CN112121651A - Tannic acid modified La-Zn (4, 4' -dipy) (OAc)2/BC composite membrane, preparation and application - Google Patents
Tannic acid modified La-Zn (4, 4' -dipy) (OAc)2/BC composite membrane, preparation and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The invention discloses a tannin modified La-Zn (4,4 '-dipy) (OAc)2/BC composite membrane, preparation and application thereof, wherein the preparation method comprises the steps of immersing the tannin modified BC membrane into MOFs raw material liquid, reacting for 24 +/-2 h, washing and drying the obtained composite membrane for multiple times by using methanol, placing the composite membrane into acetonitrile solution of lanthanum nitrate, refluxing for 2 +/-0.5 h at the temperature of 80 +/-5 ℃, finally washing for multiple times by using methanol and drying to obtain the tannin modified La-Zn (4, 4' -dipy) (OAc)2/BC composite membrane. The MOFs raw material liquid contains zinc acetate dihydrate with the concentration of 4.4 mg/mL-5.0 mg/mL and 4, 4' -bipyridyl with the concentration of 1.5 mg/mL-2.0 mg/mL. The tannin modified La-Zn (4, 4' -dipy) (OAc) prepared by the invention2the/BC composite membrane has specific adsorption effect and higher adsorption capacity on total phosphorus and ammonia nitrogen in water.
Description
Technical Field
The invention belongs to the technical field of adsorption material and material preparation and separation, and particularly relates to tannic acid modified La-Zn (4, 4' -dipy) (OAc)2a/BC composite membrane, preparation and application thereof.
Background
With the global warming and the aggravation of human activities, the eutrophication phenomenon of the water body is increasingly aggravated, and the ecological system and the water function of the water body are inhibited and destroyed. The main reason for the eutrophication of water is that a large amount of pollutants containing nitrogen, phosphorus and other nutrients enter the water. How to effectively remove the total phosphorus and ammonia nitrogen in water plays a key role in preventing water eutrophication. At present, methods for removing total phosphorus mainly comprise a biological removal process, an aluminum or ferrous salt chemical precipitation method, a crystallization method, an ion exchange method, an adsorption method and the like, and methods for removing ammonia nitrogen in water comprise a stripping method, a breakpoint chlorination method, an ion exchange method, an adsorption method and the like. Among them, the adsorption method is considered to be a simple and efficient method for removing total phosphorus and ammonia nitrogen in water because of its low cost, high and stable removal effect, simple design and easy operation.
The prior adsorbing material used for adsorbing the total phosphorus in the water body can be divided into three types of natural materials, waste residues, activated alumina and modified substances thereof and artificially synthesized materials, the adsorption capacity of the first two types of materials is generally low, and the artificially synthesized efficient phosphorus removal agent becomes the latest research direction of people. In recent years, Metal Organic Frameworks (MOFs) have become one of the hot materials for research and application in the field of adsorption and separation due to their specific advantages, such as high specific surface area, high hydrothermal stability, and stable structure.
The metal-organic framework compound generally refers to a metal-organic framework crystal material with a periodic network structure formed by an organic ligand and metal ions through a self-assembly process, combines the characteristics of a high polymer and a coordination compound, and is different from a common organic polymer and an inorganic polymer of Si-O class. As the number and coordination mode of inorganic units and organic ligands are diversified, the MOFs material has the characteristics of various types and complex structure. The MOFs material has the advantages of various structural types, large porosity and specific surface area, strong designable and controllable structure and chemical functionality, convenient post-modification and the like, and has wide application prospect in the field of adsorption and separation.
The bacterial cellulose is natural cellulose without any impurities, and has a plurality of unique properties such as fine network structure, higher mechanical strength, higher water absorption and retention performance, good biocompatibility and biodegradability. Therefore, the cellulose with the best performance and the highest use value is considered to be one of the hot spots of international biomaterial research at present. Therefore, in recent years, cellulose has been widely used for matrix studies of the adsorbent, and has an excellent adsorption effect. Researches prove that the MOFs material is suitable for application in different fields based on bacterial cellulose membrane composite materials.
Disclosure of Invention
The invention provides a tannin modified La-Zn (4, 4' -dipy) (OAc) based on rare earth element lanthanum (La), tannin, MOFs material and bacterial cellulose membrane (also called BC membrane)2A/BC composite membrane and preparation thereof, based on the methodThe obtained tannin modified La-Zn (4, 4' -dipy) (OAc)2the/BC composite membrane has specific adsorption effect and higher adsorption capacity on total phosphorus and ammonia nitrogen in water.
The technical scheme of the invention is as follows: tannin modified La-Zn (4, 4' -dipy) (OAc)2The preparation method of the/BC composite membrane comprises the following steps:
(1) soaking the BC cellulose membrane in a tannic acid aqueous solution, replacing the tannic acid aqueous solution once every 12 +/-2 hours for 6 +/-1 times in total, then washing with deionized water, then washing with ethanol, and finally drying in vacuum to obtain the tannic acid modified BC cellulose membrane;
(2) firstly weighing the tannin modified BC cellulose membrane prepared in the step (1), then adding the BC cellulose membrane into MOFs raw material liquid, reacting for 24 +/-2 hours, washing and drying the obtained composite membrane for multiple times by using methanol, and then placing the composite membrane in La (NO)3)3Refluxing in acetonitrile solution at 80 + -5 deg.C for 2 + -0.5 h, washing with methanol for several times, and drying to obtain the tannin-modified La-Zn (4, 4' -dipy) (OAc)2a/BC composite membrane;
the concentration of the aqueous solution of the tannic acid in the step (1) is 5 mg/mL-15 mg/mL;
the MOFs raw material liquid in the step (2) is a mixed solution of methanol and water in which zinc acetate dihydrate and 4,4 '-bipyridyl are uniformly dispersed, the concentration of the zinc acetate dihydrate in the MOFs raw material liquid is 4.4 mg/mL-5.0 mg/mL, and the concentration of the 4, 4' -bipyridyl is 1.5 mg/mL-2.0 mg/mL;
la (NO) described in step (2)3)3In acetonitrile of La (NO)3)3The concentration of (b) is 0.023g/mL to 0.025 g/mL.
The invention has the technical advantages that:
(1) inspired by natural adhesion of biological mussels, tannin is utilized to construct a bionic membrane adsorption material to prepare tannin modified La-Zn (4, 4' -dipy) (OAc)2A/BC composite membrane.
(2) Modification of La-Zn (4, 4' -dipy) (OAc) with tannic acid2the/BC composite membrane has specific selective adsorption capacity to total phosphorus and ammonia nitrogen.
Drawings
Fig. 1 is a graph of penetration.
FIG. 2 shows Zn (4, 4' -dipy) (OAc) produced by an example of the present invention2And La-Zn (4, 4' -dipy) (OAc)2XRD pattern of (a).
FIG. 3 shows BC, Zn (4, 4' -dipy) (OAc) prepared by an example of the present invention2、La-Zn(4,4’-dipy)(OAc)2And La-Zn (4, 4' -dipy) (OAc)2FT-IR plot for/BC.
FIG. 4 shows Zn (4, 4' -dipy) (OAc) produced by an example of the present invention2And La-Zn (4, 4' -dipy) (OAc)2TG/DTG pattern of (g).
Detailed Description
The invention is described in more detail below with reference to the following examples:
1. tannin modified La-Zn (4, 4' -dipy) (OAc) for use in pH, adsorption isotherm, adsorption kinetics and dynamic adsorption experiments2the/BC composite membrane was prepared in example 1.
2. The tannin modified La-Zn (4, 4' -dipy) (OAc) prepared by the invention2Compared with the similar products in the prior art, the/BC composite membrane has the technical advantages of greenness, rapidness, low cost and the like.
Example 1:
(1) separately weighing 5mL of methanol and 5mL of distilled water, and weighing Zn (OCOCH)3)2·2H2And placing O and 4,4 '-bipyridyl into a mixed solution of methanol/water, and stirring for 15min to uniformly mix the O and the 4, 4' -bipyridyl to obtain MOFs raw material liquid with the concentrations of zinc acetate dihydrate and 4, 5mg/mL and 1.5mg/mL respectively.
(2) 0.2g of BC cellulose membrane is soaked in 10mL of 4.8mg/mL tannic acid solution, the tannic acid solution is replaced every 12h for 6 times in total, and the BC cellulose membrane is washed by deionized water and ethanol and then dried in vacuum at 60 ℃ for 12h to prepare the tannic acid modified BC cellulose membrane.
(3) Placing the tannin modified BC cellulose membrane obtained in the step (2) into the MOFs raw material solution obtained in the step (1), placing the BC cellulose membrane and the MOFs raw material solution together in a polytetrafluoroethylene reaction kettle for reacting for 24 hours, washing and drying the obtained composite membrane for multiple times by using methanol, and then placing the composite membrane in La (NO)3)3Mixed solution of acetonitrile (nitre)Lanthanum acid concentration of 23mg/mL) at 80 deg.C for 2h, washing with methanol for multiple times, and drying to obtain tannin-modified La-Zn (4, 4' -dipyry) (OAc)2A/BC composite membrane.
Example 2
(1) Separately weighing 5mL of methanol and 5.1mL of distilled water, and weighing Zn (OCOCH)3)2·2H2And placing O and 4,4 ' -bipyridyl into a mixed solution of methanol/water, and stirring for 15min to uniformly mix the O and the 4,4 ' -bipyridyl to obtain MOFs raw material liquid with the concentrations of zinc acetate dihydrate and 4,4 ' -bipyridyl being 4.7mg/mL and 1.5mg/mL respectively.
(2) Soaking the cellulose membrane of 0.3gBC in 10mL of 4.9mg/mL tannic acid solution, replacing the tannic acid solution once every 12h for 6 times in total, washing with deionized water and ethanol, and vacuum drying at 60 ℃ for 12h to obtain the tannic acid modified BC cellulose membrane.
(3) Placing the tannin modified BC cellulose membrane obtained in the step (2) into the MOFs raw material liquid obtained in the step (1), placing the mixture into a polytetrafluoroethylene reaction kettle for reaction for 24 hours, washing the obtained composite membrane for multiple times by using methanol, drying, and placing the membrane in La (NO)3)3Refluxing the mixed solution with acetonitrile (lanthanum nitrate concentration of 25mg/mL) at 80 deg.C for 2h, washing with methanol for several times, and drying to obtain tannin-modified La-Zn (4, 4' -dipy) (OAc)2A/BC composite membrane.
Example 3
(1) Separately weighing 5mL of methanol and 5.2mL of distilled water, and weighing Zn (OCOCH)3)2·2H2And placing O and 4,4 ' -bipyridyl into a mixed solution of methanol/water, and stirring for 15min to uniformly mix the O and the 4,4 ' -bipyridyl to obtain MOFs raw material liquid with the concentrations of zinc acetate dihydrate and 4,4 ' -bipyridyl being 4.6mg/mL and 1.7mg/mL respectively.
(2) The 0.1gBC cellulose membrane was soaked in 10mL of 5mg/mL tannic acid solution, the tannic acid solution was changed every 12h for a total of 6 changes, the tannic acid modified BC cellulose membrane was washed with deionized water and ethanol and vacuum dried at 60 ℃ for 12 h.
(3) Placing the tannin modified BC cellulose membrane obtained in the step (2) into the MOFs raw material liquid obtained in the step (1), placing the mixture in a polytetrafluoroethylene reaction kettle together for reaction for 24 hours, and obtaining the composite membraneWashing with methanol for several times, drying, and purifying with La (NO)3)3Refluxing the mixed solution with acetonitrile (lanthanum nitrate concentration of 23mg/mL) at 80 deg.C for 2h, washing with methanol for several times, and drying to obtain tannin-modified La-Zn (4, 4' -dipy) (OAc)2A/BC composite membrane.
The tannic acid-modified La-Zn (4, 4' -dipy) (OAc)2Application of/BC composite membrane in adsorption of total phosphorus (TP for short) and ammonia nitrogen (NH for short) in water4-N+)。
(1) pH: by NH4Cl and KH2PO4Preparation of NH4-N+And a binary mixed solution having TP concentrations of 100mg/L each, each with H2SO4Adjusting pH of the solution to 2.0, 4.0, 6.0, adjusting pH of the solution to 7.0, 8.0, 10.0, 12.0 with NaOH, collecting 10mL of the pH-adjusted binary solution, and adding 10mg of tannic acid modified La-Zn (4, 4' -dipy) (OAc)2The membrane was subjected to the/BC complex and shaken at 298K for 24 hours. The concentrations of ammonia nitrogen and total phosphorus in water are respectively measured by a Nashin reagent colorimetric method and an ammonium molybdate spectrophotometry. The test results are: tannic acid modified La-Zn (4, 4' -dipy) (OAc)2The total phosphorus removal amount of the/BC composite membrane at the balance of pH 2, 4, 6, 7, 8, 10 and 12 is respectively 6.82mg/g, 8.21mg/g, 9.41mg/g, 28.45mg/g, 26.82mg/g, 11.21mg/g and 15.90mg/g, and the ammonia nitrogen removal amount is respectively about 18.20mg/g, 25.12mg/g, 25.84mg/g, 33.11mg/g, 31.0mg/g, 20.41mg/g and 21.54 mg/g.
(2) Adsorption isotherm: formulations of 10, 50, 100, 150, 250, 350, 500, 800 and 1000mg/L NH4-N+Solution, TP solution and NH4-N+And TP, and 10mg of tannic acid-modified La-Zn (4, 4' -dipy) (OAc)2And carrying out a/BC composite membrane, oscillating for 24 hours at 298K, and measuring the concentrations of ammonia nitrogen and total phosphorus in the water respectively by a Nashin reagent colorimetric method and an ammonium molybdate spectrophotometry. The test results are: tannic acid modified La-Zn (4, 4' -dipy) (OAc)2The saturated adsorption capacity of the/BC composite membrane to total phosphorus and ammonia nitrogen is about 370.94mg/g and 466.33mg/g respectively.
(3) Adsorption kinetics: taking NH4-N+And TP concentrations each of350mg/L of binary mixed solution, after adjusting pH to 7.0, 10mL of the solution was taken, and 10mg of tannic acid-modified La-Zn (4, 4' -dipy) (OAc)2the/BC composite membrane was immersed therein and the concentrations of remaining ammonia nitrogen and total phosphorus in water at 5, 10, 30, 60, 120, 180, 240, 360, 420, 540, 600 and 600min were measured at 298K. The test result is that the tannin is modified La-Zn (4, 4' -dipy) (OAc)2The first 120min within the composite membrane/BC absorbs NH in water4-N+And TP adsorption amount rapidly increased to 133.83mg/g and 126.08mg/g, and tannic acid modified La-Zn (4, 4' -dipy) (OAc) when adsorption time was between 120-360min2/BC composite membrane for NH in water4-N+And the adsorption capacity of TP is slowly increased, the adsorption capacity of the composite membrane tends to be balanced after 360min, and the adsorption capacity of the adsorbent tends to be saturated gradually. Tannic acid modified La-Zn (4, 4' -dipy) (OAc)2The kinetics of the total phosphorus and ammonia nitrogen removal of the/BC composite membrane is more consistent with a quasi-second-order kinetics model (R)2＝0.99)。
(4) Dynamic adsorption experiment: preparation of NH4-N+And a binary mixed solution having a TP concentration of 50mg/L each, and adding the NH4-N+The binary mixed solution of TP and La-Zn (4, 4' -dipy) (OAc) was modified with tannic acid having a diameter of 3cm at a flow rate of 0.0062L/min2A/BC composite membrane. Samples are taken every hour, and the concentrations of ammonia nitrogen and total phosphorus in the liquid after the liquid passes through the composite membrane are respectively measured. The test results are: see FIG. 1(a is a breakthrough curve for adsorbing ammonia nitrogen, b is a breakthrough curve for adsorbing total phosphorus), tannic acid modified La-Zn (4, 4' -dipy) (OAc)2/BC composite membrane pair NH4-N+And TP adsorption occurred at breakthrough points (when efflux concentration Ct (La-Zn (4, 4' -dipy) was modified by tannic acid) (OAc)2NH in liquid after/BC composite membrane4-N+Or TP concentration) to an initial concentration C0(modification of La-Zn (4, 4' -dipy) (OAc) by tannic acid)2NH in liquid before/BC composite membrane4-N+Or TP concentration) of 5% of the corresponding penetration curve is then called the penetration point). The endpoint of the breakthrough curve was taken at the inflection point near the upper end of the sigmoidal curve for the initial concentration, so the breakthrough curve reached at 480minThe end point is that the composite membrane is applied to NH in water under the conditions that the initial concentration is 50mg/L and the flow rate is 0.0062L/min4-N+And the penetration time of the TP was 8 hours. Tannic acid modified La-Zn (4, 4' -dipy) (OAc)2the/BC composite membrane has specific selective adsorption capacity to total phosphorus and ammonia nitrogen.
Consisting of Zn (4, 4' -dipy) (OAc) of FIG. 22And La-Zn (4, 4' -dipy) (OAc)2The XRD pattern of (A) shows that: at 2 θ ═ 6 °, Zn (4, 4' -dipy) (OAc)2Higher peak intensities occur, where the peak intensities belong to Zn2+La-Zn (4, 4' -dipy) (OAc) modified by rare earth element lanthanum2The peak intensity at 6 ° 2 θ is significantly reduced and a new characteristic peak appears between 30 ° and 40 ° 2 θ, which all indicate the effective loading of the rare earth element lanthanum.
The right panel 3 is Zn (4, 4' -dipy) (OAc)2And La-Zn (4, 4' -dipy) (OAc)2The FT-IR chart of (A) shows Zn (4, 4' -dipy) (OAc)2And La-Zn (4, 4' -dipy) (OAc)2In particular, at 3430cm-1Nearby appearance of-NH2Is a broad and strong characteristic peak of Zn (4, 4' -dipy) (OAc)2Characteristic peak of organic ligand 4, 4' -bipyridine in material. The material after rare earth element lanthanum intercalation is 1360cm-1Has an increased peak intensity at 1560cm-1A special vibration of the nitrate anion occurred, indicating an effective encapsulation of La element.
See FIG. 4 for Zn (4, 4' -dipy) (OAc) prepared in the examples of the present invention2And La-Zn (4, 4' -dipy) (OAc)2TG/DTG pattern of (a is Zn (4, 4' -dipy) (OAc)2TG/DTG map of (1); b is La-Zn (4, 4' -dipy) (OAc)2TG/DTG diagram) of (A), it can be known that when the MOFs material is doped with lanthanum, which is a rare earth element, the mass loss ratio Zn (4, 4' -copy) (OAc)2To increase by 20%, the doping of lanthanum element increases the thermal stability of the MOFs material. FIG. 4, graph a, shows that the MOFs are decomposed in three stages, the first stage is Zn (4, 4' -dipy) (OAc) when the temperature is raised to 100 ℃2The decomposition is started, at which point the mass is reduced by about 6%, the second stage at 187 ℃ at 112-At 187-. As shown in b in FIG. 4, La-Zn (4, 4' -dipy) (OAc)2The decomposition process at a heating rate of 10 ℃/min is also divided into three stages, 48-155 ℃, 155-.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Claims (5)
1. Tannin modified La-Zn (4, 4' -dipy) (OAc)2The preparation method of the/BC composite membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) soaking the BC cellulose membrane in a tannic acid aqueous solution, replacing the tannic acid aqueous solution once every 12 +/-2 hours for 6 +/-1 times in total, then washing with deionized water, then washing with ethanol, and finally drying in vacuum to obtain the tannic acid modified BC cellulose membrane;
(2) firstly weighing the tannin modified BC cellulose membrane prepared in the step (1), then adding the BC cellulose membrane into MOFs raw material liquid, reacting for 24 +/-2 hours, washing and drying the obtained composite membrane for multiple times by using methanol, and then placing the composite membrane in La (NO)3)3Refluxing in acetonitrile solution at 80 + -5 deg.C for 2 + -0.5 h, washing with methanol for several times, and drying to obtain the tannin-modified La-Zn (4, 4' -dipy) (OAc)2a/BC composite membrane;
the MOFs raw material liquid in the step (2) is a mixed solution of methanol and water in which zinc acetate dihydrate and 4,4 '-bipyridyl are uniformly dispersed, the concentration of the zinc acetate dihydrate in the MOFs raw material liquid is 4.4 mg/mL-5.0 mg/mL, and the concentration of the 4, 4' -bipyridyl is 1.5 mg/mL-2.0 mg/mL.
2. The tannin modified La-Zn (4, 4' -dipy) (OAc) of claim 12The preparation method of the/BC composite membrane is characterized by comprising the following steps: the concentration of the aqueous solution of the tannic acid in the step (1) is 5 mg/mL-15 mg/mL.
3. The tannin modified La-Zn (4, 4' -dipy) (OAc) of claim 12The preparation method of the/BC composite membrane is characterized by comprising the following steps: la (NO) described in step (2)3)3In acetonitrile of La (NO)3)3The concentration of (b) is 0.023g/mL to 0.025 g/mL.
4. Tannin modified La-Zn (4, 4' -dipy) (OAc)2the/BC composite membrane is characterized in that: modification of La-Zn (4, 4' -dipy) (OAc) by tannic acid of any one of claims 1 to 32The preparation method of the/BC composite membrane.
5. The tannin modified La-Zn (4, 4' -dipy) (OAc) of claim 42the/BC composite membrane is used for adsorbing ammonia nitrogen and total phosphorus in water.
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Cited By (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112871146A (en) * | 2021-01-14 | 2021-06-01 | 常州大学 | Bifunctional metal-organic framework material modified composite membrane and preparation method and application thereof |
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| WO2023218225A1 (en) * | 2022-05-12 | 2023-11-16 | Polybion, S.L. | Composite material comprising polyurethane and tanned bacterial cellulose, and method for manufacturing the same |
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