CN114452945A - Preparation method of MOF composite material adsorbent for removing toluene gas - Google Patents

Preparation method of MOF composite material adsorbent for removing toluene gas Download PDF

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CN114452945A
CN114452945A CN202210136445.7A CN202210136445A CN114452945A CN 114452945 A CN114452945 A CN 114452945A CN 202210136445 A CN202210136445 A CN 202210136445A CN 114452945 A CN114452945 A CN 114452945A
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dmf
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mof composite
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陈昊
李毅舟
魏征
王骁
姜国宝
施红旗
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719th Research Institute of CSIC
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Abstract

The invention discloses a preparation method of an MOF composite material adsorbent for removing toluene gas, which relates to the field of design of specific adsorbents and comprises two steps of preparing MIL-101(Cr) and loading Pd on the MIL-101(Cr), wherein the operation process of loading Pd on the MIL-101(Cr) comprises the following steps: a. dispersing MIL-101(Cr) in DMF, and stirring at room temperature for 30-60 min; b. pd (NO)3)2·2H2Dissolving O in DMF to form a solution, dropwise adding the solution into the system in the step (1), violently stirring for 10-20 min, then carrying out ultrasonic treatment for 20-30 min, carrying out magnetic stirring for 24h at room temperature, filtering out solid substances, and washing with DMF until the solid substances are colorless; c. drying the obtained solid substance for 24h to obtain Pd (NO)3)2MIL-101 at H2Treating for 2-4 h at 200-250 ℃ in the atmosphere; d. drying in airAnd drying for 8-10 h to obtain powder, namely the MOF composite material adsorbent for removing the toluene gas. The invention only improves Pd2+The reduction method of (2) can increase the primary removal rate of toluene to about 55%.

Description

Preparation method of MOF composite material adsorbent for removing toluene gas
Technical Field
The invention relates to the field of specific adsorbent design, in particular to a preparation method of an MOF composite material adsorbent for removing toluene gas.
Background
Toluene is a basic chemical raw material, widely used in chemical raw materials, pesticides, dye production, synthetic resin production and other applications, and is also an important component of gasoline. Owing to the wide application, the air purifier can see the figure of people in various exhaust gases and released gases, such as automobile exhaust and indoor air generated by the release of new furniture. Toluene has unpleasant special odor, toxicity, irritation, teratogenicity and carcinogenesis, so that toluene becomes one of the key objects of air treatment, and how to remove toluene efficiently is also one of the hot spots of air purification research.
For toluene treatment, the traditional adsorption method is the most common treatment method, and the traditional activated carbon is also the most common adsorbent due to the adsorption effect on various gases. However, for a specific toluene, the conventional activated carbon has a low primary removal rate, and adsorption sites are easily occupied by other gases, thereby causing low toluene adsorption efficiency. The MOF material is a novel material which is most concerned in recent years, and due to the plasticity of the pore diameter of the material, the synthesized specific MOF material with the proper pore diameter can specifically and efficiently adsorb toluene. For example, patent application publication No. CN105233872B, which is a Pd @ MIL-101 composite material and a preparation method and application thereof, discloses an adsorbent material that can be used for adsorbing toluene, but compared with activated carbon, the material can only increase the removal rate of toluene once from 30% to about 40%, and the adsorption efficiency is still insufficient for toluene treatment.
Disclosure of Invention
The invention aims to provide a preparation method of an MOF composite material adsorbent for removing toluene gas, and aims to solve the technical problem of poor adsorption effect in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an MOF composite material adsorbent for removing toluene gas comprises two steps of preparing MIL-101(Cr) and loading Pd on the MIL-101(Cr), wherein the operation process of loading Pd on the MIL-101(Cr) comprises the following steps:
a. dispersing MIL-101(Cr) in DMF, and stirring at room temperature for 30-60 min;
b. pd (NO)3)2·2H2Dissolving O in DMF to form a solution, dropwise adding the solution into the system in the step (1), violently stirring for 10-20 min, then carrying out ultrasonic treatment for 20-30 min, carrying out magnetic stirring for 24h at room temperature, filtering out solid substances, and washing with DMF until the solid substances are colorless;
c. drying the obtained solid substance for 24h to obtain Pd (NO)3)2MIL-101 at H2Treating for 2-4 h at 200-250 ℃ in the atmosphere;
d. and drying in the air for 8-10 h to obtain powder, namely the MOF composite material adsorbent for removing the toluene gas.
Preferably, the supported amount of Pd is 1-2 wt%.
More preferably, the MIL-101(Cr) preparation process comprises the following steps:
(1) mixing Cr (NO)3)3·9H2O dissolved in terephthalic acid, Cr (NO)3)3·9H2The molar ratio of O to terephthalic acid is 1: 0.9-1.2;
(2) placing the solution in ultrasonic equipment, and adding pure HNO3Said HNO3Is HNO3And Cr3+The molar ratio of (1: 1.4) - (1.5), and carrying out ultrasonic treatment until a uniform solution is obtained;
(3) transferring the solution into an autoclave, and reacting for 8-10 h at 220-250 ℃;
(4) and taking out the solid in the system, washing the obtained solid, and refluxing in a hot alcohol solvent at 70-80 ℃ for 5-8 h to obtain MIL-101 (Cr).
Furthermore, the solid obtained in the step (4) is washed by DMF and deionized water respectively for 1-3 times.
Further, the alcohol solvent in the step (4) is ethanol.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention only improves Pd2+The reduction method can improve the primary removal rate of the toluene to about 55 percent;
2. the invention improves Pd2+The reduction method of (1) can further improve the preparation method of MIL-101(Cr), and can also improve the primary removal rate of toluene to about 85 percent;
3. the MOF composite material adsorbent prepared by the invention has stable adsorption performance, and the adsorption effect is still high after the adsorbent is used for many times; toluene does not produce irreversible structural transformation to the compound, and the porous structure is stable and has strong plasticity.
Drawings
FIG. 1 is a structural morphology of an adsorbent of the MOF composite prepared in example 1;
FIG. 2 is a comparison graph of the multiple adsorption rates of the MOF composite material prepared in examples 1-4 and activated carbon on benzene, and the adsorption conditions are as follows: 20 ℃ and normal pressure; the desorption conditions are as follows: vacuumizing at 80 ℃;
FIG. 3 is a graph showing the relationship between the temperature and desorption rate of the MOF composite material and activated carbon prepared in examples 1 to 4 after adsorption of benzene;
fig. 4 is a comparison graph of the multiple adsorption rates of benzene on MOF composite materials prepared in examples 1-4 and activated carbon after high temperature heat treatment, the adsorption conditions are as follows: 20 ℃ and normal pressure; the desorption conditions are as follows: and (5) vacuumizing at 80 ℃.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described below with reference to various embodiments and the accompanying drawings, and the implementation manner of the present invention includes, but is not limited to, the following embodiments.
The invention provides a preparation method of an MOF composite material adsorbent for removing toluene gas. The following examples and comparative experiments are combined with the contents of the drawings to further illustrate the preparation process of the catalyst, the structure and the performance of the product.
Example 1
The embodiment provides a preparation method of an MOF composite material, which comprises the following steps:
1.1MIL-101(Cr) preparation method
a) Mixing 800mg Cr (NO)3)3·9H2O is blended into 328mg of terephthalic acid;
b) adding 180mg of HNO into the solution3The reactants were mixed ultrasonically until a homogeneous solution was obtained.
c) The solution was transferred to an autoclave and kept at 220 ℃ for 8 h.
d) The solid was washed with DMF and deionized water and then refluxed in hot ethanol at 70 ℃ for 5h to give MIL-101 (Cr).
Preparation method of 1.2Pd/MIL-101(Cr) composite material
a) 500mg of MIL-101(Cr) was dispersed in 10mL of DMF and stirred at room temperature for 30 min.
b) 13.5mg of Pd (NO)3)2·2H2O was mixed with 1mL of DMF solution. Dropwise adding the obtained Pd (NO)3)2·2H2O solution, vigorously stirred for about 10min, then sonicated for 20min, magnetically stirred at room temperature for 24h, washed with DMF until colorless.
c) Drying for 24h to obtain Pd (NO)3)2MIL-101, treated at 200 ℃ for 2H under an atmosphere of H2.
d) And then dried in air for 8h, and the obtained powder is named as Pd/MIL-101, and the structural morphology of the powder is shown in figure 1.
Example 2
The embodiment provides a preparation method of an MOF composite material, which comprises the following steps:
1.1MIL-101(Cr) preparation method
a) Mixing 800mg Cr (NO)3)3·9H2O is blended into 328mg of terephthalic acid;
b) 171mg of acetic acid was added to the above solution, and the reactants were ultrasonically mixed until a uniform solution was obtained.
c) The solution was transferred to an autoclave and kept at 220 ℃ for 8 h.
d) The solid was washed with DMF and deionized water, then refluxed in hot ethanol at 70 ℃ for 5h to give MIL-101 (Cr).
Preparation method of 1.2Pd/MIL-101(Cr) composite material
a) 500mg of MIL-101(Cr) was dispersed in 10mL of DMF and stirred at room temperature for 30 min.
b) 13.5mg of Pd (NO)3)2·2H2O was mixed with 1mL of DMF solution. Dropwise adding the obtained Pd (NO)3)2·2H2O solution, vigorously stirred for about 10min, then sonicated for 20min, magnetically stirred at room temperature for 24h, washed with DMF until colorless.
c) Drying for 24h to obtain Pd (NO)3)2MIL-101, treated at 200 ℃ for 2H under an atmosphere of H2.
d) Then dried in air for 8h and the resulting powder was named Pd/MIL-101-1.
Example 3
The embodiment provides a preparation method of an MOF composite material, which comprises the following steps:
1.1MIL-101(Cr) preparation method
a) Mixing 800mg Cr (NO)3)3·9H2O is blended into 328mg of terephthalic acid;
b) 180mg of nitric acid was added to the above solution and the reactants were mixed ultrasonically until a homogeneous solution was obtained.
c) The solution was transferred to an autoclave and kept at 220 ℃ for 8 h.
d) The solid was washed with DMF and deionized water and then refluxed in hot ethanol at 70 ℃ for 5h to give MIL-101 (Cr).
Preparation method of 1.2Pd/MIL-101(Cr) composite material
a) 500mg of MIL-101(Cr) was dispersed in 10mL of DMF and stirred at room temperature for 30 min.
b) 13.5mg of Pd (NO)3)2·2H2O was mixed with 1mL of DMF solution. Dropwise adding the obtained Pd (NO)3)2·2H2O solution, vigorously stirred for about 10min, then sonicated for 20min, magnetically stirred at room temperature for 24h, washed with DMF until colorless.
c) DryingPd (NO) will be obtained after 24h3)2Placing the MIL-101 in a saturated methanol solution of sodium borohydride, and reducing under the condition of ice-water bath to obtain the Pd/MIL-101-2 composite material.
Example 4
The embodiment provides a preparation method of an MOF composite material, which comprises the following steps:
1.1MIL-101(Cr) preparation method
a) Mixing 800mg Cr (NO)3)3·9H2O is blended into 328mg of terephthalic acid;
b) 171mg of acetic acid was added to the above solution, and the reactants were ultrasonically mixed until a uniform solution was obtained.
c) The solution was transferred to an autoclave and kept at 220 ℃ for 8 h.
d) The solid was washed with DMF and deionized water and then refluxed in hot ethanol at 70 ℃ for 5h to give MIL-101 (Cr).
Preparation method of 1.2Pd/MIL-101(Cr) composite material
a) 500mg of MIL-101(Cr) was dispersed in 10mL of DMF and stirred at room temperature for 30 min.
b) 13.5mg of Pd (NO)3)2·2H2O was mixed with 1mL of DMF solution. Dropwise adding the obtained Pd (NO)3)2·2H2O solution, vigorously stirred for about 10min, then sonicated for 20min, magnetically stirred at room temperature for 24h, washed with DMF until colorless.
c) Drying for 24h to obtain Pd (NO)3)2Placing the MIL-101 in a saturated methanol solution of sodium borohydride, and reducing under the condition of ice-water bath to obtain the Pd/MIL-101-3 composite material.
Control experiment 1
The MOF composite prepared in examples 1-4 and activated carbon were used as adsorbents, and 0.5g of the adsorbents were loaded into a quartz column (6.0mm i.d.300mm) and supported by a porous silica bed. 2000ppm of toluene and O of the balance gas were allowed to react at 20 deg.C2/N2(21/79, v/v) gas mixture at 100cm3Flow into the column at a flow rate of/min (normal pressure). The sample was then removed from the product collector and analyzed for product composition using gas chromatography FID, followed by a second step at (80 c),the quartz column was evacuated until the gas could not be exhausted, and the adsorption rate of adsorption was recorded for each cycle by using one cycle of adsorption and desorption, and the results are shown in fig. 2.
As can be seen from fig. 2, the MOF composite has a very high adsorption effect on toluene compared to the traditional adsorbent Activated Carbon (AC). Pd/MIL-101-1 is prepared by using acetic acid to replace nitric acid to prepare MIL-101, and Pd/MIL-101-2 is prepared by using sodium borohydride to reduce PdCl2Pd/MIL-101-3 is prepared by replacing nitric acid with acetic acid and reducing Pd (NO) with sodium borohydride3)2(ii) a As can be seen from the figure, the adsorption efficiency of Pd/MIL-101-1 and Pd/MIL-101-2 to toluene is not as good as that of Pd/MIL-101, and Pd/MIL-101-3 is basically not different from Pd/MIL-101-2.
Control experiment 2
The MOF composite prepared in examples 1-4 and activated carbon were used as adsorbents, and 0.5g of the adsorbents were loaded into a quartz column (6.0mm i.d.300mm) and supported by a porous silica bed. 2000ppm of toluene and O of the balance gas were allowed to react at 20 deg.C2/N2(21/79, v/v) gas mixture at 100cm3Flow into the column at a flow rate of/min (normal pressure). The sample was then removed from the product collector and analyzed for product composition using gas chromatography FID, followed by desorption at different temperatures by evacuating the quartz column and recording the desorption rates at different temperatures, the results of which are shown in fig. 3.
As can be seen from FIG. 3, the Pd/MIL-101 has the highest desorption temperature, can be completely desorbed at 80 ℃, and has lower desorption temperatures in other examples.
Control experiment 3
The MOF composite material prepared in the embodiment 1-4 and activated carbon are used as adsorbents, the adsorbents to be detected are roasted for 1h at 200 ℃, then 0.5g of the adsorbents are loaded into a quartz column (6.0mm I.D.300mm), and a porous silica bed is used for supporting. 2000ppm of toluene and O of the balance gas were allowed to react at 20 deg.C2/N2(21/79, v/v) gas mixture at 100cm3Flow into the column at a flow rate of/min (normal pressure). The sample was removed from the product collector, analyzed for product composition using gas chromatography FID, and then desorbed at (80 ℃) by evacuating the quartz column until no gas could be drawn off, in one goThe adsorption and desorption were carried out in one cycle, and the adsorption rate was recorded for each cycle, and the results are shown in fig. 4.
As can be seen from FIG. 4, Pd/MIL-101-1 and Pd/MIL-101-3 have poor adsorption effects, which indicates that MIL-101 prepared by using acetic acid has poor thermal stability, and the structure of the adsorbent collapses at high temperature, resulting in the decrease of the adsorption performance, while Pd/MIL-101, Pd/MIL-101-2 and activated carbon have stable structures, and the adsorption performance is not greatly influenced.
Compared with the traditional adsorbent Activated Carbon (AC), the MOF composite material has very high adsorption effect on benzene.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.

Claims (5)

1. A preparation method of an MOF composite material adsorbent for removing toluene gas comprises two steps of preparing MIL-101(Cr) and loading Pd on the MIL-101(Cr), and is characterized in that the operation process of loading Pd on the MIL-101(Cr) comprises the following steps:
a. dispersing MIL-101(Cr) in DMF, and stirring at room temperature for 30-60 min;
b. pd (NO)3)2·2H2Dissolving O in DMF to form a solution, dropwise adding the solution into the system in the step (1), violently stirring for 10-20 min, then carrying out ultrasonic treatment for 20-30 min, carrying out magnetic stirring for 24h at room temperature, filtering out solid substances, and washing with DMF until the solid substances are colorless;
c. drying the obtained solid substance for 24h to obtain Pd (NO)3)2MIL-101 at H2Treating for 2-4 h at 200-250 ℃ in the atmosphere;
d. and drying in the air for 8-10 h to obtain powder, namely the MOF composite material adsorbent for removing the toluene gas.
2. The method for preparing the MOF composite adsorbent of claim 2, wherein the Pd is supported in an amount of 1-2 wt%.
3. The method of making an MOF composite adsorbent according to any one of claims 1 or 2, wherein the MIL-101(Cr) is made by a process comprising the steps of:
(1) mixing Cr (NO)3)3·9H2O dissolved in terephthalic acid, Cr (NO)3)3·9H2The molar ratio of O to terephthalic acid is 1: 0.9-1.2;
(2) placing the solution in ultrasonic equipment, and adding pure HNO3Said HNO3Is HNO3And Cr3+The molar ratio of (1: 1.4) - (1.5), and carrying out ultrasonic treatment until a uniform solution is obtained;
(3) transferring the solution into an autoclave, and reacting for 8-10 h at 220-250 ℃;
(4) and taking out the solid in the system, washing the obtained solid, and refluxing in a hot alcohol solvent at 70-80 ℃ for 5-8 h to obtain MIL-101 (Cr).
4. The preparation method of the MOF composite material adsorbent according to claim 3, wherein the solid obtained in the step (4) is washed 1-3 times respectively by DMF and deionized water.
5. The method of preparing the MOF composite adsorbent of claim 3, wherein the alcoholic solvent in step (4) is ethanol.
CN202210136445.7A 2022-02-15 2022-02-15 Preparation method of MOF composite material adsorbent for removing toluene gas Withdrawn CN114452945A (en)

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US20160208047A1 (en) * 2015-01-20 2016-07-21 Chung Yuan Christian University Metal-organic framework polymer for solid-phase microextraction
CN111151301A (en) * 2020-01-13 2020-05-15 辽宁大学 Bifunctional heterogeneous Pd @ MIL-101@ SGO composite material and preparation method and application thereof
CN112871167A (en) * 2021-01-14 2021-06-01 浙江理工大学 MOFs (metal-organic frameworks) -packaged ultrafine alloy nanoparticles as well as preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150231600A1 (en) * 2012-09-03 2015-08-20 The University Of Liverpool Metal-organic frameworks
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