CN107638808A - A kind of method of ultra-thin two-dimension nano material repairing molecular screen membrane defect - Google Patents
A kind of method of ultra-thin two-dimension nano material repairing molecular screen membrane defect Download PDFInfo
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- CN107638808A CN107638808A CN201710990260.1A CN201710990260A CN107638808A CN 107638808 A CN107638808 A CN 107638808A CN 201710990260 A CN201710990260 A CN 201710990260A CN 107638808 A CN107638808 A CN 107638808A
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Abstract
Ultra-thin two-dimension nano material repairing molecular screen membrane defect is used to improve the method for its Steam soak separation selectivity the present invention relates to a kind of.Transient metal sulfide two-dimensional material is scattered in N vinyl pyrrolidones（NVP）In solution, transient metal sulfide ultrathin nanometer piece is obtained by ultrasound, centrifugation, then wash away NVP with isopropanol and be configured to transient metal sulfide nanometer sheet/isopropanol modification solution.Four-way hollow fiber molecular sieve one end is sealed with fluid sealant, the other end is connected by fluid sealant with glass tube, and molecular screen membrane is immersed in modification solution, and it is sucked by vacuum.The present invention is adsorbed transient metal sulfide nanometer sheet around defect using the capillary force of molecular screen membrane intergranular defect, and then so as to effectively reduce the intergranular defect pore size of film.The separation selectivity conspicuousness of molecular screen membrane after being modified using this method is improved, and flux fall is smaller, and segregational stability is good.
Description
Technical field
The present invention relates to a kind of method and device of decorating molecule sieve membrane intergranular defect, more particularly to a kind of raising molecular sieve
Film Steam soak improves the method and device of dehydration of organic solvent separation selectivity energy, belongs to moisture vapor permeable molecule sieve membrane application
Field.
Background technology
Organic solvent has very important status in modern industry, is widely used in chemical industry, food, medicine, environmental protection
The demand of organic solvent is increasingly increased with field, every profession and trades such as electronics.It is chemistry that organic solvent, which is produced and processed and recycled,
Industrial important component.In the production of organic solvent and during recycling, often because technique, reaction etc. it is various because
Element, cause to introduce plurality of impurities in solvent, and most common of which impurity is water, its content is most and is difficult to remove.It is organic molten
The dehydration and purifying of agent are a very universal and important processes in commercial Application.Some organic solvents are easily formed closely with water
Boiling or azeotropic mixture, separated for this kind of mixture, conventional isolation technics, such as azeotropic distillation, compression rectification, extraction essence
Evaporate and adsorb, there is low benefit, high energy consumption, technological process complexity, and it is often huge with environmental pollution, environmental protection pressure
Greatly.Therefore, production efficiency and cyclic utilization rate, the reduction production process energy consumption and reduction waste discharge of organic solvent how to be improved
Have become the focus of global industry circle concern, and the innovation for strengthening high-purity dehydration of organic solvent technology turns into industry lifting
One important channel.
Molecular screen membrane Steam soak dehydration technique is a kind of new UF membrane dehydration technique, has product purity height, sets
The standby advantage such as floor space is small, process is easily controllable, simple to operate and environmental pollution is small.Because molecular screen membrane is molecular sieve crystal
Formed on porous supporting body surface by Hydrothermal Synthesiss intergrowth, the different chis such as gap, crack are also easy to produce between film layer crystal
The defects of very little duct.When NaA molecular sieve membrane, which is used for dehydration of organic solvent, to be separated, one side NaA molecular sieve membrane has one in itself
A little intergranular defects, on the other hand when feed water content it is very low when molecular screen membrane structure cell can shrink and cause film the defects of become big,
It is very poor so as to the Steam soak separating effect of film.Have for the permeable molecular screen membrane development intergranular defect modification technique of existing defects
Beneficial to the separating property for improving film, the application cost of film is saved, promotes the popularization and application of film.
The content of the invention
The present invention is repaiied by transient metal sulfide nanometer sheet decorating molecule sieve membrane to molecular screen membrane intergranular defect
Mend, to improve its separation selectivity to dehydration of organic solvent.
The first aspect of the invention, there is provided：
A kind of molecular screen membrane, transient metal sulfide nanometer sheet is filled with the surface defect of molecular screen membrane.
In one embodiment, the transition metal in described transient metal sulfide more preferably from IV B races, V B races,
VI B races, VII B races, VIII, I B races element；More preferably IV B races, V B races, group vib, VII B races element；Further preferably
For VI B races element.
In one embodiment, transient metal sulfide preferably is selected from molybdenum disulfide, tungsten disulfide, titanium disulfide or two sulphur
Change niobium.
In one embodiment, described molecular screen membrane refers to NaA, T-shaped, CHA, ZSM-5, MOR, NaY molecular sieve film.
In one embodiment, the pattern of described transient metal sulfide nanometer sheet is individual layer sheet, and equivalent diameter is big
It is small in 50~80nm.
In one embodiment, described molecular screen membrane is carried on supporter, the configuration molecular screen membrane branch of supporter
Support body type body is configured as chip, tubular type or hollow fiber form.
The second aspect of the invention, there is provided：
A kind of dispersion liquid for molecular screen membrane repairing, it is dispersion liquid of the transient metal sulfide nanometer sheet in alcohols solvent.
In one embodiment, described alcohols solvent is one or more of mixed in methanol, ethanol or isopropanol
Close.
The third aspect of the invention, there is provided：
A kind of preparation method of dispersion liquid for molecular screen membrane repairing, comprises the following steps：By transient metal sulfide powder
It is dispersed in NVP（NVP）In, handled in the presence of ultrasound, then take and contain by centrifugal treating again
There is the supernatant of the transient metal sulfide nanometer sheet of stripping；Supernatant is cleaned with alcohols solvent, gets rid of Transition Metal Sulfur
NVP in compound nanometer sheet, obtain the dispersion liquid for molecular screen membrane repairing.
In one embodiment, described transient metal sulfide powder and NVP（NVP）Weight
Volume ratio is 10~50mg：10~100ml.
In one embodiment, ultrasonic 1~10h of action time；The time of centrifugal treating is 5~20min.
The fourth aspect of the invention, there is provided：
A kind of method for repairing and mending of molecular screen membrane, comprises the following steps：
Molecular screen membrane is dipped in dispersion liquid, by way of negative-pressure ward, transient metal sulfide nanometer sheet is filled in point
In the defects of sub- sieve membrane surface；Molecular screen membrane is taken out again, dried.
In one embodiment, above-mentioned method for repairing and mending can be repeated several times.
In one embodiment, the time of negative-pressure ward is 1~10h.
In one embodiment, baking step is dried 1~20 hour in 60~90 DEG C of baking oven.
The fifth aspect of the invention, there is provided：
Application of the above-mentioned molecular screen membrane in infiltration evaporation or Steam soak process.
In one embodiment, described application, solvent dehydration process is referred to.
In one embodiment, described solvent is in alcohols solvent, esters solvent, ether solvent or benzene kind solvent
One or more of mixing.
In one embodiment, 100~120 DEG C of feeding temperature in infiltration evaporation or Steam soak process, per-meate side
Absolute pressure is 10~3000Pa.
The sixth aspect of the invention, there is provided：
Above-mentioned dispersion liquid is for repairing the application in molecular screen membrane surface defect.
Beneficial effect
The present invention is using transient metal sulfide nanometer sheet as modification source, and molecular screen membrane intergranular defect is due to capillary force Preferential adsorption
Transient metal sulfide nanometer sheet, reduce intergranular defect, so as to reach the purpose of decorating molecule sieve membrane.This method operation letter
Just, it is not necessary to which the experimental provision especially processed, the separation selectivity of the molecular screen membrane through this method modification can significantly improve.
Brief description of the drawings
Fig. 1 is the installation drawing used；
Fig. 2 is individual layer two-dimensional material WS2Transmission electron microscope picture；
Fig. 3 is individual layer two-dimensional material W S2Transmission electron microscope picture；
Fig. 4 is NaA molecular sieve membrane surface electromicroscopic photograph before modification；
Fig. 5 is NaA molecular sieve membrane surface electromicroscopic photograph after modification；
Fig. 6 is the ethanol/water system Steam soak separating property that the front and rear NaA molecular sieve membrane of modification is used for different material water content
Contrast；
Fig. 7 is the isopropanol/water system Steam soak separation property that the front and rear NaA molecular sieve membrane of modification is used for different material water content
Can contrast；
Embodiment
The present invention is described in further detail below by embodiment.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted specific skill in embodiment
Art or condition person, carried out according to the technology described by document in the art or condition or according to product description.Examination used
Agent or the unreceipted production firm person of instrument, being can be by the conventional products of acquisition purchased in market.Word " comprising " used herein,
"comprising", " having " or its any other variant are intended to cover including for non-exclusionism.E.g., including list key element technique,
Method, article or equipment are not necessarily limited by those key elements, but can be not expressly set out including other or belong to this work
Skill, method, article or the intrinsic key element of equipment.
In technical scheme provided by the invention, can be used for repair molecular screen membrane surface the defects of, here the defects of refer to
The various sizes of defect duct such as caused gap, crack between film layer crystal, after surface defect occurs in molecular screen membrane, it may appear that
The problems such as separation factor declines.Here molecular screen membrane can refer to NaA, T-shaped, CHA, ZSM-5, MOR, NaY molecular sieve film etc..
In method for repairing and mending of the present invention, transient metal sulfide nanometer sheet is employed as main healant,
Two-dimensional material of the transient metal sulfide as individual layer, it has hydrophily, and NaA molecular sieve membrane surface is also hydrophilic, is had
Preferable surface combines effect.
The transition metal in transient metal sulfide used in the present invention is mainly selected from IV B races, V B races, VI B
Race, VII B races, VIII B races, I B races element；More preferably IV B races, V B races, VI races, VII B races element.
Under the conditions of more preferable, transient metal sulfide is molybdenum disulfide, tungsten disulfide, titanium disulfide or curing
Niobium.
Here transient metal sulfide nanometer sheet in use is dispersed in alcohols solvent, forms dispersion liquid,
Described alcohols solvent is one or more of mixing in methanol, ethanol or isopropanol.The preparation method of this dispersion liquid,
Comprise the following steps：Transient metal sulfide powder is dispersed in NVP（NVP）In, in the presence of ultrasound
Handled, two-dimensional material can be peeled off by ultrasound into individual layer, thickness only has 1~2 nanometer, then passes through centrifugation again
Processing, take the supernatant containing the transient metal sulfide nanometer sheet peeled off；Supernatant is cleaned with alcohols solvent, got rid of
The NVP crossed in nano metal sulfide piece, obtain the dispersion liquid for molecular screen membrane repairing.Preferable
In embodiment, transient metal sulfide powder and NVP（NVP）W/v be 10~50mg：10
~100ml；1~10h of action time of ultrasound；The time of centrifugal treating is 5~20min.By can be two-dimentional material by ultrasound
Material is peeled off into individual layer, and thickness only has 1~2 nanometer, and the defects of NaA molecular sieve membrane typically within several nanometers, so
Just decorative material can be embedded in defect or in blemish surface by suction.
Based on above-mentioned repairing dispersion liquid, the method for repairing and mending step of molecular screen membrane provided by the invention is：By molecular sieve
Film is dipped in dispersion liquid, by way of negative-pressure ward, transient metal sulfide nanometer sheet is filled in molecular screen membrane surface
In defect；Molecular screen membrane is taken out again, dried.In order that method for repairing and mending is more preferable, above-mentioned method for repairing and mending can be repeated several times, excellent
In the embodiment of choosing, the time of negative-pressure ward is 1~10h, and baking step is that drying 1~20 is small in 60~90 DEG C of baking oven
When.
Molecular screen membrane is more preferable applied to that can be shown in infiltration evaporation or Steam soak process after repairing is passed through
Separating effect, separation process here includes but is not limited to solvent dehydration process, and solvent here can be alcohols solvent, ester
One or more of mixing in class solvent, ether solvent or benzene kind solvent, in some embodiments, infiltration evaporation or
100~120 DEG C of feeding temperature in Steam soak process, the absolute pressure of per-meate side is 10~3000Pa.
Embodiment 1
The preparation of repairing tungsten disulfide dispersion liquid：
30mg tungsten disulphide powders are dispersed in 60ml NVPs（NVP）In, surpassed with ultrasonic cell disrupte machine
Sound, by dispersion ultrasound 4h under 400W.Sample is centrifuged into 10min with 10000rpm after supersound process, taken containing two sulphur peeled off
Change the supernatant of tungsten, after addition isopropanol is well mixed, then by centrifuging removal upper strata NVP, lower floor is obtained containing two peeled off
The precipitation of tungsten sulfide, then cleaned with isopropanol, separated repeatedly, to remove NVP solution, prepare containing the different of tungsten disulfide nano slices
Propanol dispersion liquor.Nanometer sheet is characterized by transmission electron microscope, as shown in Figures 2 and 3, tungsten disulfide is individual layer sheet knot
Structure, equivalent diameter size show hexagon lattice structure in 50~80nm or so, tungsten disulfide material, and lattice constant is
0.32nm, illustrate that supersound process will not reduce WS2The hexagonal structure of material.
The repairing of NaA molecular sieve membrane：
Using device as shown in Figure 1.
Tube-type hollow fiber NaA molecular sieve membrane is placed in baking oven, 70 DEG C of dryings 10 hours.
As shown in figure 3, modification before NaA molecular sieve membrane surface in addition to containing substantial amounts of sieve particle, include perhaps
More intergranular pore channels.
Doughnut NaA molecular sieve membrane one end is sealed, other end connection vavuum pump, is put into modification solution, vacuum is taken out
Inhale 10 hours.NaA molecular sieve membrane after modification is placed in baking oven, 70 DEG C of dryings 10 hours.
NaA molecular sieve membrane surface electromicroscopic photograph after modification is as shown in Figure 5.From fig. 4 it can be seen that modified through tungsten disulfide
Molecular screen membrane surface is because multi-time modification nanometer sheet is deposited on around defect after the repairing that time is 10 hours, compared with Fig. 4, figure
5 intergranular pore channels have effectively reduced.
Steam soak characterizes experiment：
Using investigation of the molecular screen membrane Steam soak before and after modification to the separation selectivity energy of ethanol/water system, operating condition：Enter
100 DEG C of material temperature degree, the absolute pressure of per-meate side is 100Pa, as shown in fig. 6, can be most to the separation selectivity of ethanol/water system after modification
Height improves 8 times.
Steam soak experiment, operating condition are done to isopropanol/water using the front and rear doughnut NaA molecular sieve membrane of modification：
100 DEG C of feeding temperature, the absolute pressure of per-meate side is 100Pa, as shown in fig. 7, to the separation selectivity of isopropanol/water system after modification
Energy highest improves 12 times.
Embodiment 2
The preparation of repairing titanium disulfide dispersion liquid：
20mg titanium disulfides end is dispersed in 80ml NVPs（NVP）In, it is ultrasonic with ultrasonic cell disrupte machine,
By dispersion ultrasound 3h under 600W.Sample is centrifuged into 15min with 12000rpm after supersound process, taken containing the titanium disulfide peeled off
Supernatant, add isopropanol it is well mixed after, then by centrifuging remove upper strata NVP, lower floor obtains the curing containing stripping
The precipitation of titanium, then cleaned with isopropanol, separated repeatedly, to remove NVP solution, prepare the isopropanol containing titanium disulfide nanometer sheet
Dispersion liquid.
The repairing of NaA molecular sieve membrane：
Using device as shown in Figure 1.
Tube-type hollow fiber NaA molecular sieve membrane is placed in baking oven, 80 DEG C of dryings 8 hours.
Doughnut NaA molecular sieve membrane one end is sealed, other end connection vavuum pump, is put into modification solution, vacuum is taken out
Inhale 10 hours.NaA molecular sieve membrane after modification is placed in baking oven, 65 DEG C of dryings 8 hours.
Steam soak characterizes experiment：
Using investigation of the molecular screen membrane Steam soak before and after modification to the separation selectivity energy of ethanol/water system, operating condition：Enter
110 DEG C of material temperature degree, the absolute pressure of per-meate side is 200Pa, and 6 are improved to the separation selectivity energy highest of ethanol/water system after modification
Times.
Steam soak experiment, operating condition are done to isopropanol/water using the front and rear doughnut NaA molecular sieve membrane of modification：
105 DEG C of feeding temperature, the absolute pressure of per-meate side is 500Pa, and the separation selectivity energy highest of isopropanol/water system is lifted after modification
7 times.
Embodiment 3
The preparation of repairing molybdenum disulfide dispersion liquid：
10mg molybdenum disulfide powders are dispersed in 80ml NVPs（NVP）In, surpassed with ultrasonic cell disrupte machine
Sound, by dispersion ultrasound 6h under 300W.Sample is centrifuged into 10min with 8000rpm after supersound process, taken containing the curing peeled off
The supernatant of molybdenum, after addition isopropanol is well mixed, then by centrifuging removal upper strata NVP, lower floor is obtained containing two sulphur peeled off
Change the precipitation of molybdenum, then cleaned, separated repeatedly with isopropanol, to remove NVP solution, prepare the isopropyl containing molybdenum disulfide nano sheet
Alcohol dispersion liquid.
The repairing of NaA molecular sieve membrane：
Using device as shown in Figure 1.
Tube-type hollow fiber NaA molecular sieve membrane is placed in baking oven, 60 DEG C of dryings 9 hours.
Doughnut NaA molecular sieve membrane one end is sealed, other end connection vavuum pump, is put into modification solution, vacuum is taken out
Inhale 7 hours.NaA molecular sieve membrane after modification is placed in baking oven, 75 DEG C of dryings 6 hours.
Steam soak characterizes experiment：
Using investigation of the molecular screen membrane Steam soak before and after modification to the separation selectivity energy of ethanol/water system, operating condition：Enter
105 DEG C of material temperature degree, the absolute pressure of per-meate side is 600Pa, and 5 are improved to the separation selectivity energy highest of ethanol/water system after modification
Times.
Steam soak experiment, operating condition are done to isopropanol/water using the front and rear doughnut NaA molecular sieve membrane of modification：
110 DEG C of feeding temperature, the absolute pressure of per-meate side is 300Pa, and the separation selectivity energy highest of isopropanol/water system is lifted after modification
7 times.
Embodiment 4
The preparation of repairing curing niobium dispersion liquid：
40mg curing niobium powders are dispersed in 50ml NVPs（NVP）In, surpassed with ultrasonic cell disrupte machine
Sound, by dispersion ultrasound 6h under 200W.Sample is centrifuged into 5min with 15000rpm after supersound process, taken containing the curing peeled off
The supernatant of niobium, after addition isopropanol is well mixed, then by centrifuging removal upper strata NVP, lower floor is obtained containing two sulphur peeled off
Change the precipitation of niobium, then cleaned, separated repeatedly with isopropanol, to remove NVP solution, prepare the isopropyl containing curing niobium nanometer sheet
Alcohol dispersion liquid.
The repairing of NaA molecular sieve membrane：
Using device as shown in Figure 1.
Tube-type hollow fiber NaA molecular sieve membrane is placed in baking oven, 80 DEG C of dryings 6 hours.
Doughnut NaA molecular sieve membrane one end is sealed, other end connection vavuum pump, is put into modification solution, vacuum is taken out
Inhale 6 hours.NaA molecular sieve membrane after modification is placed in baking oven, 80 DEG C of dryings 8 hours.
Steam soak characterizes experiment：
Using investigation of the molecular screen membrane Steam soak before and after modification to the separation selectivity energy of ethanol/water system, operating condition：Enter
120 DEG C of material temperature degree, the absolute pressure of per-meate side is 600Pa, and 4 are improved to the separation selectivity energy highest of ethanol/water system after 2 modifications
Times.
Steam soak experiment, operating condition are done to isopropanol/water using the front and rear doughnut NaA molecular sieve membrane of modification：
115 DEG C of feeding temperature, the absolute pressure of per-meate side is 350Pa, and the separation selectivity energy highest of isopropanol/water system is lifted after modification
8 times.
Claims (10)
1. a kind of molecular screen membrane, it is characterised in that transient metal sulfide nanometer is filled with the surface defect of molecular screen membrane
Piece.
2. molecular screen membrane according to claim 1, it is characterised in that the transition metal in described transient metal sulfide
It preferably is selected from IV B races, V B races, VI B races, VII B races, VIII B races, I B races element；In described transient metal sulfide
Transition metal is more preferably IV B races, V B races, VI races, VII B races element.
3. molecular screen membrane according to claim 1, it is characterised in that described molecular screen membrane refer to NaA, T-shaped, CHA,
ZSM-5, MOR, NaY molecular sieve film etc.；The pattern of described transient metal sulfide nanometer sheet is individual layer sheet, and equivalent diameter is big
It is small in 50~80nm；Described molecular screen membrane is carried on supporter, the configuration molecular screen membrane support build body structure of supporter
Type is chip, tubular type or hollow fiber form.
4. a kind of dispersion liquid for molecular screen membrane repairing, it is characterised in that refer to transient metal sulfide nanometer sheet in alcohols
Dispersion liquid in solvent；Described alcohols solvent is one or more of mixing in methanol, ethanol or isopropanol.
5. the preparation method of the dispersion liquid for being used for molecular screen membrane repairing described in claim 4, it is characterised in that including following step
Suddenly：Transient metal sulfide powder is dispersed in NVP（NVP）In, handled in the presence of ultrasound,
Then the supernatant containing the transient metal sulfide nanometer sheet peeled off is taken by centrifugal treating again；Supernatant alcohols is molten
Agent is cleaned, and gets rid of the NVP in transient metal sulfide nanometer sheet, is obtained for molecular screen membrane repairing
Dispersion liquid；Described transient metal sulfide powder and NVP（NVP）W/v be 10~50mg：
10~100ml；1~10h of action time of ultrasound；The time of centrifugal treating is 5~20min.
6. a kind of method for repairing and mending of molecular screen membrane, it is characterised in that comprise the following steps：Molecular screen membrane is dipped in claim 4
In described dispersion liquid, by way of negative-pressure ward, transient metal sulfide nanometer sheet is set to be filled in molecular screen membrane surface
In defect；Molecular screen membrane is taken out again, dried.
7. the method for repairing and mending of molecular screen membrane according to claim 6, it is characterised in that method for repairing and mending is repeatedly；Negative pressure
The time of suction is 1~10h；Baking step is dried 1~20 hour in 60~90 DEG C of baking oven.
8. application of the molecular screen membrane in infiltration evaporation or Steam soak process described in claim 1.
9. application according to claim 8, it is characterised in that refer to solvent dehydration process；Described solvent is selected from alcohols
One or more of mixing in solvent, esters solvent, ether solvent or benzene kind solvent；Infiltration evaporation or vapor permeability
100~120 DEG C of feeding temperature in journey, the absolute pressure of per-meate side is 10~3000Pa.
10. the dispersion liquid described in claim 4 is for repairing the application in molecular screen membrane surface defect.
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| CN115986125A (en) * | 2023-03-15 | 2023-04-18 | 中国华能集团清洁能源技术研究院有限公司 | Two-dimensional transition metal sulfide catalyst and lithium-sulfur battery based on same |
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| CN110280146A (en) * | 2019-06-14 | 2019-09-27 | 南京工业大学 | A kind of method that three-dimensional netted organic flexible material repairs molecular screen membrane defect |
| CN110280146B (en) * | 2019-06-14 | 2021-12-17 | 南京工业大学 | Method for repairing defects of molecular sieve membrane by using three-dimensional mesh organic flexible material |
| CN115986125A (en) * | 2023-03-15 | 2023-04-18 | 中国华能集团清洁能源技术研究院有限公司 | Two-dimensional transition metal sulfide catalyst and lithium-sulfur battery based on same |
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| CN107638808B (en) | 2019-10-15 |
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