CN1175922C - Preparing process and application of composite biolipid/cellulose acetate membrane - Google Patents
Preparing process and application of composite biolipid/cellulose acetate membrane Download PDFInfo
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- CN1175922C CN1175922C CNB021421064A CN02142106A CN1175922C CN 1175922 C CN1175922 C CN 1175922C CN B021421064 A CNB021421064 A CN B021421064A CN 02142106 A CN02142106 A CN 02142106A CN 1175922 C CN1175922 C CN 1175922C
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Abstract
A high molecular material of ellulose acetate is dissolved in a solvent. Biologic ester is added to the solution. A film is prepared by an L-S phase transition method. The biologic ester which is filled is uniformly distributed in the frame of the film structure material. Micro and trace quantities of organic toxic pollutants enter the film in an infiltration mode, and the film is enriched with the pollutants. Accordingly, the purpose of the preenrichment of samples in environmental monitoring and the purpose of removing the micro and trace quantities of organic toxic pollutants are achieved. The components in the cellulose acetate film which is used account for the following weight ratios: cellulose acetate accounts for 16 to 22%; dioxane accounts for 5 to 15%; propanone accounts for 55 to 75%; magnesium perchlorate accounts for 1 to 4%; neutral ester accounts for 0.1 to 6%. The film preparation conditions comprises: the film preparation temperature is from 25 to 40 DEG C; the evaporation time is from 20 to 60s; the temperature of cooling bath is from 15 to 25 DEG C.
Description
Technical field
The present invention relates to environmental monitoring and pollution control technology field, relate in particular to a kind of preparation method of biological species ester/cellulose acetate composite film.
Background technology
With natural or artificial synthetic macromolecule membrane, be motive force with outside energy or chemical potential difference, to bi-component or multi-component solute separate with solvent, the method for classification, purification and enrichment, be referred to as membrane separation process.Synthetic film can be divided into organic (polymer) film and inoranic membrane, and wherein most important membrane material is an organic matter, i.e. polymer or big molecule.Selecting which kind of polymer is not random as membrane material, and will be according to its specific structure and character.Make polymeric membrane polymeric material commonly used and be cellulose and derivative thereof, polysulfones, polyether sulfone, polypropylene cyanogen, polyamide, Kynoar, polyether-ketone etc.Many hydrophilic polymers can be used as membrane material, and modal is exactly cellulose and derivative thereof.Cellulose has the linear chain structure of rule, and degree of crystallinity is very high, owing to form intermolecular hydrogen bonding between high-crystallinity and the hydroxyl, though this class material highly-hydrophilic is water insoluble.Cellulose and derivative thereof not only can be used for micro-filtration and ultrafiltration, also can be used for counter-infiltration, gas separation and dialysis.The seventies, the membrane separation technique of China still is in conceptual phase, in recent years, along with the introduction of technology and obtaining of the successes achieved in research, a collection of effective membrane separation device has obtained successful application in fields such as water treatment, industrial separation, wastewater treatment, laboratory separation gradually.The micro-filtration of above-mentioned application of membrane separation technology film or ultrafiltration principle, big molecule organic pollution is separated with water, and the application in environmental project mainly comprises the processing of waste water such as being applied to electroplating wastewater, oil-containing, degreasing waste water, textile waste, electrophoretic paint, papermaking, radioactivity, skyscraper.Up to the present, membrane science and technology are applied to environmental area, study various membrane materials, device is quite a lot to the removal of big molecule organic pollution.(NF membrane is held back mechanism research to organic to Luo Min etc., ACTA Scientiae Circumstantiae, 2000,20 (5): 523-527) the research NF membrane is to the organic mechanism of holding back, with U.S. TriSep company's T S80 NF membrane is example, finds that it is to determine by the interaction relationship between organic architectural feature (as molecular weight, polarity) and the organic matter/film is common to organic removal.The TS80 NF membrane is 90.3% to the average removal rate of TOC.(cellulose affinity chromatography film is used for removing the endotoxin of pharmaceutical preparation to Wei Guilin etc., membrane science and technology, 2000,20 (4): 52-54) with the cellulose membrane be matrix, after the activation, bonding shitosan aglucon is prepared into the affinity chromatography film medium, investigates this film to the endotoxic removal in the pharmaceutical preparation.But these films are based on the physical separation effect to the removal of pollutant, can not be used for enrichment or removal molecular weight less than the hydrophobic organic pollution materials of 1000 trace.
Aspect environmental monitoring, the pollution of trace such as organo-chlorine pesticide and dioxin and trace toxic organic pollutant more and more comes into one's own.This pollutant has potential ecology and health threat, and the concentration in water is generally part per billion (ppb, or μ g/L), even is low to moderate part per trillion (ppt, or ng/L).Traditional sample concentration pretreatment technology mainly adopts initiatively enrichment process, as environmental monitoring department generally adopt water sample liquid/liquid extraction, XAD resin absorption, solid phase extraction (Solid-phaseextraction, SPE), the precipitation method etc.These methods are very little for content in the water body, have cumulative bad, and the lipophilicity toxic organic pollutant accumulation ability that risk of toxicity is big is relatively poor, can not satisfy the requirement of low detection limit, high enriching quantity far away, perhaps has the phenomenon of a large amount of matrix interference assay determinations.The nineties begins, and the passive type Sampling techniques obtain fast development, as SPME and semipermeable membrane sampling device.The most representative in the semipermeable membrane sampling device is that (U.S.patents 5,098,573 and 5 for trioleate-semipermeable membrane Sampling techniques, 395,426) be that the biological species ester is encapsulated in the low-density polyethylene film,, constituting membrane module, is a kind of device of sandwich structure.This technology at home and abroad water body priority pollutant monitoring aspect obtained successful application, this Sampling techniques can be simulated organic pollution via the partition equilibrium process of water to organism ester fat phase, and the data that obtained more can embody the biological available state part of water pollutant.But the device that this technology constituted is simple in structure, and packaged ester flows in the middle of two-layer low density plastics's film easily, and forms ester and drip, and reduced bioaccumulation efficiency; The low density polyethylene films that is used to encapsulate trioleate is hydrophobic, does not directly contact with water, and is therefore quite slow to close ester organic pollutant enrichment speed, needs equilibration time long; In addition this device also exist can not purify, the easy unfavorable factor such as leakage of ester.
Summary of the invention
The objective of the invention is to prepare a kind of biological species ester that is used for enrichment water body organic toxic micropollutants and purifies waste water/poly-cellulose acetate composite film material preparation method.Technology of the present invention and equipment are simple, and is easy to prepare, is easy to realize.
The present invention realizes above-mentioned purpose like this: utilize the cellulose acetate family macromolecule as frame material, the biological species ester of filling is evenly distributed in the structural material framework, make that by the film synthesis technique film outside is hydrophilic, inner close ester, the suitable molecular weight of the size in outer surface aperture passes through less than 1000 molecule.Specific practice is: macromolecular material is that material of preparing such as cellulose acetate class (comprising cellulose acetate, cellulose diacetate and Triafol T etc.) toast in vacuum desiccator, and solvent for use is acetone and dioxane; Biological species ester (can be dissolved in the fatty glyceride and the phosphide of preparation liquid, as glycerol trioleate or phosphoglyceride) is an additive; Additive also comprises conventional additives such as analyzing pure magnesium perchlorate.Film fluid component proportion scope is as the criterion can make uniform films.Each component proportion is as follows in the CAM: it is 16-22% that cellulose acetate accounts for weight percentage ranges; Dioxane accounts for 5-15%; Acetone accounts for 55-75%; Magnesium perchlorate accounts for 1-4%, and the biological species ester accounts for 0.1-6%.Specific practice is for to put into the ground triangular flask in proportion with material of preparing, and triangular flask places 40 ℃ of dissolvings of baking oven until the dissolving of film liquid evenly, can make film.With liquid-solid (L-S) phase transformation legal system film, the system film temperature is 25-40 ℃ in the toilet, and evaporation time is 20～60s, and the cooling bath temperature is about 20 ℃.The film that makes is rinsed out remaining solvent with the water that flows, store in the distilled water.With the film thickness that makes is the 40-60 micron, and quality is even, light oyster white.In the film forming condition, the system film temperature is high more, and the shrinkage factor of film is big more, and the film top layer is fine and close more, and its aperture is more little.The compacted zone that the film for preparing under the above-mentioned condition of the present invention surface forms can prevent that the inner ester of film from dripping leakage, and the foreign molecules amount is easy to then enter that film is inner reaches balance mutually with ester less than 1000 pollutant.
The present invention requires equipment: rectifier unit guarantees that the purification of solvent is complete; Vacuum drying chamber is used for the oven dry of membrane material; The toilet guarantees the cleaning of system membrane environment, constant temperature and humidity.
The principle of the technical scheme of foundation of the present invention is: lipophilic organic pollution is according to the similar principle enrichment in organism fat easily that mixes, and its concentration in water is low more, and the enrichment degree in fat is big more.Can construct biomimetic material based on this principle, promptly add the biological species ester in the film liquid of the poly-cellulose acetate of preparation, the biological species ester is uniformly distributed in the polymeric membrane, forms small one by one ester storehouse.Be dissolved in the water body toxic organic pollutant because in water body with the biological species ester in different solubility and certain concentration difference is arranged, thereby can enter and be enriched in the ester along concentration difference by a large amount of micropores of film surface distributed.The concentration of pollutant in ester and the concentration ratio in water body are constant K under the equilibrium condition, and its numerical value is proportional to the ester water partition coefficient of pollutant.For example, to the ester water partition coefficient greater than 10
7The dioxin pollution thing, its enrichment multiple is a thousands of times (the enrichment multiple of conventional liquid-liquid extraction or SPE is generally less than 10,000 times, and the organic pollution that is about in 10 premium on currency is concentrated in 1 milliliter of organic solvent).
Can adopt two kinds of method wash-outs or be dissolved into the toxic organic pollutant of institute's enrichment in the organic solvent again: when with enrichment the composite membrane of organic pollution when being soaked in the hexane class organic solvent, originally the organic pollution that was dissolved in the biological species ester can be owing to the different solubility in different organic solvents has certain concentration difference, pollutant can enter organic solvent along concentration difference by the micropore of film surface distributed, and the concentration of pollutant in ester and the concentration ratio in organic solvent are constant K under the equilibrium condition
1, regulate the rate of recovery by the ratio of regulating organic solvent and trioleate.Again through conventional analytical method purifying, concentrate the concentration C of back mensuration pollutant in organic solvent
1According to this concentration and K
1Relation calculate the concentration C of pollutant in ester.Relation according to C and K is calculated the concentration C of pollutant in water body
wAnother kind method is with carrene composite membrane to be dissolved fully, removes macromolecular trioleate with the molecular sieve gel chromatograph, remain little molecular moiety again through conventional analytical method purifying, concentrate the concentration C of back mensuration pollutant in organic solvent
1Relation according to C and K is calculated the concentration C of pollutant in water body
w
The method that hexane class organic solvent is handled composite membrane can be used for the purification membrane material.Before sampling, remove pollutant (for example using the Soxhlet method for extracting) in the film, can get rid of the interference of background contaminants in the analytical work with the solvent cyclic washing.
The method that hexane class organic solvent is handled composite membrane can be used for handling used membrane material equally, therefore when being used to purify water or during environmental monitoring, composite film material can be reused.
Description of drawings
Fig. 1 is the fine structure of cellulose acetate-trioleate (1.5%) composite membrane of the present invention's preparation, and wherein A is a full face, and B is the section photo, and C is the reverse side photo.
The specific embodiment
Embodiment 1: cellulose acetate-trioleate composite membrane (wherein trioleate content 0.5%)
Test as follows with film formulation: the weight of each component is respectively cellulose acetate 18g; Dioxane 10g; Acetone 70g; Magnesium perchlorate 2g, biological species ester 1.5g.Filming technology: L-S phase inversion method; Evaporation time is 60 seconds, and the cooling bath temperature is 23～24 ℃.Fig. 1 is the stereoscan photograph of the positive and negative and section of composite membrane, and table 1 is the basic physical and chemical performance of prepared composite membrane.
The basic physical and chemical performance of table 1 cellulose acetate-trioleate (1.5%) composite membrane
| Mechanical strength (kg) | Thickness (μ m) | Ash content (%) | Moisture content (%) |
| 12 | 40 | 11.9 | 0.43 |
| Porosity (%) | The equilibrium temperature scope | Stable pH range | Ester is revealed check (aqueous medium) |
| 55 | 5～40℃ | 4～9 | Do not detect |
Embodiment 2: utilize the organo-chlorine pesticide in cellulose acetate-trioleate (1.5%) composite film material enrichment water of making
The above-mentioned composite film material of about 0.1g is put into the circulating water of laboratory preparation, and wherein 5 kinds of organo-chlorine pesticide concentration respectively are 2 μ g/L.Every 0.5,1,2,4,8,14, the 20d sampling through hexane dialysis 24h, is analyzed the concentration of organo-chlorine pesticide in the hexane with GC/ECD, and is scaled the content of agricultural chemicals in the cellulose acetate composite film in the experimentation.Chromatographiccondition is: HP5890GC/ECD detector, HP-5 type 60m * 0.32m * 0.25um quartz capillary column, carrier gas: high-purity N
2Initial temperature: 85 ℃, per minute rises to 180 ℃ for 10 ℃, stops 15 minutes; Per minute rises to 280 ℃ for 20 ℃, stops 20 minutes.Injector temperature: 250 ℃, detector temperature: 280 ℃.
Table 2 is cellulose acetate composite film enriching quantities to organo-chlorine pesticide.As can be seen from Table 2, cellulose acetate-trioleate composite membrane is very fast to the enrichment of 5 kinds of organo-chlorine pesticides, and in the time of 20d, it is linear that the enrichment curve is, and enriching quantity is as shown in table 2 over time.Behind the 20d, the enriching quantity of 5 kinds of organo-chlorine pesticides calculated with weight in wet base be respectively 9.7,4.7,28.9,17.8 and 9.5 μ g/g.
Table 2, cellulose acetate-trioleate (1.5%) composite membrane is to the enrichment of organo-chlorine pesticide
Enriching quantity (μ g/g)
Time (d)
Lindane drinox heptachlor epoxy 4,4 '-DDT hexachloro-benzene
4 1.98±0.82 1.00±0.47 3.21±0.58 1.11±0.38 2.59±2.21
8 2.11±0.50 2.38±0.41 8.45±0.18 6.52±0.58 4.31±0.81
14 9.82±0.06 3.07±0.69 9.45±1.59 6.10±0.82 9.12±0.38
20 9.67±0.41 4.72±0.52 28.9±1.04 17.84±2.06 9.51±0.16
Embodiment 3: utilize cellulose acetate-trioleate (1.5%) composite film material of making that the organochlorine micropollutant water is purified
Six kinds of organo-chlorine pesticides in experiment lab simulation water are respectively trefanocide, lindane, and heptachlor, drinox, dieldrite, DDT, initial concentration are made as 10 μ g/L.Get the 50ml Simulated Water and the 0.1g membrane material is put into the 100ml triangular flask simultaneously, low speed concussion on the shaking table.1,2,4,8,12,24,48, behind the 96h triangular flask is taken off, film carefully takes out, and with soft paper the moisture on the film is blotted, and weighs and record at once.Film is put into the dialysis of 20ml hexane dark place.Behind the 24h, film dialysis fully, dislysate is got 5ml, and to be concentrated into 0.2ml to be analyzed.
Simulated Water in the triangular flask adds rate of recovery indicant 2,4,5, and 6-tetrachloro meta-xylene and PCB-209 use the 20ml petroleum ether extraction, gets 10ml and moves into the K.D. inspissator, and high-purity N 2 is blown to 0.5ml.
Gas chromatograph: GC5890/ECD-63Ni, and use HP-5 quartz capillary column (25m * 0.22mm * 0.33um), 250 ℃ of injector temperatures, 280 ℃ of detector temperatures.Heating schedule: initial 85 ℃ of column temperature (keeping 2min), rise to 180 ℃ (15min) with 10 ℃/min of speed, 20 ℃/min of speed rises to 280 ℃ (20min).Carrier gas high-purity N 2, column cap is pressed 20psi; The detection limit of six kinds of organo-chlorine pesticides is respectively 42.1,62.3, and 164.7,24.1,27.9 and 136.4pg.
The simulating pollution water body is after composite film material purifies, and organo-chlorine pesticide content reduces greatly, reduces to 0.02～0.34 μ g/L by 10 μ g/L behind the 96h.Except that lindane, composite membrane for height lipophilicity in the water, residual quantity is low but the most serious trefanocide, heptachlor, drinox, the dieldrite, 4 of harm, removal effects such as 4 '-DDT are all more than 99%, concrete outcome sees Table 3.
Target compound change in concentration in table 3 Simulated Water (μ g/L)
Time (h) Fo Leling lindane heptachlor drinox dieldrite 4 ' 4-DDT
0 10.00 10.00 10.00 10.00 10.00 10.00
1 1.28 1.91 1.29 0.88 1.45 1.97
2 0.71 1.49 0.43 0.83 0.74 1.32
4 0.57 1.64 0.33 0.49 0.63 1.34
8 0.26 1.21 0.43 0.39 0.41 0.63
12 0.11 0.69 0.18 0.18 0.11 0.51
24 0.11 1.01 0.18 0.08 0.10 0.40
48 0.04 0.39 0.14 0.04 0.04 0.02
96 0.03 0.34 0.08 0.02 0.02 0.02
The 96-h clearance
99.7 96.6 99.2 99.8 99.8 99.8
(％)
Claims (4)
1, a kind of biological species ester/cellulose acetate composite film preparation methods the steps include:
Cellulose acetate family macromolecule material dissolves in solvent, is added biological species ester and additive, place baking oven 25-45 ℃ dissolving evenly until the dissolving of film liquid; With liquid-solid phase conversion legal system film, 25-40 ℃ of system film temperature, evaporation time is 20-60s, the cooling bath temperature is 15-25 ℃; The film water that makes is rinsed out remaining solvent, store in the distilled water;
Described cellulose acetate family macromolecule material is poly-cellulose acetate;
Described solvent is dioxane and acetone;
Described biological species ester is that fatty glyceride is or/and phosphide;
Described additive is a magnesium perchlorate;
By weight percentage, cellulose acetate family macromolecule material 16-22%, dioxane 5-15%, acetone 55-75%, additive 1-4%, biological species ester 0.1-6%.
2, preparation method as claimed in claim 1, it is characterized in that, surface at liquid-solid phase conversion legal system film forms a compacted zone, and this compacted zone can prevent that the inner ester of film from dripping leakage, and the foreign molecules amount can enter less than 1000 pollutant and innerly reaches balance mutually with ester.
3, the described preparation method of claim 1 is characterized in that, described cellulose acetate family macromolecule material is that cellulose acetate, cellulose diacetate are or/and Triafol T.
4, preparation method as claimed in claim 1 is characterized in that, described biological species ester is that glycerol trioleate is or/and phosphoglyceride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100504355C (en) * | 2004-04-02 | 2009-06-24 | 中国科学院生态环境研究中心 | Biological effective phosphor determining method |
| CN100491262C (en) * | 2004-07-02 | 2009-05-27 | 中国科学院生态环境研究中心 | Biological lipid/high molecular composite adsorbent for removing persistent organism from water and its preparing process |
| CN100431690C (en) * | 2006-12-01 | 2008-11-12 | 山西大同大学 | Compound absorbent embedded lipid in cellulose acetate/cyanoethyl cellulose acetate commixture, its preparation method and application |
| CN101830088B (en) * | 2010-04-26 | 2012-08-08 | 山西大同大学 | Lecithin/acetate composite enrichment material with chitosan/acetate surface coating |
| CN103111190B (en) * | 2013-03-05 | 2014-11-19 | 天津工业大学 | Method for preparing hollow fiber membranes by melt extrusion process |
| CN108236846A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院宁波城市环境观测研究站 | A kind of polymer compound film and preparation method thereof |
| CN106823851B (en) * | 2017-02-21 | 2019-09-27 | 中国科学院生态环境研究中心 | A kind of polymer absorbant/cellulose acetate composite film material and the preparation method and application thereof |
| CN106917263B (en) * | 2017-03-24 | 2019-03-22 | 马鞍山中创环保科技有限公司 | A method of heavy metal ion exchange fiber is prepared using discarded acetate fiber |
| EP3603780A4 (en) | 2017-03-30 | 2020-12-16 | Toray Industries, Inc. | Separation film and production method therefor |
| CN112743943B (en) * | 2020-12-30 | 2023-09-26 | 上海海洋大学 | Controlled release type degradable active packaging film and preparation method and application thereof |
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