CN118955936B - Bromine-functionalized porous coordination polymer, preparation method and application in natural gas purification - Google Patents
Bromine-functionalized porous coordination polymer, preparation method and application in natural gas purification Download PDFInfo
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- 239000013259 porous coordination polymer Substances 0.000 title claims 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims 4
- 239000003345 natural gas Substances 0.000 title claims 2
- 238000000746 purification Methods 0.000 title claims 2
- 238000002360 preparation method Methods 0.000 title 1
- 239000003446 ligand Substances 0.000 claims 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 6
- 238000000034 method Methods 0.000 claims 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 4
- 239000002253 acid Substances 0.000 claims 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 4
- 229910052794 bromium Inorganic materials 0.000 claims 4
- 125000004429 atom Chemical group 0.000 claims 3
- 150000002500 ions Chemical class 0.000 claims 3
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 claims 2
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 239000013078 crystal Substances 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000013110 organic ligand Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- 238000004729 solvothermal method Methods 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- 230000003213 activating effect Effects 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
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Abstract
The invention relates to the technical field of crystal materials and natural gas purification, in particular to a bromine functionalized porous coordination polymer, a preparation method and natural gas purification application. The chemical molecular formula of the porous coordination polymer is [ Ni 3(OH)(TMBTTP)(BDC-Br)3 ], the crystal material of the polymer has novel structure and stable framework, and two kinds of cages of cylindrical shape and spindle shape exist. The specific surface area is 822.7 m 2 g−1, and the pore size distribution is 6.2-6.8A. The permanent pore channels and the proper pore size and the bromo-modified pore environment make the porous coordination polymer suitable for the purification of natural gas.
Description
Technical Field
The invention relates to the technical field of crystal materials and natural gas purification, in particular to a bromine functionalized porous coordination polymer, a preparation method and natural gas purification application.
Background
Natural gas, which has relatively low carbon emissions as an energy source, is considered a clean substitute for traditional fossil energy sources such as gasoline and diesel. The main component of natural gas is methane (CH 4) and other components, including hydrocarbons such as carbon dioxide (CO 2), ethane (C 2H6) and propane (C 3H8). However, the presence of CO 2 in natural gas reduces its combustion efficiency and even causes pipeline corrosion during transportation. Therefore, the removal of CO 2 from natural gas is critical to improving the quality of natural gas and ensuring the pipeline transportation safety. In addition, C 2H6 and C 3H8 are separated and recovered from natural gas, so that the conversion rate of CH 4 is improved, C 2H6 and C 3H8 are utilized to the maximum extent, and the production benefit is improved. The adsorption technology is an important scheme for removing CO 2 because of the advantages of mild operation conditions, small energy loss and the like, and the core technology is to develop an advanced adsorption material. Therefore, efforts have been made to find and develop novel porous adsorbent materials in order to further provide materials capable of CO 2 adsorption with high efficiency, high selectivity and low energy consumption.
Porous Coordination Polymer (PCP) crystalline porous materials formed by self-assembly of metal ions/clusters and organic ligands, PCP materials exhibit excellent properties in terms of gas adsorption and separation due to their customizable structure, controllable pore properties and high specific surface area, and are widely paid attention and favour to researchers and markets. The surface of the pore canal of the PCP material can realize the accurate identification of the adsorbate molecules through the molecular/atomic-level functional site design, so as to improve the selectivity and the binding force of the adsorption process. In addition, PCP materials have extremely high specific surface areas, which can provide a large adsorption surface. In view of the above characteristic advantages of PCP materials, the present invention adopts a dual ligand strategy to prepare a PCP with a cage-shaped porous structure by using a solvothermal synthesis method. The selected dicarboxylic acid ligand is modified with bromine (Br) atoms, so that the porous cavity of the prepared PCP realizes Br functional modification. The structure, the porous characteristic and the application performance of the material in natural gas adsorption and purification are confirmed by utilizing characterization and testing methods such as single crystal X-ray diffraction, gas adsorption, mixed gas fixed bed separation and the like. The material related by the invention has the basic characteristics of being used as an adsorbent for purifying natural gas, and has the potential of commercial development.
Disclosure of Invention
It is an object of the present invention to provide a bromo-functionalized porous coordination polymer having the chemical formula [ Ni 3(OH)(TMBTTP)(BDC-Br)3 ], wherein one of the ligands used is 4,4' - (2, 4, 6-trimethylbenzene-1, 3, 5-triphenyl) tripyridine TMBTTP, the second ligand is H 2 BDC-Br is 2-bromoterephthalic acid, designated PCP-Br;
Further, the crystal structure of the PCP-Br belongs to a trigonal system, the space group is P-31c, and the unit cell parameters are a= 16.943 (3) a, b= 16.943 (3) a, c= 15.034 (6) a, and alpha=beta=90 o,γ =120o.
Further, in the three-dimensional framework structure of PCP-Br, the crystallographic asymmetric structural unit thereof comprises 1 Ni (II) ion, 1/3-OH group, 1H 2 BDC-Br ligand and 1/3 TMBTTP ligand;
The Ni (II) ion coordinates 6 atoms in an octahedral configuration, including 4 carboxyl O atoms from different H 2 BDC-Br ligands, 1O atom of the-OH group, and 1N atom from TMBTTP ligands;
Three adjacent Ni (II) ions are bridged by 1-OH group and 6 carboxyl groups of six different H 2 BDC-Br ligands to form a typical trinuclear metal cluster [ Ni 3(μ3-OH)(COO)6 ];
Each metal cluster is alternately connected with an H 2 BDC-Br ligand to form a three-dimensional porous structure with acs topological configuration, and the TMBTTP ligand is connected with a [ Ni 3(μ3-OH)(COO)6 ] cluster to further divide the three-dimensional porous structure into a three-dimensional framework with pacs topological structure.
Further, in the PCP-Br structure, there are a cylindrical cage a and a spindle-shaped cage B, wherein the upper and lower planes of the cylindrical cage a contain 3 [ Ni 3(μ3-OH)(COO)6 ] clusters and 1 TMBTTP ligand, respectively, the walls of the cylinder are occupied by six H 2 BDC-Br, and the bottom diameter and height of the cylindrical cage a are 7.9 and 2.7 a, respectively;
The upper and lower vertexes of the spindle-shaped cage B are respectively occupied by 1[ Ni 3(μ3-OH)(COO)6 ] cluster, 3 [ Ni 3(μ3-OH)(COO)6 ] clusters are uniformly distributed in the middle part, the vertexes and the middle cluster are connected through H 2 BDC-Br ligands, the middle three [ Ni 3(μ3-OH)(COO)6 ] clusters are connected through TMBTTP ligands, the distance between the vertexes of the spindle-shaped cage is 8.2A, and the diameter of the middle position is 8.1A.
The invention also provides a preparation method of the bromine functionalized porous coordination polymer, which comprises the following steps:
Under the sealing condition, the organic ligands 4,4' - (2, 4, 6-trimethylbenzene-1, 3, 5-triphenyl) tripyridine (TMBTTP), 2-bromoterephthalic acid (H 2 BDC-Br) and nickel nitrate hexahydrate (Ni (NO 3)2·6H2 O) are dissolved in a mixed solution of N, N-dimethylacetamide and water, a proper amount of acid is added to adjust the acidity of the solution, a sample is obtained through solvothermal reaction, and then the sample is activated, so that the PCP-Br porous coordination polymer crystal material is obtained.
Further, the temperature of the solvothermal reaction is 90-120 ℃ and the reaction time is 18-48 hours.
Further, the molar ratio of the organic ligands TMBTTP, H 2 BDC-Br and Ni (NO 3)2·6H2 O) is 1 (3-5);
every 0.1 mmol of TMBTTP corresponds to 10-12.5 mL of DMA;
the volume ratio of the DMA to the water is 1 (0.1-0.4);
every 1-mL of DMA corresponds to 10-30 mu L of 52-wt% tetrafluoroboric acid aqueous solution.
Further, the method for activating the bromine functionalized porous coordination polymer sample comprises the following steps of firstly washing the synthesized sample with ethanol three times, soaking the washed sample in an ethanol solution for 48 hours, continuously stirring and replacing ethanol for 6 times during the period, filtering, and then drying in a vacuum oven at 100 ℃ for 5 hours to obtain an activated sample.
A third object of the present invention is to provide the use of said bromine functionalized porous coordination polymer in the purification of natural gas.
The bromine-containing porous coordination polymer crystal material has the beneficial technical effects that the bromine-containing porous coordination polymer crystal material is novel in structure and stable in frame, and has two kinds of cages, namely a cylindrical cage and a spindle cage. The specific surface area of the bromine-based porous coordination polymer material PCP-Br is 822.7 m 2g−1, and the pore size distribution of the PCP-Br is 6.2-6.8A. The permanent pore channels and the proper pore size and the bromo-modified pore environment make the porous coordination polymer suitable for the purification of natural gas.
Drawings
FIG. 1 is a photograph of a single crystal of PCP-Br under a microscope;
FIG. 2 is a photograph of a sample of powdery crystals of PCP-Br;
FIG. 3 is a structural diagram of the Ni metal center in PCP-Br;
FIG. 4 is a three-dimensional framework structure of PCP-Br
FIG. 5 is a diagram showing the structure of a cylindrical cage A and a spindle cage B in PCP-Br;
FIG. 6 is a powder X-ray diffraction pattern of synthesized PCP-Br after treatment under various conditions;
FIG. 7 is a thermogravimetric curve of PCP-Br;
FIG. 8 is an infrared spectrum of PCP-Br;
FIG. 9 is a 77K nitrogen adsorption isotherm plot and pore size distribution plot of PCP-Br;
FIG. 10 is a one-component adsorption isotherm plot of CH 4 and other components (CO 2、C2H6、C3H8) for PCP-Br at 298K and 313K and 100 kPa;
FIG. 11 is a graph of the heat of adsorption of PCP-Br against CH 4 and other components (CO 2、C2H6、C3H8);
FIG. 12 is a schematic diagram of the equimolar dynamic breakthrough of PCP-Br against CH 4 and other components (CO 2、C2H6、C3H8) at 298K;
FIG. 13 is a cycle chart of a dynamic gas adsorption separation test for PCP-Br.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Organic ligands TMBTTP (0.01 mmol) and H 2 BDC-Br (0.03 mmol) were sonicated in DMA of 1mL, ni (NO 3)2·6H2 O (0.03 mmol) was dissolved in deionized water of 0.1 mL, and after mixing the two, 10. Mu.L of an aqueous tetrafluoroboric acid solution (52 wt%) was added and enclosed in a pressure-resistant glass bottle.
Example 2
Organic ligands TMBTTP (0.02 mmol) and H 2 BDC-Br (0.06 mmol) were sonicated in DMA of 2 mL, ni (NO 3)2·6H2 O (0.08 mmol) was dissolved in deionized water of 0.3 mL, and after mixing the two, 30. Mu.L of aqueous tetrafluoroboric acid (52 wt%) was added and enclosed in a pressure-resistant glass bottle.
Example 3
Organic ligands TMBTTP (0.04 mmol) and H 2 BDC-Br (0.20 mmol) were sonicated in 5. 5mL DMA, ni (NO 3)2·6H2 O (0.2 mmol) was dissolved in 1.5. 1.5mL deionized water, and after mixing the two, 100. Mu.L of aqueous tetrafluoroboric acid (52 wt%) was added and enclosed in a pressure-resistant glass bottle.
Example 4
Organic ligands TMBTTP (0.1 mmol) and H 2 BDC-Br (0.4 mmol) were sonicated in 10 mL DMA, ni (NO 3)2·6H2 O (0.5 mmol) was dissolved in 2 mL deionized water, and after mixing the two, 200. Mu.L of aqueous tetrafluoroboric acid (52 wt%) was added and enclosed in a pressure-resistant glass bottle.
The test results of the products obtained in the above examples are the same, and the porous coordination polymer crystals obtained in example 1 were taken for the determination of the crystal structure, specifically as follows:
(1) Crystal structure determination:
Single crystals of the appropriate size were selected under a microscope and data collected using Bruker SMART APEXII CCD diffractometer. Absorption correction was performed using the SADABS program. And F2 is subjected to a direct method and a full matrix least squares method by using SHELXL-2014 to solve and refine structural data. The crystallography procedure employs a single package Olex2 integrated system. All non-hydrogen atoms are refined anisotropically. The position and thermal parameters of hydrogen atoms are determined, and the refinement of the structure is realized through geometric calculation. The contribution of disordered solvent molecules was treated using the squieeze program implemented in PLATON. The structure is shown in figures 3-5. The crystallographic data are shown in table 1.
TABLE 1 crystallographic data of metal-organic framework materials
The crystal photograph of FIG. 1 shows that the morphology of PCP-Br is spindle-shaped, the crystallization degree is better, and the crystal size is between 0.05 and 0.35 mm.
The method of the invention is used for amplifying and synthesizing PCP-Br, and the obtained powder sample is shown in figure 2, which proves that the PCP-Br can be amplified and synthesized with the mass of 0.25 g.
The three-dimensional framework diagrams of the metal center structure diagrams of FIGS. 3 and 4 show that in the three-dimensional framework structure of the PCP-Br, the crystallographically asymmetric structural unit thereof contains 1 Ni (II) ion, 1/3-OH group, 1H 2 BDC-Br ligand and 1/3 TMBTTP ligand;
The Ni (II) ion coordinates 6 atoms in an octahedral configuration, including 4 carboxyl O atoms from different H 2 BDC-Br ligands, 1O atom of the-OH group, and 1N atom from TMBTTP ligands;
Three adjacent Ni (II) ions are bridged by 1-OH group and 6 carboxyl groups of six different H 2 BDC-Br ligands to form a typical trinuclear metal cluster [ Ni 3(μ3-OH)(COO)6 ];
Each metal cluster is alternately connected with an H 2 BDC-Br ligand to form a three-dimensional porous structure with acs topological configuration, and the TMBTTP ligand is connected with a [ Ni 3(μ3-OH)(COO)6 ] cluster to further divide the three-dimensional porous structure into a three-dimensional framework with pacs topological structure.
The cage structure schematic diagram of FIG. 5 shows that in the PCP-Br structure, a cylindrical cage A and a spindle-shaped cage B exist, wherein the upper and lower planes of the cylindrical cage A respectively contain 3 [ Ni 3(μ3-OH)(COO)6 ] clusters and 1 TMBTTP ligand, the walls of the cylinder are occupied by six H 2 BDC-Br, and the diameter and height of the bottom surface of the cylindrical cage A are 7.9 and 2.7A respectively;
The upper and lower vertexes of the spindle-shaped cage B are respectively occupied by 1[ Ni 3(μ3-OH)(COO)6 ] cluster, 3 [ Ni 3(μ3-OH)(COO)6 ] clusters are uniformly distributed in the middle part, the vertexes and the middle cluster are connected through H 2 BDC-Br ligands, the middle three [ Ni 3(μ3-OH)(COO)6 ] clusters are connected through TMBTTP ligands, the distance between the vertexes of the spindle-shaped cage is 8.2A, and the diameter of the middle position is 8.1A.
The powder sample obtained by amplifying synthesis is subjected to powder X-ray diffraction characterization, and an X-ray powder diffraction spectrum of FIG. 6 shows that the prepared PCP-Br porous coordination polymer powder is pure phase and completely coincides with a diffraction peak fitted with a monocrystal structure, and the crystal structure of the sample is kept unchanged after the sample is subjected to soaking in an organic solution, gas adsorption test and aqueous solution treatment with pH of 4 to 10, so that the porous coordination polymer has certain chemical stability.
The thermogravimetric curve of fig. 7 shows that the thermal stability of the PCP-Br porous coordination polymer reaches 370 ℃.
The infrared spectrum of the porous coordination polymer of FIG. 8 further demonstrates the coordination between the metal and the ligand in PCP-Br.
(2) Characterization of specific surface area
Fig. 9 is an N 2 adsorption isotherm of the PCP-Br porous coordination polymer material of the present invention under conditions of P/P 0 =1 and 77K. As can be seen from the figure, the saturated N 2 uptake of PCP-Br reaches 234.0 cm 3/g−1 (STP). Through fitting and analysis of adsorption data, PCP-Br specific surface area is 822.7 m 2/g−1, and pore size distribution is 6.2-6.8A.
(3) Adsorption and separation performance characterization:
FIG. 10 is a one-component adsorption isotherm plot of CH 4、CO2、C2H6 and C 3H8 for PCP-Br of the present invention at 298K and 313K and P/P 0 of 1.0. As can be seen from the figure, the saturated absorption capacity of the porous coordination polymer crystal material PCP-Br on CH 4、CO2、C2H6 and C 3H8 under the conditions of 298K and 1 bar is 15.93 cm 3/g、53.14 cm3/g、64.61 cm3/g、75.76 cm3/g, and the maximum absorption capacity on CH 4、CO2、C2H6 and C 3H8 under the environmental conditions of 313K and 1 bar is 11.47 cm 3/g、37.02 cm3/g、47.64 cm3/g、66.23 cm3/g, respectively. It can be seen that PCP-Br has a significant difference in adsorption properties for CH 4、CO2、C2H6 and C 3H8, indicating its potential for separating CH 4/CO2/C2H6/C3H8 mixed gas.
FIG. 11 is a graph showing the heat of adsorption of PCP-Br against CH 4 and other components (CO 2、C2H6、C3H8) according to the present invention. In the porous coordination polymer PCP-Br material, the near zero adsorption Q st values of CH 4、CO2、C2H6 and C 3H8 were 18.9 kJ/mol, 24.8 kJ/mol, 32.1 kJ/mol and 44.5 kJ/mol, respectively. The calculation result shows that the PCP-Br material has different adsorption forces on four gas molecules, and the adsorption strength sequence is C 3H8>C2H6>CO2>CH4.
FIG. 12 is a schematic diagram of the equimolar dynamic breakthrough of PCP-Br of the present invention for CH 4 and other components (CO 2、C2H6、C3H8) under 298K conditions. An adsorption-breakthrough test of a four-component natural gas mixture was performed using a multicomponent adsorption breakthrough curve analyzer. One pass through column (inner diameter 6 mm) was packed with activated sample 1.2 g to form a fixed bed. And (3) adjusting the gas flow rate to ensure that the CH 4/CO2/C2H6/C3H8 volume percent concentration ratio in the four-component mixed natural gas is 1:1:1:1, and allowing the four-component mixed natural gas to pass through the filled bed. The total flow rate of the mixed gas passing through the adsorption column was 2 mL/min, and the test temperature was 298: 298K. By continuously passing the mixture through a PCP-Br bed and monitoring the change in CH 4/CO2/C2H6/C3H8 concentration at the adsorbent bed outlet over time, a breakthrough curve for CH 4/CO2/C2H6/C3H8 was drawn. From the figure, CH 4 passes through the PCP-Br bed at first, and then after a certain time interval, the penetration time difference between CO 2、C2H6, C 3H8.CO2、C2H6 and C 3H8 and CH 4 in the porous coordination polymer crystal material bed is 18.2, 35.9 and 58.1 min/g respectively, and the result shows that PCP-Br can realize separation of CH 4/CO2/C2H6/C3H8 natural gas mixture and has the potential of becoming a natural gas purification separation material.
FIG. 13 is a graph showing the cycle penetration of the PCP-Br test adsorption separation CH 4/CO2/C2H6/C3H8 mixed natural gas of the present invention. After the adsorptive separation process of CH 4/CO2/C2H6/C3H8 mixed natural gas, the sample can be regenerated by purging in He atmosphere at a flow rate of 30 mL/min at 100 ℃. As can be seen from the graph, there is no significant change in performance after three cycles. The PCP-Br has proved to have potential as a high-efficiency and renewable gas separation material in the aspect of industrially adsorbing and separating CH 4/CO2/C2H6/C3H8 mixed natural gas.
Claims (6)
1. A bromine functionalized porous coordination polymer is characterized in that the chemical molecular formula of the bromine functionalized porous coordination polymer is [ Ni 3(OH)(TMBTTP)(BDC-Br)3 ], one of the ligands used is 4,4' - (2, 4, 6-trimethylbenzene-1, 3, 5-triphenyl) tripyridine TMBTTP, the second ligand is H 2 BDC-Br which is 2-bromoterephthalic acid and is named as PCP-Br;
The crystal structure of the PCP-Br belongs to a trigonal system, the space group is P-31c, and the unit cell parameters are a= 16.943 (3) a, b= 16.943 (3) a, c= 15.034 (6) a, and alpha=beta=90 o,γ = 120o;
In the three-dimensional framework structure of the PCP-Br, a crystallographically asymmetric structural unit of the PCP-Br comprises 1 Ni (II) ion, 1/3-OH group, 1H 2 BDC-Br ligand and 1/3 TMBTTP ligand;
The Ni (II) ion coordinates 6 atoms in an octahedral configuration, including 4 carboxyl O atoms from different H 2 BDC-Br ligands, 1O atom of the-OH group, and 1N atom from TMBTTP ligands;
Three adjacent Ni (II) ions are bridged by 1-OH group and 6 carboxyl groups of six different H 2 BDC-Br ligands to form a typical trinuclear metal cluster [ Ni 3(μ3-OH)(COO)6 ];
Each metal cluster is alternately connected with an H 2 BDC-Br ligand to form a three-dimensional porous structure with acs topological configuration, and the TMBTTP ligand is connected with a [ Ni 3(μ3-OH)(COO)6 ] cluster to further divide the cluster into a three-dimensional framework with pacs topological structure;
In the PCP-Br structure, there are a cylindrical cage a and a spindle-shaped cage B, wherein the upper and lower planes of the cylindrical cage a contain 3 [ Ni 3(μ3-OH)(COO)6 ] clusters and 1 TMBTTP ligand, respectively, the walls of the cylinder are occupied by six H 2 BDC-Br, the bottom diameter and height of the cylindrical cage a are 7.9 and 2.7 a, respectively;
The upper and lower vertexes of the spindle-shaped cage B are respectively occupied by 1[ Ni 3(μ3-OH)(COO)6 ] cluster, 3 [ Ni 3(μ3-OH)(COO)6 ] clusters are uniformly distributed in the middle part, the vertexes and the middle cluster are connected through H 2 BDC-Br ligands, the middle three [ Ni 3(μ3-OH)(COO)6 ] clusters are connected through TMBTTP ligands, the distance between the vertexes of the spindle-shaped cage is 8.2A, and the diameter of the middle position is 8.1A.
2. A method of preparing the bromo-functionalized porous coordination polymer of claim 1, comprising the steps of:
Under the sealing condition, the organic ligands 4,4' - (2, 4, 6-trimethylbenzene-1, 3, 5-triphenyl) tripyridine, 2-bromoterephthalic acid and nickel nitrate hexahydrate are dissolved in a mixed solution of N, N-dimethylacetamide and water, and a proper amount of acid is added to adjust the acidity of the solution, wherein the acid is 52wt% tetrafluoroboric acid aqueous solution, a sample is obtained through solvothermal reaction, and then the sample is activated, so that the PCP-Br porous coordination polymer crystal material is obtained.
3. The method for preparing a bromine functionalized porous coordination polymer according to claim 2, wherein the solvothermal reaction temperature is 90-120 ℃ and the reaction time is 18-48 hours.
4. The method of preparing a bromo-functionalized porous coordination polymer according to claim 2, characterized in that:
The molar ratio of the organic ligand TMBTTP to H 2 BDC-Br to Ni (NO 3)2·6H2 O) is 1 (3-5);
Every 0.1 mmol of TMBTTP corresponds to 10-12.5 mL of N, N-dimethylacetamide;
the volume ratio of the N, N-dimethylacetamide to the water is 1 (0.1-0.4);
every 1-mL of N, N-dimethylacetamide corresponds to 10-30 mu L of 52 wt% tetrafluoroboric acid aqueous solution.
5. The method for preparing a bromine functionalized porous coordination polymer according to claim 2, wherein the method for activating the sample comprises the steps of washing the synthesized sample three times with ethanol, immersing the washed sample in an ethanol solution for 48 hours, continuously stirring and replacing ethanol for 6 times during the washing, filtering, and drying in a vacuum oven at 100 ℃ for 5 hours to obtain an activated sample.
6. Use of a bromo-functionalized porous coordination polymer according to claim 1 in the purification of natural gas.
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