CN114797750A - Cross-linked starch-based composite adsorbent and preparation method and application thereof - Google Patents
Cross-linked starch-based composite adsorbent and preparation method and application thereof Download PDFInfo
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- CN114797750A CN114797750A CN202210428406.4A CN202210428406A CN114797750A CN 114797750 A CN114797750 A CN 114797750A CN 202210428406 A CN202210428406 A CN 202210428406A CN 114797750 A CN114797750 A CN 114797750A
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
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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
- C02F1/288—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
Abstract
The invention provides a crosslinked starch-based composite adsorbent and a preparation method and application thereof, belonging to the technical field of sewage treatment. According to the invention, cross-linked starch is used as a carrier, and by utilizing the large amount of hydroxyl in cross-linked starch molecules and the large amount of negative charges on the surfaces of particles, nano magnesium hydroxide adsorbent particles can be firmly adhered to the surfaces of the cross-linked starch particles by forming hydrogen bonds and electrostatic adsorption; the cross-linked starch has low water solubility, high alkali resistance and high heat resistance, can generate depressions and holes on the surface of the cross-linked starch on the basis of keeping complete round particles of the starch after alkalization treatment in an alkaline environment, enhances the magnesium hydroxide adsorption capacity of the cross-linked starch, has no agglomeration phenomenon of loaded nano magnesium hydroxide, not only can improve the filtration performance of the nano magnesium hydroxide, but also can improve the settlement performance of adsorption products, and the prepared cross-linked starch-based composite adsorbent has good filterability and can be quickly settled, can be effectively separated by a conventional filtration mode, and has simple subsequent treatment.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a crosslinked starch-based composite adsorbent and a preparation method and application thereof.
Background
The nano magnesium hydroxide has small particle size, large specific surface area, large charge carried on the surface of the particle, strong adsorbability and thermal stability, is widely used as an inorganic flame retardant, and also plays a great role as an adsorbent in the environmental protection field, such as the fields of heavy metal wastewater treatment, acid wastewater neutralization, printing and dyeing wastewater decolorization, flue gas desulfurization and the like. However, the magnesium hydroxide has small particle size and large specific surface area, so that the magnesium hydroxide and floc particles formed after heavy metal ions are adsorbed are small and suspended in water for a long time, and are difficult to precipitate and separate, even centrifugal separation is needed, so that the production and use costs are increased.
Disclosure of Invention
The invention aims to provide a cross-linked starch-based composite adsorbent and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a cross-linked starch-based composite adsorbent, which comprises the following steps:
mixing the cross-linked starch, an alkalizer and water, and carrying out alkalization treatment to obtain an alkalized product;
and mixing the alkalized product with a magnesium salt solution, and carrying out precipitation reaction to obtain the cross-linked starch-based composite adsorbent.
Preferably, the crosslinking agent used for crosslinking the starch is epichlorohydrin.
Preferably, the alkalizer comprises sodium hydroxide solution; the mass concentration of the sodium hydroxide solution is 15%.
Preferably, the mass ratio of the cross-linked starch to the alkalizer is 5 (4-7); the temperature of the alkalization treatment is 30-60 ℃, and the time is 0.5-1 h.
Preferably, the mass concentration of the magnesium salt solution is 7%; the mass ratio of the magnesium salt solution to the cross-linked starch is (20-40): 5.
Preferably, the time of the precipitation reaction is 0.5-1 h.
Preferably, after the precipitation reaction is completed, the method further comprises: and washing and drying the obtained precipitation product in sequence to obtain the cross-linked starch-based composite adsorbent.
Preferably, the washing comprises water washing and acetone washing which are carried out in sequence.
The invention provides a cross-linked starch-based composite adsorbent prepared by the preparation method in the technical scheme, which comprises cross-linked starch and nano magnesium hydroxide loaded on the cross-linked starch.
The invention provides application of the cross-linked starch-based composite adsorbent in the technical scheme in adsorption of heavy metal ions.
The invention provides a preparation method of a cross-linked starch-based composite adsorbent, which comprises the following steps: mixing the cross-linked starch, an alkalizer and water, and carrying out alkalization treatment to obtain an alkalized product; and mixing the alkalized product with a magnesium salt solution, and carrying out precipitation reaction to obtain the cross-linked starch-based composite adsorbent. The invention takes the cross-linked starch as a carrier, utilizes the large (20 microns) particles of the cross-linked starch without viscosity, and can greatly improve the filterability of suspension after absorbing the magnesium hydroxide, thereby overcoming the problem of poor filterability caused by the extremely small nano magnesium hydroxide particles; in addition, the cross-linked starch has low water solubility, high alkali resistance and high heat resistance, and the cross-linked starch can generate depressions and holes on the surface of the cross-linked starch on the basis of keeping complete round particles of the starch after being subjected to alkalization treatment in an alkaline environment, so that the magnesium hydroxide adsorption capacity of the cross-linked starch is enhanced; moreover, the surface of the cross-linked starch has a large amount of active hydroxyl groups, and the particle surface also carries a large amount of negative charges, so that magnesium hydroxide particles can be adsorbed on the surface of the starch particles, hydrogen bonds are formed, the surface energy of the magnesium hydroxide nanoparticles is reduced, and the agglomeration of the magnesium hydroxide is prevented, therefore, the loaded nano magnesium hydroxide has no agglomeration phenomenon, the particle size of the cross-linked starch particles is large, the suspension has no viscosity, the filtering performance of the nano magnesium hydroxide can be improved, the settling performance of an adsorption product (floc formed after adsorption of heavy metal ions) can be improved, the prepared cross-linked starch-based composite adsorbent has good filtering performance and can be quickly settled, the separation can be effectively realized through a conventional filtering mode, and the subsequent treatment is simple.
The raw materials used in the invention have low price, the production cost is low, the preparation process is simple, the nano magnesium hydroxide in the prepared cross-linked starch-based composite adsorbent can generate strong ion exchange and surface complexation with heavy metal ions in sewage, the purpose of removing soluble heavy metal ions is achieved, and the heavy metal ions (Cu) in the sewage can be treated 2+ 、Pb 2+ 、Cd 2+ 、Ni 2+ ) The flocculant has good adsorption performance, and the flocs formed after adsorption can be quickly separated from the water body through simple filtration, so that the flocculant is easy to popularize and apply.
Drawings
FIG. 1 is an electron micrograph of cross-linked starch of example 2;
FIG. 2 is an electron micrograph of a cross-linked starch-based composite adsorbent prepared in example 2;
FIG. 3 is an infrared spectrum of a cross-linked starch of example 2 and a cross-linked starch-based composite adsorbent prepared therefrom;
fig. 4 is an XRD pattern of the cross-linked starch of example 2 and the prepared cross-linked starch-based composite adsorbent.
Detailed Description
The invention provides a preparation method of a cross-linked starch-based composite adsorbent, which comprises the following steps:
mixing the cross-linked starch, an alkalizer and water, and performing alkalization treatment to obtain an alkalized product;
and mixing the alkalized product with a magnesium salt solution, and carrying out precipitation reaction to obtain the cross-linked starch-based composite adsorbent.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention mixes the cross-linked starch, the alkalizer and the water, and carries out alkalization treatment to obtain an alkalized product. In the present invention, the crosslinking agent used for crosslinking the starch is preferably epichlorohydrin. The preparation process of the cross-linked starch is not particularly limited in the invention, and the cross-linked starch can be prepared according to a method well known in the field; in the embodiment of the invention, the preparation method of the crosslinked starch specifically comprises the following steps: putting 20g of corn starch into a flask, adding 50mL of NaCl aqueous solution with the mass concentration of 1%, adding 130mL of deionized water, and uniformly stirring in a water bath at 30 ℃; dropwise adding 4mL of NaOH solution with the mass concentration of 15% into the reaction system, uniformly stirring, dropwise adding 0.5-1.5 mL (more preferably 0.8-1.2 mL) of crosslinking agent epichlorohydrin, and reacting at constant temperature for 5 h; after the reaction is finished, pouring the obtained starch slurry into a Buchner funnel for suction filtration, adding distilled water into precipitates for washing, adjusting the pH value of the precipitates to be neutral by using commercially available hydrochloric acid, washing the precipitates for three times by using distilled water, then washing the precipitates for two times by using absolute ethyl alcohol, putting the obtained product into a vacuum drying oven at the temperature of 60 ℃ for drying until the weight is constant, and grinding and screening the product to obtain the crosslinked starch.
In the present invention, the alkalizing agent preferably comprises sodium hydroxide solution; the mass concentration of the sodium hydroxide solution is preferably 15%; the solvent used for the sodium hydroxide solution is preferably water.
In the invention, the mass ratio of the crosslinked starch to the alkalizer is preferably 5 (4-7), and more preferably 5 (5-6). The invention has no special limit on the using amount of the water, and the cross-linked starch can form suspension.
In the invention, the cross-linked starch, the alkalizer and the water are preferably mixed by adding the cross-linked starch into the water, stirring to form a uniform suspension, and injecting the alkalizer by using an injection pump; the time for injecting the alkalizing agent is preferably 0.5 h. The stirring rate is not particularly limited in the present invention, and the materials are uniformly mixed according to a process well known in the art.
In the invention, the temperature of the alkalization treatment is preferably 30-60 ℃, more preferably 40-50 ℃, and the time is preferably 0.5-1 h.
In the alkalization process, the starch granules are formed by combining an amorphous area and a microcrystalline area, the shell of the starch granules is basically formed by the microcrystalline area, and the microcrystalline area of the starch is damaged in the alkalization process to form more pits and holes on the surface of the cross-linked starch granules; moreover, the alkalizer reacts with hydroxyl on the starch C6 to generate oxygen anions, so that the negative charge on the surface of the starch is increased, and the reaction formula of the alkalizer and the starch hydroxyl is as follows:
after an alkalized product is obtained, the alkalized product is mixed with a magnesium salt solution for precipitation reaction to obtain the cross-linked starch-based composite adsorbent.
In the invention, the magnesium salt in the magnesium salt solution preferably comprises magnesium sulfate heptahydrate, and the mass concentration of the magnesium salt solution is preferably 7%; the mass ratio of the magnesium salt solution to the crosslinked starch is preferably (20-40): 5, and more preferably (30-40): 5.
The invention preferably adopts a syringe pump to drop the magnesium salt solution into the reactor; the dropping rate is not particularly limited in the present invention, and may be carried out according to a procedure well known in the art. In the invention, a small amount of magnesium salt solution is dripped into a large amount of alkalizer solution to generate magnesium hydroxide with small particles, and the magnesium hydroxide can be completely adsorbed on the surface of the crosslinked starch to form the load type composite material.
In the present invention, the time of the precipitation reaction is preferably calculated from the dropwise addition of the magnesium salt solution; the dripping time is preferably 0.5h, and the precipitation reaction time is preferably 0.5-1 h. During the precipitation reaction, sodium hydroxide reacts with magnesium sulfate to produce magnesium hydroxide, and the produced sodium sulfate can be washed with water with almost no by-product.
In the present invention, after the precipitation reaction is completed, it is preferable to further include: the obtained precipitation products are sequentially carried outWashing and drying to obtain the cross-linked starch-based composite adsorbent, which is recorded as ISt-Mg (OH) 2 。
According to the invention, the precipitated product is naturally settled for 1.5h at room temperature, the obtained supernatant is poured off, and the lower layer of the obtained pulp is washed. In the present invention, the washing preferably includes water washing and acetone washing which are sequentially performed; preferably, deionized water is adopted for multiple times of suction filtration washing until the pH value of the filtrate is unchanged; the acetone washing process is not particularly limited in the present invention, and may be performed according to a process well known in the art. In the present invention, the drying is preferably performed in vacuum, and the drying temperature is preferably 40 ℃.
The invention provides a cross-linked starch-based composite adsorbent prepared by the preparation method in the technical scheme, which comprises cross-linked starch and nano magnesium hydroxide loaded on the cross-linked starch.
The invention provides application of the cross-linked starch-based composite adsorbent in the technical scheme in adsorption of heavy metal ions. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art. In the present invention, the heavy metal ion preferably includes Cu 2+ 、Pb 2+ 、Cd 2+ And Ni 2+ One or more of them.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the preparation method of the cross-linked starch is as follows: taking 20g of corn starch, putting the corn starch into a flask, adding 50mL of NaCl aqueous solution with the mass concentration of 1%, then adding 130mL of deionized water, and uniformly stirring in a water bath at the temperature of 30 ℃; 4mL of NaOH solution with the mass concentration of 15% is dripped into the reaction system, 0.5-1.5 mL of cross-linking agent epichlorohydrin is dripped after uniform stirring, and the reaction is carried out for 5 hours at constant temperature; after the reaction is finished, pouring the obtained starch slurry into a Buchner funnel for suction filtration, adding distilled water into precipitates for washing, adjusting the pH value of the precipitates to be neutral by using commercially available hydrochloric acid, washing the precipitates for three times by using distilled water, then washing the precipitates for two times by using absolute ethyl alcohol, putting the obtained product into a vacuum drying oven at the temperature of 60 ℃ for drying until the weight is constant, and grinding and screening the product to obtain the crosslinked starch.
Example 1
Adding 40mL of distilled water into a reactor, adding 5g of crosslinked starch (the dosage of the crosslinking agent epichlorohydrin is 0.8mL), stirring to form uniform suspension, injecting 4g of NaOH solution (the mass concentration is 15%) into the reactor by using a syringe pump for 0.5h, alkalifying for 1h at 30 ℃, dropwise adding 20g of magnesium sulfate heptahydrate solution (the mass concentration is 7%) into the reactor by using the syringe pump for 0.5h, and reacting for 0.5h to obtain white suspension;
and naturally settling the white suspension at room temperature for 1.5h, pouring out the supernatant, performing suction filtration and washing on the lower white slurry with deionized water for multiple times until the pH value of the filtrate is unchanged, washing with acetone, and performing vacuum drying at 40 ℃ to obtain the crosslinked starch-based composite adsorbent.
Example 2
Adding 40mL of distilled water into a reactor, adding 5g of crosslinked starch (the dosage of the crosslinking agent epichlorohydrin is 1.0mL), stirring to form uniform suspension, injecting 5g of NaOH solution (the mass concentration is 15%) into the reactor by using a syringe pump for 0.5h, alkalifying at 40 ℃ for 1h, then dropwise adding 30g of magnesium sulfate heptahydrate solution (the mass concentration is 7%) into the reactor by using the syringe pump for 0.5h, and reacting for 0.5h to obtain white suspension;
and naturally settling the white suspension at room temperature for 1.5h, pouring out the supernatant, performing suction filtration and washing on the lower white slurry with deionized water for multiple times until the pH value of the filtrate is unchanged, washing with acetone, and performing vacuum drying at 40 ℃ to obtain the crosslinked starch-based composite adsorbent.
Example 3
Adding 40mL of distilled water into a reactor, adding 5g of crosslinked starch (the dosage of the crosslinking agent epichlorohydrin is 1.5mL), stirring to form uniform suspension, injecting 7g of NaOH solution (the mass concentration is 15%) into the reactor by using a syringe pump for 0.5h, alkalifying at 40 ℃ for 1h, dropwise adding 40g of magnesium sulfate heptahydrate solution (the mass concentration is 7%) into the reactor by using the syringe pump for 0.5h, and reacting for 0.5h to obtain white suspension;
and naturally settling the white suspension at room temperature for 1.5h, pouring out the supernatant, performing suction filtration and washing on the lower white slurry with deionized water for multiple times until the pH value of the filtrate is unchanged, washing with acetone, and performing vacuum drying at 40 ℃ to obtain the crosslinked starch-based composite adsorbent.
Example 4
Adding 40mL of distilled water into a reactor, adding 5g of crosslinked starch (the dosage of the crosslinking agent epichlorohydrin is 0.5mL), stirring to form uniform suspension, injecting 7g of NaOH solution (the mass concentration is 15%) into the reactor by using a syringe pump for 0.5h, alkalifying for 1h at 60 ℃, dropwise adding 20g of magnesium sulfate heptahydrate solution (the mass concentration is 7%) into the reactor by using the syringe pump for 0.5h, and reacting for 0.5h to obtain white suspension;
and naturally settling the white suspension at room temperature for 1.5h, pouring out the supernatant, performing suction filtration and washing on the lower white slurry with deionized water for multiple times until the pH value of the filtrate is unchanged, washing with acetone, and performing vacuum drying at 40 ℃ to obtain the crosslinked starch-based composite adsorbent.
Characterization of
1) SEM characterization is carried out on the cross-linked starch of the example 2 and the prepared cross-linked starch-based composite adsorbent, and the obtained results are shown in the figure 1-2; FIG. 1 is an electron micrograph of cross-linked starch; FIG. 2 is an electron micrograph of a cross-linked starch-based composite adsorbent; as can be seen from FIGS. 1-2, the surface of the crosslinked starch granules is smooth, and part of the granules have small pits with the grain size of about 20 microns; after alkalization and magnesium salt addition, the particles are shrunk, and the surfaces of the particles are covered with powdery attachments which are magnesium hydroxide; the magnesium hydroxide attached to the surface of the starch particles has extremely small particle size and is not agglomerated at the nanometer level.
2) For the crosslinked starch ISt of example 2 and the prepared crosslinked starch-based composite adsorbent ISt-Mg (O)H) 2 Performing infrared characterization, and obtaining an infrared spectrogram shown in figure 3; as can be seen from FIG. 3, 1639cm in cross-linked starch -1 The absorption peak is the absorption peak of moisture in an amorphous area, and 993cm -1 The peak at (a) is related to the intramolecular hydrogen bonding of the hydroxyl group at C6. After the crosslinked starch is loaded with magnesium hydroxide, the thickness of the crosslinked starch is 3701cm -1 A sharp absorption peak appears, which is formed by Mg (OH) 2 Due to stretching vibration of the middle O-H bond. 1698cm -1 The absorption peak at (A) is caused by stretching vibration of the carbonyl group, which indicates Mg (OH) 2 The surface is adsorbed and bonded to form a new chemical bond. 1018cm -1 The peak is the stretching vibration absorption peak of C1-O-C4 in the starch skeleton, and when loaded with Mg (OH) 2 Post, C1-O-C4 and Mg (OH) 2 A new hydrogen band is formed between the hydroxyl groups in the compound, so that the peak intensity is obviously enhanced.
3) XRD test was performed on the cross-linked starch of example 2 and the prepared cross-linked starch-based composite adsorbent, and the obtained results are shown in fig. 4; as can be seen from fig. 4, there are distinct diffraction peaks at 15 °, 17 °, 18 ° and 21 ° in the cross-linked starch, which indicates that there are intact microcrystalline regions in the cross-linked starch. After the alkalization reaction of the crosslinked starch, the diffraction peak completely disappeared, which indicates that the microcrystalline region was destroyed. While small diffraction peaks, which are diffraction peaks of magnesium hydroxide, appear at 38 °, 50 ° and 58 °.
4) Directly filtering the white suspension obtained in the embodiment 1-4 respectively until 400mL of filtrate is obtained;
the filtration rate V is the volume V of liquid passing through per unit of filtration cross-sectional area a per unit of time t, V ═ V/(At), and is given in m/s;
calculating the filtration rate according to the time required for obtaining 400mL of filtrate, wherein the filtration rate of the nano magnesium hydroxide is v 1 ＝400/(At 1 ) The filtration rate of the composite material is v 2 ＝400/(At 2 ) The amount of increase in filtration rate is (v) 2 -v 1 )/v 1 ＝(t 1 -t 2 )/t 2 。
In example 1, the filtering time of the nano magnesium hydroxide is 4h, the filtering time of the composite material is 27min, and the filtering rate is improved by 788.9%.
In example 2, the filtering time of the nano magnesium hydroxide is 4 hours, the filtering time of the composite material is 30min, and the filtering rate is improved by 700.0%.
In example 3, the filtration time of the nano magnesium hydroxide is 4h, the filtration time of the composite material is 50min, and the filtration rate is improved by 380.0%.
In example 4, the filtering time of the nano magnesium hydroxide is 4h, the filtering time of the composite material is 83min, and the filtering rate is improved by 189.2%.
Application example 1
To contain Cu 2+ 、Pb 2+ 、Cd 2+ And Ni 2+ The water sample is simulated sewage, wherein the content of each ion is 20mg/L, the cross-linked starch-based composite adsorbent prepared in example 1 is used as an adsorbent, the adding amount of the adsorbent is 300mg/L, the adsorbent is added into the simulated sewage, the mixture is stirred for 40min and then is kept stand for adsorption for 1h, and the removal rate of the metal ions is measured.
The results show that the adsorbent is used for Cu 2+ The removal rate of (1) was 94.7% and Pb 2+ The removal rate of (2) was 91.5%, Cd 2+ The removal rate of (2) was 89.7%, Ni 2+ The removal rate of (2) was 30.8%.
Application example 2
To contain Cu 2+ 、Pb 2+ 、Cd 2+ And Ni 2+ The water sample is simulated sewage, wherein the content of each ion is 20 mg/L; the crosslinked starch-based composite adsorbent prepared in example 2 was used as an adsorbent, the amount of the adsorbent added was 300mg/L, the adsorbent was added to simulated wastewater, stirred for 40min, and then allowed to stand for 1h for adsorption, and the metal ion removal rate was measured.
The results show that the adsorbent is used for Cu 2+ Removal rate of (2) is 100%, Pb 2+ The removal rate of (2) was 95.1%, Cd 2+ The removal rate of (2) is 90.2%, Ni 2+ The removal rate of (2) was 35.9%.
Application example 3
To contain Cu 2+ 、Pb 2+ 、Cd 2+ And Ni 2+ The water sample is simulated sewage, wherein the content of each ion is 20 mg/L; mixing all the above materialsThe crosslinked starch-based composite adsorbent prepared in example 3 was used as an adsorbent, the amount of the adsorbent added was 300mg/L, the adsorbent was added to simulated wastewater, stirred for 40min, and then allowed to stand for adsorption for 1h, and the metal ion removal rate was measured.
The results show that the adsorbent is used for Cu 2+ The removal rate of (1) was 92.5%, Pb 2+ The removal rate of (2) was 89.4%, Cd 2+ The removal rate of (2) was 87.2%, Ni 2+ The removal rate of (3) was 27.6%.
Application example 4
To contain Cu 2+ 、Pb 2+ 、Cd 2+ And Ni 2+ The water sample is simulated sewage, wherein the content of each ion is 20 mg/L; the crosslinked starch-based composite adsorbent prepared in example 4 was used as an adsorbent, the amount of the adsorbent added was 300mg/L, the adsorbent was added to simulated wastewater, stirred for 40min, allowed to stand for adsorption for 1h, and the metal ion removal rate was measured.
The results show that the adsorbent is used for Cu 2+ The removal rate of (1) was 77.8% and Pb 2+ Removal rate of (2) was 75.4%, Cd 2+ The removal rate of (2) was 72.7%, Ni 2+ The removal rate of (2) was 15.5%.
Test data
0.03g of the composite material prepared in example 1 was added to 100mL of the simulated sewage of application example 1, stirred for 40min, and allowed to stand for 1h, and then the supernatant was taken out and turbidity was measured. The turbidity of the water body is the turbidity brought by the composite material after the composite material is added.
In application example 1, after 0.03g of the composite material is added, the initial turbidity of the water body is 13.98 NTU; after standing for 1h, the turbidity was 0.213 NTU; after standing for 2h, the turbidity was 0.053 NTU. When magnesium hydroxide with the same concentration is added, the initial turbidity of the water body is 246.5NTU, after standing for 1 hour, the turbidity is 82.83NTU, and after 2 hours, the turbidity is 71.47 NTU; the composite material can realize the rapid solid-liquid separation.
After 0.03g of composite material is added in the application example 2, the initial turbidity of the water body is 13.54NTU, and the turbidity of the water body is 0.192NTU after the water body is kept stand for 1 h.
After 0.03g of composite material is added in application example 3, the initial turbidity of the water body is 14.20NTU, and the turbidity of the water body is 0.327NTU after standing for 1 h.
After 0.03g of composite material is added in the application example 4, the initial turbidity of the water body is 14.26NTU, and the turbidity of the water body is 0.926NTU after the water body is kept stand for 1 hour.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the cross-linked starch-based composite adsorbent is characterized by comprising the following steps of:
mixing the cross-linked starch, an alkalizer and water, and carrying out alkalization treatment to obtain an alkalized product;
and mixing the alkalized product with a magnesium salt solution, and carrying out precipitation reaction to obtain the cross-linked starch-based composite adsorbent.
2. The method according to claim 1, wherein the cross-linking agent for cross-linking the starch is epichlorohydrin.
3. The method of claim 1, wherein the alkalizer comprises a sodium hydroxide solution; the mass concentration of the sodium hydroxide solution is 15%.
4. The preparation method according to claim 1 or 3, wherein the mass ratio of the crosslinked starch to the alkalizer is 5 (4-7); the temperature of the alkalization treatment is 30-60 ℃, and the time is 0.5-1 h.
5. The method according to claim 1, wherein the magnesium salt solution has a mass concentration of 7%; the mass ratio of the magnesium salt solution to the cross-linked starch is (20-40): 5.
6. The method according to claim 1 or 5, wherein the precipitation reaction time is 0.5 to 1 hour.
7. The method of claim 1, further comprising, after the precipitation reaction is completed: and washing and drying the obtained precipitation product in sequence to obtain the cross-linked starch-based composite adsorbent.
8. The production method according to claim 7, wherein the washing comprises water washing and acetone washing in this order.
9. The cross-linked starch-based composite adsorbent prepared by the preparation method of any one of claims 1 to 8, which is characterized by comprising cross-linked starch and nano magnesium hydroxide loaded on the cross-linked starch.
10. Use of the cross-linked starch-based composite adsorbent according to claim 9 for adsorbing heavy metal ions.
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| CN115873311A (en) * | 2022-12-23 | 2023-03-31 | 江西广源新材料有限公司 | Starch-based magnesium salt powder, preparation method and application thereof, energy cable composite material and preparation method thereof |
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