieve in the step (1) is added, and the mixture is stirred and mixed uniformly;
(3) under nitrogen (nitrogen flow rate 40mL/min), 0.339g NaBH4Slowly dripping the solution dissolved in 200mL of water into the solution obtained in the step (2);
(4) carrying out suction filtration on the suspension obtained in the step (3), cleaning for three times, and then drying for 8h at the temperature of 60 ℃ in vacuum;
(5) and (4) grinding the biochar-loaded nano zero-valent iron blocks obtained in the step (4) into powder to obtain the biochar-loaded nano zero-valent iron composite material with the ratio of C/Fe to 2: 1.
The experiment for degrading sulfamethoxazole by using the biochar-loaded nano zero-valent iron composite material is carried out in a 1L three-neck flask, the initial concentration Co of 250mL of simulated sulfamethoxazole in a reaction system is 100mg/L, and the adding amount of the biochar-loaded nano zero-valent iron composite material is 0.5 g. In the reaction process, the rotating speed of the magnetic stirrer is 200r/min, so that the biochar-loaded nano zero-valent iron composite material is fully and uniformly mixed with the solution, 250 mu L of supernatant fluid is extracted from the reaction system within a set time and filtered by a 45nm filter membrane, and the change of the sulfamethoxazole concentration along with the time is measured, and the result is shown in figure 3. The example has the same effect on removing the sulfamethoxazole as the sulfamethoxazole, and can be recycled at least 5 times.
Example 6
The preparation steps of the composite material of Fe-3: 1 biochar loaded with nano zero-valent iron are as follows:
(1) taking cow dung, drying to constant weight, carrying out high-temperature thermal cracking for 6 hours in a muffle furnace at 600 ℃ to prepare biochar, and carrying out thermal cracking on the biochar by using a raw material formula 1:1, soaking in mixed acid of hydrochloric acid and hydrofluoric acid (the concentration of the hydrochloric acid is 1mol/L and the concentration of the hydrofluoric acid is 1mol/L), washing with water to be about neutral, drying at 60 ℃ for 24 hours to constant weight, grinding, and sieving with a 60-mesh sieve;
(2)0.9929g of ferrous sulfate heptahydrate is added into 250mL of water, 0.6g of cow dung biochar which is sieved by a 60-mesh sieve in the step (1) is added, and the mixture is stirred and mixed uniformly;
(3) under nitrogen (nitrogen flow rate 50mL/min), 0.2714g of NaBH was added4Slowly dripping the solution dissolved in 200mL of water into the solution obtained in the step (2);
(4) carrying out suction filtration on the suspension obtained in the step (3), cleaning for three times, and then drying for 8h at the temperature of 60 ℃ in vacuum;
(5) and (4) grinding the biochar-loaded nano zero-valent iron blocks obtained in the step (4) into powder to obtain the biochar-loaded nano zero-valent iron composite material with the ratio of C to Fe to 3 to 1.
The experiment for degrading sulfamethoxazole by using the biochar-loaded nano zero-valent iron composite material is carried out in a 1L three-neck flask, the initial concentration Co of 250mL of simulated sulfamethoxazole in a reaction system is 100mg/L, and the adding amount of the biochar-loaded nano zero-valent iron composite material is 0.5 g. In the reaction process, the rotating speed of the magnetic stirrer is 200r/min, so that the biochar-loaded nano zero-valent iron composite material is fully and uniformly mixed with the solution, 250 mu L of supernatant fluid is extracted from the reaction system within a set time and filtered by a 45nm filter membrane, and the change of the sulfamethoxazole concentration along with the time is measured, and the result is shown in figure 3. The example has the same effect on removing the sulfamethoxazole as the sulfamethoxazole, and can be recycled at least 5 times.
Example 7
The reaction steps of the composite material of Fe-1: 3 biochar loaded nano zero-valent iron and initial water pH-2 sulfamethoxazole solution are as follows:
(1) 250mL sulfamethoxazole with the initial concentration Co of 100mg/L, pH ═ 2 is prepared;
(2) adding the sulfamethoxazole solution in the step (1) into a three-neck flask with the volume of 1L, and adding 0.5g of the biochar-supported nano zero-valent iron composite material prepared in the example 3 for reaction;
(3) setting the rotating speed of the electric stirrer to 200r/min, and fully and uniformly mixing the biochar-loaded nano zero-valent iron composite material with the solution;
(4) 250. mu.L of the supernatant was extracted from the reaction system over a 45nm mixed cellulose filter for a predetermined period of time, and the change in sulfamethoxazole concentration with time was measured, and the results are shown in FIG. 4. The example has the same effect on removing the sulfamethoxazole as the sulfamethoxazole, and can be recycled at least 5 times.
Example 8
The reaction steps of the composite material of Fe-1: 3 biochar loaded nano zero-valent iron and initial water pH-4 sulfamethoxazole solution are as follows:
(1) 250mL sulfamethoxazole with the initial concentration Co of 100mg/L, pH ═ 4 is prepared;
(2) adding the sulfamethoxazole solution in the step (1) into a three-neck flask with the volume of 1L, and adding 0.5g of the biochar-supported nano zero-valent iron composite material prepared in the example 3 for reaction;
(3) setting the rotating speed of the electric stirrer to 200r/min, and fully and uniformly mixing the biochar-loaded nano zero-valent iron composite material with the solution;
(4) 250. mu.L of the supernatant was extracted from the reaction system over a 45nm mixed cellulose filter for a predetermined period of time, and the change in sulfamethoxazole concentration with time was measured, and the results are shown in FIG. 4. The example has the same effect on removing the sulfamethoxazole as the sulfamethoxazole, and can be recycled at least 5 times.
Example 9
The reaction of the composite material of Fe-1: 3 biochar loaded nano zero-valent iron and initial water sulfamethoxazole solution comprises the following steps:
(1) 250mL sulfamethoxazole with the initial concentration Co of 100mg/L, pH ═ 6 is prepared;
(2) adding the sulfamethoxazole solution in the step (1) into a three-neck flask with the volume of 1L, and adding 0.5g of the biochar-supported nano zero-valent iron composite material prepared in the example 3 for reaction;
(3) setting the rotating speed of the electric stirrer to 200r/min, and fully and uniformly mixing the biochar-loaded nano zero-valent iron composite material with the solution;
(4) 250. mu.L of the supernatant was extracted from the reaction system over a 45nm mixed cellulose filter for a predetermined period of time, and the change in sulfamethoxazole concentration with time was measured, and the results are shown in FIG. 4. The example has the same effect on removing the sulfamethoxazole as the sulfamethoxazole, and can be recycled at least 5 times.
Example 10
The reaction steps of the composite material of Fe-1: 3 biochar loaded nano zero-valent iron and initial water pH-7 sulfamethoxazole solution are as follows:
(1) 250mL sulfamethoxazole with the initial concentration Co of 100mg/L, pH ═ 7 is prepared;
(2) adding the sulfamethoxazole solution in the step (1) into a three-neck flask with the volume of 1L, and adding 0.5g of the biochar-supported nano zero-valent iron composite material prepared in the example 3 for reaction;
(3) setting the rotating speed of the electric stirrer to 200r/min, and fully and uniformly mixing the biochar-loaded nano zero-valent iron composite material with the solution;
(4) 250. mu.L of the supernatant was extracted from the reaction system over a 45nm mixed cellulose filter for a predetermined period of time, and the change in sulfamethoxazole concentration with time was measured, and the results are shown in FIG. 4. This example showed comparable removal of sulfamethoxazole to sulfamethoxazole.
Example 11
The reaction steps of the composite material of Fe-1: 3 biochar loaded nano zero-valent iron and the initial water pH-10 sulfamethoxazole solution are as follows:
(1) 250mL sulfamethoxazole with the initial concentration Co of 100mg/L, pH ═ 10 is prepared;
(2) adding the sulfamethoxazole solution in the step (1) into a three-neck flask with the volume of 1L, and adding 0.5g of the biochar-supported nano zero-valent iron composite material prepared in the example 3 for reaction;
(3) setting the rotating speed of the electric stirrer to 200r/min, and fully and uniformly mixing the biochar-loaded nano zero-valent iron composite material with the solution;
(4) 250. mu.L of the supernatant was extracted from the reaction system over a 45nm mixed cellulose filter for a predetermined period of time, and the change in sulfamethoxazole concentration with time was measured, and the results are shown in FIG. 4. This example showed comparable removal of sulfamethoxazole to sulfamethoxazole.
FIG. 1 is an XPS diagram of cow dung biochar and cow dung biochar loaded nano zero-valent iron composite material. Fig. 2 is a partial detail view of Fe in fig. 1, and it can be seen from fig. 1 and fig. 2 that nano zero-valent iron particles are successfully loaded on the biochar carrier, and have little influence on the structure of the biochar material.
FIG. 3 is a comparison graph of the kinetics curves of the biological carbon loaded nano zero-valent iron composite material prepared by different carbon-iron ratios for degrading sulfamethoxazole. As can be seen from FIG. 3, when C/Fe is 3:1, the removal rate of sulfamethoxazole by the composite material of the biochar-loaded nano zero-valent iron after 0.5 hour of reaction is only about 70%; when C/Fe is 2: when the reaction time is 1, the removal rate of the composite material of the biochar loaded nano zero-valent iron to sulfamethoxazole is only about 19 percent after the reaction time is 0.5 hour; when C/Fe is 1:1, the removal rate of sulfamethoxazole by the composite material of the charcoal-loaded nano zero-valent iron is only about 25 percent after the reaction is carried out for 0.5 hour; with the increase of the content of the nano zero-valent iron, the removal effect of the composite material on sulfamethoxazole is enhanced, and when the C/Fe is 1:2, the removal rate of the composite material of the biochar loaded nano zero-valent iron on sulfamethoxazole is close to 100% after the reaction for 25 min; when C/Fe is 1:3, the removal rate of sulfamethoxazole by the biochar-supported nano zero-valent iron composite material reacting for 5min reaches 100%, when C/Fe is 1:4, the reaction time and the removal rate are basically consistent with those of the biochar-supported nano zero-valent iron composite material reacting for 1:3, and the biochar-supported nano zero-valent iron composite material reacting for 1:3 is the best material because the economic cost of the biochar-supported nano zero-valent iron composite material reacting for 1:3 is lower than that of the biochar-supported nano zero-valent iron composite material reacting for 1: 4.
FIG. 4 shows the relationship between the removal rate and the reaction time at different pH values of 1:3, and it can be seen that the reaction is fastest at weakly acidic pH values, but the difference between the reaction time and the removal rate is very small at neutral and weakly alkaline pH values.
It will be understood by those skilled in the art that the foregoing is only exemplary of the present invention, and is not intended to limit the invention, which is intended to cover any variations, equivalents, or improvements therein, which fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of a livestock and poultry manure biochar loaded nano zero-valent iron composite material is characterized by comprising the following steps:
(1) drying the livestock and poultry manure to constant weight, heating and cracking the dried livestock and poultry manure to prepare biochar, and mixing the obtained livestock and poultry manure biochar with a raw material according to a volume ratio of 1: soaking in 0.8-1.2% mixed acid of hydrochloric acid and hydrofluoric acid, washing with water to pH6.7-7.3, oven drying to constant weight, grinding, and sieving;
(2) adding the biochar obtained by sieving in the step (1) into a ferrous sulfate solution, stirring and mixing uniformly, and slowly dropwise adding a sodium borohydride solution under the protection of nitrogen to obtain a suspension;
(3) and (3) carrying out suction filtration on the turbid liquid obtained in the step (2), cleaning, drying in a vacuum oven, and grinding into powder to obtain the livestock and poultry manure biochar loaded nano zero-valent iron composite material.
2. The preparation method of the livestock and poultry manure biochar loaded nano zero-valent iron composite material according to claim 1, wherein the volume ratio of hydrochloric acid to hydrofluoric acid in the step (1) is 1: 1; preferably, the livestock manure is cow manure.
3. The preparation method of the livestock and poultry manure biochar loaded nano zero-valent iron composite material as claimed in claim 1, wherein the cracking is to crush the livestock and poultry manure to 2-6cm, seal the livestock and poultry manure with tinfoil paper, and thermally crack the livestock and poultry manure at 650 ℃ for 5-7 hours under the condition of oxygen deficiency of 550-; preferably, the concentration of hydrochloric acid in the step (1) is 0.9-1.1mol/L, and the concentration of hydrofluoric acid is 0.9-1.1 mol/L; preferably, the soaking time in the step (1) is 10-14h, the soaking process is accompanied by mechanical stirring, and the soaking process is repeated for 2-4 times.
4. The preparation method of the livestock and poultry manure biochar loaded nano zero-valent iron composite material as claimed in claim 1, wherein the drying to constant weight is drying at 55-65 ℃ for 22-26 h; preferably, the sieving is 60 mesh sieving.
5. The preparation method of the livestock and poultry manure biochar-loaded nano zero-valent iron composite material as claimed in claim 1, wherein the concentration of the ferrous sulfate solution is 0.035-0.045 mol/L; preferably, the concentration of the sodium borohydride solution is 0.09-0.11mol/L, and the dropping speed is 12-14 mL/min; preferably, the molar ratio of the sodium borohydride solution to the ferrous sulfate solution is 2: 1.
6. The preparation method of the livestock and poultry manure biochar-loaded nano zero-valent iron composite material as claimed in claim 1, wherein the cleaning in the step (3) is water cleaning; preferably, the oven temperature in the step (3) is 55-65 ℃, and the drying time is 7-9 h.
7. The preparation method of the livestock manure biochar-loaded nano zero-valent iron composite material as claimed in claim 1, wherein the mass ratio of carbon to iron in the livestock manure biochar-loaded nano zero-valent iron composite material is 1/4-1/2, or 3; preferably, the mass ratio of carbon to iron in the livestock and poultry manure biochar loaded nano zero-valent iron composite material is 1:4, 1:3, 1:2 or 3:1, and more preferably 1: 3.
8. The application of the livestock manure biochar loaded nano zero-valent iron composite material is characterized in that the livestock manure biochar loaded nano zero-valent iron composite material prepared by the preparation method of any one of claims 1 to 7 is added into a solution containing sulfamethoxazole and/or sulfisoxazole to remove the sulfamethoxazole.
9. The application of the livestock manure biochar loaded nano zero-valent iron composite material as claimed in claim 8, wherein the ratio of the initial concentration of sulfamethoxazole and sulfisoxazole in the solution containing sulfamethoxazole and/or sulfisoxazole to the mass of the livestock manure biochar loaded nano zero-valent iron composite material added is 0.9-1.2 g/L: 5g of the total weight.
10. The application of the livestock and poultry manure biochar loaded nano zero-valent iron composite material as claimed in claim 8, wherein the pH of the solution containing sulfamethoxazole and/or sulfisoxazole is 2-10, preferably the pH is 4-10, and more preferably the pH is 4-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010894905.3A CN112023925B (en) | 2020-08-31 | 2020-08-31 | Preparation method and application of livestock and poultry manure biochar loaded nano zero-valent iron composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010894905.3A CN112023925B (en) | 2020-08-31 | 2020-08-31 | Preparation method and application of livestock and poultry manure biochar loaded nano zero-valent iron composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112023925A true CN112023925A (en) | 2020-12-04 |
| CN112023925B CN112023925B (en) | 2023-04-07 |
Family
ID=73586841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010894905.3A Active CN112023925B (en) | 2020-08-31 | 2020-08-31 | Preparation method and application of livestock and poultry manure biochar loaded nano zero-valent iron composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112023925B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159267A (en) * | 2020-09-21 | 2021-01-01 | 中山大学 | Method for reducing pollution of sulfanilamide antibiotics and resistance genes thereof in maggot manure compost |
| CN113042000A (en) * | 2021-03-23 | 2021-06-29 | 福州大学 | Chicken manure derived biochar loaded nano zero-valent iron composite material and preparation method and application thereof |
| CN113403346A (en) * | 2021-07-01 | 2021-09-17 | 黑龙江省农业科学院农村能源与环保研究所 | Method for producing biogas by joint anaerobic fermentation of pig farm liquid dung and corn straws treated by biochar loaded with nano zero-valent iron |
| CN113857231A (en) * | 2021-08-18 | 2021-12-31 | 广东工业大学 | Preparation of iron-based biochar wave-absorbing material and method for repairing mercury-contaminated soil through microwave synergy |
| CN114105290A (en) * | 2021-11-24 | 2022-03-01 | 江苏泰源环保科技股份有限公司 | Preparation method and application of modified blue algae biochar loaded nano zero-valent iron material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106914216A (en) * | 2017-03-08 | 2017-07-04 | 井冈山大学 | A kind of preparation of feces of livestock and poultry charcoal and its method for removing sulfa antibiotics in water removal |
| CN108439570A (en) * | 2018-05-22 | 2018-08-24 | 徐建 | Charcoal loads nano zero valence iron activation sodium peroxydisulfate system and its preparation and application |
| CN109603751A (en) * | 2019-01-10 | 2019-04-12 | 生态环境部南京环境科学研究所 | A kind of preparation method of charcoal load zero-valent iron composite material |
| WO2019110568A1 (en) * | 2017-12-07 | 2019-06-13 | University Of Copenhagen | Composite comprising green rust and carbon for environmental remediation |
| CN110586038A (en) * | 2019-10-18 | 2019-12-20 | 华中农业大学 | Biochar loaded nano zero-valent iron material and application thereof |
| US20200024162A1 (en) * | 2019-03-28 | 2020-01-23 | Central South University | Method and device for sewage treatment |
| CN110898812A (en) * | 2019-11-30 | 2020-03-24 | 河南永泽环境科技有限公司 | Preparation method and application of novel magnetic microalgae-based complexing agent |
| CN111569831A (en) * | 2020-04-21 | 2020-08-25 | 哈尔滨工业大学 | Long-term stable biochar-zero-valent iron composite material and one-step preparation method thereof |
-
2020
- 2020-08-31 CN CN202010894905.3A patent/CN112023925B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106914216A (en) * | 2017-03-08 | 2017-07-04 | 井冈山大学 | A kind of preparation of feces of livestock and poultry charcoal and its method for removing sulfa antibiotics in water removal |
| WO2019110568A1 (en) * | 2017-12-07 | 2019-06-13 | University Of Copenhagen | Composite comprising green rust and carbon for environmental remediation |
| CN108439570A (en) * | 2018-05-22 | 2018-08-24 | 徐建 | Charcoal loads nano zero valence iron activation sodium peroxydisulfate system and its preparation and application |
| CN109603751A (en) * | 2019-01-10 | 2019-04-12 | 生态环境部南京环境科学研究所 | A kind of preparation method of charcoal load zero-valent iron composite material |
| US20200024162A1 (en) * | 2019-03-28 | 2020-01-23 | Central South University | Method and device for sewage treatment |
| CN110586038A (en) * | 2019-10-18 | 2019-12-20 | 华中农业大学 | Biochar loaded nano zero-valent iron material and application thereof |
| CN110898812A (en) * | 2019-11-30 | 2020-03-24 | 河南永泽环境科技有限公司 | Preparation method and application of novel magnetic microalgae-based complexing agent |
| CN111569831A (en) * | 2020-04-21 | 2020-08-25 | 哈尔滨工业大学 | Long-term stable biochar-zero-valent iron composite material and one-step preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| TANG XIANGYU等: "Strengthen recovery characteristics of copper smelting slag with biochar", 《JOURNAL OF CENTRAL SOUTH UNIVERSITY (SCIENCE AND TECHNOLOGY) 》 * |
| ZHANG T等: "Hydrogen Peroxide Activated by Biochar-Supported Sulfidated Nano Zerovalent Iron for Removal of Sulfamethazine: Response Surface Method Approach", 《INTERNATIONAL JOURNAL OF ENVIRONMENTAL RESEARCH AND PUBLIC HEALTH》 * |
| 邓俊敏: "生物炭负载纳米零价铁在还原及氧化体系下对污染物的去除研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
| 钟金魁等: "生物炭对抗生素环境行为的影响研究进展", 《安全与环境学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159267A (en) * | 2020-09-21 | 2021-01-01 | 中山大学 | Method for reducing pollution of sulfanilamide antibiotics and resistance genes thereof in maggot manure compost |
| CN113042000A (en) * | 2021-03-23 | 2021-06-29 | 福州大学 | Chicken manure derived biochar loaded nano zero-valent iron composite material and preparation method and application thereof |
| CN113403346A (en) * | 2021-07-01 | 2021-09-17 | 黑龙江省农业科学院农村能源与环保研究所 | Method for producing biogas by joint anaerobic fermentation of pig farm liquid dung and corn straws treated by biochar loaded with nano zero-valent iron |
| CN113857231A (en) * | 2021-08-18 | 2021-12-31 | 广东工业大学 | Preparation of iron-based biochar wave-absorbing material and method for repairing mercury-contaminated soil through microwave synergy |
| CN114105290A (en) * | 2021-11-24 | 2022-03-01 | 江苏泰源环保科技股份有限公司 | Preparation method and application of modified blue algae biochar loaded nano zero-valent iron material |
| CN114105290B (en) * | 2021-11-24 | 2023-11-17 | 江苏泰源环保科技股份有限公司 | Preparation method and application of modified blue algae biochar loaded nano zero-valent iron material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112023925B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112023925B (en) | Preparation method and application of livestock and poultry manure biochar loaded nano zero-valent iron composite material | |
| CN105236507B (en) | The method that the adsorbent being combined using beta cyclodextrin chitosan and walnut shell charcoal removes the Cr VI in waste water | |
| CN106362690A (en) | Magnetic biochar adsorbing material and preparation method thereof | |
| CN104941589B (en) | Preparation method of porous biological carbon heavy metal adsorbing material based on cotton straw | |
| Yusuff et al. | ZnCl2-modified eucalyptus bark biochar as adsorbent: preparation, characterization and its application in adsorption of Cr (VI) from aqueous solutions | |
| CN110813239A (en) | Preparation method of biochar-loaded lanthanum-doped iron oxide | |
| CN107185503B (en) | The preparation method of the charcoal of immobilized beta-cyclodextrin for sticking cadmium ion | |
| CN107983314A (en) | A kind of biological carbon composite of sodium alginate-calcium ion modification and preparation method thereof and purposes | |
| CN108315016A (en) | A kind of porous magnetic humic acid/charcoal particle and preparation method thereof for heavy metal reparation | |
| CN109534432A (en) | The preparation method of the biological carbon modified material of phosphorus in a kind of removal eutrophication water | |
| CN104941605A (en) | Active carbon adsorbent with good effects of removing formaldehyde and removing odors | |
| CN106732361A (en) | A kind of preparation method of the sludge base charcoal of the paper powder that adulterates | |
| CN109647351B (en) | Bagasse loaded iron hydroxide adsorbent and preparation method and application thereof | |
| CN105854800A (en) | Method for preparing modified charcoal by utilizing aquatic plant wastes and hydrochloric acid | |
| CN109201087A (en) | A method of utilizing dissolved organic matter NOM in green bio charcoal efficient catalytic degradation environment | |
| WO2022199445A1 (en) | Composite biochar for preventing and treating heavy metal pollution and preparation method therefor | |
| CN110368907A (en) | A kind of remover and preparation method thereof removed for arsenic in waste water, cadmium ion depth | |
| CN106145379A (en) | Photocatalysis biological adsorption agent and its preparation method and application | |
| CN101912767B (en) | Method for preparing modified furfural residue heavy metal adsorbent | |
| CN107081137A (en) | Lignin graft bentonite load nano zero-valence iron composite material and preparation method thereof | |
| CN108191181B (en) | A kind of urban river sediment cleanser and its production method | |
| CN112121762A (en) | Preparation method of biomass charcoal-based filter material loaded with nano zero-valent iron | |
| CN108671897A (en) | A kind of preparation and its application of modified straw fiber adsorbing material | |
| CN104628150B (en) | The method that compound photocatalysis biological adsorption agent processes percolate | |
| CN108906054A (en) | A kind of forming method using Fenton iron cement preparation ozone oxidation nbsCOD catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |