Mononuclear Cu(I) Complex Crystal Material, Preparation Method, Load and Device

Abstract

The present invention discloses a mononuclear Cu(I) complex crystal material, a preparation method, a loading substance and a device. The crystal material has a chemical formula of CuC 16 H 15 N3F6P, and a molecular structure of [Cu(dmp)(CH3CN)][PF6], where dmp is 2,9-dimethyl-1,10-phenanthroline. The crystal material of the present invention has good stability and ethylene selective adsorption, and can efficiently separate ethylene / ethane mixed gas. The production and preparation process of this material is simple, with high yield and good controllability.

Description

Technical Field

[0001] The present invention relates to the field of chemical engineering and technology, and particularly to a mononuclear Cu(I) complex crystal material, a preparation method, a loading material and a device suitable for the separation of ethylene / ethane. Background Art

[0002] Ethylene (C2H4) is one of the largest chemical products in the world and is widely used in the manufacture of polymers such as polyethylene, polyvinyl chloride, polystyrene and other organic chemicals. Steam cracking and ethane dehydrogenation are the main methods for producing ethylene. In these production processes, ethane (C2H6) impurities will inevitably be introduced. Therefore, the separation and purification of ethylene is of great significance in the petrochemical field. However, due to their extremely similar physical and chemical properties, the separation of ethylene and ethane is difficult. Traditional gas separation methods such as cryogenic distillation and solvent absorption often have disadvantages such as high energy consumption, long time consumption and large equipment investment. In order to reduce the energy consumption required for separation and reduce costs, it is urgent to develop more efficient, energy-saving and environmentally friendly separation technologies. Adsorption separation technology has the advantages of low energy consumption, simple operation and relatively low cost, and is gradually replacing traditional distillation separation technology. The core of adsorption separation technology lies in the selection of adsorbents.

[0003] As a new adsorption separation technology between physical adsorption and chemical adsorption, the π-complexation adsorption separation method has good industrial application prospects. All along, the research hotspots in this field have mainly focused on loading Ag(I) and Cu(I) on suitable carriers to form composite materials to achieve the separation of ethylene and ethane. When Cowan et al. first used two examples of Ag(I) mononuclear complexes to separate ethylene / ethane, it was found that their performance exceeded that of many other composite materials. However, up to now, there are few studies on using mononuclear complexes as π-complexing agents to adsorb and separate ethylene / ethane, especially mononuclear Cu(I) complexes, and the achievements obtained are even scarcer.

[0004] The information disclosed in this background art section is only intended to enhance the overall understanding of the present invention and should not be regarded as an admission or any form of suggestion that this information constitutes prior art already known to those of ordinary skill in the art. Summary of the Invention

[0005] The purpose of the present invention is to provide a mononuclear Cu(I) complex crystal material, a preparation method, a loading material and a device, and a highly selective ethylene adsorption crystal material with excellent performance is obtained, which has good stability and ethylene selective adsorption, can efficiently separate ethylene / ethane mixed gas, and the production and preparation process of this material is simple, with high yield and good controllability.

[0006] To achieve the above object, an embodiment of the present invention provides a mononuclear Cu(I) complex crystal material, the chemical formula of which is CuC16 H 15 N3F6P, with the molecular structure of [Cu(dmp)(CH3CN)][PF6], where dmp is 2,9-dimethyl-1,10-phenanthroline.

[0007] In one or more embodiments of the present invention, the crystal material is triclinic, with the space group P-1, and satisfies: the unit cell parameters α = 87.33(4)°, β = 106.13(3)°, γ = 117.31(5)°.

[0008] In one or more embodiments of the present invention, the crystal material is obtained by the coordination reaction of 2,9-dimethyl-1,10-phenanthroline and monovalent copper.

[0009] In one or more embodiments of the present invention, the monovalent copper is provided by at least any one of the following: Cu2O, CuCl, Cu2SO4.

[0010] In one or more embodiments of the present invention, the preparation method of the mononuclear Cu(I) complex crystal material includes the following steps: (1) Prepare the crystallization material for providing Cu + ; (2) Dissolve the crystallization material and the ligand in dichloromethane for a coordination reaction to obtain the target crystal.

[0011] The [Cu(dmp)(CH3CN)][PF6] material obtained by the present invention is used for the selective separation of ethylene / ethane mixed gas after removing the coordinated acetonitrile molecules under vacuum and at 100 °C.

[0012] In one or more embodiments of the present invention, the preparation of the crystallization material in step (1) includes slowly adding the HPF6 solution to the acetonitrile solution containing Cu2O, stirring evenly and filtering, and placing the filtrate under low-temperature conditions for crystallization.

[0013] In one or more embodiments of the present invention, the molar ratio of the crystallization material to the ligand calculated based on Cu2O in step (2) is 1:(1 - 2).

[0014] In one or more embodiments of the present invention, in step (1), for every 1 mmol of Cu2O, the amount of acetonitrile solution used is 5 - 10 mL.

[0015] In one or more embodiments of the present invention, the molar ratio of Cu2O to HPF6 in step (1) is 1:(3 - 4), that is, for every 1 mmol of Cu2O in step (1), the amount of HPF6 used is 3 - 4 mmol.

[0016] In one or more embodiments of the present invention, the concentration of the HPF6 solution is 6-7 mol / L.

[0017] In one or more embodiments of the present invention, in step (2), for every 1 mmol of Cu2O, the dosage of dichloromethane is 30-50 ml.

[0018] In one or more embodiments of the present invention, the loading substance includes a carrier and the mononuclear Cu(I) complex crystal material as described above attached to the carrier.

[0019] In one or more embodiments of the present invention, the device includes a main body for providing a loading cavity, and the loading cavity contains the mononuclear Cu(I) complex crystal material as described above or the loading substance as described above. Here, the device can be a single adsorber or adsorption tower or adsorption tank, etc., or a complete set of equipment equipped with an adsorber or adsorption tank, etc.

[0020] Compared with the prior art, the mononuclear Cu(I) complex crystal material, preparation method, loading substance and device according to the embodiments of the present invention efficiently obtain a high-quality crystal material, which has good stability and ethylene selective adsorption property, and can efficiently separate ethylene / ethane mixed gas. The production and preparation process of this material is simple, with high yield and good controllability. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is the coordination structure diagram of [Cu(dmp)(CH3CN)][PF6] in one embodiment of the present invention, where N1-N3 refer to nitrogen atoms and Cu1 refers to the coordinated copper(I) atom;

[0022] Figure 2 It is the powder x-ray diffraction pattern of [Cu(dmp)(CH3CN)][PF6] in one embodiment of the present invention;

[0023] Figure 3 It is the thermogravimetric curve of [Cu(dmp)(CH3CN)][PF6] in one embodiment of the present invention;

[0024] Figure 4 It is the ethylene single-component adsorption curve of [Cu(dmp)(CH3CN)][PF6] in one embodiment of the present invention;

[0025] Figure 5 It is the ethane single-component adsorption curve of [Cu(dmp)(CH3CN)][PF6] in one embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0026] The following will describe in detail the specific embodiments of the present invention with reference to the accompanying drawings. It should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0027] Unless otherwise clearly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "having" etc. will be understood to include the stated elements or components, without excluding other elements or other components.

[0028] Including but not limited to the following examples, the reactions are carried out under a protective atmosphere such as nitrogen or argon. In the following examples, the reaction is carried out under a nitrogen atmosphere.

[0029] Example 1

[0030] The preparation process of the crystal material in this example is as follows: Slowly add 1.33 mL of 6.8 M HPF6 solution to an acetonitrile (15 mL) solution containing Cu2O (3 mmol), stir evenly, filter, place the filtrate under low temperature conditions of -20 °C for crystallization. After several hours, blue Cu(PF6) microcrystals can be obtained. Filter and wash with a small amount of acetonitrile. Dissolve 1 mmol of Cu(PF6) crystals and 1 mmol of 2,9-dimethyl-1,10-phenanthroline (dmp) in 30 mL of dichloromethane, stir to produce yellow microcrystals, and filter and then perform vacuum drying.

[0031] The yield of the mononuclear Cu(I) complex crystal material prepared in this example is 68.2%.

[0032] The characterization of the mononuclear Cu(I) complex crystal material prepared in this example is as follows:

[0033] (1) Crystal structure determination

[0034] Select a single crystal of appropriate size under a microscope. At room temperature, on a Bruker SMARTApex II CCD single crystal diffractometer, use graphite-monochromated Mo Kα to test the structure. Use the APEXII program to collect data and determine the unit cell. The structure data is normalized and absorption corrected using the SAINT and SADABS programs. Use the SHELXTL-97 program for structure analysis. All non-hydrogen atom coordinates are obtained by difference Fourier synthesis method. The atomic coordinates and anisotropic temperature factors are corrected using full matrix least squares method, and all hydrogen atoms are added theoretically. The structure diagram is shown in Figure 1 , and the crystallographic data is shown in Table 1.

[0035] Table 1 Crystallographic data of the complex

[0036]

[0037] Figure 1 The structural diagram shows that Cu(I) coordinates with an organic ligand dmp and an acetonitrile molecule to form a three-coordinate planar triangular configuration.

[0038] (2) Powder X-ray diffraction for phase purity determination

[0039] The phase purity of the red bulk crystal product obtained in this example was characterized using a Bruker D8 Advance powder X-ray diffractometer. As Figure 2 shown, the simulated curve was obtained by simulating the single crystal structure data using Mercury software. The results show that the mononuclear Cu(I) complex crystal material has reliable phase purity, providing guarantee for its application in adsorption separation materials.

[0040] (3) Thermogravimetric analysis

[0041] The obtained complex crystal was subjected to thermogravimetric analysis using a Pyris Diamond TG-DTA thermogravimetric analyzer to determine the thermal stability of the complex by the weight loss and thermal changes of the crystal. The stability of this crystal material was investigated using thermogravimetric analysis. Figure 3 It shows that this crystal material has high stability.

[0042] (4) Adsorption performance test

[0043] The obtained complex crystal material was studied for its adsorption performance of ethylene and ethane using an IGA-100 gravimetric sorption analyzer. Figure 4 The ethylene single-component adsorption curve in Figure 5 shows that [Cu(dmp)(CH3CN)][PF6] has good adsorption capacity for ethylene gas. However,

[0044] Example 2

[0045] The preparation process of the crystal material in this example is as follows: 1.33 mL of 6.8 M HPF6 solution was slowly added to a solution of Cu2O (3 mmol) in acetonitrile (15 mL), stirred evenly, filtered, and the filtrate was placed at -20 °C for crystallization. After several hours, blue Cu(PF6) microcrystals were obtained, filtered, and washed with a small amount of acetonitrile. 1 mmol of Cu(PF6) and 1.5 mmol of 2,9-dimethyl-1,10-phenanthroline (dmp) were dissolved in 30 mL of dichloromethane, stirred to produce yellow microcrystals, and then filtered and dried under vacuum.

[0046] The yield of the mononuclear Cu(I) complex crystal material prepared in this example is 78.1%, and the crystal structure of the product is detected to conform to Figure 1 and the crystal form structure shown in Table 1. Moreover, the purity and thermal stability of the sample in this example both meet the application requirements. At the same time, the sample in this example has a high selective adsorption capacity for ethylene, while it hardly adsorbs ethane at all, which is basically consistent with Figures 4 - 5 as shown.

[0047] Example 3

[0048] The preparation process of the crystal material in this example is as follows: Slowly add 1.33 mL of 6.8 M HPF6 solution to an acetonitrile (15 mL) solution containing Cu2O (3 mmol), stir evenly, filter, place the filtrate under low-temperature conditions of -20 °C for crystallization. After several hours, blue Cu(PF6) microcrystals can be obtained. Filter and wash with a small amount of acetonitrile. Dissolve 1 mmol of Cu(PF6) and 2 mmol of 2,9-dimethyl-1,10-phenanthroline (dmp) in 30 mL of dichloromethane, stir to produce yellow microcrystals, and perform vacuum drying after filtration.

[0049] The yield of the mononuclear Cu(I) complex crystal material prepared in this example is 80.6%, and the crystal structure of the product is detected to conform to Figure 1 and the crystal form structure shown in Table 1. Moreover, the purity and thermal stability of the sample in this example both meet the application requirements. At the same time, the sample in this example has a high selective adsorption capacity for ethylene, while it hardly adsorbs ethane at all, which is basically consistent with Figures 4 - 5 as shown.

[0050] Example 4

[0051] The preparation process of the crystal material in this example is as follows: Slowly add 1.5 mL of 6 M HPF6 solution to an acetonitrile (24 mL) solution containing CuCl (2.4 mmol), stir evenly, filter, place the filtrate under low-temperature conditions of -20 °C for crystallization. After several hours, blue Cu(PF6) microcrystals can be obtained. Filter and wash with a small amount of acetonitrile. Dissolve 1 mmol of Cu(PF6) and 1 mmol of 2,9-dimethyl-1,10-phenanthroline (dmp) in 40 mL of dichloromethane, stir to produce yellow microcrystals, and perform vacuum drying after filtration.

[0052] The yield of the mononuclear Cu(I) complex crystal material prepared in this example is 65.5%, and the crystal structure of the product is detected to conform to Figure 1 and the crystal form structure shown in Table 1. Moreover, the purity and thermal stability of the sample in this example both meet the application requirements. At the same time, the sample in this example has a high selective adsorption capacity for ethylene, while it hardly adsorbs ethane at all, which is basically consistent with Figures 4 - 5 as shown.

[0053] Example 5

[0054] In this example, the preparation process of the crystal material is as follows: Slowly add 1 mL of 7M HPF6 solution to an acetonitrile (14.7 mL) solution containing Cu2SO4 (2.1 mmol), stir evenly, filter, place the filtrate under low temperature conditions of -20 °C for crystallization. After several hours, blue Cu(PF6) microcrystals can be obtained, filter, and wash with a small amount of acetonitrile. Dissolve 1 mmol of Cu(PF6) and 1 mmol of 2,9-dimethyl-1,10-phenanthroline (dmp) in 50 mL of dichloromethane, stir to produce yellow microcrystals, and perform vacuum drying after filtration.

[0055] The yield of the mononuclear Cu(I) complex crystal material prepared in this example is 66.7%, and the crystal structure of the product is detected to conform to Figure 1 the crystal form structure shown in and Table 1, and the purity and thermal stability of the example sample both meet the application requirements. At the same time, the sample in this example has a high selective adsorption capacity for ethylene, and hardly adsorbs ethane, which is basically consistent with Figures 4 - 5 that shown.

[0056] Example 6

[0057] In this example, the preparation process of the crystal material is as follows: Slowly add 1.76 mL of 6.8M HPF6 solution to an acetonitrile (30 mL) solution containing Cu2O (3 mmol), stir evenly, filter, place the filtrate under low temperature conditions of -20 °C for crystallization. After several hours, blue Cu(PF6) microcrystals can be obtained, filter, and wash with a small amount of acetonitrile. Dissolve 1 mmol of Cu(PF6) and 2 mmol of 2,9-dimethyl-1,10-phenanthroline (dmp) in 30 mL of dichloromethane, stir to produce yellow microcrystals, and perform vacuum drying after filtration.

[0058] The yield of the mononuclear Cu(I) complex crystal material prepared in this example is 81.0%, and the crystal structure of the product is detected to conform to Figure 1 the crystal form structure shown in and Table 1, and the purity and thermal stability of the example sample both meet the application requirements. At the same time, the sample in this example has a high selective adsorption capacity for ethylene, and hardly adsorbs ethane, which is basically consistent with Figures 4 - 5 that shown.

[0059] The crystal materials obtained including but not limited to those in the above examples all meet Figure 1In the shown configuration, Cu(I) coordinates with an organic ligand dmp and an acetonitrile molecule to form a three-coordinated planar triangular configuration. Meanwhile, like the sample obtained in Example 1, the samples obtained in each example all have good thermal stability and a high selective adsorption capacity for ethylene, thus being able to separate ethylene / ethane mixed gases.

[0060] The foregoing description of the specific exemplary embodiments of the present invention is for purposes of illustration and exemplification. These descriptions are not intended to limit the invention to the precise forms disclosed, and obviously, many changes and variations are possible in light of the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical applications, so that those skilled in the art can implement and utilize various different exemplary embodiments of the present invention as well as various different selections and changes. The scope of the present invention is intended to be defined by the claims and their equivalents.

Claims

1. Application of a mononuclear Cu(I) complex crystal material in ethylene adsorption and separation, with the chemical formula CuC 16 H 15 N3F6P, and the molecular structure is [Cu(dmp)(CH3CN)][PF6], where dmp is 2,9-dimethyl-1,10-phenanthroline.

2. Use of the mononuclear Cu(I) complex crystal material according to claim 1 in ethylene adsorption and separation, characterized in that, The crystal material is triclinic, with the space group P-1, and satisfies: the unit cell parameters α = 87.33(4)°, β = 106.13(3)°, γ = 117.31(5)°.

3. Use of the mononuclear Cu(I) complex crystal material according to any one of claims 1-2 in the adsorption and separation of ethylene, characterized in that, The crystal material is obtained by a coordination reaction of the organic ligand 2,9-dimethyl-1,10-phenanthroline and monovalent copper.

4. Use of the mononuclear Cu(I) complex crystal material as described in claim 3 in ethylene adsorption and separation, characterized in that, The monovalent copper is provided by at least any one of the following: Cu2O, CuCl, Cu2SO4.

5. Use of the mononuclear Cu(I) complex crystal material according to claim 4 in ethylene adsorption and separation, characterized in that, The method for preparing the mononuclear Cu(I) complex crystal material includes the following steps: (1) Prepare a crystalline material for providing Cu + ; (2) Dissolve the crystalline material and the ligand in dichloromethane for a coordination reaction to obtain the target crystal.

6. Use of the mononuclear Cu(I) complex crystal material as described in claim 5 in the adsorption and separation of ethylene, characterized in that, The preparation of the crystalline material in step (1) includes slowly adding an HPF6 solution to an acetonitrile solution containing Cu2O, stirring evenly and filtering, and crystallizing the filtrate under low-temperature conditions.

7. Use of the mononuclear Cu(I) complex crystal material according to claim 6 in ethylene adsorption and separation, characterized in that, In step (1), the molar ratio of Cu2O to HPF6 is 1:(3 - 4).

8. Use of the mononuclear Cu(I) complex crystal material as described in claim 5 in the adsorption and separation of ethylene, characterized in that, In step (2), the molar ratio of the crystalline material to the ligand is 1:(1 - 2), where the amount of the crystalline material is calculated based on Cu2O.

9. A load for use in the adsorption and separation of ethylene, comprising a carrier and the mononuclear Cu(I) complex crystal material as described in any one of claims 1 - 8 attached to the carrier.

10. A device for use in the adsorption and separation of ethylene, comprising a main body for providing a loading cavity, and the mononuclear Cu(I) complex crystal material as described in any one of claims 1 - 8 or the load as described in claim 9 is accommodated in the loading cavity.

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