CN108503851A - A kind of metal-organic framework material of high stability and preparation method thereof for efficient acetylene/carbon dioxide selection separation absorption - Google Patents
A kind of metal-organic framework material of high stability and preparation method thereof for efficient acetylene/carbon dioxide selection separation absorption Download PDFInfo
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- CN108503851A CN108503851A CN201810359433.4A CN201810359433A CN108503851A CN 108503851 A CN108503851 A CN 108503851A CN 201810359433 A CN201810359433 A CN 201810359433A CN 108503851 A CN108503851 A CN 108503851A
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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
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- 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
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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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- 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
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract
It being used for efficient C the present invention relates to a kind of2H2/CO2The metal-organic framework material of high stability and preparation method thereof of selection separation absorption.Its preparation is to obtain homogeneous crystalline material using solvent thermal process first, secondly multiple exchange of solvent is carried out using anhydrous propanone and anhydrous methylene chloride in succession, then material removal hole is interior with the solvent molecule being coordinated under vacuum conditions, the crystalline material that can be used for gas absorption after finally obtaining activation and detach.The secondary structure unit for the metal-organic framework material that the present invention synthesizes is different from classical Zn4O and Zn N Zn coordination modes have Zn O (OH), Zn O (COOH) and Zn NH2Three kinds of different coordination modes, enhance the stability of frame material to a certain extent.CO can be effectively prevented after the three-dimensional crystal frame material activation of structure2Storage and selectively efficient storage C2H2.In addition, the material has excellent chemical stability, thermal stability and cyclical stability, there is potential application prospect.
Description
Technical field
The invention belongs to the preparations of environment and energy field gas absorption and piece-rate system, and in particular to one kind is for efficient
C2H2/CO2The metal-organic framework material of high stability and preparation method thereof of selection separation absorption, the metal organic frame material
Material can be used for C2H2/CO2High efficiency selected separation absorption.
Background technology
The fast development of science and technology and the increasingly raising of human living standard propose higher challenge to energy and material.Acetylene
(C2H2), be commonly called as wind coal, acetylene, can be used to illuminate, welding and cut-out metal (oxy arc), and manufacture acetaldehyde, acetic acid, benzene,
The base stock of the important materials such as synthetic rubber, synthetic fibers.As a kind of very important industrial chemicals, acetylene is widely answered
Used in the fields such as petrochemical industry and electronics industry.But the acetylene of the technique productions such as petroleum fractionating and cracking contains some seriously
Influence a small amount of carbon dioxide impurities of the follow-up utilization benefit of acetylene.Therefore, C is effectively realized2H2/CO2Efficient selecting property separation inhale
It is attached to be particularly important.Traditional sorbing material is gradually new by other due to there are the drawbacks such as the separation poor, high energy consumption of adsorption effect
Emerging porous material substitution.
Metal-organic framework material (Metal-organicFramework, MOFs) is as a kind of emerging porous crystalline material
Material causes the wide of various circles of society by being self-assembly of with metal center by organic ligand by its irreplaceable advantage
General concern.There is superelevation to compare table for the porous adsorbing material traditional compared to molecular sieve and activated carbon etc., metal-organic framework material
Area and pore volume, adjustable aperture size, a series of advantages such as be easy to functionalization.These significant advantages so that metal is organic
Frame material shows huge application potential in gas storage with separation field.
So far, since the physico-chemical property of acetylene molecule and carbon dioxide molecule is very close to (acetylene and carbon dioxide
Aerodynamic size be respectivelyWithThe boiling point of acetylene and carbon dioxide is respectively
189.3K and 194.7K), there is efficient C2H2/CO2The metal-organic framework material of Selective Separation absorption is actually rare.This
Outside, there are a small amount of vapor and acidic corrosive gas in the acetylene steam of practical application.Therefore, this require one it is excellent
C2H2/CO2Selective Separation sorbing material must also have good water stability and chemical stability.Present invention employs one
Kind more coordinated organic ligand 3,4-AHBAs simple and easy to get utilize the organic ligand and the success of aqueous zinc nitrate
Assemble a kind of chemical stability and thermal stability high gas absorption and separation material.The secondary structure unit of the material is not
It is same as classical Zn4O and Zn-N-Zn coordination modes have Zn-O (OH), Zn-O (COOH) and Zn-NH2Three kinds of different coordinations
Pattern.Its three-dimensional crystal frame material built has one-dimensional diamond shape flexibility duct, after activation, can effectively prevent CO2
Storage and selectively efficient storage C2H2.Moreover, which has excellent chemical stability, thermal stability and follows
Ring stability greatly meets multiple requirements of the practical application to sorbing material, be metal-organic framework material in structure
New Century Planned Textbook is provided in terms of design and performance prediction, advances metal-organic framework material in gas absorption and answering in terms of detaching
With progress.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of metal-organic framework material of high stability
And preparation method thereof, which can be used for C2H2/CO2High efficiency selected separation absorption.
The present invention adopts the following technical scheme that：
For efficient C2H2/CO2The preparation method of metal-organic framework material of the high stability of selection separation absorption includes
Following steps：
(1) by organic ligand 3,4-AHBA (3-amino-4-hydroxybenzoic acid) and Zn
(NO3)2·6H2O is dissolved in the mixed solution of DMF, acetonitrile, ethyl alcohol and deionized water, reacts 1 under the conditions of 80 DEG C~90 DEG C
~3 days, obtain homogeneous crystalline material；
(2) the homogeneous crystalline material that above-mentioned steps obtain is exchanged repeatedly, so in anhydrous propanone using exchange of solvent method
It is exchanged in anhydrous methylene chloride afterwards multiple, is separated by least half an hour every time, in material removal hole and the solvent of coordination point
Son, be then sequentially placed into 273K it is 1 day lower, 1 day at room temperature, until vacuum state reaches 5 μm of Hg and remains unchanged, to obtain
For efficient C2H2/CO2The metal-organic framework material of the high stability of selection separation absorption.
In above-mentioned technical proposal, the organic ligand 3,4-AHBA and Zn (NO3)2·6H2The quality of O
Than being 1：2.
DMF, acetonitrile, ethyl alcohol and the deionized volume ratio is 20：3：3：1.
The specific advantageous effect of the present invention is：
(1) organic ligand that excavates of the present invention is different from traditional organic carboxyl acid ligand, is a kind of simple and easy to get five to match
Position organic ligand, coordination environment with a greater variety is provided for metal ion.
(2) secondary structure unit of the metal-organic framework material that the present invention designs and synthesizes, the material is different from classics
Zn4O and Zn-N-Zn coordination modes have Zn-O (OH), Zn-O (COOH) and Zn-NH2Three kinds of different coordination modes, this is solely
Special coordination mode considerably improves the stability of material.Experiment shows that the material has excellent chemical stability and heat
Stability.
(3) the three-dimensional crystal frame material of its structure has one-dimensional diamond shape flexibility duct, and the duct is in removal duct
Solvent molecule when diamonding can occur, narrower bore road is become from macropore shape.Narrower bore road after deformation can be prevented selectively
The entrance of carbon dioxide molecule, selectively adsorbs acetylene molecule, to realize C2H2/CO2High efficiency selected separation absorption.
(4) in addition, the material has good cyclical stability, after 6 recycle, absorption total amount of the material to acetylene
Almost without changing.Also, the material reactivates in the air that humidity is more than 70% after static 1 year, C2H2/CO2
High efficiency selected separation absorption do not change.
The material greatly meets multiple requirements of the practical application to sorbing material, exists for metal-organic framework material
New Century Planned Textbook is provided in terms of structure design and performance prediction, advances metal-organic framework material in gas absorption and in terms of detaching
Application progress.
Description of the drawings
Fig. 1 is the crystal structure schematic diagram of metal-organic framework material ZJU-196.
Fig. 2 is the crystal structure figure of metal-organic framework material ZJU-196 and MIL-53.
Fig. 3 is X-ray diffraction (XRD) figure of metal-organic framework material ZJU-196 and MIL-53.
Fig. 4 is X-ray diffraction (XRD) figure of metal-organic framework material ZJU-196 and the ZJU-196a after activation.
Fig. 5 is X-ray diffraction (XRD) figure of the chemical stability of metal-organic framework material ZJU-196.
Fig. 6 is Cs of metal-organic framework material ZJU-196a under the conditions of 298K2H2And CO2One pack system adsorption curve
Figure.
Fig. 7 is the C of metal-organic framework material ZJU-196a2H2And CO2Breakthrough experiment and cyclical stability curve graph.
Specific implementation mode
Below in conjunction with the example content that the present invention is furture elucidated, but these examples are not intended to limit the protection model of the present invention
Enclose, based on the technical solutions of the present invention, those skilled in the art need not make the creative labor can make it is each
Kind modification or deformation are still within protection scope of the present invention.
Example：
(1) solvent thermal process synthetic crystal material is used, by 10.0mg, the organic ligand 3- amino -4- hydroxyls of 0.065mmol
Metal salt Zn (the NO of yl benzoic acid (3-amino-4-hydroxybenzoic acid) and 20.0mg, 0.0674mmol3)2·
6H2O is in solvent (DMF：MeCN：EtOH:H2O, 2.0mL/0.3mL/0.3mL/0.1mL) under environment sonic oscillation five minutes to equal
Even dissolving reacts 3 days under the conditions of 85 DEG C, obtains homogeneous crystalline material.
(2) use exchange of solvent method activate after crystalline material, in order in material removal hole and be coordinated it is molten
The crystalline material that agent molecule is activated, the about 120mg samples for obtaining above-mentioned steps first with exchange of solvent method are anhydrous
It is exchanged in acetone about 5 times, is then exchanged in anhydrous methylene chloride about 10 times, be separated by least half an hour every time, then exist successively
273K is 1 day lower, 1 day at room temperature, until vacuum state reaches 5 μm of Hg and remains unchanged, finally obtains and can be used for height after activation
Imitate C2H2/CO2The about 85mg crystalline materials of selection separation absorption.
(3) crystalline material after activation is completed into 196K-CO under the mixed solution protective condition of acetone and dry ice2It is complete to inhale
Attached experiment, the parameters such as pore volume to obtain crystalline material.Then, respectively in mixture of ice and water condition (273K) and room temperature water
The C of crystalline material is completed under bath condition (298K)2H2And CO2One pack system adsorption curve.
The metal-organic framework material that the present invention synthesizes (is named as ZJU-196, ZJU- is named as after activation when unactivated
Crystal structure 196a) is as shown in Figure 1, the organic ligand of the material is that one kind five is matched different from traditional polycarboxylic acid organic ligand
The organic ligand of position；The secondary structure unit of the material is different from classical Zn4O and Zn-N-Zn coordination modes have Zn-O
(OH), Zn-O (COOH) and Zn-NH2Three kinds of different coordination modes, the unique coordination mode considerably improve material
Stability；Its three-dimensional crystal frame material built has one-dimensional diamond shape flexibility duct, and pore size size isFig. 2 and Fig. 3 shows that ZJU-196 and star MOF MIL-53 are extremely similar, all has one-dimensional diamond shape soft
The variation tendency in property duct and duct is also identical.Fig. 4 shows that ZJU-196 and the phase transformation of the ZJU-196a after activation are reversible,
ZJU-196 is changed into ZJU-196a after the solvent molecule in removal duct, and ZJU-196a is impregnated in different solvent environments
ZJU-196 can be restored within about 30 minutes.As shown in Figure 5, which has excellent chemical stability, point
It is not impregnated 2 days in pH=2 to pH=12, the crystal structure of the material keeps complete.The metal-organic framework material is in 298K items
C under part2H2And CO2One pack system adsorption curve it is as shown in Figure 6 a, as seen from the figure, the ZJU-196a after activation is in normal temperature and pressure
The carbon dioxide of lower absorption can be ignored, and selectively adsorbs acetylene molecule and reach 83.5cm3g-1(108.5cm3cm-3)。
Its C2H2With CO250：50 gas segregation ratio are current peak (Fig. 6 b) up to 25.0.The breakthrough experiment of Fig. 7 a shows this
Material can detach C actually actively2H2And CO2, the acetylene that purity is higher than 97% can be obtained.The material also has excellent
Cyclical stability, after 6 recycle, which changes to the absorption total amount of acetylene.The material is greatly full
Foot multiple requirements of the practical application to sorbing material are metal-organic framework material in terms of structure design and performance prediction
New Century Planned Textbook is provided, metal-organic framework material is advanced and is in progress with the application for detaching aspect in gas absorption.
Claims (4)
1. one kind being used for efficient C2H2/CO2The preparation method of the metal-organic framework material of the high stability of selection separation absorption,
It is characterised in that it includes following steps：
(1) by organic ligand 3,4-AHBA (3-amino-4-hydroxybenzoic acid) and Zn
(NO3)2·6H2O is dissolved in the mixed solution of DMF, acetonitrile, ethyl alcohol and deionized water, reacts 1 under the conditions of 80 DEG C~90 DEG C
~3 days, obtain homogeneous crystalline material；
(2) the homogeneous crystalline material that above-mentioned steps obtain is exchanged repeatedly using exchange of solvent method in anhydrous propanone, is then existed
It exchanges multiple in anhydrous methylene chloride, is separated by least half an hour every time, in material removal hole and the solvent molecule of coordination, so
After be sequentially placed into 273K it is 1 day lower, 1 day at room temperature, until vacuum state reaches 5 μm of Hg and remains unchanged, to be used for
Efficient C2H2/CO2The metal-organic framework material of the high stability of selection separation absorption.
2. according to claim 1 be used for efficient C2H2/CO2The metal organic frame of the high stability of selection separation absorption
The preparation method of material, which is characterized in that the organic ligand 3,4-AHBA and Zn (NO3)2·6H2O's
Mass ratio is 1：2.
3. according to claim 1 be used for efficient C2H2/CO2The metal organic frame of the high stability of selection separation absorption
The preparation method of material, which is characterized in that DMF, acetonitrile, ethyl alcohol and the deionized volume ratio is 20：3：3：1.
4. the metal-organic framework material that method according to any one of claims 1-4 prepares.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608652A (en) * | 2018-12-17 | 2019-04-12 | 中国科学院福建物质结构研究所 | MOFs crystalline material and its preparation, application |
| CN112619611A (en) * | 2020-12-11 | 2021-04-09 | 太原理工大学 | Acetylene efficient separation material |
| CN112742163A (en) * | 2020-12-22 | 2021-05-04 | 海南大学 | Application of MOFs material based on cuprous-alkynyl chemistry in acetylene/carbon dioxide separation |
| CN113278159A (en) * | 2021-05-26 | 2021-08-20 | 江西师范大学 | Iron-nickel metal organic framework material for separating acetylene/carbon dioxide mixed gas and preparation method thereof |
| CN114031783A (en) * | 2021-10-21 | 2022-02-11 | 西安工业大学 | Metal organic framework material and preparation method and application thereof |
| CN114805841A (en) * | 2022-06-10 | 2022-07-29 | 浙江大学 | Cu-MOF material for separating acetylene/carbon dioxide and having three-high performance and preparation method thereof |
| CN115386099A (en) * | 2022-09-14 | 2022-11-25 | 海南大学 | Preparation method of metal organic framework material of rigid-flexible framework, obtained product and application |
| CN115831286A (en) * | 2022-11-24 | 2023-03-21 | 南京工业大学 | Prediction method of MOF film lattice defects |
| CN116120584A (en) * | 2023-02-28 | 2023-05-16 | 西北大学 | Metal organic framework compound, preparation method and application |
| CN116328730A (en) * | 2021-12-23 | 2023-06-27 | 上海科技大学 | Flexible metal organic framework material and preparation method and application thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608652A (en) * | 2018-12-17 | 2019-04-12 | 中国科学院福建物质结构研究所 | MOFs crystalline material and its preparation, application |
| CN109608652B (en) * | 2018-12-17 | 2020-06-30 | 中国科学院福建物质结构研究所 | MOFs crystal material and preparation and application thereof |
| CN112619611A (en) * | 2020-12-11 | 2021-04-09 | 太原理工大学 | Acetylene efficient separation material |
| CN112742163B (en) * | 2020-12-22 | 2023-03-10 | 海南大学 | Application of MOFs material based on cuprous-alkynyl chemistry in acetylene/carbon dioxide separation |
| CN112742163A (en) * | 2020-12-22 | 2021-05-04 | 海南大学 | Application of MOFs material based on cuprous-alkynyl chemistry in acetylene/carbon dioxide separation |
| CN113278159A (en) * | 2021-05-26 | 2021-08-20 | 江西师范大学 | Iron-nickel metal organic framework material for separating acetylene/carbon dioxide mixed gas and preparation method thereof |
| CN114031783A (en) * | 2021-10-21 | 2022-02-11 | 西安工业大学 | Metal organic framework material and preparation method and application thereof |
| CN116328730A (en) * | 2021-12-23 | 2023-06-27 | 上海科技大学 | Flexible metal organic framework material and preparation method and application thereof |
| CN114805841A (en) * | 2022-06-10 | 2022-07-29 | 浙江大学 | Cu-MOF material for separating acetylene/carbon dioxide and having three-high performance and preparation method thereof |
| CN114805841B (en) * | 2022-06-10 | 2022-12-23 | 浙江大学 | Cu-MOF material for separating acetylene/carbon dioxide and having three-high performance and preparation method thereof |
| CN115386099A (en) * | 2022-09-14 | 2022-11-25 | 海南大学 | Preparation method of metal organic framework material of rigid-flexible framework, obtained product and application |
| CN115386099B (en) * | 2022-09-14 | 2023-09-19 | 海南大学 | Preparation method of metal organic framework material of rigid-flexible framework, obtained product and application |
| CN115831286A (en) * | 2022-11-24 | 2023-03-21 | 南京工业大学 | Prediction method of MOF film lattice defects |
| CN115831286B (en) * | 2022-11-24 | 2023-09-15 | 南京工业大学 | Prediction method of MOF film lattice defects |
| CN116120584A (en) * | 2023-02-28 | 2023-05-16 | 西北大学 | Metal organic framework compound, preparation method and application |
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