CN109647202A - The method of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane - Google Patents
The method of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane Download PDFInfo
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- CN109647202A CN109647202A CN201811572246.0A CN201811572246A CN109647202A CN 109647202 A CN109647202 A CN 109647202A CN 201811572246 A CN201811572246 A CN 201811572246A CN 109647202 A CN109647202 A CN 109647202A
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- hollow fiber
- nanofiltration membrane
- proton absorbent
- high concentration
- external pressure
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- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
-
- 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
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Abstract
The invention belongs to nanofiltration field of membrane preparation, more particularly to a kind of method of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane, the ultrafiltration membranes that include the following steps: to receive doughnut are immersed in 4-30s in water phase, after taking-up is dried, it is immersed in 10-60s in organic phase again, taking-up, which is placed in 80-100 DEG C of baking oven, carries out heat treatment 0.5-10mins to get required product；Wherein the water phase includes polyamine, proton absorbent and water；The organic phase includes polynary acyl chlorides and n-hexane.The concentration of the polyamine is 1-3% (w/w), and the concentration of proton absorbent is 0.5-6% (w/w)；This technology is the improvement to interfacial polymerization in hollow fiber nanofiltration membrane preparation.The selectivity of bear electricity hollow fiber nanofiltration membrane can be substantially improved using high concentration proton absorbent, while guaranteeing higher flux again, and this method is simple and convenient, it is at low cost, it is easy to serialization, large-scale production.
Description
Technical field
The invention belongs to nanofiltration field of membrane preparation, and in particular to a kind of high concentration proton absorbent continuous production External Pressure Type
The method of hollow fiber nanofiltration membrane.
Background technique
Nanofiltration membrane is mostly flat or rolling at present, and hollow fiber form nanofiltration membrane is less, but due to its strong stain resistance and
As research hotspot.Preparing hollow fiber form nanofiltration membrane, there are mainly two types of methods, in directly being formed by spining technology
Hollow fiber nanofiltration membrane, another kind are to obtain ultra-thin separating layer by surface modification (predominantly interfacial polymerization) on the basis of basement membrane
Obtain composite nanometer filtering film.Composite nanometer filtering film becomes main stream approach because its flux is big, separation accuracy is high.Composite membrane includes bear
Electricity, lotus positive electricity two types.Under normal conditions, the pollutant in water mostly exists with the colloidal form of bear electricity, thus lotus positive electricity
Nanofiltration membrane is easier to be contaminated, therefore in market based on bear electrolemma.In the preparation process of highly selective hollow fiber nanofiltration membrane,
Proton absorbent dosage is about within the scope of 0.1-0.5%, such as CN101524626A, although higher, the water flux of selectivity
About 40LMH still has certain gap compared with the rolled film of commercialization.
At present in hollow fiber nanofiltration membrane preparation method, existing highly selective hollow fiber nanofiltration membrane also has in high throughput
Hollow fiber nanofiltration membrane, but the two cannot be considered in terms of.In production practice, discovery and doughnut distinctive " core liquid " (rolling, plate
So-called " core liquid " is not present in film etc.) related: in basement membrane, desalination layer integration production process, " the core of Hollow Fiber Ultrafiltration basement membrane
Liquid " always exists, and cause water phase to be diluted, be unevenly distributed, drying and interfacial polymerization process in diffusion and plate membrane
The problems such as generating larger difference, to affect taking into account for selectivity and water flux.And the doughnut that only the two is taken into account is received
Filter membrane material could be competed with rolling nanofiltration in existing market, and advantage is embodied in terms of anti-pollution, so, the two, which is taken into account, is
The key of the hollow fiber nanofiltration membrane marketization is most important.
Summary of the invention
Aiming at the problem that selectivity and water flux of hollow fiber nanofiltration membrane cannot be considered in terms of, the purpose of the present invention is to provide
A kind of method of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane, to overcome the defect.
The present invention to achieve the above object, using following technical scheme:
A kind of method of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane, including following steps
It is rapid:
Hollow Fiber Ultrafiltration basement membrane is immersed in 4-30s in water phase, after taking-up is dried, then is immersed in 10- in organic phase
60s, taking-up, which is placed in 80-130 DEG C of baking oven, carries out heat treatment 0.5-10mins to get required product；
Wherein the water phase includes polyamine, proton absorbent and water；The organic phase include polynary acyl chlorides with
And n-hexane.
The Hollow Fiber Ultrafiltration basement membrane is polysulfones, in polyether sulfone, Kynoar, polyacrylonitrile, polyvinyl chloride
It is a kind of.
The proton absorbent is organic base or inorganic base.The proton absorbent be sodium hydroxide, sodium phosphate,
Triethylamine, the mixing of one or more of 4-dimethylaminopyridine.
The concentration of the polyamine is 2-8% (w/w), and the concentration of proton absorbent is 0.5-6% (w/w)；
Preferably, the concentration of proton absorbent is 4% (w/w)
The concentration of the polynary acyl chlorides is 0.05~1% (w/w).
Compared with prior art, the beneficial effects of the present invention are:
This technology is the improvement to interfacial polymerization in hollow fiber nanofiltration membrane preparation.Utilize high concentration proton absorbent
The selectivity of bear electricity hollow fiber nanofiltration membrane can be substantially improved, while guaranteeing higher flux again, and this method is simple
It is convenient, it is at low cost, it is easy to serialization, large-scale production.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, below with reference to embodiment pair
The present invention is described in further detail.
A kind of method of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane, including following steps
It is rapid:
Hollow Fiber Ultrafiltration basement membrane is immersed in 4-30s in water phase, after taking-up is dried, then is immersed in 10-60s in organic phase,
Taking-up, which is placed in 80-130 DEG C of baking oven, carries out heat treatment 0.5-10mins to get required product；The wherein water phase packet
Include polyamine, proton absorbent and water；The organic phase includes polynary acyl chlorides and n-hexane.
The Hollow Fiber Ultrafiltration basement membrane is polysulfones, in polyether sulfone, Kynoar, polyacrylonitrile, polyvinyl chloride
It is a kind of.The proton absorbent is organic base or inorganic base.
The concentration of the polyamine is 1-3% (w/w), and the concentration of proton absorbent is 0.1-6% (w/w)；
The concentration of the polynary acyl chlorides is 0.05-0.2% (w/w).
Embodiment 1:
Water phase: 2g piperazine (organic amine), 0.5g triethylamine (proton absorbent), 100g deionized water.
Organic phase: 0.1g pyromellitic trimethylsilyl chloride (polynary acyl chlorides), 100g n-hexane (organic solvent).
Interfacial polymerization process: Hollow Fiber Ultrafiltration polyether sulfone basement membrane is immersed in 10s in water phase, takes out naturally dry
10min.It is submerged again and 20s in organic phase.After taking out 1min, 2min is put into 100 DEG C of baking ovens to get doughnut nanofiltration
Film product is immersed in be measured in deionized water.
Embodiment 2
Water phase: 2g piperazine (organic amine), 0.5gNaOH (proton absorbent), 100g deionized water.
Organic phase: 0.1g pyromellitic trimethylsilyl chloride, 100g n-hexane.
Interfacial polymerization process: Hollow Fiber Ultrafiltration polysulfones basement membrane is immersed in 4s in water phase, takes out naturally dry 10min.
It is submerged again and 10s in organic phase.After taking out 1min, it is put into 10min in 80 DEG C of baking ovens and is produced to get hollow fiber nanofiltration membrane
Product are immersed in be measured in deionized water.
Embodiment 3
A phase: 2g piperazine, 1g4- dimethylamino naphthyridine, 100g deionized water.
B phase: 0.1g pyromellitic trimethylsilyl chloride, 100g n-hexane.
Interfacial polymerization process: Hollow Fiber Ultrafiltration basement membrane is immersed in 40s in A phase, takes out naturally dry 10min.Again will
It is immersed in 60s in B phase.After taking-up, it is put into 0.5min in 100 DEG C of baking ovens and is immersed in get hollow fiber nanofiltration membrane product
It is to be measured in ionized water.
Embodiment 4: embodiment 4 is same as Example 1, and difference is only that the dosage of triethylamine is 2g.
Embodiment 5: embodiment 5 is same as Example 1, and difference is only that the dosage of triethylamine is 4g.
Embodiment 6: embodiment 6 is same as Example 1, and difference is only that the dosage of triethylamine is 6g.
Comparative example 1: comparative example 1 is same as Example 1, and difference is only that not include proton absorbent in water phase, i.e. water phase
Are as follows: 2g piperazine (organic amine), 100g deionized water.
Nano filter membrane separating property test method.
Test fluid: being respectively adopted 2000mg/L sodium chloride (NaCl) solution and 2000mg/L magnesium sulfate (MgSO4) solution is surveyed
Examination.
Operating parameter: it is tested using nanofiltration membrane evaluation instrument, pressure 0.5MPa, 25 DEG C, pH=7.0, the rate of recovery 15%.
Calculation formula:
Rejection R=(CI-CO)/CI*100%, wherein CI is water inlet conductance, and CO is water outlet conductance；
Flux F=V/ (A*T), wherein V is to produce water volume, and A is membrane area, and T is time of measuring.
Table 1 is nano filter membrane separating property comparison；
Table 1
Conclusion: as can be seen from the above table, under high concentration triethylamine concentration (embodiment 5), the choosing of hollow fiber nanofiltration membrane
Selecting property and water flux have promotes (opposite embodiment 1-4) by a relatively large margin.But continue growing triethylamine concentration (embodiment 6) instead
Properties of product can be made to decline.
The above is only a preferred embodiment of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes in the specific implementation manner and application range, and the content of the present specification should not be construed as to the present invention
Limitation.
Claims (7)
1. a kind of method of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane, which is characterized in that packet
Include following step:
Hollow Fiber Ultrafiltration basement membrane is immersed in 4-30s in water phase, after taking-up is dried, then 10-60s in organic phase is immersed in, takes
It is placed in 80-130 DEG C of baking oven out and carries out heat treatment 0.5-10mi n to get required product；
Wherein the water phase includes polyamine, high concentration proton absorbent and water；The organic phase includes polynary acyl chlorides
And n-hexane.
2. the side of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane according to claim 1
Method, which is characterized in that the Hollow Fiber Ultrafiltration basement membrane is polysulfones, polyether sulfone, Kynoar, polyacrylonitrile, polychlorostyrene second
One of alkene.
3. the side of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane according to claim 1
Method, which is characterized in that the proton absorbent is organic base or inorganic base.
4. the side of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane according to claim 1
Method, which is characterized in that the proton absorbent is sodium hydroxide, sodium phosphate, triethylamine, one of 4-dimethylaminopyridine
Or a variety of mixing.
5. the side of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane according to claim 1
Method, which is characterized in that the concentration of the polyamine is 2-8% (w/w), and the concentration of proton absorbent is 0.5-6% (w/w).
6. the side of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane according to claim 1
Method, which is characterized in that the concentration of proton absorbent is 4% (w/w).
7. the side of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane according to claim 1
Method, which is characterized in that the concentration of the polynary acyl chlorides is 0.05-1% (w/w).
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| CN201811572246.0A CN109647202A (en) | 2018-12-21 | 2018-12-21 | The method of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030076013A (en) * | 2002-03-22 | 2003-09-26 | 주식회사 효성 | Nanofiltration composite membrane and the process for the preparing the same |
| CN103768963A (en) * | 2014-01-23 | 2014-05-07 | 南通苏通分离工程科技有限公司 | Preparation method for polyamide composite nanofiltration membrane |
-
2018
- 2018-12-21 CN CN201811572246.0A patent/CN109647202A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030076013A (en) * | 2002-03-22 | 2003-09-26 | 주식회사 효성 | Nanofiltration composite membrane and the process for the preparing the same |
| CN103768963A (en) * | 2014-01-23 | 2014-05-07 | 南通苏通分离工程科技有限公司 | Preparation method for polyamide composite nanofiltration membrane |
Non-Patent Citations (1)
| Title |
|---|
| 时钧 主编: "《膜技术手册》", 31 January 2001, 化学工业出版社 * |
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Application publication date: 20190419 |