CN115678024B - Fluorosilicate MOF material and preparation method and application thereof - Google Patents
Fluorosilicate MOF material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of industrial gas adsorption separation, and discloses a novel fluorosilicate metal-organic framework material for separating acetylene and carbon dioxide and a preparation method thereof 2+ Inorganic anions SiF 6 2‑ And the organic ligand meta-tetra (4-pyridyl) porphin is heated to obtain the unit structure of Cu (TPyP) (SiF) 6 ) The microporous metal-organic framework material of (2) has relatively large specific surface area; the novel fluorosilicate MOF material has proper pore diameter and fluorinated functional site, can enhance the recognition of acetylene through the action of hydrogen bond, and can be used for C 2 H 2 /CO 2 The mixed gas is adsorbed and separated, and the separation selectivity is higher, the adsorption capacity is larger, and the separation performance is excellent.
Description
Technical Field
The invention relates to the technical field of industrial gas separation, in particular to a fluorosilicate porous hybrid material, a preparation method thereof and application thereof in gas adsorption separation.
Background
Acetylene is an important chemical raw material, and is the basic raw material of acetaldehyde, acetic acid, benzene, synthetic rubber and synthetic fiber, and is generally required to meet the requirement of high purity to achieve high yield and high safety. In industry, acetylene production is mainly derived from methane combustion and thermal hydrocarbon cracking, where carbon dioxide is a notable impurity whose presence reduces acetylene purity, negatively impacting subsequent use. Therefore, in order to obtain acetylene having a purity satisfying the industrial requirements, it is necessary to remove the carbon dioxide impurities mixed in. Most of the existing separation processes adopt energy-intensive solvent extraction and low-temperature distillation methods to separate the mixture of acetylene and carbon dioxide, but the separation difficulty is high due to the fact that the boiling points of the two are very close (189.3K for acetylene and 194.7K for carbon dioxide), and the energy efficiency of the methods is low and the method is not friendly to the environment. It is therefore necessary to develop a novel separation technique at normal temperature and pressure to efficiently separate acetylene and carbon dioxide.
In recent years, gas separation and purification by adsorbent-based separation techniques have attracted considerable attention in the academia and industry, which makes it possible for future separation techniques to shift from conventional energy-intensive cryogenic distillation to energy-efficient adsorbent separation processes. The adsorption separation is used as an energy-saving and efficient separation technology, has the characteristics of low energy consumption, simplicity in operation and the like, and can obtain higher separation selectivity. With the development of adsorption separation materials such as carbon materials, molecular sieves, porous polymers and the like, adsorption separation technology has made great progress in the field of gas separation.
Metal-organic framework materials are of great interest in terms of their readily adjustable pore size/shape and internal surface modification. In the field of gas separation, compared with the traditional gas adsorbent, the metal-organic framework has larger specific surface area, and the separation performance meeting specific functions can be obtained by adjusting the pore channel size, the configuration, the central metal cations and other behaviors of the framework, so that the metal-organic framework has great potential in the fields of low-carbon hydrocarbon gas separation and purification. For example SIFSIX-21-Cu prepared by Zaworotko et al [1] They layered ligand 3, 5-dimethyl-1H-pyrazol-4-yl methanol solution in ethylene glycol solution of copper hexafluorosilicate, sealed and stood to obtain blue/purple small crystals, the separation selectivity of the prepared material is 10, compared with the invention, the adsorption amount of acetylene and carbon dioxide is 87.36cm respectively 3 /g，33.6cm 3 /g(Kumar Naveen,Mukherjee Soumya,Harvey-Reid Nathan C.,Bezrukov Andrey A.,Tan Kui,Martins Vinicius,Vandichel Matthias,Pham Tony,van Wyk Lisa M.,Oyekan Kolade,Kumar Amrit,Forrest Katherine A.,Patil Komal M.,Barbour Leonard J.,Space Brian,Huang Yining,Kruger Paul E.,Zaworotko Michael J..Breaking the trade-off between selectivity and adsorption capacity for gas separation[J]Chem,2021,7 (11)). Hong Maochun et al SIFSIX-tpa-Cu [2] By a crystal culture method of dispersing a methanol solution of tris (pyridin-4 yl) amine on an aqueous solution of copper hexafluorosilicate, standing at room temperature for 1 week, separating to obtain dark purple bulk crystals, the prepared material having a high adsorption amount for two gases and acetylene of 185cm 3 Per g, carbon dioxide of 107cm 3 Per g, but IAST selectivity is only 5.3 (Li Hao, liu Caiping, chen Cheng, di Zhengyi, yuan Daqiang, pang Jiandong, wei Wei, mingyan, hong Maochun.an Unprecedented Pillar-Cage Fluorinated Hybrid Porous Framework with Highly Efficient Acetylene Storage and Separation [ J)].Angewandte Chemie International Edition,2021,60(14))。
Disclosure of Invention
The invention aims to overcome the conventional separation C 2 H 2 /CO 2 The method has the problems of high energy consumption and high cost, and provides the novel fluorosilicate MOF material with larger adsorption capacity and higher separation selectivity at normal temperature and normal pressure.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]。
TPyP is meta-tetra (4-pyridyl) porphine.
In a second aspect, the present invention provides the above fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]The preparation method comprises the following steps:
uniformly dispersing m-tetra (4-pyridyl) porphin in an organic solvent to obtain a m-tetra (4-pyridyl) porphin solution; dissolving copper hexafluorosilicate in a solvent to obtain a copper hexafluorosilicate solution; dropwise adding the copper hexafluorosilicate solution into the meta-tetra (4-pyridyl) porphine solution at 60-70 ℃ (preferably 70 ℃), reacting for 8-10h (preferably 10 h), and performing aftertreatment on the obtained reaction solution to obtain the fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]；
The ratio of the amount of meta-tetra (4-pyridyl) porphine to copper hexafluorosilicate species is 1:1.75-2.15 (preferably 1:2); the organic solvent is acetic acid or methanol (preferably acetic acid); the solvent is ethanol or water (preferably ethanol).
In the selected solvent and organic solvent, the prepared fluorosilicate porous hybrid material has higher purity.
Further, the volume of the organic solvent is 30 to 50mL/mol (preferably 40 mL/mol) based on the amount of the substance of meta-tetra (4-pyridyl) porphine.
Further, the volume of the solvent is 10 to 20mL/mol (preferably 13 mL/mol) based on the amount of the substance of copper hexafluorosilicate.
Preferably, the dripping speed of the copper hexafluorosilicate solution is 0.05-0.2mL/s.
In particular, the present invention recommends that both solutions be preheated at 60-70 ℃ (preferably 70 ℃) before the copper hexafluorosilicate solution is added dropwise to the meta-tetra (4-pyridyl) porphine solution. Typically 50-60min, in the embodiments of the present invention, the preheating time is 50min. The invention also recommends that the copper hexafluorosilicate solution is continuously shaken in the dripping process to prevent the copper hexafluorosilicate solution from settling before dripping.
Further, the post-treatment is as follows: the reaction solution is placed for one day at room temperature and then filtered, the obtained filter cake is washed by absolute ethyl alcohol and absolute methyl alcohol (preferably washed three times), and the fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) is obtained after drying 6 )]。
In a third aspect, the present invention also provides the fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]In separation C 2 H 2 /CO 2 Application in mixed gas.
The fluorosilicate MOF material of the present invention features that the metal salt is copper hexafluorosilicate and the organic ligand is m-tetra (4-pyridyl) porphine, and through the anion column and porphyrin ligand and C, the fluorosilicate MOF material has proper pore size and fluoridized functional site 2 H 2 Hydrogen bond and strong interaction formed between the two materials can enhance the recognition of acetylene, and can be used for separating C 2 H 2 /CO 2 Mixing the gases and dividingThe solid adsorbent has high separation selectivity and high adsorption capacity, and is excellent in both properties.
The adsorption-based gas separation is an environment-friendly and efficient separation technology, wherein the metal-organic framework material has a remarkable prospect in separating industrial gas due to the characteristics of adjustable pore diameter, high specific surface area, easiness in functionalization and the like. Because the novel fluorosilicate MOF material has proper pore diameter and fluorinated functional site, the recognition of acetylene can be enhanced through the action of hydrogen bond, and C is realized 2 H 2 /CO 2 And separating the mixed gas at normal temperature and normal pressure. The novel fluorosilicate MOF material provided by the invention is a material with excellent separation selectivity and acetylene adsorption capacity.
Compared with the prior art, the invention has the following beneficial effects:
(1) The metal salt used in the fluorosilicate porous hybrid material is copper hexafluorosilicate, and the organic ligand is m-tetra (4-pyridyl) porphin, so that the fluorosilicate porous hybrid material is an anion pillared metal organic framework material with proper pore diameter and fluoride functional position;
(2) The fluorosilicate porous hybrid material has proper pore diameter and fluorinated functional site, and through the hydrogen bond and strong interaction between the anion column and porphyrin and acetylene, the recognition of acetylene by the material is enhanced, so that the adsorption quantity of acetylene is higher than that of carbon dioxide, and separation C is realized 2 H 2 /CO 2 The capability of mixed gas, high separation selectivity, high adsorption capacity and high separation performance.
Drawings
Figure 1 is an XRD pattern of the novel fluorosilicate MOF material prepared in example 1.
Fig. 2 is a nitrogen adsorption and desorption isotherm at 77K for the novel fluorosilicate MOF material prepared in example 1.
FIG. 3 is a C of a novel fluorosilicate MOF material prepared in example 1 2 H 2 /CO 2 Adsorption graph.
FIG. 4 is a graph of the fluorosilicate hybridization material prepared in example 1 at 296K C 2 H 2/ CO 2 IAST selectivity map of the mixed gas.
FIG. 5 is example 1C at 296K 2 H 2 Adsorption isotherm data fitting graph of gas
FIG. 6 is a graph of CO at 296K for example 1 2 Adsorption isotherm data fitting graph of gas
Detailed Description
The technical scheme of the invention is further specifically described below through specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
0.075mmol,48mg of meta-tetra (4-pyridyl) porphine is dispersed in 3mL of acetic acid with shaking, designated as solution A; 0.15mmol,32mg of copper hexafluorosilicate was dissolved in 2mL of ethanol, designated solution B, and solution A, B was simultaneously preheated in an oven at 70℃for 50min. Slowly adding the solution B into the solution A by shaking at 70 ℃ at the dropwise adding rate of 0.05-0.2mL/s. The mixed solution was kept in an oven at 70℃for 10 hours, and left at room temperature for one day after taking out. And after the reaction is finished, filtering to obtain dark red powder, flushing with absolute ethyl alcohol and absolute methyl alcohol for three times, and vacuum drying at 70 ℃ to obtain the novel fluorosilicate MOF material.
The purity was first verified by powder X-ray diffraction and as shown in figure 1, [ Cu (TPyP) (SiF) was demonstrated by XRD pattern of the novel fluorosilicate MOF material 6 )]The permanent porosity of the material was determined by measuring the nitrogen adsorption and desorption isotherm at 77K, as shown in FIG. 2, and the specific surface area was measured to be 534.8m 2 The temperature/g, 77K is maintained by liquid nitrogen.
The gas separation capability of the fluorosilicate porous hybrid material prepared in this example is detected, and before the gas adsorption separation capability detection, the guest solvent in the framework is removed by activation treatment: the powder sample of the as-synthesized novel fluorosilicate polymofe material product was first subjected to at least 8 solvent exchanges with dry methanol over two days, and then vacuum pulled on a Micromeritics ASAP 2020 instrument at a temperature rise rate of 5c to 65 c for 24 hours until a pre-measurement vent rate of 4mmHg/min.
The detected gas is C 2 H 2 And CO 2 The temperature is 296K, the temperature can be stabilized by a low-temperature constant-temperature tank, the test pressure is 0-1 bar, and the used gas and the purity thereof comprise: n (N) 2 (>99.999％)、He(99.999％)、C 2 H 2 (99.99％)、CO 2 (99.99％)。
The dry methanol used for the exchange was HPLC grade methanol produced by Alfa Aesar.
The gas adsorption test results are shown in fig. 3 and 4:
as shown in FIG. 3, the gas adsorption test was performed using a Micromeritics ASAP 2020 full-automatic adsorber, and the result shows that the adsorption amount of acetylene is 92.1cm at 296K and 1bar 3 Per g, adsorption capacity of carbon dioxide 77.9cm 3 /g。
As shown in FIG. 4, C was calculated by IAST at 296K, 1bar 2 H 2 /CO 2 The IAST selectivity was 7 (50/50, v/v). Therefore, the novel fluorosilicate MOF material has excellent adsorption capacity and separation selectivity of gas.
The gas adsorption selectivity IAST is calculated as follows:
the pure component isotherm data of acetylene and carbon dioxide are calculated by fitting with a double-site langmuir-freude isotherm model:
saturated capacity of A gas component, C 1 And C 2 Is Freund's constant, b 1 And b 2 Is Langmuir constant, temperature dependent, C 1 、C 2 And b 1 、b 2 Obtained by Origin software fitting, p is pressure.
Pure gas adsorption equation parameters obtained based on the fitting define C 2 H 2 /CO 2 Ideal gas adsorption separation theory (IAST) model for separationType (2):
x 1 and x 2 To at partial pressure p 1 And p 2 The molar loading of the adsorption phase and the gas phase are balanced, S ads I.e. the IAST value, is calculated by Origin software.
Example 2 (reaction temperature different from example 1)
0.0778mmol,48mg of meta-tetra (4-pyridyl) porphine is dispersed in 3mL of acetic acid, 0.1556mmol,32mg of copper hexafluorosilicate is dissolved in 2mL of ethanol, the molar ratio of ligand to salt is 1:2, preheating for 50 minutes at 60 ℃ in an oven. The salt solution is dripped into the ligand solution at 60 ℃ and kept at the temperature of 60 ℃ for one night, and the dark red product is obtained after filtration and drying. The desired material was successfully prepared at this temperature, but characterization showed that the material was not pure.
Example 3 (reaction ligand to salt ratio different from example 1)
0.0778mmol,48mg of meta-tetra (4-pyridyl) porphine is dispersed in 3mL of acetic acid, 0.0778mmol,16mg of copper hexafluorosilicate is dissolved in 2mL of ethanol, the molar ratio of ligand to salt is 1:1, preheating for 50 minutes at 70 ℃ in an oven. The salt solution is dripped into the ligand solution at 70 ℃ and kept at 70 ℃ for one night, and the dark red product is obtained after filtration and drying. The product obtained in this ratio is impure and has ligand which is not fully reacted.
Comparative example 1
0.25mmol,150mg of m-tetrakis (4-pyridyl) porphine and 2.5mmol,515mg of copper hexafluorosilicate were dissolved in 10ml of N, N-dimethylformamide and the mixed solution was placed in an oven at 120℃for heating reaction for 2 days. And filtering after the reaction is finished to obtain mauve powder, flushing with water and absolute methanol for three times respectively, drying under vacuum to obtain mauve products, and performing XRD test to obtain the non-synthesized required material.
Comparative example 2
0.25mmol,150mg of meta-tetra (4-pyridyl) porphine is dispersed and dissolved in 5mL of methanol, 0.5mmol,103mg of copper hexafluorosilicate is dissolved in 5mL of water, the two are mixed, heated and refluxed for 12 hours at 65 ℃, filtered, washed and dried to obtain the desired product.
Comparative example 3
0.25mmol,150mg of meta-tetra (4-pyridyl) porphine is dispersed in 8mL of chloroform, 0.25mmol,51.5mg of copper hexafluorosilicate is dissolved in 2mL of methanol, the two are mixed, the mixed solution is heated and refluxed for 12 hours at 65 ℃, and the desired product is not obtained after filtration, washing and drying.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. Fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]The preparation method is characterized by comprising the following steps:
uniformly dispersing m-tetra (4-pyridyl) porphin in an organic solvent to obtain a m-tetra (4-pyridyl) porphin solution; dissolving copper hexafluorosilicate in a solvent to obtain a copper hexafluorosilicate solution; dripping the copper hexafluorosilicate solution into the meta-tetra (4-pyridyl) porphine solution at 60-70 ℃, reacting for 8-10h, and performing post-treatment on the obtained reaction solution to obtain the fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]；
The ratio of the amount of the substance of the meta-tetra (4-pyridyl) porphine to the copper hexafluorosilicate is 1:1.75-2.15; the organic solvent is acetic acid or methanol; the solvent is ethanol or water.
2. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]The preparation method of (2) is characterized in that: the volume of the organic solvent is 30-50mL/mol based on the amount of the substance of m-tetra (4-pyridyl) porphine.
3. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]The preparation method of (2) is characterized in that: the solvent bodyThe total amount of the copper hexafluorosilicate is 10-20mL/mol.
4. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]The preparation method of (2) is characterized in that: the dripping speed of the hexafluorosilicic acid copper solution is 0.05-0.2mL/s.
5. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]The preparation method of (2) is characterized in that: the temperature of the reaction was 70 ℃.
6. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]The preparation method of (2) is characterized in that: the organic solvent is acetic acid.
7. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]The preparation method of (2) is characterized in that: the solvent is ethanol.
8. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]The preparation method of (2) is characterized in that the post-treatment is as follows: standing the reaction solution at room temperature for one day, filtering, washing the obtained filter cake with absolute ethyl alcohol and absolute methyl alcohol in sequence, and drying to obtain the fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]。
9. A fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]。
10. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF 6 )]In separation C 2 H 2 /CO 2 Application in mixed gas.
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