CN112121767A - Hydrophobic MIL-53-Al for VOCs adsorption and preparation method thereof - Google Patents

Hydrophobic MIL-53-Al for VOCs adsorption and preparation method thereof Download PDF

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CN112121767A
CN112121767A CN202010981363.3A CN202010981363A CN112121767A CN 112121767 A CN112121767 A CN 112121767A CN 202010981363 A CN202010981363 A CN 202010981363A CN 112121767 A CN112121767 A CN 112121767A
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hydrophobic
vocs
adsorption
preparation
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CN112121767B (en
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刘庆岭
史佳琦
付凯旋
韩瑞
吕双春
宋春风
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention belongs to the field of VOCs treatment, and particularly relates to hydrophobic MIL-53-Al for VOCs adsorption and a preparation method thereof. The preparation method adopts a self-assembly method, and comprises the steps of dissolving N-tetradecyl phosphoric acid in absolute ethyl alcohol to form a clear solution, then adding activated MIL-53-Al powder, standing, stirring for 5min every 2h, fully mixing, reacting for a period of time, filtering the obtained product, centrifugally washing, and drying in vacuum to obtain the hydrophobic MIL-53-Al. The whole preparation process is simple and easy to implement, is mild and friendly to environment, does not need a precise instrument, and the modified MIL-53-Al shows excellent acetone adsorption selectivity under high relative humidity, so that the method has wide application prospect in industrial production for adsorbing water-containing VOCs.

Description

Hydrophobic MIL-53-Al for VOCs adsorption and preparation method thereof
Technical Field
The invention belongs to the field of VOCs treatment, and particularly relates to hydrophobic MIL-53-Al for VOCs adsorption and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) such as benzene, toluene, acetone, trichloroethylene and the like discharged from various industries have harmful effects (such as carcinogenic effect) on human health, and can cause stratospheric ozone consumption, photochemical smog and the formation of some toxic byproducts, thereby bringing serious threats to the ecological environment. Due to these negative effects, VOCs are of great interest in the field of environmental control.
Currently, various pollution control technologies for VOCs have been developed, including condensation, adsorption, catalytic oxidation, and incineration, wherein adsorption of VOCs using porous adsorbents is considered to be an economical and efficient treatment process. The key to the adsorption process is the type and nature of the adsorbent. Among a plurality of adsorbing materials, metal organic framework Materials (MOFs) have wide application prospects in the field of VOCs adsorption due to large specific surface area, rich porosity, various framework structures and easily-modified surface properties. However, most MOFs have strong hydrophilicity, and their ability to remove VOCs in a wet gas stream is limited in view of the inevitable presence of water vapor in industrial processes and the competitive adsorption with organic contaminants. Therefore, the development of hydrophobic MOFs material has important significance for the adsorption removal of VOCs in actual polluted airflow.
Disclosure of Invention
The invention aims to provide hydrophobic MIL-53-Al for adsorbing VOCs and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of hydrophobic MIL-53-Al for VOCs adsorption comprises the steps of dissolving N-tetradecylphosphoric acid in absolute ethyl alcohol by a self-assembly method, stirring to obtain a clear solution, adding activated MIL-53-Al powder, standing, and stirring for 5min every 2h to fully mix. After reacting for a period of time, filtering the obtained product, and obtaining the hydrophobic MIL-53-Al after centrifugal washing and vacuum drying.
The activation process of the ground MIL-53-Al comprises the steps of placing the MIL-53-Al in a muffle furnace for roasting and activating, wherein the roasting temperature is 250-450 ℃, and the roasting time is 1-3 h.
The mol ratio of the activated MIL-53-Al to the N-tetradecyl phosphoric acid is 2-10: 1.
The reaction time of the activated MIL-53-Al and the N-tetradecyl phosphoric acid is 6-20 h.
Preferably, the reaction time of the activated MIL-53-Al and the N-tetradecyl phosphoric acid is 12 hours, and the molar ratio of the activated MIL-53-Al to the N-tetradecyl phosphoric acid is 10: 1.
The application also comprises hydrophobic MIL-53-Al for absorbing VOCs, which is obtained by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the MIL-53-Al takes low-cost, light and non-toxic metal aluminum as a central atom, is economical and environment-friendly in synthesis, has larger specific surface area and excellent thermal stability, and is a good candidate material as a VOCs adsorbent. And the N-tetradecyl phosphoric acid not only has a longer hydrophobic alkyl chain, but also can be coordinated with aluminum to form a strong Al-O-P bond, so that the N-tetradecyl phosphoric acid is grafted to a framework of MIL-53-Al through a self-assembly process, and the material is endowed with remarkably enhanced water resistance. The whole preparation process is simple and easy to implement, is mild and friendly to environment, and does not need to use a precise instrument. More importantly, the hydrophobically modified material (MIL-53-Al @ C)14) The acetone dynamic adsorption performance is hardly influenced by moisture, and the composite adsorbent has excellent cyclic usability and regenerability under high relative humidity, and has wide application prospect in adsorbing water-containing VOCs in actual industry.
Drawings
FIG. 1 shows MIL-53-Al @ C as a sample in example 114-XRD spectrum of 1 and original MIL-53-Al;
FIG. 2 shows MIL-53-Al @ C as a sample in example 114-1 and the static water uptake profile of the original MIL-53-Al;
FIG. 3 shows MIL-53-Al @ C as a sample in example 114-1 and raw MIL-53-Al acetone dynamic adsorption profiles at different relative humidities;
FIG. 4 shows MIL-53-Al @ C as a sample in example 114Graph of acetone adsorption capacity 10 cycles at 90% RH.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.
Example 1: a0.8 g MIL-53-Al powder sample is weighed and placed in a muffle furnace to be roasted for 2.5h at 330 ℃ for standby. 0.11g N-tetradecylphosphonic acid was weighed in a ratio of 10:1 (MIL-53-Al: N-tetradecylphosphonic acid after activation, molar ratio), dissolved in absolute ethanol and stirred at room temperature for 30min to form a clear solution. Adding activated MIL-53-Al into the solution, and standing. Thereafter, the reaction mixture was stirred every 2 hours for 5min to mix well. Filtering the solid product after 12h, washing with anhydrous ethanol for 3 times by centrifugation, and vacuum drying to obtain hydrophobic MIL-53-Al, labeled MIL-53-Al @ C14-1。
MIL-53-Al@C14XRD spectra of-1 and original MIL-53-Al are shown in figure 1, and it can be seen that after the introduction of N-tetradecylphosphoric acid, the characteristic diffraction peak of Al-MOF is retained, which indicates that the framework structure of the material still remains intact, but the position of the peak is slightly shifted to the right, and probably the introduction of N-tetradecylphosphoric acid leads to the reduction of interplanar distance. In addition, the peak shape of each diffraction peak is sharp, which also indicates that the crystallinity of the modified material is good.
FIG. 2 shows MIL-53-Al @ C14The static water absorption of-1 and original MIL-53-Al, the material before modification has certain hydrophilicity, and the static water absorption is 9.07%. After N-tetradecylphosphoric acid is introduced into the framework, the static water absorption capacity of the sample is only 2.49 percent, and is reduced by 72.55 percent, which shows that the hydrophobicity is enhanced.
FIG. 3 shows MIL-53-Al @ C14The acetone dynamic adsorption amounts of-1 and the original MIL-53-Al under different relative humidities, and the saturated adsorption amounts of MIL-53-Al to acetone are respectively reduced by 28.45%, 44.90% and 62.95% in the process that the humidity is gradually increased from 0% RH to 90% RH. And the presence of moisture to MIL-53-Al @ C14The effect of-1 adsorption of acetone is very slight, even if the humidity reaches 90% RH,the acetone adsorption amount is not reduced, so that the material grafted with the N-tetradecylphosphoric acid by the self-assembly method has excellent hydrophobicity and acetone adsorption selectivity.
FIG. 4 shows MIL-53-Al @ C 141 acetone adsorption capacity at 90% RH for 10 cycles. MIL-53-Al @ C14-1 maintained a very stable dynamic adsorption capacity for at least 10 cycles, the acetone adsorption capacity of the material did not decrease at all after 10 cycles, fluctuated only within a very small range (1-2mg/g), exhibiting excellent cyclability and reproducibility.
Example 2
The reaction time of the activated MIL-53-Al and N-tetradecylphosphoric acid was shortened to 6 hours, and the rest of the procedure was the same as in example 1. The resulting sample MIL-53-Al @ C14-2 dynamic adsorption of acetone in a dry atmosphere of 132.64mg/g vs MIL-53-Al @ C14The ratio of-1 is improved, which shows that the reaction time is shortened, so that the grafting amount of the alkyl phosphoric acid is reduced, the influence on the pore structure of the material is small, and the adsorption performance is enhanced. But the hydrophobicity was poor compared to the sample in example 1 and the static water uptake increased to 4.32%.
Example 3
The reaction time of MIL-53-Al and N-tetradecylphosphoric acid after activation was extended to 20 hours, and the procedure was the same as in example 1. The resulting sample MIL-53-Al @ C14The dynamic adsorption capacity of-3 to acetone under dry conditions decreased to 104.21mg/g, indicating that the reaction time increased with more alkylphosphoric acid grafted onto the MIL-53-Al backbone, the porosity and specific surface area of the starting material decreased and the adsorption capacity to acetone decreased, but the sample showed better hydrophobicity with a static water absorption of 1.85%.
Example 4
The molar ratio of MIL-53-Al to N-tetradecylphosphoric acid after activation was changed from 10:1 to 15:1, and the procedure was otherwise the same as in example 1. The resulting sample MIL-53-Al @ C14The acetone adsorption capacity of-4 at RH 0% is only slightly increased to 126.99mg/g, while the hydrophobicity is obviously weakened and the static water absorption capacity is increased to 3.86%.
Example 5
The molar ratio of MIL-53-Al to N-tetradecylphosphoric acid after activation was changed from 10:1 to 2:1, and the procedure was otherwise the same as in example 1. The resulting sample MIL-53-Al @ C14The dynamic adsorption capacity of-5 to acetone is only 24.56mg/g, which shows that the use of alkyl phosphoric acid in this case is too much, and most of the pores of MIL-53-Al are blocked after grafting, and the adsorption performance is greatly reduced, but the sample shows the best hydrophobicity, and the static water absorption capacity is only 1.34%.
Comparative example 1:
n-octadecyl phosphate with a longer carbon chain was selected as the hydrophobic reagent for modification, and the remaining steps and conditions were the same as in example 1. The resulting sample MIL-53-Al @ C18-1 dynamic adsorption of acetone 100.36mg/g, with MIL-53-Al @ C14The reduction was 18.75% compared to-1. Meanwhile, the hydrophobicity of the sample is weaker than that of MIL-53-Al @ C14Static water uptake increased to 3.82% 1. This is probably due to the greater steric hindrance of the n-octadecyl phosphate and the lower degree of grafting on the MIL-53-Al skeleton.
Comparative example 2
N-dodecyl phosphate with a relatively short carbon chain is further selected as a hydrophobic reagent for modification, and the rest steps and conditions are the same as those in example 1. The resulting sample MIL-53-Al @ C12The dynamic adsorption capacity of the-1 to acetone is 116.59mg/g and is still less than MIL-53-Al @ C14-1. In addition, due to the short alkyl chain, the hydrophobicity of the sample is poor, and the static water absorption under the same condition is the highest and is 4.84%.
As is clear from examples 1 to 5 and comparative examples 1 to 2, the N-tetradecylphosphoric acid self-assembly method is effective in improving the hydrophobicity of MIL-53-Al. The material prepared in example 1 has a relatively high acetone adsorption capacity. The adsorption behavior of the adsorbent is hardly affected by humidity, and the adsorbent shows excellent cyclic regeneration performance under high humidity, and is suitable for adsorption removal of VOCs in actual industrial production. In addition, the longer reaction time and the increased dosage of the N-tetradecyl phosphoric acid are beneficial to improving the hydrophobicity of the material, but the longer reaction time or the excessive dosage of the N-tetradecyl phosphoric acid can block the pores of the MIL-53-Al, so that the adsorption performance is poor. Therefore, when the reaction time is 12 hours and the molar ratio of MIL-53-Al to N-tetradecylphosphoric acid is 10:1, the overall performance of the modified material is the best.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.

Claims (7)

1. A preparation method of hydrophobic MIL-53-Al for absorbing VOCs is characterized in that a self-assembly method is adopted, N-tetradecyl phosphoric acid is dissolved in absolute ethyl alcohol to form a clear solution, then activated MIL-53-Al powder is added to be fully mixed, after the reaction is finished, the obtained product is filtered, and the hydrophobic MIL-53-Al can be prepared through centrifugal washing and vacuum drying.
2. The method of claim 1, wherein the mixing is performed by first allowing to stand and then stirring every 2 hours for 5 min.
3. The preparation method of the hydrophobic MIL-53-Al for adsorbing VOCs according to claim 1, wherein the MIL-53-Al is activated by placing the MIL-53-Al in a muffle furnace for roasting at 250-450 ℃ for 1-3 h.
4. The method of claim 1, wherein the molar ratio of activated MIL-53-Al to N-tetradecylphosphoric acid is 2-10: 1.
5. The method of claim 1, wherein the reaction time of the activated MIL-53-Al and N-tetradecylphosphoric acid is 6-20 hours.
6. The method of claim 1, wherein the reaction time of the activated MIL-53-Al and N-tetradecylphosphoric acid is 12 hours, and the molar ratio of the activated MIL-53-Al to N-tetradecylphosphoric acid is 10: 1.
7. Hydrophobic MIL-53-Al for adsorption of VOCs obtained by the method of any one of claims 1 to 6.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321815A (en) * 2021-06-24 2021-08-31 天津工业大学 MOF material with phospholipid bilayer grafted on surface, preparation method and application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586050A (en) * 2019-09-18 2019-12-20 天津大学 Hydrophobic Y molecular sieve for VOCs adsorption and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586050A (en) * 2019-09-18 2019-12-20 天津大学 Hydrophobic Y molecular sieve for VOCs adsorption and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YUDAI KAWASE等: "Ti cluster-alkylated hydrophobic MOFs for photocatalytic production of hydrogen peroxide in two-phase systems", 《CHEMCOMM》 *
YUXIU SUN等: "A molecular-level superhydrophobic external surface to improve the stability of metal–organic frameworks", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321815A (en) * 2021-06-24 2021-08-31 天津工业大学 MOF material with phospholipid bilayer grafted on surface, preparation method and application

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