CN112844321B - Synthesis preparation of series column-supported metal organic framework materials and application of series column-supported metal organic framework materials in low-carbon hydrocarbon separation - Google Patents
Synthesis preparation of series column-supported metal organic framework materials and application of series column-supported metal organic framework materials in low-carbon hydrocarbon separation Download PDFInfo
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Abstract
The synthesis and preparation of series column-supported metal organic framework materials and the separation application of low carbon hydrocarbon thereof belong to the technical field of crystalline porous material preparation and gas separation. The D-camphoric acid series pillared microporous MOF material is formed by cheap and easily obtained organic ligand D-camphoric acid (cam), columnar ligand pyrazine (pyz), 2-aminopyrazine (apyz), triethylene diamine (dabco), metallic copper salt, cobalt salt and nickel salt under the solvothermal condition. The MOF crystal structure has higher porosity, and meanwhile, the MOF crystal structure has a regular pore channel structure, the size of a channel is slightly larger than the dynamic size of a low-carbon hydrocarbon molecule, so that a structural basis is provided for the adsorption and separation of the low-carbon hydrocarbon gas molecule, and the MOF material is applied to the efficient adsorption and separation of ethane/ethylene mixed gas. The ethane gas molecules and the framework have stronger acting force, so that the effect of preferentially adsorbing ethane gas in the ethane-ethylene mixed gas is realized, the ethylene component in the mixed gas is purified, and the energy consumption is reduced.
Description
Technical Field
The invention belongs to the technical field of crystalline porous material preparation and gas separation, and particularly relates to a synthesis preparation method of a D-camphoric acid series pillared Metal Organic Framework (MOF), which is characterized in that the series MOF can realize the purification of ethylene from ethane/ethylene mixed gas with low energy consumption.
Background
Ethylene (C) 2 H 4 ) Is an important chemical basic raw material, and can be used for preparing rubber and plastics, processing alcohol and the like. The scale of production, yield and technology of ethylene mark a state of the state petrochemical industry. It is usually carried out by ethane (C) 2 H 6 ) By-products such as ethane, etc., are inevitably produced during the steam cracking and thermal decomposition of ethylene, and in order to obtain a high-purity polymer-grade ethylene product, it is often necessary to perform an ethylene purification operation, C 2 H 6 /C 2 H 4 The separation of (2) is also of particular importance. At present, the methodThe industrial separation technology is one of the most energy-intensive processes in chemical industry, and because ethylene and ethane have similar molecular size and volatility, a large rectifying tower with 120-180 trays and a high reflux ratio are required, so that the production energy consumption is greatly improved. Thus, exploring and developing separation C 2 H 4 /C 2 H 6 Efficient and energy-saving separation methods and materials for the separation of mixtures are highly desirable. In recent years, adsorption separation technology has attracted much attention because of its simplicity of operation, low energy consumption, and high separation selectivity, and the core of the separation technology lies in the development of a suitable adsorbent material in order to achieve both adsorption capacity and adsorption selectivity.
Metal organic framework Materials (MOFs) are organic-inorganic hybrid materials with intramolecular pores formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds, are novel porous materials with periodic three-dimensional structures, and are widely applied to the fields of gas storage and separation, catalysis, drug sustained release and the like. Compared with the traditional porous adsorbent materials (such as activated carbon, zeolite molecular sieves, carbon molecular sieves, silica gel, resin and the like), the MOFs has a unique pore structure which is particularly represented in the aspects of high porosity, adjustable pore structure, easy functionalization and the like, and the structural characteristics enable the MOFs to generate different host-guest interactions and/or screening effects aiming at different gas molecules to achieve the purpose of separating gas economy and energy. For C 2 H 6 /C 2 H 4 The separation of the mixture system, the MOFs material can selectively adsorb the ethylene due to the pi bond interaction between the unsaturated metal vacancy and the ethylene or due to the pore size sieving effect, in other words, the adsorption of the ethylene is more favorable for both the consideration of the dynamic factor and the thermodynamic factor. In actual production, if ethylene products with higher purity are obtained, a plurality of adsorption-desorption cycles are required, so that the production energy consumption is obviously improved, and the industrial application of the ethylene products is restricted. Therefore, the ethane preferential adsorbent material can be applied to the actual chemical production process more energy-saving and with low cost. The invention adopts chiral carboxylic acid organic ligand D-camphoric acid (D-cam) and columnar shapeNitrogen-containing organic ligands pyrazine (pyz), 2-aminopyrazine (apyz), triethylene diamine (dabco) and metallic copper salt, cobalt salt and nickel salt are self-assembled under the solvothermal condition to form a series of pillared microporous MOF materials. The crystal structure of the series of MOF materials has higher porosity and a pore structure with a regular shape, and provides a structural basis for adsorption and separation of low-carbon hydrocarbon gas molecules. In addition, the series of MOF materials show preferential adsorption to ethane gas in ethane/ethylene mixed gas adsorption, so that the efficient purification of ethylene is realized.
Disclosure of Invention
The invention aims to provide a preparation method of a D-camphoric acid series pillared microporous MOF material, and the series MOF material can be used for high-efficiency purification of ethylene in separation of ethane/ethylene mixed gas.
The pillared microporous MOF material is characterized in that the organic ligands are as follows: one of columnar ligands pyrazine (pyz), 2-aminopyrazine (apyz) and triethylene diamine (dabco) and D-camphoric acid (D-cam) react with a metal source (copper, cobalt and nickel) under solvothermal conditions to prepare a green, purple and blue-green blocky crystal material, wherein the chemical molecular formula of the blocky crystal material is M-cam-L, and M = Cu, co and Ni; l = pyz, apyz, dabco);
in particular M 2 C 24 H 32 O 8 N 2 [M 2 (cam) 2 (pyz)](M-cam-pyz)、M 2 C 24 H 33 O 8 N 3 [M 2 (cam) 2 (apyz)](M-cam-apyz)、M 2 C 26 H 40 O 8 N 2 [M 2 (cam) 2 (dabco)](M-cam-dabco), wherein M is Cu, co and Ni, cam is D-camphoric acid, pyz is pyrazine, apyz is 2-aminopyrazine, and dabco is triethylene diamine; the metal in the metal source is selected from one of copper, cobalt and nickel.
The M-cam-L (M = Cu, co, ni; L = pyz, apyz, dabco) material belongs to the monoclinic system and the space group is
Wherein the unit cell parameters of the Cu-cam-pyz are as follows:
α＝90°，β＝90°，γ＝90°；
the Co-cam-pyz unit cell parameters were:
α＝89.7(3)°，β＝90.7(2)°，γ＝89.4(2)°；
the Ni-cam-pyz unit cell parameters are:
α＝90°，β＝90°，γ＝90°；
the unit cell parameters of Cu-cam-apyz are as follows:
α＝89.05(15)°，β＝89.52(13)°，γ＝88.33(14)°；
the Co-cam-apyz unit cell parameters are:
α＝89.78(8)°，β＝91.67(9)°，γ＝89.30(6)°；
the Ni-cam-apyz unit cell parameters are:
α＝89.6(2)°，β＝91.8(2)°，γ＝90.7(2)°；
the Cu-cam-dabco unit cell parameters are:
α＝89.5(9)°，β＝90.41(5)°，γ＝89.83(31)°；
the Co-cam-dabco unit cell parameters are:
α＝90°，β＝90°，γ＝90°；
the Ni-cam-dabco unit cell parameters are:
α＝90.0(3)°，β＝87.4(3)°，γ＝87.3(3)°。
in M-cam-L (M = Cu, co, ni; L = pyz, apyz, dabco), every second M 2+ The ion coordinates with four eight O atoms from different cam carboxylic acid ligands, two N atoms from additional L ligands, ultimately determining a coordination number of 5 for the metal center; in the smallest asymmetric cell, four μ 4 Cam through the carboxyl O atom and two μ 4 L is coordinated to two M (II) centers. The coordination mode finally forms a copper double-wheel paddle Secondary Building Unit (SBU), each binuclear metal SBU is coordinated with four crystallographically independent cam, and the coordination is circulated in such a way to form a two-dimensional layered structure, and meanwhile, two crystallographically independent L organic ligands are connected in the up-down direction of the layered structure to form a final column support type frame. Therefore, the dual-core metal SBU can be regarded as a ten-connection topological node, and finally, the ten-connection topological node is formedA classical pcu topology network. Furthermore, the ligands are disordered in the M-cam-dabco framework structure.
The synthesis method of the M-cam-L material mainly comprises the following steps:
preparing Cu-cam-pyz by dissolving organic ligands D-camphoric acid (cam), pyrazine (pyz) and copper acetate in N, N-Dimethylacetamide (DMA) and water (H) under sealed condition 2 O) and tetrafluoroboric acid (HBF) 4 ) The crystal sample of the metal organic framework is obtained through solvothermal reaction in the mixed solution of (1).
And (2) preparing Co-cam-pyz, namely dissolving organic ligands D-camphoric acid, pyrazine and cobalt nitrate in N, N-Dimethylacetamide (DMA) under a sealed condition, and obtaining a crystal sample of the metal organic framework through a solvothermal reaction.
And (3) preparing Ni-cam-pyz, namely dissolving organic ligands D-camphoric acid, pyrazine and nickel nitrate in N, N-Dimethylformamide (DMF) under a sealed condition, and carrying out solvothermal reaction to obtain a crystal sample of the metal organic framework.
Preparing Cu-cam-apyz, namely dissolving an organic ligand D-camphoric acid, 2-aminopyrazine and copper acetate in a mixed solution of N, N-Dimethylformamide (DMF), water and tetrafluoroboric acid under a sealed condition, and carrying out a solvothermal reaction to obtain a crystal sample of the metal organic framework.
And (2) preparing Co-cam-apyz, namely dissolving organic ligands D-camphoric acid, 2-aminopyrazine and cobalt chloride in a mixed solution of N, N-Dimethylacetamide (DMA) and water under a sealed condition, and carrying out a solvothermal reaction to obtain a crystal sample of the metal organic framework.
And (2) preparing Ni-cam-apyz, namely dissolving organic ligands D-camphoric acid, 2-aminopyrazine and nickel nitrate in a mixed solution of N, N-Dimethylacetamide (DMA) and water under a sealed condition, and carrying out solvothermal reaction to obtain a crystal sample of the metal organic framework.
Preparing Cu-cam-dabco, namely dissolving organic ligands D-camphoric acid, triethylene diamine and copper acetate in a mixed solution of N, N-Dimethylformamide (DMF), methanol, water and tetrafluoroboric acid under a sealed condition, and obtaining a crystal sample of the metal organic framework through solvothermal reaction.
Preparing Co-cam-dabco by dissolving organic ligands D-camphoric acid, triethylene diamine and cobalt nitrate in a mixed solution of N, N-Dimethylformamide (DMF), methanol and tetrafluoroboric acid under a sealed condition, and carrying out a solvothermal reaction to obtain a crystal sample of the metal organic framework.
Preparing Ni-cam-dabco by dissolving organic ligands D-camphoric acid, triethylene diamine and nickel nitrate in a mixed solution of N, N-Dimethylformamide (DMF), ethanol and tetrafluoroboric acid under a sealed condition, and obtaining a crystal sample of the metal organic framework through a solvothermal reaction
The proportion of the organic ligand D-camphoric acid (cam), L (pyz, apyz, dabco) and metal salt in the technical scheme of M-cam-L is 1 (1-9) to 0.1-10; DMF/DMA, CH in mixed solvent 3 OH/CH 3 CH 2 OH、H 2 O and HBF 4 The volume ratio of (1-80) to 1; the solvent thermal reaction temperature is 70-120 ℃, and the reaction time is 2-72 h.
After DMF or DMA washing, methanol and dichloromethane solvent exchange and vacuum solvent molecule removal (namely an activation process) are carried out on the obtained M-cam-L material, the M-cam-L material is used for separating ethane-ethylene mixed gas, alkane is preferentially adsorbed in the separation process, one-step purification of ethylene can be realized, and the separation condition can be both normal temperature and 0-100 KPa.
The invention prepares a series of pillared microporous MOF materials based on cheap and easily-obtained organic ligands D-camphoric acid (cam), pyrazine (pyz)/2-aminopyrazine (apyz)/triethylene diamine (dabco) and metal source copper/cobalt/nickel. The specific beneficial effects of MOF materials are shown as follows:
(1) The organic ligands D-camphoric acid (cam), pyrazine (pyz)/2-aminopyrazine (apyz)/triethylene diamine (dabco) used in the material synthesis have simpler structure and relatively low price. The pillared structure forms a regular pore channel shape, wherein columnar ligands and metal centers are replaced, thereby regulating the physical and chemical properties of the pore channels of the MOF material.
(2) The crystal structure of the finally obtained MOF material has a regular pore channel structure, and the pore channel size is slightly larger than the low-carbon hydrocarbon molecular dynamics size, so that a structural basis is provided for the adsorption process of the gases.
(3) The MOF material has a pore channel structure with a regular shape, and ethane gas molecules and the framework have stronger acting force, so that the effect of preferentially adsorbing ethane gas in the ethane-ethylene mixed gas is realized, the ethylene component in the mixed gas is purified, and the energy consumption in the separation process is reduced.
Drawings
FIG. 1 is a schematic representation of the three-dimensional crystal structure of M-cam-pyz (M = Cu, co, ni) in the present invention.
Fig. 2 is a schematic diagram of the three-dimensional crystal structure of M-cam-apyz (M = Cu, co, ni) in the present invention.
FIG. 3 is a schematic diagram of the three-dimensional crystal structure of M-cam-dabco (M = Cu, co, ni) in the present invention (ligand disorder). FIG. 4 is a powder diffraction pattern of a freshly synthesized sample of M-cam-L (M = Cu, co, ni; L = pyz, apyz, dabco) and a sample after adsorption testing in accordance with the present invention.
FIG. 5 is a graph showing the single component adsorption of ethane and ethylene by M-cam-L (M = Cu, co, ni; L = pyz, apyz, dabco) under 298K conditions in accordance with the present invention.
FIG. 6 is a graph showing the breakthrough of an ethane/ethylene mixture at 298K for M-cam-L (M = Cu, co, ni; L = pyz, apyz, dabco) in the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
the first step is as follows: 10mg of D-camphoric acid, 16mg of pyrazine and 20mg of anhydrous copper acetate were weighed and dissolved in a mixed solution of 3mL of N, N-Dimethylacetamide (DMA), 3mL of water and 75. Mu.L of tetrafluoroboric acid. After sonication and obtaining a homogeneous solution, the solution was then transferred to a 20mL glass reaction flask and reacted at 95 ℃ for 48h to obtain the Cu-cam-pyz crystalline sample with a yield of 70% (calculated on the basis of the metal salt).
Example 2:
the first step is as follows: 10mg of D-camphoric acid, 28mg of pyrazine and 29mg of cobalt nitrate hexahydrate were weighed and dissolved in 8mL of N, N-Dimethylacetamide (DMA). After sonication and homogeneous solution was obtained, the sample was transferred to a 20mL glass reaction flask and reacted at 95 ℃ for 48h to obtain the Co-cam-pyz crystalline sample with a yield of 66% (based on the metal salt).
Example 3:
the first step is as follows: 10mg of D-camphoric acid, 16mg of pyrazine and 15mg of nickel nitrate hexahydrate were weighed and dissolved in 5mL of N, N-Dimethylformamide (DMF). After ultrasonic treatment and obtaining of a homogeneous solution, the solution is transferred into a 20mL glass reaction flask and is subjected to isothermal reaction at 120 ℃ for 48 hours to obtain the Ni-cam-pyz crystalline sample with the yield of 50% (calculated on the basis of metal salts).
Example 4:
the first step is as follows: 10mg of D-camphoric acid, 19mg of 2-aminopyrazine and 24mg of anhydrous copper acetate are weighed and dissolved in a mixed solution of 3mL of N, N-Dimethylformamide (DMF), 3mL of water and 75. Mu.L of tetrafluoroboric acid. After sonication and homogeneous solution was obtained, the solution was transferred to a 20mL glass reaction flask and reacted at 80 ℃ for 48h to obtain the Cu-cam-apyz crystalline sample with a yield of 55% (based on the metal salt).
Example 5:
the first step is as follows: 10mg of D-camphoric acid, 19mg of 2-aminopyrazine and 24mg of cobalt chloride hexahydrate were weighed and dissolved in a mixed solution of 3mL of N, N-Dimethylacetamide (DMA) and 3mL of water. After ultrasonic treatment and homogeneous solution obtaining, the sample is transferred into a 20mL glass reaction bottle and reacts at a constant temperature of 105 ℃ for 48 hours to obtain the Co-cam-apyz crystalline sample with a yield of 60% (calculated based on metal salt).
Example 6:
the first step is as follows: 10mg of D-camphoric acid, 14mg of 2-aminopyrazine and 29mg of nickel nitrate hexahydrate were weighed and dissolved in a mixed solution of 3mL of N, N-Dimethylacetamide (DMA) and 3mL of water. After ultrasonic treatment and homogeneous solution obtaining, the solution is transferred into a 20mL glass reaction bottle and reacted for 48 hours at a constant temperature of 105 ℃ to obtain the Ni-D cam-apyz crystalline sample with 50% yield (calculated based on metal salt).
Example 7:
the first step is as follows: 20mg of D-camphoric acid, 30mg of triethylene diamine and 40mg of anhydrous copper acetate were weighed and dissolved in a mixed solution of 3mL of N, N-Dimethylformamide (DMF), 2mL of methanol, 1mL of water and 400. Mu.L of tetrafluoroboric acid. After sonication and obtaining a homogeneous solution, the solution was then transferred into a 20mL glass reaction flask and reacted at 80 ℃ for 48h to obtain the Cu-cam-dabco crystalline sample with a yield of 50% (based on the metal salt).
Example 8:
the first step is as follows: 10mg of D-camphoric acid, 11mg of triethylenediamine, and 30mg of cobalt nitrate hexahydrate were weighed and dissolved in a mixed solution of 3mL of N, N-Dimethylformamide (DMF), 2mL of methanol, and 60. Mu.L of tetrafluoroboric acid. After sonication and obtaining a homogeneous solution, the solution was then transferred into a 20mL glass reaction flask and reacted at 105 ℃ for 48h to obtain the Co-cam-dabco crystalline sample with a yield of 53% (based on the metal salt).
Example 9:
the first step is as follows: 20mg of D-camphoric acid, 30mg of triethylene diamine and 40mg of nickel nitrate hexahydrate were weighed and dissolved in a mixed solution of 4mL of N, N-Dimethylformamide (DMF), 4mL of ethanol and 100. Mu.L of tetrafluoroboric acid. After sonication and obtaining a homogeneous solution, it was subsequently transferred into a 20mL glass reaction flask and reacted at 105 ℃ for 48h to obtain the Ni-cam-dabco crystalline sample in a yield of 38% (based on the metal salt).
The second step is that: selecting a single crystal sample with proper size and good crystallization, collecting diffraction data by using a single crystal diffractometer under the condition of 298K, and refining by using related structure analysis software Olex2 to obtain a crystal structure. The specific structure is shown in the attached drawings of the specification. The purity of the bulk preparation samples was confirmed by X-ray powder diffraction techniques.
The third step: in order to remove solvent molecules in the pore channels of the material, the crystalline sample obtained above is washed by DMF or DMA and then soaked in absolute methanol solvent, the solvent exchange process lasts for 6 times, and finally dichloromethane is used as an exchange solvent for treatment for 3 times. The exchanged sample is degassed at 100 ℃ under vacuum for 12h to prepare the material for testing gas adsorption.
The fourth step: and (3) carrying out a single-component static adsorption test, loading the material into an adsorption tube, and collecting the data of the adsorption curve of ethane and ethylene at 25 ℃.
The fifth step: the test material was loaded onto a separation column, purged with nitrogen at 100 ℃ for 5h, then purged with a 50/50 ethane/ethylene mixture, and the signal was detected by a mass spectrometer to collect the breakthrough curve data.
The crystal structures in FIGS. 1-3 show that: the M-cam-L (M = Cu, co, ni; L = pyz, apyz, dabco) has a dual-core metal SBU structure, and has regular pore channels along the directions of a and b axes, wherein every two M in the structure 2+ The ions are coordinated in a double-bladed coordination mode with eight O atoms from four different cam ligands, and two N atoms from different L ligands.
The powder diffraction pattern in fig. 4 shows: the freshly prepared sample was good in purity and good in crystallization. Meanwhile, the sample after the adsorption test still keeps good crystallinity.
The ethane-ethylene single component adsorption curve in fig. 5 shows: M-cam-L has better adsorption capacity and potential separation possibility to ethane and ethylene gas, and the adsorption capacity of ethane is larger under the same pressure of a low-pressure area, which indicates that the molecular force of the framework and the ethane gas is stronger. The phenomenon lays a foundation for the series of materials to preferentially capture ethane gas in ethane-ethylene mixed gas to realize one-step ethylene purification.
The ethane-ethylene mixture breakthrough curves in fig. 6 show that: the series of column support materials have good separation capacity on ethane-ethylene mixed gas, and ethane is adsorbed in a separation column in a certain time, so that a pure ethylene product can be directly obtained. This phenomenon confirms their good ethane/ethylene separation capacity. The results show that the series of microporous materials have a regular channel space structure and show good separation performance on ethane and ethylene. Meanwhile, the invention provides beneficial reference for the application of the pillared metal-organic framework material in energy-saving and efficient separation of olefin and alkane mixtures.
The foregoing is a preferred embodiment of the present invention, but the present invention should not be limited to the disclosure of this embodiment. Therefore, equivalents and modifications may be made thereto without departing from the spirit of the disclosure.
Claims (7)
- A D-camphoric acid series pillared microporous MOF material is characterized in that the chemical molecular formula of the material is M-cam-L, wherein M = Cu, co or Ni; l = pyz, apyz, one of dabco, cam is D-camphoric acid, pyz is pyrazine, apyz is 2-aminopyrazine, dabco is triethylenediamine.
- 2. The D-camphoric acid series pillared microporous MOF material of claim 1, wherein the organic ligand and the metal source are reacted under solvothermal conditions to produce a green, violet, or blue-green bulk crystalline material having a specific chemical formula of M 2 C 24 H 32 O 8 N 2 [M 2 (cam) 2 (pyz)](M-cam-pyz)、M 2 C 24 H 33 O 8 N 3 [M 2 (cam) 2 (apyz)](M-cam-apyz)、M 2 C 26 H 40 O 8 N 2 [M 2 (cam) 2 (dabco)](M-cam-dabco), wherein M is Cu, co and Ni, cam is D-camphoric acid, pyz is pyrazine, apyz is 2-aminopyrazine, and dabco is triethylene diamine;wherein the Cu-cam-pyz unit cell parameters are as follows:
α＝90°，β＝90°，γ＝90°；
the Co-cam-pyz unit cell parameters were:
α＝89.7(3)°，β＝90.7(2)°，γ＝89.4(2)°；
the Ni-cam-pyz unit cell parameters are:
α＝90°，β＝90°，γ＝90°；
the Cu-cam-apyz unit cell parameters are:
α＝89.05(15)°，β＝89.52(13)°，γ＝88.33(14)°；
the Co-cam-apyz unit cell parameters are:
α＝89.78(8)°，β＝91.67(9)°，γ＝89.30(6)°；
the Ni-cam-apyz unit cell parameters are:
α＝89.6(2)°，β＝91.8(2)°，γ＝90.7(2)°；
the Cu-cam-dabco unit cell parameters are:
α＝89.5(9)°，β＝90.41(5)°，γ＝89.83(31)°；
the Co-cam-dabco unit cell parameters were:
α＝90°，β＝90°，γ＝90°；
the Ni-cam-dabco unit cell parameters are:
α＝90.0(3)°，β＝87.4(3)°，γ＝87.3(3)°。
- 3. a method of making a D-camphoric acid series pillared microporous MOF material of claim 1, comprising the steps of:dissolving D-camphoric acid, pyrazine and copper acetate in a mixed solution of N, N-Dimethylacetamide (DMA), water and tetrafluoroboric acid, stirring by ultrasonic oscillation, carrying out solvothermal reaction under the reaction condition of 70-120 ℃, keeping the temperature for 2-72 h, and washing;preparing Co-cam-pyz, namely dissolving organic ligands D-camphoric acid, pyrazine and cobalt nitrate in N, N-Dimethylacetamide (DMA), stirring by ultrasonic oscillation, carrying out solvothermal reaction under the reaction condition of 70-120 ℃, keeping the temperature for 2-72 h, and washing;dissolving organic ligands D-camphoric acid, pyrazine and nickel nitrate in N, N-Dimethylformamide (DMF), stirring by ultrasonic oscillation, carrying out solvent thermal reaction under the reaction condition of 100-140 ℃, keeping the temperature for 8-72 h, and washing;dissolving organic ligands D-camphoric acid, 2-aminopyrazine and copper acetate in a mixed solution of N, N-Dimethylformamide (DMF), water and tetrafluoroboric acid, stirring by ultrasonic oscillation, carrying out solvent thermal reaction under the reaction condition of 70-100 ℃, keeping the temperature for 2-48 h, and washing;preparing Co-cam-apyz, namely dissolving an organic ligand D-camphoric acid, 2-aminopyrazine and cobalt chloride in a mixed solution of N, N-Dimethylacetamide (DMA) and water, stirring by ultrasonic oscillation, carrying out solvothermal reaction under the reaction condition of 80-120 ℃, keeping the temperature for 2-48 h, and washing;dissolving organic ligands D-camphoric acid, 2-aminopyrazine and nickel nitrate in a mixed solution of N, N-Dimethylacetamide (DMA) and water, stirring by ultrasonic oscillation, carrying out solvent thermal reaction under the reaction condition of 80-140 ℃ and constant temperature for 6-72 h, and washing;dissolving organic ligands D-camphoric acid, triethylene diamine and copper acetate in a mixed solution of N, N-Dimethylformamide (DMF), methanol, water and tetrafluoroboric acid, stirring by ultrasonic oscillation, carrying out solvent thermal reaction under the reaction condition of 50-120 ℃, keeping the temperature for 5-48 h, and washing;preparing Co-cam-dabco, dissolving organic ligands D-camphoric acid, triethylene diamine and cobalt nitrate in a mixed solution of N, N-Dimethylformamide (DMF), methanol and tetrafluoroboric acid, stirring by ultrasonic oscillation, carrying out solvent thermal reaction under the reaction condition of 80-140 ℃ and constant temperature for 4-72 h, and washing;the preparation of Ni-cam-dabco comprises the steps of dissolving organic ligands D-camphoric acid, triethylene diamine and nickel nitrate in a mixed solution of N, N-Dimethylformamide (DMF), ethanol and tetrafluoroboric acid, stirring by ultrasonic oscillation, carrying out solvent thermal reaction under the reaction condition of 80-140 ℃, keeping the temperature for 4-72 h, and washing.
- 4. The method according to claim 3, wherein the Cu-cam-apyz/dabco solvothermal reaction temperature is 85 ℃, the Cu/Co-cam-pyz solvothermal reaction temperature is 95 ℃, the Co/Ni-cam-apyz/dabco solvothermal reaction temperature is 105 ℃, the Ni-cam-pyz solvothermal reaction temperature is 120 ℃, and the temperature is kept constant for 48 hours.
- 5. The method of claim 3, wherein the Cu-cam-pyz is prepared by mixing the organic ligand D-camphoric acid, pyrazine and metal salt copper acetate in a molar ratio of 1 (2-6) to (1-6); DMA and H in mixed solvent 2 O and HBF 4 The volume ratio of (10-60) to 1;in the preparation of Co-cam-pyz, the molar ratio of an organic ligand D-camphoric acid to pyrazine to a metal salt cobalt nitrate is 1 (3-9) to 1-5; the volume of the solvent DMA is 2-20 mL;in the preparation of Ni-cam-pyz, the molar ratio of an organic ligand D-camphoric acid, pyrazine and metal salt nickel nitrate is 1 (1-5) to 1-5; the volume of the solvent DMA is 2-20 mL;in the preparation of Cu-cam-apyz, the molar ratio of an organic ligand D-camphoric acid, 2-aminopyrazine and metal salt copper acetate is 1 (1-9) to 1-10; DMF, H in mixed solvent 2 O and HBF 4 The volume ratio of (10-60) to 1;in the preparation of Co-cam-apyz, the molar ratio of an organic ligand D-camphoric acid, 2-aminopyrazine and metal salt cobalt chloride is 1 (1-8) to 0.1-10; DMA and H in mixed solvent 2 The volume ratio of O is 1 (0.1-10);in the preparation of Ni-cam-apyz, the molar ratio of an organic ligand D-camphoric acid, 2-aminopyrazine and metal salt nickel nitrate is 1 (1-8) to 0.1-10; DMA and H in mixed solvent 2 The volume ratio of O is 1 (0.1-10);in the preparation of Cu-cam-dabco, the molar ratio of an organic ligand D-camphoric acid, triethylene diamine and metal salt copper acetate is 1 (1-8) to 1-10; DMA and CH in mixed solvent 3 OH、H 2 O and HBF 4 The volume ratio of (1-50) to 1;in the preparation of Co-cam-dabco, the molar ratio of an organic ligand D-camphoric acid, triethylene diamine and metal salt cobalt nitrate is 1 (1-8) to 1-10; DMF, CH in mixed solvent 3 OH and HBF 4 The volume ratio of (10-80) to 1;in the preparation of Ni-cam-dabco, the molar ratio of an organic ligand D-camphoric acid, triethylene diamine and metal salt nickel nitrate is 1 (1-8) to 1-10; DMF, CH in mixed solvent 3 CH 2 OH and HBF 4 The volume ratio of (10-80) to (10-80) is 1.
- 6. The method of claim 5, wherein the organic ligand D-camphoric acid, pyrazine and metal salt copper acetate are present in a molar ratio of 1; DMA and H in mixed solvent 2 O and HBF 4 The volume ratio of (1);in the preparation of Co-cam-pyz, the molar ratio of an organic ligand D-camphoric acid to pyrazine to a metal salt cobalt nitrate is 1; the volume of the solvent DMA is 8mL;in the preparation of Ni-cam-pyz, the molar ratio of an organic ligand D-camphoric acid to pyrazine to a metal salt nickel nitrate is 1; the volume of the solvent DMA is 5mL;in the preparation of Cu-cam-apyz, the molar ratio of an organic ligand D-camphoric acid, 2-aminopyrazine and a metal salt copper acetate is 1; DMF and H in mixed solvent 2 O and HBF 4 The volume ratio of (1);in the preparation of Co-cam-apyz, the molar ratio of an organic ligand D-camphoric acid, 2-aminopyrazine and a metal salt cobalt chloride is 1; DMA and H in mixed solvent 2 The volume ratio of O is 1;in the preparation of Ni-cam-apyz, the molar ratio of an organic ligand D-camphoric acid, 2-aminopyrazine and a metal salt nickel nitrate is 1; DMA and H in mixed solvent 2 The volume ratio of O is 1;in the preparation of Cu-cam-dabco, the molar ratio of an organic ligand D-camphoric acid, triethylene diamine and a metal salt copper acetate is 1; DMA and CH in mixed solvent 3 OH、H 2 O and HBF 4 The volume ratio of (1) is 7.5;in the preparation of Co-cam-dabco, the molar ratio of an organic ligand D-camphoric acid, triethylene diamine and a metal salt cobalt nitrate is 1; DMF, CH in mixed solvent 3 OH and HBF 4 In a volume ratio of 50;in the preparation of Ni-cam-dabco, the molar ratio of an organic ligand D-camphoric acid, triethylene diamine and a metal salt nickel nitrate is 1; DMF, CH in mixed solvent 3 CH 2 OH and HBF 4 The volume ratio of (1) to (40).
- 7. The application of the D-camphoric acid series pillared microporous MOF material disclosed by claim 1 or 2, as an adsorption material, the material can be used for preferentially adsorbing ethane from an ethane/ethylene mixed gas, and purifying ethylene from the ethane/ethylene mixed gas in an energy-saving and low-cost manner, so that the high-efficiency adsorption separation of the ethane/ethylene mixed gas is realized.
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