CN114106344B - Preparation method of aluminum metal organic framework material Al-MIL-53 - Google Patents
Preparation method of aluminum metal organic framework material Al-MIL-53 Download PDFInfo
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Abstract
The invention relates to a preparation method of an aluminum metal organic framework material Al-MIL-53, which comprises the following steps: mixing a mixed solvent consisting of a solubilizer, water and dimethylformamide, an aluminum source and an organic ligand to obtain a mixed solution, wherein the organic ligand is terephthalic acid or 2-amino terephthalic acid; the mixed solution is reacted for 30 to 96 hours at the temperature of 100 to 250 ℃ under autogenous pressure, and the solid in the reaction product is collected, dried and roasted. The method can reduce the use of organic solvents, and the preparation process is more environment-friendly.
Description
Technical Field
The invention relates to a preparation method of an aluminum metal organic framework material Al-MIL-53.
Background
The metal organic framework materials (Metal Organic Frameworks, MOFs for short) are a class of microporous materials with large pore diameters and high specific surface areas. The specific surface area of the material is far larger than that of a molecular sieve with similar pore channels, and the coordination capacity of the ligand can be regulated and changed. In addition, the synthesis process is simpler, has the characteristics of no need of template agent, low synthesis temperature, direct mixing preparation of metal ions and organic ligands and the like, and therefore, the method has good industrial application prospect.
Al-MIL-53 is made of AlO 4 (OH) 2 The octahedron and the carboxyl of terephthalic acid are self-assembled to form the three-dimensional framework structure material with one-dimensional diamond pore canal. The material can autonomously adjust the shape and the size of a pore canal when adsorbing polar molecules and hydrocarbon molecules, namely a framework generates a breathing effect, namely the material is converted from a macroporous form to a narrow pore form after guest molecules are removed, and the conversion process is reversible and does not damage the structure. The skeleton of the material has high specific surface area and special respiration effect, and has great potential for adsorption and separation of aromatic hydrocarbon. Research shows that the material has the advantage of doubling the adsorption capacity of the existing molecular sieve in the field of adsorption separation of C8 aromatic hydrocarbon, and is one of the substitutional materials for adsorption separation of C8 aromatic hydrocarbon in the future.
In the synthesis of MIL-53, different solvents have different reaction characteristics, such as when Dimethylformamide (DMF) is used as a solvent, the crystallization temperature required by the reaction is lower, and is generally 150 ℃; and the yield is higher, generally can reach about 80 percent, and the obtained product has large adsorption capacity. When all water is used as a solvent, the crystallization temperature required by the reaction is high, and is generally 220 ℃; and the yield is lower, generally about 40%, and the adsorption capacity is smaller. If a mixed solvent composed of a part of DMF and a part of water is used, the obtained result is changed according to the composition ratio of the two solvents, the advantages of the two solvents cannot be well maintained, and the defects of the two solvents are overcome. The main reason for this difference is that the two reactants have different solubilities in different solvents, terephthalic acid has a large solubility in organic solvents and a small solubility in water; aluminum nitrate has high solubility in water and low solubility in organic solvents, and thus, the reaction is incomplete when water is used as a solvent, and the yield is low. Therefore, how to ensure the adsorption capacity and yield of the synthetic product by using the mixed solvent of water and DMF becomes the key of whether MIL-53 can realize industrial production.
CN105384762a discloses a method for synthesizing MILs-53 (Al), which uses aluminium hydroxide and terephthalic acid as raw materials and hydrofluoric acid as auxiliary agent, and the obtained product has XRD, nitrogen adsorption curve, etc. similar to common synthesis method, and the method has the advantages of mild synthesis condition and low cost. The main disadvantage of this method is the need to use highly toxic hydrofluoric acid.
CN109173341a discloses a method for separating xylene mixture by using metal organic framework material MILs-53 (Cr) as adsorption stationary phase. And detecting the concentration of the xylene mixture in the treated solution by utilizing gas chromatography, and calculating to obtain the adsorption quantity and selectivity. The separation factor reaches 22, and the adsorption capacity reaches 8.2mol/kg. The saturated adsorption capacity can reach 95% or more in half an hour.
Disclosure of Invention
The invention aims to provide a preparation method of an aluminum metal organic framework material Al-MIL-53, which can reduce the use of organic solvents and is more environment-friendly in preparation process.
In order to achieve the above object, the present invention provides a method for preparing an aluminum metal organic framework material Al-MIL-53, comprising: mixing a mixed solvent consisting of a solubilizer, water and dimethylformamide, an aluminum source and an organic ligand to obtain a mixed solution, wherein the organic ligand is terephthalic acid or 2-amino terephthalic acid; the mixed solution is reacted for 30 to 96 hours at the temperature of 100 to 250 ℃ under autogenous pressure, and the solid in the reaction product is collected, dried and roasted.
In the technical scheme of the method, the use amount of the organic solvent dimethylformamide is reduced and the cost is reduced due to the addition of the solubilizer and the water, so that the preparation process is more environment-friendly and the higher product yield is maintained. Compared with the Al-MIL-53 material prepared by adopting a water-containing solvent system in the prior art, the toluene adsorption capacity of the Al-MIL-53 material prepared by the method is larger.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is an XRD spectrum of Al-MIL-53 material prepared in example 1 and examples 4-6 of the present invention;
FIG. 2 is an SEM photograph of an Al-MIL-53 material prepared in example 1 of the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Compared with the preparation method adopting water as a solvent, the preparation method can reduce the reaction temperature, shorten the crystallization time, improve the yield of the Al-MIL-53 material and the like, and simultaneously reduce the cost for preparing the Al-MIL-53 material, and the preparation process is more environment-friendly. The toluene adsorption capacity of the Al-MIL-53 material prepared by the method is larger than that of the Al-MIL-53 material prepared by a solvent system containing water and a system using water as a solvent.
The invention provides a preparation method of an aluminum metal organic framework material Al-MIL-53, which comprises the following steps: mixing a mixed solvent consisting of a solubilizer, water and dimethylformamide, an aluminum source and an organic ligand to obtain a mixed solution, wherein the organic ligand is terephthalic acid or 2-amino terephthalic acid; the mixed solution reacts for 30 to 96 hours at the temperature of 100 to 250 ℃ under autogenous pressure, and the solid in the reaction product is collected, dried and roasted.
The method for removing the solid product from the hydrothermal reaction product is not particularly limited, and may be, for example, filtration, centrifugal separation, vacuum filtration, or the like. Heat resistant closed vessels are well known to those skilled in the art and may be, for example, autoclaves, tetrafluoroethylene hydrothermal reaction kettles, and the like.
According to the present invention, the solubilizing agent is selected from one or more of quaternary ammonium salt, quaternary phosphonium salt, polyethylene oxide, polypropylene oxide and alkylbenzene sulfonate. Wherein the quaternary ammonium salt can be selected from one or more of dimethyl dodecyl benzyl ammonium chloride, dimethyl tetradecyl benzyl ammonium chloride and tetrabutyl ammonium chloride; the quaternary phosphonium salt may be selected from tributyl dodecyl phosphonium chloride and/or tributyl tetradecyl phosphonium chloride; the weight average molecular weight of the polyethylene oxide may vary within a wide range, for example from 1000 to 50000; the weight average molecular weight of the polypropylene oxide may vary within a wide range, for example from 1000 to 50000; the alkylbenzene sulfonate may be one or more selected from dodecylbenzene sulfonate, tetradecyl benzene sulfonate and petroleum sulfonate.
According to the present invention, the content of the solubilizer in the mixed solvent is 0.1 to 5% by weight, the content of water is 49 to 90% by weight, and the content of dimethylformamide is 9 to 50% by weight. Preferably, the content of the solubilizer is 0.1 to 3% by weight, the content of water is 49 to 85% by weight, and the content of dimethylformamide is 12 to 50% by weight.
According to the invention, the molar ratio of the aluminium source to the organic ligand can vary within a wide range, for example can be 1: (0.8-1.5), the weight ratio of the mixed solvent to the aluminum source may also be varied within a wide range, for example, (10-30): 1. wherein the aluminium source may be selected from aluminium nitrate and/or aluminium chloride. The organic ligand may be selected from terephthalic acid, wherein the terephthalic acid may be an amino-modified terephthalic acid, such as 2-amino terephthalic acid.
In a preferred embodiment, the molar ratio of aluminum source to organic ligand is 1: (0.8 to 1.5), preferably 1: (1-1.2), the weight ratio of the mixed solvent to the aluminum source is (10-30): 1. preferably (12 to 20): 1.
according to the invention, the reaction temperature may be 140 to 220℃and the time may be 50 to 80 hours.
According to the invention, after the heat-resistant closed container is cooled to room temperature after the hydrothermal reaction is finished, the solid product is taken out, washed and dried. The liquid used for washing is not particularly limited, and may be any liquid that does not react with the solid product, for example, deionized water or ethanol. Drying is a procedure well known to those skilled in the art and may be carried out, for example, in a thermostatted oven, and the drying temperature may be 50 to 120℃and the time may be 1 to 24 hours.
According to the invention, the roasting temperature can be 220-400 ℃ and the time is 1-96 hours; preferably, the calcination temperature is 250-350 ℃ and the time is 8-24 hours. The atmosphere for firing is not particularly limited, and may be an air atmosphere or an inert atmosphere containing an inert gas or nitrogen, which is well known to those skilled in the art, such as helium, argon, or the like.
In a preferred embodiment of the invention, the method may comprise: and mixing the solubilizer, water and dimethylformamide to obtain a mixed solvent, and dissolving the metal source and the organic ligand in the mixed solvent to obtain a mixed solution. The order of mixing the solubilizer, water and dimethylformamide is not particularly limited, for example, water and dimethylformamide may be mixed first and then the solubilizer may be added to obtain a mixed solvent, or the solubilizer and dimethylformamide may be mixed and then water may be added to obtain a mixed solvent, and other mixing modes are not described herein.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The starting materials in examples and comparative examples are both commercially available.
The saturated adsorption capacity of the adsorption material sample for toluene vapor was measured by an atmospheric pressure gas phase flow method: the sample is dried and cooled after being activated for 4 hours by introducing nitrogen at 200 ℃, then the sample is placed in a sample cell, the sample cell is placed in a constant temperature water bath at 35 ℃, and toluene vapor is carried by the nitrogen to continuously pass through the sample cell until the sample reaches adsorption equilibrium. Toluene partial pressure was 0.5MPa. The adsorption capacity of the sample to be measured was calculated from the mass difference between the sample before and after toluene adsorption by the following formula:
wherein, C is adsorption capacity, and the unit is mg/g; m is m 1 The unit of the mass of the sample to be measured before toluene adsorption is g; m is m 2 The unit is g for the mass of the sample to be measured after adsorption of toluene.
The adsorption selectivity of the adsorption material sample to C8 aromatic hydrocarbon at normal temperature is examined by adopting a liquid-phase static adsorption balance test: an adsorption test solution with 20% mass fractions of each component was prepared from 1,3, 5-Triisopropylbenzene (TIPB) and four C8 aromatic isomers. The composition of the test solution before and after adsorption was analyzed by means of a gas chromatograph (Agilent 7890; column: HP-INNOWAX,20 m.times.0.18 mm,0.18 μm): 200mg of the sample dried at 200 ℃ for 6 hours is added into 6g of test solution, the test solution is placed at 25 ℃ for 48 hours to reach adsorption balance, the supernatant is extracted for chromatographic analysis, TIPB is taken as an internal standard substance, and the adsorption selectivity of unit mass sample to each isomer of C8 aromatic hydrocarbon can be calculated by the concentration change of liquid phase components before and after adsorption by taking the TIPB as the internal standard substance and assuming that the TIPB is not adsorbed at all.
The adsorption capacity of the adsorbent material for component i was calculated as follows:
wherein: a is that i Represents the adsorption capacity of component i, mg/g;
M 0 the mass of an internal standard substance in the adsorption liquid is represented as g;
C i0 representing the mass fraction of component i in the adsorption liquid;
C m0 indicating the mass fraction of the internal standard in the adsorption liquid;
C i representing the mass fraction of component i in the adsorption equilibrium liquid;
C m indicating the mass fraction of the internal standard in the adsorption equilibrium liquid.
The adsorption selectivity of the adsorbent material for components i and j was calculated as follows:
wherein: beta i/j Representing the selectivity coefficient of component i versus component j;
A i 、A j the adsorption capacity of the components i and j are respectively shown as mg/g;
C i 、C j the mass fractions of components i and j in the adsorption equilibrium solution are respectively shown.
Yield of MILs-53 material = actual yield/theoretical yield x 100 mass%.
Example 1
50g of water was mixed with 9.4g of Dimethylformamide (DMF), and 0.6g of dimethyldodecylbenzyl ammonium chloride was added thereto to uniformly mix them, thereby obtaining a mixed solvent. 3.75g (0.01 mol) of aluminum nitrate nonahydrate and 1.66g (0.01 mol) of terephthalic acid were dissolved in the mixed solvent, and after stirring for about 0.5 hour, the mixed solution was transferred to a stainless steel reaction vessel lined with polytetrafluoroethylene and reacted at 150℃for 72 hours under closed conditions. After the reaction was completed, the mixture was cooled to 25 ℃. The solid product obtained by the reaction is washed by deionized water, filtered under reduced pressure, the solid obtained by the filtration is dried at 80 ℃ for 12 hours, and baked at 330 ℃ in an air atmosphere for 10 hours to obtain Al-MIL-53 material a, the yield is 78 mass percent, the toluene adsorption amount is shown in table 1, the adsorption selectivity of the solid product to each isomer of C8 aromatic hydrocarbon is measured by static adsorption balance, the result is shown in table 2, the XRD spectrogram is shown in figure 1, and the SEM image is shown in figure 2.
Example 2
Al-MIL-53 material was prepared as in example 1, except that 0.06g of dimethyldodecylbenzyl ammonium chloride was used in the preparation of the mixed solvent, and reacted, dried and calcined to give Al-MIL-53 material b having a yield of 80 mass% and a toluene adsorption amount shown in Table 1, and adsorption selectivity to each isomer of C8 aromatic hydrocarbon was measured by static adsorption equilibrium shown in Table 2.
Example 3
Al-MIL-53 material was prepared as in example 1, except that 0.3g of dimethyldodecylbenzyl ammonium chloride, 30g of water and 28.3g of dimethylformamide were used in the preparation of the mixed solvent, and reacted, dried and calcined to give Al-MIL-53 material C having a yield of 79 mass% and a toluene adsorption amount shown in Table 1, and adsorption selectivity to each isomer of C8 aromatic hydrocarbon was measured by static adsorption equilibrium and shown in Table 2.
Example 4
Al-MIL-53 material was prepared as in example 1, except that the mixed solvent was prepared by using tributyl dodecyl phosphonium chloride instead of dimethyl dodecyl benzyl ammonium chloride in an equivalent amount, and the Al-MIL-53 material d was obtained by reaction, drying and calcination, with a yield of 79% by mass, and the toluene adsorption amount shown in Table 1, and the adsorption selectivity of each isomer of C8 aromatic hydrocarbon was measured by static adsorption equilibrium shown in Table 2.
Example 5
Al-MIL-53 material was prepared as in example 1, except that the mixed solvent was prepared by substituting an equivalent amount of polyethylene oxide (weight average molecular weight: 1200) for dimethyldodecylbenzyl ammonium chloride, and reacted, dried and calcined to give Al-MIL-53 material e in 76 mass% yield, the toluene adsorption amount of which was shown in Table 1, and the adsorption selectivity of which to each isomer of C8 aromatic hydrocarbon was measured by static adsorption equilibrium was shown in Table 2.
Example 6
Al-MIL-53 material was prepared as in example 1, except that the mixed solvent was prepared by using equal amount of tetradecyl benzenesulfonate instead of dimethyl dodecylbenzyl ammonium chloride, and reacted, dried and calcined to obtain Al-MIL-53 material f with a yield of 77 mass%, the toluene adsorption amount of which was shown in Table 1, and the adsorption selectivity of each isomer of C8 aromatic hydrocarbon was measured by static adsorption equilibrium and shown in Table 2.
Comparative example 1
3.75g of aluminum nitrate and 1.66g of terephthalic acid were dissolved in 56.6g of DMF solvent without adding a solubilizing agent, stirred for about 0.5 hour, and after transferring the mixed solution into a stainless steel reaction kettle lined with polytetrafluoroethylene and sealing, the temperature was raised to 150 ℃ for reaction for 72 hours. After the reaction was completed, the mixture was naturally cooled to 25 ℃. The solid product obtained by the reaction was washed with deionized water, filtered under reduced pressure, the solid obtained by the filtration was dried at 80℃for 12 hours, and calcined at 330℃in an air atmosphere for 10 hours to obtain Al-MIL-53 material A having a yield of 80 mass%, the toluene adsorption capacity was shown in Table 1, and the static adsorption equilibrium results were shown in Table 2.
Comparative example 2
3.75g of aluminum nitrate and 1.66g of terephthalic acid were dissolved in 60g of water without adding a solubilizing agent, stirred for about 0.5 hour, and after transferring the mixed solution into a stainless steel reaction kettle lined with polytetrafluoroethylene and sealing, the temperature was raised to 220 ℃ for reaction for 72 hours. After the reaction was completed, the mixture was naturally cooled to 25 ℃. Washing the solid product obtained by the reaction with deionized water, filtering under reduced pressure, drying the solid obtained by the filtering at 80 ℃ for 12 hours, roasting at 330 ℃ in an air atmosphere for 10 hours to obtain Al-MIL-53 material B, wherein the yield is 40 mass%, the toluene adsorption capacity is shown in table 1, and the static adsorption balance result is shown in table 2.
Comparative example 3
MIL-53 material C was prepared in the same manner as in example 1 except that no solubilizing agent was added to the mixed solvent, which was obtained by mixing 50g of water with 9.4g of dimethylformamide.
TABLE 1
| MIL-53 Material numbering | Toluene adsorption capacity, mg/g | |
| Example 1 | a | 425 |
| Example 2 | b | 433 |
| Example 3 | c | 430 |
| Example 4 | d | 429 |
| Example 5 | e | 422 |
| Example 6 | f | 431 |
| Comparative example 1 | A | 426 |
| Comparative example 2 | B | 18 |
| Comparative example 3 | C | 38 |
TABLE 2
The method can reduce the use of the organic solvent dimethylformamide, the preparation process is more environment-friendly, and compared with the Al-MIL-53 material prepared by a pure water system and an aqueous system, the Al-MIL-53 material prepared by the method has better C8 aromatic hydrocarbon adsorption selectivity and can keep better toluene adsorption quantity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (9)
1. A preparation method of an aluminum metal organic framework material Al-MIL-53 comprises the following steps: mixing a mixed solvent consisting of a solubilizer, water and dimethylformamide, an aluminum source and an organic ligand to obtain a mixed solution, wherein the organic ligand is terephthalic acid or 2-amino terephthalic acid; reacting the mixed solution at 100-250 ℃ under autogenous pressure for 30-96 hours, collecting solids in a reaction product, drying and roasting; wherein the solubilizer is selected from one or more of dimethyl dodecyl benzyl ammonium chloride, dimethyl tetradecyl benzyl ammonium chloride, tetrabutyl ammonium chloride, tributyl dodecyl phosphonium chloride, tributyl tetradecyl phosphonium chloride, polyethylene oxide with weight average molecular weight of 1000-50000, polypropylene oxide with weight average molecular weight of 1000-50000, dodecyl benzene sulfonate, tetradecyl benzene sulfonate and petroleum sulfonate.
2. The method according to claim 1, wherein the content of the solubilizer in the mixed solvent is 0.1 to 5 wt%, the content of the water is 49 to 90 wt%, and the content of the dimethylformamide is 9 to 50 wt%.
3. The method according to claim 2, wherein the content of the solubilizer in the mixed solvent is 0.1 to 3 wt%, the content of the water is 49 to 85 wt%, and the content of the dimethylformamide is 12 to 50 wt%.
4. The method of claim 1, wherein the molar ratio of the aluminum source to the organic ligand is 1: (0.8-1.5), wherein the weight ratio of the mixed solvent to the aluminum source is (10-30): 1.
5. the method of claim 4, wherein the molar ratio of the aluminum source to the organic ligand is 1: (1-1.2), wherein the weight ratio of the mixed solvent to the aluminum source is (12-20): 1.
6. the method of claim 1, wherein the reaction is carried out at a temperature of 140-220 ℃ for a time of 50-80 hours.
7. The method of claim 1, wherein the firing temperature is 220-400 ℃ for 3-24 hours.
8. The method of claim 1, wherein the aluminum source is selected from aluminum nitrate and/or aluminum chloride.
9. The method according to claim 1, wherein the method comprises: and dissolving the aluminum source and the organic ligand in the mixed solvent to obtain the mixed solution.
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| CN104378981A (en) * | 2012-06-11 | 2015-02-25 | 圣安德鲁斯大学董事会 | Synthesis of mofs |
| CN104497032A (en) * | 2014-11-21 | 2015-04-08 | 中国石油大学(华东) | Nanoscale aluminium-based metal-organic framework structure material and preparation method thereof |
| CN105384762A (en) * | 2015-10-16 | 2016-03-09 | 同济大学 | Synthesis method for metal organic framework material MIL-53 (Al) |
| WO2017052474A1 (en) * | 2015-09-23 | 2017-03-30 | Nanyang Technological University | A metal-organic framework nanosheet |
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| CN104378981A (en) * | 2012-06-11 | 2015-02-25 | 圣安德鲁斯大学董事会 | Synthesis of mofs |
| CN104497032A (en) * | 2014-11-21 | 2015-04-08 | 中国石油大学(华东) | Nanoscale aluminium-based metal-organic framework structure material and preparation method thereof |
| WO2017052474A1 (en) * | 2015-09-23 | 2017-03-30 | Nanyang Technological University | A metal-organic framework nanosheet |
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