CN106902785B - A kind of metal-organic framework material and preparation method thereof for the storage of superelevation acetylene and the separation absorption of gas efficient selective - Google Patents
A kind of metal-organic framework material and preparation method thereof for the storage of superelevation acetylene and the separation absorption of gas efficient selective Download PDFInfo
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- CN106902785B CN106902785B CN201710151280.XA CN201710151280A CN106902785B CN 106902785 B CN106902785 B CN 106902785B CN 201710151280 A CN201710151280 A CN 201710151280A CN 106902785 B CN106902785 B CN 106902785B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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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- 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/002—Use of gas-solvents or gas-sorbents in vessels for acetylene
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract
The invention discloses a kind of metal-organic framework materials and preparation method thereof for the storage of superelevation acetylene and the separation absorption of gas efficient selective.Organic ligand H is prepared first4TTCA‑NH2, then solvent thermal process is used to obtain homogeneous crystalline material, multiple exchange of solvent is then carried out, the solvent molecule in material hole with coordination, the crystalline material after being activated finally are removed.The Metal Porous-Organic material that the present invention synthesizes, with exposed amino group specific surface area with higher, therefore the acetylene adsorbance with superelevation simultaneously.As lewis base site, the acetylene molecule of exposed amino group Preferential adsorption linear type electron deficient, weaker to the adsorption of carbon dioxide molecule and methane molecule, therefore, which shows excellent C2H2/CO2And C2H2/CH4Efficient selective separates absorption property, has potential application prospect in the Selective Separation adsorbing domain of functional gas.
Description
Technical field
The invention belongs to the preparations of gas absorption and separation system, and in particular to a kind of metal-organic framework material (name
For ZJU-195) and preparation method thereof, which can be used for the storage of superelevation acetylene and C2H2/CO2And C2H2/CH4High efficiency selected
Property separation absorption.
Background technique
The fast development of science and technology and the 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 cutting 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 techniques production such as petroleum fractionating and cracking contain it is some serious
Influence a small amount of impurity of the subsequent utilization benefit of acetylene, such as methane and carbon dioxide.Therefore, the high reserves of acetylene are effectively realized
Storage and C2H2/CO2And C2H2/CH4Efficient selecting property separation absorption be particularly important.Traditional adsorbent material is due to existing
The drawbacks such as separation poor, the energy consumption height of adsorption effect are gradually replaced by other emerging porous materials.
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 its irreplaceable advantage by being self-assembly of with metal center by organic ligand
General concern.There is superelevation to compare table for the porous adsorbing material traditional compared to molecular sieve and active 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 make metal organic
Frame material shows huge application potential with separation field in gas storage.
So far, using metal-organic framework material as C2H2Adsorbent material it is much.But it is higher in guarantee
Acetylene adsorbance has efficient C simultaneously2H2/CO2And C2H2/CH4Selective Separation is adsorbed actually rare, is particularly due to
C2H2And CO2Similar molecular dimension and electronegativity, C2H2/CO2Efficiently separate it is more difficult.The present invention devises a kind of completely new
Organic ligand and successfully synthesize a kind of unique metal-organic framework material using this ligand, which has exposed amino
Group and higher specific surface area, therefore the acetylene adsorbance of superelevation is showed, while C with higher2H2/CO2And C2H2/
CH4Selective Separation absorption provides New Century Planned Textbook in terms of structure design and performance prediction for metal-organic framework material, promotes
Metal-organic framework material is in gas absorption and separates the application of aspect and is in progress.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which it is organic to provide a kind of metal containing exposed amino group
Frame material and preparation method thereof, the material can be used for the storage of superelevation acetylene and C2H2/CO2And C2H2/CH4Efficient selective
Separation absorption.
The present invention adopts the following technical scheme:
For the storage of superelevation acetylene and C2H2/CO2And C2H2/CH4The metal organic frame of efficient selective separation absorption
The preparation method of material, includes the following steps:
(1) Suzuki coupling reaction is used, by 5- boric acid pinacol ester -1,3- dimethyl isophthalate, 3,5- dibromobenzenes
Amine, Anhydrous potassium carbonate are dissolved in dioxane, and it is small that logical argon gas 1 is stirred using triphenylphosphine palladium as catalyst, under room temperature
When, temperature is increased to 85 DEG C, is reacted 72 hours under gas shield, after reaction, is extracted, dried, filtered, recrystallization mentions
It is pure, obtain esterification ligand Me4TPTC-NH2；
(2) hydrolysis is used, esterification ligand obtained above is suspended in sodium hydrate aqueous solution while being added two
Six ring of oxygen flows back 12 hours at 100 DEG C, after being cooled to room temperature, adjusts solution ph to 3 using hydrochloric acid solution, filters, mistake
It uses deionized water to adjust the pH value of filtrate as neutrality when filter, obtains final product H through vacuum drying4TTCA-NH2；
(3) by H4TTCA-NH2With Cu (NO3)2·2.5H2O is dissolved in DMF and the mixed liquor of deionized water, and first is added
Acid reacts 1 day under the conditions of 85 DEG C, obtains homogeneous crystalline material；
(4) the homogeneous crystalline material that above-mentioned steps obtain is exchanged repeatedly, often in anhydrous propanone using exchange of solvent method
It is secondary to be separated by least half an hour, to remove in material hole and the solvent molecule of coordination, then it is sequentially placed into that 273K is 1 day lower, room temperature
Lower 1 day, 323K lower 6 hours, 373K lower 3 hours, at the same keep 5 μm of Hg vacuum state, obtain for superelevation acetylene store with
And C2H2/CO2And C2H2/CH4The metal-organic framework material of efficient selective separation absorption.
In above scheme, catalyst described in step 1) is triphenylphosphine palladium, 5- boric acid pinacol ester -1,3-
Dimethyl isophthalate, 3,5- dibromo aniline, Anhydrous potassium carbonate molar ratio be 3:1:10.
Organic ligand H described in step 3)4TTCA-NH2With Cu (NO3)2·2.5H2The molar ratio of O is 1:4.
The volume ratio of DMF described in step 3), deionized water and formic acid are 60:40:1.
The specific beneficial effect of the present invention is:
(1) the organic ligand H that the present invention designs and synthesizes4TTCA-NH2Have the characteristics that organic polycarboxylic, contains ammonia simultaneously
Base functional group.This ligand and the metal-organic framework material that copper salt is self-assembly of contain exposed amino group and higher
Specific surface area, therefore show the acetylene adsorbance of superelevation；As lewis base site, exposed amino group Preferential adsorption straight line
The acetylene molecule of type electron deficient, weaker to the adsorption of carbon dioxide molecule and methane molecule, therefore, which shows
Excellent C2H2/CO2And C2H2/CH4Efficient selective separates absorption property.
(2) metal-organic framework material of existing report is as C2H2Adsorbent material, guaranteeing that higher acetylene adsorbance is same
When have efficient C2H2/CO2And C2H2/CH4Actually rare, the especially C of Selective Separation absorption2H2And CO2Due to similar
Molecular dimension and electronegativity, which are difficult to realize, to be efficiently separated.The metal-organic framework material of the present patent application protection is in room temperature condition
Down with the acetylene adsorbance (214.2cm of superelevation3·g-1) and relatively high C2H2/CO2And C2H2/CH4Select separation.?
Under room temperature, C2H2And CH4Separation be up to 64.6, the C of hardly possible separation2H2And CO2Separation also have 12.7.This hair
It is bright devise a kind of completely new organic ligand and successfully synthesize a kind of metal containing exposed amino group using this ligand have
Machine frame frame material, the material have efficient C while ensuring superelevation acetylene adsorbance2H2/CO2And C2H2/CH4Selectivity
Separation absorption proposes New Century Planned Textbook in terms of structure design and performance prediction for metal-organic framework material, and advancing metal has
Machine frame frame material is in progress in gas absorption with the application for separating aspect.
Detailed description of the invention
Fig. 1 is the crystal structure figure of metal-organic framework material ZJU-195.
Fig. 2 is X-ray diffraction (XRD) figure of metal-organic framework material.
Fig. 3 is the full adsorpting data curve graph of nitrogen of metal-organic framework material ZJU-195.
Fig. 4 is C of metal-organic framework material ZJU-195a under the conditions of 298K and 273K after activation2H2、CO2And CH4
One pack system adsorption curve.
Fig. 5 is C of metal-organic framework material ZJU-195a under the conditions of 298K and 273K2H2/CO2And C2H2/CH4Selection
Partition coefficient curve figure
Fig. 6 is the C of metal-organic framework material ZJU-195a2H2、CO2And CH4Isothermal adsorption enthalpy data graphs.
Specific embodiment
Below in conjunction with the example content that the present invention is furture elucidated, but these examples are not intended to limit protection model of the invention
Enclose, based on the technical solutions of the present invention, those skilled in the art do not need to make the creative labor can make it is each
Kind modification or deformation are still within protection scope of the present invention.
Example: (1) Suzuki coupling reaction is used, by 5- boric acid pinacol ester -1,3- isophthalic diformazan of 9.61g (30mmol)
Dimethyl phthalate, 3, the 5- dibromo aniline of 2.51g (10mmol), the potassium carbonate of 13.9g (100mmol) and 0.15g (0.2mmol)
Catalyst Pd (PPh3)2Cl2, it is dissolved in the dioxane of 100mL according to the stoichiometric ratio uniform dissolution of setting, is stirred under room temperature
It mixes logical argon gas 1 hour, increases temperature to 85 DEG C, sustained response 72 hours under protection of argon gas.After reaction, by reaction solution
It is extracted three times with chloroform (being commonly called as chloroform) and deionized water, takes lower organic layer that anhydrous magnesium sulfate drying is added, stand half
It is filtered after hour and obtains solid powder under heating in vacuum state.Finally by solid powder with dry toluene recrystallize purification from
And obtain esterification ligand Me4TPTC-NH2。
(2) by the Me of obtained 2.39g (5mmol)4TPTC-NH2It is added to the sodium hydroxide water of the 1.0mol/L of 100mL
In solution, 20mL dioxane is added, flows back 12 hours, is cooled to room temperature at 100 DEG C.Then the salt of 6mol/L is used
Acid solution adjusts the pH value of reaction solution to 3 or so, filters after static half an hour, and when filtering is rinsed with deionized water, until filter
The pH value of liquid is neutrality, and solid vacuum drying after filtering is obtained 2.00g final product H4TTCA-NH2.
(3) solvent thermal process is used, by the organic ligand H of 12.0mg, 0.0285mmol4TTCA-NH2With 26.5mg,
Metal salt Cu (the NO of 0.114mmol3)2·2.5H2O is in solvent (DMF:H2O, 6.0mL/4.0mL) sonic oscillation five divides under environment
Clock is added 100 μ L formic acid, reacts 1 day under the conditions of 85 DEG C, obtain homogeneous crystalline material to uniform dissolution.
(4) in order to remove the crystalline material that in material hole and the solvent molecule of coordination is activated, first with molten
Agent exchange process exchanges the about 100mg sample that above-mentioned steps obtain about 10 times in anhydrous propanone, is separated by least half an hour every time,
Then successively 1 day at 273K, 1 day at room temperature, 323K lower 6 hours, 373K lower 3 hours, while keeping the vacuum shape of 5 μm of Hg
State can be used for the storage of superelevation acetylene and C after finally obtaining activation2H2/CO2And C2H2/CH4The pact of Selective Separation absorption
65mg crystalline material.
(5) crystalline material after activation is completed into 77K-N under the conditions of protection of liquid nitrogen2Full adsorption experiment, to obtain crystalline substance
The parameters such as specific surface area, the pore volume of body material.Then, respectively in mixture of ice and water condition (273K) and room-temperature water bath condition
The C of crystalline material is completed under (298K)2H2、CO2And CH4One pack system adsorption curve.
The metal-organic framework material containing exposed amino group that the present invention synthesizes (is named as ZJU-195, orders after activation
Entitled ZJU-195a) crystal structure is as shown in Figure 1.Fig. 1 a is organic ligand H4TTCA-NH2Schematic diagram；Fig. 1 c and Fig. 1 d is
Two kinds of hole basket structures of ZJU-195；Fig. 1 e, Fig. 1 f and Fig. 1 b are the ZJU-195 three-dimensional crystal knot presented from a axis, b axis and c-axis
Composition.As shown in Figure 1, there is the crystal structure of ZJU-195 exposed amino group to have relatively high porosity simultaneously.Fig. 2
For the x-ray diffraction pattern of ZJU-195, as seen from the figure, the crystal structure of crystal structure and simulation that solvent thermal process synthesizes is very
Coincide, and ZJU-195a vacuum take off solvent after do not lose original three-dimensional crystalline structure.The metal-organic framework material
77K nitrogen adsorbed entirely as shown in figure 3, as seen from the figure, which is presented typical I- type adsorption curve, the suction of nitrogen under 77K
Attached amount is 601.9cm3·g-1, corresponding BET is 1721.9m2·g-1.The metal-organic framework material is in 298K and 273K
C2H2、CO2And CH4One pack system adsorption curve it is as shown in Figure 4.As seen from the figure, the acetylene absorption of superelevation is presented in ZJU-195a
Amount, the adsorbance of acetylene reaches 275.6cm under the conditions of 273K3·g-1, the adsorbance of acetylene reaches under the conditions of 298K
214.2cm3·g-1；Also, no matter under the conditions of 273K or under the conditions of 298K, the C of ZJU-195a2H2Adsorbance is much high
In CO2And CH4Adsorbance, further demonstrated that material to C2H2/CO2And C2H2/CH4Selective Separation absorption.The material
C2H2/CO2And C2H2/CH4Selection separation it is as shown in Figure 5.As seen from the figure, at room temperature, C2H2And CH4Separation
Coefficient is up to 64.6, the C of hardly possible separation2H2And CO2Separation also have 12.7.The C of the material2H2、CO2And CH4Isothermal inhale
Attached enthalpy as shown in fig. 6, ZJU-195 to C2H2The active force of molecule is apparently higher than CO2Molecule and CH4Molecule further demonstrates road
The presence of this easy exposed amino group in alkali site is greatly promoted material to C2H2/CO2And C2H2/CH4Selective Separation absorption.
Claims (2)
1. one kind is for the storage of superelevation acetylene and C2H2/CO2And C2H2/CH4The metal of efficient selective separation absorption has machine frame
The preparation method of frame material, which comprises the steps of:
(1) Suzuki coupling reaction is used, by 5- boric acid pinacol ester -1,3- dimethyl isophthalate, 3,5- dibromo anilines, nothing
Aqueous carbonate potassium is dissolved in organic solvent dioxane, and logical argon gas 1 is stirred using triphenylphosphine palladium as catalyst, under room temperature
Hour, temperature is then increased to 85 DEG C, is reacted 72 hours under gas shield, after reaction, is extracted, dried, filtered, weight
Crystallization and purification obtains esterification ligand Me4TPTC-NH2；The 5- boric acid pinacol ester -1,3- dimethyl isophthalate, 3,
5- dibromo aniline, Anhydrous potassium carbonate molar ratio be 3:1:10；
(2) hydrolysis is used, esterification ligand obtained above is suspended in sodium hydrate aqueous solution, dioxane is added,
It flows back at 100 DEG C 12 hours, after being cooled to room temperature, solution ph is adjusted to 3 using hydrochloric acid solution, filtering, when filtering adopts
It is neutrality with the pH value that deionized water adjusts filtrate, obtains final product H through vacuum drying4TTCA-NH2；
(3) by H4TTCA-NH2With Cu (NO3)2·2.5H2O is dissolved in DMF and the mixed liquor of deionized water, and formic acid is added,
It is reacted 1 day under the conditions of 85 DEG C, obtains homogeneous crystalline material；Wherein organic ligand H4TTCA-NH2With Cu (NO3)2·2.5H2O's rubs
You are than being 1:4；The volume ratio of the DMF, deionized water and formic acid are 60:40:1；
(4) the homogeneous crystalline material that above-mentioned steps obtain is exchanged repeatedly in anhydrous propanone using exchange of solvent method, each phase
The vacuum state of 5 μm of Hg is then kept, is successively set to remove the solvent molecule in material hole and being coordinated every at least half an hour
It is 1 day lower in 273K, 1 day at room temperature, 323K it is 6 hours lower, 373K lower 3 hours, obtain for superelevation acetylene storage and C2H2/CO2
And C2H2/CH4The metal-organic framework material of efficient selective separation absorption.
2. the metal-organic framework material that the method as described in claim 1 prepares.
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| CN112657471B (en) * | 2020-12-11 | 2022-05-20 | 太原理工大学 | Preparation method of low-concentration acetylene efficient trapping agent |
| CN113278159B (en) * | 2021-05-26 | 2022-09-09 | 江西师范大学 | Iron-nickel metal organic framework material for separating acetylene/carbon dioxide mixed gas and preparation method thereof |
| CN113583250B (en) * | 2021-08-09 | 2022-04-19 | 河海大学 | Zinc-based metal organic framework and synthesis method and application thereof |
| CN113667136B (en) * | 2021-09-09 | 2022-09-30 | 浙江大学 | Ultrahigh-stability and low-cost metal-organic framework material for efficiently separating acetylene/carbon dioxide and preparation method thereof |
| CN114805828B (en) * | 2022-03-25 | 2023-05-16 | 浙江师范大学 | Metal organic frame material and preparation method thereof |
| CN114887601B (en) * | 2022-05-20 | 2024-02-02 | 金宏气体股份有限公司 | For C 2 H 2 /C 2 H 4 MOF material with efficient separation performance and preparation method and application thereof |
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