CN105289340B - A kind of formates tubular type hybridized film, preparation method and application for aromatic hydrocarbons/alkane separation - Google Patents
A kind of formates tubular type hybridized film, preparation method and application for aromatic hydrocarbons/alkane separation Download PDFInfo
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Abstract
A kind of formates tubular type hybridized film, preparation method and application for aromatic hydrocarbons/alkane separation, belongs to technical field of membrane separation.Its step includes：The formic acid salt particle of suitable particle diameter is prepared using solvent-thermal method；Formates/polymer film liquid, ultrasonic disperse, standing and defoaming are prepared using blending method；Formates/polymer separating layer is combined by the ceramic film outer surface of porous pipe type of the negative pressure cross-flow filtration method after silane coupler modified；Hybridized film is dried in vacuo 0.1~4h at 30~120 DEG C, strengthens separating layer stability, repeatedly filter process, multilayer film is made.It is with low cost the invention provides a kind of preparation method of new formates tubular type hybridized film, it is simple to operate, and obtained hybridized film infiltration evaporation is functional, with higher permeation flux, mechanical strength has a greater degree of improvement.
Description
Technical field
The present invention relates to a kind of preparation method of the formates tubular type hybridized film for aromatic hydrocarbons/alkane separation, belong to film point
From technical field.
Background technology
Petrochemical industry is mainstay of the national economy industry, and with the fast development of China's economy, petrochemical industry is also located
In rapid growth period, the demand of ethene can also be reached unprecedented vigorous.Naphtha is main ethylene cracking material, by C4-
C12Aliphatic hydrocarbon, the band composition such as branched aliphatic hydrocarbons and aromatic hydrocarbon.Aromatic component is difficult to convert into alkene during cracking technology, right
The contribution very little of olefin yield.Therefore it is to reduce the production of the set technical process that rational Porous deproteinized bone processing is carried out to cracking stock
The good approach that cost and implementation process energy consumption are effectively utilized.Further, since aromatic hydrocarbons is difficult cracking, pyrolysis furnace and defeated pipe are easily caused
Road coking influence heat transference efficiency.Other aromatic hydrocarbons can be used not only for catalytic reforming process, and be also the blending of clean gasoline
Agent.In consideration of it, naphtha is before pyrolysis furnace is delivered into, aromatic component therein should be carried out to removing separation, raising is entirely split
Solve the production capacity and utilization efficiency of heat energy of technique, it is to avoid coking phenomenon and the circuit pollution of conveying material, and then be cracking stock
The sustainable development made full use of with refinery of resource provides an effective process route.The point of theory separated from mixture
Analysis, from C4To C10Alkane/aromatic hydrocarbons mixture in isolate the process of aromatic hydrocarbons be extremely difficult.Because carbon number
Close aromatic hydrocarbons and the boiling point difference of alkane less, easily form azeotropic mixture, and relative volatility is close to 1, using azeotropic
The traditional handicrafts such as rectifying, extracting rectifying and liquid-liquid extraction all have energy consumption greatly, and cost of investment is high, and flow is complicated, must plus aid in
The shortcomings of agent and limited input concentration scope, therefore need to further explore new separation method.
Infiltration evaporation (pervaporation) membrane separation technique is a kind of efficient, cleaning new membrane separation process, is utilized
Seperation film is different to the dissolving diffusivity of component in liquid mixture and realizes and separates, with traditional azeotropic distillation and extracting rectifying
Compare, Pervaporation Technology can save energy 1/2-2/3,50% of operating cost less than traditional separation method.In addition, permeate
Vaporisation techniques also have process operation simple, are not required to introduce the third components such as nonvariant boiling reagent, extractant, technical process and product are to ring
The pollution in border is small, is not limited by VLE relation, is adapted to separation azeotrope and by mixing that the close component of boiling point is constituted
Compound, is particularly suitable for use in the removing of the relatively low component of concentration in mixture, the infiltration evaporation separation of aromatic hydrocarbons/alkane is reduction naphtha
Arene content, the potential technology of Optimization of Ethylene cracking stock.
Current more and more deep with what is studied novel film materials, the research for the system has obtained numerous be engaged in and oozed
The favor of vaporization scholar thoroughly.Separation system includes benzene/cyclohexane, toluene/n-heptane, benzene/n-hexane, toluene/isooctane mixing
The systems such as thing.Current research focus, which is still concentrated on, finds separating property and film forming that novel film materials lift component to be separated
In the improvement and optimization of method.At present, although the filming performance of polymer membrane is excellent, but its heat endurance is poor, especially
When separating organic matter/organic-compound system, the stability problem of polymer membrane has fettered its industrialization.In addition because of high score
The low mechanical strength of sub- polymer film, also causes researchers to begin to focus on and develop the more preferable film of mechanical strength.Compared to high score
Sub- polymer film, addition inorganic component can effectively improve the heat endurance, mechanical property, permeability of polymer film in high polymer
Energy and selectivity etc..
Metal coordinating polymer has potential application prospect and attracting structure because of it, and research is increasingly becoming in recent years
Focus, receive extensive concern in fields such as catalysis, optics, material, storage, separation.With formic acid this short bridge ligand and d
The metallic element in area accumulates a series of material M (HCOO) to be formed by the active force of stronger coordinate bond or weaker2·H2O(M
=Mn, Fe, Co, Ni, Cu) (II) and they remove the material of hydrone or object, with a variety of different structures, from one-dimensional hole
Road all once had been reported to two layer structures and tridimensional network, and they do not only have programmable topological structure and good
Heat endurance, and small molecule can be made reversibly to pass through with stable nanoscale duct, so as to be selective catalysis, molecule
The design of the materials such as identification, ultra-high purity separation and micropore equipment provides foundation.Why formic acid, which is that one kind is widely used, is matched somebody with somebody
Body, is because this part contains the group carboxyl oxygen atom of easy and metal-complexing.With traditional porous material zeolite, activity
Charcoal compares, and formates has its unique superior part, is mainly manifested in following several respects：(1) it is easy to by coordinationization
Method is obtained；(2) advance design can be carried out from the selection of metal ion, part；(3) size in the hole in skeleton, shape
Shape, arrangement and property have virtually limitless possibility；(4) between transition metal ions and feature object in stephanoporate framework
May occur the coupling of chemistry, so as to cause the discovery and acquisition of new multifunctional material.
The invention provides a kind of preparation method of formates tubular type hybridized film, transition metal ions in formates is utilized
The pi-electron coordination of unoccupied orbital and aromatic hydrocarbons, is conducive to improving adsorptivity of the film to aromatic hydrocarbons, and the stable nanoscale duct of formates
The resistance to mass tranfer of aromatic component is effectively reduced, so as to increase the flux of hybridized film.
The content of the invention
It is an object of the invention to provide a kind of preparation method of formates tubular type hybridized film, for aromatic hydrocarbons/alkane system
Separation.Prepare formates using solvent-thermal method, using blending method by Formate Doped into polymer, cross-flow is driven by negative pressure
Ceramic porous film outer surface of the filtration method after silane coupler modified is combined formates/polymer, forms having for even compact
Machine/inorganic hybrid membrane.The formates tubular type hybridized film prepared using this kind of method has excellent separating effect to aromatic hydrocarbons/alkane.
This method comprises the following steps：
(1) formic acid salt particle is prepared using solvent-thermal method；
(2) by polymer formulation into solution, formic acid salt particle is added, ultrasonic disperse is configured to formates/polymer film
Liquid；
(3) tubular type inorganic porous membrane is immersed into the silane coupler with amino to pre-process, its surface is carried feature
Group amino, rinses and dries；
(4) under -0.02~-0.09MPa suction function, by step (2) formates/polymer film liquid in step (3)
Inorganic porous membrane surface negative pressure cross-flow filtration for a period of time, makes formates/polymer be compounded in inorganic porous membrane surface；
(5) the formates tubular type hybridized film for preparing step (4) vacuum drying in the range of 30~120 DEG C；
(6) repeat step (4), (5) are several times.
Step (1) described formates is formates (such as Co (HCOO) that function is preferentially transmitted with aromatic hydrocarbons2·2H2O, Cu
(HCOO)2·2H2O, Fe (HCOO)2·2H2O)；The polymer is polymer (such as polyethers that function is preferentially transmitted with aromatic hydrocarbons
Copolyamide (PEBA), polyvinyl alcohol (PVA), poly 4 vinyl pyridine (P4VP), polyacrylic acid (PAA) etc.).The solvent can
To be water, methanol, ethanol, isopropanol, n-butanol, N, N-2- NMFs (DMF), N, N-2- methylacetamides (DMAc),
1-METHYLPYRROLIDONE) etc..
In the methods of the invention, described inorganic porous membrane is that aperture is milipore filter or micro- between 50 nanometers to 100 microns
Filter membrane, the membrane material of described inorganic porous membrane is Al2O3、TiO2、ZrO2Or SiO2Oxide.
The preparation for the formates tubular type hybridized film that the preparation method of the present invention is obtained, formates particle diameter is 300nm-
1000nm, step (2) formates particulate load amount is 0.1%~20wt% of polymer.Formates/polymer film liquid is inorganic
0.1~4h of porous film surface negative pressure cross-flow filtration.
Formates tubular type hybridized film of the present invention is used for the method for aromatics separation/alkane, point of the mixed system of aromatic hydrocarbons/alkane
It it is 30-80 DEG C from temperature.
The principle of technical solution of the present invention is：Porous formic acid salt material is added in the polymer, utilizes transition in formates
The unoccupied orbital of metal ion and the pi-electron of aromatic hydrocarbons are coordinated, and improve adsorption capacity of the film to aromatic hydrocarbons, and the stable nanometer of formates
Level duct is effectively reduced the resistance to mass tranfer of aromatic component, so as to increase the flux of hybridized film.Negative pressure cross-flow filtration is used simultaneously
Method improves settlement issues of the formates in film liquid, improves the load capacity of formates, enhancing hybridized film and aromatic hydrocarbons in separation system
Affinity.In addition, vacuum drying oven, which is dried, can accelerate solvent evaporation rate, increase the free volume of film, be conducive to improving flux,
So as to improve the combination property of formates/polymer film.
The polyether co-polyamide (PEBA) that the present invention is used is a kind of common by firm polyamide segment and the polyethers of softness section
Combinate form into rubbery block copolymers, the performance of membrane material can be adjusted according to soft and hard segments content, hard nylon segment is carried
For enough mechanical strengths, soft polyether segment provides larger free volume.Current most study be PEBA-2533,
PEBA-3533, PEBA-4033, PEBA-6333, PEBA-7233, PEBA-1657 etc., wherein PEBA-2533 not only have superior
Mechanical performance, good chemical property and heat endurance, and with superior separating property, especially for some fragrance
Compound or volatile organic matter have very high selectivity.On the one hand, soft segment not only contributes to small molecule transmission, and to aromatic hydrocarbons
There is compatibility, it is ensured that film has preferable differential permeability, on the other hand, hard section can suppress being swelled for film, it is ensured that its is resistance to
By property.
Except membrane material, the present invention has machine/inorganic ceramic tubular membrane from negative pressure cross-flow filtration legal system, due to cobaltous formate
Special construction, generally exist in organic solvent in suspension form, therefore settlement issues are inevitable.Using party's legal system
Standby composite membrane mild condition, method are simple, separating layer is thinner than film made from coating process, can pass through the compound number of plies control of regulation and control
The thickness of separating layer processed.Negative pressure cross-flow filtration method has not only been played can improve the excellent of separating layer compactness under negative pressure cross-flow effect
Point, solves settlement issues of the cobaltous formate in film liquid again, so as to improve the load capacity of cobaltous formate, enhances hybridized film to dividing
The affinity of aromatic hydrocarbons in vitro system, so as to improve the separating property of film.Method that the present invention is provided is simple and easy to apply, raw material is cheap,
And the composite membrane prepared has preferable separating effect and stability, and prospect is widely applied with potential.
Compared with prior art, the present invention has the advantage that：
First, the preparation process of formates is simple, with low cost, and particle diameter can be adjusted by changing synthesis condition
Control, optimizes the particle diameter of formic acid salt particle, strengthens its compatibility with polymer, and then improve the separating property of film.
2nd, tubular type Co (HCOO) is prepared using negative pressure cross-flow filtration method2·2H2O hybridized films, can effectively improve formates
Settlement issues in film liquid, improve the load capacity of formates.
3rd, the seperation film assembled has significant raising in terms of mechanical strength, resistance to swelling.
The present invention is described in further detail below in conjunction with brief description of the drawings and embodiment.
Brief description of the drawings
Fig. 1 is the Co (HCOO) of embodiment 22·2H2O/PEBA film surface scan electronic microscope photos.
Embodiment
The present invention is elaborated with specific embodiment below in conjunction with the accompanying drawings, but the present invention is not limited to following implementation
Example.
Embodiment 1
Inorganic porous membrane is used for aluminum oxide (Al2O3) material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1~0.2 μm,
Membrane area is 28cm2, pre-process the silane coupler that uses for 3- aminopropyls-trimethoxy silane, the amido link used that carries
Polymer is polyether co-polyamide (PEBA2533), and source metal is cobalt carbonate (CoCO3, molecular weight is 118.94) organic ligand
For formic acid, (HCOOH, molecular weight is that 46.03), the solvent of polyether co-polyamide is n-butanol.
Preparation condition and method：
(1) Co (HCOO) is prepared using solvent-thermal method2·2H2O.(weigh 3g cobalt carbonates to be added in 10ml water, then will
50ml formic acid solutions are added dropwise in above-mentioned reaction solution, and the stirring reaction 6h when being added dropwise, centrifugation 1h obtains lower sediment, and vacuum is done
It is dry, pink powder shape crystal is obtained, is fully ground, particle diameter is about 300nm.)
(2) with the PEBA solution 100ml of n-butanol preparation 6%, it is uniformly dispersed, adds under magnetic agitation effect
0.12g Co(HCOO)2·2H2O, i.e. Co (HCOO)2·2H2O load capacity is 2%, ultrasonic disperse.
(3) it is inoranic membrane surface is carried NH2, tubular type inoranic membrane is pre-processed：Inoranic membrane is immersed 0.2wt%'s
2h in 3- aminopropyls-trimethicone ethanol solution；
(4) take out inoranic membrane to be rinsed with deionized water, in dry 2h at 110 DEG C in vacuum drying chamber；
(5) film liquid of ultrasonic disperse is pumped into outside inoranic membrane by cross-flow filtration device using vacuum pump using circulatory water after taking out
Vacuum is maintained at -0.08MPa, time 30min on the outside of surface, film, makes Co (HCOO)2·2H2O/PEBA film liquids are compounded in film
Outer surface；
(6) inoranic membrane is taken out, vacuum drying treatment in 120 DEG C of baking ovens is put into, obtains the separating layer of dense uniform.
(7) (5)-(6) process is repeated 2 times.
The formates tubular type hybridized film of above-mentioned preparation is subjected to infiltration evaporation performance test in infiltration evaporation membrane cisterna.
Test condition is：Material liquid is toluene level 10wt% toluene/n-heptane system, and experimental temperature is 40 DEG C, film
Downstream lateral pressure is 440Pa.
The infiltration evaporation film properties measured are：Permeation flux 711gm-2·h-1, separation factor is 3.2.
Embodiment 2
Inorganic porous membrane is used for aluminum oxide (Al2O3) material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1~0.2 μm,
Membrane area is 28cm2, pre-process the silane coupler that uses for 3- aminopropyls-trimethoxy silane, the amido link used that carries
Polymer is polyether co-polyamide (PEBA2533), and source metal is cobalt carbonate (CoCO3, molecular weight is 118.94) organic ligand
For formic acid, (HCOOH, molecular weight is that 46.03), the solvent of polyether co-polyamide is n-butanol.
Preparation condition and method：
(1) Co (HCOO) is prepared using solvent-thermal method2·2H2O.(weigh 3g cobalt carbonates to be added in 10ml water, then will
50ml formic acid solutions are added dropwise in above-mentioned reaction solution, are stirred at room temperature after reaction 6h, and centrifugation 1h obtains lower sediment, and vacuum is done
It is dry, pink powder shape crystal is obtained, is ground, particle diameter is about 300nm.)
(2) with the PEBA solution 100ml of n-butanol preparation 6%, it is uniformly dispersed, adds under magnetic agitation effect
0.24g Co(HCOO)2·2H2O, i.e. Co (HCOO)2·2H2O load capacity is 4%, ultrasonic disperse.
(3) it is inoranic membrane surface is carried NH2, tubular type inoranic membrane is pre-processed：Inoranic membrane is immersed 0.2wt%'s
2h in 3- aminopropyls-trimethicone ethanol solution；
(4) take out inoranic membrane to be rinsed with deionized water, in dry 2h at 110 DEG C in vacuum drying chamber；
(5) film liquid of ultrasonic disperse is pumped into outside inoranic membrane by cross-flow filtration device using vacuum pump using circulatory water after taking out
Vacuum is maintained at -0.08MPa, time 30min on the outside of surface, film, makes Co (HCOO)2·2H2O/PEBA film liquids are compounded in film
Outer surface；
(6) inoranic membrane is taken out, vacuum drying treatment in 120 DEG C of baking ovens is put into, obtains the separating layer of dense uniform.
(7) (5)-(6) process is repeated 2 times.
The formates tubular type hybridized film of above-mentioned preparation is subjected to infiltration evaporation performance test in infiltration evaporation membrane cisterna.
Test condition is：Material liquid is toluene level 10wt% toluene/n-heptane system, and experimental temperature is 40 DEG C, film
Downstream lateral pressure is 440Pa.
The infiltration evaporation film properties measured are：Permeation flux 771gm-2·h-1, separation factor is 5.1.
Co(HCOO)2·2H2O/PEBA film surface scan electronic microscope photos is shown in Fig. 1.
Embodiment 3
Inorganic porous membrane is used for aluminum oxide (Al2O3) material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1~0.2 μm,
Membrane area is 28cm2, pre-process the silane coupler that uses for 3- aminopropyls-trimethoxy silane, the amido link used that carries
Polymer is polyether co-polyamide (PEBA2533), and source metal is cobalt carbonate (CoCO3, molecular weight is 118.94) organic ligand
For formic acid, (HCOOH, molecular weight is that 46.03), the solvent of polyether co-polyamide is n-butanol.
Preparation condition and method：
(1) Co (HCOO) is prepared using solvent-thermal method2·2H2O.(weigh 3g cobalt carbonates to be added in 10ml water, then will
50ml formic acid solutions are added dropwise in above-mentioned reaction solution, are stirred at room temperature after reaction 6h, and centrifugation 1h obtains lower sediment, and vacuum is done
It is dry, pink powder shape crystal is obtained, is ground, particle diameter is about 300nm.)
(2) with the PEBA solution 100ml of n-butanol preparation 6%, it is uniformly dispersed, adds under magnetic agitation effect
0.48g Co(HCOO)2·2H2O, i.e. Co (HCOO)2·2H2O load capacity is 8%, ultrasonic disperse.
(3) it is inoranic membrane surface is carried NH2, tubular type inoranic membrane is pre-processed：Inoranic membrane is immersed 0.2wt%'s
2h in 3- aminopropyls-trimethicone ethanol solution；
(4) take out inoranic membrane to be rinsed with deionized water, in dry 2h at 110 DEG C in vacuum drying chamber；
(5) film liquid of ultrasonic disperse is pumped into outside inoranic membrane by cross-flow filtration device using vacuum pump using circulatory water after taking out
Vacuum is maintained at -0.08MPa, time 30min on the outside of surface, film, makes Co (HCOO)2·2H2O/PEBA film liquids are compounded in film
Outer surface；
(6) inoranic membrane is taken out, vacuum drying treatment in 120 DEG C of baking ovens is put into, obtains the separating layer of dense uniform.
(7) (5)-(6) process is repeated 2 times.
The formates tubular type hybridized film of above-mentioned preparation is subjected to infiltration evaporation performance test in infiltration evaporation membrane cisterna.Test
Condition is：Material liquid is toluene level 10wt% toluene/n-heptane system, and experimental temperature is 40 DEG C, and film downstream lateral pressure is
440Pa。
The infiltration evaporation film properties measured are：Permeation flux 1238gm-2·h-1, separation factor is 3.3.
Embodiment 4
Inorganic porous membrane is used for aluminum oxide (Al2O3) material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1~0.2 μm,
Membrane area is 28cm2, pre-process the silane coupler that uses for 3- aminopropyls-trimethoxy silane, the amido link used that carries
Polymer is polyether co-polyamide (PEBA2533), and source metal is cobalt carbonate (CoCO3, molecular weight is 118.94) organic ligand
For formic acid, (HCOOH, molecular weight is that 46.03), the solvent of polyether co-polyamide is n-butanol.
Preparation condition and method：
(1) Co (HCOO) is prepared using solvent-thermal method2·2H2O.(weigh 1.5g cobalt carbonates to be added in 10ml water, then
50ml formic acid solutions are added dropwise in above-mentioned reaction solution, are stirred at room temperature after reaction 6h, centrifugation 1h obtains lower sediment, vacuum is done
It is dry, pink powder shape crystal is obtained, is ground, particle diameter is about 500nm.)
(2) with the PEBA solution 100ml of n-butanol preparation 6%, it is uniformly dispersed, adds under magnetic agitation effect
0.48g Co(HCOO)2·2H2O, i.e. Co (HCOO)2·2H2O load capacity is 8%, ultrasonic disperse.With ethanol by 3- aminopropyls-
Trimethicone is configured to 0.2wt% solution 500ml；
(3) it is inoranic membrane surface is carried NH2, tubular type inoranic membrane is pre-processed：Inoranic membrane is immersed 0.2wt%'s
2h in 3- aminopropyls-trimethicone ethanol solution；
(4) take out inoranic membrane to be rinsed with deionized water, in dry 2h at 110 DEG C in vacuum drying chamber；
(5) film liquid of ultrasonic disperse is pumped into outside inoranic membrane by cross-flow filtration device using vacuum pump using circulatory water after taking out
Vacuum is maintained at -0.08MPa, time 30min on the outside of surface, film, makes Co (HCOO)2·2H2O/PEBA film liquids are compounded in film
Outer surface；
(6) inoranic membrane is taken out, vacuum drying treatment in 120 DEG C of baking ovens is put into, obtains the separating layer of dense uniform.
(7) (5)-(6) process is repeated 2 times.
The formates tubular type hybridized film of above-mentioned preparation is subjected to infiltration evaporation performance test in infiltration evaporation membrane cisterna.
Test condition is：Material liquid is toluene level 10wt% toluene/n-heptane system, and experimental temperature is 40 DEG C, film
Downstream lateral pressure is 440Pa.
The infiltration evaporation film properties measured are：Permeation flux 568gm-2·h-1, separation factor is 5.3.
Embodiment 5
Inorganic porous membrane is used for aluminum oxide (Al2O3) material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1~0.2 μm,
Membrane area is 28cm2, pre-process the silane coupler that uses for 3- aminopropyls-trimethoxy silane, the amido link used that carries
Polymer is polyether co-polyamide (PEBA2533), and source metal is cobalt carbonate (CoCO3, molecular weight is 118.94) organic ligand
For formic acid, (HCOOH, molecular weight is that 46.03), the solvent of polyether co-polyamide is n-butanol.
Preparation condition and method：
(1) Co (HCOO) is prepared using solvent-thermal method2·2H2O.(weigh 3g cobalt carbonates to be added in 10ml water, then will
50ml formic acid solutions are added dropwise in above-mentioned reaction solution, are stirred at room temperature after reaction 6h, and centrifugation 1h obtains lower sediment, and vacuum is done
It is dry, pink powder shape crystal is obtained, is ground, particle diameter is about 300nm.)
(2) with the PEBA solution 100ml of n-butanol preparation 6%, it is uniformly dispersed, adds under magnetic agitation effect
0.48g Co(HCOO)2·2H2O, i.e. Co (HCOO)2·2H2O load capacity is 8%, ultrasonic disperse.
(3) it is inoranic membrane surface is carried NH2, tubular type inoranic membrane is pre-processed：Inoranic membrane is immersed 0.2wt%'s
2h in 3- aminopropyls-trimethicone ethanol solution；
(4) take out inoranic membrane to be rinsed with deionized water, in dry 2h at 110 DEG C in vacuum drying chamber；
(5) film liquid of ultrasonic disperse is pumped into outside inoranic membrane by cross-flow filtration device using vacuum pump using circulatory water after taking out
Vacuum is maintained at -0.08MPa, time 30min on the outside of surface, film, makes Co (HCOO)2·2H2O/PEBA film liquids are compounded in film
Outer surface；
(6) inoranic membrane is taken out, vacuum drying treatment in 120 DEG C of baking ovens is put into, obtains the separating layer of dense uniform.
(7) (5)-(6) process is repeated 2 times.
The formates tubular type hybridized film of above-mentioned preparation is subjected to infiltration evaporation performance test in infiltration evaporation membrane cisterna.
Test condition is：Material liquid is toluene level 10wt% toluene/n-heptane system, and experimental temperature is 60 DEG C, film
Downstream lateral pressure is 440Pa.
The infiltration evaporation film properties measured are：Permeation flux 821gm-2·h-1, separation factor is 12.3.
Embodiment 6
Inorganic porous membrane is used for aluminum oxide (Al2O3) material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1~0.2 μm,
Membrane area is 28cm2, pre-process the silane coupler that uses for 3- aminopropyls-trimethoxy silane, the amido link used that carries
Polymer is polyether co-polyamide (PEBA2533), and source metal is cobalt carbonate (CoCO3, molecular weight is 118.94) organic ligand
For formic acid, (HCOOH, molecular weight is that 46.03), the solvent of polyether co-polyamide is n-butanol.
Preparation condition and method：
(1) Co (HCOO) is prepared using solvent-thermal method2·2H2O.(weigh 3g cobalt carbonates to be added in 10ml water, then will
50ml formic acid solutions are added dropwise in above-mentioned reaction solution, and the stirring reaction 6h when being added dropwise, centrifugation 1h obtains lower sediment, and vacuum is done
It is dry, pink powder shape crystal is obtained, is fully ground, particle diameter is about 300nm.)
(2) with the PEBA solution 100ml of n-butanol preparation 6%, it is uniformly dispersed, adds under magnetic agitation effect
0.12g Co(HCOO)2·2H2O, i.e. Co (HCOO)2·2H2O load capacity is 4%, ultrasonic disperse.
(3) it is inoranic membrane surface is carried NH2, tubular type inoranic membrane is pre-processed：Inoranic membrane is immersed 0.2wt%'s
2h in 3- aminopropyls-trimethicone ethanol solution；
(4) take out inoranic membrane to be rinsed with deionized water, in dry 2h at 110 DEG C in vacuum drying chamber；
(5) film liquid of ultrasonic disperse is pumped into outside inoranic membrane by cross-flow EGR using vacuum pump using circulatory water after taking out
Vacuum is maintained at -0.08MPa, time 30min on the outside of surface, film, makes Co (HCOO)2·2H2O/PEBA film liquids are compounded in film
Outer surface；
(6) inoranic membrane is taken out, vacuum drying treatment in 120 DEG C of baking ovens is put into, obtains the separating layer of dense uniform.
(7) (5)-(6) process is repeated 1 times.
The formates tubular type hybridized film of above-mentioned preparation is subjected to infiltration evaporation performance test in infiltration evaporation membrane cisterna.
Test condition is：Material liquid is toluene level 10wt% toluene/n-heptane system, and experimental temperature is 40 DEG C, film
Downstream lateral pressure is 440Pa.
The infiltration evaporation film properties measured are：Permeation flux 1002gm-2·h-1, separation factor is 2.3.
Claims (8)
1. the preparation method of a kind of formates tubular type hybridized film for aromatic hydrocarbons/alkane separation, it is characterised in that including following step
Suddenly：
(1) formic acid salt particle is prepared using solvent-thermal method；
(2) by polymer formulation into solution, formic acid salt particle is added, ultrasonic disperse is configured to formates/polymer film liquid；
(3) tubular type inorganic porous membrane is immersed into the silane coupler with amino to pre-process, its surface is carried functional groups
Amino, rinses and dries；
(4) it is under -0.02~-0.09MPa suction function, step (2) formates/polymer film liquid is inorganic in step (3)
Porous film surface negative pressure cross-flow filtration for a period of time, makes formates/polymer be compounded in inorganic porous membrane surface；
(5) the formates tubular type hybridized film for preparing step (4) vacuum drying in the range of 30~120 DEG C；
(6) repeat step (4), (5) are several times；
Formates is selected from Co (HCOO)2·2H2O, Cu (HCOO)2·2H2O、Fe(HCOO)2·2H2O；Polymer is polyethers copolymerization
Acid amides (PEBA).
2. according to the method for claim 1, it is characterised in that the solvent of configuration solution is selected from water, methanol, ethanol, isopropanol, just
Butanol, N, N-2- NMFs (DMF), N, N-2- methylacetamides (DMAc), 1-METHYLPYRROLIDONE.
3. according to the method for claim 1, it is characterised in that inorganic porous membrane is that aperture is super between 50 nanometers to 100 microns
Filter membrane or microfiltration membranes, the membrane material of inorganic porous membrane is Al2O3、TiO2、ZrO2Or SiO2。
4. according to the method for claim 1, it is characterised in that formates/polymer film liquid is wrong in inorganic porous membrane surface negative pressure
Flow through 0.1~4h of filter.
5. according to the method for claim 1, it is characterised in that formates particle diameter is 300nm-1000nm.
6. according to the method for claim 1, it is characterised in that step (2) formates particulate load amount is the 0.1wt% of polymer
~20wt%.
7. the either method according to claim 1-6 prepares formates tubular type hybridized film.
8. the either method according to claim 1-6, which prepares formates tubular type hybridized film, is used for aromatic hydrocarbons/alkane separation.
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