CN105597705B - One kind has excellent CO2Absorption and the ultramicropore covalent triazine framework material and preparation method of separating property - Google Patents

One kind has excellent CO2Absorption and the ultramicropore covalent triazine framework material and preparation method of separating property Download PDF

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CN105597705B
CN105597705B CN201510634254.3A CN201510634254A CN105597705B CN 105597705 B CN105597705 B CN 105597705B CN 201510634254 A CN201510634254 A CN 201510634254A CN 105597705 B CN105597705 B CN 105597705B
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covalent triazine
ultramicropore
framework material
selective separation
covalent
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CN105597705A (en
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仲崇立
王可可
黄宏亮
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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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

Abstract

One kind has excellent CO2Absorption and the ultramicropore covalent triazine framework material and preparation method of separating property, described covalent triazine framework material is the stephanoporate framework material being polymerized by organic monomer in the presence of catalyst zinc chloride by covalent bond.The specific surface area of described covalent triazine framework material is 100~3000m2/ g, aperture arePore volume is 0.05~0.5cm3/g.Organic monomer flumaronitrile is well mixed with zinc chloride, loads ampoule bottle, vacuumizes sealing；Mixture is polymerized in tube furnace under certain temperature for having excellent CO2Absorption and the ultramicropore covalent triazine framework material of separating property.The material not only possesses high stability, and to CO2With very high adsorption capacity, separation selectivity and good reproducibility.

Description

One kind has excellent CO2Absorption and the ultramicropore covalent triazine framework material of separating property And preparation method
Technical field
It is more particularly to a kind of that there is efficient CO the invention belongs to the preparation field of nano-porous materials2Absorption and separation property The design and synthesis of the ultramicropore covalent triazine framework material of energy.
Background technology
A large amount of uses of fossil fuel, discharge substantial amounts of CO2Waste gas, its content in an atmosphere is set to increase year by year, from And cause global warming and add the risk of environmental degradation.The whole world faces the urgent task of GHG emissions mitigation at present.Respectively State just falls over each other to develop CO2While reclaiming and utilize technology, new technology and industry are also arisen at the historic moment.
Coal-burning power plant is CO2Concentration emission source, the whole world about 40% CO2Discharge comes from the flue gas in power plant (CO2/N2Mixture).On the other hand, biological methane is as a kind of novel energy, has cleaning, efficient, safe and renewable etc. Feature.With the fast development of China's economy, if carrying out Efficient Conversion to the annual caused inferior biomass of flood tide to produce life Thing methane, it can dramatically realize energy-conservation and the bi-directional objects of emission reduction.But CO2As the major impurity in biological methane, To biological methane as the equal important of the applicability of fuel and calorific value etc..Therefore, from CO2/N2And CO2/CH4It is mixed CO is effectively separated in compound2It is most important.
Although widely used amine solvent chemical absorption method in industry at present, there is consumed energy during solvent reclamation for it Greatly, the problems such as equipment life is short.Have that technical process is simple, device based on the advanced PSA Technology for receiving poromerics The advantages that operating flexibility is big, energy consumption is relatively low, there is important application in chemical field.Wherein porous organic framework materials are demonstrated by Good CO2Adsorption separation performance, and easily regenerate.
Covalent triazine framework material (CTFs) is one of which porous organic framework materials.It is passed through by organic architecture block Covalent key connection obtains the framework material with triazine structure.CTFs has high specific surface area, low skeletal density, structure more Sample, high chemical stability and heat endurance.Most it is worth noting that CTFs can be modified in molecule rank, so as to assign Its unique structure and characteristic are given, possesses preferable application prospect in gas absorption separation etc..Also, relative to Sonogashira coupled reactions, Suzuki coupled reactions, Yamamoto coupled reactions and alkynes trimerization reaction etc. need expensive The reaction environment of noble metal catalyst and harshness, synthesis CTFs series only need cheap catalysis based on triazine polymerisation Agent, and reduce the influence to environment without organic solvent in reaction.
Because it is extremely difficult and expensive to compress complete flue gas, CO is separated in physical absorption2During Ultra-microporous is very favorable.In general, the porous material with ultra-microporous is to CO2With preferable separation choosing Selecting property.But it is still a difficult point effectively to design and synthesize the framework material with ultramicropore.
The content of the invention
In order to be effectively obtained ultramicropore framework material and solve CO existing for prior art2Adsorbent poor selectivity is asked Inscribe, the present invention has synthesized one kind using the strategy design for reducing monomer size has excellent CO2Absorption and the ultra micro of separating property Hole covalent triazine framework material.Described covalent triazine framework material is to CO2With high adsorbance, separation selectivity and easily Regeneration.
The technical scheme is that：One kind has excellent CO2Absorption and the ultramicropore covalent triazine skeleton of separating property Material, it is the stephanoporate framework material being polymerized by organic monomer in the presence of catalyst and under certain temperature by covalent bond Material.Its specific surface area is 100~3000m2/ g, aperture are(and mainly withBased on), pore volume be 0.05~ 0.5cm3/g.Organic monomer is flumaronitrile during preparation；Catalyst is zinc chloride.
It can be prepared using ion thermal response one-step method.Specific step is：Zinc chloride and the mixing of monomer flumaronitrile are equal It is even, load reaction bulb, vacuumize sealing, reacted in tube furnace and obtain black solid, then ground, successively with water, watery hydrochloric acid Solution and methanol wash away metal salt and obtain having excellent CO2Absorption and the ultramicropore covalent triazine framework material of separating property
The temperature of above-mentioned reaction is 350~600 DEG C, preferably 350-400 DEG C.The mol ratio of flumaronitrile and zinc chloride is 1: 2~1:10.
The ultramicropore covalent triazine framework material of the present invention is used for CO2Selective Separation, particularly for CO2With N2Or/and CH4Selective Separation.
CO2With N2Or/and CH4The temperature of Selective Separation be 273K-298K.
Compared with prior art, the advantages of the present invention are as follows：
1. preparing raw material is cheap, catalyst and organic solvent without costliness.
2. there is excellent CO2Absorption and the ultramicropore covalent triazine framework material of separating property have high specific surface area, Ultramicropore, high microporosity and high nitrogen content.
3. there is excellent CO2Absorption and the ultramicropore covalent triazine framework material of separating property have high chemical stability And heat endurance.
4. there is excellent CO2Absorption and the ultramicropore covalent triazine framework material of separating property have high CO2Adsorbance And to N2And CH4With high selectivity.
5. there is excellent CO2Absorption and the ultramicropore covalent triazine framework material CO absorption of separating property2After can be very good Regeneration, can be with Reusability.
Brief description of the drawings
Fig. 1 has excellent CO for synthesis2Absorption and the reaction scheme of the ultramicropore covalent triazine framework material of separating property.
In Fig. 2, a is the N under the covalent triazine framework material 77K that embodiment 2 and example 7 obtain2Adsorption/desorption isotherms, b For pore size distribution curve.
In Fig. 3, a is the scanning electron microscope (SEM) photograph for the covalent triazine framework material that embodiment 2 obtains, and b is transmission electron microscope picture.
In Fig. 4, a is the thermogravimetric analysis figure for the covalent triazine framework material that embodiment 2 obtains, and b tests for chemical stability Figure.
In Fig. 5, a and b be respectively covalent triazine framework material that embodiment 2 obtains under 298K and 273K to CO2、N2With CH4Adsorption isotherm.
In Fig. 6, a and b be respectively covalent triazine framework material that embodiment 7 obtains under 298K and 273K to CO2、N2With CH4Adsorption isotherm.
Fig. 7 is the obtained covalent triazine framework material of embodiment 2 to CO2/N2And CO2/CH4Selective figure.
Fig. 8 is the covalent triazine framework material CO that embodiment 2 obtains2The reproducibility of absorption.
Embodiment
The present invention is further illustrated by the following examples, but the present invention is not limited to following examples.
The preparation of the covalent triazine framework material of embodiment 1
0.6g (7.7mmol) monomer flumaronitriles and 2.1g (15.4mmol) zinc chloride are well mixed, are fitted into ampoule bottle, Vacuumize sealing.350 DEG C are heated to 10 DEG C/min in tube furnace and keep 40h in the temperature, be then down to room temperature.Will The product grinding arrived, metal salt is washed away with water and watery hydrochloric acid, then washed three times with water and methanol, obtained in 150 DEG C of vacuum drying black Color solid.
The preparation of the covalent triazine framework material of embodiment 2
0.6g (7.7mmol) monomer flumaronitriles and 2.1g (15.4mmol) zinc chloride are well mixed, are fitted into ampoule bottle, Vacuumize sealing.400 DEG C are heated to 10 DEG C/min in tube furnace and keep 40h in the temperature, be then down to room temperature.Will The product grinding arrived, metal salt is washed away with water and watery hydrochloric acid, then washed three times with water and methanol, obtained in 150 DEG C of vacuum drying black Color solid.
The preparation of the covalent triazine framework material of embodiment 3
0.6g (7.7mmol) monomer flumaronitriles and 2.1g (15.4mmol) zinc chloride are well mixed, are fitted into ampoule bottle, Vacuumize sealing.600 DEG C are heated to 10 DEG C/min in tube furnace and keep 40h in the temperature, be then down to room temperature.Will The product grinding arrived, metal salt is washed away with water and watery hydrochloric acid, then washed three times with water and methanol, obtained in 150 DEG C of vacuum drying black Color solid.
The preparation of the covalent triazine framework material of embodiment 4
0.6g (7.7mmol) monomer flumaronitriles and 10.5g (77mmol) zinc chloride are well mixed, are fitted into ampoule bottle, Vacuumize sealing.350 DEG C are heated to 10 DEG C/min in tube furnace and keep 40h in the temperature, be then down to room temperature.Will The product grinding arrived, metal salt is washed away with water and watery hydrochloric acid, then washed three times with water and methanol, obtained in 150 DEG C of vacuum drying black Color solid.
The preparation of the covalent triazine framework material of embodiment 5
0.6g (7.7mmol) monomer flumaronitriles and 10.5g (77mmol) zinc chloride are well mixed, are fitted into ampoule bottle, Vacuumize sealing.400 DEG C are heated to 10 DEG C/min in tube furnace and keep 40h in the temperature, be then down to room temperature.Will The product grinding arrived, metal salt is washed away with water and watery hydrochloric acid, then washed three times with water and methanol, obtained in 150 DEG C of vacuum drying black Color solid.
The preparation of the covalent triazine framework material of embodiment 6
0.6g (7.7mmol) monomer flumaronitriles and 10.5g (77mmol) zinc chloride are well mixed, are fitted into ampoule bottle, Vacuumize sealing.600 DEG C are heated to 10 DEG C/min in tube furnace and keep 40h in the temperature, be then down to room temperature.Will The product grinding arrived, metal salt is washed away with water and watery hydrochloric acid, then washed three times with water and methanol, obtained in 150 DEG C of vacuum drying black Color solid.
The preparation of the covalent triazine framework material of embodiment 7
0.6g (7.7mmol) monomer flumaronitriles and 2.1g (15.4mmol) zinc chloride are well mixed, are fitted into ampoule bottle, Vacuumize sealing.500 DEG C are heated to 10 DEG C/min in tube furnace and keep 40h in the temperature, be then down to room temperature.Will The product grinding arrived, metal salt is washed away with water and watery hydrochloric acid, then washed three times with water and methanol, obtained in 150 DEG C of vacuum drying black Color solid.
The Chemical Stability Characterization of the covalent triazine framework material of embodiment 8
By the covalent triazine framework material (0.06g) that embodiment 2 obtains be immersed in 4ml boiling water, 4M HCl solutions and 0.1M NaOH solutions.After immersion 1 day, filtering, washed three times with water and methanol respectively, black solid is obtained in 150 DEG C of vacuum drying Drying.

Claims (5)

1. one kind is used for CO2With N2Or/and CH4Selective Separation ultramicropore covalent triazine framework material, it is characterised in that Covalent triazine framework material specific surface area is 100~3000m2/ g, aperture areAnd mainly withBased on, pore volume is 0.05~0.5cm3/g。
2. one kind described in claim 1 is used for CO2With N2Or/and CH4Selective Separation ultramicropore covalent triazine skeleton material The preparation method of material, it is characterised in that monomer one-step method in the presence of catalyst is polymerized, and concretely comprises the following steps：By monomer Flumaronitrile and catalyst zinc chloride are well mixed, and are loaded reaction bulb, are vacuumized, and are sealed, in tube furnace reaction obtain black and consolidate Body, grinding, washes away zinc chloride with water, dilute hydrochloric acid solution and methanol successively and obtains the covalent triazine skeleton material with ultra-microporous Material；The mol ratio of flumaronitrile and zinc chloride is 1:2~1:10；Reaction temperature used is 350~600 DEG C.
3. one kind described in claim 1 is used for CO2With N2Or/and CH4Selective Separation ultramicropore covalent triazine skeleton material Expect to be used for CO2Selective Separation.
4. one kind described in claim 1 is used for CO2With N2Or/and CH4Selective Separation ultramicropore covalent triazine skeleton material Expect to be used for CO2With N2Or/and CH4Selective Separation.
5. one kind described in claim 1 is used for CO2With N2Or/and CH4Selective Separation ultramicropore covalent triazine skeleton material The application of material, for CO2With N2Or/and CH4Selective Separation, it is characterised in that the temperature of separation is 273K-298K.
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CN106268690A (en) * 2016-08-31 2017-01-04 北京化工大学 A kind of for carbon dioxide adsorption and framework material separated and preparation method thereof
CN106902771B (en) * 2017-03-27 2019-09-10 武汉大学 A kind of preparation method and application of magnetism covalent triazine porous material
CN109762142B (en) * 2019-01-25 2021-05-11 河北工业大学 Conjugated polymer material for regulating and controlling carbon dioxide adsorption based on photothermal effect
CN112657472B (en) * 2020-12-21 2024-02-13 吉林师范大学 Ionic covalent triazine skeleton polymer material and preparation method and application thereof

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JP4750303B2 (en) * 2001-03-23 2011-08-17 水澤化学工業株式会社 Mesoporous silica alumina gel, humidity control agent and catalyst support

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JP4750303B2 (en) * 2001-03-23 2011-08-17 水澤化学工業株式会社 Mesoporous silica alumina gel, humidity control agent and catalyst support

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