CN109316977A - A kind of MOF/MOP/metal hydroxide ceramic composite membrane and preparation method - Google Patents
A kind of MOF/MOP/metal hydroxide ceramic composite membrane and preparation method Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 31
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 31
- 239000000919 ceramic Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 8
- 238000001338 self-assembly Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 230000008595 infiltration Effects 0.000 claims description 9
- 238000001764 infiltration Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003491 array Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- -1 Oxygen Compound Chemical class 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 235000012489 doughnuts Nutrition 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000003446 ligand Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000009738 saturating Methods 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of MOF/MOP/ metal hydroxides ceramic composite membrane and preparation method, belong to UF membrane field.The present invention is using ceramic tube as substrate, a certain amount of MOP particle is filled in metal hydroxides nano-array using dynamic self-assembly membrane formation process, and be added after ligand and compensate for defect using the MOF particle that metal hydroxides induction is prepared for homologous metal, further enhance the stability of composite membrane.Preparation process of the present invention is simple, lower cost for material, has certain separating effect for aromatic hydrocarbons/alkane system, there is certain directive significance for MOP-MOF group compound film.
Description
Technical field
The present invention relates to a kind of infiltration vaporization separation film and its technologies of preparing, belong to UF membrane field.
Background technique
According to dissolution-diffusion mechanism, infiltration evaporation is widely used in tradition as a kind of membrane technology of efficient maturation
Separation method is difficult to isolated system, the compound as similar in boiling point, azeotrope, the compound etc. of thermodynamic instability.It realizes
Membrane process with high-performance and high stable is the key problem in seperation film field.Therefore, select suitable membrane material to close weight
It wants, not only improves the selectivity improved to aromatic hydrocarbon molecule, and be conducive to improve stability.
The Typical Representative of 2D sheet layer material is metal hydroxides, such as Co (OH)2、Ni(OH)2、Mg(OH)2Deng with vertical
Straight array structure.MOP is the monodimension nanometer material as made of the assembling of independent molecule, phenyl ring abundant, unsaturated metal position
The advantages such as point, stability, solubility facilitate the raising of performance, it is possible to prevente effectively from agglomeration, guarantee high load and
Even dispersibility.In addition Cu in MOP molecule2+On d track and benzene ring structure in π track formed with the π track on aromatic hydrocarbon molecule
D- it is pi-conjugated effect and π-πconjugation further improve composite membrane to the adsorptive selectivity of aromatic hydrocarbon molecule.This outer membrane leads to
The guarantee of amount has benefited from the porosity of MOP high.MOF is a kind of to pass through self assembly with metal ion or metal cluster and organic ligand
What journey was formed has the crystalline state porous material of periodical infinite network structure, and with large specific surface area, aperture is adjustable, porosity
High, duct can functionalization, size tunable the features such as, cause extensive concern in seperation film field.Pass through metal hydroxides
Source metal and MOF ligand coordination connection function enhancing composite membrane stability.The present invention utilizes the limit of metal hydroxides
Domain space fixes MOP particle, prepares defective MOP/ hydroxide composite membrane by dynamic self-assembly, passes through on this basis
MOF ligand and the coordination of source metal improve its stability, and this method is simple and easy, at low cost, are prepared with to composite membrane
Certain reference.
Summary of the invention
The object of the present invention is to provide a kind of for aromatic hydrocarbons/alkane system infiltration evaporation separation MOF/MOP/ hydroxide
Ceramic composite membrane and preparation method.
A kind of preparation method of MOF/MOP/ metal hydroxides ceramic composite membrane, which comprises the following steps:
(1) ceramic bases cleaned up are impregnated in Dopamine hydrochloride solution and carry out 1~60min of pretreatment, taken out
It is washed with deionized and is impregnated repeatedly up to washing away the free poly-dopamine in surface completely afterwards, is finally dried in vacuo in an oven；
(2) precursor solution A needed for preparing metal hydroxides described in product, the solute packet of precursor solution A
Include soluble metallic salt and hexa；
(3) by treated, ceramic bases are placed in precursor solution A prepared by step (2), are put into reaction in baking oven
Carry out growth in situ；Through reaction after a period of time, film is used into deionized water repeated flushing after taking out in reaction kettle, is put into baking
It is dried in vacuo in case, obtains metal hydroxides nano-chip arrays film；
(4) MOP is dissolved in solvent and is stirred, MOP casting solution is made, by dynamic self-assembly membrane formation process by MOP
It is filled in metal hydroxides nano-chip arrays, metal hydroxides/MOP composite membrane is made；
(5) organic ligand precursor solution B needed for preparing MOF, precursor solution B use solvent B；
(6) that metal hydroxides obtained/MOP composite membrane is placed in organic ligand presoma prepared by step (5) is molten
In liquid B, it is put into reaction in baking oven and is grown；Through reaction after a period of time, film is used into step (5) after taking out in reaction kettle
The solvent of middle use carries out repeated flushing, is put into baking oven and is dried in vacuo, obtains the particle stabilized metal hydroxides nanometer of MOF
MOP film, that is, MOF/MOP/ metal hydroxides ceramic composite membrane of array auxiliary preparation.
Heretofore described metal hydroxides is nanometer sheet layer structure, and forms orthogonal array structure with substrate,
It is divided into Co (OH)2With Ni (OH)2Deng.In heretofore described precursor solution A the concentration of metal salt be 0.02mol/L~
The molar concentration of 0.06mol/L, metal salt and hexa is 3:1-1:3.
Molecule base MOP is selected from tBu-MOP, SO3One or more of-MOP and OH-MOP.
Heretofore described ceramic substrate material is Al2O3、TiO2、ZrO2Or SiO2Oxide, have plate, tubular type and in
Three kinds of forms of hollow fiber, the ceramic pipe type substrate aperture are between 10 nanometers to 1 micron.
The reaction temperature of growth in situ described in step (3) of the present invention be 80 DEG C~120 DEG C, the reaction time be 1h~
24h。
The concentration of casting solution described in step (4) of the present invention is 1.7g/L~5.5g/L, and the time of dynamic self-assembly is
5min~10min.
The concentration of organic ligand is 0.02mol/L~0.05mol/L in step (5) of the present invention, and MOP stablizes in solvent B.
MOF described in step (6) of the present invention growth reaction temperature be 100 DEG C~135 DEG C, reaction temperature be 1h~
48h。
Composite membrane of the invention is for aromatic hydrocarbons/alkane system infiltration evaporation separation.
Technical principle of the invention: ceramic bases are impregnated into the combination that film and substrate can be enhanced in Dopamine hydrochloride solution
Power.Then ceramic bases are impregnated in the precursor solution of metal hydroxides, are placed in reaction kettle and grow in an oven,
It is rinsed and is dried in vacuo with a large amount of deionized waters after taking-up.Then MOP particle is filled in nanometer by dynamic self-assembly membrane formation process
In array, finally by hydro-thermal reaction, make organic ligand needed for preparing MOF material and the gold in the metal hydroxides
The complexation reaction of category source forms MOF particle, enhances the stability of its composite membrane.The composite membrane utilizes metal hydroxides nanometer sheet
Confinement space fills MOP particle, and MOP enhances film as a kind of effect of the stability of the porous material combination MOF of molecule base
Performance and stability.
Detailed description of the invention
The scanning electron microscope of Fig. 1 ceramic bases surface and section characterization.
Fig. 2 embodiment of the present invention 1Co (OH)2Film surface and the scanning electron microscope of section characterization.
Fig. 3 embodiment of the present invention 1tBu-MOP/Co (OH)2The scanning electron microscope of composite film surface and section characterization.
Fig. 4 embodiment of the present invention 1MOF/tBu-MOP/Co (OH)2The scanning electron microscope table of composite film surface and section
Sign.
Specific embodiment
Vapour further is permeated to the aromatic hydrocarbons of MOF/MOP/ hydroxide composite membrane of the invention/alkane below with reference to embodiment
Change separating property to be described in detail.However, the present invention is not limited to following embodiments.
Embodiment 1
Compound membrane preparation method:
(1) ceramic bases are pre-processed: weighs 50mmol trishydroxymethylaminomethane, 2g Dopamine hydrochloride, 5mmol
CuSO4With 19.6mmol H2O2It is dissolved in 1000mL deionized water, substrate is impregnated in 10min in prepared solution, use
A large amount of deionized water is rinsed and is impregnated repeatedly, until not fading, is dried in vacuo in 50 DEG C of baking ovens.
(2) compound concentration is 0.2mol/L Co (NO3)2·6(H2O) and the solution of 0.2mol/L hexa, mix
It carries out being stirred by ultrasonic uniformly after conjunction；Ceramic bases are placed in precursor solution, 6h are reacted in 90 DEG C of baking oven, after taking-up
It is rinsed with deionized water and impregnates and be dried in vacuo, obtain Co (OH)2Film.
(3) it weighs 330mg tBu-MOP to be dissolved in 120mL N-Methyl pyrrolidone, be made very by the method for taking out negative pressure
Reciprocal of duty cycle reaches 0.095MPa, makes Co (OH) after carrying out 10min2A certain amount of tBu-MOP particle is filled in nanometer sheet.
(4) it weighs 0.39g benzimidazole and is dissolved in 60mLN, in dinethylformamide, ultrasonic agitation keeps it all molten
Solution.It transfers the solution into reaction kettle, and by tBu-MOP/Co (OH)2Film is placed in ligand solution, in 135 DEG C of baking oven
Reaction is for 24 hours.It is rinsed well after taking-up with DMF, and is activated with DMF and methylene chloride, is finally dried in vacuo in 120 DEG C of baking oven
Obtain MOF/MOP/ hydroxide composite membrane.
The composite membrane of preparation is subjected to infiltration evaporation performance test, test system is toluene/n-heptane (1:1) mixture,
Feeding liquid temperature is 40 DEG C.
The performance of the saturating toluene of the composite membrane measured is as follows: flux is 269g/ (m2H), separation factor 2.3.
Embodiment 2
Compound membrane preparation method:
(1) ceramic bases are pre-processed: weighs 50mmol trishydroxymethylaminomethane, 2g Dopamine hydrochloride, 5mmol
CuSO4With 19.6mmol H2O2It is dissolved in 1000mL deionized water, substrate is impregnated in 10min in prepared solution, use
A large amount of deionized water is rinsed and is impregnated repeatedly, until not fading, is dried in vacuo in 50 DEG C of baking ovens.
(2) compound concentration is 0.2mol/L Co (NO3)2·6(H2O) and the solution of 0.2mol/L hexa, mix
It carries out being stirred by ultrasonic uniformly after conjunction；Ceramic bases are placed in precursor solution, 9h are reacted in 90 DEG C of baking oven, after taking-up
It is rinsed with deionized water and impregnates and be dried in vacuo, obtain Co (OH)2Film.
(3) it weighs 330mg tBu-MOP to be dissolved in 120mL N-Methyl pyrrolidone, be made very by the method for taking out negative pressure
Reciprocal of duty cycle reaches 0.095MPa, makes Co (OH) after carrying out 10min2A certain amount of tBu-MOP particle is filled in nanometer sheet.
(4) it weighs 0.39g benzimidazole and is dissolved in 60mLN, in dinethylformamide, ultrasonic agitation keeps it all molten
Solution.It transfers the solution into reaction kettle, and by tBu-MOP/Co (OH)2Film is placed in ligand solution, in 135 DEG C of baking oven
Reaction is for 24 hours.It is rinsed well after taking-up with DMF, and is activated with DMF and methylene chloride, is finally dried in vacuo in 120 DEG C of baking oven
Obtain MOF/MOP/ hydroxide composite membrane.
The composite membrane of preparation is subjected to infiltration evaporation performance test, test system is toluene/n-heptane (1:1) mixture,
Feeding liquid temperature is 40 DEG C.
The performance of the saturating toluene of the composite membrane measured is as follows: flux is 346g/ (m2H), separation factor 2.9.
Embodiment 3
Compound membrane preparation method:
(1) ceramic bases are pre-processed: weighs 50mmol trishydroxymethylaminomethane, 2g Dopamine hydrochloride, 5mmol
CuSO4With 19.6mmol H2O2It is dissolved in 1000mL deionized water, substrate is impregnated in 10min in prepared solution, use
A large amount of deionized water is rinsed and is impregnated repeatedly, until not fading, is dried in vacuo in 50 DEG C of baking ovens.
(2) compound concentration is 0.2mol/L Co (NO3)2·6(H2O) and the solution of 0.2mol/L hexa, mix
It carries out being stirred by ultrasonic uniformly after conjunction；Ceramic bases are placed in precursor solution, 12h is reacted in 90 DEG C of baking oven, are taken out
It is rinsed afterwards with deionized water and impregnates and be dried in vacuo, obtain Co (OH)2Film.
(3) it weighs 330mg tBu-MOP to be dissolved in 120mL N-Methyl pyrrolidone, be made very by the method for taking out negative pressure
Reciprocal of duty cycle reaches 0.095MPa, makes Co (OH) after carrying out 10min2A certain amount of tBu-MOP particle is filled in nanometer sheet.
(4) it weighs 0.39g benzimidazole and is dissolved in 60mLN, in dinethylformamide, ultrasonic agitation keeps it all molten
Solution.It transfers the solution into reaction kettle, and by tBu-MOP/Co (OH)2Film is placed in ligand solution, in 135 DEG C of baking oven
Reaction is for 24 hours.It is rinsed well after taking-up with DMF, and is activated with DMF and methylene chloride, is finally dried in vacuo in 120 DEG C of baking oven
Obtain MOF/MOP/ hydroxide composite membrane.
The composite membrane of preparation is subjected to infiltration evaporation performance test, test system is toluene/n-heptane (1:1) mixture,
Feeding liquid temperature is 40 DEG C.
The performance of the saturating toluene of the composite membrane measured is as follows: flux is 382g/ (m2H), separation factor 3.4.
Embodiment 4
Compound membrane preparation method:
(1) ceramic bases are pre-processed: weighs 50mmol trishydroxymethylaminomethane, 2g Dopamine hydrochloride, 5mmol
CuSO4With 19.6mmol H2O2It is dissolved in 1000mL deionized water, substrate is impregnated in 10min in prepared solution, use
A large amount of deionized water is rinsed and is impregnated repeatedly, until not fading, is dried in vacuo in 50 DEG C of baking ovens.
(2) compound concentration is 0.2mol/L Co (NO3)2·6(H2O) and the solution of 0.2mol/L hexa, mix
It carries out being stirred by ultrasonic uniformly after conjunction；Ceramic bases are placed in precursor solution, 9h are reacted in 90 DEG C of baking oven, after taking-up
It is rinsed with deionized water and impregnates and be dried in vacuo, obtain Co (OH)2Film.
(3) it weighs 330mg tBu-MOP to be dissolved in 120mL N-Methyl pyrrolidone, be made very by the method for taking out negative pressure
Reciprocal of duty cycle reaches 0.095MPa, makes Co (OH) after carrying out 5min2A certain amount of tBu-MOP particle is filled in nanometer sheet.
(4) it weighs 0.39g benzimidazole and is dissolved in 60mLN, in dinethylformamide, ultrasonic agitation keeps it all molten
Solution.It transfers the solution into reaction kettle, and by tBu-MOP/Co (OH)2Film is placed in ligand solution, in 135 DEG C of baking oven
Reaction is for 24 hours.It is rinsed well after taking-up with DMF, and is activated with DMF and methylene chloride, is finally dried in vacuo in 120 DEG C of baking oven
Obtain MOF/MOP/ hydroxide composite membrane.
The composite membrane of preparation is subjected to infiltration evaporation performance test, test system is toluene/n-heptane (1:1) mixture,
Feeding liquid temperature is 40 DEG C.
The performance of the saturating toluene of the composite membrane measured is as follows: flux is 254g/ (m2H), separation factor 2.1.
Claims (10)
1. a kind of preparation method of MOF/MOP/ metal hydroxides ceramic composite membrane, which comprises the following steps:
(1) ceramic bases cleaned up are impregnated in Dopamine hydrochloride solution and carry out 1~60min of pretreatment, used after taking-up
Deionized water washing is impregnated repeatedly up to washing away the free poly-dopamine in surface completely, is finally dried in vacuo in an oven；
(2) solute of precursor solution A needed for preparing metal hydroxides described in product, precursor solution A include can
Soluble metal salts and hexa；
(3) by treated, ceramic bases are placed in precursor solution A prepared by step (2), are put into reaction in baking oven and are carried out
Growth in situ；Through reaction after a period of time, film is used into deionized water repeated flushing after taking out in reaction kettle, is put into baking oven
It is dried in vacuo, obtains metal hydroxides nano-chip arrays film；
(4) MOP is dissolved in solvent and is stirred, MOP casting solution is made, is filled MOP by dynamic self-assembly membrane formation process
In metal hydroxides nano-chip arrays, metal hydroxides/MOP composite membrane is made；
(5) organic ligand precursor solution B needed for preparing MOF, precursor solution B use solvent B；
(6) metal hydroxides obtained/MOP composite membrane is placed in organic ligand precursor solution B prepared by step (5)
In, it is put into reaction in baking oven and is grown；Through reaction after a period of time, by film in step (5) after being taken out in reaction kettle
The solvent of use carries out repeated flushing, is put into baking oven and is dried in vacuo, obtains the particle stabilized metal hydroxides nanometer battle array of MOF
MOP film, that is, MOF/MOP/ metal hydroxides ceramic composite membrane of column auxiliary preparation.
2. according to the method for claim 1, which is characterized in that metal hydroxides is selected from Co (OH)2With Ni (OH)2。
3. according to the method for claim 1, which is characterized in that the concentration of metal salt is 0.02mol/L in precursor solution A
The molar concentration of~0.06mol/L, metal salt and hexa is 3:1-1:3.
4. according to the method for claim 1, which is characterized in that ceramic substrate material Al2O3、TiO2、ZrO2Or SiO2Oxygen
Compound, there is three kinds of plate, tubular type and doughnut forms, and the ceramic pipe type substrate aperture is between 10 nanometers to 1 micron.
5. according to the method for claim 1, which is characterized in that the reaction temperature of growth in situ described in step (3) is
80 DEG C~120 DEG C, the reaction time is 1h~for 24 hours.
6. according to the method for claim 1, which is characterized in that molecule base MOP is selected from tBu-MOP, SO3- MOP and OH-MOP
One or more of；The concentration of casting solution described in step (4) is 1.7g/L~5.5g/L, and the time of dynamic self-assembly is
5min~10min.
7. according to the method for claim 1, which is characterized in that in step (5) concentration of organic ligand be 0.02mol/L~
0.05mol/L, MOP stablize in solvent B.
8. according to the method for claim 1, which is characterized in that MOF described in step (6) growth reaction temperature be
100 DEG C~135 DEG C, reaction temperature is 1h~48h.
9. the MOF/MOP/ metal hydroxides Ceramic Composite being prepared according to the described in any item methods of claim 1-8
Film.
10. the MOF/MOP/ metal hydroxides Ceramic Composite being prepared according to the described in any item methods of claim 1-8
The application of film, for aromatic hydrocarbons/alkane system infiltration evaporation separation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811243967.7A CN109316977B (en) | 2018-10-24 | 2018-10-24 | A kind of MOF/MOP/metal hydroxide ceramic composite membrane and preparation method |
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| CN104415670A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework membrane and preparation method and application thereof |
| CN105233702A (en) * | 2015-10-17 | 2016-01-13 | 大连理工大学 | Preparation method for forming metal organic framework ZIF-67 film by utilizing cobalt nano array layer conversion |
| WO2017004682A1 (en) * | 2015-07-08 | 2017-01-12 | Commonwealth Scientific And Industrial Research Organisation | Composition and system for gas storage |
| CN108579468A (en) * | 2018-04-18 | 2018-09-28 | 北京工业大学 | A kind of MOP/ hydroxide ceramics composite membrane, preparation method and application |
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| CN104415670A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework membrane and preparation method and application thereof |
| WO2017004682A1 (en) * | 2015-07-08 | 2017-01-12 | Commonwealth Scientific And Industrial Research Organisation | Composition and system for gas storage |
| CN105233702A (en) * | 2015-10-17 | 2016-01-13 | 大连理工大学 | Preparation method for forming metal organic framework ZIF-67 film by utilizing cobalt nano array layer conversion |
| CN108579468A (en) * | 2018-04-18 | 2018-09-28 | 北京工业大学 | A kind of MOP/ hydroxide ceramics composite membrane, preparation method and application |
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| CN114392653A (en) * | 2021-12-31 | 2022-04-26 | 大连海川博创环保科技有限公司 | Spraying industry waste gas treatment method taking ozone catalytic function ceramic membrane as catalytic separation material |
| CN114392653B (en) * | 2021-12-31 | 2024-01-12 | 大连海川博创环保科技有限公司 | Waste gas treatment method for spraying industry by taking ozone catalytic functional ceramic membrane as catalytic separation material |
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