CN105712312A - Composite carbon molecular sieve and preparation method thereof - Google Patents
Composite carbon molecular sieve and preparation method thereof Download PDFInfo
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- CN105712312A CN105712312A CN201410713435.0A CN201410713435A CN105712312A CN 105712312 A CN105712312 A CN 105712312A CN 201410713435 A CN201410713435 A CN 201410713435A CN 105712312 A CN105712312 A CN 105712312A
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Abstract
The invention relates to a composite carbon molecular sieve and a preparation method thereof. The preparation method of the composite carbon molecular sieve comprises a step of raw material carbonization, wherein the raw material comprises a microporous material and a polymer material. The composite carbon molecular sieve prepared by the method combines the advantages of the microporous material and the polymer material, has a regular microporous structure and a high specific surface area, also has high strength, and is expected to have potential application value in the field of gas storage and separation.
Description
Technical field
The present invention relates to a kind of new separation material, especially can be applicable to the complex carbon molecules sieve material that gas separates, with and preparation method thereof.
Background technology
Material with carbon element is 20th century a kind of new adsorbents of growing up of the seventies, it is a kind of excellent nonpolar material with carbon element, can be used for the nitrogen separating in air, compared with traditional deep cooling high pressure nitrogen producing craft, it is few that this method has investment cost, and speed is fast, low cost and other advantages.The synthetic material that a kind of phosphorus content that most of material with carbon elements are all made up through high temperature pyrolysis carbonization under inert gas shielding of polymer is significantly high.It has the properties such as high temperature resistant, intensity is high, thus can be widely applied to the field such as absorbent preparation and aerospace industry.Such material structure is easily controlled, renewable, and density is relatively larger, and stability is good again, thus can recycle for a long time.But owing to the permeability of Carbon Molecular Sieve Membrane itself is very low, it is usually no more than 5GPU, and owing to the fragility of this material is very big, in some degree, therefore limits its further commercial Application.
Metal-organic framework materials (MOFs) is that a class is with metal ion for junction point, organic ligand has the cancellated novel porous materials of three-dimensional periodic for supporting composition, owing to it has the advantages such as degree of crystallinity, various structures be controlled, become the porous material of new generation after zeolite and CNT, it all has a wide range of applications in catalysis, energy storage and separation.
Having researcher to begin one's study in recent years and through high temperature cabonization prepared by MOFs porous carbon materials, they find that the sharp material with carbon element prepared in this way is due to the introducing of nitrogen-containing group and metallic element etc., can improve its energy storage capability.It is contemplated that take the advantage of MOFs material and polymeric material into consideration, to prepare a kind of new material with some strength and high specific surface area.
Summary of the invention
The preparation method that present invention firstly provides a kind of complex carbon molecules sieve, including the step that raw material carries out carbonization, wherein, comprises poromerics and polymeric material in described raw material.
Further, the present invention provides the complex carbon molecules prepared by said method to sieve.
The advantage of poromerics and polymeric material tied by complex carbon molecules sieve material prepared by the method for the present invention, has regular microcellular structure and high specific surface area, and has higher-strength, is expected to have potential using value in gas storage with separation field.
Accompanying drawing explanation
Accompanying drawing 20 width of the present invention, is respectively as follows:
Fig. 1 is the ZIF-108 nano-particle x-ray diffraction pattern of embodiment 1 synthesis；
Fig. 2 is the ZIF-108 nano-particle scanning electron microscope diagram of embodiment 1 synthesis；
Fig. 3 is N under the ZIF-108 nano-particle 77K that embodiment 1 synthesizes2Adsorption isotherm line chart, wherein, filled circles represents absorption, and open circles represents desorption；
Fig. 4 is the pore size distribution curve of the ZIF-108 nano-particle of embodiment 1 synthesis；
Fig. 5 is the thermal gravimetric analysis curve of the ZIF-108 nano-particle of embodiment 1 synthesis；
Fig. 6 is the X-ray diffractogram of described polymer P 84；
The thermal gravimetric analysis curve of polymer P 84 described in Fig. 7；
Fig. 8 is the x-ray diffraction pattern of product A in embodiment 1；
Fig. 9 is the x-ray diffraction pattern of product B in embodiment 1；
Figure 10 is the x-ray diffraction pattern of products C in embodiment 1；
Figure 11 is the x-ray diffraction pattern of product D in comparative example；
Figure 12 is product A N under 77K in embodiment 12Adsorption isotherm line chart, wherein, filled circles represents absorption, and open circles represents desorption；
Figure 13 is product B N under 77K in embodiment 12Adsorption isotherm line chart, wherein, filled circles represents absorption, and open circles represents desorption；
Figure 14 is products C N under 77K in embodiment 12Adsorption isotherm line chart, wherein, filled circles represents absorption, and open circles represents desorption；
Figure 15 is product D N under 77K in comparative example2Adsorption isotherm line chart, wherein, filled circles represents absorption, and open circles represents desorption；
Figure 16 is the pore size distribution curve of product A in embodiment 1；
Figure 17 is the pore size distribution curve of product B in embodiment 1；
Figure 18 is the pore size distribution curve of products C in embodiment 1；
Figure 19 is the pore size distribution curve of middle product D in comparative example；
Figure 20 is product A in embodiment, B, C and the infrared analysis spectrogram of product D and polymer raw material P84 in comparative example.
Detailed description of the invention
If no special instructions, heretofore described and material proportion relation be mass ratio.
Of the present invention and complex carbon molecules sieve preparation method, including the step that raw material is carried out carbonization, wherein said raw material comprises poromerics and polymeric material.
In detailed description of the invention, described poromerics is can carbonization poromerics.Preferred zeolite imidazate frame structure material (i.e. ZIF material).Preferred poromerics is ZIF-108.
In detailed description of the invention on the other hand, described polymeric material is selected from polyimide-based polymer, polysulfones-like polymer, polyether sulfone polymer or polyether-ether-ketone polymer.Preferred polyimide-based polymer.Especially preferred polyimides (P84).
More specifically in embodiment, described in method of the present invention and raw material be poromerics, polymeric material and the solvent mixture according to mass ratio 1:1～10:100～500；Described solvent therein is selected from DMF (nitrogen, nitrogen-dimethylformamide), DMAc (nitrogen, nitrogen-dimethyl acetylamide), NMP (N-Methyl pyrrolidone), THF (oxolane) or its mixture.Preferred DMF (nitrogen, nitrogen-dimethylformamide).As one of concrete optimal way, described film forming raw material is by by poromerics, polymeric material and 1～120 hour gained of solvent mix and blend.
In detailed description of the invention, described carbonization is that raw material heats up the process of pyrolysis under inert gas shielding, and described intensification is syllogic temperature-rise period, and every section of heating rate is 0.1～15 DEG C/min, maximum temperature (Tmax) 500～900 DEG C, in maximum temperature constant temperature 1～10 hour.More specifically in embodiment, described intensification pyrolytic process includes:
A. with the heating rate of 10～15 DEG C/min from 30 DEG C of heating to 250 DEG C；
B. with the heating rate of 1～5 DEG C/min from 250 DEG C of heating to (Tmax-15) DEG C；
C. with the heating rate of 0.1～0.5 DEG C/min from (Tmax-15) DEG C heating is to TmaxDEG C；
D. at maximum temperature TmaxStop 2 hours.
Described noble gas therein is selected from nitrogen, helium or argon；Inert gas flow 1～1000 ml/min.
In the preparation method of the complex carbon molecules sieve of present invention described above, the optimal way combination in any of involved technical characteristic in each concrete technical scheme and the technical scheme that obtains are also within the application scope.The present invention as described below is concrete one of preferred embodiment, and described preparation method comprises the steps:
A. film forming raw material is prepared: by ZIF-108, P84 and DMF according to mass ratio 1:1～10:100～500 Homogeneous phase mixing, be stirred at room temperature 2～24 hours；
B. step a gained mixture high temperature cabonization processes, and temperature-rise period includes:
B-1. with the heating rate of 10～15 DEG C/min from 30 DEG C of heating to 250 DEG C；
B-2. with the heating rate of 1～5 DEG C/min from 250 DEG C of heating to (Tmax-15) DEG C；
B-3. with the heating rate of 0.1～0.5 DEG C/min from (Tmax-15) DEG C heating is to TmaxDEG C；
B-4. at maximum temperature TmaxStop 2 hours.
Described noble gas therein is selected from nitrogen, helium or argon；Inert gas flow 1～1000 ml/min.
Of the present invention and complex carbon molecules sieve, the preparation method of the complex carbon molecules sieve that arbitrarily technical scheme is addressed above prepare.
Specific examples below, for further illustrating present disclosure, should not be construed as any type of restriction of the present invention.
Embodiment 1
(1) ZIF-108 is prepared:
Weigh 0.318 gram of Zinc diacetate dihydrate (Zn (Ac)2·2H2O) being dissolved in 16 milliliters of nitrogen, in nitrogen-dimethylformamide (DMF), 0.328 gram of 2-nitroimidazole (nim) is dissolved in 40 milliliters of nitrogen, in nitrogen-dimethylformamide.The former joining mixed room temperature in the latter react 2.5 hours, centrifugal after having reacted, every time with 20 milliliters of nitrogen, nitrogen-dimethylformamide supersound washing 15 minutes, centrifugal afterproduct is stand-by.
At scanning electron microscope diagram sheet, X-ray diffraction detection product: this product has regular crystal formation (such as Fig. 1), shows that product morphology is uniformly (such as Fig. 2), granular size is nanoscale.N2Adsorption experiment demonstrates this material and has microcellular structure (Fig. 3), and its specific surface area is 1371m2/ g.Pore size distribution curve (such as Fig. 4) also demonstrates that this material aperture is concentrated mainly on 0.5 ran, has micropore canals (less than 2 nanometers).
Thermogravimetric analysis experiment proves that this poromerics at high temperature can be decomposed (such as Fig. 4), therefore can effectively introduce metallic element and nitrogen substance etc..For the ease of contrast, give X-ray diffraction analysis figure (such as Fig. 5) and the thermal gravimetric analysis curve (such as Fig. 6) of a kind of polymer precursor material P84 simultaneously.
(2) preparation of complex carbon molecules sieve raw material mixed liquor:
ZIF-108 material obtained by step 1 is mixed in P84 according to different proportion, concretely comprises the following steps and weigh 1.1916 grams of P84 and be dissolved in appropriate DMF, stir 24 hours；By ZIF-108 material (concrete ratio is shown in following table), ultrasonic disperse is in DMF, subsequently according to (WZIF-108+WP84): WDMFP84 solution is mixed by the ratio of=1:12.7 with ZIF-108 dispersion liquid, stirs 24 hours, wherein W representation quality.
(3) complex carbon molecules sieve material is prepared in carbonization:
By step 2 gained mixed liquor under 30 ml/min argon shields 80 DEG C dry 24 hours, at 150 DEG C, constant-temperature constant is cooled to room temperature after slight 6 hours, and heat up carbonization subsequently, and carbonisation is:
A. with the heating rate of 11.6 DEG C/min from 30 DEG C of heating to 250 DEG C；
B. with the heating rate of 3.85 DEG C/min from 250 DEG C of heating to 585 DEG C；
C. with the heating rate of 0.25 DEG C/min from 585 DEG C of heating to 600 DEG C；
D. 2 hours are stopped at maximum temperature 600.
It is prepared for complex carbon molecules sieve product A, B, C when 3 kinds of different content ZIF108 respectively, such as table 1.Their X-ray diffraction analysis result is distinguished as shown in Figure 8,9, 10.Visible about 20 degree have significantly wide bag, and corresponding to (002) crystal face of graphite, about 43 degree have more weak wide wrap, (100) crystal face of correspondence graphite, it was demonstrated that this material have with graphite-like like structure, for unformed material with carbon element.N2Adsorption experimental results is respectively as shown in Figure 12,13,14, it was demonstrated that described complex carbon molecules sieve material has microcellular structure, wherein product A, specific surface area respectively 22.6m that B, C are corresponding2/ g, 190.24m2/ g, 185.5m2/ g.Pore size distribution curve, respectively as shown in Figure 16,17,18, also demonstrates that described complex carbon molecules sieve material aperture is concentrated mainly on 0.68 ran equally, has micropore canals.Infrared analysis result as shown in figure 20, wherein 3000cm-1The characteristic peak of corresponding O-H, 2172,2110cm-1The characteristic peak of corresponding carbonyl, 1586cm-1The characteristic peak of-C=C-, 715cm on corresponding aromatic rings-1On corresponding aromatic rings=characteristic peak of C-H.Comparing with product D, its infrared spectrum fits like a glove, and after doping ZIF108 material is described, its framing structure does not change, and is still micro-pore carbon material.
Embodiment 2
As a comparison case, 1.1916 grams of polymer Ps 84 are weighed, by WP84: WDMFThe ratio of=1:12.7 adds 15.0835 grams of DMF prepared polymer solutions, stirs 24 hours, wherein W representation quality, and carbonization, with embodiment 1 step (3), obtains product D.The X-ray diffractogram (such as Figure 11) of product D proves that this material is undefined structure.N2Adsorption experiment (such as Figure 15) proves that product D has microcellular structure, its specific surface area respectively 91.71m2/ g.Pore size distribution curve (such as Figure 19) shows that the aperture of product D is concentrated mainly on 0.68 ran, has micropore canals.But compared with materials A, B and C, material D fragility is bigger.
Table 1
| Production code member | WZIF-108/WP84 | (WZIF-108+WP84): WDMF | Carburizing temperature |
| A | 9% | 1:12.7 | 600℃ |
| B | 14% | 1:12.7 | 600℃ |
| C | 26% | 1:12.7 | 600℃ |
| D | 0% | 1:12.7 | 600℃ |
Claims (10)
1. the preparation method of complex carbon molecules sieve, including the step that raw material carries out carbonization, it is characterised in that comprise poromerics and polymeric material in described raw material.
2. method according to claim 1, it is characterised in that described poromerics is can carbonization poromerics.
3. method according to claim 1, it is characterised in that described poromerics is zeolite imidazole ester frame structure material.
4. method according to claim 1, it is characterised in that described polymeric material is selected from polyimide-based polymer, polysulfones-like polymer, polyether sulfone polymer or polyether-ether-ketone polymer.
5. method according to claim 4, it is characterised in that described polymeric material is polyimide-based polymer.
6. method according to claim 1, it is characterised in that described raw material is poromerics, polymeric material and the solvent mixture according to mass ratio 1:1～10:100～500；
Described solvent is selected from DMF, DMAc, NMP, THF or its mixture.
7. method according to claim 1; it is characterized in that; described carbonization is that raw material heats up the process of pyrolysis under inert gas shielding; described intensification is syllogic temperature-rise period; every section of heating rate is 0.1～15 DEG C/min; maximum temperature 500～900 DEG C, in maximum temperature constant temperature 1～10 hour.
8. method according to claim 7, it is characterised in that described intensification pyrolytic process includes:
A. with the heating rate of 10～15 DEG C/min from 30 DEG C of heating to 250 DEG C；
B. with the heating rate of 1～5 DEG C/min from 250 DEG C of heating to (Tmax-15) DEG C；
C. with the heating rate of 0.1～0.5 DEG C/min from (Tmax-15) DEG C heating is to TmaxDEG C；
D. at maximum temperature TmaxStop 2 hours.
9. method according to claim 4, it is characterised in that described noble gas is selected from nitrogen, helium or argon；Inert gas flow 1～1000 ml/min.
10. a complex carbon molecules sieve, prepared by the method described in any claim in claim 1～9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112044273A (en) * | 2019-06-05 | 2020-12-08 | 中国石油天然气股份有限公司 | Carbon molecular sieve membrane with improved permeability and selectivity and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112044273A (en) * | 2019-06-05 | 2020-12-08 | 中国石油天然气股份有限公司 | Carbon molecular sieve membrane with improved permeability and selectivity and preparation method and application thereof |
| CN112044273B (en) * | 2019-06-05 | 2023-04-25 | 中国石油天然气股份有限公司 | Carbon molecular sieve membrane with improved permeability and selectivity, and preparation method and application thereof |
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Application publication date: 20160629 |