CN113244883A - Preparation method and application of blue algae modified charcoal-loaded nano zero-valent iron material - Google Patents
Preparation method and application of blue algae modified charcoal-loaded nano zero-valent iron material Download PDFInfo
- Publication number
- CN113244883A CN113244883A CN202110092097.3A CN202110092097A CN113244883A CN 113244883 A CN113244883 A CN 113244883A CN 202110092097 A CN202110092097 A CN 202110092097A CN 113244883 A CN113244883 A CN 113244883A
- Authority
- CN
- China
- Prior art keywords
- valent iron
- nano zero
- blue algae
- biochar
- drying
- 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.)
- Pending
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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Soil Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a preparation method and application of a blue algae modified biochar loaded nano zero-valent iron material, which comprises the following specific steps: s1, primary carbonization; s2, secondary carbonization; s3, post-processing; s4, loading nanometer zero-valent iron: setting the iron-carbon ratio of the blue algae modified charcoal loaded nano zero-valent iron material as a: b, modifying the cyanobacteria organismThe carbon adding amount is bg: s4-1, KBH with configuration concentration of 0.3M4Solution a x 100 ml; s4-2, FeSO with configuration concentration of 0.179M4·7H2O solution a x 100 ml; s4-3, FeSO4·7H2B g modified cyanobacteria biochar is added into the O solution; s4-4, FeSO4·7H2Dropwise adding all KBH into O solution4Aging the solution for 30-60min with anhydrous ethanol as stabilizer under nitrogen; s4-5, filtering solid components in the mixed solution, and washing for several times; s4-6, drying the solid components, sealing and storing to obtain the blue algae modified biochar nano zero-valent iron material which is applied to water treatment and soil remediation and has the functions of adsorbing, degrading and holding organic pollutants.
Description
Technical Field
The invention relates to a preparation method of a blue algae modified biochar loaded nano zero-valent iron material, in particular to a method for degrading tetracycline by using the blue algae modified biochar nano zero-valent iron material and application thereof, and belongs to the technical field of water treatment.
Background
In recent years, blue-green algae are developed in freshwater lakes in China almost every year, and a large amount of blue-green algae still has toxicity after being fished ashore and dehydrated, so that environmental pollution is caused by random disposal, and the safety of soil and underground water is endangered. At present, the harmless recycling mode of blue algae mainly comprises the synergistic fermentation of multi-component mixed materials, the utilization of nitrogen source nutrients, the deep removal of algal toxins, the preparation of activated carbon and the like, and is mainly applied to the fields of soil and solid waste, and the environmental problems brought by livestock and poultry breeding are mostly expressed in the overproof antibiotic content in underground water and surface water and the like.
Meanwhile, the biochar has the characteristics of large specific surface area, rich surface functional groups and the like, and is more and more concerned by researchers, metal ions with a reduction function are loaded into the biochar, so that the specific surface area of the biochar can be further enlarged, a target pollutant can be degraded through an oxidation-reduction effect, the algae mud is prepared into the biochar, and the nano metal ions are loaded, so that a high-efficiency adsorption and degradation function can be realized, the antibiotic pollution of a water body is removed, and the method is a way for developing the blue-green algae resource in the future.
Disclosure of Invention
Aiming at the existing technical problems, the invention provides a preparation method and application of a blue algae modified biochar loaded nano zero-valent iron material, so as to develop a blue algae resource approach and solve the problem of incomplete existing soil remediation technology.
In order to realize the aim, the invention provides a preparation method of a blue algae modified biochar loaded nano zero-valent iron material, which comprises the following specific steps:
s1, primary carbonization: drying and crushing blue algae, carbonizing in inert atmosphere, heating from room temperature to 300 ℃, keeping for 1-2h, and cooling to obtain the primary carbon material.
Further, the drying is freeze drying or drying in an oven at 80-105 ℃.
Further, the temperature rising rate of the carbonization is 5 ℃/min, and the nitrogen flow is 50-100 ml/min.
S2, secondary carbonization: crushing the primary carbon material, and mixing the crushed primary carbon material with KOH according to the mass ratio of 1: 2-3, adding deionized water to ensure that the KOH concentration is 20-40%; and drying the obtained mixture, carbonizing in an inert atmosphere, heating from room temperature to 700 ℃, keeping for 1-3h, and cooling to obtain a crude carbon material.
In the technical scheme, the carbon material is further expanded by alkalization treatment, and the internal porosity and the specific surface area of the carbon are increased. And through further high-temperature heating, the functional groups on the surface of the carbon are activated, so that the active point positions in the carbon material are increased, and the adsorption and holding effects on pollutants are enhanced.
Furthermore, the crushing is realized by a crusher and then a 100-mesh sieve is sieved.
Further, the drying is carried out in an oven at the temperature of 80-90 ℃.
Further, the temperature rising rate of the carbonization is 5 ℃/min, and the nitrogen flow is 50-100 ml/min.
S3, post-processing: coarse carbonAdding 20-40% of HNO into the material3Or HCl, shaking in a shaking table, removing supernatant, washing the obtained solid to be neutral, and drying to obtain the modified blue algae biochar.
In the technical scheme, the acid solution is added into the coarse carbon material to modify the carbon material, so that the types and the activity of functional groups on the surface of the carbon material are further increased, and the adsorption effect of the carbon material on pollutants is favorably enhanced.
Further, the conditions of the shaking table are that the temperature is room temperature, the speed is 60-160r/min, and the shaking time is 2-3 h.
Further, the drying is carried out in an oven at 60-90 ℃.
S4, loading nanometer zero-valent iron: setting the iron-carbon ratio of the blue algae modified charcoal loaded nano zero-valent iron material as a: b, when the adding amount of the modified blue algae biochar is b g:
s4-1, KBH with configuration concentration of 0.3M4The solution a is multiplied by 100ml and is stirred for 30-60min under the protection of nitrogen;
s4-2, FeSO with configuration concentration of 0.179M4·7H2O solution a is multiplied by 100ml, and is stirred for 30-60min under the protection of nitrogen;
s4-3, FeSO4·7H2B g modified cyanobacteria biochar is added into the O solution, and the mixture is stirred for 30-60min under the protection of nitrogen;
s4-4, FeSO4·7H2Dropwise adding all KBH into O solution4Adding a proper amount of absolute ethyl alcohol as a stabilizer under the protection of nitrogen, and aging for 30-60 min;
s4-5, filtering solid components in the mixed solution, and washing the solid components for several times by using ultrapure water and absolute ethyl alcohol;
s4-6, transferring the solid components into a vacuum drying oven, drying, sealing and storing to obtain the blue algae modified biochar nano zero-valent iron material.
Specifically, the iron-carbon ratio is 1: 1, when the addition amount of the modified blue algae biochar is 1g, KBH with the concentration of 0.3M is prepared4100ml of FeSO with a concentration of 0.179M4·7H2O solution 100 ml.
Preparing an iron-carbon ratio of 2:1, when the addition amount of the modified blue algae biochar is 1g, KBH with the concentration of 0.3M is prepared4200ml of FeSO with a concentration of 0.179M4·7H2O solution 200 ml.
Preparing a material with an iron-carbon ratio of 1: 2, when the addition amount of the modified blue algae biochar is 2g, KBH with the concentration of 0.3M is prepared4100ml of FeSO with a concentration of 0.179M4·7H2O solution 100 ml.
The iron-carbon ratio prepared by the technical scheme is 1: 1, the reaction principle is as follows:
Moreover, the invention also provides application of the blue algae modified biochar loaded nano zero-valent iron material prepared by the method in water treatment and soil remediation.
Furthermore, the blue algae modified biochar loaded nano zero-valent iron material has the functions of adsorbing, degrading and holding organic pollutants.
The blue algae modified biochar prepared by the method has larger specific surface area and can load more iron ions, so that the blue algae modified biochar loaded with the nano zero-valent iron-based material has stronger degradation capability. Meanwhile, the algae biochar has richer functional groups and has a chelation effect with iron ions, so that the iron ions are more stably fixed on the surface of the biochar, and under the condition that pollutants exist, the iron ions and the biochar are broken by the action force between the iron ions and the pollutants, and the simple substance iron is used as a reducing agent to reduce the target pollutants into small molecular substances, so that the pollutants are degraded.
In summary, compared with the prior art, the invention has the technical advantages that:
1. the carbon material is pyrolyzed under the inert condition after alkalization, the aperture of the carbon material is obviously improved, meanwhile, the carbon material is further acidified after pyrolysis, and after continuous alkalization, pyrolysis and acidification, the characteristic that the blue algae modified biochar loaded nanometer zero-valent iron material has larger specific surface area and porosity compared with the current reported material.
2. The blue algae modified charcoal-loaded nano zero-valent iron material has a carbon adsorption material with a high specific surface area and abundant surface functional groups, can effectively solve the problem of secondary pollution of blue algae, and can fully utilize blue algae to prepare active carbon due to the abundant and easily-accessible nature of blue algae, thereby fully utilizing resources.
3. Compared with the existing carbon adsorption material, the blue algae modified charcoal loaded nano zero-valent iron material greatly improves the adsorption efficiency on organic pollutants, reduces the risk of migration and transformation of the pollutants in an environmental medium, and has good application prospect.
Drawings
FIG. 1a is a graph showing the relationship between the influence of the cyanobacteria modified biochar nano zero-valent iron-based material prepared in example 1 on Tetracycline (TC) degradation at different reaction times;
FIG. 1b is a graph showing the relationship between the influence of the cyanobacteria modified biochar nano zero-valent iron-based material prepared in example 1 on the adsorption of Tetracycline (TC) at different dosages and different reaction times;
FIG. 1c is a graph showing the relationship between the influence of the cyanobacteria modified biochar nano zero-valent iron-based material prepared in example 2 on the adsorption of Tetracycline (TC) at different dosages and different reaction times;
FIG. 1d is a graph showing the relationship between the influence of the cyanobacteria modified biochar nano zero-valent iron-based material prepared in example 3 on the adsorption of Tetracycline (TC) at different dosages and different reaction times;
FIG. 2a is a Scanning Electron Microscope (SEM) image of the cyanobacteria modified biochar nano zero-valent iron-based material prepared in example 1;
FIG. 2b is a Scanning Electron Microscope (SEM) image of the cyanobacteria modified biochar nano zero-valent iron-based material prepared in example 1 after Tetracycline (TC) degradation;
FIG. 3a is an X-ray diffraction (XRD) pattern of the cyanobacteria modified biochar nano zero-valent iron material prepared in example 1;
fig. 3b is an X-ray diffraction (XRD) pattern of the cyanobacteria modified biochar nano zero-valent iron-based material prepared in example 1 after Tetracycline (TC) degradation.
Detailed Description
The invention is further illustrated by the following figures and examples. It will be evident to those skilled in the art that the invention is not limited to the details of the following illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the following description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Example 1:
1-1, preparing a mixture with an iron-carbon ratio of 1: 1, the blue algae modified biochar nano zero-valent iron material comprises the following specific steps:
1-1-1, collecting blue algae fished by a fishing station, drying the blue algae in a drying oven at 105 ℃, crushing the blue algae by a crusher, placing the crushed blue algae in a quartz boat in a tubular furnace, and carbonizing the blue algae under the protection of nitrogen. The heating rate is required to be 5 ℃/min, the nitrogen flow is required to be 50ml/min, the heating temperature is firstly increased from room temperature to 300 ℃, the temperature is kept for 1h and then the carbon material is cooled to room temperature, and the obtained carbon material is marked as ZC 300.
1-1-2, further crushing the carbon material ZC300 by a crusher, and sieving by a 100-mesh sieve. And then mixing the undersize product with KOH according to the mass ratio of 1: 2 and deionized water is added to bring the KOH concentration to 20%. And then placing the mixture in an oven for drying at 80 ℃, then placing the mixture in a tube furnace, and carrying out carbonization treatment under the protection of nitrogen. Heating temperature is firstly increased from room temperature to 700 ℃, the temperature increasing condition is that the temperature increasing speed is 5 ℃/min, the nitrogen flow is 50ml/min, the temperature is kept for 2h, then the carbon material is cooled to room temperature, and the obtained carbon material is marked as KOH-ZC 700.
1-1-3, adding 20% of HNO into carbon material KOH-ZC7003Firstly shaking the table at room temperature at a speed of 60r/min for 2 h; and then removing the supernatant, washing the carbon material with a large amount of deionized water to be neutral, placing the carbon material in an oven, and drying the carbon material at the temperature of 60 ℃, wherein the obtained carbon material is marked as GXC700, namely the modified blue algae biochar (ZBC).
1-1-4, KBH with the concentration of 0.3M4Solution: first, 1.59g of KBH is weighed4Adding into 100ml of ultrapure water, and stirring the solution for 30min under the protection of nitrogen; then, 0.179M FeSO was prepared4·7H2O solution, i.e. weighing 4.59g FeSO4·7H2O, adding the mixture into 100ml of ultrapure water for dissolving, and stirring for 30min under the protection of nitrogen; 1g of ZBC was added to FeSO4·7H2Stirring in the O solution for 30min under the protection of nitrogen; subsequently, KBH was added dropwise4Introducing nitrogen to protect the solution, adding a proper amount of absolute ethyl alcohol as a stabilizer, and aging for 30 min; and then, filtering the solid component, washing the solid component for a plurality of times by using ultrapure water and absolute ethyl alcohol, finally transferring the solid component into a vacuum drying oven for drying, and then sealing and storing, wherein the iron-carbon ratio is 1: 1, blue algae modified charcoal nano zero-valent iron material nZVI @ ZBC (1: 1).
The nZVI @ ZBC (1: 1) prepared by the method is researched, fig. 2a is a Scanning Electron Microscope (SEM) picture of the blue algae modified biochar nano zero-valent iron material, fig. 3a is an X-ray diffraction (XRD) picture of the blue algae modified biochar nano zero-valent iron material, and it can be seen that iron nanoparticles are loaded on the surface of the blue algae modified biochar and are an adsorption degradation material with redox function.
1-2, verifying the adsorption degradation efficiency of nZVI @ ZBC (1: 1) on Tetracycline (TC), and specifically comprising the following steps:
1-2-1, weighing 40mg of nZVI @ ZBC (1: 1), placing the nZVI @ ZBC into a 50ml glass centrifuge tube with PTFE material, adding 30ml of TC solution with the concentration of 50mg/L into the tube, and oscillating the tube for 30min in a constant temperature oscillator, wherein the temperature in the oscillator is set to be 25 ℃, and the oscillation speed is 150 r/min.
1-2-2, filtering with 0.45 mu m PTFE filter membrane after the reaction is finished, detecting the concentration of TC in the solution after the reaction by liquid chromatography, and obtaining the removal rate of TC by nzVI @ ZBC (1: 1) to be 98.2 percent by calculation.
1-2-3, setting different reaction times, namely setting the constant temperature oscillation time to be 1min, 2min, 5min, 10min, 20min, 30min and 60min respectively, measuring the concentration of TC in the solution after the adsorption is finished according to the experimental steps and the operation method, and calculating to obtain that the TC removal rates corresponding to the groups are 65.1%, 78.2%, 85.5%, 90.1%, 97.8%, 98.2% and 98.5% respectively, wherein the results are shown in a figure 1a and a figure 1 b.
1-2-4, and setting different adding amounts, namely weighing the nZVI @ ZBC (1: 1) with the mass of 20mg, 30mg and 40mg respectively, carrying out experiments according to the steps of the method, measuring the TC concentration in the solution after adsorption is finished, and calculating to obtain the TC removal rates of 88.1%, 94.5% and 98.2% respectively corresponding to each group, wherein the results are shown in figure 1 b. As can be seen, the optimum adsorption condition was found to be when the amount of nZVI @ ZBC added was 40mg and the reaction time was 20 min.
Moreover, the nZVI @ ZBC (1: 1) after Tetracycline (TC) degradation is studied, fig. 2b is a Scanning Electron Microscope (SEM) image after the Tetracycline (TC) degradation of the blue algae modified biochar nano zero-valent iron-based material, and fig. 3b is an X-ray diffraction (XRD) image after the Tetracycline (TC) degradation of the blue algae modified biochar nano zero-valent iron-based material, so that the nZVI @ ZBC has a high adsorption degradation function.
In addition, the specific surface area and the pore volume of nZVI @ ZBC (1: 1) obtained in example 1 are tested, and as shown in table 1 below, it can be known that the characteristics of nZVI @ ZBC (1: 1) are higher than those of currently reported carbon adsorbing materials, that is, the material prepared by the method can greatly improve the adsorption efficiency of organic pollutants and reduce the migration and conversion risks of pollutants in an environmental medium.
Table 1: examples average specific surface area and pore volume of prepared samples
| Sample (I) | Specific surface area (m)2/g） | Total pore volume (cm)3/g) | Average pore diameter (nm) |
| nZVI@ZBC（1：1） | 70.58 | 0.158 | 8.98 |
Example 2:
2-1, preparing a mixture with an iron-carbon ratio of 2:1, the blue algae modified biochar nano zero-valent iron material comprises the following specific steps:
2-1-1, freeze-drying the collected blue algae in a freeze dryer, crushing the blue algae by a crusher, sieving the crushed blue algae by a sieve of 100 meshes, putting the crushed blue algae into a tubular furnace for carbonization, raising the temperature from room temperature to 300 ℃ at the rate of 5 ℃/min and the flow of nitrogen of 0.5L/min, keeping the temperature for 2 hours, and cooling the blue algae to the room temperature to obtain the carbon material labeled as ZC 300.
2-1-2, firstly, mixing carbon material ZC300 according to the mass ratio of 1: 3 adding KOH and mixing evenly, adding deionized water to ensure that the KOH concentration is 30 percent. And (3) placing the mixture in an oven for drying at 105 ℃, then placing the mixture in a tube furnace, and carrying out carbonization treatment under the protection of nitrogen. The heating temperature is started from room temperature, the heating rate is 5 ℃/min, the nitrogen flow is 100ml/min, the temperature is increased to 700 ℃, the temperature is kept for 3h, then the carbon material is cooled to room temperature, and the obtained carbon material is marked as KOH-ZC 700.
2-1-3, adding 40% HCl into the cooled carbon material, and shaking the carbon material by a shaking table at room temperature and at the speed of 160r/min for 3 h. And (3) removing supernatant after standing, washing the carbon material to be neutral by using a large amount of deionized water, and drying in a drying oven at 90 ℃ to obtain the modified blue algae biochar (ZBC).
2-1-4, 200ml of 0.3M KBH4Solution: first, 3.18g of KBH was weighed4Adding into 200ml of ultrapure water, and stirring the solution for 45min under the protection of nitrogen; then configure 0.17FeSO of 9M concentration4·7H2O solution, i.e. weighing 9.18g FeSO4·7H2O, adding the mixture into 200ml of ultrapure water for dissolving, and stirring for 45min under the protection of nitrogen; 1g of ZBC was added to FeSO4·7H2Stirring in the O solution for 45min under the protection of nitrogen; subsequently, KBH was added dropwise4Introducing nitrogen to protect the solution, adding a proper amount of absolute ethyl alcohol as a stabilizer, and aging for 45 min; and then, filtering the solid component, washing the solid component for a plurality of times by using ultrapure water and absolute ethyl alcohol, finally transferring the solid component into a vacuum drying oven for drying, and then sealing and storing the solid component, wherein the iron-carbon ratio is 2:1, blue algae modified charcoal nano zero-valent iron material nZVI @ ZBC (2: 1).
Research on the nZVI @ ZBC (2: 1) prepared by the method shows that the surface of the blue algae modified charcoal is loaded with iron nanoparticles, and the blue algae modified charcoal is an adsorption degradation material with redox function.
2-2, verifying the adsorption degradation efficiency of nZVI @ ZBC (2: 1) on Tetracycline (TC), and specifically comprising the following steps:
2-2-1, weighing 20mg of nZVI @ ZBC (2: 1), placing the nZVI @ ZBC into a 50ml glass centrifuge tube with PTFE material, adding 30ml of TC solution with the concentration of 50mg/L, and oscillating the mixture in a constant temperature oscillator for 60min at the temperature of 25 ℃ and the oscillation speed of 180 r/min.
2-2-2, after completion of the reaction, the reaction mixture was filtered through a 0.45. mu. mPTFE filter, and the TC concentration in the solution after the reaction was measured by liquid chromatography, whereby the removal rate of TC by nzVI @ ZBC (2: 1) was 95.4%.
2-2-3, setting different reaction times, namely constant temperature oscillation time as 1min, 2min, 5min, 10min, 20min, 30min and 60min respectively, and the dosage of nZVI @ ZBC (2: 1) as 20mg respectively, according to the experimental steps and the operation method, measuring the TC concentration in the solution after adsorption is finished, and calculating to obtain that the TC removal rates of each group are 47%, 66%, 79%, 92%, 94% and 96%, respectively, and the result is shown in figure 1 c.
2-2-4, and setting different adding amounts, namely weighing the nZVI @ ZBC (2: 1) with the mass of 20mg, 30mg and 40mg respectively, carrying out experiments according to the steps of the method, measuring the TC concentration in the solution after adsorbing for 60min, and calculating to obtain the TC removal rates of 96.0%, 96.4% and 96.8% respectively corresponding to each group, wherein the results are shown in figure 1 c.
Example 3:
3-1, preparing a mixture with an iron-carbon ratio of 1: 2, the blue algae modified biochar nano zero-valent iron material comprises the following specific steps:
3-1-1, collecting blue algae, drying in a drying oven at 105 ℃, crushing by using a crusher, putting into a tube furnace for carbonization treatment, wherein the heating rate is 5 ℃/min, the nitrogen flow is 80ml/min, the heating temperature is increased from room temperature to 300 ℃, and is kept for 1.5h, and the obtained carbon material is marked as ZC 300.
3-1-2, crushing the cooled ZC300, and sieving the crushed ZC300 with a 100-mesh sieve according to the mass ratio of 1: 2.5 adding KOH, mixing evenly, adding deionized water to ensure that the concentration of the KOH is 25 percent, placing the mixture in a drying oven at 90 ℃ for drying, and then placing the dried mixture in a tubular furnace for carbonization under the condition of nitrogen protection. The temperature rise condition is that the temperature rise rate is 5 ℃/min, the nitrogen flow is 75ml/min, the temperature is raised from the room temperature to 700 ℃, the temperature is kept for 2.5h, then the temperature is cooled to the room temperature, and the obtained carbon material is marked as KOH-ZC 700.
3-1-3, adding 30% of HNO3 into the cooled KOH-ZC700, and then oscillating by a shaker at room temperature and 100r/min for 2.5 h. And standing, removing supernatant, washing the carbon material with a large amount of deionized water to be neutral, placing the carbon material in an oven, and drying at 85 ℃ to obtain the modified blue algae biochar (ZBC).
3-1-4, KBH with the concentration of 0.3M4Solution: first, 1.59g of KBH is weighed4Adding into 100ml of ultrapure water, and stirring the solution for 60min under the protection of nitrogen; then, 0.179M FeSO was prepared4·7H2O solution, i.e. 4.59g FeSO4·7H2O, adding the mixture into 100ml of ultrapure water for dissolving, and stirring for 60min under the protection of nitrogen; 2g of ZBC were then added to FeSO4·7H2Stirring in O solution for 60min under the protection of nitrogen; subsequently, KBH was added dropwise4Introducing nitrogen to protect the solution, adding a proper amount of absolute ethyl alcohol as a stabilizer, and aging for 60 min; filtering solid component, washing with ultrapure water and anhydrous ethanol for several times, transferring into vacuum drying oven, drying, sealing, and storingNamely the iron-carbon ratio is 1: 2, blue algae modified charcoal nano zero-valent iron material nZVI @ ZBC (1: 2).
Research on the nZVI @ ZBC (1: 2) prepared by the method shows that the surface of the blue algae modified charcoal is loaded with iron nanoparticles, and the blue algae modified charcoal is an adsorption degradation material with redox function.
3-2, verifying the adsorption degradation efficiency of nZVI @ ZBC (1: 2) to Tetracycline (TC) through experiments, and specifically comprising the following steps:
3-2-1, weighing 20mg of nZVI @ ZBC (1: 2), placing the nZVI @ ZBC into a 50ml glass centrifuge tube with PTFE material, adding 30ml of TC solution with the concentration of 50mg/L, and shaking for 30min in a constant temperature oscillator, wherein the temperature in the oscillator is set to be 25 ℃, and the shaking speed is 150 r/min.
3-2-2, adsorbing, filtering with 0.45 mu m PTFE filter membrane, detecting the concentration of TC in the reacted solution by liquid chromatography, and obtaining the removal rate of TC by nZVI @ ZBC (1: 2) of 90.3 percent by calculation.
3-2-3, setting different reaction times, namely constant temperature oscillation time as 1min, 2min, 5min, 10min, 20min, 30min and 60min respectively, and the dosage of nZVI @ ZBC (2: 1) as 20mg, according to the experimental steps and the operation method, measuring the TC concentration in the solution after adsorption is finished, and calculating to obtain that the TC removal rates of each group are respectively 35%, 41%, 54%, 62%, 75%, 84% and 91%, and the results are shown in figure 1 d.
3-2-4, and setting different adding amounts, namely weighing the nZVI @ ZBC (1: 2) with the mass of 20mg, 30mg and 40mg respectively, carrying out the experiment according to the steps of the method, measuring the TC concentration in the solution after adsorbing for 60min, and calculating to obtain the TC removal rates of 91.0%, 91.9% and 92.7% respectively corresponding to each group, wherein the result is shown in figure 1 d.
From the specific technical solutions of examples 1 to 3 and fig. 1b to 1d, it can be seen that, when the iron-carbon ratio of the blue algae modified biochar nano zero-valent iron-based material is 2:1, the addition amount of the carbon material is 40mg, and the reaction time is 20min, the adsorption degradation efficiency of the blue algae modified biochar nano zero-valent iron-based material on Tetracycline (TC) is more prominent.
In conclusion, the blue algae modified biochar nano zero-valent iron material has a good pore structure, rich surface functional groups and redox capability, has a good removal effect on antibiotics, and is an ideal adsorption degradation agent. The popularization and application of the material of the invention can not only save resources, but also be beneficial to protecting the ecological environment, and finally achieve the purposes of treating pollution and reducing the pollution treatment cost.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of a blue algae modified charcoal loaded nano zero-valent iron material is characterized by comprising the following specific steps:
s1, primary carbonization: drying and crushing blue algae, carbonizing in an inert atmosphere, heating from room temperature to 300 ℃, keeping for 1-2h, and cooling to obtain a primary carbon material;
s2, secondary carbonization: crushing the primary carbon material, and mixing the crushed primary carbon material with KOH according to the mass ratio of 1: 2-3, adding deionized water to ensure that the KOH concentration is 20-40%; drying the obtained mixture, carbonizing in an inert atmosphere, heating from room temperature to 700 ℃, keeping for 1-3h, and cooling to obtain a crude carbon material;
s3, post-processing: adding 20-40% of HNO into the crude carbon material3Or HCl, placing in a shaking table for shaking, removing supernatant, washing the obtained solid to be neutral, and drying to obtain modified blue algae biochar;
s4, loading nanometer zero-valent iron: setting the iron-carbon ratio of the blue algae modified charcoal loaded nano zero-valent iron material as a: b, when the adding amount of the modified blue algae biochar is b g:
s4-1, KBH with configuration concentration of 0.3M4The solution a is multiplied by 100ml and is stirred for 30-60min under the protection of nitrogen;
s4-2, with a concentration of 0.179MFeSO4·7H2O solution a is multiplied by 100ml, and is stirred for 30-60min under the protection of nitrogen;
s4-3, FeSO4·7H2B g modified cyanobacteria biochar is added into the O solution, and the mixture is stirred for 30-60min under the protection of nitrogen;
s4-4, FeSO4·7H2Dropwise adding all KBH into O solution4Adding a proper amount of absolute ethyl alcohol as a stabilizer under the protection of nitrogen, and aging for 30-60 min;
s4-5, filtering solid components in the mixed solution, and washing the solid components for several times by using ultrapure water and absolute ethyl alcohol;
s4-6, transferring the solid components into a vacuum drying oven, drying, sealing and storing to obtain the blue algae modified biochar nano zero-valent iron material.
2. The preparation method of the cyanobacteria modified biochar-loaded nano zero-valent iron-based material according to claim 1, wherein in step S1, the drying is freeze drying or drying in an oven at 80-105 ℃.
3. The preparation method of the cyanobacteria modified biochar-loaded nano zero-valent iron material according to claim 1, wherein in step S1, the temperature rise rate of carbonization is 5 ℃/min and the nitrogen flow rate is 50-100 ml/min.
4. The method for preparing the cyanobacteria modified biochar-loaded nano zero-valent iron-based material according to claim 1, wherein in the step S2, the crushing is performed by a crusher and then a 100-mesh sieve is passed through.
5. The preparation method of the cyanobacteria modified biochar-loaded nano zero-valent iron-based material according to claim 1, wherein in step S2, the drying is carried out by placing in an oven at 80-90 ℃ for drying.
6. The preparation method of the cyanobacteria modified biochar-loaded nano zero-valent iron material according to claim 1, wherein in step S2, the temperature rise rate of carbonization is 5 ℃/min and the nitrogen flow rate is 50-100 ml/min.
7. The preparation method of the cyanobacteria modified biochar loaded nano zero-valent iron material as claimed in claim 1, wherein in step S3, the shaking table is at room temperature, at a speed of 60-160r/min, and at a shaking time of 2-3 h.
8. The preparation method of the cyanobacteria modified biochar-loaded nano zero-valent iron-based material according to claim 1, wherein in step S3, the drying is carried out by placing in an oven at 60-90 ℃.
9. The application of the blue algae modified biochar loaded nano zero-valent iron material prepared by the method of any one of claims 1 to 8 in water treatment and soil remediation.
10. The application of the cyanobacteria modified biochar loaded nano zero-valent iron series material according to claim 9, wherein the cyanobacteria modified biochar loaded nano zero-valent iron series material has the effects of adsorbing, degrading and holding organic pollutants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110092097.3A CN113244883A (en) | 2021-01-23 | 2021-01-23 | Preparation method and application of blue algae modified charcoal-loaded nano zero-valent iron material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110092097.3A CN113244883A (en) | 2021-01-23 | 2021-01-23 | Preparation method and application of blue algae modified charcoal-loaded nano zero-valent iron material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113244883A true CN113244883A (en) | 2021-08-13 |
Family
ID=77180815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110092097.3A Pending CN113244883A (en) | 2021-01-23 | 2021-01-23 | Preparation method and application of blue algae modified charcoal-loaded nano zero-valent iron material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113244883A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100579A (en) * | 2022-01-26 | 2022-03-01 | 北京师范大学 | Eucalyptus biochar loaded nano zero-valent iron composite material and preparation method thereof |
| 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 |
| CN114477324A (en) * | 2022-01-24 | 2022-05-13 | 中交上海航道局有限公司 | Method for preparing domestic sewage composite treatment material based on river course spirogyra |
| CN114477698A (en) * | 2022-02-11 | 2022-05-13 | 江南大学 | Application of ferric chloride mediated cyanobacteria-based biochar in removing zero-valent mercury in flue gas |
| CN114917869A (en) * | 2022-05-11 | 2022-08-19 | 浙江科技学院 | Preparation method of waste green tea charcoal for preferential adsorption of heavy metals |
| CN115196739A (en) * | 2022-07-08 | 2022-10-18 | 昆明理工大学 | Method for improving catalytic degradation rate of methylene blue in dye wastewater |
| CN115872471A (en) * | 2022-12-16 | 2023-03-31 | 重庆科技学院 | Method for treating water eutrophication by using algae-based biochar loaded nano zero-valent iron |
| CN117101692A (en) * | 2023-04-27 | 2023-11-24 | 江苏中吴环保产业发展有限公司 | Preparation method and application of nitriding-enriched nano zero-valent iron/biochar composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017518879A (en) * | 2014-10-13 | 2017-07-13 | 広東省生態環境技術研究所 | Iron-based bio-charcoal material, its preparation method, and its application for heavy metal contamination treatment of soil |
| CN110586038A (en) * | 2019-10-18 | 2019-12-20 | 华中农业大学 | Biochar loaded nano zero-valent iron material and application thereof |
| CN110787771A (en) * | 2019-10-25 | 2020-02-14 | 天津大学 | Modified blue algae biochar and preparation method and application thereof |
| CN111704191A (en) * | 2020-06-28 | 2020-09-25 | 南通大学 | Preparation method and application of cyanobacteria biochar material with efficient riboflavin adsorption |
| CN112058227A (en) * | 2020-08-31 | 2020-12-11 | 中国环境科学研究院 | Preparation method and application of blue algae modified biochar with high adsorption efficiency |
-
2021
- 2021-01-23 CN CN202110092097.3A patent/CN113244883A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017518879A (en) * | 2014-10-13 | 2017-07-13 | 広東省生態環境技術研究所 | Iron-based bio-charcoal material, its preparation method, and its application for heavy metal contamination treatment of soil |
| CN110586038A (en) * | 2019-10-18 | 2019-12-20 | 华中农业大学 | Biochar loaded nano zero-valent iron material and application thereof |
| CN110787771A (en) * | 2019-10-25 | 2020-02-14 | 天津大学 | Modified blue algae biochar and preparation method and application thereof |
| CN111704191A (en) * | 2020-06-28 | 2020-09-25 | 南通大学 | Preparation method and application of cyanobacteria biochar material with efficient riboflavin adsorption |
| CN112058227A (en) * | 2020-08-31 | 2020-12-11 | 中国环境科学研究院 | Preparation method and application of blue algae modified biochar with high adsorption efficiency |
Non-Patent Citations (1)
| Title |
|---|
| 王向宇: "《环境工程中的纳米零价铁水处理技术》", 31 October 2016, 北京：冶金工业出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114477324A (en) * | 2022-01-24 | 2022-05-13 | 中交上海航道局有限公司 | Method for preparing domestic sewage composite treatment material based on river course spirogyra |
| CN114477324B (en) * | 2022-01-24 | 2023-11-10 | 中交上海航道局有限公司 | Method for preparing domestic sewage composite treatment material based on river course spirogyra |
| CN114100579A (en) * | 2022-01-26 | 2022-03-01 | 北京师范大学 | Eucalyptus biochar loaded nano zero-valent iron composite material and preparation method thereof |
| CN114477698A (en) * | 2022-02-11 | 2022-05-13 | 江南大学 | Application of ferric chloride mediated cyanobacteria-based biochar in removing zero-valent mercury in flue gas |
| CN114917869A (en) * | 2022-05-11 | 2022-08-19 | 浙江科技学院 | Preparation method of waste green tea charcoal for preferential adsorption of heavy metals |
| CN114917869B (en) * | 2022-05-11 | 2024-02-13 | 浙江科技学院 | Preparation method of waste green tea biochar for preferential adsorption of heavy metals |
| CN115196739A (en) * | 2022-07-08 | 2022-10-18 | 昆明理工大学 | Method for improving catalytic degradation rate of methylene blue in dye wastewater |
| CN115872471A (en) * | 2022-12-16 | 2023-03-31 | 重庆科技学院 | Method for treating water eutrophication by using algae-based biochar loaded nano zero-valent iron |
| CN117101692A (en) * | 2023-04-27 | 2023-11-24 | 江苏中吴环保产业发展有限公司 | Preparation method and application of nitriding-enriched nano zero-valent iron/biochar composite material |
| CN117101692B (en) * | 2023-04-27 | 2024-03-22 | 江苏中吴环保产业发展有限公司 | Preparation method and application of nitriding-enriched nano zero-valent iron/biochar composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113244883A (en) | Preparation method and application of blue algae modified charcoal-loaded nano zero-valent iron material | |
| WO2021082761A1 (en) | Lanthanum carbonate modified co-pyrolysis sludge biochar and preparation method and application thereof | |
| CN112058227A (en) | Preparation method and application of blue algae modified biochar with high adsorption efficiency | |
| CN105903436A (en) | Biomass carbon-loaded nano zero-valent iron material as well as preparation method and application thereof | |
| CN112844385A (en) | Biochar adsorption catalytic material capable of being recovered by magnetic force, preparation method and application | |
| CN106186161A (en) | A kind of pig manure charcoal is utilized to remove the method for lead in polluted-water | |
| CN104096540A (en) | Preparation method of adsorption and catalysis material for removing heavy metals and organic pollutants in municipal sludge | |
| CN111871374A (en) | Preparation method and application of magnetic biochar | |
| CN109678249A (en) | A kind of ecological floating island dephosphorization composite interstitial substance and preparation method thereof | |
| CN113943030B (en) | Biomass carbon-coated nano zero-valent iron composite material for treating chlorobenzene-polluted water body by activating peroxymonosulfate and preparation and application thereof | |
| CN109046466A (en) | A kind of photochemical catalyst and its preparation method and application that the derivative carbon-based material of ZIF-8 is CdS-loaded | |
| CN113441142B (en) | Preparation method and application of oxygen vacancy-rich graphene-loaded porous nano ferroelectric oxide catalyst | |
| CN112076721A (en) | Adsorption-activation multifunctional composite material and application thereof | |
| CN110433789B (en) | Method for preparing photocatalytic biochar composite material by utilizing eichhornia crassipes accumulated nano zinc oxide | |
| CN111468070A (en) | Simple, convenient and efficient preparation method of magnetically separable biomass dye adsorbent | |
| CN115779905A (en) | Iron oxide biochar taking blue-green algae in Taihu lake as raw material, preparation method thereof and application thereof in water treatment | |
| CN1915849A (en) | Method for preparing composite assembled object of magnetic ferriferous oxide/ molecular sieve of Nano zeolite | |
| CN112934174B (en) | Preparation method and application of organosilane modified biomass charcoal | |
| CN109382073B (en) | Preparation method and application of alkali fusion fly ash modified pig manure biochar | |
| CN113578300A (en) | Ag-g-C3N4Biological carbon composite material and preparation method and application thereof | |
| CN112429818A (en) | Electrolysis stone filter material for sewage dephosphorization and preparation method and application thereof | |
| CN112844303A (en) | Water purification sludge/sodium silicate composite adsorbent, preparation method thereof and application thereof in treating ammonia nitrogen in water body | |
| CN116726880B (en) | Magnetic biochar and preparation method and application thereof | |
| CN115888791B (en) | High-stability pyrrhotite photo-Fenton catalyst, and preparation method and application thereof | |
| CN113198431B (en) | Preparation and application of carbonized sodium alginate-coated or iron/manganese cross-linked modified biochar |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210813 |