CN116239786A - Metal organic framework material for separating carbon dioxide mixed gas, and preparation method and application thereof - Google Patents
Metal organic framework material for separating carbon dioxide mixed gas, and preparation method and application thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 95
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 76
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 54
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000001530 fumaric acid Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 235000019253 formic acid Nutrition 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 150000000703 Cerium Chemical class 0.000 claims abstract description 5
- 150000002362 hafnium Chemical class 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 13
- 239000003463 adsorbent Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical group Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- 150000003754 zirconium Chemical class 0.000 claims description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical group [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 46
- 230000035515 penetration Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 9
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 230000000274 adsorptive effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
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- 238000001144 powder X-ray diffraction data Methods 0.000 description 4
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- 238000005119 centrifugation Methods 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical group [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 125000000349 (Z)-3-carboxyprop-2-enoyl group Chemical group O=C([*])/C([H])=C([H])\C(O[H])=O 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention discloses a metal organic framework material for separating carbon dioxide mixed gas, a preparation method and application thereof. Weighing a proper amount of metal salt, adding deionized water, adding formic acid after ultrasonic treatment for 5-10 min, stirring the obtained mixed solution at 600rpm for 10min, adding fumaric acid, stirring the obtained mixed solution at room temperature for 12h again, centrifuging, washing with water and ethanol, and drying to obtain MOF-801 for separating carbon dioxide mixed gas; the metal salt is zirconium salt, cerium salt or hafnium salt. The preparation method of the invention is simple, low in cost, environment-friendly, good in repeatability, capable of amplifying, green and nontoxic in both synthetic raw materials and solvents, and can be matched with MOFs synthesized by high-temperature solvothermal synthesis in terms of application in terms of gas separation performance, and can continuously separate CO at normal temperature and normal pressure 2 /N 2 Or CO 2 /CH 4 Is an excellent candidate for MOFs in industrial applications.
Description
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to a metal organic framework material for separating carbon dioxide mixed gas and a green synthesis method thereof.
Background
With the development of society and the progress of technology, the global energy situation is becoming more and more intense. Admittedly, gas separation has played a significant role as an important purification method in the energy industry. At present, the traditional separation technology such as low-temperature distillation accounts for 10-15% of the world energy consumption. And non-thermally driven adsorptive separation is considered a low cost, efficient and environmentally friendly separation technique.
Since two industrial revolution, excessive emissions of carbon dioxide resulting from the massive use of fossil fuels are a major cause of "greenhouse gases". The greenhouse effect can cause global warming, ice layer melting, sea level rising and other hazards, and greatly influences daily life of people. The traditional method for treating the carbon dioxide utilizes amine solution to carry out chemical absorption on the carbon dioxide, but due to the defects of high requirement on production equipment, high regeneration cost of the adsorbent and the like, development of a carbon dioxide adsorbent with high efficiency, low price and strong regeneration capability is urgently needed. Metal-organic frameworks (MOFs) tend to exhibit excellent gas adsorption and separation properties due to their high porosity, adjustable pore channels and surface chemistry. However, how to design MOFs materials with both high selectivity and high gas adsorption capacity remains a challenging challenge.
Early developed adsorbents such as zeolites and activated carbon have shown some utility in gas separation. Although these materials are inexpensive, they have poor separation efficiency due to limitations of high adjustability and structural diversity, and cannot meet practical industrial applications. Currently, one possible approach is to separate industrial gases by designing porous adsorbents of adjustable structure. The high and diversified functions not only can reduce energy consumption, but also can improve separation efficiency to the maximum extent through design.
The traditional method for synthesizing MOFs (metal-organic frameworks) materials such as solvothermal synthesis, hydrothermal synthesis and the like consumes a certain amount of energy, and most of organic ligands are expensive, and even if a certain separation performance is obtained, the industrial large-scale application is still difficult to realize due to cost limitation. Therefore, it is very necessary to prepare a novel adsorbent having a high adsorption capacity and separation selectivity by a green synthesis method.
Disclosure of Invention
The invention aims to provide a green synthesis method of a metal organic framework material for separating carbon dioxide mixed gas, which aims to solve the problems of huge energy consumption and high cost in the synthesis process of MOFs materials and promote the industrialization process of MOFs materials in the field of gas separation.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a metal organic framework material for carbon dioxide mixed gas separation, wherein the metal organic framework material for carbon dioxide mixed gas separation is MOF-801, and the preparation method comprises the following steps: weighing a proper amount of metal salt, adding deionized water, adding formic acid after ultrasonic treatment for 5-10 min, stirring the obtained mixed solution at 600rpm for 10min, adding fumaric acid, stirring the obtained mixed solution at room temperature for 12h again, centrifuging, washing with water and ethanol, and drying to obtain MOF-801 for carbon dioxide mixed gas separation; the metal salt is zirconium salt, cerium salt or hafnium salt.
Further, the metal organic framework material for separating the carbon dioxide mixed gas is prepared from zirconium salt, namely zirconium chloride.
Further, the metal organic framework material for separating the carbon dioxide mixed gas is characterized in that the cerium salt is ammonium cerium nitrate.
Further, the metal organic framework material for separating the carbon dioxide mixed gas is characterized in that the hafnium salt is hafnium chloride.
Further, the MOF-801 specific surface area for separating the carbon dioxide mixed gas is 573.0234-817.8636 m 2 /g, with
Is a cage-shaped hole.
Further, the metal organic framework material for separating the carbon dioxide mixed gas comprises the metal salt, namely fumaric acid=1:1 according to the mol ratio.
The invention provides an application of a metal organic framework material for separating carbon dioxide mixed gas as an adsorbent in separating carbon dioxide in the carbon dioxide mixed gas.
Further, the carbon dioxide mixed gas comprises CO 2 And N 2 And/or CH 4 Is a mixed gas of (a) and (b).
Further, the method comprises the following steps: and adding a metal organic framework material for separating the carbon dioxide mixed gas into the carbon dioxide mixed gas.
Further, the metal organic framework material for separating the carbon dioxide mixed gas is activated before adsorption, and the activation method comprises the following steps: the metal organic framework material for carbon dioxide mixed gas separation was placed in methanol for 36h, solvent exchange was performed, fresh methanol was exchanged every 6h during the period, and after the exchange was completed, the activated product was centrifugally separated and dried under vacuum at 60 ℃.
The beneficial effects of the invention are as follows:
1. the organic ligand fumaric acid used in the invention is a green and cheap organic ligand, conjugated maleyl in the structure and mu-OH site pair CO in the metal cluster 2 Can generate polarization effect, thereby achieving high-efficiency CO adsorption 2 Is a target of (a).
2. The metal organic framework material synthesized by the invention depends on the mu-OH binding site and double bond pair CO in the metal cluster 2 Realize polarization effect on CO 2 /N 2 And CO 2 /CH 4 Selective physical adsorption, thus its isothermal adsorption enthalpy (28.50 kJ. Mol -1 ) Far less than other MOFs materials, the characteristic greatly reduces the regeneration cost of the adsorbent for recycling, and has important practical significance.
3. The MOF-801 series material prepared by the invention is used for simulating the bi-component gas (CO) of the tail gas of an actual gas engine 2 /N 2 15:85; penetration experiments in v) show that the material can completely separate CO in up to 100 minutes 2 And N 2 . Thereby indicating that the material can be effectively and effectivelyRealization of CO 2 /N 2 Is separated with high selectivity.
4. The MOF-801 series material synthesized by the invention has excellent chemical stability and thermal stability. XRD after thermogravimetric test and adsorption separation shows that the material has good stability and regenerability.
5. The invention prepares a series of metal organic framework materials with mild reaction conditions, large yield and high stability by a green synthesis method, and the metal organic framework materials are used in CO 2 /N 2 And CO 2 /CH 4 The method has great application prospect in the field of selective separation and adsorption and the aspect of alleviating greenhouse effect.
6. The MOFs preparation method disclosed by the invention is simple to operate, good in repeatability and good in thermal stability and separation cycle stability.
Drawings
FIG. 1 is a diagram of N of a metal organic framework material MOF-801 (Zr) synthesized according to the present invention 2 Single component adsorption curve and pore size distribution at 77K.
FIG. 2 is an N of a metal organic framework material MOF-801 (Ce) synthesized according to the present invention 2 Single component adsorption curve and pore size distribution at 77K.
FIG. 3 is an N of a metal organic framework material MOF-801 (Hf) synthesized according to the present invention 2 Single component adsorption curve and pore size distribution at 77K.
Fig. 4 is an X-ray powder diffraction (PXRD) pattern of a metal-organic framework material synthesized in accordance with the present invention.
FIG. 5 is a schematic representation of CO of a metal organic framework material synthesized in accordance with the present invention 2 And N 2 Graph of single component adsorption at 298K.
FIG. 6 is a schematic representation of CO of a metal organic framework material synthesized in accordance with the present invention 2 And CH (CH) 4 Graph of single component adsorption at 298K.
FIG. 7 is a schematic representation of CO of a metal organic framework material synthesized in accordance with the present invention 2 Isothermal adsorption enthalpy graph.
FIG. 8 is a graph showing the penetration of MOF-801 (Zr) as a metal organic framework material synthesized in accordance with the present invention.
FIG. 9 is a graph showing the penetration of MOF-801 (Ce) metal organic framework materials synthesized according to the present invention.
FIG. 10 is a graph of the penetration of the metal organic framework material MOF-801 (Hf) synthesized in accordance with the present invention.
FIG. 11 shows the metal organic framework material MOF-801 (Zr) synthesized in the invention in CO 2 /N 2 Three-pass graph under mixed gas condition with volume ratio of 1:1.
FIG. 12 is a powder X-ray diffraction (PXRD) pattern of the metal organic framework material MOF-801 (Zr) synthesized in the present invention after 7 cycles of adsorptive separation.
FIG. 13 is a powder X-ray diffraction (PXRD) diagram of the metal organic framework material MOF-801 (Ce) synthesized in accordance with the present invention after 7 cycles of adsorptive separation.
FIG. 14 is a powder X-ray diffraction (PXRD) pattern of the metal organic framework material MOF-801 (Hf) synthesized in the present invention after 7 cycles of adsorptive separation.
Detailed Description
In order that the manner in which the invention is practiced, its advantages and details are readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof. It is intended that the scope of the invention be limited not by this disclosure, but by this disclosure, by the claims and their equivalents.
Example 1 preparation of Metal organic framework Material for carbon dioxide gas Mixed separation (one) Metal organic framework Material for carbon dioxide gas Mixed separation (MOF-801 (Zr))
The preparation method comprises the following steps: zirconium chloride (350 mg,1.5 mmol) was weighed into a 100mL round bottom flask, 8mL of deionized water was added, sonicated for 5-10 min, 2mL of formic acid was added after complete dissolution, the resulting mixed solution was stirred at 600rpm for 10min, then fumaric acid (174 mg,1.5 mmol) was added, the resulting mixed solution was again stirred at room temperature for 12h to give a white solid, the product was collected by centrifugation, washed three times with water and ethanol, respectively, and finally dried in a thermostatically oven for carbon dioxide mixed gas separation, MOF-801, labeled MOF-801 (Zr).
(II) preparation of Metal organic framework Material (MOF-801 (Ce)) for carbon dioxide Mixed gas separation
The preparation method comprises the following steps: ammonium cerium nitrate (82 mg,1.5 mmol) was weighed into a 100mL round bottom flask, 8mL of deionized water was added, ultrasound was performed for 5-10 min, 2mL of formic acid was added after complete dissolution, the resulting mixed solution was stirred at 600rpm for 10min, then fumaric acid (174 mg,1.5 mmol) was added, the resulting mixed solution was again stirred at room temperature for 12h, a white solid was produced, the product was collected by centrifugation, washed three times with water and ethanol respectively, and finally dried in a thermostatted oven for carbon dioxide mixed gas separation, MOF-801, labeled MOF-801 (Ce).
Preparation of metal organic framework Material (MOF-801 (Hf)) for carbon dioxide Mixed gas separation
The preparation method comprises the following steps: hafnium chloride (480 mg,1.5 mmol) was weighed into a 100mL round bottom flask, 8mL of deionized water was added, sonicated for 5-10 min, 2mL of formic acid was added after complete dissolution, the resulting mixed solution was stirred at 600rpm for 10min, then fumaric acid (174 mg,1.5 mmol) was added, the resulting mixed solution was again stirred at room temperature for 12h to yield a white solid, the product was collected by centrifugation, washed three times with water and ethanol, respectively, and finally dried in a thermostatted oven for carbon dioxide mixed gas separation, designated MOF-801 (Hf).
(IV) characterization
Activating: in order to remove solvent molecules in the pores of the material to obtain an activated crystalline material, the metal-organic framework material is first activated by a solvent exchange process. 300mg of MOF-801 serving as a metal organic framework material for separating carbon dioxide mixed gas is placed in dry methanol to be soaked for 36 hours, solvent exchange is carried out, fresh methanol is exchanged every 6 hours, an activated product is centrifugally separated after exchange is completed, vacuum drying is carried out at 60 ℃ for 6 hours, vacuum activation is carried out at 120 ℃ for 12 hours, and finally about 250mg of activated MOF-801 serving as a metal organic framework material is obtained.
Completing 77K-N of the activated crystal material under the condition of liquid nitrogen 2 And (5) carrying out adsorption experiments to obtain parameters such as specific surface area and the like of the crystal material. FIG. 1 shows the metal organic framework material MOF-801 (Zr) synthesized in this example at 77KN 2 Adsorption-desorption graph. As can be seen from FIG. 1, the prepared MOF-801 (Zr) has typical micropore characteristics, and the pore size is about
FIG. 2 shows the metal organic framework material MOF-801 (Ce) synthesized in this example at 77K N 2 Adsorption-desorption graph. As can be seen from FIG. 2, the prepared MOF-801 (Ce) has typical micropore characteristics, and the pore size is about +.>
FIG. 3 shows the metal organic framework material MOF-801 (Hf) at 77K N synthesized in this example 2 Adsorption-desorption graph. As can be seen from FIG. 3, the prepared MOF-801 (Hf) has typical microporous characteristics with pore size of about +.>
Fig. 4 is an X-ray powder diffraction (PXRD) pattern of the metal-organic framework material synthesized in this example. As can be seen from FIG. 4, the prepared MOF-801 series material is consistent with diffraction peaks obtained by simulation, and the crystallinity of the material is proved to be good, and the phase purity is high.
Then respectively completing CO of the crystal material at the corresponding temperature under the temperature control conditions of 273K and 298K 2 ，N 2 ，CH 4 Single component adsorption curve. FIG. 5 is a schematic representation of CO from a metal organic framework material synthesized in accordance with the present example 2 And N 2 Graph of single component adsorption at 298K. As can be seen from FIG. 5, under 298K conditions, the resulting material has good CO 2 Adsorption performance, wherein MOF-801 (Ce) exhibits the highest adsorption capacity, in contrast to N 2 Almost negligible adsorption of (C) proves that the material is resistant to CO 2 /N 2 Has excellent separation potential. FIG. 6 is a schematic representation of CO of a metal organic framework material synthesized in accordance with the present example 2 And CH (CH) 4 Graph of single component adsorption at 298K. As can be seen from fig. 6, the material is specific to CH 4 Is far lower than CO 2 Indicating that the material has good CO 2 /CH 4 Separation divingForce. FIG. 7 is a schematic representation of CO of a metal organic framework material synthesized in accordance with the present example 2 Isothermal adsorption enthalpy graph. As can be seen from FIG. 7, the prepared material was specific to CO 2 The adsorption enthalpy of the catalyst is 22-30 kJ mol -1 In which MOF-801 (Ce) and CO 2 Has the maximum adsorption enthalpy of 28.4kJ mol -1 。
Example 2 use of metal organic framework materials for carbon dioxide gas mixture separation
The method (one) is as follows:
activating: in order to remove solvent molecules in the pores of the material to obtain an activated crystalline material, the metal-organic framework material is first activated by a solvent exchange process. 300mg of MOF-801 serving as a metal organic framework material for separating carbon dioxide mixed gas is placed in dry methanol to be soaked for 36 hours, solvent exchange is carried out, fresh methanol is exchanged every 6 hours, an activated product is centrifugally separated after exchange is completed, vacuum drying is carried out at 60 ℃ for 6 hours, vacuum activation is carried out at 120 ℃ for 12 hours, and finally about 250mg of activated MOF-801 serving as a metal organic framework material is obtained.
Gas separation: taking 1.2g of activated MOF-801 material, and completing the penetration simulation of the tail gas of the simulated fuel engine on dynamic adsorption gas penetration equipment. Respectively at CO 2 And N 2 The separation performance and the separation cycle stability of the material on the mixed gas are tested under the mixed gas atmosphere with the volume ratio of 15:85 or 50:50, and the material can be regenerated only by purging with 10mL/min helium at 80 ℃ after each penetration is finished, so that the excellent regenerability of the material is proved.
(II) characterization
FIG. 8 is a graph showing the penetration of MOF-801 (Zr) as a metal organic framework material synthesized in accordance with the present invention. As can be seen from FIG. 8, MOF-801 (Zr) has good CO 2 /N 2 The separation capacity showed effective separation durations of 30min (50/50, v/v) and 55min (15/85, v/v), respectively.
FIG. 9 is a graph showing the penetration of MOF-801 (Ce) metal organic framework materials synthesized according to the present invention. As can be seen from FIG. 9, MOF-801 (Ce) has good CO 2 /N 2 Separation ability of 70min (50/50, v/v) and 90mi, respectivelyn (15/85, v/v).
FIG. 10 is a graph of the penetration of the metal organic framework material MOF-801 (Hf) synthesized in accordance with the present invention. As can be seen from FIG. 10, MOF-801 (Ce) has good CO 2 /N 2 The separation capacity showed effective separation durations of 44min (50/50, v/v) and 56min (15/85, v/v), respectively.
FIG. 11 shows the metal organic framework material MOF-801 (Zr) synthesized in the invention in CO 2 /N 2 Three-pass graph under mixed gas condition with volume ratio of 1:1. As can be seen from FIG. 11, the prepared MOF-801 (Zr) has stable performance in the three-cycle penetration test, and the separation effect is not changed significantly.
FIG. 12 is a powder X-ray diffraction (PXRD) pattern of the metal organic framework material MOF-801 (Zr) synthesized in the present invention after 7 cycles of adsorptive separation. As can be seen from fig. 12, the prepared MOF-801 (Zr) has a complete structure after 7 adsorption cycle tests, which proves that the material has excellent structural stability in practical application.
FIG. 13 is a powder X-ray diffraction (PXRD) diagram of the metal organic framework material MOF-801 (Ce) synthesized in accordance with the present invention after 7 cycles of adsorptive separation. As can be seen from fig. 13, the prepared MOF-801 (Ce) has a complete structure after 7 adsorption cycle tests, which proves that the material has excellent structural stability in practical application.
FIG. 14 is a powder X-ray diffraction (PXRD) pattern of the metal organic framework material MOF-801 (Hf) synthesized in the present invention after 7 cycles of adsorptive separation. As can be seen from FIG. 14, the prepared MOF-801 (Hf) has a complete structure after 7 adsorption cycle tests, which proves that the material has excellent structural stability in practical application.
Claims (8)
1. The metal organic framework material for separating the carbon dioxide mixed gas is MOF-801, and the preparation method comprises the following steps: weighing a proper amount of metal salt, adding deionized water, adding formic acid after ultrasonic treatment for 5-10 min, stirring the obtained mixed solution at 600rpm for 10min, adding fumaric acid, stirring the obtained mixed solution at room temperature for 12h again, centrifuging, washing with water and ethanol, and drying to obtain MOF-801 for carbon dioxide mixed gas separation; the metal salt is zirconium salt, cerium salt or hafnium salt.
2. A metal organic framework material for carbon dioxide mixed gas separation according to claim 1, characterized in that the zirconium salt is zirconium chloride; the cerium salt is ceric ammonium nitrate; the hafnium salt is hafnium chloride.
3. The metal organic framework material for carbon dioxide mixed gas separation according to claim 1, wherein the MOF-801 specific surface area for carbon dioxide mixed gas separation is 573.0234-817.8636 m 2 /g, with
Is a cage-shaped hole.
4. A metal organic framework material for carbon dioxide mixed gas separation according to claim 1, characterized in that the metal salt is fumaric acid=1:1 in molar ratio.
5. Use of a metal organic framework material for carbon dioxide gas mixture separation as claimed in claim 1 as an adsorbent for separating carbon dioxide from carbon dioxide gas mixture.
6. The use according to claim 5, wherein the carbon dioxide gas mixture comprises CO 2 And N 2 And/or CH 4 Is a mixed gas of (a) and (b).
7. The use according to claim 6, characterized in that the method is as follows: a metal organic framework material for carbon dioxide mixed gas separation as claimed in claim 1 is added to the carbon dioxide mixed gas.
8. Use according to claim 5, 6 or 7, characterized in that the metal organic framework material for carbon dioxide mixed gas separation is activated before adsorption, the activation method comprising the steps of: the metal organic framework material for carbon dioxide mixed gas separation was placed in methanol for 36h, solvent exchange was performed, fresh methanol was exchanged every 6h during the period, and after the exchange was completed, the activated product was centrifugally separated and dried under vacuum at 60 ℃.
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