CN111992187A - Heavy metal ion adsorption material and preparation method and application thereof - Google Patents
Heavy metal ion adsorption material and preparation method and application thereof Download PDFInfo
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- CN111992187A CN111992187A CN202010832142.XA CN202010832142A CN111992187A CN 111992187 A CN111992187 A CN 111992187A CN 202010832142 A CN202010832142 A CN 202010832142A CN 111992187 A CN111992187 A CN 111992187A
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- sodium alginate
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 113
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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
- B01J20/22—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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- 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
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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
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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
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- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a heavy metal ion adsorption material, a preparation method and application thereof, wherein the material is sodium alginate and Fe3O4@SiO2The magnetic sodium alginate composite material formed by nano particles, wherein the sodium alginate is used as a skeleton, has a porous structure and is magnetic Fe3O4@SiO2The nano particles are filled in the pores of the sodium alginate. The magnetic sodium alginate composite material has high adsorption capacity on heavy metals such as lead, nickel, cadmium, cobalt, copper, magnesium, zinc and the like in wastewater, particularly has good selectivity on lead ions, and can adsorb lead ions to the maximum extentThe amount reaches 137mg/g, and the adsorption rate reaches 83 percent. The method has good reusability and convenient magnetic separation, can still maintain 85% of adsorption effect after being reused for ten times, and has wide application prospect in the aspect of removing heavy metal ions in sewage.
Description
Technical Field
The invention relates to a metal ion adsorption material and a preparation method and application thereof, belonging to the field of polymer composite adsorbents.
Background
With the rapid development of human economic activities and the continuous progress of science and technology, the problem of water environment pollution is more serious, and the polluted water body contains a large amount of heavy metal ions, has strong reactivity in water and has serious threats to human health and ecological systems. The treatment method of the heavy metal polluted water body comprises a chemical precipitation method, a biological remediation method, an adsorption method and the like. Among them, the adsorption method has received wide attention from people because of its high working efficiency and environmental friendliness.
The magnetic nano-adsorption material has the characteristics of high dispersity, large specific surface area, easy separation under a magnetic field and the like. Although they are promising sewage treatment materials, there are some problems such as easy aggregation in aqueous solution, because the magnetic nano materials have magnetism, attract each other, and are not easy to diffuse, and even under the action of acidic conditions, the magnetic nano materials are easy to react with acidic substances, thereby generating new pollution problems. The focus of research is now to find a material that covers the surface of a magnetic material to improve its stability. Sodium alginate, which is a common natural polysaccharide, can form a good colloid and is an excellent material capable of covering the surface of a magnetic material.
Sodium alginate is a green and environment-friendly natural heavy metal adsorbent with development prospect due to the characteristics of no toxicity, no harm, biocompatibility and degradability, and is also widely applied to heavy metal treatment in recent years. The sodium alginate material has rich active groups and a porous structure, the magnetic particles can be well wrapped in the gaps, the pollutants are mainly adsorbed in the inner gaps, the separation problem after the adsorption of the composite gel can be well solved by adding the magnetic material, and secondary pollution to the environment is avoided.
Disclosure of Invention
The invention aims to provide a heavy metal ion adsorption material, and a preparation method and application thereof, and aims to solve the problems that in the prior art, a polymer material adsorbent has few adsorption types of heavy metals in sewage and is difficult to adapt to the current sewage treatment with complex heavy metal composition.
In order to achieve the purpose, the invention adopts the following technical scheme:
a heavy metal ion adsorbing material is prepared from sodium alginate and Fe3O4@SiO2The magnetic sodium alginate composite material formed by nano particles, wherein the sodium alginate is used as a skeleton, has a porous structure and is magnetic Fe3O4@SiO2The nano particles are filled in the pores of the sodium alginate.
Sodium alginate and Fe3O4@SiO2The weight ratio of the nano particles is (10-5): 1.
A process for preparing the adsorbing material of metal ions from sodium alginate and Fe3O4@SiO2The heavy metal ion adsorption material is prepared from calcium chloride serving as a raw material by a physical blending method at normal temperature of an aqueous solution.
The preparation method of the metal ion adsorption material comprises the following specific steps:
step 1, dissolving sodium alginate in water, and then dissolving Fe3O4@SiO2Pouring the nano particles into a sodium alginate solution, and stirring to uniformly disperse the nano particles to form a suspension;
and 3, washing the prepared gel beads with water, drying, and grinding by using a stirrer to obtain the heavy metal ion adsorbing material.
In the step 2, CaCl2The concentration of the solution is 0.2mol/L, and the standing time is 8-12 h.
In step 3, the gel beads are washed with water for at least 5 times and dried in an oven at a temperature of 60 ℃.
The metal ion adsorption material disclosed by the invention is applied to adsorption of heavy metal ions in sewage as a heavy metal adsorbent. Wherein the heavy metal ions are one or more of lead ions, cadmium ions, nickel ions, cobalt ions, copper ions, magnesium ions and the like.
The pH value of the sewage is controlled to be 2-6, and the sewage has better adsorption effect.
The metal ion adsorbing material of the invention is used for adsorbing Pb2+Has high selectivity, and can be used for Pb2+/Cu2+、 Pb2+/Cd2+、Pb2+/Co2+Or Pb2+/Ni2+For Pb in the mixture2+Separation and recovery.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the prepared heavy metal magnetic composite material adsorbent has wide applicability, has obvious adsorption effect on heavy metals such as lead, nickel, cadmium, copper, cobalt, magnesium and the like in sewage, and particularly has good lead ion selectivity, the maximum adsorption amount reaches 137mg/g, and the removal rate reaches 83%;
(2) the magnetic composite material adsorbent prepared by the invention has good reusability and convenient magnetic separation, can still maintain 85% of adsorption effect after being reused for ten times, and has wide application prospect in the aspect of removing heavy metal ions in sewage;
(3) the preparation method of the heavy metal magnetic composite material adsorbent is simple, mild in condition and easy to operate, and can be industrially popularized and produced.
Drawings
FIG. 1 is a schematic diagram of the synthesis of the magnetic sodium alginate composite material in example 1;
FIG. 2 is a diagram showing a physical diagram and a magnetic separation effect of the magnetic sodium alginate composite material in example 1;
FIG. 3 is an infrared spectrum of the magnetic sodium alginate composite material in example 1;
FIG. 4 is the XRD pattern of the magnetic sodium alginate composite material in example 1;
FIG. 5 is a Raman spectrum of the magnetic sodium alginate composite material of example 1;
FIG. 6 is a thermogravimetric analysis curve of the magnetic sodium alginate composite material in example 1;
FIG. 7 is a scanning electron microscope of the magnetic sodium alginate composite material in example 1;
FIG. 8 is a schematic diagram of the adsorption mechanism of the magnetic sodium alginate composite material in example 2;
FIG. 9 is a schematic diagram of competitive adsorption of heavy metal ions by the magnetic sodium alginate composite material in example 2;
fig. 10 is a schematic view of recycling of the magnetic sodium alginate composite material in example 2.
Detailed Description
The invention is further described below with reference to the following examples, which are intended to illustrate the invention but not to limit it further.
Example 1
The present embodiment includes the following steps
(1) Preparation of magnetic sodium alginate composite material
Preparation of magnetic sodium alginate composite material (SA/Fe) by physical blending method3O4@SiO2) Preparing materials: sodium Alginate (SA), Fe3O4@SiO2Calcium chloride (CaCl)2). Firstly, dissolving SA in deionized water according to the mass ratio of 2%, magnetically stirring, and then adding SA: fe3O4@SiO2Is 5:1, taking Fe3O4@SiO2Pouring the solid into sodium alginate solution, and stirring to uniformly disperse the solid. At the same time, CaCl with the concentration of 0.2mol/L is prepared2And (3) solution. Finally, a separating funnel is used for containing the magnetic sodium alginate suspension, and the magnetic sodium alginate suspension is dripped into the prepared CaCl2Standing in the solution for 10h to make Ca2+Further permeating into the pellet, performing gelation reaction to obtain magnetic sodium alginate (SA/Fe)3O4@SiO2) The gel beads are then washed with water at least 5 times, dried in an oven at a temperature of 60 ℃ and ground with a blender until ready for use. The specific preparation of the magnetic sodium alginate gel beads is shown in the schematic diagram 1, and FIG. 2 shows the prepared magnetic sodium alginate composite material (SA/Fe)3O4@SiO2) The shape and appearance of the magnetic separation medium and the magnetic separation effect under the condition of an external magnetic field. As clearly seen from (a) and (b) in fig. 2, the prepared magnetic sodium alginate composite material has a smooth surface and a black ball shape. It can be seen from fig. 2 (c) that when the magnetic sodium alginate composite material microspheres are placed in water, the microspheres rapidly migrate and aggregate in the direction of the magnetic field under the action of the external magnetic field, which indicates that the magnetic adsorbent can be completely separated from the reaction system by the external magnetic field, thereby reducing the loss of the adsorbent and avoiding secondary pollution.
(2) Magnetic sodium alginate composite material infrared analysis
Fourier infrared spectroscopy can be used to analyze the surface functional groups of the composite material and determine the intermolecular interactions, FIG. 3 shows sodium alginate without magnetic material (SA) and sodium alginate with magnetic material (SA/Fe)3O4@SiO2) An infrared spectrum. Sodium alginate is 3435.4cm-1、1611.6cm-1、1397.5cm-1、1127cm-1The characteristic absorption band is caused by-OH bond stretching vibration, -COOH bond symmetric stretching vibration, -COOH bond antisymmetric stretching vibration, and-C-O bond stretching vibration. Fe3O4At 3401.5cm-1、581.2cm-1The typical absorption peak at (a) is caused by stretching of the Fe — O bond. For SiO2@Fe3O4Except for 3401.5cm-1、581.2cm-1Outside the absorption peak everywhere, at 734.6.cm-1、1082.8cm-1460.8.cm-1The absorption peaks at (A) were the results of the symmetric stretching vibration of Si-O-Si bond, the anti-vibration stretching vibration of Si-O-Si bond, and the bending stretching vibration of O-Si-O bond, confirming that the silica layer was successfully coated with Fe3O4The above. Magnetic sodium alginate (SA/Fe) in the figure3O4@SiO2) The composite material simultaneously generates sodium alginate and Fe3O4@SiO2Characteristic absorption peak of (B), indicating the formation of SA/Fe3O4@SiO2And (c) a complex.
(3) XRD analysis of magnetic sodium alginate composite material
FIG. 4 is the XRD pattern of magnetic sodium alginate, and the 2 theta values are the main diffraction peaks of sodium alginate at 31.6 deg., 45.4 deg., 56.6 deg. and 66.3 deg.. SA/Fe3O4@SiO2Has an XRD pattern in which Fe appears at a 2 theta value of 35.8 DEG3O4And other dispersion diffraction characteristics are shown by crystalline and non-crystalline parts in the magnetic sodium alginate particles. From this, it can be deduced that the magnetic sodium alginate contains Fe3O4Crystalline particles and thus the composite particles also have magnetic properties.
(4) Raman spectrogram analysis of magnetic sodium alginate composite material
FIG. 5 is a Raman spectrum of the sodium alginate and magnetic sodium alginate composite material, which can be seen by comparing two groups of peaks at 115.4cm-1、1087.9cm-1、1308.6cm-1、1418.6cm-1、1630.4cm-1、2945.8cm-1The peaks of sodium alginate are sharper, especially 2945.8cm-1With encapsulated Fe3O4After the material is compounded, the peak intensity of the material is weakened and is relatively gentle.
(5) Analysis of thermal stability of magnetic sodium alginate composite material
SA/Fe shown in FIG. 63O4@SiO2The thermal decomposition curve of the magnetic composite material is very similar to that of sodium alginate, and the main difference is that the decomposition temperature is increased at the beginning of the second stageThe temperature is raised to about 230 ℃, the two substances form hydrogen bonds to cause thermal decomposition, and the result shows that the magnetic sodium alginate (SA/Fe)3O4@SiO2) The thermal stability of the composite material is compared with that of sodium alginate.
(6) Scanning electron microscope analysis of magnetic sodium alginate composite material
The microscopic morphology of the magnetic sodium alginate composite material was observed by scanning electron microscopy, as shown in the figure. 7, the magnetic sodium alginate composite material is granular, the surface area of the magnetic sodium alginate composite material can be increased due to the rough surface of the magnetic sodium alginate composite material, and the adsorption effect of the material on heavy metal ions can be increased. The surface of the magnetic sodium alginate composite particle can be seen to have grains, and the enlarged image shows that the grains are provided with small holes, so that heavy metal ions can enter the material through the small holes during adsorption, and the holes can enable the magnetic sodium alginate composite particle to better adsorb the heavy metal ions from the outside.
Example 2
The present embodiment includes the following steps
(1) Mechanism for adsorbing heavy metal ions by magnetic sodium alginate composite material
The main mechanism of the magnetic sodium alginate composite material for adsorbing heavy metal ions comprises functional groups such as-OH, -COOH and the like and Pb2+、Co2+、Cu2+Plasma metal ion to form complex with Ca2+With Pb2+、Co2+The plasma metal ions are ion exchanged, and the specific process is shown in figure 8.
(2) Influence of pH on adsorption of metal ions by magnetic sodium alginate composite material
Lead ion solutions with different pH values have important influence on the adsorption of lead ions by the hydrogel. The adsorption performance of the hydrogel to lead ions can be different due to different pH values of lead ion solutions. In the test, under the condition that other conditions (the adsorption time is 120min, the lead ion concentration is 500mg/L, and the temperature is 15 ℃) are the same, the pH value of the metal ion solution is used as a unique variable, and the influence of the pH value of the heavy metal ion solution on the lead ion adsorption performance of the hydrogel is tested. Taking 6 250mL conical flasks, respectively adding 0.2g of dried hydrogel powder, and then respectively adding 500mg/L heavy metal ion solutions with different pH values (2, 3, 4, 5 and 6). Stirring at 200r/min for 120 min. After standing and precipitating, taking supernatant to absorb a proper amount of the supernatant for dilution. The lead ion concentration was measured with an atomic absorption spectrophotometer.
As can be seen from Table 1, as the pH continued to increase, the adsorption amount slightly decreased after a peak. This is because at a low pH, the functional groups on the surface of the adsorbent are protonated, and the adsorbent and the metal ions in the solution carry the same charge, and the two repel each other, hindering the adsorption of the metal ions by the adsorbent; when the pH value exceeds the optimum value for the adsorbent, the adsorption amount is slowly reduced due to H in solution in an acidic environment+Occupies active adsorption points on the composite material, so that a competitive relationship is generated between the composite material and heavy metal ions, the adsorption of the magnetic sodium alginate composite material to the heavy metal ions is influenced, and the adsorption rate is reduced.
When the pH value is increased from 2.0 to 4.0, the magnetic sodium alginate hydrogel is aligned to Pb2+The adsorption amount of (2) is increased from 68.13 to about 133.45, and when the pH exceeds 4, the magnetic sodium alginate composite material (SA/Fe)3O4@SiO2) The adsorption amount of (2) starts to decrease, probably because Pb is present when the solution pH is greater than 42+Onset of Pb (OH)2And (4) precipitating. Thus, Pb in subsequent experiments2+The pH value of the solution is controlled to be about 4. The adsorption principle of other four ions is similar, so the pH value is controlled to be about 5.
TABLE 1 influence of pH on the adsorption of lead ions by magnetic sodium alginate composite
(3) Analysis of different adsorption times of magnetic sodium alginate composite material
Preparing 500mg/L metal ion solution, measuring 100mL solution, adjusting the most suitable pH value, weighing 0.2g adsorbent, putting into the solution, stirring for 4 hours, absorbing every 10min for the first two hours, and absorbing every 20min for the last two hours. The supernatant was diluted 1mL and tested with an atomic spectrophotometer. The adsorption performance of the magnetic sodium alginate composite adsorbent on heavy metals is measured at different times (10min, 20min, 30min, 40min, 60min, 80min, 120min, 150min, 180min and 240 min). And performing data analysis and test results according to the tested results, and respectively drawing up a dynamics pseudo first-order equation, a dynamics pseudo second-order equation and a particle internal diffusion equation.
The influence of the contact time on the adsorption of heavy metals by the magnetic sodium alginate is analyzed to find that the magnetic sodium alginate composite material (SA/Fe)3O4@SiO2) The magnetic sodium alginate composite material has strong adsorption capacity and fast adsorption rate to heavy metal ions, and in the earlier stage of adsorption, the adsorption rate is fast because the proportion of ion concentration in a solution is high and more groups are on the magnetic sodium alginate. The adsorption amount of the composite material rises linearly within 100min, the content of metal ions is smaller and smaller along with the increase of the adsorption time, the adsorption sites on the composite material are filled with the metal ions, and at the moment, the electrostatic force between the ions in the adsorption phase and the ions remained in the solution is stronger and stronger, so the adsorption amount after 100min is gradually stable. When the adsorption time reaches about 120min, the adsorption capacity of the magnetic sodium alginate composite material reaches a saturated state. Composite material pair Pb2+The adsorption capacity is 137mm/g, the adsorption rate is 83 percent, and the adsorption capacity is specific to Cu2+、Co2+、Ni2+、Cd2+The adsorption amounts of (A) were 51mg/g, 49mg/g, 38mg/g and 28mg/g, respectively, and the adsorption rates were 29%, 18%, 15% and 13%, respectively.
TABLE 2 kinetics parameters of adsorption of lead ions by magnetic sodium alginate composite material
Table 2 shows that the first order kinetic model is not sufficient to describe Pb2+The adsorption process of the ions can be seen to show a good linear relationship, as shown in the table3-4 calculated correlation coefficient (R)20.969) correlation coefficient (R) higher than quasi-first order20.940). These results indicate Pb2+The adsorption to the magnetic composite material follows a quasi-second-order rate model, and the adsorption mode is chemical adsorption. In the initial stage, the composite material contains a large number of vacancy active sites for adsorbing Pb2+Ions, and as the active sites are gradually occupied, a concentration difference is formed between the surface and the inside of the composite material, thereby promoting Pb2+The ions diffuse into the composite and the rate of adsorption depends on diffusion into the particles. The results show that Pb2+The adsorption process on the magnetic sodium alginate composite material is mainly based on chemical adsorption and is mainly controlled by the interaction of surface binding sites and the diffusion of the surface binding sites into polymer microbeads.
(4) Competitive adsorption assay
Competitive adsorption experiments are carried out in a binary metal system, and SA/Fe is investigated3O4@SiO2The selectivity of the ion exchange membrane is 4-5, the adsorption time is 120min, and the experiment is carried out under the condition that the concentration of each ion solution is 500 mg/L. The concentration of heavy metal ions was measured by an atomic spectrophotometer, and Table 3 shows the adsorption amount Q of the heavy metal ion hydrogeleDistribution coefficient (K)d) Coefficient of selectivity (K)s). According to the table, the competitive adsorption capacity of the hydrogel to the heavy metal ions is obtained, and a column diagram of the competitive adsorption of the hydrogel to the heavy metal ions is obtained, as shown in FIG. 9. Calculated KdAnd KsThe values are listed in tables 3-5. In binary metal systems, Cu2+、Cd2+、Co2+、Ni2+Isocompetitive cation pair of Pb2+The adsorption of (b) has no effect. When four metals exist, the magnetic sodium alginate composite material corresponds to Pb2+K ofdValue much greater than Cu2+、Cd2+、Co2+、Ni2+Corresponding KdThe value is obtained. KsThe higher the value is, the higher the magnetic sodium alginate composite material is to Pb2 +The bonding capability of the copper-based alloy is obviously stronger than that of Cu2+、Cd2+、 Co2+、Ni2+. The result shows that the magnetic sodium alginate composite material is in Pb2+/Cu2+、Pb2+/Cd2+、Pb2+/Co2+And Pb2+/Ni2+For Pb in the mixture2+Has higher selectivity in separation and recovery.
TABLE 3 competitive adsorption capacity, partition coefficient and selectivity system for composite materials to heavy metal ions
(5) Analysis of reusability of magnetic sodium alginate composite material
Through experimental research on the adsorption performance of the magnetic sodium alginate composite material on heavy metal ions at different temperatures, the adsorption capacity of the adsorption material for adsorbing the heavy metal ions can be changed along with the change of the temperature, and the adsorption capacity is affected differently according to the difference of the ions. And then, researching the regenerability of the composite material, and for the adsorbent, in addition to investigating whether the adsorption performance of the material is high-efficiency or not, testing the cyclic regeneration performance of the adsorbent, wherein the recycling performance is an important standard for measuring the practical application performance of an adsorption material. Mainly Pb2+And (3) performing adsorption and desorption experimental analysis on the magnetic sodium alginate composite material as an experimental object so as to detect the recycling performance of the magnetic sodium alginate composite material. As can be seen from FIG. 10, the data of ten adsorption-desorption tests carried out by three sets of parallel tests shows that the adsorption amount is reduced, but the decrement amplitude of each time is not large, and the desorption rate is reduced from about 97% to about 84%, which proves that the magnetic sodium alginate composite material has good renewable performance, and the composite material has magnetism, and can be better separated from the heavy metal ion solution, so that the characteristic of repeated reutilization of the composite material is greatly enhanced.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A heavy metal ion adsorbing material is characterized in that: the material is sodium alginate and Fe3O4@SiO2The magnetic sodium alginate composite material formed by nano particles, wherein the sodium alginate is used as a skeleton, has a porous structure and is magnetic Fe3O4@SiO2The nano particles are filled in the pores of the sodium alginate.
2. The heavy metal ion adsorbing material according to claim 1, wherein: sodium alginate and Fe3O4@SiO2The weight ratio of the nano particles is (10-5): 1.
3. A method for producing the metal ion adsorbing material according to claim 1 or 2, characterized in that: with sodium alginate, Fe3O4@SiO2The heavy metal ion adsorption material is prepared from calcium chloride serving as a raw material by a physical blending method at normal temperature of an aqueous solution.
4. The method for producing a metal ion adsorbing material according to claim 3, wherein: the method comprises the following specific steps:
step 1, dissolving sodium alginate in water, and then dissolving Fe3O4@SiO2Pouring the nano particles into a sodium alginate solution, and stirring to uniformly disperse the nano particles to form a suspension;
step 2, dripping the magnetic suspension into CaCl2Standing in the solution to make Ca2+Further permeating into the pellet to carry out gelation reaction to obtain magnetic sodium alginate gel pellet;
and 3, washing the prepared gel beads with water, drying, and grinding by using a stirrer to obtain the heavy metal ion adsorbing material.
5. The method for producing a metal ion adsorbing material according to claim 4, wherein: said step (c) isIn 2, CaCl2The concentration of the solution is 0.2mol/L, and the standing time is 8-12 h.
6. The method for producing a metal ion adsorbing material according to claim 4, wherein: in step 3, the gel beads are washed with water for at least 5 times and dried in an oven at a temperature of 60 ℃.
7. Use of the metal ion adsorbing material according to claim 1 or 2 as a heavy metal adsorbent for adsorbing heavy metal ions in sewage.
8. Use according to claim 7, characterized in that: the heavy metal ions are one or more of lead ions, cadmium ions, nickel ions, cobalt ions, copper ions, magnesium ions and the like.
9. Use according to claim 7, characterized in that: the pH value of the sewage is controlled to be 2-6.
10. The metal ion adsorbing material according to claim 1 or 2, which is used for adsorbing Pb2+/Cu2+、Pb2+/Cd2+、Pb2+/Co2+Or Pb2+/Ni2+For Pb in the mixture2+The use of the separation and recovery of (a).
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