CN101357302A - Preparation method of cellulose acetate nano filter-membrane - Google Patents
Preparation method of cellulose acetate nano filter-membrane Download PDFInfo
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- CN101357302A CN101357302A CNA2008101212863A CN200810121286A CN101357302A CN 101357302 A CN101357302 A CN 101357302A CN A2008101212863 A CNA2008101212863 A CN A2008101212863A CN 200810121286 A CN200810121286 A CN 200810121286A CN 101357302 A CN101357302 A CN 101357302A
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- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000005266 casting Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 238000005345 coagulation Methods 0.000 claims description 11
- 230000015271 coagulation Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000004907 flux Effects 0.000 abstract description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 10
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 9
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 9
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 238000001728 nano-filtration Methods 0.000 description 7
- 241000050051 Chelone glabra Species 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000000108 ultra-filtration Methods 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- XDQITMCFPPPMBC-TUANDBMESA-N scutelloside Natural products OC[C@H]1O[C@@H](O[C@@H]2O[C@@H]3C[C@H]4[C@H](O)[C@@H](O)[C@@](O)(CO3)[C@@H]24)[C@H](O)[C@@H](O)[C@@H]1O XDQITMCFPPPMBC-TUANDBMESA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 235000014347 soups Nutrition 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920002160 Celluloid Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 244000046146 Pueraria lobata Species 0.000 description 1
- 235000010575 Pueraria lobata Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
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- 238000005191 phase separation Methods 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
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Abstract
The invention discloses a preparation method of a cellulose acetate nano filter membrane. The preparation method comprises the following steps: 1) the cellulose acetate is put into a solvent, stirred, added with a nonsolvent additive and stirred, then a mixture is obtained, the mixture stands still, and then casting membrane liquid is obtained; 2) the casting membrane liquid is made into a wet membrane with the thickness being 250mum by striking, then the wet membrane stands still in the air; (3) the wet membrane treated by the steps is immersed in distilled water for gel bath treatment, therefore, an asymmetrical membrane is obtained; and 4) ethanol water exchange treatment and pure cyclohexane exchange treatment are sequentially carried out on the asymmetrical membrane, then the cellulose acetate nano filter membrane is obtained. The nano filter membrane obtained by the preparation method has big flux and obvious separating effect.
Description
Technical field
The present invention relates to a kind of preparation method of cellulose acetate nano filter-membrane.
Background technology
Membrane separation technique is that an emerging separating substances is purified and concentration technology continued operation at normal temperatures, no phase transformation; The advantage that energy-saving and environmental protection are arranged in the large-scale production; Especially the suitable heat-sensitive substance that adds thermal lability, thus swift and violent in the development of fields such as food, medicine, water treatment.Membrane technology mainly is to extract active material from Chinese medicine in the application of the field of Chinese medicines.The content of active speciality is low in the Chinese medicine, uses a large amount of organic solvents in the traditional handicraft leaching process often, therefore exist extracting method complexity, efficient low, pollute and heavily wait shortcoming, and membrane technology can address the above problem preferably.Dong Jie etc. with the inorganic ceramic membrane of 0.2 μ m to liquid medicine micro-filtration in the root of large-flowered skullcap after, its leading indicator composition has improved 4～9% at the relative amount that contains admittedly in the thing.Hangzhou water treatment centers employing NF membrane isolation technics replaces the evaporation and concentration in the former root of kudzu vine aqueous solution concentration technology, and energy consumption has only 1/9 of former technology, and product yield has improved 10～20%, means to have improved economic benefit.In sum, the superiority of membrane separation technique is fairly obvious.
Cellulose acetate (CA) is a kind of common membrane material, is used for milipore filter, counter-infiltration and NF membrane already.Compare with other materials, the cellulose acetate wide material sources, inexpensive, have metastable physico-chemical property, chlorine resistance and a good in oxidation resistance.
Patent (CN1660305A) has been described a kind of new process that utilizes cellulose acetate-celluloid to mix dull and stereotyped micro-filtration membrane separating clarifying traditional Chinese medicine liquid.Compare with traditional soup production method, this technology has that normal-temperature operation, active ingredient are not destroyed, advantage such as with short production cycle, and soup clarity can improve 80-90%, and physical and chemical stability is good.
Randa Haddad etc. utilizes phase inversion to make NF membrane by control polymer concentration and annealing temperature.Ramzi Hadj Lajimi etc. utilizes shitosan acid and mosanom that film is carried out surface modification again on this basis and makes its acquisition positive charge or negative electrical charge.
Zhou Jinsheng etc. have prepared the asymmetric NF membrane of CA/CTA blend, can realize unit price is effectively separated with multivalent anions, and effectively remove small organic molecule, and the NaCl salt rejection rate is 15～60%, Na
2SO
4Rejection is 85～98%, holds back relative molecular weight between 200～600.
Y.Yip etc. have set up non-solvent steam at cellulose acetate/acetone/aqueous systems and have induced the phase separation model, theoretically factors such as relative humidity, solvent evaporates degree, air speed, evaporating temperature, initial film thickness and polymer concentration are brought in this model.
People such as Randa Haddad adopt acetone: formamide is the CA casting solution that 2: 1 mixed solvent is mixed with 20-22wt%, scrapes the wet film of making 250 μ m thickness, directly is immersed in 4 ℃ distilled water coagulation bath 1h, then 60-80 ℃ of annealing down.The film of this method gained mainly is at the bitter desalination, but high desalination rate is 86%, and the permeability of water is lower, only is 9.6L.m
-2.h
-1Because the CA concentration ratio is bigger in the casting solution that is disposed, viscosity is very big, and stirring and dissolving is difficulty comparatively evenly, is difficult for knifing, and film forming procedure than higher, and has adopted a large amount of formamides to the requirement of temperature and time in the casting film process, belong to toxic solvent.
Summary of the invention
The technical problem to be solved in the present invention provides that a kind of technology is easy, the preparation method of the cellulose acetate nano filter-membrane of environment-friendly type, utilizes that the prepared filter membrane flux of the inventive method is big, separating effect is obvious.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of cellulose acetate nano filter-membrane, may further comprise the steps:
1), cellulose acetate put into solvent stirred 22～26 hours, and then add nonsolvent additive and stirred 2～5 hours, left standstill at last 65～75 hours, casting solution;
2), under 10～30 ℃ of temperature and 50～75% relative humidity conditions, above-mentioned casting solution is scraped the wet film of making 250 μ m thickness on clean glass plate or nonwoven, make wet film rest on the volatilization of carrying out solvent in the air again, time of repose is 1～30 minute;
3), handle carrying out coagulation bath in 5～25 ℃ of distilled water of wet film immersion after the above-mentioned volatilization processing, until the abundant gel of wet film; Obtain asymmetric membrane;
4) be after exchange of 30～70% ethanol waters and the exchange of pure cyclohexane are handled, to get cellulose acetate nano filter-membrane through volumetric concentration successively, with above-mentioned asymmetric membrane.
Improvement as the preparation method of cellulose acetate nano filter-membrane of the present invention: the amount ratio of solvent and cellulose acetate is 100ml (solvent): 8～20g (cellulose acetate) in the step 1), and the volume ratio of solvent and nonsolvent additive is 4～25: 1.
Further improvement as the preparation method of cellulose acetate nano filter-membrane of the present invention: the solvent in the step 1) is an acetone, 1,4-dioxane, oxolane or chloroform.
Further improvement as the preparation method of cellulose acetate nano filter-membrane of the present invention: the nonsolvent additive in the step 1) is water, methyl alcohol or ethanol.
The preparation method of cellulose acetate nano filter-membrane of the present invention, traditional non-solvent/solvent coagulation bath method control gelation rate is improved: reduce gel speed by in casting solution, adding non-solvent, reduce gel speed thereby replace traditional exchange rate that in coagulation bath, adds solvent change solvent and non-solvent.Preparation method of the present invention is the pure water coagulation bath that adopts safety and environmental protection, thereby makes NF membrane.In the present invention, with non-solvent---water directly adds in the casting solution; Comparing with the method that people such as Randa Haddad adopts, is to have changed the non-solvent formamide into the pure water non-solvent; Therefore the present invention's environmental protection more, and preparation process is simple and safe, and operation is few, has avoided the NF membrane aftertreatment technology of very complicated among the general preparation method.The asymmetric membrane of step 3) gained of the present invention is film in uneven thickness, and its thickness is generally 100～200 μ m.Adopt the cellulose acetate nano filter-membrane film of the inventive method gained, test through evaluation criterion: its flux is big, and salt rejection rate is higher, and PEG400, PEG600 and PEG1000 rejection are all higher; Warp is to root of large-flowered skullcap water extract nanofiltration separation, and the active ingredient separating effect is obvious.
In sum, the present invention adopts non-solvent---and water is the additive of casting solution, has reduced the pollution that produces in the film preparation process, has reduced the use amount of organic solvent, has saved cost.Simultaneously, by adjusting the preparation condition of film, can obtain the film in different apertures, and can be used for the isolation and purification of plant extracts.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is the surface (a) of embodiments of the invention 1 film that obtains and the electromicroscopic photograph of section (b);
Fig. 2 is the surface (a) of contrast experiment 1 film that obtains and the electromicroscopic photograph of section (b);
Fig. 3 is the HPLC collection of illustrative plates that the prepared NF membrane of the present invention is used for root of large-flowered skullcap extract;
Among the figure: a is the collection of illustrative plates of scutelloside standard items; B is the pretreated collection of illustrative plates of extract; C is the collection of illustrative plates that nanofiltration sees through liquid.
The specific embodiment
The preparation method of embodiment 1, a kind of cellulose acetate nano filter-membrane, carry out following steps successively:
1), acetone (AC) that 12g cellulose acetate (CA) is put into 100ml stirred 24 hours, and then adds the water (H of 25ml
2O for example can select distilled water for use) stirred 2 hours, left standstill at last 72 hours, get casting solution;
2), under 15 ℃ temperature and 60% relative humidity (air) condition, adopt scraper on clean glass plate, to scrape the wet film of making 250 μ m thickness above-mentioned casting solution; Make wet film again under the condition of above-mentioned identical temperature and humidity, rest on the volatilization of carrying out solvent on the glass plate, time of repose is 1 minute;
3), handle carrying out coagulation bath in the 15 ℃ of distilled water of wet film immersion after the above-mentioned volatilization processing, until the abundant gel of wet film, film-forming; Obtain the uniform asymmetric membrane of thickness; Its thickness is 100～200 μ m.
4), under room temperature (0～35 ℃) condition, it is in 30%, 50%, 70% the ethanol water each 3～5 hours that above-mentioned asymmetric membrane is immersed in volumetric concentration successively, its effect is the non-solvent water that exchanges out in the asymmetric membrane.Then, immerse again in the pure cyclohexane did exchange in 3～5 hours and handle after, cellulose acetate nano filter-membrane.
The preparation method of embodiment 2, a kind of cellulose acetate nano filter-membrane is with step 2) in temperature make 25 ℃ into, make relative humidity into 75%, time of repose was made into 5 minutes; All the other are with embodiment 1.
The preparation method of embodiment 3, a kind of cellulose acetate nano filter-membrane changes the consumption of the cellulose acetate in the step 1) into 15g; All the other are with embodiment 1.
The preparation method of embodiment 4, a kind of cellulose acetate nano filter-membrane changes the consumption of the cellulose acetate in the step 1) into 15g; All the other are with embodiment 2.
NF membrane to the foregoing description 1～4 gained is carried out performance evaluation, and appreciation condition is: effectively the face diameter is 0.07m, and the feed liquid flow velocity is 2.74L.min
-1, feed temperature is 25 ℃, and test pressure is 0.5MPa, and initial NaCl salinity is 5%, and initial p EG400 concentration is 50ppm.Test result is as shown in table 1:
Table 1
| Casting solution composition CA (g): AC (ml): H 2O(ml) | Temperature | Humidity | Time of repose (prevapourising time) | Flux (L.m -2.h -1) | Salt rejection rate | The PEG400 rejection | |
| Embodiment 1 | 12∶100∶25 | 15℃ | 60％ | 1min | 22 | 81％ | 73％ |
| |
12∶100∶25 | 25℃ | 75％ | |
15 | 82％ | 80％ |
| Embodiment 3 | 15∶100∶25 | 15℃ | 60％ | 1min | 13 | 72％ | 61％ |
| |
15∶100∶25 | 25℃ | 75％ | 5min | 10 | 75％ | 75％ |
In order to prove preparation method's of the present invention superiority, the inventor has made following contrast test,
Contrast test 1,
Step 1) is made into: the acetone (AC) of 12g cellulose acetate (CA) being put into 100ml stirred 24 hours, left standstill then 72 hours, got casting solution.The step 2 of cancellation embodiment 1) leave standstill step, promptly scrape the wet film of making 250 μ m thickness after, directly carry out the coagulation bath of step 3) and handle without leaving standstill (volatilization that is solvent).All the other are with embodiment 1.
In like manner,
Step 1) is made into: the acetone (AC) of 12g cellulose acetate (CA) being put into 100ml stirred 24 hours, left standstill then 72 hours, got casting solution; The step 2 of cancellation embodiment 2) leave standstill step, all the other are with embodiment 2.
Contrast test 3,
Step 1) is made into: the acetone (AC) of 15g cellulose acetate (CA) being put into 100ml stirred 24 hours, left standstill then 72 hours, got casting solution.The step 2 of cancellation embodiment 3) leave standstill step, all the other are with embodiment 3.
Step 1) is made into: the acetone (AC) of 15g cellulose acetate (CA) being put into 100ml stirred 24 hours, left standstill then 72 hours, got casting solution.The step 2 of cancellation embodiment 4) leave standstill step, all the other are with embodiment 4.
NF membrane to above-mentioned contrast test 1～4 gained is carried out performance evaluation, and appreciation condition is the same.Test result is as shown in table 2:
Table 2
| Casting solution composition CA (g): AC (ml): H 2O(ml) | Temperature | Humidity | Flux (L.m -2.h -1) | Salt rejection rate | The PEG400 rejection | |
| Contrast test 1 | 12∶100∶0 | 15℃ | 60％ | 32 | 96％ | 56％ |
| |
12∶100∶0 | 25℃ | 75％ | 28 | 91％ | 60％ |
| Contrast test 3 | 15∶100∶0 | 15℃ | 60％ | 18 | 83％ | 48％ |
| |
15∶100∶0 | 25℃ | 75％ | 15 | 88％ | 62％ |
Contrast according to above table 1 and table 2, can learn: scrape that the wet film that makes is placed certain hour in air so that the prepared NF membrane in partial solvent volatilization back to the rejection of PEG400, more directly immerses film prepared in the non-solvent (distilled water) rejection of PEG400 is wanted high; Therefore, proposed by the inventionly in air, leave standstill certain hour to the effect of being significantly improved of NF membrane performance.
The preparation method of embodiment 5, a kind of cellulose acetate nano filter-membrane, carry out following steps successively:
1), 8g cellulose acetate (CA) is put into 1 of 100ml, the middle stirring of 4-dioxane (DIO) 24 hours, and then the water (H of adding 6ml
2O) stirred 2 hours, left standstill at last 72 hours, get casting solution;
2), under 10 ℃ of temperature and 50% relative humidity condition, adopt scraper on clean nonwoven, to scrape the wet film of making 250 μ m thickness above-mentioned casting solution; Make wet film again under the condition of above-mentioned identical temperature and humidity, rest on the volatilization of carrying out solvent on the nonwoven, time of repose is 10 minutes;
3), handle carrying out coagulation bath in the 5 ℃ of distilled water of wet film immersion after the above-mentioned volatilization processing, until the abundant gel of wet film, film-forming; Obtain asymmetric membrane in uneven thickness; Its thickness is 100～200 μ m.
4), at ambient temperature, it is in 30%, 50%, 70% the ethanol water each 3～5 hours that above-mentioned asymmetric membrane is immersed in volumetric concentration successively, and its effect is the non-solvent water that exchanges out in the asymmetric membrane.Then, immerse again in the pure cyclohexane did exchange in 3～5 hours and handle after, cellulose acetate nano filter-membrane.
The preparation method of embodiment 6, a kind of cellulose acetate nano filter-membrane is with step 2) in temperature make 30 ℃ into, make relative humidity into 75%, time of repose was made into 30 minutes; All the other are with embodiment 5.
The preparation method of embodiment 7, a kind of cellulose acetate nano filter-membrane changes the consumption of the cellulose acetate in the step 1) into 20g; Making to carry out step 3) into coagulation bath in 25 ℃ of distilled water handles; All the other are with embodiment 5.
The preparation method of embodiment 8, a kind of cellulose acetate nano filter-membrane is with step 2) in temperature make 30 ℃ into, make relative humidity into 75%, time of repose was made into 30 minutes; All the other are with embodiment 7.
NF membrane to the foregoing description 5～8 gained is carried out performance evaluation, and appreciation condition is the same.Test result is as shown in table 3:
Table 3
| Casting solution composition CA (g): AC (ml): H 2O(ml) | Temperature | Humidity | Time of repose (prevapourising time) | Flux (L.m -2.h -1) | Salt rejection rate | The | |
| Embodiment | |||||||
| 5 | 8∶100∶6 | 10℃ | 50％ | 10min | 165 | 77％ | 66 |
| Embodiment | |||||||
| 6 | 8∶100∶6 | 30℃ | 75％ | 30min | 64 | 82％ | 80％ |
| Embodiment 7 | 20∶100∶6 | 10℃ | 50％ | 10min | 58 | 68％ | 78 |
| Embodiment | |||||||
| 8 | 20∶100∶6 | 30℃ | 75％ | 30min | 38 | 75％ | 75％ |
In order to prove preparation method's of the present invention superiority, the inventor has made following contrast test again:
Step 1) is made into: (CA) puts into 1 of 100ml with the 8g cellulose acetate, stirs 24 hours in the 4-dioxane (DIO), leaves standstill then 72 hours, gets casting solution; The step 2 of cancellation embodiment 5) leave standstill step, promptly scrape the wet film of making 250 μ m thickness after, directly carry out the coagulation bath of step 3) and handle without leaving standstill (volatilization that is solvent).All the other are with embodiment 5.
In like manner,
Step 1) is made into: the DIO that 8g cellulose acetate (CA) is put into 100ml stirred 24 hours, left standstill then 72 hours, got casting solution; The step 2 of cancellation embodiment 6) leave standstill step, all the other are with embodiment 6.
Contrast test 7,
Step 1) is made into: the DIO that 20g cellulose acetate (CA) is put into 100ml stirred 24 hours, left standstill then 72 hours, got casting solution; The step 2 of cancellation embodiment 7) leave standstill step, all the other are with embodiment 7.
Step 1) is made into: the DIO that 20g cellulose acetate (CA) is put into 100ml stirred 24 hours, left standstill then 72 hours, got casting solution; The step 2 of cancellation embodiment 8) leave standstill step, all the other are with embodiment 8.
NF membrane to above-mentioned contrast test 5～8 gained is carried out performance evaluation, and appreciation condition is the same.Test result is as shown in table 4:
Table 4
| Casting solution composition CA (g): AC (ml): H 2O(ml) | Temperature | Humidity | Flux (L.m -2.h -1) | Salt rejection rate | The PEG400 | |
| Contrast test | ||||||
| 5 | 8∶100∶0 | 10℃ | 50％ | 191 | 86％ | 43 |
| Contrast test | ||||||
| 6 | 8∶100∶0 | 30℃ | 75％ | 86 | 93％ | 62％ |
| Contrast test 7 | 20∶100∶0 | 10℃ | 50％ | 73 | 90％ | 59 |
| Contrast test | ||||||
| 8 | 20∶100∶0 | 30℃ | 75％ | 51 | 92％ | 54％ |
Contrast according to above table 3 and table 4, can learn: scrape that the wet film that makes is placed certain hour in air so that the prepared NF membrane in partial solvent volatilization back to the rejection of PEG400, more directly immerses film prepared in the distilled water rejection of PEG400 is wanted high; Therefore, proposed by the inventionly in air, leave standstill certain hour to the effect of being significantly improved of NF membrane performance.
Embodiment 9, scutelloside are purified:
1), adopt the method that decocts to obtain root of large-flowered skullcap extract:
Take by weighing the 105g radix scutellariae medicinal materials and add 1.5～2L decocting and boil to boiling, slow fire continues to decoct 1h, leaves standstill, and filter and obtain Chinese medicine stoste, sampling, the Chinese medicine stoste of the gained of will take a sample is again carried out centrifugation and is got its supernatant, takes a sample; The supernatant of sampling gained is carried out ultrafiltration, get ultrafiltration trapped fluid and ultrafiltration respectively and see through liquid.
2), nanofiltration concentration process:
Ultrafiltration is seen through liquid adopt the cellulose acetate nano filter-membrane of preparation method's gained of the present invention to carry out nanofiltration, get nanofiltration and see through liquid.
To above-mentioned steps 1) ultrafiltration of gained sees through liquid and step 2) nanofiltration of gained sees through liquid and adopts the HPLC method to measure the scutelloside relative amount respectively, all the same commentary valency of condition conditions such as test feed temperature, flow; The result is respectively as (b) among Fig. 3 with (c).
According to content shown in Figure 3, can learn: after the prepared nanofiltration membrane treatment of the present invention, the most impurity in the root of large-flowered skullcap extract are trapped, and have realized the separation of root of large-flowered skullcap extract.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1, a kind of preparation method of cellulose acetate nano filter-membrane is characterized in that may further comprise the steps:
1), cellulose acetate put into solvent stirred 22～26 hours, and then add nonsolvent additive and stirred 2～5 hours, left standstill at last 65～75 hours, casting solution;
2), under 10～30 ℃ of temperature and 50～75% relative humidity conditions, above-mentioned casting solution is scraped the wet film of making 250 μ m thickness on clean glass plate or nonwoven, make wet film rest on the volatilization of carrying out solvent in the air again, time of repose is 1～30 minute;
3), handle carrying out coagulation bath in 5～25 ℃ of distilled water of wet film immersion after the above-mentioned volatilization processing, until the abundant gel of wet film; Obtain asymmetric membrane;
4) be after exchange of 30～70% ethanol waters and the exchange of pure cyclohexane are handled, to get cellulose acetate nano filter-membrane through volumetric concentration successively, with above-mentioned asymmetric membrane.
2, the preparation method of cellulose acetate nano filter-membrane according to claim 1 is characterized in that: the amount ratio of solvent and cellulose acetate is 100ml: 8～20g in the described step 1), and the volume ratio of solvent and nonsolvent additive is 4～25: 1.
3, the preparation method of cellulose acetate nano filter-membrane according to claim 2 is characterized in that: the solvent in the described step 1) is an acetone, 1,4-dioxane, oxolane or chloroform.
4, the preparation method of cellulose acetate nano filter-membrane according to claim 3 is characterized in that: the nonsolvent additive in the described step 1) is water, methyl alcohol or ethanol.
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| CN101879416A (en) * | 2010-04-30 | 2010-11-10 | 浙江大学 | Method for preparing cellulose composite sodium filter membrane |
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| CN105327623A (en) * | 2015-12-03 | 2016-02-17 | 中国科学院化学研究所 | Cellulose acetate nanofiltration membrane and preparing method thereof |
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