CN108745004A - A kind of preparation method and application of the mixed substrate membrane containing nano-grade molecular sieve with lamella and caged collaboration sieving actoion - Google Patents
A kind of preparation method and application of the mixed substrate membrane containing nano-grade molecular sieve with lamella and caged collaboration sieving actoion Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention discloses a kind of preparation method and application of the mixed substrate membrane containing nano-grade molecular sieve with lamella and caged collaboration sieving actoion.Preparation method is：First in graphitized carbon nitride (g-C3N4) zeolite imidazole skeleton ester material ZIF-8 is introduced in situ in dispersion liquid, then above-mentioned composite material is distributed in polyether block amide copolymer, the polyether block amide gas separation membrane for cooperateing with sieving actoion with lamella and caged is prepared using solution casting method；Prepared film is homogeneous dense film, and wet-film thickness is controlled at 50 ~ 500 μm.The preparation process of inorganic material provided by the invention is easily-controllable, g-C3N4Between the nanoscale twins of the composite material of ZIF-8 and g-C3N4Three s-triazine rings hole be CO2Provide channel；Obtained film acid-fast alkali-proof, flexibility is good, uses it for gas separation, has excellent comprehensive performance；It can effectively Selective Separation CO2, it is CO2Transmission provide fast transferring channel.
Description
Technical field
The present invention relates to a kind of preparation method and application for the mixed substrate membrane containing nano-grade molecular sieve for cooperateing with sieving actoion with lamella and caged,
Belong to gas separation membrane technical field.
Background technology
Mixed substrate membrane containing nano-grade molecular sieve is a kind of composite membrane being added to inorganic material in organic polymer, due to its excellent separation
Performance prepares the hot spot simple, economical and practical, the persons that become current research study.The introducing of inorganic particulate in mixed substrate membrane containing nano-grade molecular sieve
On the one hand the accumulation for having interrupted strand, accelerates the transmission of gas molecule, improves the permeability of gas.On the other hand, nothing
Machine particle can not only increase the affinity to object gas, and can also provide matched with target gas molecules kinetic diameter
Diffusion admittance, 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.However if interface compatibility is poor between polymer and filler in MMMs, it is possible to generate non-selectivity
There is phenomena such as hardening of polymer and hole plug in cavity, so as to cause the deterioration of film properties.Therefore, it polymer and inorganic fills out
The selection of material is most important to the development of MMMs.
A kind of thermoplastic elastomer (TPE) that polyether co-polyamide is made of PA polyamide hard segments and PE polyether soft segments gathers
Amide crystallized domains provide mechanical strength, and polyethers amorphous domain provides high permeability.It is that one kind typically has been commercialized
Rubbery block copolymers, have very high thermal stability, mechanical stability, acid and alkali-resistance and organic solvent resistance, become most
One of promising material.
Graphitized carbon nitride（g-C3N4）With good thermal stability and chemical stability, and it is normal to be proved to be room temperature
Depress most stable of carbonitride obform body.Constitute graphite-phase g-C3N4Basic structural unit be C6N7, interlamellar spacing is about
0.326nm, g-C3N4On C with N atoms on lone pair electrons can interact to form the big pi bond of similar phenyl ring, and then formed
The conjugated system of height delocalization.In addition to this, during thermal condensation, planar end has fault of construction, and there are amino（-
NH2）And imino group（-NH）Equal functional groups.g-C3N4These characteristics show it to CO2Good affinity, but with it come
Detach CO2Research it is seldom, this may be because of g-C3N4Interlamellar spacing be less than CO2Molecular dimension, to CO2Resistance it is larger.
Invention content
The present invention is intended to provide it is a kind of with lamella and caged collaboration sieving actoion mixed substrate membrane containing nano-grade molecular sieve preparation method and
Using specially in graphitized carbon nitride surface original position loaded zeolite imidazate framework material, and being added to polyether block acyl
In amine copolymer object PEBA, it is applied to CO2/N2Separation.Find that the mixed substrate membrane containing nano-grade molecular sieve has higher CO in2Infiltration
Coefficient and separation factor.
In the present invention, ZIF-8 is supported on g-C in situ3N4On, on the one hand increase g-C3N4Interlamellar spacing, on the other hand,
ZIF-8 also provides channel for gas diffusion；Overcome " g-C3N4Interlamellar spacing be less than CO2Molecular dimension, to CO2Resistance
It is larger " the problem of；G-C in the present invention3N4In negative electricity, with Zn2+Electrostatic interaction so that ZIF-8 is successfully loaded to g-C3N4
On lamella；By adjusting g-C3N4With the ratio of ZIF-8, the regulation and control of the interlamellar spacing of composite material, the modification scope of interlamellar spacing are realized
It is 2 ~ 4.The zeolite imidazole skeleton ester material ZIF-8 introduced in the present invention is for CO2/N2It is CO when separation2It provides quickly
Channel improves CO2Infiltration coefficient and separation factor.
The present invention provides a kind of preparation methods of the mixed substrate membrane containing nano-grade molecular sieve with lamella and caged collaboration sieving actoion, first
In g-C3N4Zeolite imidazole skeleton ester material ZIF-8 is introduced in dispersion liquid in situ, it is embedding that above-mentioned composite material is then distributed to polyethers
In section amide, is prepared using solution casting method and cooperate with the polyether block amide gas of sieving actoion to detach with lamella and caged
Film；Prepared film is homogeneous dense film, and wet-film thickness is controlled at 50 ~ 500 μm.
In above-mentioned preparation method, the polyamide segment of polyether block amide is polyamide nylon -12, and polyether segment is poly- four
Hydrogen furans；In above-mentioned preparation method, the ratio that composite material accounts for mixed substrate membrane containing nano-grade molecular sieve gross mass is 0.5~5wt%.
In above-mentioned preparation method, the interlamellar spacing of the composite material is 2 ~ 4.
In above-mentioned preparation method, include the following steps：
Step 1: preparing graphitized carbon nitride g-C3N4：
G-C is synthesized by thermal polymerization3N4：Dried urea is put into flange form tubular heater, protection air-flow is adjusted
Speed is 10 ~ 200mLmin-1, with 1 ~ 10 °C of min-1Heating rate rise to 350 ~ 850 °C, 2 ~ 10h of calcining at constant temperature, then from
So it is down to 25 °C；Obtain the g-C of unpurified yellow3N4Powder；
By the g-C of the unpurified yellow of gained3N4Powder is dispersed in water, and 1 ~ 3h is ultrasonically treated under the frequency of 10 ~ 50MHz
Afterwards, after the 5 ~ 100min of centrifuge for being 5000 ~ 15000r/min with rotating speed, lower sediment is dry in 80 ~ 110 °C of vacuum
Dry 4 ~ 72h, is made g-C in dry case3N4Powder is for use；
Step 2: preparing g-C3N4With ZIF-8 composite materials（It is named as CNZ）：
By the g-C prepared by step 13N4Powder disperses the solution A for being made into 10 ~ 150g/L in methyl alcohol, and ultrasound 1 ~ 5h dispersions are equal
It is even；Then zinc nitrate hexahydrate is added in solution A, continuing 0.5 ~ 3h of ultrasound makes Zn2+It is fixed on g-C3N4On, it is named as molten
Liquid B；
Then solution B is poured into the methanol solution of 2-methylimidazole of a concentration of 10 ~ 100g/L, rotating speed be 100 ~
12 ~ 48h of stirring reaction synthesis g-C on 500rpm, the magnetic stirring apparatus that temperature is 15 ~ 40oC3N4With the composite material of ZIF-8；It is quiet
12 ~ 48h is set, supernatant liquor is removed, after lower sediment is washed three times with methanol, obtains the suspension C containing CNZ；
Step 3: preparing casting solution：
The suspension C of prepared CNZ is dissolved in the solution D that 30 ~ 200g/L is made into n,N-dimethylacetamide, by solution D
At a temperature of the frequency of 10 ~ 50MHz, 20 ~ 70 °C after 0.5 ~ 4h of ultrasonic disperse, polyether block amide copolymerization is added thereto
Object, then 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
Uniform casting solution, is named as product E, and in 25 °C of constant temperature deaerations 12 ~ for use for 24 hours；
The solid content that polymer substrate is adjusted when preparing casting solution is 3 ~ 25wt%；
Step 4: preparing film：
The product E 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.
In above-mentioned preparation method, in step 1, the protection gas is one kind in nitrogen or inert gas, inert gas packet
Include one kind in argon gas, helium.
In above-mentioned preparation method, in step 1, g-C3N4Mass ratio with water is 0.5 ~ 50:300~5000；In step 2,
g-C3N4The mass ratio of powder and zinc nitrate hexahydrate is 1 ~ 20：0.5 ~ 5, the molar ratio of zinc nitrate hexahydrate and 2-methylimidazole
It is 1 ~ 10：4~700.
The present invention provides the mixed-matrixes that sieving actoion is cooperateed with lamella and caged being prepared by the above method
Film.
Cooperate with the mixed substrate membrane containing nano-grade molecular sieve of sieving actoion in separation CO with lamella and caged the present invention provides above-mentioned2In answer
With.Obtained film is for detaching CO2/N2, gas permeability, the effective area of film infiltration are tested using constant pressure variant area method
For 1 ~ 12.56cm2, scavenging is using H2, scavenging flow velocity is 10~60mLmin-1, feeding gas flow velocity is 10~60mLmin-1,
The flow of feed side and per-meate side is obtained with flow measurement, and per-meate side constituent content is measured with gas-chromatography；Test temperature is room temperature,
Pressure difference is 0.1~0.5MPa.
Beneficial effects of the present invention：
（1）g-C3N4Between the nanoscale twins of ZIF-8 composite materials CNZ and C3N4Hole on upper three s-triazine ring is CO2It provides
Channel；
（2）ZIF-8 with flexible back bone and high porosity is conducive to CO2Diffusion；
（3）g-C3N4On lone pair electrons interact the big pi bond to be formed can be with CO2π-π complexing interactions occur, promote
CO2Transmission；
（4）The preparation process of inorganic material provided by the invention is simple and easy to control, and the preparation process of mixed substrate membrane containing nano-grade molecular sieve is easy to operate, institute
Film acid-fast alkali-proof obtained, flexibility is good, uses it for gas separation, has excellent comprehensive performance；It can be effectively selective
Detach 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 27.
Embodiment 1：Prepare addition 1.5wt% g-C3N4Mixed substrate membrane containing nano-grade molecular sieve, steps are as follows：
Step 1: g-C3N4Preparation：
G-C is synthesized by thermal polymerization3N4.Dried urea is put into flange form tubular heater, protection air-flow is adjusted
Speed is 100mLmin-1, with 10 °C of min-1Heating rate rise to 850 °C, calcining at constant temperature 10h, then be down to 25 °C naturally.
By the g-C of the unpurified yellow of gained3N4Powder is dispersed in water（g-C3N4Mass ratio with water is 30:5000）,
Under the frequency of 50MHz be ultrasonically treated 3h after, with rotating speed be 12000r/min centrifuge 60min after, lower sediment is existed
For 24 hours, g-C is made in 100 °C of vacuum drying chamber drying3N4Powder is for use；
Step 2: the preparation of casting solution：
By the g-C prepared by step 13N4Powder is dissolved in the solution A that 100g/L is made into n,N-dimethylacetamide, will be molten
Polyether block amide copolymer, wherein g- is added after temperature is 60 °C of lower ultrasonic disperse 4h in frequencies of the liquid A in 50MHz thereto
C3N4Mass ratio with polyether block amide copolymer is 1.5:100.Use magnetic stirring apparatus in rotating speed for 500rpm, temperature again
Uniform casting solution is formed to being completely dissolved to stir 48h in 80oC, is named as product B, and for use for 24 hours in 25 °C of constant temperature deaerations；
Step 3: film preparation：
The product B 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 25oC, humidity makes solvent volatilize 48h in 60% thermostatic drying chamber, then is done in the vacuum drying chamber of 60oC
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
221Barrer, CO2/N2Selectivity is 28.Compared with comparative example 1, g-C is added3N4Mixed substrate membrane containing nano-grade molecular sieve do not reducing pure polyethers
Under the premise of the selectivity of block amides film, infiltration coefficient increases substantially.
Embodiment 2：The mixed substrate membrane containing nano-grade molecular sieve of addition 1.5wt% CNZ is prepared, steps are as follows：
Step 1: g-C3N4Preparation：
G-C is synthesized by thermal polymerization3N4.Dried urea is put into flange form tubular heater, protection air-flow is adjusted
Speed is 100mLmin-1, with 5 °C of min-1Heating rate rise to 850 °C, calcining at constant temperature 6h, then be down to 25 °C naturally.It will
The g-C of the unpurified yellow of gained3N4Powder is dispersed in water（g-C3N4Mass ratio with water is 20:3000）, in 30MHz
Frequency under be ultrasonically treated 2h after, with rotating speed be 10000r/min centrifuge 20min after, by lower sediment at 80 °C
Vacuum drying chamber is dried for 24 hours, and g-C is made3N4Powder is for use；
Step 2: g-C3N4With ZIF-8 composite materials（It is named as CNZ）Preparation：
By the g-C prepared by step 13N4Powder disperses the solution A for being made into 50g/L in methyl alcohol, and ultrasonic 3h is uniformly dispersed.So
A certain amount of zinc nitrate hexahydrate is added in solution A afterwards, is named as solution B.Continuing ultrasound 2h makes Zn2+It is fixed on g-C3N4
On.Solution B is poured into later in the methanol solution of 2-methylimidazole of a concentration of 30g/L, is 300rpm, temperature 30 in rotating speed
48h reaction synthesis ZIF-8 are stirred on the magnetic stirring apparatus of oC, are stood 12h, are removed supernatant liquor, lower sediment washes three with methanol
After secondary, the suspension C containing CNZ, wherein g-C are obtained3N4Mass ratio with ZIF-8 is 10:1；
Step 3: the preparation of casting solution：
The suspension C of prepared CNZ is dissolved in the solution D that 50g/L is made into n,N-dimethylacetamide, and solution D is existed
Polyether block amide, wherein g-C is added after temperature is 20 °C of lower ultrasonic disperse 2h in the frequency of 20MHz thereto3N4It is embedding with polyethers
The mass ratio of section amide copolymer is 1.5:100.It in rotating speed is to be stirred in 70oC for 300rpm, temperature to use magnetic stirring apparatus again
Uniform casting solution is formed to being completely dissolved for 24 hours, is named as product E, and for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product E 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
It is dry for 24 hours；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
238Barrer, CO2/N2Selectivity is 34.
Embodiment 3：The mixed substrate membrane containing nano-grade molecular sieve of addition 1.5wt% CNZ is prepared, steps are as follows：
Step 1: g-C3N4Preparation：
G-C is synthesized by thermal polymerization3N4.Dried urea is put into flange form tubular heater, protection air-flow is adjusted
Speed is 120mLmin-1, with 8 °C of min-1Heating rate rise to 850 °C, calcining at constant temperature 7h, then be down to 25 °C naturally.It will
The g-C of the unpurified yellow of gained3N4Powder is dispersed in water（g-C3N4Mass ratio with water is 10:3000）, in 20MHz
Frequency under be ultrasonically treated 3h after, with rotating speed be 12000r/min centrifuge 30min after, by lower sediment at 90 °C
Vacuum drying chamber dries 48h, and g-C is made3N4Powder is for use；
Step 2: g-C3N4With ZIF-8 composite materials（It is named as CNZ）Preparation：
By the g-C prepared by step 13N4Powder disperses the solution A for being made into 80g/L in methyl alcohol, and ultrasonic 4h is uniformly dispersed.So
A certain amount of zinc nitrate hexahydrate is added in solution A afterwards, is named as solution B.Continuing ultrasound 3h makes Zn2+It is fixed on g-C3N4
On.Solution B is poured into later in the methanol solution of 2-methylimidazole of a concentration of 30g/L, is 500rpm, temperature 40 in rotating speed
48h reaction synthesis ZIF-8 are stirred on the magnetic stirring apparatus of oC, are stood 48h, are removed supernatant liquor, lower sediment washes three with methanol
After secondary, the suspension C containing CNZ, wherein g-C are obtained3N4Mass ratio with ZIF-8 is 5:1；
Step 3: the preparation of casting solution：
The suspension C of prepared CNZ is dissolved in the solution D that 80g/L is made into n,N-dimethylacetamide, and solution D is existed
Polyether block amide, wherein g-C is added after temperature is 50 °C of lower ultrasonic disperse 3h in the frequency of 30MHz thereto3N4It is embedding with polyethers
The mass ratio of section amide copolymer is 1.5:100.It in rotating speed is to be stirred in 80oC for 500rpm, temperature to use magnetic stirring apparatus again
Uniform casting solution is formed to being completely dissolved for 24 hours, is named as product E, and for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product E of step 3 is cast on clean glass plate or polyfluortetraethylene plate, the thickness for controlling wet film is 200 μ
M in temperature is 30oC, humidity makes solvent volatilization for 24 hours, then in the vacuum drying chamber of 80oC do in 30% thermostatic drying chamber
It is dry for 24 hours；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
248Barrer, CO2/N2Selectivity is 36.
Embodiment 4：The mixed substrate membrane containing nano-grade molecular sieve of addition 1.5wt% CNZ is prepared, steps are as follows：
Step 1: g-C3N4Preparation：
G-C is synthesized by thermal polymerization3N4.Dried urea is put into flange form tubular heater, protection air-flow is adjusted
Speed is 150mLmin-1, with 10 °C of min-1Heating rate rise to 550 °C, calcining at constant temperature 5h, then be down to 25 °C naturally.It will
The g-C of the unpurified yellow of gained3N4Powder is dispersed in water（g-C3N4Mass ratio with water is 5:2000）, 30MHz's
Under frequency be ultrasonically treated 3h after, with rotating speed be 15000r/min centrifuge 50min after, by lower sediment at 100 °C
Vacuum drying chamber dries 48h, and g-C is made3N4Powder is for use；
Step 2: g-C3N4With ZIF-8 composite materials（It is named as CNZ）Preparation：
By the g-C prepared by step 13N4Powder disperses the solution A for being made into 100g/L in methyl alcohol, and ultrasonic 3h is uniformly dispersed.So
A certain amount of zinc nitrate hexahydrate is added in solution A afterwards, is named as solution B.Continuing ultrasound 2h makes Zn2+It is fixed on g-C3N4
On.Solution B is poured into later in the methanol solution of 2-methylimidazole of a concentration of 30g/L, is 500rpm, temperature 30 in rotating speed
48h reaction synthesis ZIF-8 are stirred on the magnetic stirring apparatus of oC, are stood 48h, are removed supernatant liquor, lower sediment washes three with methanol
After secondary, the suspension C containing CNZ, wherein g-C are obtained3N4Mass ratio with ZIF-8 is 2:1；
Step 3: the preparation of casting solution：
The suspension C of prepared CNZ is dissolved in the solution D that 80g/L is made into n,N-dimethylacetamide, and solution D is existed
Polyether block amide, wherein g-C is added after temperature is 60 °C of lower ultrasonic disperse 4h in the frequency of 50MHz thereto3N4It is embedding with polyethers
The mass ratio of section amide copolymer is 1.5:100.It in rotating speed is to be stirred in 60oC for 300rpm, temperature to use magnetic stirring apparatus again
Uniform casting solution is formed to being completely dissolved for 24 hours, is named as product E, and for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product E 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 volatilize 48h in 50% thermostatic drying chamber, then is done in the vacuum drying chamber of 60oC
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
253Barrer, CO2/N2Selectivity is 36.
Embodiment 5：The mixed substrate membrane containing nano-grade molecular sieve of addition 1.5wt% CNZ is prepared, steps are as follows：
Step 1: g-C3N4Preparation：
G-C is synthesized by thermal polymerization3N4.Dried urea is put into flange form tubular heater, protection air-flow is adjusted
Speed is 100mLmin-1, with 5 °C of min-1Heating rate rise to 650 °C, calcining at constant temperature 5h, then be down to 25 °C naturally.It will
The g-C of the unpurified yellow of gained3N4Powder is dispersed in water（g-C3N4Mass ratio with water is 5:2000）, 30MHz's
Under frequency be ultrasonically treated 3h after, with rotating speed be 15000r/min centrifuge 60min after, by lower sediment at 110 °C
Vacuum drying chamber dries 48h, and g-C is made3N4Powder is for use；
Step 2: g-C3N4With ZIF-8 composite materials（It is named as CNZ）Preparation：
By the g-C prepared by step 13N4Powder disperses the solution A for being made into 120g/L in methyl alcohol, and ultrasonic 5h is uniformly dispersed.So
A certain amount of zinc nitrate hexahydrate is added in solution A afterwards, is named as solution B.Continuing ultrasound 3h makes Zn2+It is fixed on g-C3N4
On.Solution B is poured into later in the methanol solution of 2-methylimidazole of a concentration of 30g/L, is 500rpm, temperature 40 in rotating speed
48h reaction synthesis ZIF-8 are stirred on the magnetic stirring apparatus of oC, are stood 48h, are removed supernatant liquor, lower sediment washes three with methanol
After secondary, the suspension C containing CNZ, wherein g-C are obtained3N4Mass ratio with ZIF-8 is 1:1；
Step 3: the preparation of casting solution：
The suspension C of prepared CNZ is dissolved in the solution D that 80g/L is made into n,N-dimethylacetamide, and solution D is existed
Polyether block amide, wherein g-C is added after temperature is 70 °C of lower ultrasonic disperse 4h in the frequency of 50MHz thereto3N4It is embedding with polyethers
The mass ratio of section amide copolymer is 1.5:100.It in rotating speed is to be stirred in 80oC for 500rpm, temperature to use magnetic stirring apparatus again
Uniform casting solution is formed to being completely dissolved for 24 hours, is named as product E, and for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product E 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 volatilize 48h in 60% thermostatic drying chamber, then is done in the vacuum drying chamber of 80oC
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
281Barrer, CO2/N2Selectivity is 43.
Embodiment 6：The mixed substrate membrane containing nano-grade molecular sieve of addition 1.5wt% CNZ is prepared, steps are as follows：
Step 1: g-C3N4Preparation：
G-C is synthesized by thermal polymerization3N4.Dried urea is put into flange form tubular heater, protection air-flow is adjusted
Speed is 150mLmin-1, with 5 °C of min-1Heating rate rise to 550 °C, calcining at constant temperature 8h, then be down to 25 °C naturally.It will
The g-C of the unpurified yellow of gained3N4Powder is dispersed in water（g-C3N4Mass ratio with water is 3:1000）, 50MHz's
After being ultrasonically treated 3h under frequency, with rotating speed be 12000r/min centrifuge 30min after, lower sediment is true at 80 °C
Empty drying box dries 72h, and g-C is made3N4Powder is for use；
Step 2: g-C3N4With ZIF-8 composite materials（It is named as CNZ）Preparation：
By the g-C prepared by step 13N4Powder disperses the solution A for being made into 100g/L in methyl alcohol, and ultrasonic 5h is uniformly dispersed.So
A certain amount of zinc nitrate hexahydrate is added in solution A afterwards, is named as solution B.Continuing ultrasound 2h makes Zn2+It is fixed on g-C3N4
On.Solution B is poured into later in the methanol solution of 2-methylimidazole of a concentration of 30g/L, is 500rpm, temperature 30 in rotating speed
48h reaction synthesis ZIF-8 are stirred on the magnetic stirring apparatus of oC, are stood 48h, are removed supernatant liquor, lower sediment washes three with methanol
After secondary, the suspension C containing CNZ, wherein g-C are obtained3N4Mass ratio with ZIF-8 is 1:2；
Step 3: the preparation of casting solution：
The suspension C of prepared CNZ is dissolved in the solution D that 80g/L is made into n,N-dimethylacetamide, and solution D is existed
Polyether block amide, wherein g-C is added after temperature is 50 °C of lower ultrasonic disperse 3h in the frequency of 30MHz thereto3N4It is embedding with polyethers
The mass ratio of section amide copolymer is 1.5:100.It in rotating speed is to be stirred in 60oC for 300rpm, temperature to use magnetic stirring apparatus again
Uniform casting solution is formed to being completely dissolved for 24 hours, is named as product E, and for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product E 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 volatilize 48h in 40% thermostatic drying chamber, then is done in the vacuum drying chamber of 60oC
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
242Barrer, CO2/N2Selectivity is 41.
Embodiment 7：The mixed substrate membrane containing nano-grade molecular sieve of addition 0.5wt% CNZ is prepared, steps are as follows：
Step 1: g-C3N4Preparation：
G-C is synthesized by thermal polymerization3N4.Dried urea is put into flange form tubular heater, protection air-flow is adjusted
Speed is 20mLmin-1, with 3 °C of min-1Heating rate rise to 550 °C, calcining at constant temperature 5h, then be down to 25 °C naturally.By institute
The g-C of the unpurified yellow obtained3N4Powder is dispersed in water（g-C3N4Mass ratio with water is 3:5000）, in the frequency of 20MHz
Under rate be ultrasonically treated 3h after, with rotating speed be 8000r/min centrifuge 30min after, the vacuum by lower sediment at 80 °C
Drying box dries 48h, and g-C is made3N4Powder is for use；
Step 2: g-C3N4With ZIF-8 composite materials（It is named as CNZ）Preparation：
By the g-C prepared by step 13N4Powder disperses the solution A for being made into 50g/L in methyl alcohol, and ultrasonic 3h is uniformly dispersed.So
A certain amount of zinc nitrate hexahydrate is added in solution A afterwards, is named as solution B.Continuing ultrasound 3h makes Zn2+It is fixed on g-C3N4
On.Solution B is poured into later in the methanol solution of 2-methylimidazole of a concentration of 30g/L, is 300rpm, temperature 40 in rotating speed
48h reaction synthesis ZIF-8 are stirred on the magnetic stirring apparatus of oC, are stood 48h, are removed supernatant liquor, lower sediment washes three with methanol
After secondary, the suspension C containing CNZ, wherein g-C are obtained3N4Mass ratio with ZIF-8 is 1:1；
Step 3: the preparation of casting solution：
The suspension C of prepared CNZ is dissolved in the solution D that 80g/L is made into n,N-dimethylacetamide, and solution D is existed
Polyether block amide, wherein g-C is added after temperature is 70 °C of lower ultrasonic disperse 4h in the frequency of 50MHz thereto3N4It is embedding with polyethers
The mass ratio of section amide copolymer is 0.5:100.It in rotating speed is to be stirred in 80oC for 500rpm, temperature to use magnetic stirring apparatus again
Uniform casting solution is formed to being completely dissolved for 24 hours, is named as product E, and for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product E 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 volatilize 48h in 60% thermostatic drying chamber, then is done in the vacuum drying chamber of 80oC
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
241Barrer, CO2/N2Selectivity is 39.
Embodiment 8：The mixed substrate membrane containing nano-grade molecular sieve of addition 2.5wt% CNZ is prepared, steps are as follows：
Step 1: g-C3N4Preparation：
G-C is synthesized by thermal polymerization3N4.Dried urea is put into flange form tubular heater, protection air-flow is adjusted
Speed is 50mLmin-1, with 8 °C of min-1Heating rate rise to 850 °C, calcining at constant temperature 5h, then be down to 25 °C naturally.By institute
The g-C of the unpurified yellow obtained3N4Powder is dispersed in water（g-C3N4Mass ratio with water is 3:5000）, in the frequency of 50MHz
Under rate be ultrasonically treated 3h after, with rotating speed be 12000r/min centrifuge 50min after, the vacuum by lower sediment at 80 °C
Drying box dries 48h, and g-C is made3N4Powder is for use；
Step 2: g-C3N4With ZIF-8 composite materials（It is named as CNZ）Preparation：
By the g-C prepared by step 13N4Powder disperses the solution A for being made into 100g/L in methyl alcohol, and ultrasonic 5h is uniformly dispersed.So
A certain amount of zinc nitrate hexahydrate is added in solution A afterwards, is named as solution B.Continuing ultrasound 3h makes Zn2+It is fixed on g-C3N4
On.Solution B is poured into later in the methanol solution of 2-methylimidazole of a concentration of 30g/L, is 500rpm, temperature 40 in rotating speed
48h reaction synthesis ZIF-8 are stirred on the magnetic stirring apparatus of oC, are stood 48h, are removed supernatant liquor, lower sediment washes three with methanol
After secondary, the suspension C containing CNZ, wherein g-C are obtained3N4Mass ratio with ZIF-8 is 1:1；
Step 3: the preparation of casting solution：
The suspension C of prepared CNZ is dissolved in the solution D that 150g/L is made into n,N-dimethylacetamide, and solution D is existed
Polyether block amide, wherein g-C is added after temperature is 70 °C of lower ultrasonic disperse 4h in the frequency of 50MHz thereto3N4It is embedding with polyethers
The mass ratio of section amide copolymer is 2.5:100.It in rotating speed is to be stirred in 80oC for 500rpm, temperature to use magnetic stirring apparatus again
Uniform casting solution is formed to being completely dissolved for 24 hours, is named as product E, and for use for 24 hours in 25 °C of constant temperature deaerations；
Step 4: film preparation：
The product E 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 volatilize 48h in 60% thermostatic drying chamber, then is done in the vacuum drying chamber of 80oC
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
310Barrer, CO2/N2Selectivity is 46.
Compared with comparative example 1, the CO of the mixed substrate membrane containing nano-grade molecular sieve obtained by embodiment 1 ~ 82Infiltration coefficient and CO2/N2Selectivity is
It is significantly improved.It will be apparent that the collaboration sieving actoion of lamella and caged is CO2Transmission provide channel.Comparison is implemented
Example 1 ~ 6 is found with C3N4：The increase of ZIF-8 mass ratioes, CO2Infiltration coefficient and CO2/N2Selectivity first increases to be reduced afterwards,
C3N4：ZIF-8=1:When 1, CO2Infiltration coefficient and CO2/N2Selectivity reaches maximum value.Comparative example 5,7 and 8, find with
The increase of CNZ contents, the CO of mixed substrate membrane containing nano-grade molecular sieve2Infiltration coefficient increases, and CO2/N2Selectivity first increase and reduce afterwards, when CNZ's
When content 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 (10)
1. a kind of preparation method of the mixed substrate membrane containing nano-grade molecular sieve with lamella and caged collaboration sieving actoion, it is characterised in that：Exist first
Zeolitic imidazolate framework material ZIF-8 is introduced in situ in graphitization nitrogen carbide dispersion liquid, forms composite material CNZ, it then will be upper
It states composite material to be distributed in polyether block amide copolymer, be prepared with lamella and caged collaboration sieve using solution casting method
The polyether block amide gas separation membrane being allocated as；Prepared film is homogeneous dense film, and wet-film thickness is controlled at 50 ~ 500 μm.
2. the preparation method of the mixed substrate membrane containing nano-grade molecular sieve according to claim 1 with lamella and caged collaboration sieving actoion,
It is characterized in that：The polyamide segment of polyether block amide copolymer is polyamide nylon -12, and polyether segment is PolyTHF.
3. the preparation method of the mixed substrate membrane containing nano-grade molecular sieve according to claim 1 with lamella and caged collaboration sieving actoion,
It is characterized in that：The mass ratio that composite material accounts for mixed substrate membrane containing nano-grade molecular sieve gross mass is 0.5~5wt%.
4. the preparation method of the mixed substrate membrane containing nano-grade molecular sieve according to claim 1 with lamella and caged collaboration sieving actoion,
It is characterized in that：By adjusting g-C3N4With the ratio of ZIF-8, realize that the regulation and control of the interlamellar spacing of composite material, interlamellar spacing are 2 ~ 4.
5. the preparation method of the mixed substrate membrane containing nano-grade molecular sieve according to claim 1 with lamella and caged collaboration sieving actoion,
It is characterized in that：Include the following steps：
Step 1: preparing graphitized carbon nitride g-C3N4：
G-C is synthesized by thermal polymerization3N4：Dried urea is put into flange form tubular heater, protection air-flow speed is adjusted
For 10 ~ 200mLmin-1, with 1 ~ 10 °C of min-1Heating rate rise to 350 ~ 850 °C, 2 ~ 10h of calcining at constant temperature, then it is natural
It is down to 25 °C；Obtain the g-C of unpurified yellow3N4Powder；
By the g-C of unpurified yellow3N4Powder is dispersed in water, under the frequency of 10 ~ 50MHz be ultrasonically treated 1 ~ 3h after, with turn
After speed is 5 ~ 100min of centrifuge of 5000 ~ 15000r/min, by lower sediment in 80 ~ 110 °C of vacuum drying chamber
Dry 4 ~ 72h, is made g-C3N4Powder is for use；
Step 2: preparing g-C3N4With ZIF-8 composite materials CNZ：
By the g-C prepared by step 13N4Powder disperses the solution A for being made into 10 ~ 150g/L in methyl alcohol, and ultrasound 1 ~ 5h dispersions are equal
It is even；Then zinc nitrate hexahydrate is added in solution A, continuing 0.5 ~ 3h of ultrasound makes Zn2+It is fixed on g-C3N4On, it is named as molten
Liquid B；
Then solution B is poured into the methanol solution of 2-methylimidazole of a concentration of 10 ~ 100g/L, rotating speed be 100 ~
12 ~ 48h of stirring reaction synthesis g-C on 500rpm, the magnetic stirring apparatus that temperature is 15 ~ 40oC3N4With the composite material of ZIF-8；It is quiet
12 ~ 48h is set, supernatant liquor is removed, after lower sediment is washed three times with methanol, obtains the suspension C containing CNZ；
Step 3: preparing casting solution：
The suspension C of prepared CNZ is dissolved in the solution D that 30 ~ 200g/L is made into n,N-dimethylacetamide, by solution D
At a temperature of the frequency of 10 ~ 50MHz, 20 ~ 70 °C after 0.5 ~ 4h of ultrasonic disperse, it is total that polyether block amide is added into solution D
Polymers, then use magnetic stirring apparatus rotating speed for 100 ~ 500rpm, temperature be in 20 ~ 90oC 12 ~ 48h of stirring to being completely dissolved shape
At uniform casting solution, it is named as product E, and in 25 °C of constant temperature deaerations 12 ~ for use for 24 hours；
The solid content that polymer substrate is adjusted when preparing casting solution is 3 ~ 25wt%；
Step 4: preparing film：
The product E 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.
6. the preparation method of the mixed substrate membrane containing nano-grade molecular sieve according to claim 5 with lamella and caged collaboration sieving actoion,
It is characterized in that：In step 1, the protection gas is one kind in nitrogen or inert gas, and inert gas includes in argon gas, helium
One kind.
7. the preparation method of the mixed substrate membrane containing nano-grade molecular sieve according to claim 5 with lamella and caged collaboration sieving actoion,
It is characterized in that：In step 1, g-C3N4Mass ratio with water is 0.5 ~ 50:300~5000；In step 2, g-C3N4Powder and six
The mass ratio of nitric hydrate zinc is 1 ~ 20：0.5 ~ 5, the molar ratio of zinc nitrate hexahydrate and 2-methylimidazole is 1 ~ 10：4~700.
8. what a kind of claim 1 ~ 7 any one of them preparation method was prepared has lamella and caged collaboration sieving actoion
Mixed substrate membrane containing nano-grade molecular sieve.
9. a kind of mixed substrate membrane containing nano-grade molecular sieve according to any one of claims 8 with lamella and caged collaboration sieving actoion is in separation CO2In answer
With.
10. application according to claim 9, it is characterised in that：Obtained there is lamella and caged to cooperate with sieving actoion
Mixed substrate membrane containing nano-grade molecular sieve for detaching CO2/N2, gas permeability is tested using constant pressure variant area method, the effective area of film infiltration is
1~12.56cm2, scavenging is using H2, scavenging flow velocity is 10~60mLmin-1, feeding gas flow velocity is 10~60mLmin-1, former
The flow of material side and per-meate side is obtained with flow measurement, and per-meate side constituent content is measured with gas-chromatography；Test temperature is room temperature, pressure
Difference is 0.1~0.5MPa.
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| CN110935322B (en) * | 2019-11-29 | 2021-10-01 | 山东大学 | High-flux alpha-C-containing3N4/Ag3PO4Forward osmosis membrane of composite material and preparation method thereof |
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