CN108654564B - Preparation method and application of a coordination polymer porous material - Google Patents

Abstract

The invention discloses a preparation method and application of a coordination polymer porous material. The chemical formula of the coordination polymer porous material is (Me)₂NH₂)[Co₃(DCPN)₂(μ₃‑OH)(H₂O)]·11H₂And O, DCPN in the formula represents a 5- (3',5' -dicarboxyphenyl) nicotinic acid anion ligand. The preparation process of the porous coordination polymer material is also disclosed, and the porous coordination polymer material is prepared through the reaction of ligand 5- (3',5' -dicarboxyphenyl) nicotinic acid and cobalt salt in solvent. The application of the coordination polymer porous material as an adsorbent is also disclosed. The coordination polymer porous material provided by the invention can be used as an adsorbent, can be used for preparing materials for storage, separation, catalysis, sensing, molecular recognition and the like, and has a good application prospect.

Description

Preparation method and application of a coordination polymer porous material

technical field

The invention relates to a preparation method and application of a coordination polymer porous material.

Background technique

Metal-organic frameworks (MOFs, Metal-Organic Frameworks), also known as porous coordination polymers, are a class of crystalline porous materials. Porous MOFs are rich in pores and have good performance in adsorption separation, fluorescence sensing, catalysis, magnetism and other fields, and have received extensive attention. This type of material is a coordination polymer with periodic network structure and regular pores formed by using organic ligands containing carboxylic acid, phosphoric acid or nitrogen to connect with metal ions or metal clusters through coordination bonds, and the organic ligands are used as linkers. (linker), metal ions or metal clusters as nodes. The organic ligands used as linkers can be modified and the length can be controlled. There are many kinds of metal elements in the nodes that can participate in the coordination, and the MOFs material structure is rich. Compared with traditional inorganic porous molecular sieves and activated carbon materials, MOFs have the advantages of adjustable pore size, adjustable pore surface, and selective adsorption of gas molecules. By modifying or optimizing the linker or node, the gas adsorption and separation, catalysis, opto-electromagnetic and other properties of the material can be effectively improved.

Ethylene is an important chemical raw material for polymer production, and the purity of the raw material determines the quality of the product. Acetylene is the main by-product of ethane cracking to produce ethylene (about 1% by volume). In ethylene polymerization, acetylene will poison and deactivate the catalyst. In addition, the product of ethane cracking also contains a small amount of excess ethane. The separation of ethylene and ethane, as one of the most important industrial processes, has a very high energy consumption (7GJ·t ^-1 ), which accounts for the largest proportion of ethane production. 75-85% of the cost. Therefore, the removal of acetylene and ethane from ethylene with high efficiency and low energy consumption has attracted much attention of scientists.

At present, some scientists have synthesized and used MOFs porous materials to separate and remove ethane or acetylene from ethylene at room temperature and normal pressure, which reduces energy consumption and saves separation costs. It is a very promising separation method. However, existing materials are capable of separating and _purifying ethylene from _two components or _C2H4 / _C2H2 , and multiple purifications are required to achieve the polymer grade >99.95% requirement. The MOFs that can separate and purify ethylene from the three-component C ₂ H ₂ /C ₂ H ₄ /C ₂ H ₆ have not yet been reported.

SUMMARY OF THE INVENTION

In order to overcome the shortcomings of the existing MOFs porous material technology, one of the purposes of the present invention is to provide a coordination polymer porous material, and the second purpose of the present invention is to provide a preparation method of this coordination polymer porous material. The third purpose of the invention is to provide the application of the coordination polymer porous material, which can solve the problems of high energy consumption and three-component purification of ethylene in the separation and purification process in the prior art.

The technical scheme adopted by the present invention is:

A coordination polymer porous material, the chemical formula is (Me ₂ NH ₂ )[Co ₃ (DCPN) ₂ (μ ₃ -OH)(H ₂ O)]·11H ₂ O, where DCPN represents 5-(3 ',5'-dicarboxyphenyl)nicotinic acid anion ligand. This coordination polymer porous material is hereinafter referred to as TJT-100.

The porous material is a three-dimensional framework material with one-dimensional channels formed by DCPN and a trinuclear Co cluster connected, in which the trinuclear Co cluster unit is composed of two six-coordinated Co(II) and one five-coordinated Co(II). II) linked together by μ ₃ -OH.

，b＝11.9980

，c＝32.450

。The crystal form of the porous material belongs to the orthorhombic system, the space group is Pbca, and the unit cell parameter is: a=23.539

, b=11.9980

, c=32.450

.

The preparation method of the coordination polymer porous material is prepared by reacting the ligand 5-(3',5'-dicarboxyphenyl)nicotinic acid with cobalt salt in N,N-dimethylformamide solvent .

In the preparation method, the molar ratio of 5-(3',5'-dicarboxyphenyl)nicotinic acid to cobalt salt is 1:1.

In the preparation method, the cobalt salt is a divalent Co salt.

In the preparation method, the N,N-dimethylformamide solvent is a mixed solution composed of N,N-dimethylformamide and water.

In the preparation method, the reaction temperature is 120°C to 180°C, and the reaction time is 48h to 96h.

Application of this coordination polymer porous material as adsorbent.

Further, the adsorbent used is a C ₂ s gas adsorbent.

The beneficial effects of the present invention are:

The coordination polymer porous material of the present invention can be used as an adsorbent to prepare materials such as storage, separation, catalysis, sensing, molecular recognition, etc., and has good application prospects.

details as follows:

(1) The coordination polymer porous material provided by the present invention has good thermal stability, which can be stable to 573K; chemical stability is also very good, if it is soaked in an aqueous solution of 2≤pH≤12 for 24h, the frame structure will not destroyed;

(2) Under the condition of 298K and normal pressure, the coordination polymer porous material synthesized by the present invention has good separation performance of ethylene/acetylene and ethylene/ethane, and can adsorb and separate two main impurities of acetylene and ethane in industrial ethylene components, high-purity ethylene with a purity of >99.997% can be obtained.

(3) Under the condition of 298K and normal pressure, the coordination polymer porous material synthesized by the present invention has good acetylene/ethylene/acetylene three-component gas separation performance, and can adsorb and separate two main impurities, acetylene and ethane. components, high-purity ethylene with a purity of >99.997% can be obtained.

Description of drawings

Fig. 1 is the three-dimensional structure schematic diagram of the porous material TJT-100 of the present invention;

2 is a schematic diagram of the crystal synthesis process and activation process of the porous material TJT-100 of the present invention;

Fig. 3 is the crystal structure diagram of the porous material TJT-100 of the present invention: (a) trinuclear cluster unit of cobalt; (b) ligand 5-(3',5'-dicarboxyphenyl)nicotinic acid and cobalt salt Coordination structure diagram;

Figure 4 is the simulated adsorption site map of the porous material TJT-100 of the present invention: (a) the adsorption site map of C ₂ H ₂ in the pores; (b) the adsorption site map of C ₂ H ₄ in the pores; (c) ) The adsorption site map of C ₂ H ₆ in the pores;

Fig. 5 is the thermogravimetric curve comparison diagram of the porous material TJT-100 of the present invention before and after activation;

Fig. 6 is the raw material powder of the porous material TJT-100 of the present invention and the X-ray diffraction pattern after treatment;

Fig. 7 is the X-ray diffraction pattern of the porous material TJT-100 of the present invention processed under different temperature conditions;

Fig. 8 is the X-ray diffraction pattern of the porous material TJT-100 of the present invention treated under different pH conditions;

Fig. 9 is the adsorption isotherm diagram of acetylene, ethylene and ethane under the condition of 298K of porous material TJT-100 of the present invention;

Fig. 10 is the adsorption isotherm diagram of acetylene under different temperature conditions of porous material TJT-100 of the present invention;

Fig. 11 is the adsorption isotherm diagram of ethylene of porous material TJT-100 of the present invention under different temperature conditions;

Fig. 12 is the adsorption isotherm diagram of ethane of the porous material TJT-100 of the present invention under different temperature conditions;

Fig. 13 is the experimental data diagram of the breakthrough curve of the adsorption fixed bed prepared by the porous material TJT-100 of the present invention under the conditions of 298K and one atmospheric pressure to the gas mixture ethylene/acetylene with a volume ratio of 99:1;

Figure 14 is an experimental curve diagram of ethylene gas obtained by the adsorption fixed bed prepared by the porous material TJT-100 of the present invention under the conditions of 298K and one atmospheric pressure for the gas mixture ethylene/acetylene gas with a volume ratio of 99:1: (a) Separation C The gas chromatogram of the detected outlet gas in the process of ₂ H ₂ /C ₂ H ₄ mixed gas; (b) the gas chromatogram of the detected outlet gas after TJT-100 adsorbed the C ₂ H ₂ /C ₂ H ₄ mixed gas saturated;

Fig. 15 is the experimental data diagram of the breakthrough curve of the adsorption fixed bed prepared by the porous material TJT-100 of the present invention under the conditions of 298K and one atmospheric pressure to the gas mixture ethylene/ethane with a volume ratio of 99:1;

Figure 16 is an experimental curve diagram of ethylene gas obtained by the adsorption fixed bed prepared by the porous material TJT-100 of the present invention under the conditions of 298K and one atmospheric pressure from the gas mixture ethylene/ethane gas with a volume ratio of 99:1: (a) Separation Gas chromatogram of detected outlet gas in the process of C ₂ H ₆ /C ₂ H ₄ mixed gas; (b) Gas chromatogram of detected outlet gas after TJT-100 adsorbed C ₂ H ₆ /C ₂ H ₄ mixture saturated ;

Fig. 17 is the experimental data diagram of the breakthrough curve of the gas mixture acetylene/ethane/ethylene with a volume ratio of 0.5:0.5:99 for the adsorption fixed bed prepared by the porous material TJT-100 of the present invention at 298K and one atmospheric pressure;

Figure 18 is an experimental curve diagram of ethylene gas obtained by the adsorption fixed bed prepared by the porous material TJT-100 of the present invention at 298K and an atmospheric pressure to a gas mixture with a volume ratio of 0.5:0.5:99 separated from acetylene/ethane/ethylene: ( a) The gas chromatogram of the outlet gas detected in the process of separating the C ₂ H ₂ /C ₂ H ₄ /C ₂ H ₆ mixed gas; (b) the gas phase of the outlet gas detected after TJT-100 adsorbed the three-component mixed gas saturated Chromatogram.

Detailed ways

A coordination polymer porous material, the chemical formula is (Me ₂ NH ₂ )[Co ₃ (DCPN) ₂ (μ ₃ -OH)(H ₂ O)]·11H ₂ O, where DCPN represents 5-(3 ',5'-dicarboxyphenyl)nicotinic acid (H ₃ DCPN) anion ligand, which is the anion of H ₃ DCPN deprotonated; Me in the formula represents a methyl group.

Further, the porous material is a three-dimensional framework structure material with one-dimensional channels formed by connecting DCPN (DCPN ^3- ) with a trinuclear Co cluster, wherein the trinuclear Co cluster unit is composed of two six-coordinated Co(II) and a penta-coordinated Co(II) linked together by μ ₃ -OH. A schematic diagram of the three-dimensional structure of this coordination polymer porous material can be seen in Figure 1.

，b＝11.9980

，c＝32.450

。Further, the crystal form of the porous material belongs to the orthorhombic system, the space group is Pbca, and the unit cell parameter is: a=23.539

, b=11.9980

, c=32.450

.

The preparation method of the coordination polymer porous material is prepared by reacting the ligand 5-(3',5'-dicarboxyphenyl)nicotinic acid with cobalt salt in N,N-dimethylformamide solvent .

Preferably, in the preparation method, the molar ratio of 5-(3',5'-dicarboxyphenyl)nicotinic acid to cobalt salt is 1:1.

Preferably, in the preparation method, the cobalt salt is a divalent Co salt; more preferably, the cobalt salt is at least one of CoCl ₂ , Co(NO ₃ ) ₂ , and Co(CH ₃ COO) ₂ ; and further preferably, The cobalt salt is CoCl ₂ , and CoCl ₂ ·6H ₂ O is selected for specific use.

Preferably, in the preparation method, the N,N-dimethylformamide solvent is a mixed solution composed of N,N-dimethylformamide (DMF) and water; further preferably, in the mixed solution, the volume of DMF and water is The ratio is (4～6):1.

Preferably, in the preparation method, the reaction temperature is 120°C～180°C, and the reaction time is 48h～96h; more preferably, the reaction temperature is 140°C～160°C, and the reaction time is 70h～75h.

Application of this coordination polymer porous material as adsorbent.

Further, the adsorbent used is a C ₂ s gas adsorbent; preferably, the C ₂ s gas is selected from acetylene, ethylene or ethane.

Further, the application of this coordination polymer porous material as an adsorbent in the separation and purification of ethylene gas, and further, the application of this coordination polymer porous material as an adsorbent in the separation and purification of ethylene gas in acetylene/ethylene. Application, or the application of this coordination polymer porous material as an adsorbent in the separation and purification of ethylene gas in ethane/ethylene, or the application of this coordination polymer porous material as an adsorbent in the separation and purification of acetylene/ethylene/ethane applications in ethylene gas.

Further, the coordination polymer porous material needs to be activated before being used as an adsorbent.

Preferably, the activation treatment is specifically: first soaking the coordination polymer porous material in methanol for solvent exchange, then drying, placing it in an activation workstation, and vacuuming at 140°C to 160°C for 20h to 30h to obtain an activated product.

The content of the present invention will be further described in detail below through specific embodiments.

The raw materials and reagents used in the present invention are respectively: ligand 5-(3',5'-dicarboxyphenyl)nicotinic acid (H ₃ DCPN); N,N-dimethylformamide (AR); chlorine hexahydrate Cobalt (AR). These starting materials are available from conventional commercial sources.

Preparation and activation of porous MOFs TJT-100 single crystal

Ligand H ₃ DCPN was synthesized with reference to prior art methods; ligand H ₃ DCPN (57.0 mg, 0.2 mmol), CoCl ₂ ·6H ₂ O (48.0 mg, 0.2 mmol), DMF (20 mL), ultrapure water ( 4mL) was added to the hydrothermal reactor, heated to 150° C. for 72 hours to obtain blue-purple TJT-100 single crystal with a yield of 78%.

The sample should be activated before testing the adsorption curve. The activation process is as follows: soak an appropriate amount of crystals in methanol for 24 hours for solvent exchange, then suck out the methanol and add methanol to soak for 24 hours. The activation workstation was evacuated at 150° C. for 24 hours to obtain the activated sample. The crystal synthesis process and activation process are shown in Figure 2.

Structural characterization of TJT-100 before and after activation

)射线，以ω扫描方式收集数据，利用直接法进行解析，然后用差值傅立叶函数法和最小二乘法求出全部非氢原子坐标，最后用最小二乘法对结构进行修正。化合物的氢原子通过理论加氢法得到。计算工作在PC机上使用SHELXTL程序完成。详细的晶体测定数据见表1。表中的TJT-100a表示活化后的TJT-100。活化前后的结构图参见图2。Single crystal X-ray diffraction data were collected on a Rigaku Oxford Diffraction Gemini diffractometer using Cu Kα (λ = 0.71073

) rays, collect data by ω scanning method, use direct method to analyze, then use difference Fourier function method and least square method to obtain all non-hydrogen atom coordinates, and finally use least square method to correct the structure. The hydrogen atoms of the compounds are obtained by theoretical hydrogenation. Computational work is done on a PC using the SHELXTL program. The detailed crystal determination data are shown in Table 1. TJT-100a in the table represents activated TJT-100. The structural diagrams before and after activation are shown in Figure 2.

Table 1 Crystal determination data

Note: ^a R ₁ =∑||F ₀ |-|F _C ||/∑|F ₀ |; ^b wR ₂ =∑[w(F ₀ ² -F _C ² ) ² ]/∑[w(F ₀ ² ) ² ] ^1/2 .

Fig. 3 is the crystal structure diagram of the porous material TJT-100 of the present invention, Fig. 3(a) is the trinuclear cluster unit (SBU) of cobalt; Fig. 3(b) is the ligand 5-(3', 5'-two Coordination diagram of carboxyphenyl)nicotinic acid with cobalt salts.

Fig. 4 is the simulated adsorption site diagram of the porous material TJT-100 of the present invention, Fig. 4(a) is the adsorption site diagram of C ₂ H ₂ in the pore channel; Fig. 4 (b) is the adsorption site diagram of C ₂ H ₄ in the pore channel Adsorption site map; Figure 4(c) is the adsorption site map of C ₂ H ₆ in the pores.

Thermal stability characterization of porous MOFs material TJT-100

The thermal stability of porous MOFs material TJT-100 was obtained by thermogravimetric analysis (TGA) and variable temperature powder diffraction (PXRD). The TJT-100 provided by the invention has good thermal stability and can be stable to 523K. The thermogravimetric curve is shown in Figure 5. Fig. 6 is the raw material powder of the porous material TJT-100 of the present invention and the X-ray diffraction pattern after treatment; Fig. 7 is the X-ray diffraction pattern of the porous material TJT-100 of the present invention treated under different temperature conditions.

At the same time, in the present invention, the synthesized TJT-100 is directly immersed in an aqueous solution of 2≤pH≤12, and its frame structure is not damaged through powder diffraction (PXRD) measurement and characterization, which shows its good chemical stability, and the corresponding powder diffraction See Figure 8 for characterization.

Characterization of Gas Adsorption Properties of Porous MOFs Material TJT-100

The activated porous material TJT-100 was put into a quartz sample tube, and then its acetylene (C ₂ H ₂ ), ethylene (C ₂ H 4 ) and ethylene (C 2 H 4 ) and acetylene (C 2 H ₄ ) and Ethane (C ₂ H ₆ ) gas adsorption isotherms. Fig. 9 is the adsorption isotherm diagram of acetylene, ethylene and ethane under the condition of 298K for the porous material TJT-100 of the present invention. Figures 10-12 are the adsorption isotherms of acetylene, ethylene and ethane under different temperature conditions, respectively, of the porous material TJT-100 of the present invention.

Application example 1 (making of TJT-100 as the packing adsorption fixed bed and separation of two-component mixed gas):

The TJT-100 powder sample was filled into the center of a quartz tube with an inner diameter of 8 mm and a length of 45 cm, and was compacted and packed. The column was heated at a constant temperature of 423K for 24 hours in a He atmosphere, cooled to 298K, and a mixed gas of C ₂ H ₄ /C ₂ H ₂ with a total flow rate of 2mL·min- ¹ and a volume ratio of 99:1 was introduced into the column under one atmosphere. , the absolute concentration of the gas (C _o /C _i , the molar concentration of each component at the gas outlet / the molar concentration of the gas inlet) was detected by a quadrupole mass spectrometer (HPR20, Hiden). The obtained breakthrough curve experimental data diagram is shown in FIG. 13 . In Fig. 13, the absolute time of gas entering the packing is taken as the abscissa, the absolute concentration of C _o /C _i as the ordinate, and the purity of the outlet is detected by gas chromatography (GC-9160, Shanghai Ouhua). Under the condition of 298K and normal pressure, the ethylene/acetylene mixed gas with a separation volume ratio of 99:1 of TJT-100 synthesized by the present invention can obtain ethylene with a purity of >99.997%, and the obtained experimental data is shown in Figure 14. Figure 14 is an experimental curve diagram of ethylene gas obtained by the adsorption fixed bed prepared by the porous material TJT-100 of the present invention under the conditions of 298K and one atmospheric pressure to the gas mixture ethylene/acetylene gas with a volume ratio of 99:1; Figure 14(a) Gas chromatogram of C ₂ H ₂ and C ₂ H ₄ content detected in the outlet gas in the process of separating C ₂ H ₂ /C ₂ H ₄ mixed gas (the peak at 0.6-0.7min is the O ₂ peak involved in the pipeline) , the spectrum shows that there is no C ₂ H ₂ peak in the outlet gas during the separation process; Figure 14(b) After TJT-100 adsorbs the C ₂ H ₂ /C ₂ H ₄ mixed gas and is saturated, C 2 H 2 and C ₂ H ₂ and C are detected in the outlet gas The gas chromatogram of ₂ H ₄ content (the peak at 0.6-0.7 min is the O ₂ peak participating in the pipeline).

Application example 2 (making of TJT-100 as a filler adsorption fixed bed and separation of C ₂ H ₄ /C ₂ H ₆ -minute mixed gas with a volume ratio of 99:1):

The TJT-100 powder sample was filled into the center of a quartz tube with an inner diameter of 8 mm and a length of 45 cm, and was compacted and packed. The column was heated at a constant temperature of 423K for 24 hours in a He atmosphere, cooled to 298K, and a mixed gas of C ₂ H ₄ /C ₂ H ₆ with a total flow rate of 2mL·min- ¹ and a volume ratio of 99:1 was introduced into the column under one atmosphere. , the absolute concentration of the gas (C _o /C _i , the molar concentration of each component at the gas outlet / the molar concentration of the gas inlet) was detected by a quadrupole mass spectrometer detector (HPR20, Hiden). The obtained breakthrough curve experimental data diagram is shown in Figure 15. In Figure 15, the absolute time of the gas entering the filler is the abscissa, and the absolute concentration C _o /C _i is the ordinate. The purity of the outlet was detected by gas chromatography (GC-9160, Shanghai Ouhua). Under the condition of 298K and normal pressure, the ethylene/ethane mixed gas of TJT-100 with a separation volume ratio of 99:1 synthesized by the present invention can obtain ethylene with a purity of >99.997%, and the obtained experimental data is shown in Figure 16. Fig. 16 is the experimental curve diagram of ethylene gas obtained by the adsorption fixed bed prepared by porous material TJT-100 of the present invention under the condition of 298K and one atmospheric pressure to the gas mixture ethylene/ethane gas with a volume ratio of 99:1; Fig. 16(a ) Gas chromatogram of C ₂ H ₆ and C ₂ H ₄ content detected in the outlet gas in the process of separating C ₂ H ₆ /C ₂ H ₄ mixed gas (the peak at 0.6-0.7min is the O ₂ peak involved in the pipeline ), the spectrum shows that there is no C ₂ H ₆ peak in the outlet gas during the separation process; Figure 16(b) After TJT-100 adsorbs the C ₂ H ₆ /C ₂ H ₄ mixed gas and is saturated, C 2 H 6 and C ₂ H ₆ and Gas chromatogram of C ₂ H ₄ content (the peak at 0.6-0.7 min is the O ₂ peak participating in the pipeline).

Application example 3 (fabrication of TJT-100 as filler adsorption fixed bed and separation of C ₂ H ₂ /C ₂ H ₆ /C ₂ H ₄ three-component mixed gas with a volume ratio of 0.5:0.5:99):

The TJT-100 powder sample was filled into the center of a quartz tube with an inner diameter of 8 mm and a length of 45 cm, and was compacted and packed. The column was heated at ^a constant temperature of 423K for 24 hours in a He atmosphere, cooled to 298K, and C 2 H 2 /C 2 H 6 / C ₂ H ₂ /C ₂ H ₆ / The C ₂ H ₄ three-component gas, the absolute concentration of the gas (C _o /C _i , the gas outlet molar concentration of each component/the gas inlet molar concentration) was detected with a quadrupole mass spectrometer (HPR20, Hiden). The obtained breakthrough curve experimental data diagram is shown in Figure 17. In Figure 17, the absolute time of gas entering the filler is the abscissa, and the absolute concentration C _o /C _i is the ordinate. The purity of the outlet was detected by gas chromatography (GC-9160, Shanghai Ouhua). Under the condition of 298K and normal pressure, the three-component gas of C ₂ H ₂ /C ₂ H ₆ /C ₂ H ₄ with a separation volume ratio of 0.5:0.5:99 of TJT-100 synthesized by the present invention can be obtained with a purity of >99.997% Ethylene, the obtained experimental data is shown in Figure 18. Figure 18 is an experimental curve diagram of ethylene gas obtained by separating the gas mixture acetylene/ethane/ethylene with a volume ratio of 0.5:0.5:99 under the conditions of 298K and one atmospheric pressure by the adsorption fixed bed prepared by the porous material TJT-100 of the present invention; Figure 18 18(a) The gas chromatogram of the outlet gas detected in the process of separating the C ₂ H ₂ /C ₂ H ₄ /C ₂ H ₆ mixed gas (the peak at 0.6-0.7min is the O ₂ peak involved in the pipeline), The spectrum shows that there are no C ₂ H ₂ and C ₂ H ₆ peaks in the outlet gas during the separation process; Figure 18(b) The gas chromatogram of the outlet gas detected after TJT-100 adsorbs the three-component mixed gas saturation. It can be seen from Figure 18 that TJT-100 has the performance of simultaneously separating three components of gas, and can realize the separation of these three components of gas, which has not been reported in porous materials.

The coordination polymer porous material TJT-100 of the present invention has good thermal stability and chemical stability, and has very excellent performance in practical C2s three-component gas separation applications. The material can adsorb acetylene in the mixed gas of ethylene and acetylene, and can also adsorb ethane in the mixed gas of ethylene and ethane. It is particularly important that the material has the performance of simultaneously separating the three-component gas of ethane/ethylene/acetylene, and can To achieve the separation of these three components of the gas. After the two-component mixed gas and the three-component mixed gas are separated by this material, ethylene with a purity of >99.997% can be obtained, which has high industrial application value.

A further summary is as follows:

TJT-100 is used to adsorb acetylene in the mixed gas of ethylene and acetylene. Under industrial conditions, that is, for the mixed gas of 99:1 ethylene/acetylene, the purity of ethylene obtained by a single separation is as high as >99.997%, and high-purity ethylene can be obtained. vinyl.

TJT-100 is used to adsorb ethane in the mixed gas of ethylene and ethane. Under industrial conditions, that is, for the mixed gas of 99:1 ethylene/ethane, the purity of ethylene obtained by a single separation is as high as >99.997%, and high pure ethylene.

In particular, the porous material TJT-100 can be used as an adsorbent fixed bed packing to directly separate and purify high-purity ethylene from a three-component mixed gas of acetylene/ethylene/ethane. Under industrial conditions, that is, for acetylene/ethylene/ethane mixed gas of 0.5/0.5/99, the purity of ethylene obtained by a single separation is as high as 99.997%. Compared with the existing ethylene purification process used in industry, it can not only improve its purification efficiency Moreover, the complex synthesis steps are simple, the raw materials are easily obtained, and the existing energy consumption problems of ethylene synthesis and separation are reduced.

Claims (9)

1. A coordination polymer porous material with chemical formula of (Me)₂NH₂)[Co₃(DCPN)₂(μ₃-OH)(H₂O)]·11H₂And O, DCPN in the formula represents an anion of a 5- (3',5' -dicarboxyphenyl) nicotinic acid ligand.

2. The coordination polymer porous material according to claim 1, characterized in that: the porous material is a three-dimensional frame structure material with one-dimensional pore channels formed by connecting DCPN with a trinuclear Co cluster, wherein the trinuclear Co cluster unit is formed by two hexacoordinated Co (II) and one pentacoordinated Co (II) through mu₃-OH are linked together.

3. The coordination polymer porous material according to claim 1 or 2, characterized in that: the crystal form of the porous material belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameters are as follows:

4. the method for preparing a coordination polymer porous material according to claim 1, wherein: is prepared by reacting ligand 5- (3',5' -dicarboxyphenyl) nicotinic acid with cobalt salt in N, N-dimethylformamide solvent.

5. The method for preparing a coordination polymer porous material according to claim 4, wherein: the molar ratio of 5- (3',5' -dicarboxyphenyl) nicotinic acid to cobalt salt was 1: 1.

6. The method for preparing a coordination polymer porous material according to claim 5, wherein: the cobalt salt is a divalent Co salt.

7. The method for preparing a coordination polymer porous material according to claim 4, wherein: the N, N-dimethylformamide solvent is a mixed solution of N, N-dimethylformamide and water.

8. The method for preparing a coordination polymer porous material according to claim 4, wherein: the reaction temperature is 120-180 ℃, and the reaction time is 48-96 h.

9. Use of the coordination polymer porous material of claim 1 as an adsorbent, said adsorbent being C₂s gas adsorbent.

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