CN113952926A Method for synchronously removing arsenic and organic pollutants by ferrihydrite

nanoparticle-loaded biochar prepared by combined biological/chemical means

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A ferrihydrite-loaded nanoparticle <span class="search">biochar</span> prepared by a combined

biological/chemical approach Method for simultaneous removal of arsenic and organic pollutants

technical field

The invention belongs to the field of environmental engineering, and relates to a technology for synchronously
removing arsenic and organic pollutants, in particular to a method for synchronously removing arsenic and
organic pollutants from ferrihydrite-loaded nanoparticle biochar prepared by combined biological/chemical
means.

Background technique

The combined pollution of inorganic and organic pollutants is a common environmental pollution problem. The
combined pollution of arsenic and organic compounds is not only common in the water environment, but also in
the soil. For example, arsenic and polycyclic aromatic hydrocarbons are often detected in coking sites, mining
and metallurgy sites, and wood storage sites at the same time. Removal technologies that have been developed
for arsenic and organic pollution include adsorption, chemical precipitation, and oxidation. However, when two
or more pollutants coexist, due to different chemical properties, several treatment methods or the use of several
different materials may be required to effectively remove all pollutants, and the process is cumbersome and
complicated.

Biochar is a highly aromatic carbon-containing solid material prepared by carbonization and cracking of
biomass such as animals and plants. It has rich pore structure, large specific surface area, and high chemical and
biological stability. It has good application prospects in soil, environmental remediation, and pollutant
adsorption and degradation. The pore structure of biochar is an important indicator of its performance. The
higher the porosity, the better the pore connectivity and the stronger the adsorption capacity. However, for a
long time, the preparation of biochar is only through simple chemical modification (such as acid treatment or
alkali treatment, etc.) and the adjustment of pyrolysis temperature to change its pore structure, and it is difficult
to achieve the best effect.

Loading biochar with other materials is a common method to improve its pollutant handling capacity. Iron
minerals are common biochar loading materials, but most of the existing loading methods are simple mixing of
iron-containing reagents and biomass, followed by pyrolysis treatment or simple mixing of prepared biochar and
iron minerals. The composite biochar material is prepared by grinding, granulation and other processes. These
treatments did not take into account the further optimization of the biochar pore structure by the loading process.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the deficiencies of the prior art, and to provide a method for
synchronously removing arsenic and organic pollutants from the loaded ferrihydrite nanoparticle biochar
prepared by combined biological/chemical means, using agricultural waste as the original biomass Material, the
use of fungal mycelium in the growth process has a strong ability to penetrate biomass, and combined with acid
modification treatment and anaerobic pyrolysis to prepare biochar so that the biochar has a high specific surface
area, and by loading ferrihydrite nanoparticles, a On the one hand, the pore structure of biomass is further
optimized, and on the other hand, the composite material has the Fenton oxidation catalytic ability, and finally a
material with interconnected pores and uniform loading, which can simultaneously adsorb arsenic and catalyze
the degradation of organic matter by Fenton oxidation is obtained.

The present invention solves its technical problem by adopting the following technical solutions to realize:
A method for synchronously removing arsenic and organic pollutants from ferrihydrite nanoparticle biochar
prepared by combined biological/chemical means, the specific process steps are as follows:

(1)Pretreatment and mixing of raw biomass materials: take the following components by mass:

70 parts of cottonseed hulls, 5 parts of corncob, 10 parts of corn stalks, 8 parts of wheat bran, 5 parts of soybean
meal, 2 parts of white ash, crushed through a 20-mesh sieve, mixed evenly, added water to adjust the moisture
content to 65%, and placed in a gas exchange In a rectangular plastic semi-sealed container with a small hole,
compact it, and sterilize it by autoclaving at a temperature of 97-100 ° C for 20-30 minutes, and adjust the
moisture content to 50-65%;

(2)Mycelium inoculation and management: uniformly punch inoculation holes with a diameter of 1.3-1.5cm and
a depth of 1.8-2.4cm on the original biomass material obtained in step (1) with a punch rod, and the mycelium
clusters of about 2cm3 Insert into the inoculation hole so that the inoculation hole closely matches the mycelial
cluster, and complete the inoculation of Pleurotus chinensis mycelium under room temperature and aseptic
conditions. After 18 days of culture, the mycelium can overgrown the container. At this time, open the
rectangular plastic semi-sealed container to further grow the fungal mycelium;

Wherein, the preparation method of the described mycelium cluster is as follows: selecting a spore-bearing
Pleurotus coccidioides, collecting the spores, culturing and purifying, and under aseptic conditions, using a test
tube mouth to penetrate the agaric from the folds of the fungus , make the fungus seed pieces fall into the mouth
of the tube, and then take out the fungus seed pieces after culturing at a constant temperature of 24-26 °C for 6
hours, and cultivate at a constant temperature of 24-26 °C for 1 week. The contaminated mycelium mass is
transferred to the tube, and the mycelium cluster is formed after the tube is full of mycelium, and it is ready for
use.

The diameter of the hyphae of Pleurotus chinensis is between 0.3-1.5μm, and it is relatively uniform. A large
number of hyphae are densely arranged, crisscrossed, and branched in different directions. It can generate pores
of corresponding diameter after penetrating the biomass cell wall, and use the ability of degrading lignin,
cellulose, and hemicellulose in the cell wall of biomass materials during the growth of fungi to induce the
formation of loose pore structures inside the biomass, which is the final high ratio. Surface area biochar
preparation creates conditions.

(3)Acquisition of porous agricultural waste: After the mycelium grows for 4-8 months, the porous agricultural
waste is collected, dried and crushed, and then passed through a 60-mesh sieve for use;

(4)Chemical modification to optimize the pore structure of porous agricultural waste: soak 80-120 g of dried
porous agricultural waste in 500 mL of HCl solution with a concentration of 0.8-1.2 mol·L-1, continuously stir
and heat to 90 °C, and then naturally cool to At room temperature, the mixture was washed with deionized water
to remove excess HCl, and dried through a 60-mesh sieve;

The acid modification process makes the hyphae that penetrate the biomass cell wall easier to separate from the
biomass, creating conditions for the biochar to produce a higher specific surface area during the anaerobic
pyrolysis process.

(5)Anaerobic pyrolysis treatment: place the modified biochar obtained in the above step (4) in a muffle furnace
at 600° C., under the protection of N2, for 1 hour under anaerobic conditions, and then take it out after cooling
to room temperature;

In the method, the pore structure is optimized by acid modification treatment. After biochar is prepared by
anaerobic pyrolysis, ferrihydrite nanoparticles are synthesized and supported in the liquid phase while keeping
the biochar particles in a suspended state, and the pore structure is further reconstructed to prepare a It is a
material with interconnected pores and uniform loading, which can simultaneously adsorb heavy metals and
catalyze the degradation of organic matter by Fenton oxidation.

(6)Loading ferrihydrite nanoparticles: adding 50 g of the biochar obtained in the above step (5) into 2L solution
with a concentration of 0.1molL-1Fe(NO3)3 to prepare a load of biochar and ferrihydrite nanoparticles with a
mass ratio of 4 Ferrihydrite nanoparticle biochar, the resulting precipitate was washed several times with water
to remove excess ions and then freeze-dried.
In the process of loading ferrihydrite nanoparticles, 1 mol L-1NaOH solution was used to adjust the pH of the
system to 7.20. After stirring for 10 min, the system was stabilized for 1.5-2 hours, and then the pH was
adjusted to 7.20.

With different loadings of ferrihydrite nanoparticles, better pore remodeling morphology is preferred. Due to the
loading of ferrihydrite nanoparticles, the treatment of biochar and ferrihydrite nanoparticles with a mass ratio of
4 formed small pores, while the surface-loaded ferrihydrite nanoparticles increased the surface roughness and
increased the porosity, which was successfully achieved. Pore structure reconstruction.

The advantages and positive effects of the present invention are:

The present invention utilizes the process of biological penetration-chemical modification/pyrolysis-physical

loading to manufacture and reconstruct the pore structure of biochar, and to prepare a kind of pore
interconnected, uniformly loaded, and capable of utilizing the large specific surface area generated by the
special structure of the material itself, And a biochar modified preparation method with the synergistic Fenton
oxidation catalytic ability of biochar and ferrihydrite nanoparticles. The method of the present invention is
applied to the adsorption and degradation of arsenic and organic pollutants. In the treatment time of 45 hours,
the removal rate of arsenic and methylene blue is always higher than 96%. mg g-1, to achieve the purpose of
simultaneously removing arsenic and organic composite pollutants. Due to the abundant sources of biochar, the
effective use of various agricultural wastes not only increases economic benefits, but also avoids environmental
pollution, which is of great importance. R&D and transformation application significance.

Description of drawings

Fig. 1 is the mycelial microscope of Pleurotus pelvis and scanning electron microscope observation diagram in
the present invention;

Fig. 2 is the result diagram of pore change before and after the modified biochar-loaded ferrihydrite
nanoparticles of the present invention;

3 is a graph showing the results of the adsorption capacity of ferrihydrite nanoparticle biochar on arsenic
according to the present invention;

Fig. 4 is a graph showing the effect of different systems on the degradation of methylene blue (MB) in the
experiment of the present invention;

Fig. 5 is the free radical signal result graph in the Fenton reaction process in the experiment of the present
invention;

6 is a graph showing the results of degradation rates of methylene blue (MB) degraded by the loaded ferrihydrite
nanoparticle biochar (BF) in the experiment of the present invention for multiple cycles of each cycle;

Fig. 7 is a graph showing the selection result of the adsorption-degradation process conditions for methylene
blue (MB) by loaded ferrihydrite nanoparticle biochar (BF) in the experiment of the present invention;

Fig. 8 is the effect diagram of the synchronous removal of arsenic and organic pollutants by the loaded
ferrihydrite nanoparticle biochar according to the present invention;

detailed description

The present invention will be further described in detail below through specific examples. The following
examples are only descriptive, not restrictive, and cannot limit the protection scope of the present invention.

A method for simultaneous removal of arsenic and organic pollutants by a ferrihydrite-loaded nanoparticle
biochar prepared by combined biological/chemical means, the specific process steps and experimental
verification results are as follows:

Raw biomass material pretreatment and mixing process:

Take each component in the following parts by mass:

70 parts of cottonseed hulls, 5 parts of corncob, 10 parts of corn stalks, 8 parts of wheat bran, 5 parts of soybean
meal, 2 parts of white ash, crushed through a 20-mesh sieve, mixed evenly, added water to adjust the moisture
content to 65%, and placed in a gas exchange Put it in a small-hole rectangular plastic (8×8×25cm) semi-sealed
container, compact it, and sterilize it by autoclaving at a temperature of 97-100° C. for 20-30 minutes, and
adjust the moisture content to 50-65%.

2. Mycelium inoculation and management process:

At room temperature and sterile conditions, inoculate Pleurotus pelvis hyphae. Use a punch rod to evenly punch
15-20 inoculation holes with a diameter of about 1.5m and a depth of 1.8-2.4cm on the original biomass
material, and plug the mycelium clusters of about 2cm3 into the inoculation holes, so that the inoculation holes
are connected with the bacteria. Filament clusters are closely matched.

After inoculation, the temperature is controlled to be 23-28°C, and the humidity is 72-80%. After about 12-18
days of cultivation, the mycelium can fill the container.

The preparation method of the mycelial cluster is as follows: selecting a spore-bearing Pleurotus pilaris,
collecting the spores, and culturing and purifying. Under sterile conditions, use the mouth of the test tube to
pierce the fungus from the folds of the fungus, so that the fungus seed piece falls into the mouth of the tube.
After incubation at 24-26°C for 6 hours, the fungus seed pieces were taken out. Culture at a constant
temperature of 24-26°C for 1 week, and when the spores germinate, cut out the mycelium mass that grows
rapidly and is free of contamination by miscellaneous bacteria and transfer it to a tube.

Figure 1 shows the hyphae diagram of Pleurotus serrata. The diameter of the hyphae is between 0.3-1.5 μm,
which is relatively uniform. A large number of hyphae are densely arranged, crisscrossed, and branch in
different directions. It can generate pores of corresponding diameter after penetrating the biomass cell wall, and
use the ability of degrading lignin, cellulose, and hemicellulose in the cell wall of biomass materials during the
growth of fungi to induce the formation of loose pore structures inside the biomass, which is the final high ratio.
Surface area biochar preparation creates conditions.

3. Acquisition of porous agricultural waste: After the mycelium grows for 4-8 months, the porous agricultural
waste is collected, dried and crushed, and then passed through a 60-mesh sieve for use.

4. Chemical modification to optimize the pore structure of porous agricultural waste: Soak 80-120 g of dried
porous agricultural waste in 500 mL of HCl solution with a concentration of 0.8-1.2 mol·L-1, continuously stir
and heat to 90 °C and then naturally cool After warming to room temperature, the mixture was washed with
deionized water to remove excess HCl and dried through a 60 mesh screen.

4. Anaerobic pyrolysis treatment process

The modified biochar prepared above was placed in a muffle furnace at 600° C. under the protection of N2, and
pyrolyzed under anaerobic conditions for 1 hour, cooled to room temperature and taken out.

For the above chemical modification and anaerobic pyrolysis technology, the following modification
experiments were carried out:

A blank control: put into a porcelain crucible after weighing;

B Alkaline treatment: 100g of dry porous agricultural waste was soaked in 500ml of NaOH solution with a
concentration of 1mol·L-1 for 2 hours, and kept stirring, then centrifugally filtered, washed with deionized
water for 3 times to remove excess NaOH and dried. Then pass through a 60-mesh sieve;

C acid treatment: soak 100 g of dry porous agricultural waste in 500 mL of HCl solution with a concentration of
1 mol·L-1, continuously stir and heat to 90 °C, and then naturally cool to room temperature. The mixture is
washed with deionized water to remove excess HCl, and dried. Dry through a 60-mesh sieve.

Finally, the three kinds of treated porous agricultural wastes were placed in a muffle furnace for pyrolysis at 450
°C, 600 °C, and 750 °C, respectively, under anaerobic conditions for 1 hour. The data parameters of each
treatment are shown in Table 1. The 8-month oyster mushroom with the largest specific surface area and less
energy consumption is preferred, acid treatment, preparation conditions at 600 °C, and the preferred elemental
analysis of biochar is shown in Table 2.

Table 1 Specific surface area of biochar

As shown in Table 1, from the effect of pyrolysis temperature on the specific surface area of biochar, the
average specific surface area of biochar prepared at 750 °C is the largest, while the specific surface area of
biochar prepared at a preparation temperature of 600 °C is greater than 450 °C. of biochar.

Comparing the biochars prepared with different cultivation times, the biochars produced after 8 months of
cultivation have a larger specific surface area, indicating that the mycelium absorbs nutrients in the bacterial
rods and continuously disintegrates the structure of the biomass, thereby making the structure of the biomass
more loose. , high specific surface area biochar can be prepared. From the perspective of different modification
methods, the biochar prepared after hydrochloric acid treatment has a large specific surface area under high
temperature conditions.

In general, the longer the mycelium growth time and the higher the preparation temperature, the higher the
specific surface area of biochar prepared by HCl pretreatment. The untreated control sample could not increase
the specific surface area of biochar, and the penetration effect of fungal hyphae could not be reflected. Since the
comparative area of HCl-modified biochar is not much different after 8 months of culture at 600°C and 750°C,
and the biochar prepared at 750°C may damage the surface functional groups of biochar, it is preferable to
culture for 8 months. months, HCl aging treatment, 600 ℃ preparation conditions, and can reduce the energy
consumption in the biochar preparation process.

Table 2 Elemental analysis of preferred biochar

The elemental composition of the preferred biochar is shown in Table 2. The components of biochar are mainly
C, H, O, N and S and other elements, and the order of the content of the five elements is C ⟩O ⟩N ⟩H ⟩S. The ratios
of O/C, H/C and (O+N)/C can reflect the hydrophilicity, aromaticity and polarity of biochar. The greater the
ratio of O/C and (O+N)/C, the greater the hydrophilicity and polarity. The higher the ratio of H/C, the less
aromatic the biochar is. From the data, it can be seen that the preferred biochar has greater hydrophilicity,
polarity and aromaticity.

5. Process of loading ferrihydrite nanoparticles

25, 50 and 62.5g of the above biochar were added to 2L of 0.1mol L-1Fe(NO3)3 solution, respectively, to
prepare the biochar and ferrihydrite nanoparticles with mass ratios of 2, 4 and 5. Mine Nanoparticle Biochar.
And use 1mol L-1NaOH solution to adjust the pH of the system to 7.20, after stirring for 10 minutes, stabilize
the system for 1.5-2 hours, then adjust the pH to 7.20, wash the obtained precipitate with water for many times
to remove excess ions, and then freeze-dry it for later use. .

With different loadings of ferrihydrite nanoparticles, better pore remodeling morphology is preferred. Due to the
loading of ferrihydrite nanoparticles, the treatment of biochar and ferrihydrite nanoparticles with a mass ratio of
4 resulted in the formation of small pores, while the surface-loaded ferrihydrite nanoparticles increased the
surface roughness and increased the porosity, which was successfully achieved. pore structure reconstruction.

As shown in Figure 2, the pore size of modified biochar (BC) before and after loading ferrihydrite nanoparticles
(FHNPs) shows that the pore size of biochar after loading ferrihydrite nanoparticles becomes smaller, indicating
that ferrihydrite is loaded in the larger size of biochar. in the pores. Under the condition of BC:FHNPs=4, more
new pores of 1000-1200 nm appeared, which was more favorable for the adsorption of pollutants (Fig. 2a).
When the ferrihydrite nanoparticles form into the original pores and form new pores, the porosity of the
composite material does not decrease but increases, especially in the condition of BC:FHNPs=4. 20% (Fig. 2b).
From the scanning electron microscope images of the materials before and after loading ferrihydrite
nanoparticles, it can be seen that the original biochar has formed a pore-nested structure (Fig. 2c). After loading,
the ferrihydrite nanoparticles cover the surface of the biochar and enter the Inside the pores, the surface
roughness was increased (Fig. 2d), which led to the appearance of new pores and increased porosity, and the
pore structure reconstruction was successfully achieved. Through different loadings of ferrihydrite
nanoparticles, better pore reconstruction effect is preferred, that is, the condition of BC:FHNPs=4.
The following is the verification experiment of the adsorption capacity of the biochar loaded with ferrihydrite
nanoparticles in the present invention

(1) Adsorption capacity of arsenic (Example 1)

Attached isotherm (maximum adsorption capacity): the initial concentrations of As(III) and As(V) in the
isothermal experiment were 5 mg·L-1, 10 mg·L-1, 20 mg·L-1 and 40 mg·L-1, respectively. The solution was
0.1mol·L-1NaCl, and the pH of the adsorption experiment was 3.0. The experiments were divided into three
parallel groups. Weigh 0.1 g of the loaded ferrihydrite nanoparticle biochar solid to make the As(III) and As(V)
concentrations reach the final preset values, and finally adjust the pH with 0.01 mol·L-1NaOH and 0.01 mol·L-
1HCl was 3.0, the reaction was carried out in a 50 mL centrifuge tube, and the total reaction system was 20 mL.
Put it into a constant temperature shaker at a speed of 180 r·min-1. After shaking for 48 h, take out the
centrifuge tube and take 5 mL of the sample to dilute the As(III) and As(V) concentrations to be measured.

The adsorption isotherms and fitting results of As(III) and As(V) are shown in Fig. 3 and Table 3. With the
increase of the initial concentrations of As(III) and As(V), As(III) and As( The adsorption capacity of Ⅴ)
increased. When the initial concentration of As(Ⅲ) reached 600 mg·L-1, the maximum adsorption capacity of
As(Ⅲ) reached 14.566 mg·g-1, while the initial concentration of As(Ⅴ) reached 150 mg·L The adsorption
capacity of -1 reached 8.376 mg·g-1.

The obtained data were fitted with the Langmuir and Freundilich adsorption isotherm models. The Langmuir
model had an R2 of 0.997 for As(Ⅴ), and the Langmuir model could well describe the adsorption process of
As(Ⅴ) by BF, which was a monolayer adsorption. The R2 of As(III) in the Freundilich model is 0.942, which
can describe the adsorption process of As(III) by BF well.

Table 3 Langmuir and Freundlich adsorption isotherm related parameters

(2) Ability to degrade methylene blue (Example 2)

Degradation kinetics of methylene blue (MB): Weigh 0.1g of biochar (BC), ferrihydrite (FH) and biochar (BF)
loaded with ferrihydrite nanoparticles in a 50ml centrifuge tube, and weigh 20ml of 200mg ·L-1 methylene blue
solution of pH=3, then add 0.5mL 1mol·L-1 of H2O2 to the above-mentioned mixed solution, put it into a
shaker quickly, the rotating speed is 180rpm and constant temperature 25℃, start the reaction, start timing, at a
predetermined time interval (2 minutes, 10 minutes, 0.5 hours, 1 hour, 2 hours, 4 hours, 8 hours, 16 hours, 24
hours and 48 hours) quickly add 2 mL of ethanol to the reaction system to terminate the reaction, and take out
10 mL of the reaction solution, After being filtered through a 0.1 μm filter, the absorbance was measured at 665
nm to calculate the degradation amount. At the same time, methylene blue (MB) and methylene blue-H2O2
(MB-H2O2) were set as controls to compare the degradation of all systems.

As shown in Figure 4, methylene blue is only slightly degraded after 48 hours in the natural state, and the
degradation rate is about 0.03%. Under the reaction conditions of MB-H2O2, the degradation rate was 48%
after 48 hours, which was due to the oxidative property of H2O2 itself, which degraded about 50% of MB. In
the MB-BC-H2O2 system, the degradation rate of methylene blue was similar to that of MB-H2O2, indicating
that it is difficult for a single biochar to catalyze the generation of free radicals from H2O2. In the MB-FH-
H2O2 system, the degradation rate was lower than that of the MB-H2O2 and MB-BC-H2O2 systems, about
22%. The presence of ferrihydrite inhibited the degradation of methylene blue by H2O2. In the MB-BF-H2O2
system, the reaction rate was the fastest, and 60% of the degradation was completed within the first 1 hour of the
reaction, and with the extension of time, methylene blue was completely degraded after about 8 hours. It shows
that the biochar loaded with ferrihydrite nanoparticles plays a role as a catalyst in the reaction system, starting
the Fenton reaction, and the biochar loaded with ferrihydrite nanoparticles catalyzes H2O2 to generate hydroxyl
radicals, which degrades methylene blue very quickly and completely. .

As shown in Figure 5, the free radical signal of MB-BF-H2O2 treatment was detected by electron paramagnetic
resonance (EPR) spectrometer technique. The signal of hydroxyl radical (·OH) can be detected at 0.5 h, which
can explain the kinetics of the degradation reaction. The large degradation of MB within 0.5 h before the
reaction is due to the strong oxidation of ·OH. Then after 4 hours of reaction, the intensity of the free radical
signal is much greater than that at 0.5 hours of reaction. After 12 hours, 24 hours and 48 hours of reaction, the
·OH signal was basically the same as the signal intensity at 0.5 hours, which indicated that the Fenton reaction
was maintained for a long time. The ferrihydrite nanoparticle-loaded biochar acting as a catalyst has a special
pore structure, and it reacts with H2O2 to continuously generate Fe3+, which in turn converts into Fe2+,
resulting in the sustainable generation of OH.

(3) Catalytic degradation of organic matter recycling ability (Example 3)

As shown in Figure 6, two concentrations (200 and 2000 mg L-1) of methylene blue (MB) were selected to test
the reusability of biochar (BF) loaded with ferrihydrite nanoparticles, and the previous reaction BF-MB-H2O2
was recovered. The biochar loaded with ferrihydrite nanoparticles after the system reaction was repeatedly
subjected to the cyclic degradation experiment of methylene blue. After each degradation reaction, the BF was
separated from the solution, washed thoroughly with ultrapure water, and dried in an oven for use in the next
degradation experiment. After the first experiment, the biochar loaded with ferrihydrite nanoparticles can
efficiently degrade methylene blue (the degradation rate of the initial concentration of 200 and 2000 mg·L-1MB
reached 100% and 99.5%, respectively), and the subsequent methylene blue degradation rate was slow The
degradation rate of methylene blue at the 6th time was as high as 99.2% and 94.9%, respectively. After the
seventh use, the degradation rate decreased more, but still reached 92.7% and 88.2%. At two concentrations, the
degradation of methylene blue per gram of biochar loaded with ferrihydrite nanoparticles reached 276.9 mg and
2.681 g, respectively, proving the strong degradation and recycling performance of biochar loaded with
ferrihydrite nanoparticles.

(4) Simultaneous adsorption of arsenic to degrade methylene blue (Example 4)

Degradation condition process selection:

The oxidant (hydrogen peroxide) concentration, the amount of biochar loaded with ferrihydrite nanoparticles,
the effect of reaction pH and hydraulic retention time on the degradation of methylene blue are preferred.

Different amounts of biochar loaded with ferrihydrite nanoparticles (0.6 g and 1.5 g) were mixed with quartz
sand and packed in layers into a reaction column with an inner diameter of 1.5 cm and a length of 10 cm. Adjust
different oxidant (hydrogen peroxide) concentration (0.1mol L-1 and 0.2mol L-1), hydraulic retention time (8
minutes, 32 minutes and 96 minutes) and pH (gradually decrease from 4.0 to 3.0), the methylene blue
concentration is unified For 200mg L-1.

Since the biochar loaded with ferrihydrite nanoparticles plays a catalytic role, its content has little effect on the
degradation, and the peroxide concentration has no significant effect on the degradation efficiency. When the
concentration of the oxidant H2O2 is low (0.1mol L-1), A better degradation effect can be achieved (Fig. 7a).
Hydraulic retention time and pH were the main factors controlling the degradation efficiency, and the
degradation efficiency could be higher than 80% when the hydraulic retention time was 96 min at pH 3.0 (Fig.
7b).

As shown in Figure 8, As(III) is 5 mg L-1, methylene blue (MB) is 200 mg L-1, H2O2 concentration is 0.1 mol
L-1, hydraulic retention time is 32 minutes, and pH is 3.0, using 15 g of water-loaded iron The biochar material
of ore nanoparticles can simultaneously adsorb arsenic (5 mg L-1) and degrade methylene blue (200 mg L-1).

Under the optimal reaction conditions (HRT=32 minutes, pH=3.0, H2O2 concentration=0.1mol L-1), the
adsorption of arsenic and the degradation of methylene blue can achieve very good results. During the time, the
removal rate of arsenic and methylene blue was always higher than 96%. During the process, the adsorption of
arsenic reached 826 mg kg-1, and the degradation of methylene blue reached 32.6 mg kg-1.

Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled
in the art will appreciate that various substitutions, changes and modifications are possible without departing
from the spirit and scope of the invention and the appended claims, therefore , the scope of the present invention
is not limited to the contents disclosed in the embodiments.