CN113667037B - Photosensitive modified chitosan and preparation method and application thereof - Google Patents
Photosensitive modified chitosan and preparation method and application thereof Download PDFInfo
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
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- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/04—Printing inks based on proteins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/14—Printing inks based on carbohydrates
Abstract
The invention provides a preparation method of photosensitive modified chitosan, which comprises the following steps: 1) Dissolving a proper amount of chitosan and acetic acid in deionized water, and uniformly mixing to obtain a mixed solution; 2) Adding a proper amount of methacrylic anhydride into the mixed solution to obtain a reaction mixed solution, and carrying out heat preservation and stirring reaction at 40-80 ℃; the volume fraction of the methacrylic anhydride in the reaction mixture is 1-15%, preferably 6-8%; 3) And (3) after the reaction, adjusting the pH value to 7 by using sodium bicarbonate solution, and purifying and drying to obtain the photosensitive modified chitosan. The invention also provides gelatin-photosensitive modified chitosan ink prepared based on the method and application thereof. The gelatin-modified chitosan membrane provided by the invention has a microporous structure, and shows higher degree in an oil-water separation experiment>90%) and the membrane flux for higher viscosity pump oil is maintained at 1000Lm ‑2 h ‑1 The above.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a new material for environmental protection and 3D printing technology, and particularly relates to photosensitive modified chitosan, and a preparation method and application thereof.
Background
The chitosan is second most biological polysaccharide which is inferior to cellulose, has good biocompatibility and biodegradability, is cheap and easy to obtain, is nontoxic and harmless, and has a large number of amino, hydroxyl and other hydrophilic functional groups on the molecular chain of the chitosan, so that the chitosan has certain application potential in the field of oil-water separation. However, pure chitosan solution systems cannot be directly applied to 3D printing technology due to their good fluidity, and require modification or blending with other polymers.
Due to the dissolution of chitosanThe solution stability and the solubility of the agent system are poor, so that the process parameters of the chitosan in the gel printing process are easy to fluctuate, and the precise control is difficult. Therefore, in the existing gel printing materials at present, chitosan is mostly used as an additive, and related researches on using chitosan as a gel printing host material are less. Domestic Zhou Tao uses chitosan/hydroxyapatite as raw material, and prints in low temperature environment to prepare the biological scaffold with porous network structure and good toughness. In addition, foreign Li and the like [29] The method is characterized in that an industrial robot is used for controlling the relative motion between a chitosan printing liquid spray head and a cross-linking agent spray head, so that chitosan solution is rapidly cross-linked and solidified to form gel after being sprayed out according to a preset track. Meanwhile, martino et al print out a multi-layer gel structure using a similar method. However, the apparent mass of the gel is reduced after the gel is stacked layer by layer due to the influence of factors such as liquid tension and gravity in the printing process. Through the analysis, the method lays a foundation for the feasibility and the application of the chitosan gel printing, but has the problem of higher requirements on the hardware and the control precision of forming equipment.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for modifying chitosan through methacrylic anhydride to enhance the water solubility and photosensitivity of chitosan, so that the chitosan is suitable for a photocuring 3D printing technology. And (3) performing acylation reaction on methacrylic anhydride and chitosan, and introducing hydrophilic groups to obtain the methacrylic anhydride acylated chitosan with good hydrophilicity and photosensitivity. And mixing the modified chitosan with gelatin, and performing photo-curing 3D printing to prepare the super-hydrophilic and underwater oleophobic biological base oil water separation membrane material with the controllable micro-nano coarse structure.
The invention firstly provides a preparation method of photosensitive modified chitosan, which comprises the following steps:
1) Dissolving a proper amount of chitosan and acetic acid in deionized water, and uniformly mixing to obtain a mixed solution;
2) Adding a proper amount of methacrylic anhydride into the mixed solution to obtain a reaction mixed solution, and carrying out heat preservation and stirring reaction at 40-80 ℃; the volume fraction of the methacrylic anhydride in the reaction mixture is 1-15%, preferably 6-8%;
3) After the reaction, sodium bicarbonate solution is used for adjusting the pH value to 7, and the photosensitive modified chitosan is obtained after purification and drying;
preferably, the purification is achieved by dialysis treatment in deionized water for 6 days; more preferably, the drying is achieved by freeze drying.
The invention also provides the photosensitive modified chitosan prepared based on the preparation method.
The invention further provides application of the photosensitive modified chitosan in preparation of 3D printing ink.
The invention also provides a preparation method of the photosensitive 3D printing biological ink, which comprises the following steps:
a) The photosensitive modified chitosan and a photoinitiator I2959 (2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone) are dissolved in deionized water and uniformly mixed to obtain a mixed solution; preferably, the ratio of the photosensitive modified chitosan, the photoinitiator I2959 and deionized water is 10:0.5-4:1 in mg/ml;
b) Mixing the mixed solution with gelatin solution in equal volume to obtain photosensitive 3D printing biological ink;
preferably, the gelatin solution has a concentration of 5w/v% to 12w/v%.
The invention also provides photosensitive 3D printing biological ink, which contains the photosensitive modified chitosan.
Preferably, the photosensitive 3D printing bio-ink is prepared according to the preparation method.
The invention also provides application of the photosensitive 3D printing biological ink in preparation of an oil-water separation material.
The invention also provides a porous membrane for oil-water separation, which is prepared by the method comprising the following steps:
preparing a gel film by using the photosensitive 3D printing biological ink through a 3D printing method, and drying the gel film to obtain the photosensitive 3D printing biological ink;
preferably, a low-temperature spray head, a curing platform and a needle with an inner diameter of 0.41mm are used in the 3D printing process; more preferably, the speed is 6-8mm/s and the pressure is 2-0.08MPa; further preferably, the drying temperature is 37 ℃.
The invention further provides application of the porous membrane in oil-water separation.
Preferably, the oil in the oil-water separation is selected from one of pump oil, peanut oil, cyclohexane, n-heptane, petroleum ether or silicone oil.
The technical scheme of the invention has the following beneficial effects:
the invention provides photosensitive modified chitosan, which is blended with gelatin to enhance the mechanical properties of printing ink, so that photo-curing 3D printing ink is successfully prepared, and a bio-based porous membrane for oil-water separation is prepared through 3D printing. The gelatin-modified chitosan membrane provided by the invention has a microporous structure, and shows higher degree in an oil-water separation experiment>90%) and the membrane flux for higher viscosity pump oil is also maintained at 1000L m -2 h -1 The above-mentioned method shows higher separation flux for other organic solvents and low-viscosity oil products (7450L m -2 h -1 ). The water contact angle of the biomass film is measured, so that the composite material has super-hydrophilicity, has great potential in the field of oil-water separation, and can be used as a water-absorbing material for oil purification.
Drawings
FIG. 1 is a flow chart of the preparation of photosensitive modified chitosan;
FIG. 2 is a nuclear magnetic hydrogen spectrogram of a photosensitive modified chitosan structure;
FIG. 3 shows the nuclear magnetic hydrogen spectra of CH-MA with different anhydride ratios;
FIG. 4 is a graph showing the variation of the grafting ratio of CH-MA with different anhydride ratios;
FIG. 5 is an infrared spectrum of CH-MA prepared according to the invention;
FIG. 6 is an infrared spectrum of CH-MA prepared according to the invention;
FIG. 7 shows the effect of different concentrations of gelatin doped CH-MA; wherein a is 5w/v%, b is 9w/v%, and c is 12w/v%;
FIG. 8 is a SEM characterization of the bio-based film provided by the present invention;
FIG. 9 is a graph showing the effect of the biological base film provided by the invention on the wettability of water in air;
FIG. 10 is a schematic diagram of an oil-water separation device;
FIG. 11 is a diagram showing an oil-water separation process;
FIG. 12 is a graph of membrane flux and separation efficiency for different types of oil-water mixtures;
FIG. 13 is a graph showing the results of the oil-water separation cycle test of the silicone oil-water mixed system.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
Instrument and reagent
The main materials and reagents used in the present application are shown in Table 1, and the instrument and apparatus are shown in Table 2, unless otherwise stated.
TABLE 1 raw materials and reagents used in experiments
Table 2 laboratory apparatus
EXAMPLE 1 preparation of photosensitive modified chitosan (CH-MA)
Methacrylic Anhydride (MA) was added to 1.5% (w/v) Chitosan (CH) solution and reacted for 4 hours, the reaction was as shown in FIG. 1. The resulting product was added dropwise to sodium bicarbonate solution to neutralize and remove excess anhydride. And then dialyzing to obtain methacrylic acid modified chitosan (CH-MA). The influence of grafting rate on the water solubility of the modified chitosan is explored by changing the ratio of methacrylic anhydride to amino groups in the chitosan (1:1, 2:1, 4:1, 5:1, 7:1, 8:1, 10:1, 15:1 and 16:1), and the prepared modified chitosan is named as CH-MA1, CH-MA 2, CH-MA 4, CH-MA 5, CH-MA 7, CH-MA 10, CH-MA 15 and CH-MA16 respectively. The method comprises the following specific steps:
to 30.+ -. 0.5ml deionized water, 0.5.+ -. 0.025mg chitosan and 0.5.+ -. 0.08ml acetic acid were added and mixed well. Adding methacrylic anhydride with a certain proportion at 40+/-20 ℃, stirring for 3-6 hours, neutralizing unreacted methacrylic anhydride with a sodium bicarbonate solution with a certain concentration, dialyzing in deionized water for 6 days, and freeze-drying for 4 days to obtain the photosensitive chitosan fiber.
EXAMPLE 2 preparation of photosensitive 3D printing ink (CH-MA/GE)
Weighing a certain amount of CH-MA, adding 0.05-0.4wt% of I2959 photoinitiator and gelatin solution, stirring uniformly, and filling the solution into a 3D printing material cylinder to obtain the 3D printing ink.
S1, adding 200+/-10 mg of photosensitive chitosan fiber and 5-40mg (0.05-0.4 wt%) of photoinitiator I2959 (2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone) into 20ml of deionized water, and uniformly stirring to obtain a mixed solution for later use.
S2 preparation of gelatin solution: preparing 5w/v% -12w/v% gelatin solution at 40+ -5deg.C for use.
S3, preparation of ink: and (3) uniformly mixing the mixed solution obtained in the step (S1) with a gelatin solution in an equal volume at room temperature to obtain the 3D printing ink.
Example 3 characterization of ink:
successful grafting of methacrylic anhydride onto chitosan was verified using infrared spectroscopy (FTIR) and nuclear magnetic hydrogen spectroscopy (1H NMR). The measurement is carried out by using a Nicolet image 410 type infrared spectrometer, and the test resolution is 4
cm -1 The scanning times are 32 times, and the test range is 400-4000cm -1 . The characteristic that different substances have selective absorption to infrared rays with different wavelengths is utilized, the high-resolution infrared spectrum is used for detecting CH-MA, and the main body components in the sample can be qualitatively analyzed according to the characteristic peaks. At the same time can pass through 1 And (3) quantitatively analyzing the modified chitosan by H NMR, and determining the grafting rate of MA on CH. The grafting ratio (DS) of CH-MA is calculated as follows:
wherein A is H(5.5&6.0) Corresponding to vinyl proton peak, A H(3.0-4.0) Corresponding to the glucosamine ring peak.
By passing through 1 The H NMR spectrum confirms the chemical structure of CH-MA (as shown by a in fig. 2), with b in fig. 2 clearly showing 5.6 and 6.0ppm (g, 2 H,CH 2 ) Vinyl proton peak of (a), glucosamine cyclomethylene proton signal of 4.44ppm (a, 1 H,CH)，3.4-3.9ppm(c-d-e-f,5H,CH-CH-CH-CH 2 ) The glucosamine ring proton peak of (a) was found to be at 3.03ppm (b, 1 the methylene proton peak of H, CH) acylated chitosan at 1.9ppm (i, 3H, CH 3 ) The methyl proton peak at 1.78ppm (h, 3 H,CH 3 ) Methyl proton peak of methacrylic anhydride residue. No chemical shift occurs in the NMR spectrum of natural chitosan at 5.5-6.0ppm, as shown in fig. 3, and only vinyl protons at 5.5-6.0ppm will show chemical shift signals. The appearance of vinyl proton peaks confirms the grafting of methacrylate groups onto chitosan.
The degree of methacrylation of chitosan, expressed in terms of the grafting ratio, is a key parameter determining the solubility of the functionalized chitosan and the performance of the 3D printing ink, and is closely related to the molar ratio of methyl methacrylate to chitosan. CH-MA with different grafting rates is synthesized by changing the mole ratio of methacrylic anhydride to amino. As can be seen from fig. 3, when the molar feed ratio of the corresponding anhydride to the amino group was 1:1, 2:1, 4:1, 5:1, 7:1, 8:1, 10:1, 16:1, the grafting ratio of the photosensitive modified chitosan was 19.3%,22.6%, 26.9%,28.3%,31.8%,33.4%,44.3% and 61.7%, respectively. As can be seen from FIG. 4, the grafting ratio of CH-MA1 to CH-MA16 is linearly and positively correlated with the ratio of methacrylic acid used in the acylation reaction, so that the grafting ratio of the selected CH-MA can be precisely controlled by adjusting the ratio of anhydride to amino group. As can be seen from the pink region of FIG. 3, the 10-fold peaks are fewer, the solubility is poor, and as can be seen from FIG. 4, the grafting ratio of CH-MA 10 and CH-MA16 suddenly increases significantly, probably due to esterification of methacrylic anhydride with chitosan.
Infrared characterizations of different concentrations of methacrylic amidated chitosan are given in fig. 5. Pure chitosan was found at 1650cm -1 And 1590cm -1 Two characteristic peaks at which, respectively, are attributable to NH with primary amine 2 The connected c=o stretching vibration and N-H bending vibration. As can be seen from the figure, 1590cm after grafting methacrylic anhydride -1 The bending vibration peak wave number of the primary amine is shifted to 1540cm -1 The amide II of (C) has a characteristic peak, which proves the occurrence of N-acylation. And 1650cm -1 The increase in peak intensity of the stretching vibration of c=o also successfully demonstrates the introduction of methacrylic functional groups. 1620cm -1 The new peak appearing at the position corresponds to N-H in-plane bending vibration of an amide bond, 1720cm -1 The new peak appearing at this point corresponds to the c=c stretching vibration brought about by the introduction of the methacrylate group, and both peaks increase in intensity with increasing anhydride ratio. Thus, it can be seen that MA was successfully grafted onto CH.
In theory, as the proportion of methacrylic anhydride increases, the intermolecular and intramolecular hydrogen bonding of chitosan is greatly reduced, and the water solubility of the modified chitosan should be gradually increased. However, as can be seen from FIG. 4, the grafting ratio from CH-MA 8 to CH-MA16 suddenly increased to a large extent. Verification of CH-MA esterification by FT-IR, as shown in FIG. 6, functionalized chitosan was reacted at 3350cm -1 The intensity of the nearby-OH stretching vibration peak is continuously reduced and the peak is gradually widened, 1760cm -1 The occurrence of the characteristic peak of carboxyl group at the site also proves that the hydrophilic group of CH-MA is reduced due to the occurrence of the esterification reaction, and thus the water solubility is reduced.
In summary, as the MA ratio increases, the degree of acylation reaction increases, the grafting ratio of the modified chitosan gradually increases, and the intermolecular and intramolecular hydrogen bonds of the chitosan are destroyed, so that the water solubility is greatly increased, and therefore, the CH-MA with the highest grafting ratio should be selected theoretically. However, the solubility of chitosan of CH-MA 10 and above in water was found to be not good in the actual ink formulation, and it was confirmed by infrared analysis that the effect was probably due to the esterification reaction. Therefore high multiples of CH-MA are not suitable for 3D printing, the most preferred is to configure the 3D printing ink with CH-MA 8.
Example 4 photocured 3D printed biobased film
In this experiment, a low-temperature spray head, a curing platform and a needle with an inner diameter of 0.41mm are selected, and in order to enable the printing result to reach the preset internal filling parameters, the parameters such as temperature, air pressure, speed, needle type and the like during printing are required to be repeatedly adjusted. By testing the printing function, a group of proper printing parameters can be rapidly tested, and the printing parameters in the experiment are the speed of 6-8mm/s and the pressure of 2-0.08MPa. And (3) placing the printed gel film in an oven to be dried at 37 ℃ to obtain the bio-based film capable of being stored for a long time.
The effect of mixing different concentrations (5 w/v%,9w/v% and 12 w/v%) of gelatin with CH-MA was tested at the beginning of printing. As shown in fig. 7 a, the ink viscosity was too low to be formed at a gelatin concentration of 5 w/v%; as shown in FIGS. 7 b and c, inks with gelatin concentrations of 9w/v% and 12w/v% were better printable, film forming and consistently shaped, and maintained their geometric and mechanical integrity during subsequent drying. Therefore, from the economical point of view, a gelatin solution blending modified chitosan having a concentration of 9w/v% was prepared to prepare a 3D printing ink.
Example 5 measurement of Membrane Performance
1. Surface morphology characterization (SEM)
The test was performed using a Hitachi S-4800 scanning electron microscope. The main technical parameters are as follows: the secondary electron imaging resolution is 1.0nm, the multiplying power is 20-800000X, the acceleration voltage is 0.1-30 kV, and the maximum size of the sample is less than 100mm. Scanning Electron Microscopy (SEM) primarily uses secondary electron signals to observe the surface morphology of the sample. The interaction between the electron beam and the sample produces various effects in order to obtain surface morphology information of the sample and the sample by scanning the surface of the sample with an electron beam. The printed film was cut into small squares (1 cm. Times.1 cm), and the film surface morphology was studied using a scanning electron microscope.
The surface of the bio-based membrane was characterized by SEM, and the printed membrane surface as shown in fig. 8 had a distinct microporous structure with a pore size of about 2-5 μm.
2. Contact angle measurement
The dried film is soaked in deionized water to be stretched, then the moisture on the surface is absorbed by water absorbing paper, then the film is placed on a glass slide, and a contact angle measuring instrument is used for measuring the wetting angle of the surface to characterize the wettability of the film.
Fig. 9 is a test of the wettability of a film surface by water in air. When the water drop contacts the surface of the biomass film, a certain time is required for complete development on the surface, complete wetting is performed for about 0.1s, the contact angle with water in air is about 0 degrees, and super-hydrophilicity is exhibited. This shows that the membrane has wide application prospect in oil-water separation.
3. Oil-water separation experiment
In the experiment, the oil slick is mainly separated, and a mixture of different oils (n-heptane, cyclohexane, pump oil, peanut oil and petroleum ether) and water (oil-water volume ratio=3:7) is prepared, so that whether the 3D printing film can perform oil-water separation or not is tested. Deionized water was dyed with methylene blue, n-heptane, cyclohexane and petroleum ether with methyl orange for ease of observation during the experiment.
The oil-water separation experimental device is shown in fig. 10. The film with the radius of 0.7cm is loaded on a stainless steel net and then fixed between two oil-water separation pipes. The oil-water mixture is poured into a glass tube for separation, and the whole process is completely driven by gravity.
The membrane flux and separation efficiency were mainly tested during the separation process. From the osmotic volume per unit time
The flux of the membrane is as follows:
wherein V is the volume (L) of the separated oil-water mixture, A is the effective filtration area (m 2 ) T is the test time (h).
The separation efficiency is calculated by weighing the mass of the separated water, with the formula:
wherein m is 0 For the initial water mass, m Cup with cup body Mass of empty cup, m Measuring The quality of the cup and water after separation is completed.
The separation process of the oil-water mixture as shown in fig. 11: after pouring into a glass tube, water selectively passes through the biomass film under the action of gravity, while oil is blocked and stays in the upper tube, and the oil does not flow down after being observed within 1min, so that the bio-based film has the super-hydrophilic underwater oleophobic property.
The test result shows that in the oil-water separation process, when oil-water mixtures of pump oil, peanut oil, cyclohexane, n-heptane, petroleum ether and silicone oil are subjected to membrane separation according to the oil-water volume ratio of 3:7, certain difference exists in membrane performance. Figure 12 shows membrane flux and separation efficiency of bio-based membranes during separation of different oil-water mixtures. It can be seen that the membrane flux of the silicone oil is highest and can reach 7540L m -2 h -1 The separation efficiency was 98.0%. Membrane flux of cyclohexane, n-heptane and petroleum ether is 4000L m respectively - 2 h -1 ，4493L m -2 h -1 ， 4742L m -2 h -1 The oil-water separation efficiency was 98.1%,98.5% and 97.8%, respectively. Peanut oil and pump oil have lower membrane fluxes, 2300L m respectively, than the 4 oils and organic solvents described above -2 h -1 And 1276L m -2 h -1 The separation efficiency was poor, 96.3% and 95.0%. When separating oil-water mixture, the bio-based film prepared by the invention can still keep the film flux at 1000L m -2 h -1 The above separation efficiency>95%. The prepared bio-based film has good oil-water separation performance.
In siliconThe oil circulation separation test is taken as an example, and the result is shown in fig. 13, the separation efficiency in the separation process is kept above 90%, and the highest separation efficiency can reach 98.5%. The highest membrane permeation flux in the separation process can reach 7540L m -2 h -1 The flux decreased to some extent with increasing cycle number, with the last cycle flux being 5940 and 5940L m -2 h -1 . The biological-based film provided by the invention can complete 10 times of cycle tests and has good mechanical properties. While the membrane flux is finally maintained at 5000L m - 2 h -1 The oil-water separation efficiency is above 90%, which indicates that the prepared bio-based film has stable separation performance.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (6)
1. A porous membrane for oil-water separation, which is characterized by being prepared by a method comprising the following steps: preparing gel film by using photosensitive 3D printing biological ink through a 3D printing method, and drying the gel film to obtain the gel film;
the 3D printing process comprises a low-temperature spray head, a curing platform and a needle head with the inner diameter of 0.41 mm; the speed is 6-8mm/s, the pressure is 2-0.08MPa, and the drying temperature is 37 ℃;
the photosensitive 3D printing biological ink is prepared according to the following preparation method, and comprises the following steps:
a) The photosensitive modified chitosan and a photoinitiator I2959 (2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone) are dissolved in deionized water and uniformly mixed to obtain a mixed solution; the ratio of the photosensitive modified chitosan, the photoinitiator I2959 and deionized water is 10:0.5-4:1 in mg/ml;
b) Mixing the mixed solution with gelatin solution in equal volume to obtain photosensitive 3D printing biological ink; the concentration of the gelatin solution is 5w/v% -12 w/v%;
the photosensitive modified chitosan is prepared according to the following preparation method, and comprises the following steps:
1) A proper amount of chitosan and acetic acid are dissolved in deionized water, evenly mixed and configured to obtain 1.4w/v% -1.6w/v% chitosan solution;
2) Adding a proper amount of methacrylic anhydride into the mixed solution to obtain a reaction mixed solution, and carrying out heat preservation and stirring reaction at 40-80 ℃; the volume fraction of the methacrylic anhydride in the reaction mixed solution is 1-15%;
3) And (3) after the reaction, adjusting the pH value to 7 by using sodium bicarbonate solution, and purifying and drying to obtain the photosensitive modified chitosan.
2. The porous membrane of claim 1, wherein in step 1), chitosan and acetic acid are used in an amount of 0.75 to 1:1 in mg/ml, and the final concentration of acetic acid in the chitosan solution is 1.5% to 2.0%.
3. The porous membrane of claim 1, wherein in step 2), the methacrylic anhydride is present in the reaction mixture in a volume fraction of 6 to 8%.
4. The porous membrane of claim 1, wherein in step 2), the purification is achieved by dialysis treatment in deionized water for 6 days, and the drying is achieved by freeze drying.
5. Use of a porous membrane according to claim 1 for oil-water separation.
6. The use according to claim 5, wherein the oil in the oil-water separation is selected from one of pump oil, peanut oil, cyclohexane, n-heptane, petroleum ether or silicone oil.
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