TWI473646B - Fibrous membrane and a method for using the fibrous membrane for wastewater treatment - Google Patents

Description

Fiber film and method for treating waste liquid using the same

The invention relates to a fiber film, in particular to a fiber film which can be applied to a waste liquid. The invention further relates to a method of treating a waste liquid using the fibrous film.

Nowadays, the industry is developing rapidly, people's living standards are also increasing, and environmental awareness is on the rise. Therefore, the problem of waste disposal is also attached to industrial development.

The method commonly used in the prior art for treating waste liquid is, for example, flocculation after concentration of waste liquid, so that the sediment of fine particles suspended in water is condensed into a bulky floc agglomerate, and then flocculated by flotation. The object is removed from the water. However, this method can only separate the flocculent agglomerates having a large solid content from the water, and the flocculent agglomerates having a small solid content remain in the water, so the effect of purifying the waste liquid is not good.

Another way to treat waste liquid is to use a porous membrane made of a polymer and containing a plurality of micropores having a pore diameter of 0.02 to 20 micrometers (μm), which can be used to adsorb waste liquid. Contaminants, such as colloidal particles, bacteria, etc. However, if the porous membrane is saturated, it can no longer be treated by waste liquid, and the saturated porous membrane must be desorbed before continuing. It is applied to waste liquid treatment, and the recycling is repeated until the adsorption capacity is lost. However, the biggest disadvantage of the porous membrane is that it cannot be decomposed, so that the discarded porous membrane is easy to pollute the environment, and the highly polluted sludge needs to be subjected to subsequent recycling treatment, thereby increasing the cost of the waste liquid treatment.

Therefore, the material used in the prior art for treating waste liquid cannot meet the requirements of today's green materials and the effect of good waste liquid purification.

In order to solve the existing material for treating waste liquid, the waste liquid purification effect is not good, and the waste liquid containing organic substances such as benzene rings which are highly polluting, and the waste liquid of the treatment waste liquid are not green materials. Disadvantages of the present invention are to provide a fiber film which can effectively adsorb the adsorbate in the waste liquid and is an environmentally friendly material, so that it can be decomposed after use without causing environmental pollution.

In order to achieve the above object, the present invention provides a fiber film which is interwoven by a plurality of fibers having a diameter of between 100 nm and 1 μm, and the composition of the fibers is substantially high by green. Made up of molecules.

According to the present invention, the green polymer of the present invention means any polymer having decomposability, and the decomposability means that the polymer is chemically bonded by any means such as, but not limited to, light, microorganisms, or the like. The fracture or the transfer of atomic groups and the like, so that the chemical structure of the polymer is destroyed and becomes a compound having a small chain segment, so that it can be recycled and reused to become an environmentally friendly material.

Preferably, the green polymer comprises a natural green polymer and a matrix selected from the group consisting of a polyester green polymer, a polyvinyl green polymer, and the like. According to the present invention, the fiber film of the present invention is made by, but not limited to, the following method: a green polymer solution is prepared, the green polymer solution contains a natural green polymer, a matrix, and a green natural solution Polymer solvent, Wherein the natural green polymer is based on the total weight of the green polymer solution, but is not limited to 20 to 80 wt%, and the content of the matrix is, but not limited to, 10 to 20 wt%, the natural green The polymer and the content of the matrix can be adjusted to adjust the concentration and conductivity of the green polymer solution to be combined with the subsequent spinning process; the green polymer solution is spun to obtain the fiber film of the present invention, wherein the thickness of the fiber film It can be controlled by the length of the spinning time.

According to the present invention, the matrix of the present invention facilitates the spinning of the green polymer solution, thereby making the spinning process smoother. Further, the matrix makes the structure of the fiber film of the present invention more supportive.

Preferably, when the natural green polymer is chitosan, the solvent is acetic acid.

Preferably, the green polymer solution is spun by electrospinning.

According to the present invention, the natural green polymer of the present invention refers to a polymer obtained by extracting or extracting from a substance in nature or by biodegradation, such as, but not limited to, a chitin or a shell of a shell animal. Obtained in the exoskeleton.

According to the present invention, the polyester-based green polymer of the present invention means any polymer having an ester group-functional group in the main chain and having decomposability.

According to the present invention, the polyvinyl-based green polymer of the present invention means any polymer having a vinyl functional group and having decomposability in its main chain.

Preferably, the polyester green polymer is selected from the group consisting of polyglycolic acid (PGA), polylactic acid (PLA), and polyhydroxyalkanoates (PHA). , Poly(lactic-co-glycolic acid, PLGA), poly cyclic lacton, and combinations thereof.

According to the present invention, the polycyclic lactones of the present invention are, for example but not limited to, polycaprolactone (PCL) or pivalolactone (PVL).

According to the present invention, the polyhydroxy fatty acid ester of the present invention is, for example but not limited to, polyhydroxybutyrate (PHB) or polyhydroxyvalerate (PHBV).

Preferably, the polyvinyl-based green polymer is selected from the group consisting of polyethylene oxide (PEO), polyvinyl alcohol (PVA), and polyvinyl acetate. , PVAC), poly(etherketone), PEK, and combinations thereof.

Preferably, the natural green polymer is selected from the group consisting of collagen, alginate, hyaluronic acid, gelatin, chitin (chitin) ), chitosan, and combinations thereof.

Preferably, the matrix is a combination of a polyester green polymer and a polyethylene based green polymer.

Preferably, the content of the natural green polymer is 6 to 90 wt% based on the total weight of the green polymer, and the weight ratio of the polyester green polymer to the polyethylene glycol is between Between 1:5 and 5:1.

Preferably, the green polymer is a crosslinked green polymer obtained by crosslinking the natural green polymer and the substrate via a crosslinking agent.

According to the present invention, the crosslinking agent of the present invention means any of the present invention. The green polymer is branched and further branched to form a three-dimensional network-like and water-insoluble polymer, such as, but not limited to, 1,6-diisocyanatohexane (HDI), Toluene diisocyanate (TDI), epichlorohydrin (ECH), Tetraphenylporphyrin (TPP), glutraraldehyde, 1,1,3,3-tetra Methoxypropane (1,1,3,3-tetramethoxypropane) or glycerolpolyglycidylether.

According to the present invention, the "cross-linking reaction" according to the present invention means that the fiber film is immersed in a crosslinking agent solution containing a crosslinking agent and a solvent, and the solvent is any soluble. A solution of the crosslinking agent. For example, when the crosslinking agent is hexane diisocyanate, the solvent is isopropyl alcohol. Wherein the crosslinking agent is from 1 to 15% by weight, based on the total weight of the crosslinking agent solution, preferably 5% by weight. The time of the crosslinking reaction is, for example, but not limited to, 30 minutes, and the time of the crosslinking reaction can be adjusted depending on the content of the crosslinking agent in the crosslinking agent solution. Accordingly, since the material of the fiber film is substantially composed of a green polymer, the material of the fiber film is substantially composed of a crosslinked green polymer after the crosslinking reaction.

Preferably, the fiber membrane has a single layer saturated adsorption amount of between 400 and 2000 g/kg.

According to the present invention, the single layer saturated adsorption amount of the present invention is calculated by the Langmuir constant temperature adsorption equation.

The fiber film of the present invention can have a single layer saturation between 400 and 2000 g/kg by selecting different natural polymers, selecting different substrates, and adjusting various factors such as the content of the natural polymer and the matrix. Suck Attachment.

Preferably, the natural green polymer is chitosan, the polyester green polymer is polycyclolactone, and the polycyclic lactone is polycaprolactone, and the polyethylene is green high. The molecular system is polyethylene glycol, and the crosslinking agent is 1,6-diisocyanatohexane (HDI).

Preferably, the weight ratio of the polycaprolactone to the polyethylene glycol is 1:3, and the content of the natural green polymer is 52% by weight based on the total weight of the green polymer.

Preferably, the single layer saturated adsorption amount of the fibrous film is 454.5 g/kg.

Since the fiber film of the present invention has a diameter of from 100 nm to 1 μm, the fiber film of the present invention has the advantages of a large surface area and a large gap between fibers, and the fiber film of the present invention is applied to waste liquid. During the treatment, since the surface area is large and the gap between the fibers is large, the adsorbate in the waste liquid can be adsorbed in a large amount, so the adsorption effect is good, and the fiber film of the present invention has a fast adsorption rate because it conforms to the pseudo second-order adsorption power mode. Further, since the main component of the fiber film of the present invention is substantially composed of a green polymer, it can be decomposed in an ecological environment after use, and does not cause environmental pollution, so it is an environmentally friendly material. Meet the needs of today.

Further, since the single layer saturated adsorption amount of the fiber film of the present invention is between 400 and 2000 g/kg, the fiber film of the present invention has a good adsorption capacity when used for waste liquid treatment, and further increases greatly. The efficiency of purifying waste liquid.

Further, since the fiber film of the present invention is substantially composed of a crosslinked green polymer, the bond between the green polymers is strengthened, so The fiber film is not prone to cracking, and it can enhance its ability to adsorb the adsorbate in the waste liquid.

The present invention further provides a method for treating a waste liquid using a fiber film, comprising the steps of: preparing the fiber film as described above; placing the fiber film in a waste liquid, wherein the waste liquid contains an adsorbate; The fibrous film is removed from the waste liquid to obtain a treated waste liquid.

According to the present invention, the treatment time according to the present invention is, for example but not limited to, 5 minutes, 10 minutes, 15 minutes, 30 minutes, etc., and more preferably, for example, the fiber membrane adsorbs the adsorbate in the waste liquid until it is in the waste liquid. The time at which the concentration of the adsorbate reaches an equilibrium concentration.

Preferably, the adsorbate is selected from the group consisting of metals, organic dyes, and combinations thereof.

According to the present invention, the metal of the present invention is, for example but not limited to, copper ion (Cu(II)), lead ion (Pb(II)), iron ion (Fe(II)) cadmium ion, zinc ion or nickel ion. .

According to the present invention, the organic dye of the present invention refers to any molecule containing an auxochrome and a chromogen, such as a functional group containing a double bond such as, but not limited to, benzene. , toluene, xylene, phenol, cresol, naphthalene, anthracene, etc. The chromogen system is, for example but not limited to, a functional group such as a hydroxyl group, a sulfonic acid group or an amino group.

According to the present invention, the organic dye of the present invention is, for example but not limited to, an azo dye, a triaryl methane dye, an anthraquinone dye, or a heterocyclic dye. Or phthalocyanine dye, etc.

Preferably, the organic dye is sodium 2-naphthol azo-p-benzenesulfonate.

Preferably, when the weight ratio of the weight of the fiber membrane to the adsorbate in the waste liquid is greater than or equal to 0.67, the adsorption rate of the fiber membrane is greater than 60%.

According to the present invention, the adsorption rate of the fibrous film according to the present invention means [(the concentration of the adsorbate of the waste liquid - the adsorbate concentration of the waste liquid after the treatment) / the adsorbate concentration of the waste liquid] × 100%.

Preferably, the concentration of the adsorbate of the waste liquid is between 50 mg/liter (ppm) and 150 ppm, and the weight of the fiber membrane is 0.005 g, and the concentration of the adsorbate in the waste liquid after the treatment The system is between 0 and 90 ppm.

The method for treating waste liquid by using the fiber membrane of the invention has the advantages of simple steps and no need to add any chemical agent such as flocculating agent, so that the adsorbed substance in the waste liquid can be easily utilized by the fiber membrane, and the fiber membrane after use has biological decomposition. Sexuality, does not cause environmental pollution, and when the waste liquid contains an organic dye or a metal adsorbent, the fiber film can be obtained from the waste liquid, and a treated waste liquid can still be obtained, so the present invention The method for treating waste liquid by using a fiber membrane can be applied to substances containing high pollution in purification of waste liquids such as petrochemical industry, paper industry, photovoltaic industry, food industry, and textile industry, and therefore the method of the present invention has high industrial applicability.

Further, in the method for treating a waste liquid of the fiber film of the present invention, when the weight ratio of the weight of the fiber film to the adsorbate in the waste liquid is greater than or equal to 0.67, the adsorption rate of the fiber film is greater than 60%, so the present invention The method can greatly reduce the adsorption quality in the waste liquid, thereby achieving the effect of good waste liquid treatment.

In order to understand the technical features and practical functions of the present invention in detail, and in accordance with the contents of the specification, the drawings and preferred embodiments are further described to illustrate the technical means for the purpose of the present invention.

The source and composition ratios of the samples described in the experimental preparation schemes of the following examples are as follows; poly(ε-caprolactone, PCL): the number average molecular weight is between 10,000 and 80,000. The melting point is between 57 ° C and 64 ° C, model: Scientific polymer products (USA).

Polyethylene oxide (PEO): The viscosity average molecular weight is between 100,000 and 8,000,000, model: Sigma Aldrich (USA).

Chitosan (CS): Weight average molecular weight between 100,000 and 300,000, model: Acros organics (China).

Acetic acid: concentration: 99.81%.

2-naphthol azo-p-benzenesulfonate (acid orange 7, acid orange 7): melting point: 164 ° C, water solubility: at 30 ° C, 1 liter of water soluble 116 g of 2-naphthol The maximum absorption peak (λmax) of sodium p-benzene sulfonate was 483 nm.

Micropump: Model: Fusion 200 (USA).

High voltage power supply: Output voltage: 0.001 volts (kV) to 30 kV, model: SM3030-24P1R (Taiwan).

Stainless steel needle: outer diameter: 0.41 mm, inner diameter 0.72 mm, length: 5.08 cm.

Teflon tube: inner diameter 1.58 mm.

Collection roller: made of stainless steel.

UV/Vis spectrometer: wavelength range: 175 nm to 900 nm, wave width: 0.05 nm, model: Lambda 850 (USA).

Example 1

In this embodiment, a fiber film is obtained by electrospinning with polycaprolactone, polyethylene glycol and chitosan, and the fiber film is cross-linked to obtain the reinforced fiber film of the embodiment. The detailed preparation method is as follows: First, a magnet is placed in a beaker and 15 ml (mL) of acetic acid and 5 mL of deionized water are added to obtain an aqueous solution of acetic acid, followed by a weight ratio of 1:3. Polycaprolactone and polyethylene glycol in the aqueous acetic acid solution, and the total weight of the polycaprolactone and polyethylene glycol is 2 g, and uniformly stirred to the polycaprolactone and poly by a magnetic stirrer The ethylene glycol is completely dissolved in the aqueous acetic acid solution to obtain a polymer mixture in which the polycaprolactone and the polyethylene glycol are 10 weight percent (wt%) based on the total weight of the polymer mixture. Then, 2.2 g of chitosan was added to the polymer mixture, and ultrasonically oscillated until the chitosan was completely dissolved in the polymer mixture to obtain a green polymer solution.

Then, an electrospinning device is used. The electrospinning device used in the embodiment comprises a green polymer solution supply system, a high voltage power supply electrically connected to the green polymer solution supply system, and a green polymer. The solution supply system is disposed at a distance from the grounded collecting roller, wherein the green polymer solution supply system comprises a micro pump, a syringe connected to the micro pump, a Teflon tube connected to the syringe, and a metal Stainless steel needle connected by a fluorotube. The high voltage power supply includes a wire that is coupled to the stainless steel needle. The grounded collecting roller and The distance between the green polymer solution supply systems is adjustable.

Accordingly, the electrospinning apparatus and the prepared green polymer solution are used to perform the following electrospinning process: the micro pump is opened to allow the syringe to absorb the green polymer solution prepared as described above, and the green polymer solution flows out from the stainless steel needle. The speed is 0.021 ml/min (mL/min), the voltage of the high-voltage power supply is set to 15 kV, and the distance between the grounded collecting roller and the needle of the stainless steel needle is between 5 and 9 cm. The speed of the collecting drum is 700 revolutions per minute (rpm), the temperature of the electrospinning is between 30 and 40 ° C, and the time of electrospinning is 190 minutes, in the electrospinning During the process, the acetic acid of the green polymer solution will volatilize, and the remaining polycaprolactone, polyethylene glycol and chitosan in the green polymer solution will form elongated fibers and adhere to the surface of the collecting roller, and the The fibers are interlaced to obtain a fiber film having a diameter of between 100 nm and 1 μm and a thickness of 0.01 mm.

Preparing a cross-linking agent solution comprising hexamethylene diisocyanate (HDI) and isopropanol, wherein the cross-linking is based on the total weight of the cross-linking agent solution. The hexane of cyanic acid is 5 wt% (wt%), and the fiber film obtained as described above is immersed in the cross-linking agent solution to carry out a cross-linking reaction, and the time of the cross-linking reaction is 30 minutes, whereby polycaprolactone, The polyethylene glycol and the chitosan are cross-linked to obtain a crosslinked green polymer, and a reinforced fiber film is obtained. The reinforced fiber film is taken out from the crosslinking agent solution and then isopropyl alcohol is used. The reinforced fiber film is washed to wash away the cross-linking agent solution remaining on the surface of the reinforced fiber film, and the reinforced fiber film is immersed in deionized water for 15 minutes. The reinforced fiber film is taken out and dried in a vacuum oven to remove residual moisture. The drying time is 24 hours, and finally the reinforced fiber film of the embodiment is obtained, and the fiber of the reinforced fiber film is obtained. The diameter is between 100 nm and 1 μm as shown in Figure 1. The thickness of the reinforced fiber film was 0.01 mm, and the weight of the reinforced fiber film was 0.005 g.

Test example 1 This test example uses a dye solution

This test example uses four different concentrations of dye solution to draw a calibration curve of the relationship between absorbance and concentration, thereby using the equation of the calibration curve to calculate the dye solutions of different concentrations used in Test Example 2 and Test Example 3, and the dye used. The system is 2-naphthol azo-p-benzenesulfonate (acid orange 7, AO7). The detailed calibration curve is as follows: First, prepare a concentration of 1×10 ^-3 M in deionized water. - Naphthol azo-p-benzene sulfonate solution, and then diluting the 2-naphthol azo-p-benzene sulfonate solution to prepare four concentrations of 5 mg/L, 10 ppm, respectively. 25 ppm and 50 ppm of 2-naphthol azo-p-benzenesulfonate solution, and the absorbance of the four concentrations of 2-naphtholazo-p-benzenesulfonate solution was measured using an ultraviolet/visible spectrophotometer to draw The calibration curve of the relationship between absorbance and concentration, the result is shown in Figure 2. The equation of the calibration curve is y=0.0587x+0.0814, and the linear correlation coefficient (R ² ) is 0.9999, that is, the concentration of each The error between naphthol azo and sodium benzene sulfonate solution is small, so the equation of the calibration curve can be used to calculate The concentration of the unknown concentration of 2-naphthol azo benzene sulfonate solution.

Test example 2

In this test example, a 2-naphthol azo-p-benzenesulfonate solution was used as a waste liquid simulating solution to test the constant temperature adsorption mode of the reinforced fiber membrane of Example 1. The detailed test method is as follows: First, prepare the sodium 2-naphtholazo-p-benzenesulfonate solution of samples 1 to 7, and the initial concentrations of each sample are 50 ppm, 75 ppm, 100 ppm, 125 ppm, 150 ppm, respectively. 175 ppm and 200 ppm, and the pH of each sample was adjusted to 3, each sample was 50 mL and placed in a sample vial. A plurality of reinforced fiber membranes prepared in Example 1 were prepared and each strengthened. The fiber membranes were all 0.005 g, and the reinforced fiber membranes were respectively placed in each sample bottle containing each sample, and each sample bottle was thermostated to 30 ° C in a water bath method while uniformly stirring each using a magnet stirrer. The sample and the reinforced fiber film were stirred at a speed of 500 rpm. After four hours, the reinforced fiber film was taken out, and the absorbance of each sample after the treatment was measured using an ultraviolet/visible spectrophotometer, and then the measurement was performed. Each absorbance is substituted into the equation of the aforementioned calibration curve to determine the concentration of each sample after treatment, and each experimental data is brought into the equation (1) to calculate the amount of dye adsorption adsorbed by each of the strengthened fiber membranes (q) _t ).

q _t =(C _o -C _t )V/W (1)

Where q _t is the mass of the solute adsorbed by the unit mass adsorbent after t time, that is, the mass of the dye adsorbed by the unit mass of the strengthened fiber film after t time, unit: g/kg; C _o : Initial concentration of the sample, unit: ppm; C _t : concentration of the sample after t time, unit: ppm; V: volume of the sample, unit: mL; W: initial mass of the fiber film, unit: g.

Calculated dye adsorption amount (q _t) after each dye adsorption amount (q _t), respectively, into the Langmuir adsorption equation is shown below and the temperature thermostat Freundlich adsorption equation: thermostat Langmuir adsorption equation: Where q _e is the adsorption amount of the fiber film when the sample is in equilibrium concentration, the unit is: g/kg; Q is the single layer saturated adsorption capacity of the fiber film, unit g/kg; b is the Langmuir constant temperature adsorption constant ; C _e is the equilibrium concentration of the sample, the unit is: ppm; Freundlich constant temperature adsorption equation: q _e = Q _f Ce ^{1 / n} , where q _e is the adsorption amount of the fiber film when the sample is at equilibrium concentration, unit: g / kg ; Q _f is the adsorption capacity of the fiber film; n is the Freundlich constant temperature adsorption constant; C _e is the equilibrium concentration of the sample, the unit is ppm.

Subsequently each of the experimental data after linear regression Langmuir constant suction line graph (C _e / q diagram _e and C _e's) and the Freundlich constant suction line graph (LNQ diagram _e and lnC _e's), and then were calculated to strengthen The constant temperature adsorption constant and suitability of Langmuir of the fiber film and the constant temperature adsorption constant and suitability of the Freundlich of the fiber film after strengthening.

(1) Langmuir constant temperature adsorption mode of the fiber film after strengthening

As shown in Fig. 3, the slope of the trend line equation in the figure and the intercept can be used to know the single-layer saturated adsorption capacity of the fiber film after strengthening (Q, unit: g/kg), Langmuir constant adsorption constant (b, unit : m ³ /g) and a linear correlation coefficient (R ² ), which represents the suitability of the Langmuir constant temperature adsorption mode. The data is shown in Table 1 below.

(2) Freundlich constant temperature adsorption mode of the strengthened fiber film

As shown in Fig. 4, the saturated adsorption capacity of the fiber film after strengthening (Q _f , unit: g/kg), Freundlich constant temperature adsorption constant (n), and linear correlation coefficient (R ² ) can be seen from the trend line equation in the figure. ), the linear correlation coefficient represents the suitability of the Freundlich constant temperature adsorption mode. The data is shown in Table 1 below.

It can be seen from Table 1 that the constant temperature adsorption mode of the reinforced fiber film of Example 1 is in accordance with the Langmuir constant temperature adsorption mode, so that the single layer saturated adsorption amount of the reinforced fiber film of Example 1 is 454.5 g. /kg, further confirming that the fiber film of the present invention does have an effect of adsorbing the adsorbate in the solution.

In addition, since the dye used in this test is sodium 2-naphthol azo-p-benzene sulfonate, sodium 2-naphthol azo-p-benzene sulfonate is commonly used in the paper and textile industry and has an azo group. And the aromatic group compound is a highly polluting organic dye. Therefore, it can be known from the test examples that the fiber film of the present invention has the effect of adsorbing an organic dye having high pollution, so that the fiber film of the present invention can be applied. It contains highly polluting substances in the discharge of waste liquids such as petrochemical industry, paper industry, photovoltaic industry, food industry and textile industry.

(3) Adsorption rate of fiber film after strengthening

The adsorption rate of each fiber film was calculated by using the difference between the respective samples after the treatment and the respective samples before the treatment, that is, the adsorption rate of the fiber film = [(concentration of the sample before treatment - sample concentration after treatment) / The concentration of the sample before the treatment was ×100%, and the results are shown in Fig. 5.

As can be seen from Fig. 5, when 0.005 g of the reinforced fiber film is used to treat the sodium 2-naphtholazo-p-benzenesulfonate solution before the treatment at a concentration between 50 and 125 ppm, that is, sample 1 to sample 4 The adsorption rate of each of the strengthened fiber membranes is more than 80%, and when 0.005 g of the reinforced fiber membrane is treated with a concentration of 150 ppm of the treated 2-naphthol azo-p-benzenesulfonate solution, , sample 5, because the concentration of 2-naphthol azo-p-benzenesulfonate in sample 5 is relatively high, so when the fiber membrane is reinforced with the weight of 0.005 g, the adsorption position has reached saturation, so adsorption The rate will decrease, so the adsorption rate of the strengthened fiber film is about 65%, so it can be known that when the concentration of the 2-naphthol azo-p-benzenesulfonate solution is between 50 and 150 ppm, The fiber film of the present invention not only has the effect of adsorbing the dye in the solution, but its adsorption rate can be more than 65%. Further, since the weight of the reinforced fiber film used was 0.005 g, and the concentration of sodium 2-naphthol azo-p-benzene sulfonate when the concentration of the 2-naphthol azo-p-benzenesulfonate solution was 150 ppm The ratio is 7.5 mg (0.05 L × 150 mg / L), so the weight ratio of the fiber film after strengthening to the sodium 2-naphthol azo-p-benzenesulfonate is 5 mg / 7.5 mg = 0.67, so it is known When the weight ratio of the weight of the fiber membrane to the adsorbate in the waste liquid is greater than or equal to 0.67, the adsorption rate of the fiber membrane is greater than about 65%.

Test Example 3

In this test example, the adsorption dynamic mode of the reinforced fiber membrane of Example 1 was tested by using a sodium 2-naphtholazo-p-benzenesulfonate solution as a waste liquid simulating solution. The detailed test method is as follows: First, a 2-naphthol azo-p-benzenesulfonate solution having a concentration of 1×10 ^-3 M is prepared in deionized water, and then the 2-naphthol azo-p-benzene sulfonate is prepared. The sodium solution was diluted to prepare a solution of sample 2 to sample 16 in a concentration of 50 ppm of 2-naphthol azo-p-benzenesulfonate, and the pH of each sample was adjusted to 3, and each sample was 50 mL and the system was 50 mL. The sample 8 is placed in a sample bottle, wherein the sample 8 is a blank sample, and a plurality of the reinforced fiber films obtained in the first embodiment are prepared, and each of the reinforced fiber films is 0.005 g, and the reinforced fiber films are respectively obtained. Place the sample vials containing the samples of samples 9 to 16, and then thermostat each sample via a water bath to 30 ° C while uniformly stirring the samples and the reinforced fiber membranes using a magnet stirrer. After 500 rpm, samples 9 to 16 were taken out of each vial after 5, 10, 15, 30, 60, 120, 240, and 480 minutes, respectively, and sample 9 to sample 16 after treatment. As shown in Figure 6, as shown, the color of the solution from sample 9 to sample 16 after treatment The trend fades, it may be that the reinforcing fiber membrane of Example 1 into 2-naphthol azo benzene sulfonate solution for longer, the greater the amount of dye adsorption embodiment, so the lighter the color of the solution.

Then, the absorbance of each sample after the treatment is measured by using an ultraviolet/visible spectrophotometer, and then the measured absorbances are substituted into the equation of the aforementioned calibration curve to determine the concentration of each sample after the treatment, and the experimental data are obtained. It is taken into equation (2) to calculate the amount of dye adsorption (q _e ) adsorbed by each fiber film.

q _e =(C _o -C _e )V/W (1)

Where q _e is the adsorption amount of the fiber membrane when the sample is in equilibrium concentration, unit: g/kg; C _o : initial concentration of the sample, unit: ppm; C _e : equilibrium concentration of the sample, unit: ppm; V: sample Volume, unit: mL; W: initial mass of the fiber film, unit: g.

After calculating the dye adsorption amount (q _e ), the dye adsorption amount (q _e ) is respectively introduced into the pseudo first-order adsorption dynamic equation and the pseudo second-order adsorption dynamic equation: pseudo-first-order adsorption dynamic equation: , wherein Q _t and q _t are the mass of the solute adsorbed by the unit mass adsorbent after t time, that is, the mass of the dye adsorbed by the unit mass of the strengthened fiber film after t time, unit: g/kg; q _e is the adsorption amount of fiber film when the sample is at equilibrium concentration, unit: g / kg; k ₁ is the pseudo first-order adsorption constant, unit: L / min: pseudo second-order adsorption dynamic equation: , wherein Q _t and q _t are the mass of the solute adsorbed by the unit mass adsorbent after t time, that is, the mass of the dye adsorbed by the unit mass of the strengthened fiber film after t time, unit: g/kg; q _e is the adsorption amount of fiber film when the sample is in equilibrium concentration, the unit is: g/kg; k ₂ is the pseudo second-order adsorption constant, the unit is: kg/g-min; then the linear first regression is used to obtain the pseudo first-order adsorption power. The linear graph (the relationship between log(q _e -q _t ) and t) and the quasi-second-order adsorption dynamic linear graph (the relationship between t/q _t and t), and then calculate the pseudo first-order adsorption constant of the strengthened fiber membrane. And the suitability and the pseudo second-order adsorption constant of the fiber film after strengthening and the suitability, wherein the q _t value calculated by the equation (1) is 479.46 g/kg.

(1) Quasi-first-order adsorption dynamic mode

As shown in Fig. 7, the trend line equation in the figure shows the adsorption amount of the strengthened fiber film at the equilibrium concentration (q _e , unit: ppm), and the pseudo first-order adsorption constant (k ₁ , unit: L/min) and the linear correlation coefficient (R ² ), which represents the suitability of the pseudo first-order adsorption dynamic mode. The data is shown in Table 2 below.

(2) Quasi-second-order adsorption dynamic mode

As shown in Fig. 8, from the slope and intercept of the trend line equation in the figure, the adsorption amount of the strengthened fiber film at the equilibrium concentration (q _e , unit: ppm) and the pseudo second-order adsorption constant (k) can be known. ₂ , unit: kg/g-min) and a linear correlation coefficient (R ² ), which represents the suitability of the pseudo second-order adsorption dynamic mode. The data is shown in Table 2 below.

It can be seen from Table 2 that the adsorption amount (q _e ) obtained by the pseudo second-order adsorption dynamic mode is closer to the value of q _t , and the fiber membrane of the strengthened example of Example 1 can be known from the linear correlation coefficient (R ² ). It conforms to the pseudo second-order adsorption dynamic mode. Further, referring to FIG. 9 , comparing the experimental data of the sample 8 of the test example and the sample 9 to the sample 16 after the treatment and the trend line of the second-order adsorption power, the trend of the experimental data and the pseudo second-order adsorption power can be known. The lines are very close, so it can be proved that the strengthened fiber film of Example 1 conforms to the pseudo second-order adsorption power mode.

It can be known from the test examples that the fiber film of the present invention not only has the ability to adsorb the dyeing case, but also has a fast rate of adsorbing the dye because it conforms to the pseudo second-order adsorption dynamic mode.

1 is a scanning electron microscope (FE-SEM) image of a fiber film according to Example 1 of the present invention.

Fig. 2 is a calibration curve diagram showing the relationship between the absorbance and the concentration of Test Example 1 of the present invention.

Fig. 3 is a linear diagram of the Langmuir constant temperature adsorption mode of Test Example 2 of the present invention.

Fig. 4 is a linear diagram of the Freundlich constant temperature adsorption mode of Test Example 2 of the present invention.

Fig. 5 is a graph showing the relationship between the adsorption ratio of each of the reinforced fiber films of Test Example 2 of the present invention and the concentration of each sample.

Fig. 6 is a graph showing the color relationship of Samples 9 to 16 after the treatment of Test Example 3 of the present invention.

Figure 7 is a linear diagram of the pseudo first-order adsorption power mode of Test Example 3 of the present invention.

Figure 8 is a linear diagram of the pseudo second-order adsorption power mode of Test Example 3 of the present invention.

Fig. 9 is a graph showing the relationship between the experimental data of Samples 9 to 16 and the trend line of the second-order adsorption power after the treatment of Test Example 3 of the present invention.

Claims (16)

A fibrous film formed by interlacing a plurality of fibers having a diameter of between 100 nm and 1 μm, the components of the fibers being substantially composed of a green polymer; wherein the green color is high The molecular system is crosslinked by the natural green polymer and the matrix via a crosslinking agent After that. The fibrous film of claim 1, wherein the matrix is selected from the group consisting of The following groups are composed of a polyester green polymer, a polyvinyl green polymer, and the like. The fibrous film according to claim 2, wherein the polyester green polymer is selected from the group consisting of polyglycolic acid (PGA), polylactic acid (PLA), and polyhydroxy fat. Polyhydroxyalkanoates (PHA), poly(lactic-co-glycolic acid, PLGA), poly cyclic lacton, and combinations thereof. The fibrous film according to claim 2 or 3, wherein the polyvinyl-based green polymer is selected from the group consisting of polyethylene oxide (PEO), polyvinyl alcohol (PVA) ), polyvinyl acetate (PVAC), poly(etherketone), PEK, and combinations thereof. The fibrous film according to claim 4, wherein the natural green polymer is selected from the group consisting of collagen, alginate, hyaluronic acid, gelatin (gelatin) ), chitin, chitosan, and combinations thereof. The fibrous film according to claim 5, wherein the matrix is a combination of a polyester green polymer and a polyvinyl green polymer. The fibrous film according to claim 6, wherein the content of the natural green polymer is 6 to 90% by weight (wt%) based on the total weight of the green polymer, and the polyester green polymer and The polyethylene-based green polymer has a weight ratio of between 1:5 and 5:1. The fibrous film of claim 1, wherein the fibrous film has a single layer saturated adsorption amount to the dye of between 400 and 2000 g/kg. The fibrous film according to claim 8, wherein the natural green polymer is chitosan, the polyester green polymer is polycyclolactone, and the polycyclolactone is polycaprolactone. The polyethylene-based green polymer is polyethylene glycol, and the crosslinking agent is 1,6-diisocyanatohexane (HDI). The fiber film according to claim 9, wherein the weight ratio of the polycaprolactone to the polyethylene glycol is 1:3, and the content of the natural green polymer is based on the total weight of the green polymer. It is 52% by weight. The fibrous film of claim 10, wherein the fibrous film has a saturated adsorption capacity of 454.5 g/kg for the dye. A method of treating a waste liquid using a fiber membrane, comprising the steps of: preparing a fiber film according to any one of claims 1 to 11; placing the fiber film in a waste liquid for a treatment time, wherein The waste liquid contains an adsorbate; and the fiber film is removed from the waste liquid to obtain a treated waste liquid. The method of claim 12, wherein the adsorbate is selected from the group consisting of metals, organic dyes, and combinations thereof. The method of claim 13, wherein the organic dye is 2- Naphthol azo-p-benzene sulfonate. The method according to any one of claims 12 to 14, wherein the adsorption ratio of the fiber membrane is greater than 60% when the weight ratio of the weight of the fiber membrane to the adsorbate in the waste liquid is greater than or equal to 0.67. The method of any one of claims 12 to 14, wherein the concentration of the adsorbate of the waste liquid is between 50 mg/liter (ppm) and 150 ppm, and the weight of the fiber membrane is 0.005 g. The concentration of the adsorbate in the treated waste liquid is between 0 and 90 ppm.