CN110665471A - Magnetic cadmium-removing colloidal particle material and preparation method and application thereof - Google Patents
Magnetic cadmium-removing colloidal particle material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a magnetic cadmium-removing colloidal particle material which has a core-shell structure, wherein the core-shell structure is formed by coating magnetic nano particles with a high polymer material; the surface of the magnetic nano-particle is modified by a modifier containing a functional group with C-O, C-C double bond. Meanwhile, a corresponding preparation method is also established: the preparation method comprises the steps of preparing magnetic nanoparticles by taking ferric chloride and ferrous sulfate as raw materials, modifying sodium humate on the surfaces of the magnetic nanoparticles, introducing functional groups carried by the sodium humate, coating the magnetic nanoparticles with the functional groups by sodium alginate, curing in a calcium chloride solution, and drying in vacuum. The magnetic cadmium-removing colloidal particle material has the characteristics of being recyclable and low in cost, can be widely applied to systems such as water bodies and soil to separate cadmium metal ions, and is suitable for the industries of environmental protection of water and soil, pollution treatment and the like.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a magnetic cadmium-removing colloidal particle material as well as a preparation method and application thereof.
Background
Cadmium is one of heavy metals with strong toxicity, and excessive intake of cadmium can cause harm to biological health, especially human health. In recent years, the cadmium exceeding of rice caused by cadmium pollution of rice is widely concerned by people. The national soil pollution condition survey bulletin (2014) shows that the cadmium exceeding rate of the soil in China is the highest and reaches 7.0 percent. The rice belongs to crops easy to absorb and accumulate cadmium, is also a main food crop in China, about 6 adult residents in China take rice as staple food, and the quality of the rice is closely related to the health of people. Therefore, the research on the pollution control technology capable of effectively reducing the content of the cadmium in the soil, particularly the effective state in the rice field and reducing the cadmium absorption of the rice has important practical significance.
At present, two main types of strategies for treating the heavy metal cadmium pollution of soil are adopted, one is solidification, and the migration of cadmium is reduced by changing the biological effectiveness of the cadmium; the other method is removal purification, and cadmium in the soil is removed by adding an adsorbent, so that the cadmium content of the soil is reduced. Among them, the adsorption removal technology by adding an adsorbent has been widely regarded as being capable of eradicating cadmium pollution of soil.
Van Li ren et al published a paper "chemical captureand mag" on Scientific Reports, 2016,6A net removal of non-magnetic metal substructures from soil' prepared from MSC magnetic material capable of solid phase chelation and trapping of heavy metals such as Cd2+，Cu2+，Pb2+And the mixture is converted into a magnetic solid chelate, and then is separated from the soil through magnetic separation, so that the effect of removing the Cd from the farmland soil is achieved.
Chinese patent "a magnetic aminocarboxylic chelating adsorption particle material and its preparation method" (patent No. 201410080511.9 published Japanese 2015-09-09) discloses a magnetic aminocarboxylic chelating adsorption particle material for adsorption enrichment of valuable metal ions and heavy metal ions in water or soil or solid-liquid suspension system, the method comprises coating magnetic material with SiO2Introducing an amino group into the above-mentioned amino group, and then performing carboxymethylation on the amino group to obtain the compound.
In the Chinese patent application "preparation method of novel magnetic arsenic removal solid chelating agent" (patent application No. 201710135760.7 published Japanese 2018-09-25), SiO with magnetic material coated inside is used2Introducing phosphoric acid functional group, and complexing with metal ions with affinity to arsenic to obtain the powder material. The magnetic material particles are small, are easy to form colloid with soil, are difficult to recycle, and have poor reusability, and the process of the magnetic material modified by the functional groups carried by the sodium humate is not reported.
In the Chinese patent application of 'a temperature-sensitive gel type heavy metal curing agent, a heavy metal contaminated soil curing and repairing method and a curing agent recovery method' (published in patent application No. 201910134330.2, No. 2019-05-17), the curing agent can cure and recover heavy metal chromium, but the soil is heated to 52-56 ℃ when the curing agent is recovered, so that sol can leave the soil along with water, and the recycling feasibility is poor.
In the Chinese patent 'a soil heavy metal cadmium adsorption plate and application thereof' (patent No. 201410193407.0 published Japanese 2016-01-27), the adsorption plate is prepared by utilizing sodium alginate and modified corncobs, and is horizontally laid on a cadmium-polluted soil surface soil layer, and then is taken out for adsorption for 7 days and then is recovered, so that the aim of adsorbing and treating cadmium can be fulfilled.
Disclosure of Invention
The invention aims to provide a magnetic cadmium-removing colloidal particle material which is low in cost, easy to produce, stable in structure and capable of being recycled, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the magnetic cadmium-removing colloidal particle material has a core-shell structure, and the core-shell structure is formed by coating magnetic nano particles with a high polymer material; the surface of the magnetic nano-particle is modified by a modifier containing a functional group with C-O, C-C double bond.
The particle size of the magnetic cadmium-removing colloid particle material is 0.01-0.2 mm; the particle size of the magnetic nanoparticles is 200-500 nm.
The polymer material is sodium alginate and chitosan; the magnetic nano-particles are prepared by taking ferric chloride and ferrous sulfate as raw materials; the modifier is sodium humate, humus, fulvic acid and humin, and the functional group is C O, C ═ C double bond functional group such as carboxyl, phenolic group, hydroxyl, methoxyl and quinonyl.
The preparation method of the magnetic cadmium-removing colloidal particle material comprises the steps of preparing magnetic nanoparticles by taking ferric chloride and ferrous sulfate as raw materials, modifying sodium humate on the surfaces of the magnetic nanoparticles, introducing functional groups carried by the sodium humate, coating the magnetic nanoparticles with the functional groups by sodium alginate (coating agent), finally curing in calcium chloride solution (curing agent), and drying in vacuum to obtain the magnetic cadmium-removing colloidal particle material.
The preparation method of the magnetic cadmium-removing colloidal particle material comprises the following steps:
1) adding ferrous sulfate and ferric chloride into deionized water, stirring for dissolving, and heating in water bath;
2) continuously adding a mixture of ammonia water and sodium humate into the solution obtained in the step 1), continuously stirring for reaction, cooling, standing overnight, cleaning, filtering, drying and crushing to obtain surface-modified magnetic nanoparticles;
3) adding the magnetic nano-particles obtained in the step 2) into a sodium alginate solution, and stirring for reaction for 20mim-3 hours;
4) dropwise adding the uniformly stirred mixture obtained in the step 3) into a calcium chloride solution to obtain gel particles, standing overnight, washing with deionized water, and carrying out vacuum drying on the prepared colloidal particles to obtain the magnetic cadmium-removing colloidal particle material.
The mixture of ammonia water and sodium humate is prepared by the following operations: dissolving sodium humate in water, wherein the mass/volume ratio of the sodium humate to the water is 1:100 to prepare a sodium humate solution, then adding ammonia water to ensure that the volume ratio of the sodium humate solution to the ammonia water is 1:3-10, and uniformly stirring to obtain the sodium humate-ammonia water with the concentration of 15% -29%; the sodium alginate solution is prepared by the following operations: dissolving sodium alginate in water, wherein the mass ratio of the sodium alginate to the water is 1-12: 100; the calcium chloride solution is prepared by the following operations: dissolving calcium chloride in water, wherein the mass ratio of the calcium chloride to the water is 1-5: 100.
In step 1): the mass ratio of ferric chloride to ferrous sulfate is 1-2.0: 1; the temperature of the water bath is 70-120 ℃, and the temperature is increased at the speed of 5 ℃/min;
in step 2): the ratio of the mixture to the solution to be added is 6: 10; the stirring speed is 300-2000r/min, and the stirring reaction time is 20min-3 h; cooling overnight, and cleaning with deionized water for 3-8 times until pH of the solution is 7.0; filtering with filter paper, and oven drying at 60-95 deg.C;
in step 3): the mass ratio of the magnetic nano-particles to the sodium alginate solution is 10-25%;
in step 3): the temperature of vacuum drying is 50-90 ℃.
The magnetic cadmium-removing colloidal particle material is applied to inhibiting the absorption of cadmium in rice plants.
In the application, the magnetic cadmium-removing colloid particle material is directly applied to soil and then is uniformly mixed to plant rice.
The using period of the magnetic cadmium-removing colloid particle material is that when the base fertilizer is applied to the rice (namely, the base fertilizer is applied 5-10 days before the transplantation of the rice seedlings), the using amount is 2g/kg of soil or 300 kg/mu of 100-one soil.
Aiming at the problems of the existing magnetic cadmium removal material, the inventor develops a magnetic cadmium removal colloidal particle material which has a core-shell structure, wherein the core-shell structure is formed by coating magnetic nano particles with a high polymer material; the surface of the magnetic nano-particle is modified by a modifier containing a C-O, C-C double bond functional group. Meanwhile, a corresponding preparation method is established, the magnetic nano-particles are prepared by taking ferric chloride and ferrous sulfate as raw materials, sodium humate is modified on the surfaces of the magnetic nano-particles, functional groups carried by the sodium humate are introduced, the magnetic nano-particles with the functional groups are coated by sodium alginate, and finally the magnetic nano-particles are solidified in a calcium chloride solution and dried in vacuum to obtain the magnetic nano-particles. The magnetic cadmium-removing colloidal particle material has functional groups of C-O, C-C double bonds such as quinonyl, carbonyl, carboxyl, enol and the like, can chelate and adsorb cadmium ions, and has a stable structure and a wide application range. Experiments show that the cadmium content in the usable state of the rice plant root system, the iron membrane on the root surface and the stem leaf can be effectively reduced by using the cadmium-absorbing inhibitor to inhibit the cadmium absorption of the rice plant, so that the aim of reducing the cadmium accumulation of the rice is fulfilled. In addition, the colloid particle material adsorbed with cadmium can be conveniently and directly separated by using a magnet, thereby achieving the purpose of removing heavy metal cadmium in soil. In conclusion, the magnetic cadmium removal colloidal particle material has the characteristics of being recyclable and low in cost, can be widely applied to systems such as water bodies and soil for separating cadmium metal ions, and is suitable for industries such as environmental protection and pollution treatment of water and soil.
Drawings
FIG. 1 is an electron microscope image of the magnetic cadmium-removing colloidal particle material prepared by the invention, wherein: a 600 times of appearance, b 600 times of inside, c1000 times of appearance and d10000 times of appearance.
FIG. 2 is an energy spectrum of the magnetic cadmium-removing colloidal particle material prepared by the present invention.
Fig. 3 is an XRD pattern of the magnetic cadmium-removed colloidal particle material prepared by the present invention.
FIG. 4 is a photograph of the magnetic cadmium-removed colloidal particle material prepared in the present invention, in which: before the magnet is adsorbed, and after the magnet is adsorbed.
Detailed Description
Example 1 preparation of sodium humate surface-modified magnetic Material
Weighing 61g of ferric chloride hexahydrate and 42g of ferrous sulfate heptahydrate, dissolving in 1L of deionized water, stirring for dissolving, slowly heating in a water bath to 90 ℃ (5 ℃/min), then quickly and continuously adding a mixed solution prepared from 100ml of ammonia water (25%) and 500ml of sodium humate solution (5g of sodium humate is dissolved in 500ml of water), continuously stirring for 30min (300 plus 2000r/min), cooling to room temperature, standing overnight, obtaining a black precipitate which is a magnetic material modified by sodium humate, washing with deionized water for three times (until the pH value of the solution is 7.0), filtering, drying for 24h at 40 ℃, and crushing to obtain the magnetic material modified by the modifier sodium humate.
Example 2 preparation of magnetic cadmium-removing colloidal particle Material
(1) Weighing 12g of sodium alginate, adding 600ml of deionized water, and heating to dissolve to obtain a sodium alginate solution.
(2) 4.5g of the magnetic material obtained in example 1 was weighed, added to the prepared sodium alginate solution, and stirred with a cantilever stirrer for 10min to obtain a sodium alginate-embedded magnetic particle mixed solution.
(3) 20g of calcium chloride dihydrate was weighed and dissolved in 1L of deionized water to obtain a curing agent solution.
(4) And (3) sucking the mixed solution in the step (2) by using a 30ml syringe, dripping the mixed solution into 250ml of curing agent solution in the step (3) at the speed of 1 drop per second, standing overnight, washing the solidified colloidal particles by using deionized water for three times, and drying for 24 hours at the temperature of 60 ℃ in vacuum to obtain the final product, namely the magnetic cadmium-removing colloidal particle material.
As shown in FIGS. 1 to 3, in the obtained magnetic cadmium removal colloidal particle material, the functional groups were directly bonded to Fe3O4Sodium alginate is directly linked to calcium. As shown in fig. 4, the magnetic cadmium-removed colloidal particle material was separated by a magnet, showing that it can be adsorbed by a magnet and is suitable for separation by an external magnetic field.
Example 3 preparation of sodium alginate gel particulate material
(1) Weighing 12g of sodium alginate, adding 600ml of deionized water, and heating to dissolve to obtain a sodium alginate solution.
(2) 20g of calcium chloride dihydrate was weighed and dissolved in 1l of deionized water to obtain a curing agent solution.
(3) And (3) sucking the mixed solution in the step (1) by using a 30ml syringe, dripping the mixed solution into 250ml of curing agent solution in the step (2) at the speed of 1 drop per second, standing overnight, washing with deionized water for three times, and drying at the temperature of 60 ℃ in vacuum for 24 hours to obtain the sodium alginate particle material.
Example 4 adsorption of soil available cadmium by magnetic cadmium removal colloidal particle Material
The physicochemical properties of the soil to be tested are shown in table 1,
TABLE 1 physicochemical Properties of the soil tested
| Item | Soil(s) |
| pH | 6.8 |
| Total iron (g/kg) | 10.1 |
| Total cadmium (mg/kg) | 10.45 |
| Available nitrogen (mg/kg) | 172.0 |
| Available phosphorus (mg/kg) | 34.0 |
| Total potassium (g/kg) | 20.6 |
| Organic matter (g/kg) | 25.8 |
Weighing 10g of soil to be tested, adding 30ml of deionized water, adding 1g of magnetic cadmium removal colloid particle material, repeatedly treating three times in a shaking table by taking no magnetic particle material as a reference, placing the three times in the shaking table at 180r/min, continuously reacting for 10 days, and then measuring the cadmium content of the soil in the magnesium chloride extraction state.
The result is shown in table 2, the magnetic cadmium removal colloidal particle material reduces the content of the available cadmium in the soil from 1.735 to 0.572, and the adsorption amount of the magnetic cadmium removal colloidal particle material to the content of the available cadmium reaches 67.00%, which shows that the magnetic cadmium removal colloidal particle material can effectively reduce the content of the available cadmium in the soil and achieve the effect of chelating and trapping the available cadmium.
TABLE 2 content of available cadmium in soil before and after adsorption of cadmium according to the invention
| Index (I) | Type of soil | pH | MgCl2Extraction state Cd (mg/kg) | Adsorption Rate (%) |
| Cd | Soil before adsorption | 7.31 | 1.735 | |
| Soil after adsorption | 7.36 | 0.572 | 67.00 |
Example 5 magnetic cadmium removing colloidal particle Material application potting test
The test rice soil for the pot culture test is collected from unpolluted rice soil in the sweet town, the sampling depth is 0-20cm, the soil is artificially polluted, naturally dried, sieved by a 2mm sieve and uniformly mixed for later use. The basic properties of the soil are shown in table 1.
The test was processed as follows:
t1:600g soil +1.2g magnetic Material prepared in example 1
T2 g of soil 600g +1.2g of the magnetic cadmium-removing colloidal particulate material prepared in example 2
T3 soil 600g +1.2g sodium alginate gel granular material prepared in example 3
The prepared soil was filled into plastic buckets (10 cm diameter, 20cm height) each containing 600g of soil, 3 replicates per treatment, with no addition of any particulate material as Control (CK). A small amount of soil was first filled into the bottom, then an empty nylon mesh bag (8cm by 20cm) with a pore size of 45 μm was placed in the center of the bucket, and the remaining soil was then filled into the bucket, at which time the mesh bag was fixed in the center of the bucket. (the mesh bag can reduce direct contact between the root system and the soil, a relatively clean and complete root system can be obtained during harvesting, the flow of water and nutrients inside and outside the mesh bag can be guaranteed, the absorption of water and nutrients by rice is not influenced), the barreling is finished, tap water is added into each barrel, a water layer of 2cm on the surface of the soil is kept, and the barrel is placed in a greenhouse. Transplanting rice seedlings (seedlings which grow consistently after 10 days of emergence) 7 days later, keeping a water layer of 2cm, harvesting 45 days later after the rice is transplanted, collecting soil samples and rice samples, and analyzing the effective cadmium content of the soil and the total iron content of plants.
The soil available cadmium content is shown in table 3. Compared with CK, T2 can slightly reduce the content of cadmium in the soil in an available state.
TABLE 3 content of available cadmium in soil after adsorbing cadmium according to the present invention
The rice plant results are shown in table 4. The cadmium content in the iron film, root system and stem and leaf of the potted rice after being treated by the magnetic cadmium-removing colloidal particle material (T2) is the lowest, and compared with CK, the cadmium content in each part is respectively reduced by 71.96%, 62.14% and 60.00%. Except that the iron content of the iron film on the root surface is reduced by 11.87 percent, the iron content of the root system and the stem leaf is respectively increased by 147.59 percent and 27.17 percent. The effects of T1 and T3 on reducing the cadmium content of rice plants are not as good as T2. The magnetic cadmium removal colloidal particle material and the application technology thereof can inhibit the absorption and accumulation of cadmium in rice plants and reduce the cadmium content in the rice plants.
TABLE 4 cadmium and iron contents of rice plants after cadmium adsorption according to the invention
EXAMPLE 6 recovery of magnetic cadmium removal colloidal particulate material
The treatment was as follows: adding tap water into soil for harvesting rice plants, flooding for 5 days, sucking out magnetic cadmium-removing colloid particles in the soil by using a magnetic bar, putting the soil into a plastic bottle, cleaning, drying at 50 ℃, weighing, and obtaining the recovery rate shown in table 5.
TABLE 5 recovery of magnetic cadmium-removing gel particles after adsorption of cadmium according to the invention
The result shows that the recovery rate of the magnetic cadmium removing gel particles reaches 90.83 percent, which is 29 percent higher than that of iron powder, and the T3 is processed into gel, which is inconvenient to recover, thus the magnetic cadmium removing gel particles can achieve the effects of high recovery rate and easy removal from soil.
The magnetic cadmium-removing gel particles of the invention are applied as base fertilizer 5-10 days before the transplantation of rice seedlings, and specifically comprise the following components: after soil is leveled, base fertilizer and magnetic cadmium removal colloid particle materials (2g/kg soil or 300 kg/mu of 100-.
Claims (10)
1. A magnetic cadmium-removing colloidal particle material is characterized by having a core-shell structure, wherein the core-shell structure is formed by coating magnetic nano particles with a high polymer material; the surface of the magnetic nano-particle is modified by a modifier containing a C-O, C-C double bond functional group.
2. The magnetic cadmium removing colloidal particle material of claim 1, wherein: the particle size of the magnetic cadmium-removing colloidal particle material is 0.01-0.2 mm; the particle size of the magnetic nanoparticles is 200-500 nm.
3. The magnetic cadmium removing colloidal particle material of claim 1, wherein: the high polymer material is sodium alginate and chitosan; the magnetic nano-particles are prepared by taking ferric chloride and ferrous sulfate as raw materials; the modifier is sodium humate, humus, fulvic acid and humin, and the functional group is double bond functional group such as carboxyl, phenolic group, hydroxyl, methoxyl, quinonyl and the like.
4. A method for preparing the magnetic cadmium-removing colloidal particle material as set forth in claim 3, wherein: the preparation method comprises the steps of preparing magnetic nanoparticles by taking ferric chloride and ferrous sulfate as raw materials, modifying sodium humate serving as a modifier on the surfaces of the magnetic nanoparticles, introducing functional groups carried by the sodium humate, coating the magnetic nanoparticles with the functional groups by sodium alginate, curing in a calcium chloride solution, and drying in vacuum.
5. The method for preparing magnetic cadmium-removing colloidal particle material as claimed in claim 4, comprising the steps of:
1) adding ferrous sulfate and ferric chloride into deionized water, stirring for dissolving, and heating in water bath;
2) continuously adding a mixture of ammonia water and sodium humate into the solution obtained in the step 1), continuously stirring for reaction, cooling and cleaning after the reaction is finished, filtering, drying and crushing to obtain surface-modified magnetic nanoparticles;
3) adding the magnetic nano-particles obtained in the step 2) into a sodium alginate solution, and stirring for reaction for 20mim-3 hours;
4) dropwise adding the uniformly stirred mixture obtained in the step 3) into a calcium chloride solution to obtain gel particles, standing overnight, washing with deionized water, and carrying out vacuum drying on the prepared colloidal particles to obtain the magnetic cadmium-removing colloidal particle material.
6. The method for preparing magnetic cadmium-removing colloidal particle material as claimed in claim 5, wherein: the mixture of the ammonia water and the sodium humate is prepared according to the following operations: dissolving sodium humate in water, wherein the mass/volume ratio of the sodium humate to the water is 1:100, then adding ammonia water, wherein the volume ratio of the sodium humate solution to the ammonia water is 1:3-10, and uniformly stirring to obtain the sodium humate-ammonia water solution; the concentration of the ammonia water is 15% -29%; the sodium alginate solution is prepared by the following operations: dissolving sodium alginate in water, wherein the mass ratio of the sodium alginate to the water is 1-12: 100; the calcium chloride solution is prepared by the following operations: dissolving calcium chloride in water, wherein the mass ratio of the calcium chloride to the water is 1-5: 100.
7. The method for preparing magnetic cadmium-removing colloidal particle material as claimed in claim 5, wherein:
in step 1): the mass ratio of the ferric chloride to the ferrous sulfate is 1-2.0: 1; the temperature of the water bath is 70-120 ℃, and the temperature is increased at the speed of 5 ℃/min;
in step 2): the ratio of the mixture to the solution to be added is 6: 10; the stirring speed is 300-2000r/min, and the stirring reaction time is 20min-3 h; the cooling and cleaning is to cool the solution to room temperature, and after the solution stays overnight, the solution is cleaned for 3 to 8 times by deionized water until the pH value of the solution is 7.0; the filtration is carried out by using filter paper, and the drying is carried out in a constant temperature blast drying oven at the temperature of 60-95 ℃;
in step 3): the mass ratio of the magnetic nano-particles to the sodium alginate solution is 10-25%;
in step 3): the temperature of the vacuum drying is 50-90 ℃.
8. The use of the magnetic cadmium-removing colloidal particle material of claim 1 to inhibit cadmium uptake in rice plants.
9. Use according to claim 8, characterized in that: and (3) directly applying the magnetic cadmium-removing colloid particle material into soil, and then uniformly mixing to plant rice.
10. Use according to claim 9, characterized in that: the using period of the magnetic cadmium removal colloid particle material is 2g/kg of soil or 300 kg/mu of soil with the dosage when the base fertilizer is applied to the rice.
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Application publication date: 20200110 |