CN115582102A - Porous sponge adsorbent and preparation method and application thereof - Google Patents

Porous sponge adsorbent and preparation method and application thereof Download PDF

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CN115582102A
CN115582102A CN202211220539.9A CN202211220539A CN115582102A CN 115582102 A CN115582102 A CN 115582102A CN 202211220539 A CN202211220539 A CN 202211220539A CN 115582102 A CN115582102 A CN 115582102A
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adsorbent
solution
sponge
lead
porous
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CN115582102B (en
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殷凯
罗胜联
郭静
付开星
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Hunan University
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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
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
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Abstract

The invention discloses a porous sponge adsorbent and a preparation method and application thereof, wherein the preparation method of the porous sponge adsorbent comprises the following steps: s1, preparing a zeolitic imidazolate framework ZIF-L; s2, dissolving the zeolite imidazole framework ZIF-L in the S1 in N, N dimethylformamide to prepare a zeolite imidazole framework solution; s3, uniformly dispersing the zeolite imidazole framework solution in the S2; s4, heating the solution reacted in the S3, adding polyvinylidene fluoride and stirring; and S5, immersing the melamine sponge in the solution prepared in the S4, taking out the melamine sponge from the solution, and drying to obtain the melamine sponge. The electron microscope result shows that the adsorbent maintains the original three-dimensional network structure of the melamine sponge, and the zeolite imidazole framework loaded on the sponge presents a hollow annular shape. The adsorbent has excellent adsorption performance on lead and copper ions, and is mainly characterized by high adsorption capacity, high adsorption rate, high anti-interference capacity, and regeneration and cyclic utilization.

Description

Porous sponge adsorbent and preparation method and application thereof
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a porous sponge adsorbent for adsorbing heavy metal wastewater and a preparation method thereof; the invention also relates to the application of the porous adsorbent.
Background
With the acceleration of the pace of the industrialization process, the industries such as mining industry, smelting industry, electroplating industry, battery industry and the like develop rapidly, so that the discharge amount of heavy metal wastewater is increased sharply, and the serious pollution to the water environment is caused. Lead (Pb) and copper (Cu) are one of the two most widely used heavy metals, with high toxicity and non-biodegradability. Lead and copper in the water body can be enriched in fishes and other aquatic organisms, enter a human body through a food chain, and also directly enter the human body through a drinking water system, so that serious damage is caused to the human body, such as multiple organ dysfunction, birth defects and the like.
Currently, a series of methods for removing heavy metals from water have been developed, including flocculation, chemical precipitation, ion exchange, adsorption, electrolysis and membrane filtration. Among them, the adsorption method is considered to be an attractive heavy metal removal technology because of its advantages of simple design and operation, low cost, good removal effect, no secondary pollution, etc. However, the conventional adsorbent generally has poor adsorption performance, so that a novel adsorbent with high performance and high selectivity needs to be designed urgently, and the requirement of industrial application, namely easy separation, recoverability, strong anti-interference capability and the like, also needs to be met.
The invention discloses a Chinese patent with publication number CN108636387A and a preparation method and application thereof, firstly, a silane coupling agent is used for carrying out amination modification on melamine sponge, then alcohol solution of glyoxal is used for carrying out aldehyde group modification on the melamine sponge, and finally the melamine sponge and rhodamine hydrazide are refluxed and modified to obtain the iron ion adsorption sponge.
Chinese patent with publication No. CN106279033A discloses a flaky crossed ZIF-L and a preparation method thereof. The shape of the ZIF-L is a flaky cross shape, wherein the sheet forming the flaky cross shape ZIF-L is a willow leaf shape, the length of the sheet is 4.5-8.5 mu m, the thickness of the sheet is 0.2-0.4 mu m, the width of the center of the sheet is 1-3 mu m, the flaky cross shape is a cross flaky cross shape or a multi-sheet cross shape of more than three sheets, and the specific surface area of the flaky cross shape ZIF-L is more than or equal to 303m 2 (iv) g; the method comprises the steps of preparing a zinc nitrate hexahydrate aqueous solution and a 2-methylimidazole aqueous solution respectively, uniformly mixing the two aqueous solutions to obtain a mixed solution, then placing the mixed solution in a closed state, reacting at 115-135 ℃ to obtain a reaction solution, and then sequentially carrying out solid-liquid separation, washing, solvent activation and drying on the reaction solution to obtain the target product. Since the particle size of ZIF-L is small, when ZIF-L is used for adsorbing heavy metal ions in an aqueous solution, ZIF-L is very difficult to recover and the adsorption effect on heavy metal ions is poor, it is necessary to improve the above technology.
Disclosure of Invention
The invention aims to provide a porous sponge adsorbent and a preparation method thereof, and the prepared porous sponge adsorbent has high adsorption rate, high adsorption capacity, high anti-interference capacity and regeneration cycle capacity on lead and copper ions, and is easy to recover.
The invention also aims to provide application of the porous sponge adsorbent in removing lead and copper in wastewater.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of a porous sponge adsorbent comprises the following steps:
s1, preparing a zeolite imidazole framework ZIF-L;
s2, dissolving the zeolite imidazole framework ZIF-L in the S1 in N, N dimethylformamide to prepare a zeolite imidazole framework solution;
s3, uniformly dispersing the zeolite imidazole framework solution in the S2;
s4, heating the solution reacted in the step S3, adding polyvinylidene fluoride, and uniformly stirring;
and S5, immersing the melamine sponge in the solution prepared in the S4, taking out the melamine sponge from the solution, and drying to obtain the porous sponge adsorbent.
According to the invention, the zeolite imidazole framework ZIF-L is selected and dissolved in N, N dimethylformamide, so that the zeolite imidazole framework ZIF-L is uniformly dispersed, polyvinylidene fluoride is added, and then melamine sponge is immersed in the solution, and the porous sponge adsorbent is prepared through a thermally induced phase separation process, wherein the adsorbent maintains the original three-dimensional network structure of the melamine sponge, the zeolite imidazole framework can be stably adsorbed on the melamine sponge, and the loading rate of the zeolite imidazole framework on the melamine sponge is 35% -45%. The above steps are all absent, and any step cannot make the zeolite imidazole framework stably adsorbed in the melamine sponge, so that the effect that the porous sponge adsorbent is easily separated from the water phase cannot be achieved.
The zeolite imidazole framework loaded on the sponge presents a hollow annular shape, has selective adsorption on lead and copper in the wastewater, and has good adsorption effect on the lead and the copper in the wastewater.
The reason for selecting the zeolitic imidazolate framework ZIF-L in the present invention is that it can be synthesized in aqueous phase, is more environmentally friendly, and has a higher synthesis rate and a higher yield than the conventional zeolitic imidazolate framework ZIF-8.
The typical cross-linking binder polyvinylidene fluoride is selected because it has good chemical and thermal stability and can produce a porous structure during thermally induced phase separation, while N, N dimethylformamide is selected because it is miscible with most organic solvents and is commonly used as a class of low volatility solvents.
In a preferred embodiment of the invention, the mass to volume ratio of zeolitic imidazolate framework ZIF-L to melamine sponge is comprised between 1 and 3g:10-15cm 3 。
In a preferred embodiment of the present invention, ultrasonic cell disruption is used in S3 to uniformly disperse the solution of the zeolitic imidazole framework in S2.
In a preferred embodiment of the invention, the power of the ultrasonic cell disruptor in S3 is 800-1200W, and the high power enables the zeolite imidazole skeleton to be dispersed more uniformly in the N, N dimethylformamide solution.
In a preferred embodiment of the present invention, the time of the ultrasound in S3 is 5-15min. Further preferably, the ultrasonic time in S3 is 7-13min, and the adsorption performance of the prepared porous functional sponge adsorbent on lead and copper ions is optimal when the ultrasonic time is 7-13min, because the porous functional sponge adsorbent has a unique hollow annular shape which is beneficial to promoting mass transfer and accessibility of active sites.
In a preferred embodiment of the invention, the zeolitic imidazolate framework ZIF-L, the mass to volume ratio of N, N dimethylformamide to polyvinylidene fluoride is comprised between 1 and 3g:80-120mL:1-3g.
In a preferred embodiment of the invention, the temperature of the heating in S4 is 40-60 ℃.
In a preferred embodiment of the invention, the melamine sponge is repeatedly squeezed in S4 two to four times while immersed in the solution prepared in S3 to ensure sufficient contact of the melamine sponge with the solution.
In a preferred embodiment of the present invention, the drying temperature in S5 is 130-170 deg.C, and the drying time is 0.5-1.5h.
In a preferred embodiment of the present invention, the preparation method of the zeolitic imidazolate framework ZIF-L in S1 comprises the following steps:
1) Zn (NO) 3 ) 2 ·6H 2 Dissolving O and dimethyl imidazole in deionized water to obtain a solution A and a solution B respectively, and mixing the solution A and the solution B to obtain a mixed solution;
2) Stirring the mixed solution obtained in the step 1) at the temperature of 20-30 ℃ for 1-3h;
3) And after stirring, filtering the mixed solution after reaction in the step 2) to obtain a solid filtrate, washing the solid filtrate by adopting methanol and deionized water, and then freeze-drying the solid filtrate to obtain the zeimidazole framework ZIF-L.
In a preferred embodiment of the present invention, in step 1), the ratio of the amounts of zinc ions, dimethylimidazole and deionized water in the mixed solution is 1.
In a preferred embodiment of the invention, in step 1), zn (NO) is added 3 ) 2 ·6H 2 O and dimethyl imidazole are respectively dissolved in 150-250mL of deionized water to obtain solutions A and B.
In a preferred embodiment of the invention, in step 1), zn (NO) 3 ) 2 ·6H 2 The mass ratio of O to dimethyl imidazole is 5-7:14.
in a preferred embodiment of the invention, in step 2), the stirring rate is 15-40rpm.
In a preferred embodiment of the invention, in step 3), the duration of freeze-drying is between 20 and 30h.
The invention also discloses a porous sponge adsorbent prepared by using the method.
In a preferred embodiment of the invention, the loading rate of the zeolitic imidazole framework on the melamine sponge is between 35% and 45%; preferably, the loading of the zeolitic imidazole framework on the melamine sponge is from 39.82% to 40.72%.
The invention also discloses application of the porous sponge adsorbent in adsorption of lead and copper in wastewater.
In a preferred embodiment of the invention, when the pH value of the wastewater is 4-6, the removal rate of the lead and copper ions by the porous sponge adsorbent is high.
In some specific embodiments, the adsorbent has an adsorption capacity of 624.8mg/g for lead ions in a body of water.
In some specific embodiments, the adsorbent has an adsorption capacity of 588.6mg/g for copper ions in a water body.
In some embodiments, the adsorbent maintains the original three-dimensional network structure of the melamine sponge, while the zeolitic imidazole framework supported on the sponge presents a hollow annular morphology.
In some specific embodiments, the adsorption effect of the adsorbent on lead copper ions is mainly derived from nitrogen-containing functional groups contained on the surface of the adsorbent.
Compared with the prior adsorbent and the preparation method, the invention has the advantages that:
1) The porous functional sponge adsorbent prepared by the invention has the advantages of high adsorption rate, high adsorption capacity, high anti-interference capacity and regeneration cycle capacity on lead and copper ions, is easy to recover, and is suitable for large-scale industrial application;
2) The preparation method of the porous functionalized sponge adsorbent provided by the invention is simple and low in cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an SEM image of the adsorbent obtained in example 1.
Fig. 2 is an XRD spectrum of the adsorbent obtained in example 1.
Fig. 3 is a nitrogen-adsorption desorption isotherm spectrum of the adsorbent obtained in example 1.
FIG. 4 is a graph showing the kinetics of the adsorbent obtained in example 1 for lead copper ions.
FIG. 5 is an isothermal adsorption curve of lead copper ions by the adsorbent obtained in example 1.
FIG. 6 is a graph showing the effect of pH on the adsorption capacity of the adsorbent obtained in example 1 for lead and copper ions.
FIG. 7 is a graph showing the influence of coexisting ions on the adsorption capacity of the adsorbent obtained in example 1 for lead ions.
FIG. 8 is a graph showing the influence of coexisting ions on the adsorption capacity of the adsorbent obtained in example 1 for copper ions.
FIG. 9 is a graph showing the effect of natural organic substances on the adsorption capacity of the adsorbent obtained in example 1 for lead and copper ions.
FIG. 10 is a graph showing the selectivity of the adsorbent obtained in example 1 for lead copper ions.
Fig. 11 is a result of a recycling performance test of the adsorbent obtained in example 1.
FIG. 12 shows the results of a continuous flow test of the adsorbent obtained in example 1.
FIG. 13 is a Fourier infrared spectrum of the adsorbent obtained in example 1 after adsorbing lead copper ions.
FIG. 14 is a total X-ray photoelectron spectrum of the adsorbent obtained in example 1 after adsorbing lead-copper ions.
Fig. 15 is a N1s high-resolution X-ray photoelectron spectrum of the adsorbent obtained in example 1 after adsorbing lead and copper ions.
Fig. 16 shows the thermodynamic properties of different materials for lead ion adsorption.
Fig. 17 shows the thermodynamic performance of different materials for copper ion adsorption.
Fig. 18 is a graph showing the effect of the duration of ultrasound on the thermodynamic performance of lead ion adsorption.
Fig. 19 is the effect of duration of ultrasound on the thermodynamic performance of copper ion adsorption.
Detailed Description
The following detailed description of the embodiments of the present invention will be provided with reference to the accompanying drawings and examples, so that how to implement the embodiments of the present invention by using technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise specified, the raw materials and reagents in the examples of the present invention were all purchased commercially.
The analysis method in the embodiment of the invention is as follows:
the Scanning Electron Microscope (SEM) of the material is characterized by adopting a field emission scanning electron microscope of a TESCAN MIRA3 model;
the X-ray diffraction (XRD) spectrum of the material is characterized by adopting a Bruker D8 type X-ray diffractometer, the scanning speed is 10 degrees/min, and the scanning range of the 2 theta angle is 5-85 degrees;
the specific surface area and the pore size distribution (BET) of the material are characterized by an automatic specific surface area and pore size analyzer of ASAP 2460 model;
the concentration of metal ions in the solution was determined on an inductively coupled plasma mass spectrometer (ICP-MS).
Example 1: porous functionalized sponge adsorbent and preparation method thereof
The embodiment provides a porous functionalized sponge adsorbent, which is a functionalized adsorbent obtained by using melamine sponge as a structural support and fixing a zeolite imidazole framework on the surface of a melamine sponge structure by adopting an impregnation method.
The embodiment also provides a preparation method of the porous functionalized sponge adsorbent
Mixing 6gZn (NO) 3 ) 2 ·6H 2 Dissolving O and 14g of dimethyl imidazole in 200mL of deionized water respectively to obtain a solution A and a solution B, mixing the solution A and the solution B, putting the mixed solution into a constant-temperature water bath kettle at 25 ℃ for stirring for 2 hours, filtering the mixed solution after stirring to obtain a solid filtrate, washing the solid filtrate once with methanol, washing the solid filtrate twice with deionized water, and then putting the solid filtrate into a vacuum freeze dryer for drying to obtain a zeolite imidazole framework (ZIF-L). Dissolving 2g of zeolite imidazole framework in 100mL of pure N, N-dimethylformamide, putting the solution into an ultrasonic cell disruption instrument for ultrasonic treatment, after the ultrasonic treatment is finished, putting the solution obtained after the ultrasonic treatment into a 50-DEG C constant-temperature water bath kettle, slowly adding 2g of polyvinylidene fluoride into the solution, stirring for 1h to obtain uniform mixed solution, and cutting 1.5 multiplied by 5cm according to the size 3 The melamine sponge is completely immersed in the uniform mixed solution, repeatedly extruded for three times, and then the sponge is put into an oven for drying, thus obtaining the porous functionalized sponge adsorbent (MS-ZIF) 10 )。
Wherein the stirring speed of the constant-temperature water bath is 25rpm, the freeze drying time is 24 hours, the ultrasonic time is 10 minutes, the temperature of the oven is set to be 150 ℃, and the baking time is 1 hour; the working temperature of the vacuum freeze dryer is-55 ℃ and the vacuum degree is 30Pa.
Example 2: characterization of porous functionalized sponge adsorbent
The morphology of the porous functionalized sponge adsorbent prepared in example 1 was observed by scanning electron microscopy, and the results are shown in fig. 1. The detection result shows that the adsorbent maintains the original three-dimensional network structure of the melamine sponge, and the zeolite imidazole framework loaded on the sponge presents a hollow annular shape.
The crystal structure of the porous functionalized sponge adsorbent prepared in example 1 was analyzed using an X-ray diffractometer, and the results are shown in fig. 2. The detection result shows that diffraction peaks of ZIF-L and ZIF-8 simultaneously appear in the chromatogram, and the adsorbent is a mixed phase formed by the ZIF-L and the ZIF-8 and mainly comprises the ZIF-8 phase.
The specific surface area and pore size distribution of the porous functionalized sponge adsorbent prepared in example 1 were characterized by an automatic specific surface area and pore size analyzer, and the results of nitrogen adsorption-desorption isotherms thereof are shown in fig. 3. The detection result shows that the isotherm of the adsorbent belongs to the IV-type isotherm and is provided with a hysteresis loop, which indicates that the material is in a mesoporous structure.
Example 3: test of adsorption kinetics performance of porous functionalized sponge adsorbent on lead and copper ions
80mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into a glass bottle containing 80mL of lead nitrate or copper nitrate solution with an initial concentration of about 10mg/L, the glass bottle was placed in a constant temperature oscillator, the glass bottle was subjected to constant temperature oscillation at 25 ℃ and 180r/min, sampling was performed by using a syringe at oscillation times of 0, 1, 2, 5, 10, 20, 30, 45, 60 and 120 minutes, 2mL was taken each time, the remaining concentration of lead and copper ions in the sample was measured by ICP-MS after passing the sample through a 0.22 μm filter, and all the experiments were repeated twice and averaged, and the results are shown in FIG. 4.
As can be seen from FIG. 4, the adsorption of the adsorbent to lead and copper ions shows a process of 'fast first, slow second and then tend to balance', the adsorption to lead ions tends to balance in 10min, and the adsorption to copper ions tends to balance in 10min, which shows that the adsorption rate of the adsorbent to lead ions is faster than the adsorption rate to copper ions, and meanwhile, a mass transfer model is adopted to fit dynamic data, and the calculated mass transfer coefficient of lead is 7.79 multiplied by 10 -6 m/s, the mass transfer coefficient of copper is 2.54 x 10 -6 m/s。
Example 4: test of adsorption thermodynamic property of porous functional sponge adsorbent to lead and copper ions
20mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into a glass bottle containing 20mL of lead nitrate or copper nitrate solution with initial concentration of 20mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 350mg/L, 400mg/L, 500mg/L, respectively, before adding, 0.1mol/L NaOH or 0.1mol/L HCL was used to adjust the pH =5 of the solution, then the glass bottle was placed in a constant temperature oscillator and was subjected to constant temperature oscillation at 25 ℃ and 180r/min, after 24h of oscillation, sampling was performed by a syringe, the remaining concentration of lead and copper ions in the sampled liquid was measured by ICP-MS after passing through a 0.22 μm filter membrane, the average value was obtained after repeating the procedure twice, and data were plotted by a Freulich model and a Langmuir model, and the results are shown in FIG. 5.
From fig. 5, the adsorption amount of the adsorbent to lead copper ions increases with the increase of the initial lead copper concentration and then approaches to equilibrium, and comparing the fitting coefficients of the Freundlich model and the Langmuir model, the adsorption of the adsorbent to lead copper ions is more consistent with the Langmuir model, which indicates a single-layer adsorption process. In addition, the theoretical maximum adsorption capacity (q) of the adsorbent to lead and copper ions is obtained through fitting m ) 624.8mg/g and 588.6mg/g respectively.
Example 5: influence of pH on adsorption performance of porous functionalized sponge adsorbent
20mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into glass bottles containing 20mL of lead nitrate or copper nitrate solution with initial concentration of about 25mg/L, the pH of the initial solution was adjusted to 1, 2, 3, 4, 5, 6 with 0.1mol/L NaOH or 0.1mol/L HCL, the glass bottles were placed in a constant temperature oscillator and oscillated at 25 ℃ and 180r/min for 24 hours, after the oscillation was completed, sampling was performed by a syringe, the sampled liquid was filtered by a 0.22 μm filter, the remaining concentration of lead and copper ions therein was measured by ICP-MS, and the process was repeated twice for all the experiments and averaged, and the result is shown in FIG. 6.
As can be seen from fig. 6, in an extremely acidic environment with a pH value of 1 to 2, the adsorption effect of the adsorbent on lead and copper ions is negligible, when the pH value is increased to 3, the removal rate of the adsorbent on lead and copper ions is greater than 94%, and in a range of pH values of 4 to 6, the removal rate of the adsorbent on lead and copper ions is as high as 99%. The pH value of the natural water body is usually between 4 and 7, so that the adsorbent has better applicability in the pH range of the natural water body.
Example 6: influence of coexisting ions on adsorption performance of porous functional sponge adsorbent
20mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into glass bottles containing 20mL of lead nitrate or copper nitrate solution with an initial concentration of about 25mg/L, the pH of the initial solution was adjusted to 5 with 0.1mol/L NaOH or 0.1mol/L HCL, and then an amount of sodium salt, potassium salt, calcium salt or magnesium salt was added to make the concentration of coexisting ions to 0mol/L, 0.01mol/L and 0.1mol/L, and then the glass bottles were placed in a constant temperature oscillator and oscillated at 25 ℃ and 180r/min for 24 hours, after the oscillation was completed, sampling was performed using a syringe, the sampled liquid was filtered through a 0.22 μm filter, the remaining concentration of lead and copper ions therein was measured by ICP-MS, and the process was repeated twice for all the groups of experiments and then averaged, and the results are shown in FIGS. 7 and 8.
As can be seen from fig. 7 and 8, the removal rate of lead and copper ions by the adsorbent decreased with the increase in the concentration of coexisting ions, but the removal rate was still higher than 96%, indicating that the coexisting ions had little effect on the adsorption performance of the adsorbent.
Example 7: influence of natural organic matter on adsorption performance of porous functional sponge adsorbent
20mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into glass bottles containing 20mL of lead nitrate or copper nitrate solution with an initial concentration of about 25mg/L, the initial solution pH =5 was adjusted with 0.1mol/L NaOH or 0.1mol/L HCL, and then a certain amount of humic acid was added to make the humic acid concentration 0mg/L, 5mg/L, 10mg/L, 25mg/L, 50mg/L, 100mg/L and 200mg/L, and then these glass bottles were placed in a constant temperature oscillator and oscillated at 25 ℃ and 180r/min for 24 hours, after the oscillation was completed, sampling was performed with a syringe, the sampled liquid was filtered with a 0.22 μm filter membrane, the remaining concentration of lead and copper ions therein was measured with ICP-MS, and the process was repeated twice and averaged for all the experiments, and the results are shown in FIG. 9.
As can be seen from FIG. 9, the removal rate of lead and copper ions by the adsorbent is reduced with the increase of the humic acid concentration, but the removal rate is still more than 96%, which indicates that natural organic substances have little influence on the adsorption performance of the adsorbent. Therefore, the adsorbent has better anti-interference capability.
Example 8: selectivity of porous functional sponge adsorbent to lead and copper ions
Preparing 25mg/L lead nitrate, copper nitrate, sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, zinc nitrate, cadmium nitrate, nickel nitrate and mixed solutions of all ions, respectively, pouring 20mg of the porous functionalized sponge adsorbent prepared in example 1 into 20mL of the above solutions and 25mg/L of the above solutions, adjusting the pH of the initial solution to be =5 by 0.1mol/L NaOH or 0.1mol/L HCL, placing the glass bottles into a constant-temperature oscillator, oscillating for 24 hours at 25 ℃ and 180r/min, sampling by using an injector after oscillation is finished, filtering the sampled liquid by using a 0.22 mu m filter membrane, measuring the residual concentration of lead and copper ions in the filtered liquid by using ICP-MS, repeating the process twice for all the experiments, and averaging the results, wherein the results are shown in FIG. 10.
As can be seen from fig. 10, the removal rate of the lead and copper ions by the adsorbent is much higher than that of other ions, no matter when multiple divalent ions coexist or when only one metal ion exists in the solution, which indicates that the adsorbent has better selectivity for the lead and copper ions, and it can be seen that the selectivity of the adsorbent for various metal ions is ordered as follows: pb (II) > Cu (II) > Zn (II) > Ni (II) > Na (I) > Ca (II) > Cd (II) > K (I) > Mg (II).
Example 9: test result of recycling performance of porous functional sponge adsorbent
20mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into a glass bottle containing 20mL of a lead nitrate or copper nitrate solution with an initial concentration of about 25mg/L, the glass bottle was placed in a constant temperature oscillator, the glass bottle was oscillated at a constant temperature of 25 ℃ for 24 hours, a syringe was used for sampling, the sampled liquid was filtered with a 0.22 μm filter, the remaining concentration of lead and copper ions therein was measured by ICP-MS, the porous functionalized sponge adsorbent having adsorbed lead and copper ions was separated from the mixed solution, the adsorbent having been adsorbed was placed in 0.1mol/L HCl, desorbed at 25 ℃ for 4 hours and the desorbed solution concentration was measured, and then the desorbed adsorbent was placed in deionized water for 4 hours, after the completion of the soaking, the adsorbent was dried at 60 ℃ for 12 hours and used for the next adsorption-desorption cycle test after the drying treatment, and the results of the adsorption-desorption experiments described above were continued for 10 times as shown in FIG. 11.
As can be seen from fig. 11, the adsorbent has a better regeneration cyclicity, and although the removal rate of lead and copper ions by the adsorbent is reduced with the increase of the regeneration times, the removal rate of lead and copper ions after 10 cycles is still greater than 90%, which proves that the adsorbent is a sustainable high-efficiency adsorbent.
Example 10: results of a continuous flow test of a porous functionalized sponge adsorbent.
A lead nitrate solution having a concentration of 3mg/L and a copper nitrate solution having a concentration of 5mg/L were prepared as simulated wastewater, respectively, and the porous functionalized sponge adsorbent prepared in example 1 was cut into 1.5X 1.5mm 3 The size of the sample is measured, then an organic glass column with the diameter of 12mm and the length of 100mm is filled with the sample, quartz wool with the thickness of 10mm is filled at two ends of the glass column for filtration and flow division, the effective bed volume is 9.04mL, the Empty Bed Contact Time (EBCT) is set to be 7.5min, a peristaltic pump is adopted to enable the simulated wastewater to flow through the filled glass column, the liquid inlet maintains the upstream flow with the flow rate of 1.2mL/min, samples are taken at the water outlet every 12h, the sampled solution is filtered by a 0.22 mu m filter membrane, and the effluent concentration of lead and copper ions is measured by ICP-MS, and the result is shown in figure 12.
As can be seen from FIG. 12, when the effluent concentration exceeded the value (MCL) specified by the drinking water standards for daily use, the packed column treated 16.5L (1821 BV) of lead-containing wastewater and 14.8L (1630 BV) of copper-containing wastewater, indicating that the adsorbent is expected to be applied to a small-scale lead-copper wastewater treatment system.
The beneficial effects of the invention are: the porous functional sponge adsorbent provided by the invention is simple to prepare, can be used for removing lead and copper ions in wastewater, has a high adsorption rate and a high adsorption capacity, has a high anti-interference capability on environmental factors, is good in recycling performance, and is suitable for industrial application.
Example 11: the adsorption mechanism of a porous functionalized sponge adsorbent is explored.
The surface functional groups of the porous functionalized sponge adsorbent prepared in example 1 after adsorbing the lead copper ions were analyzed by fourier transform infrared spectroscopy (FTIR), and the results are shown in fig. 13. The detection result shows that when the zeolite imidazole framework is loaded on the melamine sponge, the new zeolite imidazole framework is added in the range of 840cm -l Of (a) is-CF 2 Keys and 1638cm -l C = O bonds, respectively derived from polyvinylidene fluoride and N, N dimethylformamide. After adsorbing lead and copper ions, at 1148cm -l And a C-N bond of 1584cm -l The peak intensity of the C = N bond of (a) is significantly reduced or eliminated, indicating that a chemical interaction is generated between the metal ion and the nitrogen-containing functional group on the surface of the porous functionalized sponge adsorbent.
The chemical composition of the porous functionalized sponge adsorbent prepared in example 1 after adsorbing lead and copper ions was analyzed by X-ray photoelectron spectroscopy (XPS), and the results are shown in fig. 14 and 15. The results in the general spectrum 14 show that lead and copper elements appear in the XPS spectra of the adsorbed adsorbent respectively, and the successful adsorption of lead and copper ions is verified. The result of the high-resolution N1s spectrogram 15 shows that a C-N peak at 398.6eV and a C = N peak at 400.1eV are shifted after adsorption, and new Pb-N peaks and Cu-N peaks respectively appear, so that the nitrogen-containing functional groups on the surface of the porous functionalized sponge adsorbent are proved to be main adsorption active sites.
Comparative example 1: adsorption thermodynamic performance test of pure melamine sponge on lead and copper ions
20mg of commercially available pure melamine sponge was poured into a glass bottle containing 20mL of lead nitrate or copper nitrate solution with initial concentrations of 20mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 350mg/L, 400mg/L, 500mg/L, respectively, before addition, the pH =5 of the solution was adjusted with 0.1mol/L NaOH or 0.1mol/L HCL, the glass bottle was then placed in a constant temperature oscillator, the solution was oscillated at a constant temperature of 180r/min at 25 ℃ and 180r/min, after 24 hours of oscillation, sampling was performed with a syringe, the remaining concentration of lead and copper ions in the sampled solution was measured with ICP-MS after passing through a 0.22 μm filter, all the experiments were repeated twice, averaged, and Freulich and Langmuir logarithmic model data were plotted, and the results are shown in FIGS. 16 and 17.
From fig. 16 and 17, the adsorption capacity of the adsorbent to lead and copper ions is negligible, and the maximum adsorption capacities of the adsorbent to lead and copper ions are respectively 5.9mg/g and 12.4mg/g through fitting, which shows that the sponge has poor adsorption performance, and the loaded zeolite imidazole framework plays a main adsorption role in the porous functionalized sponge adsorbent.
Comparative example 2: adsorption thermodynamic performance test of zeolite imidazole framework (ZIF-L) on lead and copper ions
20mg of the zeolitic imidazolate framework (ZIF-L) prepared in example 1 was poured into a glass bottle containing 20mL of a lead nitrate or copper nitrate solution having an initial concentration of 20mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 350mg/L, 400mg/L, 500mg/L, respectively, the pH of the solution was adjusted to 5 using 0.1mol/L NaOH or 0.1mol/L HCL before the addition, the glass bottle was placed in a constant temperature oscillator and was oscillated at 25 ℃ and 180r/min at a constant temperature, after 24 hours of oscillation, the sample was taken out using a syringe, the remaining concentration of lead and copper ions therein was measured using ICP-MS after the sample liquid passed through a 0.22 μm filter, the average value was obtained after repeating the process twice, and Freund's and Langmuir models were used to simulate the data, and the results are shown in FIGS. 16 and 17.
As can be seen from fig. 16 and 17, the adsorption capacity of the adsorbent to lead and copper ions increases with the increase of the initial lead and copper concentration, and the maximum adsorption capacities of the adsorbent to lead and copper ions obtained by fitting are 101.2mg/g and 543.4mg/g, respectively, which is inferior to that of the porous functionalized sponge adsorbent in adsorption performance because the zeolite imidazole skeleton distributed on the sponge is subjected to ultrasound to reduce particle agglomeration and increase the contact area with metal ions, thereby improving the adsorption performance.
Comparative example 3: influence of ultrasonic duration on adsorption performance of porous functionalized sponge adsorbent
Varying the sonication of the porous functionalized sponge adsorbent of example 1And (3) changing the ultrasonic time length to 5min and 15min respectively without changing other preparation conditions to prepare porous functional sponge adsorbents with different ultrasonic time lengths, which are respectively marked as MS-ZIF 5 (i.e., ultrasound duration of 5 min) and MS-ZIF 15 (i.e., the ultrasound duration was 15 min). Preparing 20mg of MS-ZIF 5 And MS-ZIF 15 Pouring into glass bottles containing 20mL of lead nitrate or copper nitrate solutions with initial concentrations of 20mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 350mg/L, 400mg/L and 500mg/L respectively, adjusting the pH =5 of the solutions by using 0.1mol/L NaOH or 0.1mol/L HCL before adding, then placing the glass bottles in a constant-temperature oscillator, oscillating at the constant temperature of 25 ℃ and 180r/min, sampling by using a syringe after 24h of oscillation, measuring the residual concentration of lead and copper ions in the sampled liquid by using an ICP-MS (inductively coupled plasma-Mass spectrometer) after the sampled liquid passes through a 0.22 mu m filter membrane, averaging after repeating the process twice according to all the experiments, and drawing by using a Freund's model and a Langmuir model to fit the data, wherein the results are shown in figures 18 and 19.
From fig. 18 and fig. 19, it can be seen that the maximum adsorption capacities of the porous functionalized sponge adsorbent for the lead and copper ions, which are prepared when the ultrasound duration is 5min, are 398.3mg/g and 422.0mg/g, respectively, and the maximum adsorption capacities of the porous functionalized sponge adsorbent for the lead and copper ions, which are prepared when the ultrasound duration is 15min, are 326.2mg/g and 342.3mg/g, respectively. The result shows that the porous functional sponge adsorbent prepared when the ultrasonic duration is 10min has the best adsorption performance on lead and copper ions because the porous functional sponge adsorbent has a unique hollow annular shape which is beneficial to promoting mass transfer and accessibility of active sites.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the appended claims are intended to be embraced therein.

Claims (10)

1. A preparation method of a porous sponge adsorbent is characterized by comprising the following steps:
s1, preparing a zeolite imidazole framework ZIF-L;
s2, dissolving a zeolitic imidazolate framework ZIF-L in the S1 in N, N-dimethylformamide to prepare a zeolitic imidazolate framework solution;
s3, uniformly dispersing the zeolite imidazole framework solution in the S2;
s4, heating the solution reacted in the step S3, adding polyvinylidene fluoride and uniformly stirring;
and S5, immersing the melamine sponge in the solution prepared in the S4, taking out the melamine sponge from the solution, and drying to obtain the porous sponge adsorbent.
2. The method of preparing the porous sponge adsorbent of claim 1, wherein: the mass-volume ratio of the zeolite imidazole framework ZIF-L to the melamine sponge is 1-3g:10-15cm 3 。
3. The method of preparing the porous sponge adsorbent of claim 1, wherein: and in the S3, ultrasonic cell disruption is adopted to uniformly disperse the zeolite imidazole framework solution in the S2.
4. A method of making the porous sponge adsorbent of claim 3, wherein: the mass-volume ratio of the zeolite imidazole framework ZIF-L to the N, N-dimethylformamide to the polyvinylidene fluoride is 1-3g:80-120mL:1-3g.
5. A process for the preparation of a porous sponge adsorbent according to any one of claims 1 to 4, characterized in that: the drying temperature in the S5 is 130-170 ℃, and the drying time is 0.5-1.5h.
6. A process for the preparation of a porous sponge adsorbent according to any of claims 1 to 4, characterized in that: the heating temperature in S4 is 40-60 ℃.
7. A process for the preparation of the porous sponge adsorbent according to any of claims 1 to 4, characterized in that the process for the preparation of zeolitic imidazolate framework ZIF-L in S1 comprises the following steps:
1) Adding Zn (NO) 3 ) 2 ·6H 2 Dissolving O and dimethyl imidazole in deionized water to obtain a solution A and a solution B respectively, and mixing the solution A and the solution B to prepare a mixed solution;
2) Stirring the mixed solution obtained in the step 1) at the temperature of 20-30 ℃ for 1-3h;
3) And after stirring, filtering the mixed solution reacted in the step 2) to obtain a solid filtrate, washing the solid filtrate by using methanol and deionized water, and freeze-drying the solid filtrate to obtain the zeolite imidazole framework ZIF-L.
8. A porous sponge adsorbent made by the method of using the porous sponge adsorbent of claims 1-7.
9. The porous sponge adsorbent of claim 8 wherein: the load rate of the zeolite imidazole framework on the melamine sponge is 35-45%; preferably, the loading of the zeolitic imidazole framework on the melamine sponge is from 39.82% to 40.72%.
10. Use of the porous sponge adsorbent of claim 8 for adsorbing lead and copper in wastewater.
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