CN113351187A - Heavy metal ion imprinted hydrogel ball and preparation method and application thereof - Google Patents
Heavy metal ion imprinted hydrogel ball and preparation method and application thereof Download PDFInfo
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- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C02F2101/10—Inorganic compounds
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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
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention discloses a preparation method of heavy metal ion imprinted hydrogel beads, which is characterized by comprising the following steps: (a) adding sodium alginate, ethylene diamine tetraacetic acid and carboxymethyl cellulose into pure water, stirring and mixing uniformly, then adding a cross-linking agent, sealing, and stirring for reaction to obtain sol; (b) dropping the sol into a heavy metal ion solution at a constant speed, and forming hydrogel beads while carrying out ion imprinting and curing; and then washing the hydrogel ball with pure water, eluting the template heavy metal ions in the ball with an acidic solution, washing with pure water, and repeatedly eluting and washing for a plurality of times to obtain the heavy metal ion imprinted hydrogel ball. The preparation method is simple, has strong selective adsorption capacity on heavy metals, is economic and efficient, can be recycled, provides a new means for realizing the efficient treatment of heavy metal pollution in water, and has wide application prospect, and the heavy metal ion imprinted hydrogel ball can specifically adsorb various heavy metal ions, and can be subjected to electrochemical or firing treatment after adsorption saturation to realize the recycling of heavy metals.
Description
Technical Field
The invention relates to a heavy metal ion imprinted hydrogel ball, and a preparation method and application thereof, and belongs to the field of heavy metal pollution control and environmental management.
Background
Heavy metal ions in the water body are difficult to naturally degrade. The excessive accumulation of heavy metals in human body can easily cause the damage of liver, kidney, reproductive system and nervous tissue. Therefore, the treatment of heavy metals in water and the resource recycling are very important. At present, the treatment method of heavy metal ions in water generally comprises the following steps: chemical precipitation, ion exchange, membrane treatment, electrolysis, adsorption, and the like. For example, patent application No. CN201810310189.2 discloses a nanofiltration membrane for heavy metal treatment and a preparation method thereof, which comprises subjecting inorganic nanoparticles and other raw materials to a series of treatments, and allowing the nanofiltration membrane substrate to enter a fluidized bed for reaction to prepare the nanofiltration membrane for heavy metal treatment, thereby solving the problem of low rejection rate of heavy metal ions by the nanofiltration membrane in the prior art and improving the sewage purification capacity of the nanofiltration membrane. The patent application with the patent application number of CN201710646514.8 discloses a heavy metal sewage treatment agent, which adopts kelp with easily obtained raw materials, and only needs to put the treatment agent into a water body to be treated when in use, so that the cost is lower, but the recovery problem of the treatment agent is not considered. Patent applicationThe patent application No. CN201910487258.1 discloses a method for selectively adsorbing and recovering heavy metals in sewage, which comprises adding carboxyl grafted chitosan and biochar composite material into sewage to selectively adsorb Cr-containing sewage3+Heavy metal ions in the interior. Therefore, in the adsorption method, the selection of a proper adsorbent is very critical to the efficient removal of heavy metal ions. The conventional adsorbing material has poor performance and poor recycling and regenerating effects, and the problems of adsorption effect, selective adsorption, cost, environmental protection, rapid separation and the like need to be considered. Therefore, the development of a green, economic and efficient heavy metal ion adsorption material convenient to recover has great significance for maintaining the ecological safety of the water body and recycling resources.
Sodium Alginate (SA) is derived from marine brown algae, and is a polymer chain type natural polysaccharide substance composed of two monomers of beta-D-mannuronic acid and alpha-L-guluronic acid. Sodium alginate has the advantages of no toxicity, degradability, abundant sources and low cost, and is commonly used for cell fixation, drug wrapping, slow release and the like. Sodium alginate in the presence of metal ions (e.g. Ca)2+、Cu2+) The sodium alginate is condensed into gel under the action of the (A), and free hydroxyl and carboxyl contained in sodium alginate molecules can be chelated with heavy metal ions to form bonds, so that the sodium alginate can be applied to the high-efficiency adsorption of the heavy metal ions in the sewage. Ethylenediaminetetraacetic acid (EDTA) is an important metal ion chelating agent, which can react with Cu2+、Cd2+The heavy metal ions form stable chelates. EDTA is introduced into the internal network structure of the hydrogel, and chelation is superposed, so that the adsorption performance of the hydrogel is greatly improved. Carboxymethyl cellulose (CMC) is a cellulose-based carboxymethyl ether derivative which is produced by taking cellulose as a raw material and has the most extensive application. CMC is easy to dissolve, easy to form film and good in mechanical property, and can be widely applied to the fields of detergent manufacture, petroleum exploitation, food processing, paper making and spinning and the like. The CMC has good film-forming property, so that the CMC is beneficial to the hydrogel to generate a spherical shape, and a large amount of-COOH and-OH exist on the molecular chain of the CMC and can coordinate with various metal ions, thereby obtaining the hydrogel ball with a three-dimensional structure.
In the prior art, Chinese patent (application No. 202011487680.6) discloses an SCP @ PEI composite hydrogel ball and a preparation method thereof, wherein modified cellulose nano-fiber and sodium alginate are mixed in proportion at normal temperature to form the SCP hydrogel ball under the action of a cross-linking agent I, the SCP ball is put into a polyethyleneimine solution, and secondary cross-linking is carried out under the action of a cross-linking agent II to obtain the SCP @ PEI composite hydrogel ball. The ball can realize the high-efficiency enrichment of various heavy metal ions in a water body through adsorption and electrostatic attraction, and the saturated adsorption quantity of the ball to Cr (VI) is up to 8mmol/g (dry weight), namely 416 mg/g. However, the technical scheme uses two crosslinking agents, the SCP @ PEI composite hydrogel ball bead can be prepared only by secondary crosslinking, the production cost is high, the process is complex, and the prepared composite hydrogel ball bead cannot perform specific or selective adsorption treatment on certain heavy metal, so that the application range of the composite hydrogel ball bead is limited.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method and application of heavy metal ion imprinted hydrogel beads, the preparation method of the heavy metal ion imprinted hydrogel beads is simple, the selective adsorption capacity for heavy metals is strong, the heavy metal ion imprinted hydrogel beads are economical, efficient and recyclable, and a new means is provided for realizing the efficient removal of heavy metals in polluted water. The heavy metal ion imprinted hydrogel ball disclosed by the invention can specifically adsorb various heavy metal ions, can realize the recycling of heavy metals through electrochemical or ignition treatment after adsorption saturation, and has a wide application prospect.
The invention is realized by the following technical scheme.
A preparation method of heavy metal ion imprinted hydrogel beads is characterized by comprising the following steps:
(a) adding sodium alginate, ethylene diamine tetraacetic acid and carboxymethyl cellulose into pure water, stirring and mixing uniformly, then adding a cross-linking agent, sealing, and stirring for reaction to obtain sol;
(b) dropping the sol into a heavy metal ion solution at a constant speed, and forming hydrogel beads while carrying out ion imprinting and curing; and then washing the hydrogel ball with pure water, eluting the template heavy metal ions in the ball with an acidic solution, washing with the pure water, and repeatedly eluting and washing for a plurality of times to obtain the heavy metal ion imprinted hydrogel ball.
In the step (a), the mass ratio of the sodium alginate to the ethylene diamine tetraacetic acid to the carboxymethyl cellulose is controlled to be 1-3: 1:1, and the concentrations of the sodium alginate, the ethylene diamine tetraacetic acid and the carboxymethyl cellulose after being added into pure water are controlled to be 0.5-2.0 wt%.
According to a preferable technical scheme, in the step (a), the cross-linking agent is glutaraldehyde, the concentration of the cross-linking agent in the reaction liquid is 0.001-0.01 wt%, the cross-linking temperature is 20-55 ℃, and the cross-linking reaction time is 5-15 hours.
Preferably, in the step (b), the template heavy metal ion for ion imprinting and curing is Cu2+、Pb2+、Cd2+、Zn2+、Ni2+、Co2+And one of Cr (VI), the concentration of heavy metal ions in the template is 0.1-0.3 mol/L, and the ion imprinting curing time is 6-15 h.
As a preferred technical scheme, in the step (b), a micro-injection pump is adopted to drop the sol into the heavy metal ion solution at a constant speed, and hydrogel beads are formed while ion imprinting and curing are carried out; wherein the dropping speed of the sol is controlled to be 60-150 drops/min, and the diameter of the hydrogel ball is controlled to be 1-5 mm.
In the step (b), the acidic solution is an inorganic acid aqueous solution, and the concentration of the eluent is controlled to be 0.1-1.0 mol/L; the inorganic acid aqueous solution comprises hydrochloric acid aqueous solution, nitric acid aqueous solution and sulfuric acid aqueous solution.
The heavy metal ion imprinted hydrogel ball prepared by the method.
The heavy metal ion imprinted hydrogel ball is applied to treatment of heavy metal polluted water.
As a preferred technical scheme, the application of the heavy metal ion imprinted hydrogel ball in the treatment of the heavy metal polluted water body comprises the following steps:
(a) adsorption of heavy metal ions
Directly adding heavy metal ion imprinted hydrogel beads into a heavy metal polluted water body, wherein the hydrogel beads can automatically adsorb heavy metal ions in sewage until the heavy metal ions are saturated:
(b) heavy metal ion recovery
Placing the heavy metal ion imprinted hydrogel beads adsorbed and saturated in the step (a) in an eluent to desorb heavy metal ions, and concentrating the heavy metal ions obtained by desorption to recover the heavy metal ions; the desorbed heavy metal ion imprinted hydrogel beads can be recycled for 5-10 times;
or directly carrying out electrochemical treatment or ignition treatment on the heavy metal ion adsorption imprinted hydrogel ball bead to recover the heavy metal ions.
As a preferred technical scheme, in the step (a), the pH value of the heavy metal polluted water body is 1-7.
The invention has the beneficial effects that:
(1) according to the invention, the green and environment-friendly raw material sodium alginate is used as a hydrogel forming agent, the good film forming property of carboxymethyl cellulose is utilized, the strong chelating effect of EDTA is utilized, the sol compounded by the three raw materials can be formed through one-time crosslinking, then the sol is dripped into a heavy metal ion solution, hydrogel beads can be formed simultaneously in the heavy metal ion imprinting and curing process, the preparation process is simple, and the production cost is low; the heavy metal ion imprinted hydrogel ball prepared by the method has the characteristics of high mechanical strength, uniform size (about 2mm in diameter), capability of realizing specific chemical adsorption and physical adsorption of trace heavy metal ions in a water body through coordination bonds and electrostatic attraction and the space stereoscopic fitting effect of an imprinting cavity left after imprinting of the heavy metal ions, green preparation, high selectivity, large adsorption quantity, reusability, convenience in heavy metal recovery and the like.
(2) Experiments prove that the heavy metal ion imprinted hydrogel ball prepared by the invention has physical adsorption besides chemical adsorption on heavy metals, and has good adsorption effect; meanwhile, the surface of the heavy metal ion imprinted hydrogel ball prepared by the invention is in layered folds, and the inside of the heavy metal ion imprinted hydrogel ball is provided with multiple cavities, so that the specific surface area of adsorption is improved, and the adsorption effect is further improved. Heavy metal ion imprinted hydrogel ball prepared by the inventionUnder neutral and alkalescent conditions, the copper-based composite material has a good adsorption effect on heavy metals, is high in selectivity and capable of being recycled, has a positive correlation between adsorption rate and initial concentration, and can be used for Cu2+The saturated adsorption capacity of the adsorbent can reach 817mg/g, and the adsorption rate exceeds 95 percent; when the heavy metal ion imprinted hydrogel ball prepared by the invention is saturated, electrochemical treatment or firing treatment can be directly carried out, so that the heavy metal can be simply and quickly recycled, and the heavy metal imprinted hydrogel ball has a good application prospect in heavy metal polluted water bodies.
Description of the drawings:
FIG. 1 is a photograph of a heavy metal ion imprinted hydrogel bead of the present invention;
FIG. 2 is an SEM image of heavy metal ion imprinted hydrogel beads of the present invention;
FIG. 3 shows that the heavy metal ion imprinted hydrogel beads adsorb Cu2+Front and back infrared spectrograms;
FIG. 4 Cu2+The initial concentration has an influence on the adsorption of the heavy metal ion imprinted hydrogel beads;
FIG. 5 shows a simulation curve of the adsorption kinetics of heavy metal ion imprinted hydrogel beads.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are not intended to limit the scope of the present invention. For the purpose of promoting an understanding of the invention, reference will now be made in detail to the embodiments of the invention illustrated in the accompanying drawings and examples.
Example 1
A preparation method of heavy metal ion imprinted hydrogel beads comprises the following steps:
(a) adding sodium alginate, ethylene diamine tetraacetic acid and carboxymethyl cellulose into pure water, stirring and mixing uniformly, then adding a cross-linking agent, sealing, and stirring for reaction to obtain sol;
(b) dropping the sol into a heavy metal ion solution at a constant speed, and forming hydrogel beads while carrying out ion imprinting and curing; and then washing the hydrogel ball with pure water, eluting the template heavy metal ions in the ball with an acidic eluent, washing with the pure water, and repeatedly eluting and washing for a plurality of times to obtain the heavy metal ion imprinted hydrogel ball.
Example 2
A preparation method of heavy metal ion imprinted hydrogel beads comprises the following steps:
(a) weighing sodium alginate, ethylene diamine tetraacetic acid and carboxymethyl cellulose, adding the sodium alginate, the ethylene diamine tetraacetic acid and the carboxymethyl cellulose into pure water according to the mass ratio of 1-3: 1:1, adding the pure water to a constant volume, controlling the concentrations of the sodium alginate, the ethylene diamine tetraacetic acid and the carboxymethyl cellulose to be 0.5-2.0 wt%, placing the mixture on a constant-temperature magnetic stirrer, keeping the temperature at 20-45 ℃, and stirring at a constant speed for 3-10 hours to fully dissolve and mix the mixture uniformly; adding a cross-linking agent glutaraldehyde, controlling the concentration of the cross-linking agent in the reaction solution to be 0.001-0.01 wt%, sealing, and carrying out magnetic stirring reaction for 5-15 h at the cross-linking temperature of 20-55 ℃ to obtain sol;
(c) dripping the prepared sol solution into a heavy metal ion solution at a constant speed of 60-150 drops/min by using a micro-injection pump, carrying out ion imprinting and curing for a period of time to simultaneously form hydrogel balls, and controlling the diameter of the hydrogel balls to be 1-5 mm; washing the hydrogel beads with pure water, eluting heavy metal ions in the hydrogel beads with an acidic solution, washing with pure water, and repeatedly eluting and washing for several times to obtain heavy metal ion imprinted hydrogel beads; wherein the heavy metal ion of the template used for ion imprinting and curing is Cu2+、Pb2+、Cd2+、Zn2+、Ni2+、Co2+And one of Cr (VI), the concentration of heavy metal ions in the template is 0.1-0.3 mol/L, and the ion imprinting curing time is 6-15 h; the acidic eluent is inorganic acid aqueous solution, and the concentration of the acidic eluent is controlled to be 0.1-1.0 mol/L; the inorganic acid aqueous solution includes hydrochloric acid aqueous solution, nitric acid aqueous solution, and sulfuric acid aqueous solution.
Example 3
A preparation method of heavy metal ion imprinted hydrogel beads comprises the following steps:
(a) weighing 3.0g of sodium alginate, ethylenediamine tetraacetic acid and carboxymethylcellulose, sequentially adding the sodium alginate, the ethylenediamine tetraacetic acid and the carboxymethylcellulose into pure water, fixing the volume to 200mL, placing the mixture on a constant-temperature magnetic stirrer, stirring at a constant speed for 6 hours, dissolving and mixing uniformly, adding 4mL of 25% glutaraldehyde solution, sealing, and stirring at 25 ℃ for reaction for 12 hours;
(b) dropping 200mL of Cu with the concentration of 0.2mol/L into the prepared sol at constant speed by using a micro-injection pump2+In the solution, ion imprinting and curing are carried out for 10 hours to form hydrogel beads; thereafter, the hydrogel beads were washed 5 times with pure water (50 mL of pure water each time), and the Cu in the hydrogel beads was eluted using 100mL of an HCl solution having a concentration of 0.5mol/L2+And washing with 200mL of pure water, repeatedly eluting and washing for 5 times to obtain the heavy metal ion imprinted hydrogel beads.
SEM and FT-IR characterization of the heavy metal ion imprinted hydrogel ball prepared in the example:
the SEM and FT-IR characterization results of the heavy metal ion imprinted hydrogel beads are shown in figures 2 and 3. As can be seen from fig. 2, which is an SEM image, the surface of the dried hydrogel bead has lamellar folds, and the hydrogel bead has multiple cavities inside, which illustrates that the hydrogel bead has a three-dimensional network cavity structure; as can be seen from FIG. 3, the absorption peak main body before and after the adsorption of the heavy metal ion imprinted hydrogel bead in the infrared spectrogram is unchanged, which indicates that the hydrogel bead has physical adsorption besides chemical adsorption of heavy metals.
For heavy metal ion imprinted hydrogel beads prepared in this example, Cu2+The adsorption effect of (2):
preparing 0.5-500 mg/L Cu2+Measuring 50mL of the solution, adjusting the pH value to 7, respectively adding 4mg (dry weight) of heavy metal ion imprinted hydrogel beads, placing in a full-temperature shaking flask cabinet, performing oscillation adsorption at 25 ℃ and 120r/min for 10h to balance the adsorption, and inspecting Cu2+The effect of the initial concentration on the adsorption is shown in fig. 4 (all adsorption experiments were repeated three times and the average value was recorded). Taking the solution after the heavy metal ion imprinted hydrogel ball adsorption balance, and detecting Cu in the adsorbed supernatant by using inductively coupled plasma-mass spectrometry (ICP-MS)2+And (4) calculating the adsorption quantity and the adsorption rate of the heavy metal ion imprinted hydrogel beads, wherein the experimental result is shown in figure 4 (all adsorption experiments are repeated three times, and the average value is recorded). As can be seen from FIG. 4, the saturated adsorption capacity of the heavy metal ion imprinted hydrogel beads reaches 817mg/g, and the adsorption rate reaches95％。
Example 4
A preparation method of heavy metal ion imprinted hydrogel beads comprises the following steps:
(a) weighing 3.0g of sodium alginate, ethylenediamine tetraacetic acid and carboxymethylcellulose, sequentially adding the sodium alginate, the ethylenediamine tetraacetic acid and the carboxymethylcellulose into pure water, fixing the volume to 200mL, placing the mixture on a constant-temperature magnetic stirrer, stirring at a constant speed for 6 hours, dissolving and mixing uniformly, adding 4mL of 25% glutaraldehyde solution, sealing, and stirring at 25 ℃ for reaction for 12 hours;
(b) dropping 200mL of Cd with the concentration of 0.2mol/L into the prepared sol at a constant speed by using a micro-injection pump2+In the solution, ion imprinting and curing are carried out for 10 hours to form hydrogel beads; then, the hydrogel beads were washed 5 times with pure water (50 mL of pure water each time), and Cd in the hydrogel beads were eluted by using 100mL of an HCl solution having a concentration of 0.5mol/L2+And washing with 200mL of pure water, repeatedly eluting and washing for 5 times to obtain the heavy metal ion imprinted hydrogel beads.
Heavy metal ion imprinted hydrogel beads prepared in this example were loaded with heavy metal Cd2+Adsorption kinetics:
preparing 5mg/L Cd2+Measuring 50mL of solution, adjusting the pH value to 7, and respectively adding 4mg (dry weight) of heavy metal ion imprinted hydrogel beads; placing in a full-temperature shaking flask cabinet at 25 deg.C, oscillating and adsorbing at a rotation speed of 120r/min, and measuring Cd in the adsorption solution at certain intervals2+And (4) concentration. Simultaneously taking the solution obtained in the step after the heavy metal ion imprinted hydrogel ball is absorbed and balanced, and detecting Cd in the absorbed supernatant by ICP-MS2+And (4) concentration. All adsorption experiments were repeated three times and the average was recorded. And calculating the adsorption quantity and the adsorption rate of the hydrogel ball. And (5) fitting adsorption kinetic equation data according to the dynamic adsorption data, wherein the result is shown in figure 5. As can be seen from FIG. 5, the adsorption kinetic equation obtained by fitting conforms to the quasi-second order rate equation, which shows that the prepared heavy metal ion imprinted hydrogel bead pair Cd2+Adsorption rate and Cd2+The initial concentration and the amount of the adsorbent are in direct proportion.
Example 5
Heavy metal ion imprinted hydrogel beads are prepared by the method of example 1.
Example 6
Heavy metal ion imprinted hydrogel beads prepared by the method of example 2.
Example 7
Heavy metal ion imprinted hydrogel beads prepared by the method of example 3.
Example 8
Heavy metal ion imprinted hydrogel beads prepared by the method of example 4.
Example 9
The application of the heavy metal ion imprinted hydrogel ball prepared by the method in treating heavy metal polluted water comprises the following specific steps:
(a) adsorption of heavy metal ions
Directly adding heavy metal ion imprinted hydrogel beads into a heavy metal polluted water body to enable the heavy metal ion imprinted hydrogel beads to adsorb heavy metal ions in sewage until the heavy metal ions are saturated, wherein the heavy metal ion imprinted hydrogel beads comprise the following two conditions:
when only one heavy metal in the heavy metal polluted water body is polluted beyond the standard, corresponding heavy metal ion imprinted hydrogel beads can be directly added (such as Cd in the heavy metal polluted water body)2+If the pollution exceeds the standard, the heavy metal ion imprinted hydrogel ball prepared in example 4 can be directly added to enable the heavy metal ion imprinted hydrogel ball to adsorb heavy metal ions in sewage until the heavy metal ions are saturated:
when the heavy metal pollution of a water body polluted by heavy metal exceeds the standard, corresponding heavy metal ion imprinted hydrogel ball beads are required to be added according to different heavy metal pollution, so that the heavy metal ion imprinted hydrogel ball beads can adsorb heavy metal ions in sewage until the heavy metal ions are saturated; when different heavy metal ion imprinted hydrogel beads are added to adsorb different heavy metal ions, multiple different heavy metal ion imprinted hydrogel beads can be added simultaneously, or can be added separately in batches;
(b) heavy metal ion recovery
Placing the heavy metal ion imprinted hydrogel beads adsorbed and saturated in the step (a) in an eluent to desorb heavy metal ions, and concentrating the heavy metal ions obtained by desorption to recover the heavy metal ions; the desorbed heavy metal ion imprinted hydrogel beads can be recycled for 5-10 times; wherein, the eluent used in the desorption process is one of dilute hydrochloric acid with the concentration of 0.1-1.0 mol/L and dilute nitric acid with the concentration of 0.1-1.0 mol/L;
or, directly carrying out electrochemical treatment or burning treatment on the heavy metal ion imprinted hydrogel beads adsorbed and saturated in the step (a) to recover the heavy metal ions.
Claims (10)
1. A preparation method of heavy metal ion imprinted hydrogel beads is characterized by comprising the following steps:
(a) adding sodium alginate, ethylene diamine tetraacetic acid and carboxymethyl cellulose into pure water, stirring and mixing uniformly, then adding a cross-linking agent, sealing, and stirring for reaction to obtain sol;
(b) dropping the sol into a heavy metal ion solution at a constant speed, and forming hydrogel beads while carrying out ion imprinting and curing; and then washing the hydrogel ball with pure water, eluting the template heavy metal ions in the ball with an acidic eluent, washing with pure water, and repeatedly eluting and washing for a plurality of times to obtain the heavy metal ion imprinted hydrogel ball.
2. The preparation method of the heavy metal ion imprinted hydrogel bead as claimed in claim 1, wherein in the step (a), the mass ratio of the sodium alginate to the ethylenediaminetetraacetic acid to the carboxymethylcellulose is controlled to be 1-3: 1:1, and the concentrations of the sodium alginate to the ethylenediaminetetraacetic acid to the carboxymethylcellulose after being added to pure water are controlled to be 0.5-2.0 wt%.
3. The method for preparing heavy metal ion imprinted hydrogel beads according to claim 1, wherein in the step (a), the crosslinking agent is glutaraldehyde, the concentration of the crosslinking agent in the reaction solution is 0.001-0.01 wt%, the crosslinking temperature is 20-55 ℃, and the crosslinking reaction time is 5-15 h.
4. The method for preparing heavy metal ion imprinted hydrogel beads according to claim 1, wherein in the step (b), the template heavy metal ion for ion imprinting and curing is Cu2+、Pb2+、Cd2+、Zn2+、Ni2+、Co2+And one of Cr (VI), the concentration of heavy metal ions in the template is 0.1-0.3 mol/L, and the ion imprinting curing time is 6-15 h.
5. The method for preparing heavy metal ion imprinted hydrogel beads according to claim 1, wherein in the step (b), the sol is dropped into the heavy metal ion solution at a constant speed by using a micro-injection pump, and the hydrogel beads are formed while ion imprinted curing is performed; wherein the dropping speed of the sol is controlled to be 60-150 drops/min, and the diameter of the hydrogel ball is controlled to be 1-5 mm.
6. The method for preparing heavy metal ion imprinted hydrogel beads according to claim 1, wherein in the step (b), the acidic eluent is an inorganic acid solution, and the concentration of the acidic eluent is controlled to be 0.1-1.0 mol/L; the inorganic acid aqueous solution comprises hydrochloric acid aqueous solution, nitric acid aqueous solution and sulfuric acid aqueous solution.
7. The heavy metal ion imprinted hydrogel beads prepared by the method of any one of claims 1 to 6.
8. The use of the heavy metal ion imprinted hydrogel bead of claim 7 in the treatment of heavy metal contaminated water.
9. Use according to claim 8, characterized in that it comprises the following steps:
(a) adsorption of heavy metal ions
Directly adding heavy metal ion imprinted hydrogel beads into a heavy metal polluted water body, so that the heavy metal ion imprinted hydrogel beads adsorb heavy metal ions in sewage until the heavy metal ions are saturated;
(b) heavy metal ion recovery
Placing the heavy metal ion imprinted hydrogel beads adsorbed and saturated in the step (a) in an eluent to desorb heavy metal ions, and concentrating heavy metal ion liquid obtained by desorption to recover the heavy metal ions; the desorbed heavy metal ion imprinted hydrogel beads can be recycled for 5-10 times;
or, directly carrying out electrochemical treatment or burning treatment on the heavy metal ion imprinted hydrogel beads adsorbed and saturated in the step (a) to recover the heavy metal ions.
10. The use according to claim 9, wherein in step (a), the pH of the heavy metal contaminated water is 1 to 7.
Priority Applications (1)
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| CN202110688437.9A CN113351187B (en) | 2021-06-23 | 2021-06-23 | Heavy metal ion imprinted hydrogel ball and preparation method and application thereof |
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| CN115010979A (en) * | 2022-06-30 | 2022-09-06 | 陕西科技大学 | High-strength chitosan/sodium alginate ion imprinted gel membrane and preparation method thereof |
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