AU2020102174A4 - A kind of modified starch/quartz sand composite microsphere and its preparation method and application - Google Patents
A kind of modified starch/quartz sand composite microsphere and its preparation method and application Download PDFInfo
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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Abstract
The invention unveils a kind of modified starch/quartz sand composite microsphere and its
preparation method and application. The composite microsphere is a core-shell structure, with
modified starch as the shell and quartz sand as the core. Wherein, the modified starch is
prepared by etherification of starch and quaternary ammonium salt modifier. The specific
preparation method is to mix and disperse the modified starch and quartz sand into aqueous
solution, and then crosslink them through epichlorohydrin with using cyclohexane as the oil
phase. According to the invention, the composite microsphere prepared by using modified
starch and quartz sand not only can effectively remove harmful substances in water body and
inhibit the growth of bacteria through adsorption, complexation and other functions, but also
can be effectively separated from water body by its own gravity for recycle and reuse. The
invention has a wide range of applications and saves cost.
Description
PATENTS ACT 1990
A kind of modified starch/quartz sand composite microsphere and its preparation
method and application
The invention is described in the following statement:-
A kind of modified starch/quartz sand composite microsphere and its
preparation method and application
The invention belongs to the technology field of wastewater treatment, involving a new
composite material and its application in water environment governing field, and
specifically relates to a kind of modified starch/quartz sand composite microsphere and
its preparation method and application.
In recent years, with the rapid development of economy and industry, water pollution is
becoming more and more serious, while water is the basic need of human survival. At the
same time, with the continuous improvement of people's living levels, higher
requirements are put forward for water quality. In view of the characteristics of current
water pollution, soluble organic substances, non-biodegradable compounds and harmful
microorganisms in water are increasing year by year, but the removal effect of this kind
of pollutants by conventional water treatment methods is not significant at present.
Concurrently, many existing water treatment disinfectants may also produce secondary
pollutants harmful to the environment, which undoubtedly brings adverse effects on
environmental protection and sustainable development. Therefore, it is a hot issue and
frontier topic in the current field of water treatment to seek water treatment disinfectants
with high efficiency, environmental protection, economy, and no secondary pollution.
As matters stand, the modified starch is usually used for sewage treatment, because starch
is a natural polymer compound of polysaccharides condensed from glucose. Moreover, it is the most abundant renewable material in nature. It is degradable and returns to nature in the form of carbon dioxide and water after degradation, which will not cause environmental pollution. Its molecular structure is mainly composed of glucose units, containing many hydroxyl groups. Besides, it can be modified by physical, chemical and biological methods, which means to change the natural characteristics of starch by introducing new functional groups into starch molecules or changing the size of starch molecules and the properties of starch granules, so that it can produce complexation with transition metal ions, humic acid substances and surfactants in water, so as to realize the removal of water-soluble organic pollutants. In this way, the starch has the combination properties of metal ion adsorption and water-soluble organic matter removal. Therefore, introducing other functional groups onto the starch sugar ring to enhance its water treatment performance is the development direction of starch-based water treatment agents in the water treatment field.
However, the size of modified starch particles is very small, and it is difficult to separate
from water quickly after removing the pollutants in water by adsorption. Because of this,
the invention grafts or binds a large number of other active functional groups onto the
starch chain to further improve the water treatment property of starch, under the premise
of ensuring its biocompatibility. At the same time, the invention seeks a simple, fast and
cheap separation method to prepare high efficiency water treatment agent with good
separation effect so as to overcome the problem that starch is not easy to be separated
from water. Moreover, the modified starch has the functions of adsorbing soluble organic
substances, non-biodegradable compounds and harmful microorganisms in polluted
water.
The present invention aims to solve the problems existing in the prior art by providing a
modified starch/quartz sand composite microsphere, a preparation method and
application thereof, so that the composite microsphere material can effectively remove
harmful substances in water bodies and inhibit bacterial growth through adsorption,
complexation and the like, and can be effectively separated from water bodies by self
gravity for recycling.
To achieve the above purpose, the present invention provides the following scheme.
The invention provides a modified starch/quartz sand composite microsphere,
characterized by having a core-shell structure, with modified starch as the shell and
quartz sand as the core. Wherein, the modified starch is prepared by etherification of
starch and quaternary ammonium salt modifier.
Preferably, the quaternary ammonium salt modifier is one of 3-Chloro-2
Hydroxypropyldimethyl benzyl ammonium chloride, 3-Chloro-2
Hydroxypropyltrimethyl ammonium chloride, 3-Chloro-2-Hydroxypropyltriethyl
ammonium chloride and 3-Chloro-2-Hydroxypropyltripropyl ammonium chloride.
Preferably, the content of the quaternary ammonium salt modifier in the modified
starch/quartz sand composite microsphere is 5 to 80wt%. The quartz sand material
accounts for 10-20% of the total weight of the modified starch.
A preparation method of modified starch/quartz sand composite microsphere
characterized by comprising following steps.
(1) Preparation of modified starch
Disperse the starch in a hydroxide aqueous solution with a mass percentage of 1-30%. Let
it alkalinize for 0.5-2h. Then add quaternary ammonium salt modifier and make them
react at 30-80°C for 0.5-4h. After the reaction is completed, ethanol is used as precipitant
to precipitate and separate and then modified starch is obtained.
(2) Preparation of modified starch/quartz sand composite microsphere
Dissolve the modified starch prepared by step (1) in water and make the mass percentage
concentration of the modified starch in the modified starch solution is 1%. After the
solution is uniform, disperse quartz sand material in the modified starch solution by
ultrasonic, add cyclohexane, and stir them uniformly, then crosslink them through
epichlorohydrin to obtain the modified starch/quartz sand composite microsphere.
Preferably, in step (1), the hydroxide aqueous solution is one of sodium hydroxide and
potassium hydroxide, and the ratio of the starch to the hydroxide aqueous solution is 1:2
5.
Preferably, in step (1), the mass ratio of that quaternary ammonium salt modifier to the
starch is 0. 1-3: 1.
Preferably, in step (2), the volume ratio of the added amount of cyclohexane to the
modified starch solution is 1-10: 1.
Preferably, in step (2), the used amount of epichlorohydrin is 0. 1-10% of that of
modified starch.
Preferably, in step (2), during the epichlorohydrin cross-linking process, the pH value of
the reaction solution is controlled at 7-10, meanwhile, the temperature is 35-65°C, and the
time is 0.5-3h.
Another object of the present invention is to provide an application of modified
starch/quartz sand composite microspheres as a water treatment agent in treating dye
wastewater and heavy metal wastewater, which is used for removing harmful substances
in wastewater and inhibiting and killing harmful microorganisms in water.
The present invention discloses the following technical effects:
1. The modified starch/quartz sand composite microsphere of the present invention can be
used as a water treatment agent to effectively adsorb and remove harmful substances
(such as dye substances, metal ions, etc.) in water. At the same time, it can inhibit and kill
harmful microorganisms in water in a short time, so as to improve the use efficiency of
materials, which has certain universality and is suitable for wastewater from printing and
dyeing, electroplating and other enterprises.
2. In addition to hydroxyl active groups, the molecular chain of the modified starch of the
present invention also possesses active groups such as quaternary ammonium salt groups.
Therefore, it not only has a strong adsorption and removal effect on pollutants that have
affinity with cationic quaternary ammonium salt groups in sewage, but also can
effectively kill harmful microorganisms in water. With the multiple effects, its sewage
treatment capacity has been greatly improved.
3. Due to the high density of quartz sand (2.61g/cm 3), the modified starch/quartz sand
composite microspheres of the present invention can effectively and quickly separate
from the water body by its own gravity and be recycled after treating wastewater.
Moreover, the quartz sand is cheap, which effectively reduces the cost.
4. The starch used in the modified starch/quartz sand composite microsphere of the
present invention is biodegradable material, and the quartz sand is inorganic mineral material, both of which have the characteristics of no toxicity, no secondary pollution, etc. The quaternary ammonium salt modifier introduced into starch molecule has good antibacterial effect and wide application range.
5. The modified starch/quartz sand composite microsphere of the present invention is an
efficient water treatment agent for treating different polluted water bodies, especially for
advanced treatment of water bodies with residual harmful substances after conventional
treatment. Besides, its implementation process is simple, and effect is remarkable.
6. The preparation method of the modified starch/quartz sand composite microspheres of
the present invention is simple in operation and short in synthesis time. Moreover, it is an
economical preparation method for obtaining high-quality water treatment agent because
its main raw materials used can be natural polymer materials with abundant sources and
low cost, which is suitable for large-scale industrial production.
Figure 1 is the infrared spectrogram of (a) quartz sand, (b) starch microspheres, (c)
quaternary ammonium salt modified starch and (d) modified starch/quartz sand
composite microspheres.
Figure 2 shows the effects of starch microspheres, quartz sand, modified starch and
modified starch/quartz sand composite microspheres on the adsorption of (a) acid green
(AG25) at solution pH.
Figure 3 shows the effects of starch microspheres, quartz sand, modified starch, and
modified starch/quartz sand composite microspheres on the adsorption of (b) methylene
orange (MO) at solution pH.
Figure 4 shows the effects of starch microspheres, quartz sand, modified starch and
modified starch/quartz sand composite microspheres on the adsorption of (c) sodium
arsenate (As) at solution pH.
Figure 5 is a schematic diagram of the germicidal removal effect of the present invention
on Escherichia coli.
The technical scheme in the embodiment of the invention will be described clearly and
completely below. Obviously, the described embodiment is only a part of the
embodiments of the invention, not all the embodiments. Based on the embodiment of the
invention, all other embodiments obtained by ordinary technical personnel in the art
without creative labour should belong to the protection scope of the invention.
To make the above-mentioned purposes, features, and advantages in the invention more
obvious and easier to understand, the present invention is further described in detail in
combination with the attached drawings and specific embodiment.
In the following embodiment, the raw material-starch used is corn starch produced by
Shandong Binzhou Jinhui Corn Development Co., Ltd., with a mass average molar mass
of about 150,000.
Embodiment 1
(1) Preparation of modified starch
Disperse the starch in a 5% sodium hydroxide aqueous solution, besides, the ratio of
starch to sodium hydroxide aqueous solution is 1:4. Let it alkalinize for 1h at 70°C. Then
add 3-Chloro-2-Hydroxypropyldimethyl benzyl ammonium chloride, in the ratio of 1:1 to
starch, and make them react at 70°C for 2h. After the reaction is completed, ethanol is used as precipitant to precipitate and separate and then modified starch is obtained. By 1 H
NMR analysis, the substitution degree of cationic quaternary ammonium salt group is
42% (mass).
(2) Preparation of modified starch/quartz sand composite microsphere
Dissolve the modified starch prepared by step (1) in water and prepare the modified
starch solution with mass percentage concentration of 1%. After the solution is uniform,
disperse quartz sand material in the modified starch solution by ultrasonic, accounting for
10% of the total weight of the modified starch, then add cyclohexane, in a volume ratio of
5:1 to modified starch, and stir them uniformly. After adjusting the pH to 8, add
epichlorohydrin accounting for 1% of modified starch weight and then crosslink them at
50°C for lh to obtain the modified starch/quartz sand composite microsphere.
The results of infrared spectrum analysis of quartz sand, starch microspheres, quaternary
ammonium salt modified starch and modified starch/quartz sand composite microspheres
are shown in Fig.1. From the curves of (b) starch microspheres, (c) quaternary
ammonium salt modified starch and (d) modified starch/quartz sand composite
microspheres, it can be seen that the broad peak with wave number of 3250cm- 1 is O-H
characteristic absorption peak; in the curves of (c) quaternary ammonium salt modified
starch and (d) modified starch/quartz sand composite microspheres, the broad peak with
wave number of 1471cm-1 is the characteristic absorption peak of quaternary ammonium
salt methyl, which proves that quaternary ammonium salt modifier has been attached to
starch molecular chain.
Using the prepared modified starch/quartz sand composite microspheres as water
treatment agent, methylene orange and acid green as simulated dye wastewater, and sodium arsenate as simulated heavy metal wastewater, and then determining the removal conditions of dyes and heavy metal salt impurities by the modified starch/quartz sand composite microspheres in the above water body through spectrophotometer and atomic absorption spectrometer respectively. Wherein, methylene orange is determined at wavelength 463nm by spectrophotometer, and acid green is determined at wavelength
642nm. Sodium arsenate is determined by atomic absorption spectrometer. As shown in
Figs. 2-4, at different pH values of the solution, starch microspheres and quartz sand have
no adsorption effect on methylene orange, acid green and sodium arsenate; compared
with quaternary ammonium salt modified starch, the adsorption capacity of modified
starch/quartz sand composite microspheres is greatly increased, and after adsorption, it is
completely separated from water in 5 minutes under the action of self-gravity, while
quaternary ammonium salt modified starch is not completely precipitated after half an
hour.
Further, taking Escherichia coli suspension (1.Ox1O8CFU/mL) as a simulated water
sample, the sterilization effect of modified starch/quartz sand composite microspheres is
observed by spectrophotometer at a wavelength of 630nm when pH is 7. As shown in
Fig.5, when the dosage of modified starch/quartz sand composite microspheres is 5mg/L,
the sterilization effect is the best, and the removal rate of Escherichia coli in water sample
is over 96%.
Embodiment 2
(1) Preparation of modified starch
Disperse the starch in a 1% sodium hydroxide aqueous solution, besides, the ratio of
starch to sodium hydroxide aqueous solution is 1:2. Let it alkalinize for 2h at 70°C. Then add 3-Chloro-2-Hydroxypropyltrimethyl ammonium chloride, in the ratio of 0.1:1 to starch, and make them react at 80°C for 4h. After the reaction is completed, ethanol is used as precipitant to precipitate and separate and then modified starch is obtained. By 1 H
NMR analysis, the substitution degree of cationic quaternary ammonium salt group is 6%
(mass).
(2) Preparation of modified starch/quartz sand composite microsphere
Dissolve the modified starch prepared by step (1) in water and prepare the modified
starch solution with mass percentage concentration of 1%. After the solution is uniform,
disperse quartz sand material in the modified starch solution by ultrasonic, accounting for
10% of the total weight of the modified starch, then add cyclohexane, in a volume ratio of
1:1 to modified starch, and stir them uniformly. After adjusting the pH to 9, add
epichlorohydrin accounting for 3% of modified starch weight and then crosslink them at
65°C for 3h to obtain the modified starch/quartz sand composite microsphere. Its test
results are the same as those in embodiment 1.
Embodiment 3
(1) Preparation of modified starch
Disperse the starch in a 30% sodium hydroxide aqueous solution, besides, the ratio of
starch to sodium hydroxide aqueous solution is 1:5. Let it alkalinize for 0.5h at 70°C.
Then add 3-Chloro-2-Hydroxypropyldimethyl benzyl ammonium chloride, in the ratio of
3:1 to starch, and make them react at 50°C for 4h. After the reaction is completed, ethanol
is used as precipitant to precipitate and separate and then modified starch is obtained. By
1 H NMR analysis, the substitution degree of cationic quaternary ammonium salt group is
61% (mass).
(2) Preparation of modified starch/quartz sand composite microsphere
Dissolve the modified starch prepared by step (1) in water and prepare the modified
starch solution with mass percentage concentration of 1%. After the solution is uniform,
disperse quartz sand material in the modified starch solution by ultrasonic, accounting for
20% of the total weight of the modified starch, then add cyclohexane, in a volume ratio of
10:1 to modified starch, and stir them uniformly. After adjusting the pH to 10, add
epichlorohydrin accounting for 0.1% of modified starch weight and then crosslink them
at 35°C for 0.5h to obtain the modified starch/quartz sand composite microsphere. Its test
results are the same as those in embodiment 1.
Embodiment 4
(1) Preparation of modified starch
Disperse the starch in a 15% sodium hydroxide aqueous solution, besides, the ratio of
starch to sodium hydroxide aqueous solution is 1:3. Let it alkalinize for 1.5h at 70°C.
Then add 3-Chloro-2-Hydroxypropyltriethyl ammonium chloride, in the ratio of 0.5:1 to
starch, and make them react at 60°C for 1.5h. After the reaction is completed, ethanol is
used as precipitant to precipitate and separate and then modified starch is obtained. By 1 H
NMR analysis, the substitution degree of cationic quaternary ammonium salt group is
16% (mass).
(2) Preparation of modified starch/quartz sand composite microsphere
Dissolve the modified starch prepared by step (1) in water and prepare the modified
starch solution with mass percentage concentration of 1%. After the solution is uniform,
disperse quartz sand material in the modified starch solution by ultrasonic, accounting for
15% of the total weight of the modified starch, then add cyclohexane, in a volume ratio of
7:1 to modified starch, and stir them uniformly. After adjusting the pH to 8, add
epichlorohydrin accounting for 7% of modified starch weight and then crosslink them at
45°C for 2h to obtain the modified starch/quartz sand composite microsphere. Its test
results are the same as those in embodiment 1.
Embodiment 5
(1) Preparation of modified starch
Disperse the starch in a 20% sodium hydroxide aqueous solution, besides, the ratio of
starch to sodium hydroxide aqueous solution is 1:2.5. Let it alkalinize for 1h at 70°C.
Then add 3-Chloro-2-Hydroxypropyltripropyl ammonium chloride, in the ratio of 0.75:1
to starch, and make them react at 55°C for 2.5h. After the reaction is completed, ethanol
is used as precipitant to precipitate and separate and then modified starch is obtained. By
1 H NMR analysis, the substitution degree of cationic quaternary ammonium salt group is
38% (mass).
(2) Preparation of modified starch/quartz sand composite microsphere
Dissolve the modified starch prepared by step (1) in water and prepare the modified
starch solution with mass percentage concentration of 1%. After the solution is uniform,
disperse quartz sand material in the modified starch solution by ultrasonic, accounting for
10% of the total weight of the modified starch, then add cyclohexane, in a volume ratio of
2:1 to modified starch, and stir them uniformly. After adjusting the pH to 10, add
epichlorohydrin accounting for 10% of modified starch weight and then crosslink them at
65°C for 2.5h to obtain the modified starch/quartz sand composite microsphere. Its test
results are the same as those in embodiment 1.
The above-mentioned embodiments only describe the preferred mode of the invention,
and do not limit the scope. Without departing from the design spirit of the invention,
various modifications and improvements made by ordinary technical personnel in the art
to the technical scheme of the invention shall fall into the protection scope determined by
the claims of the invention.
Claims (10)
1. A kind of modified starch/quartz sand composite microsphere, characterized in that it
has a core-shell structure, with modified starch as the shell and quartz sand as the core.
Wherein, the modified starch is prepared by etherification of starch and quaternary
ammonium salt modifier.
2. A kind of modified starch/quartz sand composite microsphere according to claim 1,
characterized in that the quaternary ammonium salt modifier is one of 3-Chloro-2
Hydroxypropyldimethyl benzyl ammonium chloride, 3-Chloro-2
Hydroxypropyltrimethyl ammonium chloride, 3-Chloro-2-Hydroxypropyltriethyl
ammonium chloride and 3-Chloro-2-Hydroxypropyltripropyl ammonium chloride.
3. A kind of modified starch/quartz sand composite microsphere according to claim 1,
characterized in that the content of the quaternary ammonium salt modifier in the
modified starch/quartz sand composite microsphere is 5 to 80wt%. The quartz sand
material accounts for 10-20% of the total weight of the modified starch.
4. A preparation method of modified starch/quartz sand composite microsphere
characterized by comprising following steps.
(1) Preparation of modified starch
Disperse the starch in a hydroxide aqueous solution with a mass percentage of 1-30%. Let
it alkalinize for 0.5-2h. Then add quaternary ammonium salt modifier and make them
react at 30-80°C for 0.5-4h. After the reaction is completed, ethanol is used as precipitant
to precipitate and separate and then modified starch is obtained.
(2) Preparation of modified starch/quartz sand composite microsphere
Dissolve the modified starch prepared by step (1) in water and make the mass percentage
concentration of the modified starch in the modified starch solution is 1%. After the
solution is uniform, disperse quartz sand material in the modified starch solution by
ultrasonic, add cyclohexane, and stir them uniformly, then crosslink them through
epichlorohydrin to obtain the modified starch/quartz sand composite microsphere.
5. The preparation method of modified starch/quartz sand composite microsphere
according to claim 4, characterized in that in step (1), the hydroxide aqueous solution is
one of sodium hydroxide and potassium hydroxide, and the ratio of the starch to the
hydroxide aqueous solution is 1:2-5.
6. The preparation method of modified starch/quartz sand composite microsphere
according to claim 4, characterized in that in step (1), the mass ratio of that quaternary
ammonium salt modifier to the starch is 0.1-3: 1.
7. The preparation method of modified starch/quartz sand composite microsphere
according to claim 4, characterized in that in step (2), the volume ratio of the added
amount of cyclohexane to the modified starch solution is 1-10: 1.
8. The preparation method of modified starch/quartz sand composite microsphere
according to claim 4, characterized in that in step (2), the used amount of epichlorohydrin
is 0.1-10% of that of modified starch.
9. The preparation method of modified starch/quartz sand composite microsphere
according to claim 4, characterized in that in step (2), during the epichlorohydrin cross
linking process, the pH value of the reaction solution is controlled at 7-10, meanwhile,
the temperature is 35-65°C, and the time is 0.5-3h.
10. The application of the modified starch/quartz sand composite microspheres according
to claim 1 as water treatment agent in treating dye wastewater and heavy metal
wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117696018A (en) * | 2023-12-29 | 2024-03-15 | 苏州见远检测技术有限公司 | Preparation method of pretreatment filter medium for removing residual chlorine in tap water |
| CN119774623A (en) * | 2024-12-31 | 2025-04-08 | 江西省坚基高新硅材料有限公司 | High-efficiency high-temperature acid leaching treatment process for refining high-purity quartz sand |
-
2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117696018A (en) * | 2023-12-29 | 2024-03-15 | 苏州见远检测技术有限公司 | Preparation method of pretreatment filter medium for removing residual chlorine in tap water |
| CN119774623A (en) * | 2024-12-31 | 2025-04-08 | 江西省坚基高新硅材料有限公司 | High-efficiency high-temperature acid leaching treatment process for refining high-purity quartz sand |
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