CN114345303A - Magnetic attapulgite cellulose composite microsphere and preparation method and application thereof - Google Patents
Magnetic attapulgite cellulose composite microsphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of heavy metal contaminated soil remediation, and particularly relates to a magnetic attapulgite cellulose composite microsphere and a preparation method and application thereof. The preparation method of the magnetic attapulgite cellulose composite microspheres provided by the invention comprises the following steps: mixing cellulose and ionic liquid, and heating to obtain a cellulose solution; mixing a cellulose solution, attapulgite, magnetic particles and a pore-forming agent, then dripping the obtained mixed solution into an acid solution, and filtering to obtain composite microspheres; mixing the composite microspheres, a solvent and acrylamide, then adding an initiator and acid, stirring for reaction, filtering and drying to obtain the magnetic attapulgite cellulose composite microspheres. The composite microspheres prepared by the preparation method provided by the invention can effectively solidify and stabilize cadmium ions in soil, reduce the content of biologically effective state of the cadmium ions, and reduce the absorption amount of crops to soil heavy metals.
Description
Technical Field
The invention relates to the technical field of heavy metal contaminated soil remediation, and particularly relates to a magnetic attapulgite cellulose composite microsphere and a preparation method and application thereof.
Background
Due to the rapid development of modern industry, heavy metals in the atmosphere enter water and soil through rainwater, which aggravates the problem of heavy metal pollution in the water and soil.
Attapulgite is a mineral mainly containing water-bearing magnesium-rich aluminosilicate, belonging to silicate minerals, and its basic structure is composed of two layers of silicon-oxygen tetrahedron and one layer of magnesium-oxygen octahedron, and is a natural porous material. Cellulose is the most abundant and renewable organic biopolymer in the world and is widely recognized as an important source of sustainable materials due to its strong mechanical strength, biocompatibility and thermal stability. The attapulgite and the cellulose have rich yield, low price, stronger ion exchange capacity and good adsorption performance in China. However, the cellulose has a small specific surface area, attapulgite is easily enriched, the using efficiency in soil remediation is low, and the attapulgite is difficult to recover. The magnetic organic modification overcomes the defect of difficult recovery and separation of common organic modification, and achieves the effect of saving cost and time.
The existing preparation method of the magnetic modified material generally adopts a coprecipitation method, the load material adopts cellulose to prepare microspheres, the microspheres are soft and have a spherical structure, and meanwhile, the cellulose is adopted to prepare the microspheres, so that the microspheres have fewer pore passages and are not beneficial to subsequent modification and adsorption of heavy metal cadmium.
Disclosure of Invention
The invention aims to overcome the defects that the obtained microspheres are soft, have fewer pore passages and are not beneficial to subsequent adsorption and adsorption of heavy metal cadmium in the conventional method for preparing carrier microspheres by adopting cellulose, and further provides the magnetic attapulgite cellulose composite microspheres and the preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of magnetic attapulgite cellulose composite microspheres comprises the following steps:
1) mixing cellulose and ionic liquid, and heating to obtain a cellulose solution;
2) mixing a cellulose solution, attapulgite, magnetic particles and a pore-forming agent, then dripping the obtained mixed solution into an acid solution, and filtering to obtain composite microspheres;
3) mixing the composite microspheres, a solvent and acrylamide, then adding an initiator and acid, stirring for reaction, filtering and drying to obtain the magnetic attapulgite cellulose composite microspheres.
Preferably, the dropping speed in the step 2) is 2mL/min to 3 mL/min; the acid solution is hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 0.5-1 mol/L.
Optionally, the mass ratio of the mixed solution to the acid solution in the step 2) is 1: (4-8).
Preferably, the mass ratio of the cellulose to the attapulgite to the magnetic particles to the ionic liquid is 1 (0.5-1) to (30-40);
the addition amount of the pore-forming agent is 10 to 50 percent of the total mass of the cellulose and the attapulgite;
in the step 3), the mass ratio of the composite microsphere, the solvent, the acrylamide, the initiator and the acid is 1 (200-) -300: 3-7: 0.2-0.5.
Preferably, the heating temperature in the step 1) is 90-120 ℃, and the heating time is 1-2 h;
continuously stirring the acid solution in the dropwise adding process in the step 2), and continuously stirring after the dropwise adding process is finished, wherein the stirring speed is 150-200 r/min, and the total stirring time is 0.5-1 h;
in the step 3), the reaction temperature is 35-40 ℃, the reaction time is 2-4 h, the drying temperature is 40-45 ℃, and the drying time is 8-12 h.
Preferably, the step 2) further comprises the steps of washing the composite microspheres with water and freeze-drying;
the mixing and stirring reaction steps in the step 3) are carried out under nitrogen or inert gas.
The invention does not specifically limit the types of cellulose and ionic liquid, optionally, the cellulose is selected from one of microcrystalline cellulose, cotton cellulose, straw cellulose or paper cellulose; the ionic liquid is selected from 1-allyl-3-methylimidazole chloride salt or 1-butyl-3-methylimidazole chloride salt.
Preferably, the pore former is calcium carbonate;
the magnetic particles are ferroferric oxide, and preferably, the magnetic particles are nano ferroferric oxide;
the solvent is water, the initiator is ammonium ceric nitrate, the acid is nitric acid, and the concentration of the nitric acid is 4-6 mol/L.
Preferably, the attapulgite is activated attapulgite, and the preparation method of the activated attapulgite comprises the following steps: mixing attapulgite and acid, heating and activating, filtering, washing and drying to obtain the activated attapulgite.
Preferably, in the preparation method of the activated attapulgite, the mass ratio of the attapulgite to the acid is 1: (8-10), the heating activation temperature is 80-120 ℃, the heating activation time is 3-5 h, the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
Preferably, in the preparation method of the activated attapulgite, the acid is hydrochloric acid, and the concentration of the hydrochloric acid is 2-4 mol/L;
the method also comprises the steps of washing, drying and sieving the attapulgite before mixing the attapulgite and the acid.
Preferably, the ratio of the attapulgite isThe surface area is 200-800m2The grain diameter of the magnetic attapulgite cellulose composite microspheres is 2-3 mm. The invention adopts the microsphere with the grain diameter of 2-3mm, which is beneficial to uniform sowing in the actual soil implementation and magnetic separation recovery after restoration.
The invention also provides the magnetic attapulgite cellulose composite microsphere prepared by the preparation method.
The invention also provides application of the magnetic attapulgite cellulose composite microspheres in remediation of heavy metal contaminated soil.
Preferably, the heavy metal is metallic cadmium.
The invention has the beneficial effects that:
the preparation method of the magnetic attapulgite cellulose composite microspheres provided by the invention comprises the following steps: mixing cellulose and ionic liquid, and heating to obtain a cellulose solution; mixing a cellulose solution, attapulgite, magnetic particles and a pore-forming agent, then dripping the obtained mixed solution into an acid solution, and filtering to obtain composite microspheres; mixing the composite microspheres, a solvent and acrylamide, then adding an initiator and acid, stirring for reaction, filtering and drying to obtain the magnetic attapulgite cellulose composite microspheres.
The invention utilizes the ionic liquid to dissolve cellulose, then directly adds attapulgite, magnetic particles and pore-forming agent into the cellulose solution, the limitation of traditional urea/alkali liquor to dissolve cellulose under low temperature environment is broken through by dissolving cellulose with the ionic liquid, the process of dissolving cellulose with the ionic liquid is rapid, safe, simple and easy to operate, the content of ferroferric oxide in the material can be better controlled by directly adding nano ferroferric oxide, thereby controlling the saturation magnetization of the material, acrylamide is adopted to further modify the microspheres, a large amount of amino groups can be introduced, and then heavy metal cadmium ions in soil can be effectively cured, meanwhile, the invention adopts the mode of dripping mixed liquid into acid solution to obtain composite microspheres, then acrylamide modification is carried out on the composite microspheres, when the mixed solution is dripped into the acid solution, the pore-forming agent reacts with acid to release gas, so that the composite microspheres have porous structure, meanwhile, the grafting rate of acrylamide is increased by the porous structure, so that the remediation of cadmium-polluted soil is facilitated; the invention solves the defects of small specific surface area of cellulose, easy enrichment of attapulgite and the like by mutual matching of the cellulose, the attapulgite, the magnetic particles and the pore-forming agent and the synergistic effect of the cellulose and the attapulgite complex ligand system. The prepared microsphere material is hard, the spherical structure of the microsphere material cannot be lost in practical application, and the composite microsphere has a porous structure due to the addition of the pore-forming agent, so that the subsequent modification and the adsorption of cadmium as a soil repairing agent are facilitated.
Meanwhile, the raw materials of the invention have wide sources, are low-cost and environment-friendly materials, and do not bring toxic action to the soil environment. The magnetic attapulgite cellulose composite microspheres can effectively solidify and stabilize cadmium ions in soil, reduce the content of the bioavailable state of the cadmium ions, reduce the absorption amount of crops to soil heavy metals, effectively improve the physical and chemical properties of the soil, improve the fertilizer and water retention capacity of the soil, and are easy to popularize and apply.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of magnetic attapulgite cellulose composite microspheres, which comprises the following steps:
1) mixing attapulgite (the specific surface area of attapulgite is 800 m)2/g) washing with water, removing impurities, oven drying, sieving with 400 mesh sieve, weighing 30g of sieved attapulgite, adding into 300g of 4mol/L hydrochloric acid, stirring at 90 deg.CDissolving for 4h, performing suction filtration, washing the product to be neutral, and then drying at 60 ℃ for 12h to obtain activated attapulgite;
2) taking 40g of ionic liquid 1-allyl-3 methylimidazole chloride salt, adding 1g of microcrystalline cellulose into the ionic liquid, and heating at 100 ℃ for 2 hours to completely dissolve the cellulose to obtain a cellulose solution;
3) adding 0.5g of activated attapulgite, 0.2g of nano ferroferric oxide and 0.15g of calcium carbonate into the cellulose solution obtained in the step 2), uniformly stirring, placing the mixed solution into a constant-pressure funnel, slowly dropwise adding the mixed solution into 150g of 1mol/L hydrochloric acid solution at a dropwise adding rate of 2mL/min, continuously stirring the hydrochloric acid solution in the dropwise adding process, continuously stirring after dropwise adding is finished, stirring at a stirring speed of 150r/min for 1h, filtering after stirring is finished, washing the obtained microspheres to be neutral, and freeze-drying to obtain composite microspheres;
4) adding 1g of the composite microspheres prepared in the step 3) into a 250mL three-neck flask, adding 200g of deionized water and 5g of acrylamide, and adding2Under protection, stirring at a constant speed until the materials are uniformly mixed, then adding 0.3507 g of ammonium ceric nitrate and 0.4g of nitric acid (the concentration of the nitric acid is 6mol/L) into a three-neck flask, stirring and reacting for 3 hours at 35 ℃, filtering, and drying for 12 hours at 45 ℃ in a blast drying oven to obtain the functionalized magnetic attapulgite cellulose composite microspheres, wherein the particle size of the magnetic attapulgite cellulose composite microspheres is 3 mm.
The functionalized magnetic attapulgite cellulose composite microspheres prepared in the above embodiments are tested for the effect of repairing cadmium in the cadmium-contaminated soil in an effective state.
Test 1 group: taking 1kg of cadmium-polluted soil (the content of effective cadmium in the cadmium-polluted soil is 6.48mg/kg), uniformly mixing the functionalized magnetic attapulgite cellulose composite microspheres prepared in the embodiment in the cadmium-polluted soil, wherein the adding amount of the composite microspheres is 1% of the mass of the cadmium-polluted soil, watering the cadmium-polluted soil to ensure that the water content of the cadmium-polluted soil is 40%, applying an external magnetic field to the soil after 5 weeks, separating the magnetic attapulgite cellulose composite microspheres from the soil, sampling the soil, and determining the content of the effective cadmium in the soil.
Test 2 groups: the test method is the same as the test method of the test 1 group, and the difference is that the adding amount of the composite microspheres is 3 percent of the mass of the cadmium-polluted soil.
Test 3 groups: the test method is the same as the test method of the test 1 group, and the difference is that the adding amount of the composite microspheres is 5 percent of the mass of the cadmium-polluted soil.
Blank control group: the test method is the same as the test method of test 1, except that the composite microspheres are not added into the cadmium-contaminated soil.
The testing method of the content of the effective cadmium is a Tessier continuous extraction method, and the specific testing process is that 1.0 g of a soil sample to be tested is accurately weighed and placed in a 50mL plastic centrifuge tube, and extraction is carried out according to the following five-step extraction method: 1. extraction of exchangeable states (EX): 8mL of 1mol/L magnesium chloride (MgCl)2·6H2O) oscillating the solution and 1g of soil sample to be measured in a room temperature water bath at the rotating speed of 200r/min for 1h, centrifuging for 10min, and taking supernatant to measure the concentration of cadmium ions; 2. extraction of carbonate bound state (CB): oscillating 8mL of 1mol/L sodium acetate (NaAc) solution and the residue after the first-step extraction in a room-temperature water bath at the rotating speed of 200r/min for 8h, centrifuging for 10min, and taking the supernatant to measure the concentration of cadmium ions; 3. Extraction of iron manganese oxidation state (OX): 20mL of hydroxylamine hydrochloride acetic acid aqueous solution (the concentration of hydroxylamine hydrochloride in the hydroxylamine hydrochloride acetic acid aqueous solution is 0.04mol/L, the volume percentage concentration of acetic acid is 25%) and the residue after the second step of extraction are oscillated for 4h in a constant temperature water bath with the rotating speed of 200r/min and the temperature of 96 ℃, centrifuged for 10min, and the supernatant fluid is taken to measure the concentration of cadmium ions; 4. extraction of organic bound state (OM): 5ml of hydrogen peroxide (H)2O2) 3ml of 0.02mol/L nitric acid (HNO)3) And the residue after the extraction in the third step is shaken in a thermostatic water bath at 85 ℃ for 5h, then 5ml of 3.2mol/L ammonium acetate (NH) is added4Ac) solution and 15ml of 0.02mol/L nitric acid (HNO)3) Continuously stirring at 85 deg.C for 0.5h, centrifuging for 10min, and collecting supernatant to measure cadmium ion concentration; 5. extraction of Residue (RS): and (4) digesting the residue extracted in the fourth step by aqua regia, and measuring the concentration of cadmium ions. Wherein the concentration of cadmium ions is measured at 228.8nm with an atomic absorption spectrophotometer, the exchangeable state and the carbonate bound state are referred to as bioavailable states,that is, the available cadmium content is the sum of the cadmium ion concentration measured in the extraction of exchangeable state (EX) of step 1 and the cadmium ion concentration measured in the extraction of carbonate bound state (CB) of step 2.
The test results are shown in table 1.
Table 1 example 1 effect of composite microspheres on effective cadmium remediation in cadmium contaminated soil
Example 2
The embodiment provides a preparation method of magnetic attapulgite cellulose composite microspheres, which comprises the following steps:
1) mixing attapulgite (the specific surface area of attapulgite is 800 m)2Per gram) washing with water to remove impurities, drying, sieving with a 400-mesh sieve, weighing 30 grams of sieved attapulgite, adding the attapulgite into 300 grams of hydrochloric acid with the concentration of 4mol/L, stirring and activating for 4 hours at 90 ℃, performing suction filtration, washing a product to be neutral, and drying for 12 hours at 60 ℃ to obtain the activated attapulgite;
2) taking 40g of ionic liquid 1-allyl-3 methylimidazole chloride salt, adding 1g of microcrystalline cellulose into the ionic liquid, and heating at 100 ℃ for 2 hours to completely dissolve the cellulose to obtain a cellulose solution;
3) adding 1g of activated attapulgite, 0.5g of nano ferroferric oxide and 0.2g of calcium carbonate into the cellulose solution obtained in the step 2), uniformly stirring, placing the mixed solution into a constant-pressure funnel, slowly dropwise adding the mixed solution into 150g of 1mol/L hydrochloric acid solution at a dropwise adding rate of 2mL/min, continuously stirring the hydrochloric acid solution in the dropwise adding process, continuously stirring after dropwise adding, wherein the stirring speed is 150r/min, the total stirring time is 1h, filtering after stirring, washing the obtained microspheres to be neutral, and freeze-drying to obtain composite microspheres;
4) adding 1g of the composite microspheres prepared in the step 3) into a 250mL three-neck flask, adding 200g of deionized water and 5g of acrylamide, and adding2Stirring at constant speed under protection until the mixture is uniformly mixed, and then adding 0.3507 g of ceric ammonium nitrate and 0.4g of nitre into a three-neck flaskAnd (3) stirring and reacting for 3h at 35 ℃ by using acid (the concentration of nitric acid is 6mol/L), performing suction filtration, and drying for 12h at 45 ℃ in a blast drying oven to obtain the functionalized magnetic attapulgite cellulose composite microspheres, wherein the particle size of the magnetic attapulgite cellulose composite microspheres is 3 mm.
The functionalized magnetic attapulgite cellulose composite microspheres prepared in the above embodiments are tested for the effect of repairing cadmium in the cadmium-contaminated soil in an effective state.
Test 1 group: taking 1kg of cadmium-polluted soil (the content of effective cadmium in the cadmium-polluted soil is 6.48mg/kg), uniformly mixing the functionalized magnetic attapulgite cellulose composite microspheres prepared in the embodiment in the cadmium-polluted soil, wherein the adding amount of the composite microspheres is 1% of the mass of the cadmium-polluted soil, watering the cadmium-polluted soil to ensure that the water content of the cadmium-polluted soil is 30%, applying an external magnetic field to the soil after 5 weeks, separating the magnetic attapulgite cellulose composite microspheres from the soil, sampling the soil, and determining the content of the effective cadmium in the soil.
Test 2 groups: the test method is the same as the test method of the test 1 group, and the difference is that the adding amount of the composite microspheres is 3 percent of the mass of the cadmium-polluted soil.
Test 3 groups: the test method is the same as the test method of the test 1 group, and the difference is that the adding amount of the composite microspheres is 5 percent of the mass of the cadmium-polluted soil.
Blank control group: the test method is the same as the test method of test 1, except that the composite microspheres are not added into the cadmium-contaminated soil.
The testing method of the content of the available cadmium is the same as that of the embodiment 1, and the testing results are shown in table 2.
Table 2 example 2 effective cadmium remediation effect of composite microspheres on cadmium contaminated soil
Example 3
The embodiment provides a preparation method of magnetic attapulgite cellulose composite microspheres, which comprises the following steps:
1) mixing attapulgite (the specific surface area of attapulgite is 800 m)2Per gram) washing with water to remove impurities, drying, sieving with a 400-mesh sieve, weighing 30 grams of sieved attapulgite, adding the attapulgite into 300 grams of hydrochloric acid with the concentration of 4mol/L, stirring and activating for 4 hours at 90 ℃, performing suction filtration, washing a product to be neutral, and drying for 12 hours at 60 ℃ to obtain the activated attapulgite;
2) taking 40g of ionic liquid 1-allyl-3 methylimidazole chloride salt, adding 1g of microcrystalline cellulose into the ionic liquid, and heating at 100 ℃ for 2 hours to completely dissolve the cellulose to obtain a cellulose solution;
3) adding 1g of activated attapulgite, 0.5g of nano ferroferric oxide and 0.6g of calcium carbonate into the cellulose solution obtained in the step 2), uniformly stirring, placing the mixed solution into a constant-pressure funnel, slowly dropwise adding the mixed solution into 150g of 1mol/L hydrochloric acid solution at a dropwise adding rate of 3mL/min, continuously stirring the hydrochloric acid solution in the dropwise adding process, continuously stirring after dropwise adding is finished, stirring at a stirring speed of 200r/min for 1h, filtering after stirring is finished, washing the obtained microspheres to be neutral, and freeze-drying to obtain composite microspheres;
4) adding 1g of the composite microspheres prepared in the step 3) into a 250mL three-neck flask, adding 200g of deionized water and 5g of acrylamide, and adding2Under protection, stirring at a constant speed until the materials are uniformly mixed, then adding 0.3507 g of ammonium ceric nitrate and 0.4g of nitric acid (the concentration of the nitric acid is 4mol/L) into a three-neck flask, stirring and reacting for 3 hours at 35 ℃, filtering, and drying for 12 hours at 45 ℃ in a blast drying oven to obtain the functionalized magnetic attapulgite cellulose composite microspheres, wherein the particle size of the magnetic attapulgite cellulose composite microspheres is 2 mm.
The functionalized magnetic attapulgite cellulose composite microspheres prepared in the above embodiments are tested for the effect of repairing cadmium in the cadmium-contaminated soil in an effective state.
Test 1 group: taking 1kg of cadmium-polluted soil (the content of effective cadmium in the cadmium-polluted soil is 6.48mg/kg), uniformly mixing the functionalized magnetic attapulgite cellulose composite microspheres prepared in the embodiment in the cadmium-polluted soil, wherein the adding amount of the composite microspheres is 1% of the mass of the cadmium-polluted soil, watering the cadmium-polluted soil to ensure that the water content of the cadmium-polluted soil is 50%, applying an external magnetic field to the soil after 5 weeks, separating the magnetic attapulgite cellulose composite microspheres from the soil, sampling the soil, and measuring the content of the effective cadmium in the soil.
Test 2 groups: the test method is the same as the test method of the test 1 group, and the difference is that the adding amount of the composite microspheres is 3 percent of the mass of the cadmium-polluted soil.
Test 3 groups: the test method is the same as the test method of the test 1 group, and the difference is that the adding amount of the composite microspheres is 5 percent of the mass of the cadmium-polluted soil.
Blank control group: the test method is the same as the test method of test 1, except that the composite microspheres are not added into the cadmium-contaminated soil.
The testing method of the content of the available cadmium is the same as that of the embodiment 1, and the testing results are shown in Table 3.
Table 3 example 3 effective cadmium remediation effect of composite microspheres on cadmium contaminated soil
Example 4
The embodiment provides a preparation method of magnetic attapulgite cellulose composite microspheres, which comprises the following steps:
1) mixing attapulgite (the specific surface area of attapulgite is 800 m)2Per gram) washing with water to remove impurities, drying, sieving with a 400-mesh sieve, weighing 30 grams of sieved attapulgite, adding the attapulgite into 300 grams of hydrochloric acid with the concentration of 4mol/L, stirring and activating for 4 hours at 90 ℃, performing suction filtration, washing a product to be neutral, and drying for 12 hours at 60 ℃ to obtain the activated attapulgite;
2) taking 40g of ionic liquid 1-allyl-3 methylimidazole chloride salt, adding 1g of microcrystalline cellulose into the ionic liquid, and heating at 100 ℃ for 2 hours to completely dissolve the cellulose to obtain a cellulose solution;
3) adding 1g of activated attapulgite, 0.5g of nano ferroferric oxide and 0.6g of calcium carbonate into the cellulose solution obtained in the step 2), uniformly stirring, placing the mixed solution into a constant-pressure funnel, slowly dropwise adding the mixed solution into 150g of 1mol/L hydrochloric acid solution at a dropwise adding rate of 3mL/min, continuously stirring the hydrochloric acid solution in the dropwise adding process, continuously stirring after dropwise adding is finished, stirring at a stirring speed of 200r/min for 1h, filtering after stirring is finished, washing the obtained microspheres to be neutral, and freeze-drying to obtain composite microspheres;
4) adding 1g of the composite microspheres prepared in the step 3) into a 250mL three-neck flask, adding 200g of deionized water and 7g of acrylamide, and adding2Under protection, stirring at a constant speed until the materials are uniformly mixed, then adding 0.3507 g of ammonium ceric nitrate and 0.4g of nitric acid (the concentration of the nitric acid is 5mol/L) into a three-neck flask, stirring and reacting for 3 hours at 35 ℃, filtering, and drying for 12 hours at 45 ℃ in a blast drying oven to obtain the functionalized magnetic attapulgite cellulose composite microspheres, wherein the particle size of the magnetic attapulgite cellulose composite microspheres is 2 mm.
The functionalized magnetic attapulgite cellulose composite microspheres prepared in the above embodiments are tested for the effect of repairing cadmium in the cadmium-contaminated soil in an effective state.
Test 1 group: taking 1kg of cadmium-polluted soil (the content of effective cadmium in the cadmium-polluted soil is 6.48mg/kg), uniformly mixing the functionalized magnetic attapulgite cellulose composite microspheres prepared in the embodiment in the cadmium-polluted soil, wherein the adding amount of the composite microspheres is 1% of the mass of the cadmium-polluted soil, watering the cadmium-polluted soil to ensure that the water content of the cadmium-polluted soil is 40%, applying an external magnetic field to the soil after 5 weeks, separating the magnetic attapulgite cellulose composite microspheres from the soil, sampling the soil, and determining the content of the effective cadmium in the soil.
Test 2 groups: the test method is the same as the test method of the test 1 group, and the difference is that the adding amount of the composite microspheres is 3 percent of the mass of the cadmium-polluted soil.
Test 3 groups: the test method is the same as the test method of the test 1 group, and the difference is that the adding amount of the composite microspheres is 5 percent of the mass of the cadmium-polluted soil.
Blank control group: the test method is the same as the test method of test 1, except that the composite microspheres are not added into the cadmium-contaminated soil.
The test method of the content of the available cadmium is the same as that of example 1, and the test results are shown in table 4.
TABLE 4 example 4 effective cadmium remediation effect of composite microspheres on cadmium contaminated soil
Example 5
The embodiment provides a preparation method of magnetic attapulgite cellulose composite microspheres, which comprises the following steps:
1) mixing attapulgite (the specific surface area of attapulgite is 200 m)2Per gram) washing with water to remove impurities, drying, sieving with a 400-mesh sieve, weighing 30 grams of sieved attapulgite, adding the attapulgite into 240 grams of hydrochloric acid with the concentration of 2mol/L, stirring and activating for 3 hours at 80 ℃, performing suction filtration, washing a product to be neutral, and drying for 8 hours at 60 ℃ to obtain the activated attapulgite;
2) taking 30g of ionic liquid 1-butyl-3-methylimidazole chloride salt, adding 1g of cotton cellulose into the ionic liquid, and heating at 90 ℃ for 1h to completely dissolve the cellulose to obtain a cellulose solution;
3) adding 0.5g of activated attapulgite, 0.5g of nano ferroferric oxide and 0.15g of calcium carbonate into the cellulose solution obtained in the step 2), uniformly stirring, placing the mixed solution into a constant-pressure funnel, slowly dropwise adding the mixed solution into 120g of 0.5mol/L hydrochloric acid solution at a dropwise adding rate of 2mL/min, continuously stirring the hydrochloric acid solution in the dropwise adding process, continuously stirring after dropwise adding is finished, stirring at a stirring speed of 150r/min for 0.5h, filtering after stirring is finished, washing the obtained microspheres to be neutral, and freeze-drying to obtain composite microspheres;
4) adding 1g of the composite microspheres prepared in the step 3) into a 250mL three-neck flask, adding 200g of deionized water and 3g of acrylamide, and adding2Stirring at constant speed under protection until the mixture is uniformly mixed, then adding 0.2g of ammonium ceric nitrate and 0.2g of nitric acid (the concentration of the nitric acid is 4mol/L) into a three-neck flask, stirring and reacting for 2h at 35 ℃, filtering, and drying for 8h at 40 ℃ in a forced air drying oven to obtain the cerium nitrate manganese oxideThe functionalized magnetic attapulgite cellulose composite microspheres have the particle size of 3 mm.
The functionalized magnetic attapulgite cellulose composite microspheres prepared in the above embodiments are tested for the effect of repairing cadmium in the cadmium-contaminated soil in an effective state.
Test 1 group: taking 1kg of cadmium-polluted soil (the content of effective cadmium in the cadmium-polluted soil is 6.48mg/kg), uniformly mixing the functionalized magnetic attapulgite cellulose composite microspheres prepared in the embodiment in the cadmium-polluted soil, wherein the adding amount of the composite microspheres is 1% of the mass of the cadmium-polluted soil, watering the cadmium-polluted soil to ensure that the water content of the cadmium-polluted soil is 30%, applying an external magnetic field to the soil after 5 weeks, separating the magnetic attapulgite cellulose composite microspheres from the soil, sampling the soil, and determining the content of the effective cadmium in the soil.
Blank control group: the test method is the same as the test method of test 1, except that the composite microspheres are not added into the cadmium-contaminated soil.
The test method of the content of the available cadmium is the same as that of example 1, and the test results are shown in table 5.
TABLE 5 example 5 effective cadmium remediation effect of composite microspheres on cadmium contaminated soil
Example 6
The embodiment provides a preparation method of magnetic attapulgite cellulose composite microspheres, which comprises the following steps:
1) mixing attapulgite (the specific surface area of attapulgite is 800 m)2Per gram) washing with water to remove impurities, drying, sieving with a 400-mesh sieve, weighing 30 grams of sieved attapulgite, adding the attapulgite into 300 grams of hydrochloric acid with the concentration of 4mol/L, stirring and activating for 5 hours at 120 ℃, performing suction filtration, washing a product to be neutral, and drying for 12 hours at 80 ℃ to obtain the activated attapulgite;
2) taking 40g of ionic liquid 1-butyl-3-methylimidazole chloride salt, adding 1g of straw cellulose into the ionic liquid, and heating at 120 ℃ for 2 hours to completely dissolve the cellulose to obtain a cellulose solution;
3) adding 1g of activated attapulgite, 1g of nano ferroferric oxide and 0.6g of calcium carbonate into the cellulose solution obtained in the step 2), uniformly stirring, placing the mixed solution into a constant-pressure funnel, slowly dripping the mixed solution into 320g of 1mol/L hydrochloric acid solution at a dripping speed of 3mL/min, continuously stirring the hydrochloric acid solution in the dripping process, continuously stirring after dripping is finished, stirring at a stirring speed of 200r/min for 1h, filtering after stirring is finished, washing the obtained microspheres to be neutral, and freeze-drying to obtain composite microspheres;
4) adding 1g of the composite microspheres prepared in the step 3) into a 250mL three-neck flask, adding 200g of deionized water and 5g of acrylamide, and adding2Under protection, stirring at a constant speed until the materials are uniformly mixed, then adding 0.5g of ammonium ceric nitrate and 0.5g of nitric acid (the concentration of the nitric acid is 6mol/L) into a three-neck flask, stirring and reacting for 4 hours at 40 ℃, carrying out suction filtration, and drying for 12 hours at 45 ℃ in a blast drying oven to obtain the functionalized magnetic attapulgite cellulose composite microspheres, wherein the particle size of the magnetic attapulgite cellulose composite microspheres is 2 mm.
The functionalized magnetic attapulgite cellulose composite microspheres prepared in the above embodiments are tested for the effect of repairing cadmium in the cadmium-contaminated soil in an effective state.
Test 1 group: taking 1kg of cadmium-polluted soil (the content of effective cadmium in the cadmium-polluted soil is 6.48mg/kg), uniformly mixing the functionalized magnetic attapulgite cellulose composite microspheres prepared in the embodiment in the cadmium-polluted soil, wherein the adding amount of the composite microspheres is 1% of the mass of the cadmium-polluted soil, watering the cadmium-polluted soil to ensure that the water content of the cadmium-polluted soil is 60%, applying an external magnetic field to the soil after 5 weeks, separating the magnetic attapulgite cellulose composite microspheres from the soil, sampling the soil, and measuring the content of the effective cadmium in the soil.
Blank control group: the test method is the same as the test method of test 1, except that the composite microspheres are not added into the cadmium-contaminated soil.
The test method of the content of the available cadmium is the same as that of example 1, and the test results are shown in table 6.
TABLE 6 example 6 effective cadmium remediation effect of composite microspheres on cadmium contaminated soil
Comparative example 1
The comparative example provides a preparation method of magnetic attapulgite cellulose composite microspheres, which is different from the embodiment 1 in that in the step 3), 150g of 1mol/L hydrochloric acid solution is placed in a constant-pressure funnel, then the hydrochloric acid solution is slowly dripped into the mixed solution, the dripping speed is 2mL/min, the mixed solution is continuously stirred in the dripping process, the stirring is continued after the dripping is finished, the stirring speed is 150r/min, the total stirring time is 1h, the filtering is carried out after the stirring is finished, then the obtained microspheres are washed to be neutral, and the composite microspheres are freeze-dried to obtain the magnetic attapulgite cellulose composite microspheres.
Comparative example 2 (comparing with example 1 without attapulgite)
The comparative example provides a preparation method of a magnetic cellulose composite microsphere, which comprises the following steps:
1) taking 40g of ionic liquid 1-allyl-3 methylimidazole chloride salt, adding 1.5g of microcrystalline cellulose into the ionic liquid, and heating at 100 ℃ for 2 hours to completely dissolve the cellulose to obtain a cellulose solution;
2) adding 0.2g of nano ferroferric oxide and 0.15g of calcium carbonate into the cellulose solution obtained in the step 1), uniformly stirring, placing the mixed solution into a constant-pressure funnel, slowly dropwise adding the mixed solution into 150g of 1mol/L hydrochloric acid solution at a dropwise adding rate of 2mL/min, continuously stirring the hydrochloric acid solution in the dropwise adding process, continuously stirring after dropwise adding is finished, wherein the stirring speed is 150r/min, the total stirring time is 1h, filtering after stirring is finished, washing the obtained microspheres to be neutral, and freeze-drying to obtain composite microspheres;
3) adding 1g of the composite microspheres prepared in the step 2) into a 250mL three-neck flask, adding 200g of deionized water and 5g of acrylamide, and adding2Stirring at constant speed under protection until the mixture is uniformly mixed, and then adding the mixture into a three-neck flask0.3507 g of ammonium ceric nitrate and 0.4g of nitric acid (the concentration of the nitric acid is 6mol/L) are stirred and reacted for 3 hours at the temperature of 35 ℃, the reaction product is filtered, and the reaction product is dried for 12 hours at the temperature of 45 ℃ in a blast drying oven to obtain the functionalized magnetic cellulose composite microspheres, wherein the particle size of the magnetic cellulose composite microspheres is 3 mm.
Comparative example 3 (No cellulose addition as in example 1)
The comparative example provides a preparation method of magnetic attapulgite composite microspheres, which comprises the following steps:
1) mixing attapulgite (the specific surface area of attapulgite is 800 m)2Per gram) washing with water to remove impurities, drying, sieving with a 400-mesh sieve, weighing 30 grams of sieved attapulgite, adding the attapulgite into 300 grams of hydrochloric acid with the concentration of 4mol/L, stirring and activating for 4 hours at 90 ℃, performing suction filtration, washing a product to be neutral, and drying for 12 hours at 60 ℃ to obtain the activated attapulgite;
2) taking 40g of ionic liquid 1-allyl-3 methylimidazole chloride, adding 1.5g of activated attapulgite into the ionic liquid, and heating at 100 ℃ for 2h to obtain an attapulgite solution;
3) adding 0.2g of nano ferroferric oxide and 0.15g of calcium carbonate into the attapulgite solution obtained in the step 2), uniformly stirring, placing the mixed solution into a constant-pressure funnel, slowly dropwise adding the mixed solution into 150g of 1mol/L hydrochloric acid solution at a dropwise adding rate of 2mL/min, continuously stirring the hydrochloric acid solution in the dropwise adding process, continuously stirring after dropwise adding is finished, wherein the stirring speed is 150r/min, the total stirring time is 1h, filtering after stirring is finished, washing the obtained microspheres to be neutral, and freeze-drying to obtain composite microspheres;
4) adding 1g of the composite microspheres prepared in the step 3) into a 250mL three-neck flask, adding 200g of deionized water and 5g of acrylamide, and adding2Under protection, stirring at a constant speed until the materials are uniformly mixed, then adding 0.3507 g of ammonium ceric nitrate and 0.4g of nitric acid (the concentration of the nitric acid is 6mol/L) into a three-neck flask, stirring and reacting for 3 hours at 35 ℃, carrying out suction filtration, and drying for 12 hours at 45 ℃ in a blast drying oven to obtain the functionalized magnetic attapulgite composite microspheres, wherein the particle size of the magnetic attapulgite composite microspheres is 3 mm.
Comparative example 4 (No amination compared with example 1)
The comparative example provides a preparation method of magnetic attapulgite cellulose composite microspheres, which comprises the following steps:
1) mixing attapulgite (the specific surface area of attapulgite is 800 m)2Per gram) washing with water to remove impurities, drying, sieving with a 400-mesh sieve, weighing 30 grams of sieved attapulgite, adding the attapulgite into 300 grams of hydrochloric acid with the concentration of 4mol/L, stirring and activating for 4 hours at 90 ℃, performing suction filtration, washing a product to be neutral, and drying for 12 hours at 60 ℃ to obtain the activated attapulgite;
2) taking 40g of ionic liquid 1-allyl-3 methylimidazole chloride salt, adding 1g of microcrystalline cellulose into the ionic liquid, and heating at 100 ℃ for 2 hours to completely dissolve the cellulose to obtain a cellulose solution;
3) adding 0.5g of activated attapulgite, 0.2g of nano ferroferric oxide and 0.15g of calcium carbonate into the cellulose solution obtained in the step 2), uniformly stirring, placing the mixed solution into a constant-pressure funnel, slowly dropwise adding the mixed solution into 150g of 1mol/L hydrochloric acid solution at a dropwise adding rate of 2mL/min, continuously stirring the hydrochloric acid solution in the dropwise adding process, continuously stirring after dropwise adding is finished, stirring at a stirring speed of 150r/min for 1h, filtering after stirring is finished, washing the obtained microspheres to be neutral, and freeze-drying to obtain the magnetic attapulgite-attapulgite cellulose composite microspheres.
The effect of the magnetic composite microspheres prepared in the comparative examples 1 to 4 on the effective cadmium remediation of the cadmium-contaminated soil is tested.
Comparative example 1 group: taking 1kg of cadmium-polluted soil (the content of effective cadmium in the cadmium-polluted soil is 6.48mg/kg), then uniformly mixing the magnetic attapulgite cellulose composite microspheres prepared in the comparative example 1 in the cadmium-polluted soil, wherein the adding amount of the composite microspheres is 1% of the mass of the cadmium-polluted soil, then watering the cadmium-polluted soil to ensure that the water content of the cadmium-polluted soil is 40%, applying an external magnetic field to the soil after 5 weeks, separating the magnetic attapulgite cellulose composite microspheres from the soil, sampling the soil, and determining the content of the effective cadmium in the soil.
Comparative example 2 group: the difference between the test method and the test method of the group of the comparative example 1 is that the magnetic attapulgite cellulose composite microspheres prepared in the comparative example 1 are replaced by the magnetic cellulose composite microspheres prepared in the comparative example 2.
Comparative example 3 group: the difference between the test method and the test method of the group of the comparative example 1 is that the magnetic attapulgite cellulose composite microspheres prepared in the comparative example 1 are replaced by the functionalized magnetic attapulgite composite microspheres prepared in the comparative example 3.
Comparative example 4 group: the difference between the test method and the test method of the group of the comparative example 1 is that the magnetic attapulgite cellulose composite microspheres prepared in the comparative example 1 are replaced by the magnetic attapulgite cellulose composite microspheres prepared in the comparative example 4.
Blank control group: the test method is the same as the test method of test 1, except that the composite microspheres are not added into the cadmium-contaminated soil.
The method for measuring the content of cadmium in the active state is the same as that of example 1, and the measurement results are shown in Table 7.
TABLE 7 Effect of composite microsphere in comparative example on effective cadmium remediation of cadmium contaminated soil
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (13)
1. The preparation method of the magnetic attapulgite cellulose composite microspheres is characterized by comprising the following steps:
1) mixing cellulose and ionic liquid, and heating to obtain a cellulose solution;
2) mixing a cellulose solution, attapulgite, magnetic particles and a pore-forming agent, then dripping the obtained mixed solution into an acid solution, and filtering to obtain composite microspheres;
3) mixing the composite microspheres, a solvent and acrylamide, then adding an initiator and acid, stirring for reaction, filtering and drying to obtain the magnetic attapulgite cellulose composite microspheres.
2. The preparation method according to claim 1, wherein the dropping rate in the step 2) is 2mL/min to 3 mL/min;
the acid solution is hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 0.5-1 mol/L.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the cellulose, the attapulgite, the magnetic particles and the ionic liquid is 1 (0.5-1): 30-40;
the addition amount of the pore-forming agent is 10 to 50 percent of the total mass of the cellulose and the attapulgite;
in the step 3), the mass ratio of the composite microsphere, the solvent, the acrylamide, the initiator and the acid is 1 (200-) -300: 3-7: 0.2-0.5.
4. The method according to any one of claims 1 to 3, wherein the heating temperature in step 1) is 90 ℃ to 120 ℃ and the heating time is 1h to 2 h;
continuously stirring the acid solution in the dropwise adding process in the step 2), and continuously stirring after the dropwise adding process is finished, wherein the stirring speed is 150-200 r/min, and the total stirring time is 0.5-1 h;
in the step 3), the reaction temperature is 35-40 ℃, the reaction time is 2-4 h, the drying temperature is 40-45 ℃, and the drying time is 8-12 h.
5. The preparation method according to any one of claims 1 to 4, wherein the step 2) further comprises the steps of washing the composite microspheres with water and freeze-drying;
the mixing and stirring reaction steps in the step 3) are carried out under nitrogen or inert gas.
6. The method according to any one of claims 1 to 5, wherein the cellulose is selected from one of microcrystalline cellulose, cotton cellulose, straw cellulose, or paper cellulose;
the ionic liquid is selected from 1-allyl-3-methylimidazole chloride salt or 1-butyl-3-methylimidazole chloride salt;
the pore-forming agent is calcium carbonate;
the magnetic particles are ferroferric oxide, and preferably, the magnetic particles are nano ferroferric oxide;
the solvent is water, the initiator is ammonium ceric nitrate, the acid is nitric acid, and the concentration of the nitric acid is 4-6 mol/L.
7. The preparation method of any one of claims 1 to 6, wherein the attapulgite is activated attapulgite, and the preparation method of the activated attapulgite comprises the following steps: mixing attapulgite and acid, heating and activating, filtering, washing and drying to obtain the activated attapulgite.
8. The process according to any one of claims 1 to 7, wherein in the process for preparing the activated attapulgite, the mass ratio of attapulgite to acid is 1: (8-10), the heating activation temperature is 80-120 ℃, the heating activation time is 3-5 h, the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
9. The process according to any one of claims 1 to 8, wherein in the process for preparing the activated attapulgite, the acid is hydrochloric acid, and the concentration of the hydrochloric acid is 2mol/L to 4 mol/L;
the method also comprises the steps of washing, drying and sieving the attapulgite before mixing the attapulgite and the acid.
10. The method according to any one of claims 1 to 9, wherein the reaction mixture is heated to a temperature in the reaction mixtureThe specific surface area of the attapulgite is 200-800m2The grain diameter of the magnetic attapulgite cellulose composite microspheres is 2-3 mm.
11. A magnetic attapulgite cellulose composite microsphere is characterized by being prepared by the preparation method of any one of claims 1 to 10.
12. The application of the magnetic attapulgite cellulose composite microspheres of claim 11 in the remediation of heavy metal contaminated soil.
13. Use according to claim 12, wherein the heavy metal is metallic cadmium.
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