AU2021103361A4 - Acid-resistant chitin magnetic adsorbent and preparation method and application thereof - Google Patents
Acid-resistant chitin magnetic adsorbent and preparation method and application thereof Download PDFInfo
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Abstract
An acid-resistant magnetic composite microsphere material, which uses chitin-poly(acrylic
acid) or chitin-poly(methacrylic acid) composite as the wrapping material, and with the core
surface wrapping with a layer of attapulgite magnetic material. The chitin-poly(acrylic acid) or
chitin-poly(methacrylic acid) composite microsphere material of the present invention can be
used as a high-efficiency water treatment agent for treating different polluted water bodies, and
is especially suitable for the advanced treatment of water bodies with harmful substances
remaining after conventional treatments. Moreover, the implementation process is relatively
simple which aiming at the current advanced treatment of water bodies. It requires no
renovation of the original water treatment process on a large scale but simply adding another
one step on the basis of the original process, the preparation method disclosed in the present
invention.
Description
Acid-resistant chitin magnetic adsorbent and preparation method and application
thereof
The invention relates to a water treatment agent. Specifically, it is a magnetic composite
microsphere material with a polymer material as wrapping and a magnetic material as the
core.
Water is the most basic need for human survival. However, the problem of water
pollution has become increasingly prominent along with the rapid development of
industry. Meanwhile, the continuous improvement of people's living standards has also
put forward higher requirements for water quality. In terms of the characteristics of
current water pollution, soluble organic substances and bio-refractory compounds in
water bodies are increasing year by year, but the current conventional water treatment
methods are not effective in removing this type of pollutants. At the same time, many
current water treatment chemicals may still produce secondary pollutants that are harmful
to the environment, which undoubtedly has an adverse impact on environmental
protection and sustainable development. Therefore, seeking a water treatment agent with
high efficiency, environment and cost friendliness and no secondary pollution is the
current research hot spot and frontier subject in the field of water treatment.
Natural polymers are macromolecules in the natural resources of animals, plants and
microorganisms. They are easily decomposed into water, carbon dioxide, etc. after being
discarded. In addition, as an environmentally friendly material with a wide range of
sources and non-toxic. It is worth mentioning that natural polymer materials are also a type of renewable resources that are completely separated from petroleum resources and can be defined as inexhaustible. It is precisely because of the above-mentioned excellent properties of natural polymer materials that they have been widely used in many fields such as biology, medicine and food processing. Furthermore, in the field of water treatment, natural polymers have been regarded as one of the best alternative materials for water treatment agents currently in use. The chains of natural polymers are distributed with a large number of active groups, such as free hydroxyl groups and amine groups, which have a flocculating effect.
The structural formula of chitin is R=CH 3CO- or -H.
H OH H 0
HO HO HNHR NHR H H H Hn
Chitin is one of the most excellent natural polymer materials and the second largest
natural polymer compound in the world after cellulose. It's widely present in crustaceans,
such as shrimps, crabs, insects and algae. The molecular chain of chitin contains reactive
groups -NH 2 and -OH, which will form cationic polyelectrolytes in acidic solutions and
shows good flocculation performance. In addition, chitin also has a good complexation
effect, so that it can complex with transitional metal ions, humic acids and surfactants in
the water to achieve the removal of water-soluble organic pollutants. In this way, chitin
has the comprehensive properties of flocculation, metal ion adsorption and water-soluble
organic removal. Undoubtedly, the development of water treatment agents based on
chitin is one of the important development directions in the current water treatment field.
However, chitin also has shortcomings in practical applications, especially after the
pollutants being removed by adsorption, it is sometimes difficult to effectively and
quickly separate chitin from the water body. Development of a simple and quick
separation method is undoubtedly of great significance for the further application of
chitin in water treatment.
In recent years, magnetic separation technology has been applied to the water treatment
industry. It is a technology that uses the force of a magnetic field to separate different
magnetic substances. Since the magnetic force of a magnetic substance in a magnetic
field is many times larger than gravity, it has the advantages of large processing capacity,
high liquid-solid separation efficiency and small footprint.
However, most of the compounds (including chitin) are not magnetic. If they are to be
processed by magnetic separation technology, they must be made magnetic. The
commonly used method is to organically combine such non-magnetic compounds with
magnetic materials (such as Fe, Fe304, etc.) to form a so-called core-shell microsphere
structure with magnetic materials as the core and non-magnetic materials as the shell.
Thus realizing the magnetization of the material, and then the magnetic separation
technology can be used to achieve the purpose of sewage purification. In addition, most
of these magnetic substances are easily dissolved in acidic conditions hence lose their
magnetism. The magnetic substance should be appropriately modified to improve its acid
resistance ability.
In order to further improve the performance of the chitin adsorbent and overcome the
shortcomings of difficult to rapid separate chitin from water, it is necessary to find a new
polymer material as the shell, which should not only has the functions of adsorption and complexation of chitin, but also has the efficacy of easy separation and will surely become a highly efficient water treatment agent with good magnetic separation efficiency and acid resistance ability.
The purpose of the present invention is to provide a new type of acid-resistant magnetic
composite microsphere material with composite polymer material as the wrapping
material and modified magnetic material as the core. This material can effectively remove
harmful subsistence from the water body through adsorption, complexation, etc., and can
be effectively separated from the water body through magnetic separation technology for
recycling and reuse, and it has good acid resistance ability.
Another object of the present invention is to provide a method for preparing an acid
resistant magnetic composite microsphere material.
Another object of the present invention is to provide an application of acid-resistant
magnetic composite microsphere material as a water treatment agent.
In order to achieve the purpose of the present invention, the technical solution of the
present invention is as follows:
An acid-resistant magnetic composite microsphere material, which uses chitin
poly(acrylic acid) or chitin-poly(methacrylic acid) composite as the wrapping material,
and the surface wrapped with a layer of attapulgite magnetic material as the core. The
above-mentioned acid-resistant magnetic composite microsphere material can be
obtained by grafting or blending the hydrophilic degradable material - chitin - and
synthetic polymer poly(acrylic acid) or poly(methacrylic acid). For grafting methods,
please refer to: Evaluation of the flocculation performance of carboxymethyl chitosan- graft- polyacrylamide .an novel amphoteric chemically bonded composite flocculant;
Zhen Yang, Bo Yuan, Xin Huang, Junyu Zhou, Jun Cai, Hu Yang, Aimin Li, Rongshi
Cheng, Water Research, 2012, 46(1), 107-114.
In the above mentioned acid-resistant magnetic composite microsphere material, the
content of poly(acrylic acid) or poly(methacrylic acid) in the chitin-poly(acrylic acid) or
chitin-poly(methacrylic acid) composite is 5-80% (mass).
In the above mentioned acid-resistant magnetic composite microsphere material, the
magnetic material is Fe or Fe304 coated with a layer of attapulgite, the particle size is
10nm-10Om, and the content of the attapulgite in the magnetic material is 25-75% (mass),
The magnetic material is 10-20% of the mass of the polymer composite.
The magnetic composite microsphere material of the present invention is prepared by a
reversed-phase suspension cross-linking method. The specific method is:
A method for preparing the above-mentioned acid-resistant magnetic composite
microsphere material is to mix and disperse the chitin-poly(acrylic acid) or chitin
poly(methacrylic acid) composite and the magnetic material in an acidic aqueous
solution, and then use liquid paraffin or cyclohexane, etc. as oil phase, and then formed
by cross-linking glutaraldehyde. The specific preparation method includes the following
steps:
Step 1. Dissolve the chitin-poly(acrylic acid) or chitin-poly(methacrylic acid) composite
in an acidic aqueous solution to prepare an acidic solution with a concentration of 2-10%
by mass;
Step 2. Disperse the magnetic material in an acidic solution by ultrasonic, add liquid
paraffin or cyclohexane, stir evenly, and cross-link with glutaraldehyde to form a magnetic composite microsphere material with a polymer cross-linked network structure.
The volume ratio of the added amount of liquid paraffin or cyclohexane to the acidic
aqueous solution is 1-5:1.
In the preparation method of the acid-resistant magnetic composite microsphere material,
the chitin-poly(acrylic acid) or chitin-poly(methacrylic acid) composite is a mixture of
degradable polymer material chitin and the polymer material poly(acrylic acid) or methyl
poly(acrylic acid), or the graft copolymer of chitin-poly(acrylic acid) or chitin
poly(methacrylic acid), which can be prepared by conventional methods in the art.
(Evaluation of the flocculation performance of carboxymethyl chitosan-graft
polyacrylamide, an novel amphoteric chemically bonded composite flocculant; Zhen
Yang, Bo Yuan, Xin Huang, Junyu Zhou, Jun Cai, Hu Yang, Aimin Li, Rongshi Cheng,
Water Research, 2012, 46(1), 107-114.)
In the above-mentioned preparation method of acid-resistant magnetic composite
microsphere material, the acid-resistant magnetic particles are prepared by the following
method: magnetic particles (Fe or Fe304) are dispersed in an aqueous solution to obtain a
content of 0 . 1 -1% (mass), add attapulgite (the mass ratio of attapulgite to magnetic
particles is 0.5-10:1), and react for 1-3h.
In the preparation method of the acid-resistant magnetic composite microsphere material,
the amount of glutaraldehyde is 0 . 1 -10% of the mass of the chitin-poly(acrylic acid) or
chitin-poly(methacrylic acid) composite, and the crosslinking pH value is 7-10, the cross
linking temperature is 35-45°C, and the cross-linking time is 1-3 hours.
The chitin-polyacrylamide magnetic composite microsphere material of the present
invention can be used as a water treatment agent, and has many functions such as good flocculation ability, metal ion adsorption, deodorization, decolorization and effective reduction of COD value, and has a certain universality. It is applicable to treat wastewater from printing and dyeing, electroplating and other enterprises wastewater, such as heavy metal ion wastewater, dye wastewater, etc.
The chitin-poly(acrylic acid) or chitin-poly(methacrylic acid) composite microsphere
material of the present invention can effectively remove harmful substances (such as
metal ions, dye substances, etc.) in the water body. It requires relatively short time to
complete, therefore improving the efficiency of the use of materials.
Moreover, as a biodegradable material, chitin has the characteristics of non-toxicity, no
secondary pollution, etc., and has a wide range of applications; furthermore, the magnetic
separation technology can effectively separate and gather chitin after the treatment is
completed, therefore felicitate recycle and reuse, and reducing cost even more. In
addition, the material has good acid resistance and can be used under acidic conditions as
normal.
Compared with simple chitin, the chitin-poly(acrylic acid) or chitin-poly(methacrylic
acid) composite has an carboxylic acid groups in addition to the amino and hydroxyl
active groups on the molecular chain, which has a strong adsorption and removal effect
on the pollutants that have affinity with the carboxylic acid group. Therefore, the chitin
poly(acrylic acid) or chitin-poly(methacrylic acid) composite microspheres have the dual
functions of chitin and poly(acrylic acid) or poly(methacrylic acid), and undoubtedly
improved their actual sewage treatment capacity greatly.
The chitin-poly(acrylic acid) or chitin-poly(methacrylic acid) composite microsphere
material of the present invention can be used as a high-efficiency water treatment agent for treating different polluted water bodies, and is especially suitable for the advanced treatment of water bodies that still have residual harmful substances after conventional treatments. Moreover, the implementation process is relatively simple. For the current advanced treatment of water bodies, there is no need to extensively modify the original water treatment process, and only need to add an adsorption process on the basis of the original process.
The preparation method of the chitin-poly(acrylic acid) or chitin-poly(methacrylic acid)
composite microsphere material of the present invention requires simple operation and
short synthesis time, the main raw material it used can be natural polymer products with
abundant sources, low cost, and suitable for large-scale industrialization. It is surely an
economical preparation method for obtaining high-quality water treatment agents.
Figure 1 shows the comparison of the removal of copper (*), lead (A) and mercury (m)
ions in water by magnetic composite microspheres made of two different polymer
materials.
(a): Chitin microspheres; (b): Chitin-poly(acrylic acid) composite microspheres
Figure 2 shows the comparison of the removal of methyl blue in water by magnetic
composite microspheres made of two different polymer materials.
(a): Chitin microspheres; (b): Chitin-poly(acrylic acid) composite microspheres
The following embodiments further describe the present invention, which are only used
to illustrate the present invention and should not be regard as limiting the present
invention.
Embodiment 1
Disperse the magnetic particles (Fe304) (particle size: 200nm) in the aqueous solution to
obtain a suspension with a content of 0.4% (mass), and add the attapulgite solution (the
mass ratio of attapulgite and Fe304 is 4:1) After reacting for 2 hours, magnetic particles
of Fe304 coated with attapulgite (attapulgite occupies 50% of the mass of the magnetic
particles) are obtained, and the particle size is 500nm.
The chitin and poly(acrylic acid) (mass ratio: 2:1) are mixed and dissolved in an aqueous
solution of acetic acid with a concentration of 1% by mass to prepare a solution with a
concentration of 3% by mass. After the solution is uniformly dissolved, the attapulgite
will be wrapped around magnetic particles Fe304 and dispersed in the above polymer
solution by ultrasound (magnetic particles account for 10% of the polymer material
mass), add liquid paraffin (the volume ratio of liquid paraffin to the above mixed solution
is 2.5:1), and after adjust the pH value to 10, add glutaraldehyde aqueous solution
(glutaraldehyde accounts for 1% of the mass of the polymer material), and cross-link at
35°C for 2 hours to obtain a sample of chitin-poly(acrylic acid) magnetic composite
microspheres (poly(acrylic acid) accounts for 45% of the total mass of the polymer
material).
Take the microspheres as a water treatment agent, using copper, lead, and mercury ion
solutions as simulated heavy metal sewage. Measure the removal of metal ions in the
above water under different pH conditions (acidic to weakly acidic, neutral and alkaline
conditions, heavy metal ions are prone to form hydroxide precipitates, and the amount of
adsorbent material adsorption cannot be determined), as shown in Figure 1. Figure 1
shows the result of using above-mentioned magnetic composite microspheres as a water treatment agent to detect the removal of metal ions in water. Compared with single chitin magnetic microspheres, the adsorption capacity is greatly increased under different pH conditions. And under acidic conditions, the structure and performance of the adsorbent material remain stable.
In addition, for treating dye wastewater, use methyl blue as a simulated dye wastewater,
measure the removal of methyl blue impurities in the above water by a spectrophotometer
(wavelength: 662nm) under different pH conditions, as shown in Figure 2. Figure 2
shows the result of using the above-mentioned magnetic composite microspheres as a
water treatment agent to detect the removal of methyl blue impurities in the water body.
Compared with single chitin magnetic microspheres, the adsorption capacity under
different pH conditions also significantly improved. And under acidic conditions, the
structure and performance of the adsorbent material remain stable.
Embodiment 2
Disperse the magnetic particles (Fe) (particle size: 5nm) in the aqueous solution to obtain
a suspension with a content of 0.1% (mass percentage), and add the attapulgite solution
(the mass ratio of attapulgite to Fe is 0.5:1) After reacting for 1 hour, Fe magnetic
particles coated with attapulgite (attapulgite occupies 25% of the mass of the magnetic
particles) are obtained, and the particle size is 10 nm.
Dissolve the chitin-poly(methacrylic acid) graft copolymer (grafting rate: 1.2) in a 1%
acetic acid aqueous solution to prepare a 3% solution. After the solution was uniformly
dissolved, disperse the magnetic particles Fe that wrapped with the attapulgite in the
above polymer solution (magnetic particles account for 10% of the polymer material
mass) by ultrasound, add liquid paraffin (the volume ratio of liquid paraffin to the above mixed solution is 5:1), adjust the pH to 7, and add glutaraldehyde aqueous solution
(Glutaraldehyde accounts for 3% of the mass of polymer materials), cross-link at 45°C
for 1 hour to obtain chitin-poly(methacrylic acid) magnetic composite microspheres
(poly(methacrylic acid) accounts for 58% of the total mass of polymer materials).
Preparation of chitin-poly(methacrylic acid) graft copolymer: Disperse chitin in 0.5%
acetic acid solution to prepare a solution with a concentration of 5% by mass of chitin.
After the solution is uniform, add cerium ammonium nitrate as an initiator (the amount is
1% of the moles of chitin unit), then add methacrylic acid monomer (mass ratio to chitin:
3:1), react at 55°C for 2 hours, then use acetone as precipitant to precipitate and separate
the product, then obtain chitin-poly(methacrylic acid) graft copolymer, the grafting rate is
1.2.
The microspheres were used as a water treatment agent, and copper, lead, mercury ions,
and methyl blue solutions were used as simulated sewage to determine the water
treatment conditions in the above water body. The performance was similar to that of
embodiment 1.
Embodiment 3
Disperse the magnetic particles (Fe304) (particle size: 5[m) in the aqueous solution to
obtain a 1% (mass) suspension, add the attapulgite solution (attapulgite and magnetic
particle mass ratio is 10:1), and react for 3 hours, obtain the Fe304 magnetic particles that
wrapped with attapulgite (attapulgite occupies 75% of the mass of the magnetic
particles), and the particle size is 10tm.
Dissolve chitin and poly(methacrylic acid) in a 1% acetic acid aqueous solution with a
mass mixing ratio of 1:4 to prepare a solution with a total concentration of 3%. After the solution is uniform, the magnetic particles of Fe304 that wrapped with the attapulgite are dispersed in the above polymer solution (magnetic particles account for 20% of the polymer material mass) by ultrasonic, add cyclohexane (the volume ratio of cyclohexane and the above mixed solution is 1:1), adjust the pH value to 8, add glutaraldehyde aqueous solution (pentane dialdehyde accounts for 0.1% of the mass of polymer materials), cross-linked at 35°C for 3 hours to obtain a sample of chitin-poly(methacrylic acid) magnetic composite microspheres (poly(methacrylic acid) accounts for 80% of the total mass of polymer materials).
Take the microspheres as a water treatment agent, and use copper, lead, mercury ions,
and methyl blue solutions as simulated sewage to determine the water treatment
conditions in the above-mentioned water body. The performance was similar to that of
embodiment 1.
Disperse the magnetic particles (Fe) (particle size: 100nm) in the aqueous solution to
obtain a suspension with a content of 0.25% (mass), add the attapulgite solution (the mass
ratio of attapulgite to magnetic particles is 3), and react for 1.5 hours, obtain the magnetic
particles Fe (attapulgite occupies 40% of the mass of magnetic particles) wrapped with
attapulgite, and the particle size is 320nm.
Dissolve chitin and poly(acrylic acid) in a 1% acetic acid aqueous solution with a mass
mixing ratio of 19:1 to prepare a solution with a total concentration of 3%. After the
solution is uniform, the magnetic particles Fe wrapped with attapulgite are dispersed in
the above-mentioned polymer solution (magnetic particles account for 15% of the mass
of the polymer material), add liquid paraffin (the volume ratio of liquid paraffin to the
above mixed solution is 3:1), adjust the pH to 10, add glutaraldehyde aqueous solution
(glutaraldehyde accounts for 7% of the mass of the polymer material), cross-link at 45°C
for 2.5 hours to obtain a sample of chitin-poly(acrylic acid) magnetic composite
microspheres (poly(acrylic acid) accounts for 5% of the total weight of the polymer
material).
Take the microspheres as a water treatment agent, and copper, lead, mercury ions, and
methyl blue solutions as simulated sewage to determine the water treatment conditions in
the above water body. The performance was similar to that of embodiment 1.
Embodiment 5
Disperse magnetic particles (Fe304) (particle size: 800nm) in an aqueous solution to
obtain a suspension with a content of 0.7% (mass), and add the attapulgite solution (the
mass ratio of attapulgite to magnetic particles is 6.5), reacted for 2.5 hours, and obtain the
magnetic particles Fe304 wrapped with attapulgite (attapulgite occupies 60% of the mass
of the magnetic particles), with a particle size of 6m.
Dissolve the chitin-poly(acrylic acid) graft copolymer (grafting rate: 2.5) in 1% acetic
acid aqueous solution to prepare a 3% solution. After the solution was uniform, disperse
the magnetic particles Fe304 that wrapped with attapulgite in the above polymer solution
(magnetic particles account for 10% of the polymer material mass) by ultrasonic, add
cyclohexane (the volume ratio of cyclohexane to the above mixed solution is 4:1), adjust
the pH to 9, add glutaraldehyde aqueous solution (glutaraldehyde accounts for 10% of the
mass of polymer materials), cross-link at 45°C for 1.5 hours to obtain a sample of chitin
poly(acrylic acid) magnetic composite microspheres (poly(acrylic acid) accounts for 25%
of the total mass of polymer materials).
Preparation of chitin-poly(acrylic acid) graft copolymer (grafting rate: 2.5): Disperse
chitin in 0.5% acetic acid solution, prepare a solution with a concentration of 5% by mass
of chitin. After the solution is uniform, add cerium ammonium nitrate as initiator
(addition amount is 1% of the moles of chitin unit), then add acrylic acid monomer (mass
ratio to chitin: 6:1), react at 55°C for 2 hours, Then, use acetone as a precipitant to
precipitate and separate the product to obtain a chitin-poly(acrylic acid) graft copolymer.
The grafting rate is 2.5.
Use the microspheres as a water treatment agent, and copper, lead, mercury ions, and
methyl blue solutions as simulated sewage to determine the water treatment conditions in
the above water body. The performance was similar to that of embodiment 1.
Although the present invention has been described in detail with reference to some
specific examples, it is obvious for those skilled in the art to make various changes or
modifications as long as they do not depart from the spirit and scope of the present
invention.
Claims (8)
1. An acid-resistant magnetic composite microsphere material, characterized in that it
uses chitin-poly(acrylic acid) or chitin-poly(methacrylic acid) composite as the wrapping
material with core surface wrapping with a layer of attapulgite magnetic material.
2. The acid-resistant magnetic composite microsphere material according to claim 1,
wherein the composite is obtained by grafting or blending chitin with poly(acrylic acid)
or poly(methacrylic acid).
3. The acid-resistant magnetic composite microsphere material according to claim 1,
wherein the mass percentage of poly(acrylic acid) or poly(methacrylic acid) in the chitin
poly(acrylic acid) or chitin-poly(methacrylic acid) composite is 5-80%.
4. The acid-resistant magnetic composite microsphere material according to claim 1,
characterized in that: the magnetic material is Fe or Fe304 that wrapped with a layer of
attapulgite, the particle size is 10nm-10tm, and the mass percentage of attapulgite in the
magnetic material is 25-75%, and the magnetic material is 10-20% of the mass of the
polymer composite.
5. A method for preparing the acid-resistant magnetic composite microsphere material
according to claim 1, characterized in that it comprises the following steps:
Step 1. Dissolve the chitin-poly(acrylic acid) or chitin-poly(methacrylic acid) composite
in an acidic aqueous solution to prepare an acidic solution with a concentration of 2-10%
by mass;
Step 2. Disperse the magnetic material in an acidic solution by ultrasonic, add liquid
paraffin or cyclohexane, stir evenly, and cross-link with glutaraldehyde to form a
magnetic composite microsphere material with a polymer cross-linked network structure.
The volume ratio of the added amount of liquid paraffin or cyclohexane to the acidic
aqueous solution is 1-5:1.
6. The preparation method of acid-resistant magnetic composite microsphere material
according to claim 5, characterized in that: the acid-resistant magnetic particles are
prepared by the following method: Fe or Fe304 magnetic particles are dispersed in an
aqueous solution to obtain a suspension with mass percentage of 0.1% to 1%, and the
mass ratio of the attapulgite to the magnetic particles is 0.5-10:1, and react for 1-3h.
7. The preparation method of acid-resistant magnetic composite microsphere material
according to claim 5, characterized in that: the amount of glutaraldehyde is 0.1-10% of
the mass of chitin-poly(acrylic acid) or chitin-poly(methacrylic acid) composite. The
cross-linking pH is 7-10, the cross-linking temperature is 35-45°C, and the cross-linking
time is 1-3 hours.
8. Application of the acid-resistant magnetic composite microsphere material of claim 1
in water treatment.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024123276A3 (en) * | 2022-12-07 | 2024-07-11 | T.C. Erciyes Üniversitesi | Adsorbent bead |
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2021
- 2021-06-15 AU AU2021103361A patent/AU2021103361A4/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024123276A3 (en) * | 2022-12-07 | 2024-07-11 | T.C. Erciyes Üniversitesi | Adsorbent bead |
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