CN107638808B - 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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Abstract
The present invention relates to a kind of methods for using ultra-thin two-dimension nano material repairing molecular screen membrane defect to improve its Steam soak separation selectivity.It disperses transient metal sulfide two-dimensional material in n-vinyl pyrrolidone (NVP) solution, transient metal sulfide ultrathin nanometer piece is obtained by ultrasound, centrifugation, then washes away NVP with isopropanol and is configured to transient metal sulfide nanometer sheet/isopropanol modification solution.Four-way hollow fiber molecular sieve one end is sealed with sealant, the other end is connected by sealant with glass tube, and molecular screen membrane immerses in modification solution, is sucked by vacuum to it.Transient metal sulfide nanometer sheet is adsorbed on around defect by the present invention using the capillary force of molecular screen membrane intergranular defect, and then 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 sieves
Film Steam soak improves the method and device of dehydration of organic solvent separation selectivity energy, belongs to the sieve membrane application of moisture vapor permeable molecule
Field.
Background technique
Organic solvent has very important status in modern industry, is widely used in chemical industry, food, medicine, environmental protection
Increasingly increase with fields, demand of the every profession and trade to organic solvent such as electronics.Organic solvent production and processing and recycling are chemistry
Industrial important component.In the production of organic solvent and during recycle, often because technique, reaction etc. it is various because
Element causes to introduce plurality of impurities in solvent, and one of the most common impurity is water, and 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 industrial application.Some organic solvents are easy to be formed closely with water
Boiling or azeotropic mixture separate, conventional isolation technics for this knd of mixture, such as azeotropic distillation, compression rectification, extraction essence
It evaporates and adsorbs, have the shortcomings that benefit is low, energy consumption is high, process flow is complicated, and often with environmental pollution, environmental protection pressure is huge
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
The innovation for having become the hot spot of global industry circle concern, and reinforcing high-purity dehydration of organic solvent technology becomes what industry was promoted
One important channel.
Molecular screen membrane Steam soak dehydration technique is a kind of novel UF membrane dehydration technique, has product purity height, sets
The standby advantages such as occupied area is small, process is easily controllable, easy to operate and environmental pollution is small.Since molecular screen membrane is molecular sieve crystal
It is formed on porous supporting body surface by hydrothermal synthesis intergrowth, the different rulers such as gap, crack is also easy to produce between film layer crystal
Very little defect duct.When NaA molecular sieve membrane is separated for dehydration of organic solvent, there are one for one side NaA molecular sieve membrane 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 the defect of film is caused to become larger,
To which the Steam soak separating effect of film is very poor.Have for the permeable molecular screen membrane development intergranular defect modification technique of existing defects
Conducive to the separating property for improving film, the application cost of film is saved, the popularization and application of film are promoted.
Summary of the invention
The present invention repairs molecular screen membrane intergranular defect by transient metal sulfide nanometer sheet decorating molecule sieve membrane
It mends, to improve its separation selectivity to dehydration of organic solvent.
The first aspect of the invention provides:
A kind of molecular screen membrane is filled with transient metal sulfide nanometer sheet at the surface defect of molecular screen membrane.
In one embodiment, the transition metal in the transient metal sulfide more preferably from IV B race, V B race,
VI B race, VII B race, VIII group, I B race element；More preferably IV B race, V B race, group vib, VII B race element；Further preferably
For VI B race 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, the molecular screen membrane refers to NaA, T-type, CHA, ZSM-5, MOR, NaY molecular sieve film.
In one embodiment, the pattern of the transient metal sulfide nanometer sheet is single layer sheet, and equivalent diameter is big
It is small in 50~80nm.
In one embodiment, the 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 provides:
A kind of dispersion liquid for molecular screen membrane repairing, is dispersion of the transient metal sulfide nanometer sheet in alcohols solvent
Liquid.
In one embodiment, the alcohols solvent is the mixed of one or more of methanol, ethyl alcohol or isopropanol
It closes.
The third aspect of the invention provides:
A kind of preparation method of the dispersion liquid for molecular screen membrane repairing, includes the following steps: transient metal sulfide
Powder is dispersed in n-vinyl pyrrolidone (NVP), is handled under the action of ultrasound, then passes through centrifugal treating again,
Take the supernatant of the transient metal sulfide nanometer sheet containing removing；Supernatant is cleaned with alcohols solvent, gets rid of transition gold
Belong to the n-vinyl pyrrolidone in sulfide nanometer sheet, obtains the dispersion liquid repaired for molecular screen membrane.
In one embodiment, the weight of the transient metal sulfide powder and n-vinyl pyrrolidone (NVP)
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 provides:
A kind of method for repairing and mending of molecular screen membrane, includes the following steps:
Molecular screen membrane is dipped in dispersion liquid, by way of negative-pressure ward, fills transient metal sulfide nanometer sheet
In the defect on molecular screen membrane surface；Molecular screen membrane is taken out again, drying.
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 provides:
Application of the above-mentioned molecular screen membrane in infiltration evaporation or Steam soak process.
In one embodiment, the application refers to solvent dehydration process.
In one embodiment, the 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 provides:
Above-mentioned dispersion liquid is for repairing the application in molecular screen membrane surface defect.
Beneficial effect
For the present invention using transient metal sulfide nanometer sheet as modification source, molecular screen membrane intergranular defect is preferential due to capillary force
Transient metal sulfide nanometer sheet is adsorbed, reduces intergranular defect, to achieve the purpose that decorating molecule sieve membrane.This method operation
Simplicity does not need the experimental provision especially processed, and the separation selectivity of the molecular screen membrane through this method modification can significantly improve.
Detailed description of the invention
Fig. 1 is the device figure used；
Fig. 2 is single layer two-dimensional material WS2Transmission electron microscope picture；
Fig. 3 is single layer two-dimensional material W S2Transmission electron microscope picture；
Fig. 4 is NaA molecular sieve film surface electromicroscopic photograph before modifying；
Fig. 5 is NaA molecular sieve film surface electromicroscopic photograph after modification；
Fig. 6 is that ethanol/water system Steam soak of the NaA molecular sieve membrane of modification front and back for different material water content separates
Performance comparison；
Fig. 7 is isopropanol/water system Steam soak point of the NaA molecular sieve membrane for different material water content of modification front and back
From performance comparison；
Specific embodiment
Below by specific embodiment, invention is further described in detail.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.Specific skill is not specified in embodiment
Art or condition person described technology or conditions or carry out according to the literature in the art according to product description.Examination used
Production firm person is not specified in agent or instrument, and being can be with conventional products that are commercially available.Word " comprising " used herein,
What "comprising", " having " or its any other variant were intended to cover non-exclusionism includes.E.g., including list element technique,
Method, article or equipment are not necessarily limited by those elements, but may include that other are not explicitly listed or belong to this work
Skill, method, article or the intrinsic element of equipment.
In technical solution provided by the invention, it can be used for repairing the defect on molecular screen membrane surface, defect here refers to
The various sizes of defect duct such as the gap, the crack that are generated 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-type, 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 used as main healant,
Two-dimensional material of the transient metal sulfide as single layer, with hydrophily, NaA molecular sieve film surface be also it is hydrophilic, have
Preferable surface combines effect.
Transition metal in transient metal sulfide used in the present invention is mainly selected from IV B race, V B race, VI B
Race, VII B race, VIII B race, I B race element；More preferably IV B race, V B race, VI race, VII B race element.
Under the conditions of more preferred, 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,
The alcohols solvent is the mixing of one or more of methanol, ethyl alcohol or isopropanol.The preparation method of this dispersion liquid,
Include the following steps: to be dispersed in transient metal sulfide powder in n-vinyl pyrrolidone (NVP), under the action of ultrasound
It is handled, two-dimensional material can be removed into single layer by ultrasound, thickness only has 1~2 nanometer, then passes through centrifugation again
Processing takes the supernatant of the transient metal sulfide nanometer sheet containing removing；Supernatant is cleaned with alcohols solvent, was got rid of
The n-vinyl pyrrolidone in nano metal sulfide piece is crossed, the dispersion liquid repaired for molecular screen membrane is obtained.Preferred
In embodiment, the w/v of transient metal sulfide powder and n-vinyl pyrrolidone (NVP) are 10~50mg:10
~100ml；1~10h of action time of ultrasound；The time of centrifugal treating is 5~20min.It can be two-dimentional material by passing through ultrasound
At single layer, thickness only has 1~2 nanometer for material removing, and the defect of NaA molecular sieve membrane is generally within several nanometers, in this way
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 made to be filled in molecular screen membrane surface
In defect；Molecular screen membrane is taken out again, drying.In order to keep method for repairing and mending more preferable, above-mentioned method for repairing and mending be 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 show in infiltration evaporation or Steam soak process after passing through repairing
Separating effect, separation process here includes but is not limited to solvent dehydration process, and solvent here can be alcohols solvent, ester
The mixing of one or more of 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 are 10~3000Pa.
Embodiment 1
The repairing preparation of tungsten disulfide dispersion liquid:
30mg tungsten disulphide powder is dispersed in 60ml n-vinyl pyrrolidone (NVP), with ultrasonic cell disrupte machine
Ultrasound, by dispersion ultrasound 4h under 400W.Sample is centrifuged 10min with 10000rpm after ultrasonic treatment, takes two containing removing
Isopropanol is added after mixing in the supernatant of tungsten sulfide, then by centrifugation removal upper layer NVP, lower layer is obtained containing removing
The precipitating of tungsten disulfide, then cleaned with isopropanol, separated repeatedly, to remove NVP solution, preparation contains tungsten disulfide nano slices
Isopropanol dispersion liquid.Nanometer sheet is characterized by transmission electron microscope, as shown in Figures 2 and 3, tungsten disulfide is single layer sheet
Structure, for equivalent diameter size in 50~80nm or so, tungsten disulfide material shows that hexagon lattice structure, lattice constant are
0.32nm illustrates that ultrasonic treatment 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 drying 10 hours.
As shown in figure 3, the NaA molecular sieve film surface before modification is in addition to containing a large amount of sieve particle, it further include being permitted
More intergranular pore channels.
Doughnut NaA molecular sieve membrane one end is sealed, the other end connects vacuum pump, is put into modification solution, vacuum is taken out
It inhales 10 hours.NaA molecular sieve membrane after modification is placed in baking oven, 70 DEG C drying 10 hours.
NaA molecular sieve film surface electromicroscopic photograph after modification is as shown in Figure 5.From fig. 4 it can be seen that being modified through tungsten disulfide
Time compared with Fig. 4, schemes for molecular screen membrane surface after repairing in 10 hours since multi-time modification nanometer sheet is deposited on around defect
5 intergranular pore channels have effectively reduced.
Steam soak characterization experiment:
Investigation using modification front and back molecular screen membrane Steam soak to the separation selectivity energy of ethanol/water system, operates item
Part: 100 DEG C of feeding temperature, the absolute pressure of per-meate side is 100Pa, as shown in fig. 6, selecting after modification the separation of ethanol/water system
Performance highest improves 8 times.
Steam soak experiment is done to isopropanol/water using the doughnut NaA molecular sieve membrane of modification front and back, operating condition:
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.
The repairing preparation of titanium disulfide dispersion liquid:
20mg titanium disulfide end is dispersed in 80ml n-vinyl pyrrolidone (NVP), it is super with ultrasonic cell disrupte machine
Sound, by dispersion ultrasound 3h under 600W.Sample is centrifuged 15min with 12000rpm after ultrasonic treatment, takes two sulphur containing removing
Change the supernatant of titanium, isopropanol is added after mixing, then by centrifugation removal upper layer NVP, lower layer obtains two containing removing
The precipitating of titanium sulfide, then cleaned with isopropanol, separated repeatedly, to remove NVP solution, preparation contains the different of titanium disulfide nanometer sheet
Propanol dispersion liquor.
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 drying 8 hours.
Doughnut NaA molecular sieve membrane one end is sealed, the other end connects vacuum pump, is put into modification solution, vacuum is taken out
It inhales 10 hours.NaA molecular sieve membrane after modification is placed in baking oven, 65 DEG C drying 8 hours.
Steam soak characterization experiment:
Investigation using modification front and back molecular screen membrane Steam soak to the separation selectivity energy of ethanol/water system, operates item
Part: 110 DEG C of feeding temperature, the absolute pressure of per-meate side is 200Pa, is mentioned after modification to the separation selectivity energy highest of ethanol/water system
6 times are risen.
Steam soak experiment is done to isopropanol/water using the doughnut NaA molecular sieve membrane of modification front and back, operating condition:
105 DEG C of feeding temperature, the absolute pressure of per-meate side is 500Pa, is promoted after modification to the separation selectivity energy highest of isopropanol/water system
7 times.
Embodiment 3
The repairing preparation of molybdenum disulfide dispersion liquid:
10mg molybdenum disulfide powder is dispersed in 80ml n-vinyl pyrrolidone (NVP), with ultrasonic cell disrupte machine
Ultrasound, by dispersion ultrasound 6h under 300W.Sample is centrifuged 10min with 8000rpm after ultrasonic treatment, takes two sulphur containing removing
Change the supernatant of molybdenum, isopropanol is added after mixing, then by centrifugation removal upper layer NVP, lower layer obtains two containing removing
The precipitating of molybdenum sulfide, then cleaned with isopropanol, separated repeatedly, to remove NVP solution, preparation contains the different of molybdenum disulfide nano sheet
Propanol dispersion liquor.
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 drying 9 hours.
Doughnut NaA molecular sieve membrane one end is sealed, the other end connects vacuum pump, is put into modification solution, vacuum is taken out
It inhales 7 hours.NaA molecular sieve membrane after modification is placed in baking oven, 75 DEG C drying 6 hours.
Steam soak characterization experiment:
Investigation using modification front and back molecular screen membrane Steam soak to the separation selectivity energy of ethanol/water system, operates item
Part: 105 DEG C of feeding temperature, the absolute pressure of per-meate side is 600Pa, is mentioned after modification to the separation selectivity energy highest of ethanol/water system
5 times are risen.
Steam soak experiment is done to isopropanol/water using the doughnut NaA molecular sieve membrane of modification front and back, operating condition:
110 DEG C of feeding temperature, the absolute pressure of per-meate side is 300Pa, is promoted after modification to the separation selectivity energy highest of isopropanol/water system
7 times.
Embodiment 4
The repairing preparation of curing niobium dispersion liquid:
40mg curing niobium powder is dispersed in 50ml n-vinyl pyrrolidone (NVP), with ultrasonic cell disrupte machine
Ultrasound, by dispersion ultrasound 6h under 200W.Sample is centrifuged 5min with 15000rpm after ultrasonic treatment, takes two sulphur containing removing
Change the supernatant of niobium, isopropanol is added after mixing, then by centrifugation removal upper layer NVP, lower layer obtains two containing removing
Vulcanize the precipitating of niobium, then cleaned, separated repeatedly with isopropanol, to remove NVP solution, preparation contains the different of curing niobium nanometer sheet
Propanol dispersion liquor.
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 drying 6 hours.
Doughnut NaA molecular sieve membrane one end is sealed, the other end connects vacuum pump, is put into modification solution, vacuum is taken out
It inhales 6 hours.NaA molecular sieve membrane after modification is placed in baking oven, 80 DEG C drying 8 hours.
Steam soak characterization experiment:
Investigation using modification front and back molecular screen membrane Steam soak to the separation selectivity energy of ethanol/water system, operates item
Part: 120 DEG C of feeding temperature, the absolute pressure of per-meate side is 600Pa, is mentioned after 2 modifications to the separation selectivity energy highest of ethanol/water system
4 times are risen.
Steam soak experiment is done to isopropanol/water using the doughnut NaA molecular sieve membrane of modification front and back, operating condition:
115 DEG C of feeding temperature, the absolute pressure of per-meate side is 350Pa, is promoted after modification to the separation selectivity energy highest of isopropanol/water system
8 times.
Claims (4)
1. dispersion liquid is for repairing the application in molecular screen membrane surface defect, it is characterised in that: include such as in the application
Lower step:
The dispersion liquid and preparation method thereof includes the following steps: for tungsten disulphide powder to be dispersed in n-vinyl pyrrolidone,
It is handled under the action of ultrasound, then again by centrifugal treating, takes the upper of the tungsten disulphide powder nanometer sheet containing removing
Clear liquid；Supernatant is cleaned with alcohols solvent, the n-vinyl pyrrolidone in tungsten disulphide powder nanometer sheet is got rid of, obtains
Dispersion liquid for molecular screen membrane repairing；The w/v of the tungsten disulphide powder and n-vinyl pyrrolidone is 10
~50mg:10~100ml；1~10h of action time of ultrasound；The time of centrifugal treating is 5~20min；The tungsten disulfide
The pattern of powder nanometer piece is single layer sheet, and equivalent diameter size is in 50~80nm；The alcohols solvent be methanol, ethyl alcohol or
The mixing of one or more of person's isopropanol；
Molecular screen membrane is dipped in dispersion liquid, by way of negative-pressure ward, tungsten disulphide powder nanometer sheet is made to be filled in molecule
In the defect on sieve membrane surface；Molecular screen membrane is taken out again, drying.
2. application according to claim 1, which is characterized in that the molecular screen membrane refer to NaA, T-type, CHA, ZSM-5,
MOR, NaY molecular sieve film；The molecular screen membrane is carried on supporter, and the configuration molecular screen membrane of supporter supports figure body
It is configured as chip, tubular type or hollow fiber form.
3. application according to claim 1, which is characterized in that method for repairing and mending is repeated as many times；The time of negative-pressure ward is 1~
10h；Baking step is dried 1~20 hour in 60~90 DEG C of baking oven.
4. application according to claim 1, which is characterized in that the molecular screen membrane is to be applied to infiltration evaporation solvent to take off
Water process, the solvent are selected from the mixed of one or more of alcohols solvent, esters solvent, ether solvent or benzene kind solvent
It closes；100~120 DEG C of feeding temperature during infiltration evaporation solvent dehydration, the absolute pressure of per-meate side are 10~3000Pa.
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| 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 |
| CN115986125B (en) * | 2023-03-15 | 2023-06-02 | 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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