CN116688960A - Preparation method and application of polyelectrolyte adsorption fiber composite organic frame material - Google Patents

Preparation method and application of polyelectrolyte adsorption fiber composite organic frame material Download PDF

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CN116688960A
CN116688960A CN202310697641.6A CN202310697641A CN116688960A CN 116688960 A CN116688960 A CN 116688960A CN 202310697641 A CN202310697641 A CN 202310697641A CN 116688960 A CN116688960 A CN 116688960A
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adsorption
organic frame
zif
frame material
solution
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宗鹏飞
陈家浩
杨艺轩
邱峥嵘
徐茂宁
郭利荣
王守芳
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North University of China
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North University of China
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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
    • 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]
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/20—Disposal of liquid waste

Abstract

The invention discloses a preparation method and application of a polyelectrolyte adsorption fiber composite organic frame material, and belongs to the technical field of enrichment recovery and removal of heavy metals in wastewater. The preparation method comprises the following steps: mixing sodium alginate and sodium carboxymethylcellulose into deionized water, freeze-drying to obtain sodium alginate-sodium carboxymethylcellulose fiber, solidifying the composite fiber in calcium chloride solution, vacuum-filtering, and freeze-drying again to obtain solidified composite fiber; preparing a ZIF-90 crystal material; and under the condition of room temperature, adding the solidified composite fiber into a mixed solution of chitosan and ZIF-90, soaking, putting into deionized water after the soaking is finished to wash out the chitosan solution, vacuum filtering, and thoroughly freeze-drying again to obtain the polyelectrolyte adsorption fiber composite organic frame material. The material obtained by the invention has high porosity and specific surface area, simple process, low cost, environmental protection, strong adsorption selectivity for specific metal ions and convenient recovery treatment for metals in sewage.

Description

Preparation method and application of polyelectrolyte adsorption fiber composite organic frame material
Technical Field
The invention relates to a preparation method and application of a polyelectrolyte adsorption fiber composite organic frame material, and belongs to the technical field of enrichment recovery and removal of heavy metals in wastewater.
Background
The radionuclide cobalt-60 is a pollutant which is widely focused in the nuclear industry field, and the radionuclide cobalt-60 is generated in a plurality of links of nuclear industry production such as condensed water in nuclear power facility reactors, wastewater generated by nuclear fuel plant operation and the like, and is discharged into the nature after no strict treatment procedure because of strong radioactivity. However, the application of the cobalt in the nature is very wide, especially the cobalt has higher use proportion in the field of electronic products, and the sewage discharged under various complex working conditions such as the sewage generated after the electronic products are disassembled and the sewage generated by mineral exploitation in the electronic recovery industry all contain the cobalt, so the national export relevant policy prescribes that the cobalt content in the resident drinking water should be lower than 0.05 mg/L.
The radionuclide cobalt-60 is widely applied to a plurality of fields related to biology, scientific research, medical treatment, such as plant breeding, radiation disinfection, cancer treatment, structure detection, and the like, has wide application fields and quite high economic value. If cobalt is adsorbed and recycled, not only can radioactive injury to the nature and human society caused by radioactive sewage discharge be effectively prevented, but also the recycling of metallic cobalt can be realized. Cobalt is used as rare metal, is often a companion product of other metal ores, has long-term high price in the market, and has great application prospect and wide market for enriching, recovering and removing cobalt in sewage.
Chitosan and sodium alginate are used as polysaccharide polymers extracted from nature, and have numerous applications in the fields of food, medicine, water treatment and the like, and particularly, chitosan is used as a cationic polymer and sodium alginate is used as an anionic polymer to form a chitosan/sodium alginate polyelectrolyte material, and considerable researches on adsorption and capture of heavy metal ions in water, such as polyelectrolyte membranes, polyelectrolyte microspheres, polyelectrolyte fibers and the like, are carried out. Studies have shown that Metal Organic Frameworks (MOFs) can be selectively composited by a number of adsorbent materials to strengthen the structural strength of the base material and increase the adsorption capacity for heavy metal ions by virtue of their structural stability and selective adsorption for specific metal ions. Related materials for increasing the adsorption performance and structural strength of chitosan or sodium alginate materials by compounding ZIF-8 materials are prepared in the prior art. However, no related literature report on composite modification of various materials is available.
Disclosure of Invention
The invention aims to provide a preparation method and application of a polyelectrolyte adsorption fiber composite organic frame material. The composite material prepared by the method has a high pore structure and a high specific surface area, and the preparation method is simple in process, low in cost, high in yield, environment-friendly, harmless to human bodies and free from secondary pollution to the environment after degradation, and the components are renewable materials in nature; the material is cobalt for metal ions 2+ Has stronger adsorption selectivity and can be used for recycling and treating the metallic cobalt in the sewage.
In the invention, sodium Alginate (SA) is widely applied to the fields of food, medical treatment and the like by virtue of the advantages of nature, environmental protection, human body affinity and the like, can be dissolved in water as the attribute of polysaccharide polymer, and is prepared into a spongy fiber structure by freeze drying; according to the invention, sodium alginate fiber is taken as a substrate, and sodium carboxymethylcellulose (CMC-Na) is added into sodium alginate, so that the structural strength and the porosity of the sodium alginate material after drying can be improved, and particularly, after sodium carboxymethylcellulose is added into a sodium alginate fiber structure formed by freeze drying, the adsorption performance of a polyelectrolyte material formed by compounding with chitosan on heavy metal ions is obviously improved. Then the sodium alginate-sodium carboxymethyl cellulose composite fiber is put into Chitosan (CS), and the chitosan serving as a cationic polymer material can react with the sodium alginate-sodium carboxymethyl cellulose composite fiber to form a polyelectrolyte material, namely CS-SA-CMC composite fiber, which has excellent adsorption performance. Furthermore, the ZIF-90 crystal material is added into the sodium alginate/sodium carboxymethylcellulose/chitosan composite polyelectrolyte fiber, and the organic ligand of the ZIF-90 is imidazole-2-formaldehyde (ICA), so that the adsorption selectivity of the ZIF-90 to metal ions is better. The invention combines the metal organic framework material and the polyelectrolyte fiber material, can strengthen the structural stability of the fiber, and can play a role in the heavy metal ion adsorption process better.
The invention provides a preparation method of a polyelectrolyte adsorption fiber composite organic frame material, which comprises the following steps:
s1, completely dissolving sodium alginate and sodium carboxymethylcellulose into deionized water, completely dispersing the sodium alginate and the sodium carboxymethylcellulose by magnetic stirring, pouring the mixture into a mold, and completely freeze-drying the mixture to obtain sodium alginate-sodium carboxymethylcellulose fibers;
s2, placing calcium chloride into deionized water to prepare a solution with the concentration of 10-20 g/L, completely dissolving the solution under magnetic stirring, pouring the calcium chloride solution into a culture dish, soaking the composite fiber obtained in the S1 into the culture dish, slightly pressing to ensure complete soaking, soaking the composite fiber into the deionized water after complete solidification to clean the redundant calcium chloride solution, repeating for three times, and finally removing a part of redundant water through vacuum filtration and completely freeze-drying to obtain the solidified composite fiber;
s3, adding methanol and zinc nitrate hexahydrate into a round-necked flask, magnetically stirring at the water bath temperature of 60-80 ℃ to dissolve completely, adding imidazole-2-formaldehyde and triethylamine, keeping reflux for 0.5-1.5 h, centrifugally cleaning three times by using methanol and deionized water after the reflux is finished, and finally placing the mixture at room temperature until the mixture is completely dried to obtain a ZIF-90 crystal material;
s4, preparing an acetic acid aqueous solution, adding a chitosan material, completely dissolving under magnetic stirring to form a chitosan solution, standing overnight to eliminate bubbles, and putting the ZIF-90 crystal material obtained in the S3 into the chitosan solution under magnetic stirring at 500-700 rpm/min, and stirring until the mixture is uniform;
and S5, adding the cured composite fiber obtained in the step S2 into the chitosan solution obtained in the step S4 under the condition of room temperature, slightly pressing to ensure complete soaking for 2 hours, slowly soaking in deionized water after soaking to wash away the redundant chitosan solution, removing a part of redundant water by vacuum filtration after simple washing, and completely freeze-drying again to obtain the polyelectrolyte adsorption fiber composite organic frame material loaded metal organic frame material.
Preferably, the mold in S1 is a porous plastic petri dish with a pore size of 35 mm and a single well capacity of 0.38 mL.
Preferably, the concentration of the sodium alginate solution in the S1 is 1.5-2.5 g/L, and the mass ratio of the sodium carboxymethylcellulose to the sodium alginate is 1-1.5: 3.
preferably, the rotating speed of the magnetic stirring in the step S1 is 800-1000 rpm/min, and the magnetic stirring is carried out for 2-3 hours.
Preferably, the rotation speed of magnetic stirring in the S2 is 800-1000 rpm/min, the magnetic stirring is carried out for 0.5-1 h, and the soaking time is 2-3 h.
Preferably, the rotation speed of the magnetic stirring in the step S3 is 500-700 rpm/min.
Preferably, the mass ratio of the methanol, the triethylamine, the imidazole-2-formaldehyde and the zinc nitrate hexahydrate in the S3 is 25:0.25: 1-1.5: 1 to 1.5.
Preferably, the acetic acid water in the solution in the S4 is 1% w/v, the chitosan in the chitosan solution is 1% w/v, and the mass ratio of the chitosan to the ZIF-90 material is 1:0.2 to 0.3.
Preferably, the rotation speed of magnetic stirring for dissolving the chitosan solution in the S4 is 800-1000 rpm/min, the magnetic stirring is carried out for 2-3 hours, the rotation speed of magnetic stirring after adding the ZIF-90 material is 500-700 rpm/min, and the magnetic stirring is carried out for 1-2 hours.
Preferably, in S5, the mass ratio of sodium alginate to chitosan is 1-2: 1.
the invention also provides application of the prepared polyelectrolyte adsorption fiber composite organic frame material in removing Co (II) in wastewater. The application process is as follows: the environment pollution related to the simulation of the background ion solution is simulated by adding the prepared Co (II) stock solution into a centrifuge tube, then the pH value is regulated by NaOH and HCl, and finally the adsorption material ZIF-90@CS-SA-CMC is put into the centrifuge tube for vibration adsorption for a certain time so as to complete the simulation of the adsorption process. Centrifuging the centrifugal tube after the adsorption process is finished, taking supernatant, and judging the concentration of the residual Co (II) ions by an ultraviolet spectrophotometer.
The adsorption capacity of the ZIF-90@CS-SA-CMC fiber material under different experimental conditions is judged by adjusting different parameters in the experimental process, such as pH value, adsorption process time, co (II) ion concentration, background ion and the like.
The invention has the beneficial effects that:
(1) The chitosan is extracted from crustaceans, and the sodium carboxymethyl cellulose is obtained by modifying natural cellulose, and the main materials of the chitosan are green, environment-friendly and renewable, low in cost and high in yield, and cannot cause secondary pollution to the environment after degradation, so that the metal in the sewage is conveniently recovered.
(2) The invention selects metal organic framework Materials (MOFs) to improve the performance of polyelectrolyte fibers in adsorption, and uses zinc (Zn) 2+ ) The ZIF-90 serving as a metal core can remarkably improve the structural strength after being compounded with the polyelectrolyte fiber material, and the adsorption selectivity of the ZIF-90 is also exerted, so that the adsorption efficiency of cobalt ions is high; in addition, ZIF-90 may be subjected to other modification treatments to enhance the adsorption of other specific contaminants.
Drawings
Fig. 1 is an SEM image of the polyelectrolyte-adsorbed fiber composite organic frame material of example 1 of the present invention.
Fig. 2 is an SEM image of the polyelectrolyte-adsorbed fiber composite organic frame material of example 1 of the present invention after Co (II) was adsorbed.
FIG. 3 is a Fourier transform infrared spectrum of a polyelectrolyte-adsorbed fiber composite organic frame material according to example 1 of the present invention.
FIG. 4 is a graph showing the effect of pH on Co (II) adsorption onto a polyelectrolyte adsorbent fiber composite organic frame material at a background ion of 0.001 mol/L in example 4 of the present invention.
FIG. 5 is a graph showing the effect of pH on Co (II) adsorption onto a polyelectrolyte adsorbent fiber composite organic frame material at a background ion of 0.01 mol/L in example 5 of the present invention.
FIG. 6 is a graph showing the effect of pH on Co (II) adsorption onto a polyelectrolyte adsorbent fiber composite organic frame material at a background ion of 0.10 mol/L in example 6 of the present invention.
FIG. 7 is a graph showing the effect of pH on Co (II) adsorption onto a polyelectrolyte adsorbent fiber composite organic frame material with 0.001 mol/L of Na2SO4 as background ion in example 7 of the present invention.
FIG. 8 is a graph showing the effect of pH on Co (II) adsorption onto a polyelectrolyte adsorbent fiber composite organic frame material at a background ion of 0.001 mol/L NaCl in example 8 of the present invention.
FIG. 9 is a graph showing the effect of pH on Co (II) adsorption onto polyelectrolyte adsorbent fiber composite organic frame material at 0.001 mol/L NaHCO3 as background ion in example 9 of the present invention.
FIG. 10 is a graph showing the effect of polyelectrolyte on adsorption of Co (II) at 30℃in example 10 of the present invention on the adsorption of various initial concentrations of a fibrous composite organic frame material.
FIG. 11 is a graph showing the effect of polyelectrolyte on adsorption of Co (II) at 45℃in example 11 on the adsorption of various initial concentrations of a fibrous composite organic frame material according to the present invention.
FIG. 12 is a graph showing the effect of polyelectrolyte on adsorption of Co (II) at 60℃on various initial concentrations of a fiber composite organic frame material in example 12 according to the present invention.
FIG. 13 is a graph showing the adsorption effect of Co (II) on the concentration of different adsorbents in example 13 of the present invention.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
The following is combined with the accompanying drawing and 0.001 mol/L to 0.10 mol/L of background ion NaNO 3 Influence on the adsorption effect of the invention, different background ions Na at 0.001 mol/L concentration 2 SO 4 、NaCl、NaHCO 3 Influence on the adsorption effect of the invention, co (II) concentration was studied from 3.39X10 -4 mol/L～3.39×10 -3 The invention is further described in detail in the examples of the present invention in terms of adsorption effect of the material at 30℃to 60℃in mol/L.
Example 1
The embodiment provides a preparation method of a polyelectrolyte adsorption fiber composite organic frame material, which comprises the following steps:
s1, completely blending sodium alginate and sodium carboxymethylcellulose into deionized water, wherein the concentration of a sodium alginate solution is 2.0 g/L, and the mass ratio of the selected sodium carboxymethylcellulose to the sodium alginate is 1:3, stirring for 3 hours by using a magnetic force of 1000 rpm/min, pouring the mixture into a porous plastic culture dish mold, wherein the pore size is 35 mm, and the pore size is 0.38 mL of single Kong Rongliang, and obtaining composite adsorption fiber after completely freeze-drying, which is named SA-CMC;
s2, preparing 5w% v calcium chloride solution, fully dissolving the medium calcium chloride under the magnetic stirring of 1000 rpm/min for 1h, pouring the calcium chloride solution into a culture dish, soaking the composite fiber SA-CMC obtained in the S1, slightly pressing to ensure the complete soaking, soaking into deionized water after the complete solidification for 3h to remove the redundant calcium chloride solution, repeating for three times, and finally vacuum filtration to remove a part of redundant water and complete freeze drying to obtain the solidified composite fiber SA-CMC;
s3, adding methanol and zinc nitrate hexahydrate into a round-necked flask, and after the methanol and the zinc nitrate hexahydrate are completely dissolved by magnetic stirring at 700 rpm/min at the water bath temperature of 75 ℃, adding the methanol, the triethylamine, the imidazole-2-formaldehyde and the zinc nitrate hexahydrate according to the mass ratio of 25:0.25:1:1.55, keeping reflux for 1h, centrifugally cleaning for three times by using methanol and deionized water after the reflux is finished, and finally putting the mixture into room temperature until the mixture is completely dried to obtain a ZIF-90 crystal material;
s4, preparing 1% w/v acetic acid aqueous solution, adding 1% of chitosan with a mass ratio, and completely dissolving under magnetic stirring at 1000 rpm/min for 3 hours to obtain 1% w/v chitosan solution, standing overnight to eliminate bubbles, and putting the ZIF-90 crystal material into the solution under magnetic stirring at 700 rpm/min, stirring for 1.5 hours until the mixture is uniform, wherein the mass ratio of the chitosan to the ZIF-90 crystal material is 1:0.3, obtaining ZIF-90@CS mixed solution;
s5, adding the solidified composite fiber SA-CMC obtained in the S2 into the ZIF-90@CS mixed solution obtained in the S4 under the condition of room temperature, and slightly pressing to ensure that the composite fiber SA-CMC is completely soaked for 2 hours, wherein the mass ratio of sodium alginate in the S2 fiber to chitosan in the S4 solution to ZIF-90 crystals added in the S4 is 1:1:0.3. slowly soaking in deionized water after soaking to wash out excessive chitosan solution, simply washing out, vacuum-pumping to remove a part of excessive water, and completely freeze-drying again to obtain the polyelectrolyte adsorption fiber composite organic frame material loaded metal organic frame material named ZIF-90@CS-SA-CMC.
The morphology characterization result of the obtained ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic framework material loaded metal organic framework material is shown in a graph in figure 1, and the left and right sides of the obtained ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic framework material are respectively shown in scanning electron microscope pictures under the conditions of 1 mu m and 500 nm. With reference to fig. 1, it is observed that the ZIF-90@cs-SA-CMC polyelectrolyte adsorption fiber composite organic framework material loaded metal organic framework material has irregular three-dimensional particle protrusions, which are the ZIF-90 crystal structure on the composite, indicating that the entire composite is on the fiber; the SEM morphology characterization result of the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic framework material after Co adsorption is shown in a figure 2, and the original granular protrusions are covered by the agglomeration phenomenon, so that the material has good adsorption performance;
FIG. 3 is a Fourier transform infrared spectrum of a composite organic frame material of ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber, a ZIF-90 crystalline material, and a CS-SA-CMC composite fiber material obtained by undoped ZIF-90 material in step S2. About 1545cm -1 ～1567 cm -1 at-NH 2 The characteristic peak is carried by acetamido on chitosan, and the polyelectrolyte material formed after COO-complexing with sodium alginate/sodium carboxymethylcellulose can obviously compress the characteristic peak, so that the characteristic peak is obviously shortened as can be seen from figure 3, which shows that the characteristic peak is successfully compounded into the polyelectrolyte material, and 3250 and cm of the polyelectrolyte material are attracted by static electricity in the compounding -1 ～3260 cm -1 at-OH and-NH 2 The characteristic peaks can shift obviously and shorten the hydrogen bonds, and further demonstrate the success of the composition. While because the SA-CMC composite fiber is in sodium chloride solutionWill result in a cure of 2920cm -1 ～2930cm -1 The absorption peak at the site was decreased, indicating Na on COO-thereof + Is coated with Ca 2+ Successful replacement and thus curing of the material.
The Fourier transform infrared spectrogram obtained by the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material accords with the infrared spectrogram of a ZIF-90 crystal, and the vibration absorption peak of carbonyl C=O in organic ligand imidazole-2-formaldehyde in the ZIF-90 crystal is 1660 cm -1 ～1670 cm -1 At the site, and imidazole-2-carbaldehyde at 1160 cm -1 ～1170 cm -1 Sum 950 cm -1 ～960 cm -1 The cyano absorption peak C=N at this point is shifted by Zn-N influence and becomes carbon-nitrogen bond absorption peak C-N, and Zn-N influences it at 530cm -1 ～540cm -1 From the above, it can be concluded that the ZIF-90 crystals were successfully prepared and were incorporated into ZIF-90@CS-SA-CMC composite fibers.
Taken together, the preparation of the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material is successful.
In the embodiment, in order to provide sufficient mechanical strength of the adsorbent, sodium alginate-carboxymethylcellulose sodium solidified by calcium chloride is selected as a structural substrate, ZIF-90 crystals are loaded in the process of carrying out polyelectrolyte compounding with chitosan solution, and the prepared polyelectrolyte adsorption fiber composite organic frame material has strong adsorption capacity, good affinity to human body, easy recovery and environmental protection. The ZIF-90 crystal has good ion selectivity and stable structure, so that the structural stability of the composite fiber material in a sewage environment can be further improved, the selective adsorption capacity for specific ions is improved, and meanwhile, the ZIF-90 material can be subjected to the combination of multiple functional groups, so that the adsorption of certain specific pollution is further improved. Therefore, in the comprehensive view, the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material is low in cost, environment-friendly, green and pollution-free from the recycling point of view, capable of solving the problem of complex sewage environment treatment, and capable of decomposing biological materials, and cannot cause secondary pollution to the environment. The above fully illustrates the good performance and unique advantages, and has wide prospect in the industrial sewage field.
Example 2
The embodiment provides a preparation method of a polyelectrolyte adsorption fiber composite organic frame material, which comprises the following steps:
s1, completely blending sodium alginate and sodium carboxymethylcellulose into deionized water, wherein the concentration of a sodium alginate solution is 1.0 g/L, and the mass ratio of the selected sodium carboxymethylcellulose to the sodium alginate is 1.5: 3, stirring for 3 hours by using a magnetic force of 1000 rpm/min, pouring the mixture into a porous plastic culture dish mold, wherein the pore size is 35 mm, and the pore size is 0.38 mL of single Kong Rongliang, and obtaining composite adsorption fiber after completely freeze-drying, which is named SA-CMC;
s2, placing 4 g calcium chloride into 200 mL ion water, magnetically stirring at 1000 rpm/min for 1h to enable the calcium chloride to be completely dissolved, pouring the calcium chloride solution into a culture dish, soaking the composite fiber SA-CMC obtained in the S1 into the culture dish, slightly pressing to ensure complete soaking, soaking into deionized water after complete solidification for 3h to remove redundant calcium chloride solution, repeating for three times, finally vacuum filtration to remove a part of redundant water, and completely freeze-drying to obtain solidified composite fiber SA-CMC;
s3, adding methanol and zinc nitrate hexahydrate into a round-necked flask, and adding the methanol, triethylamine, imidazole-2-formaldehyde and zinc nitrate hexahydrate according to the mass ratio of 25 after the methanol and the zinc nitrate hexahydrate are completely dissolved by magnetic stirring at 700 rpm/min at the water bath temperature of 75 ℃:0.25:1:1.55, keeping reflux for 1h, centrifugally cleaning for three times by using methanol and deionized water after the reflux is finished, and finally putting the mixture into room temperature until the mixture is completely dried to obtain a ZIF-90 crystal material;
s4, preparing 1% w/v acetic acid aqueous solution, adding 1% of chitosan with a mass ratio, and completely dissolving under magnetic stirring at 1000 rpm/min for 3 hours to obtain 1% w/v chitosan solution, standing overnight to eliminate bubbles, and putting the ZIF-90 crystal material into the solution under magnetic stirring at 700 rpm/min, stirring for 1.5 hours until the materials are uniformly mixed, wherein the mass ratio of the chitosan to the ZIF-90 material is 1:0.3, obtaining ZIF-90@CS mixed solution;
s5, adding the solidified composite fiber SA-CMC obtained in the step S2 into the ZIF-90@CS mixed solution obtained in the step S4 under the condition of room temperature, slightly pressing to ensure complete soaking for 2 hours, slowly soaking in deionized water after soaking to wash away redundant chitosan solution, removing part of redundant water by vacuum suction filtration after simple washing away, and completely freeze-drying again to obtain the polyelectrolyte adsorption fiber composite organic frame material loaded metal organic frame material named ZIF-90@CS-SA-CMC, wherein the mass ratio of sodium alginate in the S2 fiber to chitosan in the S4 solution to ZIF-90 crystals added in the S4 is 0.5:1:0.3.
compared with the ZIF-90@CS-SA-CMC composite fiber in embodiment 1, when the concentration of the sodium alginate solution is 1.0 g/L, the structure is loose after freeze-drying, the density is low, and the whole material lacks stability, so that the obtained fiber material is easy to break and decompose in a centrifuge tube after the vibration adsorption process, and the follow-up adsorption process related experiment cannot be performed.
Example 3
The embodiment provides a preparation method of a polyelectrolyte adsorption fiber composite organic frame material, which comprises the following steps:
s1, completely blending sodium alginate and sodium carboxymethylcellulose into deionized water, wherein the concentration of a sodium alginate solution is 2.0 g/L, and the mass ratio of the selected sodium carboxymethylcellulose to the sodium alginate is 1:3, stirring for 3 hours by using a magnetic force of 1000 rpm/min, pouring the mixture into a porous plastic culture dish mold, wherein the pore size is 35 mm, and the pore size is 0.38 mL of single Kong Rongliang, and obtaining composite adsorption fiber after completely freeze-drying, which is named SA-CMC;
s2, placing 4 g calcium chloride into 200 mL ion water, magnetically stirring at 1000 rpm/min for 1h to enable the calcium chloride to be completely dissolved, pouring the calcium chloride solution into a culture dish, soaking the composite fiber SA-CMC obtained in the S1 into the culture dish, slightly pressing to ensure complete soaking, soaking into deionized water after complete solidification for 3h to remove redundant calcium chloride solution, repeating for three times, finally vacuum filtration to remove a part of redundant water, and completely freeze-drying to obtain solidified composite fiber SA-CMC;
s3, adding methanol and zinc nitrate hexahydrate into a round-necked flask, and adding the methanol, triethylamine, imidazole-2-formaldehyde and zinc nitrate hexahydrate according to the mass ratio of 25 after the methanol and the zinc nitrate hexahydrate are completely dissolved by magnetic stirring at 700 rpm/min at the water bath temperature of 75 ℃:0.25:1:1.55, keeping reflux for 1h, centrifugally cleaning for three times by using methanol and deionized water after the reflux is finished, and finally putting the mixture into room temperature until the mixture is completely dried to obtain a ZIF-90 crystal material;
s4, preparing 1% w/v acetic acid aqueous solution, adding 1% of chitosan with a mass ratio, and completely dissolving under magnetic stirring at 1000 rpm/min for 3 hours to obtain 1% w/v chitosan solution, standing overnight to eliminate bubbles, and putting the ZIF-90 crystal material into the solution under magnetic stirring at 700 rpm/min, stirring for 1.5 hours until the materials are uniformly mixed, wherein the mass ratio of the chitosan to the ZIF-90 material is 1:0.2, obtaining ZIF-90@CS mixed solution;
s5, adding the solidified composite fiber SA-CMC obtained in the step S2 into the ZIF-90@CS mixed solution obtained in the step S4 under the condition of room temperature, slightly pressing to ensure complete soaking for 2 hours, slowly soaking in deionized water after soaking to wash out redundant chitosan solution, removing a part of redundant water by vacuum suction filtration after simple washing out, and completely freeze-drying again to obtain the polyelectrolyte adsorption fiber composite organic frame material loaded metal organic frame material named ZIF-90@CS-SA-CMC, wherein the mass ratio of sodium alginate in the S2 fiber to chitosan in the S4 solution to ZIF-90 crystals added in the S4 is 1:1:0.2.
compared with the ZIF-90@CS-SA-CMC composite fiber in the embodiment 1, the mass proportion of ZIF-90 crystals added in the S4 solution is smaller than that in the embodiment 1, so that the fiber material prepared in the final S5 is fragile in structure, pore channels of the fiber material are easy to collapse, and the overall structure is unstable, and therefore, the subsequent adsorption experiment is abandoned.
Example 4
The present example shows that the adsorbent concentration is 0.50 g/L and the Co (II) concentration is 5.09X 10 at 30 DEG C -4 mol/L, naNO with background ion of 0.001 mol/L 3 Under the condition, the adsorption rate condition of Co (II) on the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in the example 1 under different pH values is studied.
As shown in FIG. 4, the adsorption rate of ZIF-90@CS-SA-CMC to Co (II) was lowest at pH 2, highest at pH 3 to 4, and was stable at pH 5 to 9 with increasing pH, and was low at pH exceeding 9. The reason is probably because the ZIF-90@CS-SA-CMC surface is chitosan-sodium alginate/sodium carboxymethyl cellulose polyelectrolyte material, and the chitosan material on the surface layer can be dissolved under the condition of peracid, so that the structure of the polyelectrolyte material is damaged, and the adsorption performance is influenced. With the increase of pH, the carboxyl groups on the sodium alginate molecules are more easily ionized in a slightly acidic environment, and are negatively charged, so that Co (II) can be adsorbed and better combined. Because the amino group on the chitosan can be ionized in the acidic environment, the amino group can be better adsorbed with polyelectrolyte formed by sodium alginate-carboxymethyl cellulose sodium. Co (II) forms relatively more complex with pH exceeding 9, so that ions in solution are reduced and more difficult to capture by adsorption sites on the material.
Example 5
The present example shows that the adsorbent concentration is 0.50 g/L and the Co (II) concentration is 5.09X 10 at 30 DEG C -4 NaNO with 0.01 mol/L background ion 3 Under the condition, the adsorption rate condition of Co (II) on the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in the example 1 under different pH values is studied.
Experimental results As shown in FIG. 5, the adsorption rate of ZIF-90@CS-SA-CMC to Co (II) was lowest at pH 2, increased to 54% at pH 3-4, exhibited a plateau of about 30% -40% with pH increase of 5-9, and was less than 30% at pH exceeding 9.
Example 6
The present example shows that the adsorbent concentration is 0.50 g/L and the Co (II) concentration is 5.09X 10 at 30 DEG C -4 mol/L, the background ion is NaNO of 0.1 mol/L 3 Under the condition, the adsorption rate condition of Co (II) on the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in the example 1 under different pH values is studied.
As shown in FIG. 6, the adsorption rate of ZIF-90@CS-SA-CMC to Co (II) was lowest at pH 2, increased to 49% at pH 3-4, and tended to be smooth at pH 5-9, with an adsorption rate of about 20% -30%, and an adsorption rate of less than 20% at pH exceeding 9.
As is clear from the analysis of the adsorption efficiency and pH change of different ion backgrounds, the adsorption rate is lowest when the pH is lower than 3, the adsorption rate is highest when the pH is 3-4, the adsorption area is stable when the pH is 4-9, and the adsorption rate is gradually reduced when the pH is higher than 9. The influence of the ion background is particularly important, the ion influence is the lowest when the ion background is 0.001 mol/L, the adsorption rate is the highest about 60%, and the ion influence is the highest when the ion background is 0.10 mol/L, and the highest adsorption rate is only 49%.
Example 7
The present example shows that the adsorbent concentration is 0.50 g/L and the Co (II) concentration is 5.09X 10 at 30 DEG C -4 mol/L, na with background ion of 0.001 mol/L 2 SO 4 Under the condition, the influence of Co (II) on the adsorption rate of the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in the example 1 under different background ion environments is studied.
As shown in FIG. 7, the adsorption rate of ZIF-90@CS-SA-CMC to Co (II) was at least about 12% at pH below 3, increased to at most 44% at pH 3-4, and tended to be smooth at pH 5-9, with adsorption rates of 30% -40%, and less than 30% at pH exceeding 9.
Example 8
The present example shows that the adsorbent concentration is 0.50 g/L and the Co (II) concentration is 5.09X 10 at 30 DEG C -4 Under the NaCl condition that the mol/L of background ions is 0.001 mol/L, the influence of Co (II) on the adsorption rate of the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in example 1 under different background ion environments is studied.
As shown in FIG. 8, the adsorption rate of ZIF-90@CS-SA-CMC to Co (II) was as low as about 10% at pH below 3, increased to as high as 47% at pH 3-4, and tended to be smooth at pH 5-9, with an adsorption rate of 35% -45%, and an adsorption rate of less than 30% at pH exceeding 9.
Example 9
The present example shows that the adsorbent concentration is 0.50 g/L and the Co (II) concentration is 5.09×10 at a temperature of 30deg.C -4 mol/L NaHCO with background ion of 0.001 mol/L 3 Under the condition, the influence of Co (II) on the adsorption rate of the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in the example 1 under different background ion environments is studied.
As shown in FIG. 9, the adsorption rate of ZIF-90@CS-SA-CMC to Co (II) was at least about 8% at pH below 3, increased to at most 44% at pH 3-4, and tended to be smooth at pH 5-9, with adsorption rates of 25% -35%, and less than 25% at pH exceeding 9.
In combination, the difference between the adsorption effects of different ion backgrounds is large, especially NaHCO 3 Under the conditions, the average adsorption rate is the lowest, and the stable adsorption rate at pH 5-9 is less than 35%, presumably because bicarbonate ion (HCO) 3 - ) The cobalt ions in the solution are easy to combine to generate bicarbonate or carbonate products, so that the adsorption sites of the material are difficult to combine, free cobalt ions in the solution are reduced, the adsorption sites are more difficult to complex and adsorb, and related bicarbonate or carbonate precipitates can appear to block the pores of the solution under a more alkaline environment, so that the adsorption rate of the solution is reduced.
Example 10
This example shows that the adsorbent concentration is 0.50 g/L, the pH of the solution is=4.0, and the background ion is 0.001 mol/L NaNO at 30 DEG C 3 Under the condition, the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in example 1 by Co (II) is studied from 3.39X10 at Co (II) -4 mol/L to 3.39X10 -3 Adsorption influence on Co (II) under different initial concentrations of mol/L;
as shown in FIG. 10, the adsorption progress was gentle, the initial concentration was changed from low to high, and the lowest initial concentration was 3.39X10 -4 mol/L, the highest initial concentration is 3.39X10 -3 mol/L. Wherein C is e And q e The concentration and adsorption capacity of the remaining metal ions at equilibrium, respectively. The adsorption rate at the lowest initial concentration was low, and the adsorption capacity was about 2.42×10 -4 The adsorption capacity of the catalyst increases gradually with increasing concentration, and the adsorption capacity of the highest adsorption is about 2.88×10 -3 mol/g, at CThe reason why good adsorption rate can be maintained at a high initial concentration of o (II) is that a stronger ion driving force is generated due to the high concentration of Co (II) until the adsorption equilibrium is reached.
Example 11
This example shows that the adsorbent concentration is 0.50 g/L, the pH of the solution is=4.0, and the background ion is 0.001 mol/L NaNO at 45 DEG C 3 Under the condition, the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in example 1 by Co (II) is studied from 3.39X10 at Co (II) -4 mol/L to 3.39X10 -3 Adsorption influence on Co (II) under different initial concentrations of mol/L;
as shown in FIG. 11, the adsorption progress was gentle, the initial concentration was changed from low to high, and the lowest initial concentration was 3.39X10 -4 mol/L, the highest initial concentration is 3.39X10 -3 mol/L. Wherein C is e And q e The concentration and adsorption capacity of the remaining metal ions at equilibrium, respectively. The adsorption rate at the lowest initial concentration was low, and the adsorption capacity was about 3.66×10 -4 The adsorption capacity of the catalyst increases gradually with increasing concentration, and the adsorption capacity of the highest adsorption is about 3.68X10 -3 mol/g, which is responsible for maintaining good adsorption at high initial concentrations of Co (II), due to the higher ion driving force of Co (II) until adsorption equilibrium is reached.
Example 12
This example shows that the adsorbent concentration is 0.50 g/L, the pH of the solution is=4.0, and the background ion is 0.001 mol/L NaNO at 60 DEG C 3 Under the condition, the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in example 1 by Co (II) is studied from 3.39X10 at Co (II) -4 mol/L to 3.39X10 -3 Adsorption influence on Co (II) under different initial concentrations of mol/L;
as shown in FIG. 12, the adsorption progress was gentle, the initial concentration was changed from low to high, and the lowest initial concentration was 3.39X10 -4 mol/L, the highest initial concentration is 3.39X10 -3 mol/L. Wherein C is e And q e Respectively, remaining metal ions at equilibriumIs used for the concentration and adsorption capacity of the catalyst. The adsorption rate at the lowest initial concentration was low, and the adsorption capacity was about 4.10X10 -4 The adsorption capacity of the catalyst increases gradually with increasing concentration, and the adsorption capacity of the highest adsorption is about 4.52X10 -3 As can be seen from mol/g, the adsorption capacity of the catalyst increases with the increase of the experimental temperature, the increase is smaller at the lower initial concentration, the increase is obvious at the higher initial concentration, and the adsorption capacity is 2.88 multiplied by 10 at 30 DEG C -3 The mol/g is increased to 4.52X10 at 60 ℃ -3 mol/g。
Example 13
This example shows that the pH of the solution at 30℃is=4.0 and the background ion is NaNO of 0.001 mol/L 3 Under the condition, the removal rate comparison of Co (II) in the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in the example 1 under the condition of different adsorbent concentrations is studied.
As can be seen from FIG. 13, as the concentration of the adsorbent increases, the adsorption rate of the ZIF-90@CS-SA-CMC material also increases, and when the ZIF-90@CS-SA-CMC content is 0.66 g/L, the removal rate can reach 50%, which shows that the higher porosity and rich adsorption sites on the ZIF-90@CS-SA-CMC material can provide great advantages.
In summary, the ZIF-90@CS-SA-CMC polyelectrolyte adsorption fiber composite organic frame material prepared in the embodiment 1 has a fine microstructure, can provide larger adsorption capacity and contact specific surface area, is environment-friendly and low in cost, can be used for extracting and regenerating substances from the natural world, can efficiently recover pollutants, effectively recover metals such as cobalt, is quick and efficient in treatment of the adsorption material, does not produce secondary pollution to the environment, can enhance selective adsorption of different pollutants after being compounded with different metal organic frame materials, and can be used for sewage treatment in complex environments.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.

Claims (10)

1. The preparation method of the polyelectrolyte adsorption fiber composite organic frame material is characterized by comprising the following steps of:
s1, completely dissolving sodium alginate and sodium carboxymethylcellulose into deionized water, completely dispersing the sodium alginate and the sodium carboxymethylcellulose by magnetic stirring, pouring the mixture into a mold, and completely freeze-drying the mixture to obtain sodium alginate-sodium carboxymethylcellulose fibers;
s2, placing calcium chloride into deionized water to prepare a solution with the concentration of 10-20 g/L, completely dissolving the solution under magnetic stirring, pouring the calcium chloride solution into a culture dish, soaking the composite fiber obtained in the S1 into the culture dish, slightly pressing to ensure complete soaking, soaking the composite fiber into the deionized water after complete solidification to clean the redundant calcium chloride solution, repeating for three times, and finally removing a part of redundant water through vacuum filtration and completely freeze-drying to obtain the solidified composite fiber;
s3, adding methanol and zinc nitrate hexahydrate into a round-necked flask, magnetically stirring at the water bath temperature of 60-80 ℃ to dissolve completely, adding imidazole-2-formaldehyde and triethylamine, keeping reflux for 0.5-1.5 h, centrifugally cleaning three times by using methanol and deionized water after the reflux is finished, and finally placing the mixture at room temperature until the mixture is completely dried to obtain a ZIF-90 crystal material;
s4, preparing an acetic acid aqueous solution, adding a chitosan material, completely dissolving under magnetic stirring to form a chitosan solution, standing overnight to eliminate bubbles, and putting the ZIF-90 crystal material obtained in the S3 into the chitosan solution under magnetic stirring at 500-700 rpm/min, and stirring until the mixture is uniform;
and S5, adding the cured composite fiber obtained in the step S2 into the chitosan solution obtained in the step S4 under the condition of room temperature, slightly pressing to ensure complete soaking for 2 hours, slowly soaking in deionized water after soaking to wash away the redundant chitosan solution, removing a part of redundant water by vacuum filtration after simple washing, and completely freeze-drying again to obtain the polyelectrolyte adsorption fiber composite organic frame material loaded metal organic frame material.
2. The method for preparing the polyelectrolyte adsorption fiber composite organic frame material according to claim 1, wherein the method comprises the following steps: the die in S1 is a porous plastic culture dish, and the aperture size of the die is 35 mm and single Kong Rongliang 0.38.38 mL; the rotation speed of the magnetic stirring is 800-1000 rpm/min, and the magnetic stirring is carried out for 2-3 hours.
3. The method for preparing the polyelectrolyte adsorption fiber composite organic frame material according to claim 1, wherein the method comprises the following steps: the concentration of the sodium alginate solution in the S1 is 1.5-2.5 g/L, and the mass ratio of the sodium carboxymethylcellulose to the sodium alginate is 1-1.5: 3.
4. the method for preparing the polyelectrolyte adsorption fiber composite organic frame material according to claim 1, wherein the method comprises the following steps: and S2, magnetically stirring at a rotating speed of 800-1000 rpm/min for 0.5-1 h, and soaking for 2-3 h.
5. The method for preparing the polyelectrolyte adsorption fiber composite organic frame material according to claim 1, wherein the method comprises the following steps: s3, the rotating speed of the magnetic stirring in the step S is 500-700 rpm/min; the mass ratio of the methanol, the triethylamine, the imidazole-2-formaldehyde and the zinc nitrate hexahydrate is 25:0.25: 1-1.5: 1 to 1.5.
6. The method for preparing the polyelectrolyte adsorption fiber composite organic frame material according to claim 1, wherein the method comprises the following steps: the ratio of acetic acid to water in the acetic acid aqueous solution of S4 is 1% w/v, the chitosan in the chitosan solution is 1% w/v, and the mass ratio of chitosan to ZIF-90 material is 1: 0.2-0.3; the rotation speed of magnetic stirring for dissolving the chitosan solution is 800-1000 rpm/min, the magnetic stirring is carried out for 2-3 hours, the rotation speed of magnetic stirring after adding the ZIF-90 material is 500-700 rpm/min, and the magnetic stirring is carried out for 1-2 hours.
7. The method for preparing the polyelectrolyte adsorption fiber composite organic frame material according to claim 1, wherein the method comprises the following steps: in S5, the mass ratio of the sodium alginate to the chitosan is 1-2: 1.
8. a polyelectrolyte adsorption fiber composite organic frame material prepared by the preparation method of any one of claims 1-7.
9. Use of the polyelectrolyte adsorption fiber composite organic frame material of claim 8 for removing Co (II) from wastewater.
10. The use according to claim 9, characterized in that: adding the prepared Co (II) stock solution and the background ion solution into a centrifuge tube to simulate the related polluted environment, adjusting the pH value by NaOH and HCl, and finally, adding an adsorption material ZIF-90@CS-SA-CMC to perform vibration adsorption for 3-4 hours to complete the adsorption process; centrifuging the centrifugal tube after the adsorption process is finished, taking supernatant, and judging the concentration of the residual Co (II) ions by an ultraviolet spectrophotometer.
CN202310697641.6A 2023-06-13 2023-06-13 Preparation method and application of polyelectrolyte adsorption fiber composite organic frame material Pending CN116688960A (en)

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