CN109731552A - The metallic organic frame films of temperature-changeable operation extract the application of methane in biogas - Google Patents
The metallic organic frame films of temperature-changeable operation extract the application of methane in biogas Download PDFInfo
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- CN109731552A CN109731552A CN201910134726.7A CN201910134726A CN109731552A CN 109731552 A CN109731552 A CN 109731552A CN 201910134726 A CN201910134726 A CN 201910134726A CN 109731552 A CN109731552 A CN 109731552A
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Abstract
The invention discloses the applications that the metallic organic frame films of temperature-changeable operation extract methane in biogas.This method comprises: dissolving metal salts are obtained metal salt solution by (1) in solvent, then ligand is added in the metal salt solution, ultrasonic dissolution obtains precursor solution；(2) substrate is immersed in precursor solution described in step (1), application constant current carries out reaction and prepares metallic organic frame films；(3) metallic organic frame films described in step (2) are assembled into after membrane module for extracting methane in sewage gas.The film has good alternating temperature operational stability, has different separating properties, and repeatable operation at different temperature.Preparation speed is exceedingly fast, and the open-and-shut preparation process of operating process and good gas separating property make it possible the application of metallic organic frame films of the present invention industrially.
Description
Technical field
The invention belongs to metallic organic frame films to be applied to gas separation field, and in particular to arrive metallic organic frame films
It is applied in biogas system, obtains methane as clean energy source by removing carbon dioxide gas.
Background technique
Since 21 century, due to the continuous consumption of the fossil fuels such as non-renewable energy resources such as coal, oil and natural gas, in turn
The problem of global energy crisis of initiation, increasingly attracts wide public concern.Therefore, it is badly in need of finding at present a kind of novel renewable
Clean energy resource inhibits the further expansion of energy crisis.Methane is as a kind of new cleaning fuel, in all hydrocarbonization
Closing has highest hydrogen-carbon ratio in object, can be used for generating electricity, cook, many aspects such as heat source and fuel.Most as fossil fuel
The use of a kind of promising energy substitution product, methane will not be with the discharge of great amount of carbon dioxide gas, and then can reduce temperature
The influence of room effect is a kind of environmentally friendly new cleaning fuel.And one of the main source of methane is exactly biogas, biogas
As a kind of renewable energy, a large amount of methane is contained in constituent, but also contains a large amount of carbon dioxide simultaneously, because
This, how removing the carbon dioxide in biogas and then obtaining the methane of high-purity is main problem and challenge that we face.
As the continuous exploration and summary, more and more people of a large amount of experimental studies results proof and people start to recognize
Together, membrane separation technique will become the isolation technics of new generation in human social development.This is because with adsorbing separation, distillation and
Recrystallization etc. separation means compare, UF membrane have its specific advantage, such as: low energy consumption, high efficiency, it is easy to manufacture,
Cost of consumption is lower and reliability height etc..Similar with zeolite, metallic organic frame films are with extremely rule, high-sequential arrangement
Duct and superelevation porosity and specific surface area, this makes it be expected to the excellent candidate as separation membrane.Although boiling
Stone film has been widely studied, but also only has a small amount of zeolite membrane to be used in actual chemical separation process at present.This may
It is because the preparation difficulty of zeolite membrane is too high, because requiring template additive in many cases in its preparation, and template adds
Agent is added to need to burn out at high temperature again to prevent the duct of blocking zeolite membrane.But burning for high temperature probably makes to boil
Stone film cracks, and then substantially reduces zeolite membrane to the separating property of gas.Compared to zeolite membrane, metallic organic frame films system
Standby condition milder, and template used in the forming process of the film is solvent molecule, therefore template is from the removal in film
Also more easy.
The preparation process of metallic organic frame films is more easy, and adjustability of structure is stronger, therefore is hopeful to be applied to natural pond
The extraction of methane in gas.In addition to this, in the extraction process of methane, the highly selective methane for being conducive to obtain high-purity is produced
Product, high penetration is conducive to raising production efficiency and needs the operation temperature by adjusting film in the actual operation process, to adjust
The penetration and selectivity of film, the result then compared under different condition find optimum operation condition, to realize that largest production is imitated
Rate.Therefore the alternating temperature operational stability of film and its important.
Summary of the invention
In order to solve the disadvantage that the prior art and deficiency, the purpose of the present invention is to provide metallic organic frame films in biogas
The application of middle high efficiency extraction methane.
The object of the invention is achieved through the following technical solutions.
A kind of metallic organic frame films of temperature-changeable operation extract the application of methane in biogas, comprising the following steps:
(1) metal salt is dissolved in solvent, obtains metal salt solution；Ligand is dissolved in above-mentioned metal salt solution, ultrasound
It handles several minutes and obtains precursor solution；
(2) substrate is immersed in precursor solution described in step (1), applies constant current and reacted, obtaining metal has
Machine frame film；
(3) metallic organic frame films described in step (2) are assembled into after membrane module for extracting methane in sewage gas.
It is further preferred that the metal salt soluble zinc salt, such as Zinc diacetate dihydrate；The ligand has for solubility
Machine ligand, such as 2-methylimidazole or benzimidazole；The solvent is all kinds of organic solvents, and such as methanol, affiliated substrate is all kinds of leads
Electric substrate, such as anodised aluminium (AAO).
Still more preferably, in the precursor solution metal salt concentrations be 0.01-0.4mol/L, 2-methylimidazole it is dense
Degree is 0.016-0.32mol/L, and the concentration of benzimidazole is 0.004-0.08mol/L, and constant current is in the step (2)
0.01-2mA, reaction time 5-30min.
In step (3), it is passed through biogas in the feed side of the membrane module, per-meate side uses inert gas purge, methane
Selectivity is through the methane after being concentrated after film.
Preferably, the operation temperature of metallic organic frame films is 25 DEG C -125 DEG C.
It is further preferred that carbon dioxide and methane etc. components separation selectivity be 10-25.Components refer to 1 herein etc.:
1 in this as simulation biogas main component.
The metallic organic frame films of temperature-changeable operation, the continuous zero defect in surface have separation to carbon dioxide and methane
Effect has different separating properties, and repeatable operation at different temperature, has good alternating temperature operational stability.
Compared with prior art, the invention has the following advantages and beneficial effects:
(1) present invention directly adopt additional electric current come situ study synthesis metallic organic frame films, simple and quick height
Effect greatly shortens membrane preparation cycle compared with other traditional thin film-forming methods, and surface compact zero defect and contacts with substrate good
It is good；
(2) metallic organic frame films prepared by the present invention show good separation to the separation of carbon dioxide and methane
Effect.Compared to the metallic organic frame films that other are prepared with conventional method, the present invention selects the separation of carbon dioxide and methane
About 10 times are improved when selecting property highest.It is applicable to unused operation temperature, there is good alternating temperature operational stability.Preparation speed
Degree is exceedingly fast, and the open-and-shut preparation process of operating process and good gas separating property make metal of the present invention have machine frame
The application of frame film industrially is possibly realized.
Detailed description of the invention
Fig. 1 is the ZIF-7 in embodiment 120The surface microscopic topographic figure of -8 films；
Fig. 2 is the ZIF-7 in embodiment 120The cross-section morphology figure of -8 films；
Fig. 3 is separating property of the metallic organic frame films prepared by embodiment 1 to carbon dioxide and methane mixed gas
Figure；
Fig. 4 is separating property figure of the metal organic frame prepared by embodiment 2 to carbon dioxide and methane mixed gas；
Fig. 5 is the performance that metallic organic frame films prepared by embodiment 3 separate carbon dioxide and methane mixed gas
Figure；
Fig. 6 separates carbon dioxide and methane mixed gas for metallic organic frame films prepared by embodiment 3 long-term
Alternating temperature operational stability figure.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
To be carbon dioxide and methane with molar ratio be the gaseous mixture of 1:1 ratio for simulation biogas ingredient used in embodiment 1-3, and passes through
Following methods simulate the process that methane is extracted in biogas:
The metallic organic frame films of preparation are sealed in gas test device with vacuum seal gasket.Carrying out gaseousness
When can test, operation temperature is controlled, what feed side was passed through is the carbon dioxide and methane for being 1:1 as the molar ratio of simulation biogas
Gaseous mixture, per-meate side use inert gas purge.Then by the gas of per-meate side be passed through gas chromatographic detection carbon dioxide and
The gas penetration and separation selectivity of carbon dioxide and methane is calculated in concentration of methane gas content.
Embodiment 1
The present embodiment provides zinc salt with zinc acetate dihydrate, by direct impressed current in porous, electrically conductive substrate anodised aluminium
Upper quickly preparation ZIF-720- 8 films, and it is used for the separation of carbon dioxide and methane mixed gas at 125 DEG C, specifically include following step
It is rapid:
(1) porous, electrically conductive substance anodised aluminium is chosen as supporting layer；
(2) it weighs zinc acetate dihydrate particle 0.22g to be dissolved in 100mL methanol, then 0.13g2- methylimidazole is added thereto
Particle and 47.2mg benzimidazole particle, at room temperature ultrasound 1 minute to get arrive precursor solution.
(3) the obtained porous, electrically conductive substance anodic oxidation aluminium substrate of step (1) is immersed into step (2) obtained film forming
Precursor solution in.It is reacted 30 minutes under the function of current of 2mA, fine and close ZIF-7 can be obtained20- 8 films.
As shown in Figure 1, ZIF-720- 8 film surface densification zero defects.As shown in Fig. 2, ZIF-720- 8 film sections it is continuous and with
Substrate contact is good.
The ZIF-7 that step (3) is obtained20- 8 films carry out the separating property test of carbon dioxide and methane mixed gas, behaviour
Making temperature is 125 DEG C, as shown in figure 3, the penetration of carbon dioxide is 1.3 × 10-8mol m-2s-1Pa-1, the penetration of methane is 1.2
×10-9mol m-2s-1Pa-1, and ZIF-720- 8 films show good separating property, separation selection to carbon dioxide and methane
Property is up to 10.
Embodiment 2
The present embodiment provides zinc salt with zinc acetate dihydrate, by directly adding electric current on porous, electrically conductive substrate anodised aluminium
And then quickly prepare ZIF-720- 8 films are simultaneously used for the separation of carbon dioxide and methane mixed gas at 75 DEG C, specifically include following step
It is rapid:
(1) porous, electrically conductive substance anodised aluminium is chosen as supporting layer；
(2) two water zinc acetate particle 8.78g are weighed to be dissolved in 100mL methanol, then 2.63g2- methylimidazole is added thereto
Particle and 0.95g benzimidazole particle, ultrasound 1 minute at room temperature to get to the precursor solution for preparing metallic organic frame films.
(3) the obtained porous, electrically conductive substance anodic oxidation aluminium substrate of step (1) is immersed into step (2) obtained film forming
Precursor solution in.It is reacted 5 minutes under the function of current of 0.01mA, fine and close ZIF-7 can be obtained20- 8 films.
The surface of the film and section characterization with reference to Fig. 1-2 it is found that film surface densification zero defect, film section it is continuous (i.e. without
Gap) and contacted well with substrate.
The ZIF-7 that step (3) is obtained20- 8 films carry out the separating property test of carbon dioxide and methane mixed gas, behaviour
Making temperature is 75 DEG C, as shown in figure 4, the penetration of carbon dioxide is 1.2 × 10-8mol m-2s-1Pa-1, the penetration of methane is 8.1 ×
10-10mol m-2s-1Pa-1, and ZIF-720- 8 films show good separating property, separation selectivity to carbon dioxide and methane
Up to 15.
Embodiment 3
The present embodiment provides zinc salt with zinc acetate dihydrate, by directly adding electric current on porous, electrically conductive substrate anodised aluminium
And then quickly prepare ZIF-720- 8 films are simultaneously used for the separation of carbon dioxide and methane mixed gas at 25 DEG C, specifically include following step
It is rapid:
(1) porous, electrically conductive substance anodised aluminium is chosen as supporting layer；
(2) two water zinc acetate particle 4.39g are weighed to be dissolved in 100mL methanol, then 1.38g2- methylimidazole is added thereto
Particle and 0.5g benzimidazole particle, ultrasound 1 minute at room temperature to get to the precursor solution for preparing metallic organic frame films.
(3) the obtained porous, electrically conductive substance anodic oxidation aluminium substrate of step (1) is immersed into step (2) obtained film forming
Precursor solution in.It is reacted 20 minutes under the function of current of 1mA, fine and close ZIF-7 can be obtained20- 8 films.
The surface of the film and section characterization refer to Fig. 1-2, it is known that, film surface densification zero defect, film section it is continuous and with
Substrate contact is good.
The ZIF-7 that step (3) is obtained20- 8 films carry out the separating property test of carbon dioxide and methane mixed gas, behaviour
Making temperature is 25 DEG C, as shown in figure 5, the penetration of carbon dioxide is 1.0 × 10-8mol m-2s-1Pa-1, the penetration of methane is 4 ×
10-10mol m-2s-1Pa-1, and ZIF-720- 8 films show good separating property, separation selectivity to carbon dioxide and methane
Up to 25.
The ZIF-7 that step (3) is obtained20- 8 films carry out the long-term change of the separating property of carbon dioxide and methane mixed gas
Warm operational stability test, as shown in fig. 6, still there is good alternating temperature stable operation with the film that cools down twice by heating up three times
Property (Fig. 6 temperature curve part: a step represents an operation temperature, and slope represents heating and cooling process).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. the application that a kind of metallic organic frame films of temperature-changeable operation extract methane in biogas, which is characterized in that including with
Lower step:
(1) dissolving metal salts are obtained into solvent metal salt solution, then ligand is added in the metal salt solution, ultrasound
Dissolution obtains precursor solution；
(2) substrate is immersed in precursor solution described in step (1), application constant current carries out reaction and prepares metal organic frame
Film；
(3) metallic organic frame films described in step (2) are assembled into after membrane module for extracting methane in sewage gas.
2. application according to claim 1, which is characterized in that in the step (1), metal salt contains zinc ion, organic
Ligand is 2-methylimidazole and benzimidazole.
3. application according to claim 1, which is characterized in that metal salt is Zinc diacetate dihydrate, institute in the step (1)
Stating substrate in step (2) is conductive anodic oxidation aluminium substrate.
4. application according to claim 2, which is characterized in that metal salt concentrations are 0.01-0.4 in the precursor solution
Mol/L, the concentration of 2-methylimidazole are 0.016-0.32mol/L, and the concentration of benzimidazole is 0.004-0.08 mol/L, described
Constant current is 0.01-2mA, reaction time 5-30min in step (2).
5. application according to claim 1, which is characterized in that
In step (3), it is passed through biogas in the feed side of the membrane module, per-meate side uses inert gas purge, methane selectively
Through the methane after being concentrated after film.
6. application according to claim 1, which is characterized in that the operation temperature of the metallic organic frame films be 25 DEG C-
125 DEG C, the film is 10-25 to the separation selectivity of the components such as carbon dioxide and methane.
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| CN201910134726.7A CN109731552A (en) | 2019-02-23 | 2019-02-23 | The metallic organic frame films of temperature-changeable operation extract the application of methane in biogas |
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| CN201910134726.7A CN109731552A (en) | 2019-02-23 | 2019-02-23 | The metallic organic frame films of temperature-changeable operation extract the application of methane in biogas |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693168A (en) * | 2009-10-14 | 2010-04-14 | 大连理工大学 | Method for preparing metal organic framework film |
| US20100132549A1 (en) * | 2007-05-11 | 2010-06-03 | The Regents Of The University Of California | Adsorptive gas separation of multi-component gases |
| CN102962037B (en) * | 2012-11-01 | 2014-12-10 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
| CN107398187A (en) * | 2017-07-26 | 2017-11-28 | 华南理工大学 | It is a kind of to utilize the supper-fast method for preparing metal organic framework film of electric field poling |
-
2019
- 2019-02-23 CN CN201910134726.7A patent/CN109731552A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100132549A1 (en) * | 2007-05-11 | 2010-06-03 | The Regents Of The University Of California | Adsorptive gas separation of multi-component gases |
| CN101693168A (en) * | 2009-10-14 | 2010-04-14 | 大连理工大学 | Method for preparing metal organic framework film |
| CN102962037B (en) * | 2012-11-01 | 2014-12-10 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
| CN107398187A (en) * | 2017-07-26 | 2017-11-28 | 华南理工大学 | It is a kind of to utilize the supper-fast method for preparing metal organic framework film of electric field poling |
Non-Patent Citations (1)
| Title |
|---|
| QIANQIAN HOU ET AL.: "Ultra-Tuning of the Aperture Size in Stiffened ZIF-8_Cm Frameworks with Mixed-Linker Strategy for Enhanced CO2/CH4 Separation", 《ANGEWANDTE CHEMIE》 * |
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Application publication date: 20190510 |