CN113289585A - Preparation method of MIL-101 and derivative material thereof for adsorbing BPA in water - Google Patents
Preparation method of MIL-101 and derivative material thereof for adsorbing BPA in water Download PDFInfo
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- 239000013177 MIL-101 Substances 0.000 title claims abstract description 38
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
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- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 8
- LMOSYFZLPBHEOW-UHFFFAOYSA-N 2,5-dichloroterephthalic acid Chemical group OC(=O)C1=CC(Cl)=C(C(O)=O)C=C1Cl LMOSYFZLPBHEOW-UHFFFAOYSA-N 0.000 claims description 4
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 claims description 4
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- 238000001179 sorption measurement Methods 0.000 abstract description 76
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 85
- 230000000694 effects Effects 0.000 description 26
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
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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]
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing MIL-101 and derivative materials thereof for adsorbing BPA in water, which comprises the steps of firstly, adding a certain amount of Cr (NO)3)3·9H2Simultaneously putting O and terephthalic acid into deionized water; placing the mixed solution in a reaction kettle to obtain a dark blue solution with the pH value of 2.58, placing the dark blue solution in a high-temperature environment at 218 ℃ for reaction, and cooling to obtain a suspension with the pH value of 0.5; separating the MOF solid by using a centrifugal machine, and washing by using water, methanol and acetone; then putting the washed solid in 20mL of N, N-dimethylformamide for ultrasonic treatment, and putting the solid in an oven for drying after the ultrasonic treatment is finished to finally obtainMIL-101 as a dark green powder. The preparation method is simple and efficient, and the obtained MIL-101 and derivative materials thereof can effectively adsorb BPA components in water and meet the adsorption requirements of various types.
Description
Technical Field
The invention relates to the technical field of BPA treatment, in particular to a preparation method of MIL-101 and derivative materials thereof for adsorbing BPA in water.
Background
At present, the industrial development speed is continuously accelerated, the environment is also damaged more and more seriously, and the water pollution treatment faces very serious challenges. Bisphenol A (BPA) is an indispensable raw material in industrial production, is generally applied to the production of products such as polycarbonate plastics and the like, has great harm to the environment, and can also have negative influence on the endocrine of human bodies. With the increasing emission of BPA in the environment, the natural environment around industrial production suffers from serious pollution, and if human bodies live in such environment for a long time, the physical health will be seriously affected. Therefore, experts and scholars in related fields at home and abroad attach great importance to the serious problems caused by the experts, and professional people detect surface water of developed countries in the western part to obtain BPA content of 10-470 ng/L, and in addition, in densely populated areas, the BPA concentration is as high as 12000 ng/L. Taking the Zhujiang river basin in China as an example, the concentration of BPA contained in the Zhujiang river basin is 40-640 ng/L, and the concentration is nearly 880ng/L in a densely populated area, such as the center of Guangzhou city.
The method for treating BPA in water is mainly an adsorption method, is beneficial to reducing the pollution risk of BPA to the environment through adsorption, and has various BPA adsorption materials, including natural materials in nature such as humic acid and the like, and also including artificially manufactured materials such as activated carbon, polyamide and the like. The main indexes for judging the adsorption function comprise adsorption rate and adsorption capacity, the active carbon in the prior art has good adsorption effect on BPA, the adsorption rate is high (the equilibrium time is less than 2d), and the saturated adsorption capacity is relatively large (42-772 mg/g), but the active carbon also has certain defects, namely the adsorption capacity is difficult to exert if the active carbon is separated from the surface of the active carbon, so that the development of a new efficient adsorption material becomes a problem to be solved.
Disclosure of Invention
The invention aims to provide a preparation method of MIL-101 and derivative materials thereof for adsorbing BPA in water, the preparation method is simple and efficient, the obtained MIL-101 and derivative materials thereof can effectively adsorb BPA components in water, the adsorption requirements of various types are met, and the improvement of a sewage adsorption and purification technology is further promoted.
The purpose of the invention is realized by the following technical scheme:
a method for preparing MIL-101 and derivatives thereof for adsorbing BPA in water, the method comprising:
and 4, placing the washed solid in 15-25ml of N, N-dimethylformamide for ultrasonic treatment, and placing the solid in an oven for drying after the ultrasonic treatment to finally obtain dark green powder, namely MIL-101.
According to the technical scheme provided by the invention, the preparation method is simple and efficient, the obtained MIL-101 and the derivative material thereof can effectively adsorb BPA (bisphenol A) components in water, meet various adsorption requirements, and further promote the improvement of a sewage adsorption purification technology, so that the sewage adsorption purification technology can better play a role in degrading phenol wastewater.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing an MIL-101 material for adsorbing BPA in water according to an embodiment of the invention;
FIG. 2 is an XRD pattern of MIL-101, MIL-101-2Cl, and MIL-101-4Cl as described in an example of the present invention;
FIG. 3 is N of three MOF materials according to an embodiment of the present invention2Schematic diagram of adsorption and desorption curves;
FIG. 4 is a schematic illustration of the effect of adsorption time on MOF adsorption of BPA according to an embodiment of the present invention;
FIG. 5 is a schematic illustration of the saturated adsorption of BPA by three MOF materials according to an embodiment of the invention;
FIG. 6 is a schematic illustration of the effect of different ion concentrations on the adsorption of BPA by three MOF materials according to an embodiment of the present invention;
FIG. 7 is a graph illustrating the effect of pH on the adsorption of three MOF materials according to an embodiment of the present invention;
FIG. 8 is a graph showing the adsorption capacity and adsorption rate of MIL-101-2Cl on BPA according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The following embodiments of the present invention will be described in further detail with reference to the accompanying drawings, and fig. 1 is a schematic flow chart of a method for preparing an MIL-101 material for adsorbing BPA in water according to the embodiments of the present invention, where the method includes:
in this step, chromium nitrate nonahydrate, Cr (NO), was used3)3·9H2The dosage of O is 1.0g and 2.5 mmol; the dosage of the terephthalic acid is 0.415g and 2.5 mmol; deionized water was used at 10 mL.
By adopting the dosage of the metal and the organic ligand, on one hand, the metal reaction can be more complete under experimental conditions, and the yield is higher compared with the ligand; on the other hand, under the environment of laboratory production, the method can be safer, more energy-saving and more efficient.
the MOF here is an abbreviation for Metal Organic Framework material (Metal Organic Framework).
in this step, the centrifuged solid material was washed 3 times with water, methanol, acetone, and placed in a fume hood.
And 4, placing the washed solid in 15-25ml of N, N-dimethylformamide for ultrasonic treatment, and placing the solid in an oven for drying after the ultrasonic treatment to finally obtain dark green powder, namely MIL-101.
In this step, the mixture may be dried in an oven at 70 ℃ for 12 hours.
Here, the MIL-101 obtained finally is a MOF adsorbing material for BPA adsorption in water, and its name is a number, and there is no specific chinese name.
In the specific implementation, in the step 1, terephthalic acid can be replaced by 2, 5-dichloroterephthalic acid, and the used amount of the 2, 5-dichloroterephthalic acid is 0.588g and 2.5mmol, so that a green powder, namely MIL-101-2Cl is finally obtained in the step 4, and the MIL-101-2Cl is a derivative material of MIL-101.
In addition, terephthalic acid can be replaced by chlorophthalic acid, and the amount of the adopted chlorophthalic acid is 0.760g and 2.5 mmol; the final result in step 4 is a pale green powder, i.e., MIL-101-4Cl, which is a derivative material of MIL-101.
A large number of experiments show that the optimal effect can be achieved under the dosage, the yield is higher, the reaction is more sufficient, and the operation is safer.
The adsorption performance of the MIL-101 and the derivative material thereof obtained in the above way is explained as follows:
1) firstly, the materials MIL-101, MIL-101-2Cl and MIL-101-4Cl obtained in the above way are characterized, as shown in FIG. 2, the XRD patterns of the MIL-101, the MIL-101-2Cl and the MIL-101-4Cl in the embodiment of the invention are shown, and according to the graph shown in FIG. 2, the diffraction peak position of the synthesized MIL-101 is the same as the conclusion of literature research, so that the purity of the prepared material can be judged to be higher. Two significant diffraction peaks occurred simultaneously at 8.9 ° and 16.3 ° for MIL-101-2Cl and MIL-101-4Cl, wherein the characteristic peak positions were not significantly changed as compared with MIL-101, and thus it was seen that the Cr atom and the O atom were smoothly coordinated. In addition, the MIL-101 crystal structure is octahedron, but MIL-101-2Cl and MIL-101-4Cl are different from MIL-101, mainly reflected in the difference of the number of Cl atoms in the ligand, and the structures of the crystal structures of the two are similar to the octahedron because the coordination is not involved.
The prepared MIL-101 is characterized in that: smooth, dense, and present a micro pore structure that is not easily found. When Cl atoms are introduced into gametes, the MIL-101-2Cl surface will become smooth and dense, but the micro pore structure still disappears. After the Cl atoms are gradually increased, the smooth surface will start to transform into a rough or even somewhat concave-convex surface, and no micro pore structure will appear. For three materialsBy comparison, it can be seen that the shape surface characteristics of the different materials are not the same, and furthermore in MIL-101-4Cl the original octahedral structure cannot be seen clearly. After synthesis of the material, the structure of the crystal is not changed by the Cl atoms, but the surface characteristics of the MOF material are changed significantly, which is considered that the radius of the Cl atoms is larger than that of the H atoms
And the adsorption effect of the materials with different surface structures is different.
FIG. 3 shows N for three MOF materials according to an embodiment of the present invention2The adsorption and desorption curve is shown in a schematic diagram, and is particularly based on the test in a nitrogen 77K environment. N of MIL-1012The absorption was 779.72cm3N/g, MIL-101-2Cl and MIL-101-4Cl2The absorption was 853.64cm respectively3G and 79.36cm3In terms of/g, it can be seen that the number of Cl atoms in the ligand is related to the N of the MOF2The absorption has an effect, eventually leading to differences in specific surface area, and the specific surface area and pore information for the three MOF materials can be derived from table 1 below:
TABLE 1
It can be known that the MIL-101-2Cl has the highest specific surface area, pore size and total pore volume, which are closely related to the surface structure, and the irregular MIL-101-4Cl material has the smallest specific surface area, which is a key factor influencing the adsorption efficiency. In addition, the pore diameters of the three materials are all around 3nm, and the three materials are usually mesoporous, which is beneficial to enhancing the adsorption capacity of the three materials.
2) Kinetics of adsorption
In an aqueous system, as shown in fig. 4, which is a schematic diagram illustrating the effect of the adsorption time on the adsorption of BPA by MOFs according to the embodiment of the present invention, it can be known from experimental results that no matter which MOF material is, the adsorption equilibrium can be reached within 10min, and as the time increases, the adsorption capacity does not change. Comparing the adsorption capacities of the three MOF materials, it was found that the adsorption capacity of MIL-101 to BPA was the greatest, since the surface micro-porous structure contributed to its adsorption. When BPA is just added, BPA can be quickly adsorbed due to sufficient quantities of material channels, functional groups and the like; over time, the adsorption sites become occupied by BPA, slowing its rate and reaching equilibrium.
The adsorption data were fitted using a quasi-primary kinetic model and a quasi-secondary kinetic model, respectively, and the results are shown in table 2 below:
TABLE 2 kinetic parameters of MOF adsorption of BPA
Based on the experimental environment, the correlation coefficient R of the quasi-second-order kinetic model2All are above 0.9995, the fitting effect is better, and the data in the table 2 show that the saturated adsorption capacity (Q) of MIL-101-2Cle) Is the largest, coinciding with its possessing the largest specific surface area.
3) Adsorption isotherm
From the water system, when the concentration of BPA is different, the adsorption effect of the MOF material is also affected to a certain extent, as shown in fig. 5, which is a schematic diagram of the saturated adsorption amount of the three MOF materials to BPA in the embodiment of the present invention, when the mass concentration of the solution is continuously increased, the adsorption effect of the three materials to BPA is also enhanced, the rate of increase gradually becomes slow, and the adsorption curve is nonlinear. As can be seen from FIG. 5, the saturated adsorption amounts of MIL-101, MIL-101-2Cl and MIL-101-4Cl were 59.64, 32.41 and 10.85mg/g, respectively, and as a result, it was found that the adsorption capacity of the MOF material gradually decreased as the number of Cl atoms increased.
4) Effect of ionic Strength on adsorption Properties
From the whole adsorption process, it can be known that other ions have important influence on the adsorption effect of the MOF material, and firstly, other ions and adsorbates compete for adsorption sites, so that the adsorption effect is finally weakened; and secondly, the effective collision efficiency can be optimized and improved to a certain extent, and the adsorption effect is enhanced. From the perspective of a water system, as shown in fig. 6, which is a schematic diagram of the effect of different ion concentrations on the adsorption of BPA by three MOF materials according to the embodiment of the present invention, MIL-101-4Cl cannot effectively exert its effect under the coverage of ionic strength, and is difficult to adsorb; from the viewpoint of MIL-101 and MIL-101-2Cl, if the ionic strength is increased, the adsorption effect of both materials on BPA will be improved, but the adsorption effect of MIL-101-2Cl is better than that of MIL-101.
5) Influence of pH on adsorption Properties
The pH value of the solution changes the existing state and the charging condition of the contaminants, and finally affects the adsorption of the MOF on the contaminants, as shown in fig. 7, a schematic diagram of the adsorption effect of the pH value on three MOF materials according to the embodiment of the present invention is shown, and it can be known from fig. 7 that: when the pH value is increased, the adsorption effect of MOF on BPA is weakened, and when the three MOF materials are compared, the adsorption effect of MIL-101-4Cl is poor all the time. However, when the MIL-101-2Cl is present in a slightly acidic (pH <6) or slightly basic (pH >9) aqueous solution, the adsorption effect of the MIL-101-2Cl is obviously better than that of the MIL-101, and particularly in a strong alkaline environment, the adsorption efficiency is remarkably over three times. The pH value is changed, the adsorption effect of the MIL-101-2Cl can be improved, and for industrial wastewater with high concentration BPA and high pH value, the modified MIL-101-2Cl material can be used for treating the wastewater, so that the treatment efficiency is improved, and the cost is reduced.
Further researching the adsorption effect of the MIL-101-2Cl material on BPA in a strongly alkaline aqueous solution, preparing an alkaline BPA solution with the pH of 12, as shown in FIG. 8, which is a schematic diagram of the adsorption capacity and the adsorption rate of the MIL-101-2Cl on BPA according to the embodiment of the present invention, through the investigation of the adsorption time and different concentrations, the maximum adsorption amount is found to be 134mg/g, and the adsorption equilibrium can be reached within 10 min. In our life, the alkaline wastewater has wide sources and contains a large amount of organic matters, BPA is one of the alkaline wastewater, and the alkaline wastewater is settled by an acid precipitation method at present, but a large amount of chemicals are consumed, and the operation cost is high. The MIL-101-2Cl provided by the embodiment of the invention can effectively remove BPA in an alkaline solution, is simple to operate, is energy-saving and environment-friendly, and has a good reference value for treating alkaline wastewater.
In conclusion, the MIL-101 and the derivative material thereof prepared by the embodiment of the invention have the advantages of obvious BPA adsorption effect, high efficiency and wide application range, and are beneficial to phenol wastewater treatment, so that the adsorption requirements of various types are met, and the improvement of a sewage adsorption and purification technology is promoted.
It is noted that those skilled in the art will recognize that embodiments of the present invention are not described in detail herein.
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 changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. A method for preparing MIL-101 and derivatives thereof for adsorbing BPA in water, comprising:
step 1, simultaneously putting a certain amount of chromium nitrate nonahydrate and terephthalic acid into deionized water, and carrying out ultrasonic dissolution on the chromium nitrate nonahydrate and the terephthalic acid;
step 2, placing the mixed solution obtained in the step 1 in a reaction kettle to obtain a dark blue solution with the pH value of 2.58, placing the dark blue solution in a high-temperature environment of 215-220 ℃ for reacting for 18-20h, and naturally cooling the solution after the reaction is finished to obtain an MOF suspension with the pH value of 0.5;
step 3, separating the MOF suspension by using a centrifugal machine, washing by using water, methanol and acetone, and removing supernatant acetone;
and 4, placing the washed solid in 15-25ml of N, N-dimethylformamide for ultrasonic treatment, and placing the solid in an oven for drying after the ultrasonic treatment to finally obtain dark green powder, namely MIL-101.
2. The method for preparing MIL-101 and derivative materials thereof for adsorbing BPA in water as claimed in claim 1, wherein in step 1, chromium nitrate nonahydrate, Cr (NO) is used3)3·9H2The dosage of O is 1.0g and 2.5 mmol; the dosage of the terephthalic acid is 0.415g and 2.5 mmol; deionized water was used at 10 mL.
3. The method for preparing MIL-101 and derivatives thereof for adsorbing BPA in water according to claim 1, wherein in step 1, terephthalic acid is replaced with 2, 5-dichloroterephthalic acid, and 2, 5-dichloroterephthalic acid is used in an amount of 0.588g, 2.5 mmol;
the final result in step 4 is a green powder, namely MIL-101-2 Cl.
4. The method for preparing the MIL-101 and derivative materials thereof for adsorbing BPA in water as claimed in claim 1, wherein in the step 1, terephthalic acid is replaced by chlorophthalic acid, and the amount of the chlorophthalic acid used is 0.760g and 2.5 mmol;
the final result in step 4 is a pale green powder, namely MIL-101-4 Cl.
5. The method for preparing MIL-101 and derivative materials thereof for adsorbing BPA in water as claimed in claim 1, wherein in step 3, the centrifuged solid matter is washed 3 times with water, methanol, acetone and placed in a fume hood.
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