CN108744991A - A kind of preparation method and application of the organic and inorganic mixed substrate membrane containing nano-grade molecular sieve of doping zeolite imidazole ester skeletal porous carbon nanomaterial - Google Patents
A kind of preparation method and application of the organic and inorganic mixed substrate membrane containing nano-grade molecular sieve of doping zeolite imidazole ester skeletal porous carbon nanomaterial Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and application of the organic and inorganic mixed substrate membrane containing nano-grade molecular sieve of doping zeolite imidazole ester skeletal porous carbon nanomaterial, preparation method is：It is raw material to select zinc nitrate hexahydrate, Nickelous nitrate hexahydrate and 2-methylimidazole, and the zeolite imidazole material containing nickel is prepared by solvent-thermal method；Then using the zeolite imidazole ester material of nickel doping as presoma, zeolite imidazole ester skeletal porous carbon nanomaterial is made in 700 ~ 1000 °C of lower high-temperature calcinations；The porous carbon nanomaterial is scattered in polyether co-polyamide solution, uniform casting solution is prepared, wet-film thickness is 50 ~ 500 μm, and the mixed substrate membrane containing nano-grade molecular sieve of doping zeolite imidazole ester skeletal porous carbon nanomaterial is made by solvent evaporation method.The inorganic material of the present invention is simple and easy to get, and film-forming method is easy to operate, which is used for CO2Separation, the inorganic material of addition can effectively improve the CO of polyether co-polyamide film2Infiltration coefficient and CO2/N2Separation factor.
Description
Technical field
The present invention relates to a kind of organic and inorganic mixed substrate membrane containing nano-grade molecular sieves of doping zeolite imidazole ester skeletal porous carbon nanomaterial
Preparation method and application belongs to gas separation membrane technical field.
Background technology
With the development of industrial technology and the growth of the size of population, global warming problem has caused the pass of people
Note.Therefore, in order to reduce CO2It is discharged into air, CO is captured before combustion of fossil fuel or using effective method after burning2?
It is extremely urgent.Under normal circumstances, CO is detached from admixture of gas2Method mainly have chemisorption, physical absorption, deep cooling point
From, UF membrane etc..Membrane separation technique is since efficient, adaptable, easy to operate, low energy consumption, small investment, environmental-friendly etc. excellent
Point is commonly used for detaching CO2.But polymer film there are trade-off effects, that is, permeates between gas permeability and selectivity
Property raising be with sacrifice selectivity for cost, vice versa.And the separating property of inoranic membrane is considerably beyond on Robeson
Limit.Therefore, both materials are organically combined, are maximized favourable factors and minimized unfavourable ones, prepare with the composite membrane that has excellent performance at
For a kind of trend.And it is fine that inorganic material is added to organic and inorganic mixed substrate membrane containing nano-grade molecular sieve (MMMs) obtained in organic polymer
The advantage both combined, the defect both overcome becomes current research hotspot.
Invention content
The present invention is intended to provide a kind of organic and inorganic mixed-matrix of doping zeolite imidazole ester skeletal porous carbon nanomaterial
The preparation method and application of film, the preparation method is simple for process, applies in CO2/N2In mixed system, effectively can selectively it divide
From CO2, it is CO2Transmission provide fast transferring channel.
In mixed substrate membrane containing nano-grade molecular sieve provided by the invention, on the one hand the introducing of inorganic particulate has interrupted the accumulation of strand, accelerates
The transmission of gas molecule, improves the permeability of gas.On the other hand, inorganic particulate can not only increase the parent to object gas
And power, and can also provide with the matched diffusion admittance of target gas molecules kinetic diameter, to improve the selectivity of gas.
Therefore, mixed substrate membrane containing nano-grade molecular sieve can break trade-off effects, even more than the Robeson upper limits.Zeolite imidazole prepared by the present invention
Ester skeletal porous carbon nanomaterial is to CO2There is very strong adsorption capacity；Abundant nitrogen-atoms can be used as lewis base thereon, with acid
The CO of property2Molecule reacts, and can promote CO2Transmission.
The present invention provides a kind of organic and inorganic mixed-matrixes of doping zeolite imidazole ester skeletal porous carbon nanomaterial
Film is made of polymer substrate and additive, and polymer substrate is polyether-polyamide block copolymer, and additive is zeolite miaow
Azoles ester skeletal porous carbon nanomaterial, the mass percentage that additive accounts for mixed substrate membrane containing nano-grade molecular sieve are 0.1~10wt%.
The present invention provides a kind of organic and inorganic mixed bases of above-mentioned doping zeolite imidazole ester skeletal porous carbon nanomaterial
The preparation method of plasma membrane：It is raw material to select zinc nitrate hexahydrate, Nickelous nitrate hexahydrate and 2-methylimidazole first, passes through solvent heat
Method synthesizes the zeolite imidazole ester material of nickel doping；Then as presoma, it is made more in 700 ~ 1000 °C of lower high-temperature calcinations
Hole zeolite imidazole ester skeletal porous carbon nanomaterial；The porous carbon nanomaterial is distributed to polyether-polyamide block polymerization again
In object solution, the organic and inorganic that doping zeolite imidazole ester skeletal porous carbon nanomaterial is prepared using solvent evaporation method is mixed
Matrix membrane；Prepared film is homogeneous densified polymer film.
Above-mentioned when preparing mixed substrate membrane containing nano-grade molecular sieve, wet-film thickness is controlled at 50 ~ 500 μm.
The preparation method of the organic and inorganic mixed substrate membrane containing nano-grade molecular sieve of the doping zeolite imidazole ester skeletal porous carbon nanomaterial,
Specifically include following steps：
Step 1: preparing the zeolite imidazole ester material of nickel doping：
Zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, 2-methylimidazole are dissolved in respectively in methanol solution and are configured to concentration difference
For the solution of 0.01 ~ 0.1mol/L, 0.01 ~ 0.1mol/L, 0.08 ~ 12mol/L, be then respectively put into 4A molecular sieves stand 6 ~
Extra moisture is removed for 24 hours, obtains solution A：The methanol solution of zinc nitrate hexahydrate, solution B：The methanol of Nickelous nitrate hexahydrate is molten
Liquid and solution C：The methanol solution of 2-methylimidazole；Then, solution A, solution B and solution C are poured into three-necked flask, 20 ~
12 ~ 48h is stirred under 80oC to react, and 10 ~ 120min is centrifuged in the range of speeds of 8000 ~ 12000rpm to acquired solution,
After lower sediment in centrifuge tube is washed three times with methanol, it is placed in 60 ~ 100oC vacuum drying ovens dry 12 ~ for 24 hours to get purple powder
End is named as product D；
The grain size of the zeolite imidazole ester material of the wherein described nickel doping is 30 ~ 48nm.
Step 2: preparing zeolite imidazole ester skeletal porous carbon nanomaterial：
Product D prepared by step 1 is put into flange form tubular heater, N is adjusted2Flow velocity is 10 ~ 500mLmin-1, with
1~10°C·min-1Rate be raised to 700 ~ 1000 °C, 2 ~ 20h of calcining at constant temperature, then be down to room temperature naturally, obtain black powder, order
Entitled product E；
Step 3: preparing casting solution：
Step 2 products therefrom E is scattered in the solution F that 30 ~ 200g/L is made into n,N-dimethylacetamide, by solution F 10
After frequency, the temperature of ~ 50MHz is 20 ~ 70 °C of lower 0.5 ~ 4h of ultrasonic disperse, polyether-polyamide block copolymer is added thereto,
It in rotating speed is that 12 ~ 48h of stirring to be formed to being completely dissolved in 20 ~ 90oC for 100 ~ 500rpm, temperature to use magnetic stirring apparatus again
One casting solution, is named as casting solution G, and in 25 °C of constant temperature deaerations 12 ~ for use for 24 hours；
The solid content of polyether-polyamide block copolymer is 3 ~ 25wt% in the casting solution of preparation；
Step 4: preparing film：
The casting solution G of step 3 is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 50 ~
500 μm in temperature are 20 ~ 30oC, humidity makes solvent volatilize 24 ~ 48h in 40 ~ 60% thermostatic drying chamber, then in 40 ~ 90oC
Vacuum drying chamber in dry 24 ~ 48h；The film of gained is further dried in the air dry oven of 30 ~ 90oC, keeps properly and waits for
With.
Further, zinc nitrate hexahydrate described in step 1, Nickelous nitrate hexahydrate, 2-methylimidazole molar ratio be 1 ~
10：1~10：8~1200；5 ~ 30g 4A molecular sieves are used per 100mL methanol solutions.
The present invention provides the organic and inorganic mixed substrate membrane containing nano-grade molecular sieves of above-mentioned doping zeolite imidazole ester skeletal porous carbon nanomaterial
In separation CO2Application in gas.
In above application, obtained film is for detaching CO2/N2, the test of gas permeability is using constant pressure variable volume
The effective area of method, film infiltration is 1 ~ 12.56cm2, scavenging is using H2, scavenging flow velocity is 10~60mLmin-1, feed stream
Speed is 10~60mLmin-1, the flow of feed side and per-meate side obtains with flow measurement, per-meate side constituent content gas-chromatography
It measures；Test temperature is 20 ~ 80oC, and pressure difference is 0.1~0.8MPa.
Beneficial effects of the present invention：
1）Nitrogen in doping zeolite imidazole ester skeletal porous carbon nanomaterial is mainly in the form of pyridine nitrogen, graphite nitrogen, pyrroles's nitrogen
In the presence of these nitrogen-atoms can be used as lewis base absorption acidity CO2Molecule；
2）Zeolite imidazole ester skeletal porous carbon nanomaterial is prepared in the above method, the aperture of the material is less than the boiling of nickel doping
Stone imidazoles ester material, which has limited the diffusion (N of macromolecular2, 3.6), and to small molecule (CO2, 3.3) diffusion resistance it is smaller,
To improve CO2/N2Selectivity；
3）Zeolite imidazole ester skeletal porous carbon nanomaterial is to CO2There is very strong adsorption capacity, organic and inorganic mixed base can be enhanced
Plasma membrane is to CO2Transmission effect；
4）This method is simple for process, can effectively Selective Separation CO2, it is CO2Transmission provide fast transferring channel.
Specific implementation mode
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.
Comparative example 1：The pure polyether block amide film that solid content is 6wt% is prepared, steps are as follows：
Polyether block amide is dissolved in the solution that 6wt% is made into n,N-dimethylacetamide, by solution 30MHz frequency,
Temperature is that stirring 48h to form uniform casting solution to being completely dissolved in 70oC, for use in 25 °C of constant temperature deaeration 12h.Casting solution is existed
It is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 300 μm, temperature is 25oC, humidity exists
Make solvent volatilization 48h, then the dry 48h in the vacuum drying chamber of 60oC in 60% thermostatic drying chamber；The film of gained is 80oC's
It is further dried, keeps properly for use in air dry oven.
By pure film obtained in room temperature, CO is measured under the dry conditions that pressure difference is 0.1MPa2Infiltration coefficient be
121Barrer（1Barrer=10-10cm3(STP) cm·cm-2·s-1·cmHg-1）, CO2/N2Selectivity is 24.
Embodiment 1：The mixed substrate membrane containing nano-grade molecular sieve of the zeolite imidazole ester material of addition 1.5wt% nickel doping is prepared, steps are as follows：
Step 1: the preparation of the zeolite imidazole ester material of nickel doping：
Zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, 2-methylimidazole are dissolved in respectively in methanol solution and are configured to concentration difference
For the solution of 0.1mol/L, 0.1mol/L, 0.8mol/L, then it is respectively put into 4A molecular sieves standing 12h and removes extra moisture,
Obtain the methanol solution (being named as solution A) of zinc nitrate hexahydrate, the methanol solution (being named as solution B) of Nickelous nitrate hexahydrate and
The methanol solution (being named as solution C) of 2-methylimidazole；Then, solution A, solution B and solution C are poured into three-necked flask,
48h is stirred under 30oC to chemically react, and 20min is centrifuged in the range of speeds of 10000rpm to acquired solution, in centrifuge tube
Lower sediment washed three times with methanol after, be placed in 80oC vacuum drying ovens dry for 24 hours to get purple powder, be named as product D；
Step 2: the preparation of casting solution：
Product D prepared by step 1 is scattered in the solution E for being made into 50g/L in n,N-dimethylacetamide, solution E is existed
After temperature is 30 °C of lower ultrasonic disperse 2h polyether-polyamide block copolymer is added, wherein nickel is mixed in the frequency of 30MHz thereto
The mass ratio that miscellaneous zeolite imidazole ester material accounts for polyether-polyamide block copolymer is 1.5wt%.Existed again using magnetic stirring apparatus
Rotating speed is 300rpm, temperature is that stirring 12h to form uniform casting solution to being completely dissolved in 60oC, is named as casting solution F, and
25 °C of constant temperature deaerations 12 ~ for use for 24 hours；
Step 3: film preparation：
The product F of step 2 is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 300 μ
M in temperature is 30oC, humidity makes solvent volatilization for 24 hours, then in the vacuum drying chamber of 60oC do in 40% thermostatic drying chamber
Dry 48h；The film of gained is further dried in the air dry oven of 80oC, keeps properly for use.
By mixed substrate membrane containing nano-grade molecular sieve obtained in room temperature, CO is measured under the dry conditions that pressure difference is 0.1MPa2Infiltration coefficient be
180Barrer, CO2/N2Selectivity is 30.
Embodiment 2：The mixed substrate membrane containing nano-grade molecular sieve of addition 1.5wt% zeolite imidazole ester skeletal porous carbon nanomaterials is prepared, step is such as
Under：
Step 1: the preparation of the zeolite imidazole ester material of nickel doping：
Zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, 2-methylimidazole are dissolved in respectively in methanol solution and are configured to concentration difference
For the solution of 0.1mol/L, 0.1mol/L, 0.8mol/L, then it is respectively put into 4A molecular sieves standing 12h and removes extra moisture,
Obtain the methanol solution (being named as solution A) of zinc nitrate hexahydrate, the methanol solution (being named as solution B) of Nickelous nitrate hexahydrate and
The methanol solution (being named as solution C) of 2-methylimidazole；Then, solution A, solution B and solution C are poured into three-necked flask,
48h is stirred under 30oC to chemically react, and 20min is centrifuged in the range of speeds of 10000rpm to acquired solution, in centrifuge tube
Lower sediment washed three times with methanol after, be placed in 60oC vacuum drying ovens dry 12h to get purple powder, be named as product D；
Step 2: the preparation of zeolite imidazole ester skeletal porous carbon nanomaterial：
Product D prepared by step 1 is put into flange form tubular heater, N is adjusted2Flow velocity is 100mLmin-1, with 5 °
C·min-1Rate be raised to 800 °C, calcining at constant temperature 3h, then be down to room temperature naturally, obtain black powder, be named as product E.
Step 3: the preparation of casting solution：
Product E prepared by step 2 is scattered in the solution F for being made into 50g/L in n,N-dimethylacetamide, solution F is existed
Polyether-polyamide block copolymer, wherein zeolite is added after temperature is 30 °C of lower ultrasonic disperse 2h in the frequency of 30MHz thereto
The mass ratio that imidazate skeletal porous carbon nanomaterial accounts for polyether-polyamide block copolymer is 1.5wt%.It is stirred again using magnetic force
Device is mixed rotating speed is 300rpm, temperature is to stir to form uniform casting solution to being completely dissolved for 24 hours in 70oC, is named as casting solution G,
And it is for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product G of step 3 is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 300 μ
M in temperature is 30oC, humidity makes solvent volatilization for 24 hours, then in the vacuum drying chamber of 60oC do in 50% thermostatic drying chamber
Dry 48h；The film of gained is further dried in the air dry oven of 60oC, keeps properly for use.
By mixed substrate membrane containing nano-grade molecular sieve obtained in room temperature, CO is measured under the dry conditions that pressure difference is 0.1MPa2Infiltration coefficient be
326Barrer, CO2/N2Selectivity is 36.
Embodiment 3：The mixed substrate membrane containing nano-grade molecular sieve of addition 0.5wt% zeolite imidazole ester skeletal porous carbon nanomaterials is prepared, step is such as
Under：
Step 1: the preparation of the zeolite imidazole ester material of nickel doping：
Zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, 2-methylimidazole are dissolved in respectively in methanol solution and are configured to concentration difference
For the solution of 0.1mol/L, 0.1mol/L, 0.8mol/L, then it is respectively put into 4A molecular sieves standing 12h and removes extra moisture,
Obtain the methanol solution (being named as solution A) of zinc nitrate hexahydrate, the methanol solution (being named as solution B) of Nickelous nitrate hexahydrate and
The methanol solution (being named as solution C) of 2-methylimidazole；Then, solution A, solution B and solution C are poured into three-necked flask,
48h is stirred under 30oC to chemically react, and 20min is centrifuged in the range of speeds of 10000rpm to acquired solution, in centrifuge tube
Lower sediment washed three times with methanol after, be placed in 60oC vacuum drying ovens dry 12h to get purple powder, be named as product D；
Step 2: the preparation of zeolite imidazole ester skeletal porous carbon nanomaterial：
Product D prepared by step 1 is put into flange form tubular heater, N is adjusted2Flow velocity is 100mLmin-1, with 5 °
C·min-1Rate be raised to 800 °C, calcining at constant temperature 3h, then be down to room temperature naturally, obtain black powder, be named as product E.
Step 3: the preparation of casting solution：
Product E prepared by step 2 is scattered in the solution F for being made into 15g/L in n,N-dimethylacetamide, solution F is existed
Polyether-polyamide block copolymer, wherein zeolite is added after temperature is 30 °C of lower ultrasonic disperse 2h in the frequency of 30MHz thereto
The mass ratio that imidazate skeletal porous carbon nanomaterial accounts for polyether-polyamide block copolymer is 0.5wt%.It is stirred again using magnetic force
Device is mixed rotating speed is 300rpm, temperature is to stir to form uniform casting solution to being completely dissolved for 24 hours in 70oC, is named as casting solution G,
And it is for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product G of step 3 is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 300 μ
M in temperature is 30oC, humidity makes solvent volatilization for 24 hours, then in the vacuum drying chamber of 60oC do in 50% thermostatic drying chamber
Dry 48h；The film of gained is further dried in the air dry oven of 60oC, keeps properly for use.
By mixed substrate membrane containing nano-grade molecular sieve obtained in room temperature, CO is measured under the dry conditions that pressure difference is 0.1MPa2Infiltration coefficient be
231Barrer, CO2/N2Selectivity is 29.
Embodiment 4：The mixed substrate membrane containing nano-grade molecular sieve of addition 1wt% zeolite imidazole ester skeletal porous carbon nanomaterials is prepared, step is such as
Under：
Step 1: the preparation of the zeolite imidazole ester material of nickel doping：
Zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, 2-methylimidazole are dissolved in respectively in methanol solution and are configured to concentration difference
For the solution of 0.1mol/L, 0.1mol/L, 0.8mol/L, then it is respectively put into 4A molecular sieves standing 12h and removes extra moisture,
Obtain the methanol solution (being named as solution A) of zinc nitrate hexahydrate, the methanol solution (being named as solution B) of Nickelous nitrate hexahydrate and
The methanol solution (being named as solution C) of 2-methylimidazole；Then, solution A, solution B and solution C are poured into three-necked flask,
48h is stirred under 30oC to chemically react, and 20min is centrifuged in the range of speeds of 10000rpm to acquired solution, in centrifuge tube
Lower sediment washed three times with methanol after, be placed in 60oC vacuum drying ovens dry 12h to get purple powder, be named as product D；
Step 2: the preparation of zeolite imidazole ester skeletal porous carbon nanomaterial：
Product D prepared by step 1 is put into flange form tubular heater, N is adjusted2Flow velocity is 100mLmin-1, with 5 °
C·min-1Rate be raised to 800 °C, calcining at constant temperature 3h, then be down to room temperature naturally, obtain black powder, be named as product E.
Step 3: the preparation of casting solution：
Product E prepared by step 2 is scattered in the solution F for being made into 30g/L in n,N-dimethylacetamide, solution F is existed
Polyether-polyamide block copolymer, wherein zeolite is added after temperature is 30 °C of lower ultrasonic disperse 2h in the frequency of 30MHz thereto
The mass ratio that imidazate skeletal porous carbon nanomaterial accounts for polyether-polyamide block copolymer is 1wt%.Magnetic agitation is used again
Device is named as casting solution G rotating speed is 300rpm, temperature is to stir to form uniform casting solution to being completely dissolved for 24 hours in 70oC, and
It is for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product G of step 3 is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 300 μ
M in temperature is 30oC, humidity makes solvent volatilization for 24 hours, then in the vacuum drying chamber of 60oC do in 50% thermostatic drying chamber
Dry 48h；The film of gained is further dried in the air dry oven of 60oC, keeps properly for use.
By mixed substrate membrane containing nano-grade molecular sieve obtained in room temperature, CO is measured under the dry conditions that pressure difference is 0.1MPa2Infiltration coefficient be
265Barrer, CO2/N2Selectivity is 33.
Embodiment 5：The mixed substrate membrane containing nano-grade molecular sieve of addition 2wt% zeolite imidazole ester skeletal porous carbon nanomaterials is prepared, step is such as
Under：
Step 1: the preparation of the zeolite imidazole ester material of nickel doping：
Zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, 2-methylimidazole are dissolved in respectively in methanol solution and are configured to concentration difference
For the solution of 0.1mol/L, 0.1mol/L, 0.8mol/L, then it is respectively put into 4A molecular sieves standing 12h and removes extra moisture,
Obtain the methanol solution (being named as solution A) of zinc nitrate hexahydrate, the methanol solution (being named as solution B) of Nickelous nitrate hexahydrate and
The methanol solution (being named as solution C) of 2-methylimidazole；Then, solution A, solution B and solution C are poured into three-necked flask,
48h is stirred under 30oC to chemically react, and 20min is centrifuged in the range of speeds of 10000rpm to acquired solution, in centrifuge tube
Lower sediment washed three times with methanol after, be placed in 60oC vacuum drying ovens dry 12h to get purple powder, be named as product D；
Step 2: the preparation of zeolite imidazole ester skeletal porous carbon nanomaterial：
Product D prepared by step 1 is put into flange form tubular heater, N is adjusted2Flow velocity is 100mLmin-1, with 5 °
C·min-1Rate be raised to 800 °C, calcining at constant temperature 3h, then be down to room temperature naturally, obtain black powder, be named as product E.
Step 3: the preparation of casting solution：
Product E prepared by step 2 is scattered in the solution F for being made into 60g/L in n,N-dimethylacetamide, solution F is existed
Polyether-polyamide block copolymer, wherein zeolite is added after temperature is 30 °C of lower ultrasonic disperse 2h in the frequency of 30MHz thereto
The mass ratio that imidazate skeletal porous carbon nanomaterial accounts for polyether-polyamide block copolymer is 2wt%.Magnetic agitation is used again
Device is named as casting solution G rotating speed is 300rpm, temperature is to stir to form uniform casting solution to being completely dissolved for 24 hours in 70oC, and
It is for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product G of step 3 is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 300 μ
M in temperature is 30oC, humidity makes solvent volatilization for 24 hours, then in the vacuum drying chamber of 60oC do in 50% thermostatic drying chamber
Dry 48h；The film of gained is further dried in the air dry oven of 60oC, keeps properly for use.
By mixed substrate membrane containing nano-grade molecular sieve obtained in room temperature, CO is measured under the dry conditions that pressure difference is 0.1MPa2Infiltration coefficient be
474Barrer, CO2/N2Selectivity is 34.
Embodiment 6：The mixed substrate membrane containing nano-grade molecular sieve of addition 2.5wt% zeolite imidazole ester skeletal porous carbon nanomaterials is prepared, step is such as
Under：
Step 1: the preparation of the zeolite imidazole ester material of nickel doping：
Zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, 2-methylimidazole are dissolved in respectively in methanol solution and are configured to concentration difference
For the solution of 0.1mol/L, 0.1mol/L, 0.8mol/L, then it is respectively put into 4A molecular sieves standing 12h and removes extra moisture,
Obtain the methanol solution (being named as solution A) of zinc nitrate hexahydrate, the methanol solution (being named as solution B) of Nickelous nitrate hexahydrate and
The methanol solution (being named as solution C) of 2-methylimidazole；Then, solution A, solution B and solution C are poured into three-necked flask,
48h is stirred under 30oC to chemically react, and 20min is centrifuged in the range of speeds of 10000rpm to acquired solution, in centrifuge tube
Lower sediment washed three times with methanol after, be placed in 60oC vacuum drying ovens dry 12h to get purple powder, be named as product D；
Step 2: the preparation of zeolite imidazole ester skeletal porous carbon nanomaterial：
Product D prepared by step 1 is put into flange form tubular heater, N is adjusted2Flow velocity is 100mLmin-1, with 5 °
C·min-1Rate be raised to 800 °C, calcining at constant temperature 3h, then be down to room temperature naturally, obtain black powder, be named as product E.
Step 3: the preparation of casting solution：
Product E prepared by step 2 is scattered in the solution F for being made into 80g/L in n,N-dimethylacetamide, solution F is existed
Polyether-polyamide block copolymer, wherein zeolite is added after temperature is 30 °C of lower ultrasonic disperse 2h in the frequency of 30MHz thereto
The mass ratio that imidazate skeletal porous carbon nanomaterial accounts for polyether-polyamide block copolymer is 2.5wt%.It is stirred again using magnetic force
Device is mixed rotating speed is 300rpm, temperature is to stir to form uniform casting solution to being completely dissolved for 24 hours in 70oC, is named as casting solution G,
And it is for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product G of step 3 is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 300 μ
M in temperature is 30oC, humidity makes solvent volatilization for 24 hours, then in the vacuum drying chamber of 60oC do in 50% thermostatic drying chamber
Dry 48h；The film of gained is further dried in the air dry oven of 60oC, keeps properly for use.
By mixed substrate membrane containing nano-grade molecular sieve obtained in room temperature, CO is measured under the dry conditions that pressure difference is 0.1MPa2Infiltration coefficient be
527Barrer, CO2/N2Selectivity is 33.
Compared with comparative example 1, the CO of the mixed substrate membrane containing nano-grade molecular sieve obtained by embodiment 1 ~ 62Infiltration coefficient and CO2/N2Selectivity is
It is significantly improved.It will be apparent that the active metal sites in zeolite imidazole ester skeletal porous carbon nanomaterial and doping nitrogen pair
CO2Transmission play synergistic effect.Comparative example 1 ~ 2 finds under the same conditions, to adulterate zeolite imidazole ester skeletal porous
The CO of carbon nanomaterial mixed substrate membrane containing nano-grade molecular sieve2Infiltration coefficient and CO2/N2Selectivity is than the zeolite imidazole ester material mixing of nickel doping
The height of matrix membrane.Comparative example 3 ~ 6 finds the increase with zeolite imidazole ester skeletal porous carbon nanomaterial content, mixing
The CO of matrix membrane2Infiltration coefficient increases, and CO2/N2Selectivity first increase and reduce afterwards, when zeolite imidazole ester skeletal porous carbon is received
When the content of rice material reaches 1.5wt%, selectivity reaches maximum value.
Although invention has been described above, but the invention is not limited in above-mentioned embodiment, on
The specific implementation mode stated is only schematical, rather than restrictive, and those skilled in the art are the present invention's
Under enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to the present invention protection it
It is interior.
Claims (9)
1. a kind of organic and inorganic mixed substrate membrane containing nano-grade molecular sieve of doping zeolite imidazole ester skeletal porous carbon nanomaterial, it is characterised in that：By
Polymer substrate and additive composition, polymer substrate are polyether-polyamide block copolymer, and additive is zeolite imidazole ester bone
The porous carbon nanomaterial of frame, the mass percentage that additive accounts for mixed substrate membrane containing nano-grade molecular sieve are 0.1~10wt%.
2. a kind of organic and inorganic mixed-matrix of doping zeolite imidazole ester skeletal porous carbon nanomaterial described in claim 1
The preparation method of film, it is characterised in that：It is raw material to select zinc nitrate hexahydrate, Nickelous nitrate hexahydrate and 2-methylimidazole first,
The zeolite imidazole ester material adulterated by solvent structure nickel；Then as presoma, in 700 ~ 1000 °C of lower high temperature
Porous zeolite imidazate skeletal porous carbon nanomaterial is made in calcining；The porous carbon nanomaterial is distributed to polyethers-polyamides again
In amine block polymer solution, having for doping zeolite imidazole ester skeletal porous carbon nanomaterial is prepared using solvent evaporation method
The inorganic mixed substrate membrane containing nano-grade molecular sieve of machine-；Prepared film is homogeneous densified polymer film.
3. the organic and inorganic mixed-matrix of doping zeolite imidazole ester skeletal porous carbon nanomaterial according to claim 2
The preparation method of film, it is characterised in that：When preparing mixed substrate membrane containing nano-grade molecular sieve, wet-film thickness is controlled at 50 ~ 500 μm.
4. the organic and inorganic mixed-matrix of doping zeolite imidazole ester skeletal porous carbon nanomaterial according to claim 2
The preparation method of film, it is characterised in that：Include the following steps：
Step 1: preparing the zeolite imidazole ester material of nickel doping：
Zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, 2-methylimidazole are dissolved in respectively in methanol solution and are configured to concentration difference
For the solution of 0.01 ~ 0.1mol/L, 0.01 ~ 0.1mol/L, 0.08 ~ 12mol/L, be then respectively put into 4A molecular sieves stand 6 ~
Extra moisture is removed for 24 hours, obtains solution A：The methanol solution of zinc nitrate hexahydrate, solution B：The methanol of Nickelous nitrate hexahydrate is molten
Liquid and solution C：The methanol solution of 2-methylimidazole；Then, solution A, solution B and solution C are poured into three-necked flask, 20 ~
12 ~ 48h is stirred under 80oC to react, and 10 ~ 120min is centrifuged in the range of speeds of 8000 ~ 12000rpm to acquired solution,
After lower sediment in centrifuge tube is washed three times with methanol, it is placed in 60 ~ 100oC vacuum drying ovens dry 12 ~ for 24 hours to get purple powder
End is named as product D；
Step 2: preparing zeolite imidazole ester skeletal porous carbon nanomaterial：
Product D prepared by step 1 is put into flange form tubular heater, N is adjusted2Flow velocity is 10 ~ 500mLmin-1, with
1~10°C·min-1Rate be raised to 700 ~ 1000 °C, 2 ~ 20h of calcining at constant temperature, then be down to room temperature naturally, obtain black powder, order
Entitled product E；
Step 3: preparing casting solution：
Step 2 products therefrom E is scattered in the solution F that 30 ~ 200g/L is made into n,N-dimethylacetamide, by solution F 10
After frequency, the temperature of ~ 50MHz is 20 ~ 70 °C of lower 0.5 ~ 4h of ultrasonic disperse, polyether-polyamide block copolymer is added thereto,
It in rotating speed is that 12 ~ 48h of stirring to be formed to being completely dissolved in 20 ~ 90oC for 100 ~ 500rpm, temperature to use magnetic stirring apparatus again
One casting solution, is named as casting solution G, and in 25 °C of constant temperature deaerations 12 ~ for use for 24 hours；
The solid content of polyether-polyamide block copolymer is 3 ~ 25wt% in the casting solution of preparation；
Step 4: preparing film：
The casting solution G of step 3 is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 50 ~
500 μm in temperature are 20 ~ 30oC, humidity makes solvent volatilize 24 ~ 48h in 40 ~ 60% thermostatic drying chamber, then in 40 ~ 90oC
Vacuum drying chamber in dry 24 ~ 48h；The film of gained is further dried in the air dry oven of 30 ~ 90oC, keeps properly and waits for
With.
5. the organic and inorganic mixed-matrix of doping zeolite imidazole ester skeletal porous carbon nanomaterial according to claim 2
The preparation method of film, it is characterised in that：Zinc nitrate hexahydrate described in step 1, Nickelous nitrate hexahydrate, 2-methylimidazole rub
You are than being 1 ~ 10：1~10：8~1200.
6. the organic and inorganic mixed-matrix of doping zeolite imidazole ester skeletal porous carbon nanomaterial according to claim 2
The preparation method of film, it is characterised in that：In step 1,5 ~ 30g 4A molecular sieves are used per 100mL methanol solutions.
7. the organic and inorganic mixed-matrix of doping zeolite imidazole ester skeletal porous carbon nanomaterial according to claim 2
The preparation method of film, it is characterised in that：The grain size of the zeolite imidazole ester material of the nickel doping is 30 ~ 48nm.
8. a kind of organic and inorganic mixed-matrix of doping zeolite imidazole ester skeletal porous carbon nanomaterial described in claim 1
Film is in separation CO2Application in gas.
9. application according to claim 8, it is characterised in that：Obtained film is for detaching CO2/N2, gas permeability
Test use constant pressure variant area method, film infiltration effective area be 1 ~ 12.56cm2, scavenging is using H2, scavenging flow velocity be 10~
60mL·min-1, feeding gas flow velocity is 10~60mLmin-1, the flow of feed side and per-meate side obtains with flow measurement, permeated
Side constituent content is measured with gas-chromatography；Test temperature is 20 ~ 80oC, and pressure difference is 0.1~0.8MPa.
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| CN109663512A (en) * | 2018-12-13 | 2019-04-23 | 石河子大学 | The mixed substrate membrane containing nano-grade molecular sieve and preparation method and application of ionic liquid@hollow polyhedron filling |
| CN113578078A (en) * | 2021-07-12 | 2021-11-02 | 太原理工大学 | Preparation method and application of mixed matrix membrane based on nitrogen-doped porous carbon spheres |
| CN115463555A (en) * | 2022-08-30 | 2022-12-13 | 石河子大学 | Mixed matrix membrane based on nanosheets with adjustable metal site saturation and preparation method and application thereof |
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