CN115254044A - Preparation method of magnetic bentonite-gelatin composite microspheres for removing Cu ions in water body sediment - Google Patents
Preparation method of magnetic bentonite-gelatin composite microspheres for removing Cu ions in water body sediment Download PDFInfo
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- CN115254044A CN115254044A CN202210913377.0A CN202210913377A CN115254044A CN 115254044 A CN115254044 A CN 115254044A CN 202210913377 A CN202210913377 A CN 202210913377A CN 115254044 A CN115254044 A CN 115254044A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000013049 sediment Substances 0.000 title claims description 15
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 11
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
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- 238000000926 separation method Methods 0.000 claims description 6
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- 229910052793 cadmium Inorganic materials 0.000 description 1
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- 208000019425 cirrhosis of liver Diseases 0.000 description 1
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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
- B01J20/02—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
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/22—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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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J20/28—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
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
Abstract
A preparation method of magnetic bentonite gelatin composite microspheres for removing Cu ions in water body bottom mud comprises the following steps of dissolving ferric chloride hexahydrate in ethylene glycol to obtain a solution a; dissolving sodium acetate, ethylenediamine and bentonite in the solution a to obtain a solution b; pouring polytetrafluoroethylene and the solution b into a reaction kettle for hydrothermal reaction to obtain a solution c; centrifuging the solution c and obtaining a solid product A; drying the solid product A to obtain magnetic bentonite; putting gelatin in a small beaker, and adding distilled water to obtain a solution d; pouring the magnetic bentonite into the solution d to obtain a magnetic bentonite-gelatin mixed solution; injecting the magnetic bentonite-gelatin mixed solution into sunflower seed oil and refrigerating to obtain primary gel balls; and washing and freeze-drying the primary gel balls to obtain the magnetic bentonite-gelatin balls. The adsorption capacity of the gel balls for adsorbing Cu is greatly improved compared with that of the original bentonite.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a preparation method of magnetic bentonite-gelatin composite microspheres for removing Cu ions in water body sediment.
Background
Due to the activities of human production and living, a large amount of heavy metals exceeding standards are discharged into the environments such as water bodies, soil and the like, and environmental pollution is caused. The heavy metal pollution, which may be enriched in animals and plants, is toxic and dead in animals and plants. Heavy metals can also enter human bodies through the food chain, and once the tolerance of the human bodies is exceeded, the heavy metals cause great harm to the human bodies, such as water guarantee caused by mercury pollution and bone pain caused by cadmium pollution. Heavy metals are circularly migrated by human beings and nature, and are often enriched and stored in the bottom mud of rivers and lakes finally. Cu is a typical heavy metal element, and excessive copper can cause symptoms of liver cirrhosis, diarrhea, vomiting and the like of a human body.
At present, the heavy metal treatment method in the bottom mud mainly comprises a physical adsorption method, a chemical remediation method, a biological remediation method and the like. Wherein, the bentonite is a cheap, high-efficiency, green and safe mineral adsorbent material. Because the bentonite has limited adsorption capacity on heavy metal ions and needs to be modified by a certain means, the bentonite has been researched at present, such as acid activation, inorganic pillared modification and organic group modification (such as mercapto-amino grafting). In addition, in the previous research, the combination of the bentonite and the heavy metal cannot be extracted after the heavy metal ions are adsorbed and solidified by the bentonite material and still remains in the original environment, which still has great hidden trouble on the safety of the water body or the soil environment.
Disclosure of Invention
The invention aims to provide a preparation method of magnetic bentonite and gelatin composite microspheres for removing Cu ions in water body sediment, and aims to solve the problems in the background art.
The technical solution of the invention is as follows: a preparation method of magnetic bentonite gelatin composite microspheres for removing Cu ions in water body sediment comprises the following steps,
s1, dissolving ferric chloride hexahydrate in ethylene glycol, and mechanically stirring and fully mixing to obtain a solution a;
s2, dissolving sodium acetate, ethylenediamine and bentonite in the solution a, and mechanically stirring and fully mixing to obtain a solution b;
s3, pouring the polytetrafluoroethylene and the solution b into a reaction kettle for hydrothermal reaction to obtain a solution c;
s4, pouring the solution c into a centrifuge tube for centrifugation and washing with distilled water to obtain a solid product A;
s5, placing the solid product A in a drying oven for drying, and finally grinding and sieving to obtain magnetic bentonite;
s6, putting the gelatin into a small beaker, adding distilled water, heating, and mechanically stirring and fully mixing to obtain a solution d;
s7, pouring the magnetic bentonite into the solution d, and mechanically stirring and fully mixing to obtain a magnetic bentonite-gelatin mixed solution;
s8, putting the grease into an ice-water mixture for ice bath, and magnetically stirring the grease;
s9, injecting the magnetic bentonite-gelatin mixed solution into sunflower seed oil and refrigerating to obtain primary gel balls;
and S10, washing the primary gel balls, and freeze-drying to obtain the magnetic bentonite-gelatin composite microspheres.
Preferably, in S1, the mass of ferric chloride hexahydrate is 1-4g, and ethylene glycol is
40-60mL, the rotation speed of mechanical stirring is 300-1200r/min, and the stirring time is 30-50min.
Preferably, in S2, the mass of sodium acetate is 5-8g, the mass of ethylenediamine is 20-50ml, the mass of bentonite is 1.0 g-8.0 g, the rotation speed of mechanical stirring is 300-1200r/min, and the stirring time is 30-50min.
Preferably, in S3, the polytetrafluoroethylene is 90-220ml, the temperature of the hydrothermal reaction is 200 ℃, and the reaction time is 6-12h.
Preferably, in S5, the temperature of the drying oven is 70 to 90 ℃.
Preferably, in S6, the mass of the gelatin is 1-3g, the distilled water is 15-30mL, the heating temperature is 50-60 ℃, the rotation speed of mechanical stirring is 100-800r/min, and the stirring time is 60-80min.
Preferably, in S7, the mass of the magnetic bentonite is 0.1-2g, the rotation speed of mechanical stirring is 100-800r/min, and the stirring time is 20-40min.
Preferably, in S8, the oil is sunflower seed oil.
Preferably, in S10, the primary gel beads are washed with a 75% ethanol solution or an isopropanol solution, separated by suction filtration using a suction filtration machine, and then dried in a freeze dryer for 72 hours at a temperature of-10 to-20 ℃.
The invention has the beneficial effects that:
1. compared with the original bentonite or pure bentonite-gelatin gel spheres, the adsorption amount of the magnetic bentonite-gelatin composite microspheres for adsorbing Cu is greatly improved.
2. The bentonite adsorbing material is a gel ball, has strong water absorption capacity and magnetism, and can be separated by magnetic adsorption after adsorption is finished. Compared with the traditional bentonite curing passivator, the product has the outstanding characteristic of separation.
3. The magnetic bentonite and gelatin composite microspheres have no pollution to the environment, and even if part of products remain in water or soil and still exist in the environment as a curing passivator after being decomposed, the magnetic bentonite and gelatin composite microspheres still have certain heavy metal passivation adsorption capacity.
Drawings
FIG. 1 is an external scanning electron microscope image of the magnetic bentonite gelatin composite microsphere of the invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the cross section of the magnetic bentonite gelatin composite microsphere of the invention;
FIG. 3 is a schematic diagram of the magnetic bentonite gelatin composite microsphere of the present invention after magnetic separation;
FIG. 4 is a magnetic hysteresis curve diagram of the magnetic bentonite gelatin composite microsphere of the invention;
FIG. 5 is a Fourier infrared plot of the magnetic bentonite gelatin composite microsphere of the invention;
FIG. 6 is an X-ray photoelectron spectroscopy analysis chart of the magnetic bentonite gelatin composite microsphere of the present invention;
FIG. 7 is a comparison graph of the adsorbability of the magnetic bentonite gelatin composite microspheres of the invention and non-magnetic bentonite gelatin composite microspheres;
FIG. 8 is a graph showing the adsorption capacity of the magnetic bentonite gelatin composite microspheres and the non-magnetic bentonite gelatin composite microspheres of the present invention varying with time;
Detailed Description
The invention is further illustrated by the following examples in connection with the accompanying drawings.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Example 1, a method for preparing magnetic bentonite-gelatin composite microspheres for removing Cu ions from sediment in a water body, comprising the following steps,
s1, dissolving ferric chloride hexahydrate in ethylene glycol, and mechanically stirring and fully mixing to obtain a solution a;
s2, dissolving sodium acetate, ethylenediamine and bentonite in the solution a, and fully mixing by mechanical stirring to obtain a solution b;
s3, pouring the polytetrafluoroethylene and the solution b into a reaction kettle for hydrothermal reaction to obtain a solution c;
s4, pouring the solution c into a centrifuge tube for centrifugation and washing with distilled water to obtain a solid product A;
s5, placing the solid product A in a drying oven for drying, and finally grinding and sieving to obtain magnetic bentonite;
s6, placing the gelatin in a small beaker, adding distilled water, heating, and mechanically stirring and fully mixing to obtain a solution d;
s7, pouring the magnetic bentonite into the solution d, and mechanically stirring and fully mixing to obtain a magnetic bentonite-gelatin mixed solution;
s8, putting the grease into an ice-water mixture for ice bath, and magnetically stirring the grease;
s9, injecting the magnetic bentonite-gelatin mixed solution into sunflower seed oil and refrigerating to obtain primary gel balls;
and S10, washing the primary gel balls, and freeze-drying to obtain the magnetic bentonite-gelatin composite microspheres.
Step S6, putting gelatin into a small beaker, adding distilled water and heating to quickly dissolve the gelatin, wherein the ratio of the mass of the gelatin to the mass of the magnetic bentonite is more than 1:2, otherwise, the mixture is adhered in the extrusion process and is difficult to form balls; in the step S8, the grease is put into an ice-water mixture for ice bath, the grease can be cooled, the magnetic bentonite-gelatin mixed solution is conveniently formed in the grease, and the magnetic bentonite-gelatin mixed solution is prevented from being bonded and fused after entering the grease through magnetic stirring.
Compared with the original bentonite or pure bentonite-gelatin gel spheres, the adsorption amount of the magnetic bentonite-gelatin composite microspheres for adsorbing Cu is greatly improved; the bentonite adsorbing material is gel balls, has strong water absorbing capacity and magnetism, can be separated by adopting magnetic adsorption after adsorption is finished, and has the characteristic of outstanding separation compared with the traditional solidified passivator of the bentonite; the gel ball disclosed by the invention has no pollution to the environment, and still has certain heavy metal passivation adsorption capacity when being decomposed and still existing in the environment as a curing passivator even if part of products are remained in water or soil.
Preferably, in S1, the mass of ferric chloride hexahydrate is 1g, the volume of ethylene glycol is 40mL, the rotation speed of mechanical stirring is 1000r/min, and the stirring time is 30min.
Preferably, in S2, the mass of sodium acetate is 5g, the mass of ethylenediamine is 20ml, the mass of bentonite is 1.0g, the rotation speed of mechanical stirring is 1000r/min, and the stirring time is 30min.
Preferably, the amount of polytetrafluoroethylene in S3 is 90ml, the hydrothermal reaction temperature is 200 ℃ and the reaction time is 6 hours.
Preferably, in S5, the temperature of the drying oven is 70 ℃.
Preferably, in S6, the mass of gelatin is 1g, the distilled water is 15mL, the heating temperature is 50 ℃, the rotation speed of mechanical stirring is 500r/min, and the stirring time is 60min.
Preferably, in S7, the mass of the magnetic bentonite is 0.1g, the rotation speed of mechanical stirring is 500r/min, and the stirring time is 20min.
Preferably, in S8, the oil is sunflower oil.
Preferably, in S10, the primary gel spheres are washed by using 75% ethanol solution or isopropanol solution, separated by suction filtration by using a suction filter, and then dried in a freeze dryer for 72 hours at the temperature of-10 ℃.
s1, dissolving ferric chloride hexahydrate in ethylene glycol, and mechanically stirring and fully mixing to obtain a solution a;
s2, dissolving sodium acetate, ethylenediamine and bentonite in the solution a, and mechanically stirring and fully mixing to obtain a solution b;
s3, pouring the polytetrafluoroethylene and the solution b into a reaction kettle for hydrothermal reaction to obtain a solution c;
s4, pouring the solution c into a centrifuge tube for centrifugation and washing with distilled water to obtain a solid product A;
s5, placing the solid product A in a drying oven for drying, and finally grinding and sieving to obtain magnetic bentonite;
s6, putting the gelatin into a small beaker, adding distilled water, heating, and mechanically stirring and fully mixing to obtain a solution d;
s7, pouring the magnetic bentonite into the solution d, and mechanically stirring and fully mixing to obtain a magnetic bentonite-gelatin mixed solution;
s8, putting the grease into an ice-water mixture for ice bath, and magnetically stirring the grease;
s9, injecting the magnetic bentonite-gelatin mixed solution into sunflower seed oil and refrigerating to obtain primary gel balls;
and S10, washing the primary gel spheres, and freeze-drying to obtain the magnetic bentonite-gelatin composite microspheres.
Step S6, placing gelatin in a small beaker, adding distilled water and heating to quickly dissolve the gelatin, wherein the ratio of the mass of the gelatin to the mass of the magnetic bentonite is greater than 1:2, otherwise, the mixture is adhered in the extrusion process and is difficult to form balls; in the step S8, the grease is put into an ice-water mixture for ice bath, the grease can be cooled, the magnetic bentonite-gelatin mixed solution is conveniently formed in the grease, and the magnetic bentonite-gelatin mixed solution is prevented from being bonded and fused after entering the grease through magnetic stirring.
Compared with the original bentonite or pure bentonite-gelatin gel spheres, the adsorption amount of the magnetic bentonite-gelatin composite microspheres for adsorbing Cu is greatly improved; the bentonite adsorbing material is gel balls, has strong water absorbing capacity and magnetism, can be separated by adopting magnetic adsorption after adsorption is finished, and has the characteristic of outstanding separation compared with the traditional solidified passivator of the bentonite; the gel ball disclosed by the invention has no pollution to the environment, and still has certain heavy metal passivation adsorption capacity when being decomposed and still existing in the environment as a curing passivator even if part of products are remained in water or soil.
Preferably, in S1, the mass of ferric chloride hexahydrate is 4g, the ethylene glycol is 60mL, the rotation speed of mechanical stirring is 1200r/min, and the stirring time is 50min.
Preferably, in S2, the mass of sodium acetate is 8g, the mass of ethylenediamine is 50ml, the mass of bentonite is 8.0g, the rotation speed of mechanical stirring is 1200r/min, and the stirring time is 50min.
Preferably, in S3, the amount of polytetrafluoroethylene is 220ml, the temperature of the hydrothermal reaction is 200 ℃, and the reaction time is 12 hours.
Preferably, in S5, the temperature of the drying oven is 90 ℃.
Preferably, in S6, the mass of gelatin is 3g, the volume of distilled water is 30mL, the heating temperature is 60 ℃, the rotation speed of mechanical stirring is 800r/min, and the stirring time is 80min.
Preferably, in S7, the mass of the magnetic bentonite is 2g, the rotation speed of mechanical stirring is 800r/min, and the stirring time is 40min.
Preferably, in S8, the oil is sunflower oil.
Preferably, in S10, the primary gel spheres are washed by using 75% ethanol solution or isopropanol solution, separated by suction filtration by using a suction filter, and then dried in a freeze dryer for 72 hours at the temperature of-20 ℃.
Embodiment 3, a method for preparing magnetic bentonite-gelatin composite microspheres for removing Cu ions from sediment in water body, comprising the following steps,
s1, dissolving ferric chloride hexahydrate in ethylene glycol, and mechanically stirring and fully mixing to obtain a solution a;
s2, dissolving sodium acetate, ethylenediamine and bentonite in the solution a, and mechanically stirring and fully mixing to obtain a solution b;
s3, pouring the polytetrafluoroethylene and the solution b into a reaction kettle for hydrothermal reaction to obtain a solution c;
s4, pouring the solution c into a centrifuge tube for centrifugation and washing with distilled water to obtain a solid product A;
s5, placing the solid product A in a drying oven for drying, and finally grinding and sieving to obtain magnetic bentonite;
s6, putting the gelatin into a small beaker, adding distilled water, heating, and mechanically stirring and fully mixing to obtain a solution d;
s7, pouring the magnetic bentonite into the solution d, and mechanically stirring and fully mixing to obtain a magnetic bentonite-gelatin mixed solution;
s8, putting the grease into an ice-water mixture for ice bath, and magnetically stirring the grease;
s9, injecting the magnetic bentonite-gelatin mixed solution into sunflower seed oil and refrigerating to obtain primary gel balls;
and S10, washing the primary gel spheres, and freeze-drying to obtain the magnetic bentonite-gelatin composite microspheres.
Step S6, placing gelatin in a small beaker, adding distilled water and heating to quickly dissolve the gelatin, wherein the ratio of the mass of the gelatin to the mass of the magnetic bentonite is greater than 1:2, otherwise, the mixture is adhered in the extrusion process and is difficult to form balls; in the step S8, the grease is put into an ice-water mixture for ice bath, the grease can be cooled, the magnetic bentonite-gelatin mixed solution is conveniently formed in the grease, and the magnetic bentonite-gelatin mixed solution is prevented from being bonded and fused after entering the grease through magnetic stirring.
Compared with the original bentonite or pure bentonite-gelatin gel spheres, the adsorption amount of the magnetic bentonite-gelatin composite microspheres for adsorbing Cu is greatly improved; the bentonite adsorption material is gel balls, has strong water absorption capacity and magnetism, can be separated by magnetic adsorption after adsorption is finished, and has the characteristic of outstanding separation compared with the traditional bentonite curing passivator; the gel ball disclosed by the invention has no pollution to the environment, and still has certain heavy metal passivation adsorption capacity when being decomposed and still existing in the environment as a curing passivator even if part of products are remained in water or soil.
Preferably, in S1, the mass of ferric chloride hexahydrate is 2g, the volume of ethylene glycol is 50mL, the rotation speed of mechanical stirring is 300r/min, and the stirring time is 40min.
Preferably, in S2, the mass of sodium acetate is 6g, the mass of ethylenediamine is 40ml, the mass of bentonite is 5g, the rotation speed of mechanical stirring is 300r/min, and the stirring time is 40min.
Preferably, in S3, the amount of polytetrafluoroethylene is 120ml, the temperature of the hydrothermal reaction is 200 ℃, and the reaction time is 9 hours.
Preferably, in S5, the temperature of the drying oven is 80 ℃.
Preferably, in S6, the mass of gelatin is 2g, the distilled water is 20mL, the heating temperature is 53 ℃, the rotation speed of mechanical stirring is 100r/min, and the stirring time is 70min.
Preferably, in S7, the mass of the magnetic bentonite is 1.2g, the rotation speed of mechanical stirring is 100r/min, and the stirring time is 30min.
Preferably, in S8, the oil is sunflower oil.
Preferably, in S10, the primary gel spheres are washed by using 75% ethanol solution or isopropanol solution, separated by suction filtration by using a suction filter, and then dried in a freeze dryer for 72 hours at the temperature of-16 ℃.
Adsorption test of magnetic bentonite-gelatin composite microspheres on Cu ions
100mL of copper solutions with Cu ion concentrations of 50mg/L, 100mg/L, 200mg/L, 300mg/L and 400mg/L are respectively put into a beaker, and 0.1g of magnetic bentonite and gelatin composite microspheres are added. Stirring, mixing and oscillating by a shaking instrument at room temperature; sampling and storing every 10 minutes, and measuring the concentration of the residual copper ions in the solution by adopting an ICP (inductively coupled plasma) device of a plasma emission spectrometer; after the reaction is carried out for 1h, the concentration of the residual copper ions in the solution is reduced to 4.8mg/L, the removal rate reaches 90.6%, and after the Cu ions are removed and the adsorption reaction reaches the equilibrium, the small balls are separated from the solution by using a magnet.
As can be seen from fig. 7 and 8, the adsorption capacity of the magnetic bentonite gelatin composite microsphere of the invention is higher than that of the non-magnetic bentonite gelatin composite microsphere, which indicates that the adsorption capacity of the magnetic bentonite gelatin composite microsphere prepared by the invention to Cu ions is greatly improved.
As can be seen from fig. 3, the magnetic bentonite gelatin composite microspheres of the invention can be separated by magnetic adsorption after adsorption is completed, compared with the traditional bentonite curing passivator, the magnetic bentonite gelatin composite microspheres of the invention have the outstanding characteristic of separation, can separate materials from sewage by a magnetic technology, and have the characteristics of easy recovery and reuse and environmental friendliness.
Claims (9)
1. A preparation method of magnetic bentonite gelatin composite microspheres for removing Cu ions in water body bottom mud is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, dissolving ferric chloride hexahydrate in ethylene glycol, and mechanically stirring and fully mixing to obtain a solution a;
s2, dissolving sodium acetate, ethylenediamine and bentonite in the solution a, and fully mixing by mechanical stirring to obtain a solution b;
s3, pouring polytetrafluoroethylene and the solution b into a reaction kettle for hydrothermal reaction to obtain a solution c;
s4, pouring the solution c into a centrifuge tube for centrifugation and washing with distilled water to obtain a solid product A;
s5, placing the solid product A in a drying oven for drying, and finally grinding and sieving to obtain magnetic bentonite;
s6, putting the gelatin into a small beaker, adding distilled water, heating, and mechanically stirring and fully mixing to obtain a solution d;
s7, pouring the magnetic bentonite into the solution d, and mechanically stirring and fully mixing to obtain a magnetic bentonite-gelatin mixed solution;
s8, putting the grease into an ice-water mixture for ice bath, and magnetically stirring the grease;
s9, injecting the magnetic bentonite-gelatin mixed solution into sunflower seed oil and refrigerating to obtain primary gel balls;
and S10, washing the primary gel balls, and freeze-drying to obtain the magnetic bentonite-gelatin composite microspheres.
2. The preparation method of the magnetic bentonite-gelatin composite microsphere for removing Cu ions in sediment of water body according to claim 1, which is characterized in that: in the S1, the mass of ferric chloride hexahydrate is 1-4g, the mass of ethylene glycol is 40-60mL, the rotating speed of mechanical stirring is 300-1200r/min, and the stirring time is 30-50min.
3. The preparation method of the magnetic bentonite-gelatin composite microsphere for removing Cu ions in sediment of water body according to claim 1, which is characterized in that: in the S2, the mass of the sodium acetate is 5-8g, the mass of the ethylenediamine is 20-50ml, the mass of the bentonite is 1.0-8.0 g, the rotation speed of mechanical stirring is 300-1200r/min, and the stirring time is 30-50min.
4. The preparation method of the magnetic bentonite-gelatin composite microsphere for removing Cu ions in sediment of water body according to claim 1, which is characterized in that: in S3, the polytetrafluoroethylene is 90-220m l, the temperature of the hydrothermal reaction is 200 ℃, and the reaction time is 6-12h.
5. The preparation method of the magnetic bentonite-gelatin composite microsphere for removing Cu ions in sediment of water body according to claim 1, which is characterized in that: in S5, the temperature of the drying oven is 70-90 ℃.
6. The preparation method of the magnetic bentonite-gelatin composite microsphere for removing Cu ions in sediment of water body according to claim 1, which is characterized in that: in S6, the mass of the gelatin is 1-3g, the volume of the distilled water is 15-30mL, the heating temperature is 50-60 ℃, the rotation speed of mechanical stirring is 100-800r/min, and the stirring time is 60-80min.
7. The preparation method of the magnetic bentonite-gelatin composite microsphere for removing Cu ions in sediment of water body according to claim 1, which is characterized in that: in S7, the mass of the magnetic bentonite is 0.1-2g, the rotation speed of mechanical stirring is 100-800r/min, and the stirring time is 20-40min.
8. The preparation method of the magnetic bentonite-gelatin composite microsphere for removing Cu ions in sediment of water body according to claim 1, which is characterized in that: in S8, the oil is sunflower seed oil.
9. The preparation method of the magnetic bentonite-gelatin composite microsphere for removing Cu ions in the sediment of the water body according to claim 1, which is characterized by comprising the following steps: in the step S10, the primary gel balls are washed by using 75% ethanol solution or isopropanol solution, are subjected to suction filtration and separation by using a suction filter, and are dried in a freeze dryer for 72 hours at the temperature of-10 to-20 ℃.
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| CN104891513A (en) * | 2015-05-05 | 2015-09-09 | 济南大学 | Preparation method of magnetic bentonite |
| CN108355621A (en) * | 2018-03-21 | 2018-08-03 | 成都理工大学 | A kind of magnetic porous bentonite chitosan compound microsphere and preparation method thereof |
| CN109260515A (en) * | 2018-11-26 | 2019-01-25 | 华南理工大学 | A kind of adjustable hydrogel of structure size and its preparation method and application |
| CN109603771A (en) * | 2019-01-10 | 2019-04-12 | 盐城工学院 | A kind of preparation method of chitosan magnetic-montmorillonite-based nano complex microsphere |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891513A (en) * | 2015-05-05 | 2015-09-09 | 济南大学 | Preparation method of magnetic bentonite |
| CN108355621A (en) * | 2018-03-21 | 2018-08-03 | 成都理工大学 | A kind of magnetic porous bentonite chitosan compound microsphere and preparation method thereof |
| CN109260515A (en) * | 2018-11-26 | 2019-01-25 | 华南理工大学 | A kind of adjustable hydrogel of structure size and its preparation method and application |
| CN109603771A (en) * | 2019-01-10 | 2019-04-12 | 盐城工学院 | A kind of preparation method of chitosan magnetic-montmorillonite-based nano complex microsphere |
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