WO2012058877A1 - Method for preparing fenton-like catalytic membrane - Google Patents

Method for preparing fenton-like catalytic membrane Download PDF

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WO2012058877A1
WO2012058877A1 PCT/CN2011/070858 CN2011070858W WO2012058877A1 WO 2012058877 A1 WO2012058877 A1 WO 2012058877A1 CN 2011070858 W CN2011070858 W CN 2011070858W WO 2012058877 A1 WO2012058877 A1 WO 2012058877A1
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solution
fenton
iron
catalytic membrane
preparing
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PCT/CN2011/070858
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French (fr)
Chinese (zh)
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马军
张瑛洁
张丽
李莉
刘增贺
杨蓉
曹天静
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哈尔滨工业大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/145—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing embedded catalysts
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Definitions

  • the invention belongs to the field of water treatment.
  • Fenton Oxidation Technology is a promising water treatment technology and the most active and eye-catching area in advanced oxidation technology research for more than a decade.
  • Fenton oxidation technology has a good effect on the treatment of refractory organic pollutants in water, it has the following disadvantages in practical applications: 1 H 2 O 2 utilization rate is not high, organic matter degradation is incomplete; 2 simple Fenton reaction must be When the pH value is ⁇ 3, the acidity of the actual wastewater is generally not more than 3, and the extremely low acidity requirement increases the water treatment cost.
  • the invention solves the technical problem that the existing Fenton oxidation technology has low utilization rate of H 2 O 2 , secondary pollution and small application range, and provides a preparation method of the Fenton-like catalytic membrane.
  • the PVDF powder and the additive were mixed at a mass ratio of 10 to 8:1, and the sol, PVDF was added.
  • the molar ratio of the powder to the total molar ratio of the iron compound and the n-butyl titanate is 1:0.05-4, and then the solvent is added according to the mass ratio of the PVDF powder to the solvent of 7:35-45 to obtain a casting solution;
  • the casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
  • the preparation method of the second kind of Fenton catalytic membrane in the invention can also be carried out according to the following steps: 1. Dissolving 20 mL of n-butyl titanate In 100 mL of absolute ethanol, then add 5 mL of diethanolamine and stir at room temperature to obtain solution A. 2. Dissolve the iron compound in 20 mL of absolute ethanol and 4 mL. In the double distilled water, the concentration of the compound of iron is 0.01 ⁇ 10mol/L, and then the concentrated nitric acid is added to the solution B to adjust the pH value to 3 to obtain the solution C; Under the condition of 300r/min speed stirring, the solution C is added dropwise to the solution A at a rate of 1 drop/second to obtain a sol; 4.
  • the PVDF powder and the additive are 10 ⁇ 8:1.
  • the mass ratio is mixed, and the molar ratio of the moles of the PVDF powder to the iron compound and the n-butyl titanate is 1:0.05 ⁇ 4, and the mass ratio of the PVDF powder to the solvent is 7:35 ⁇ 45, the solvent is added to obtain a casting solution; 5.
  • the casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
  • the catalyst prepared by the first method can efficiently and rapidly catalyze hydrogen peroxide, and the decomposition rate of hydrogen peroxide increases with the addition of the catalytic membrane, and the highest 98%, it has good adsorption and oxidation functions for organic matter in water, and the pH value of polluted water is not high, at pH 3 ⁇ 11 Hydrogen peroxide treatment is catalyzed in the range and reused.
  • the preparation method has simple steps and is easy to control.
  • the preparation method of the invention is easy to realize, and can realize industrial production, and the product has broad application prospects in the water treatment industry, and the economic benefit is considerable.
  • a novel Fenton-like catalytic membrane was prepared by sol-gel in-situ blending using a modified Fenton oxidation technique using a modified membrane-fixed catalyst to efficiently and efficiently catalyze the degradation of dye wastewater. It can prevent the precipitation and loss of catalyst in the conventional Fenton process, achieve efficient use of the catalyst, and has the advantages of simple preparation process, low cost and easy control of reaction.
  • the catalyst prepared by the second method can efficiently and rapidly catalyze hydrogen peroxide, and the decomposition rate of hydrogen peroxide increases with the addition of the catalytic membrane, and the highest 98%, it has good adsorption and oxidation functions for organic matter in water, and the pH value of polluted water is not high, at pH 3 ⁇ 11 Hydrogen peroxide treatment is catalyzed in the range and reused.
  • the method has the advantages of simple preparation process and low cost. The advantages of high catalytic efficiency, high recycling efficiency and easy control of the reaction.
  • the preparation method of the invention is easy to realize, and can realize industrial production, and the product has broad application prospects in the water treatment industry, and the economic benefit is considerable.
  • the Fenton-like catalytic membrane prepared by the method is combined with an oxidizing agent for water treatment, and the oxidizing agent is hydrogen peroxide and ozone, and can be combined with sodium persulfate, potassium persulfate, ammonium persulfate or potassium hydrogen persulfate, and can also be used.
  • the oxidizing agent is hydrogen peroxide and ozone, and can be combined with sodium persulfate, potassium persulfate, ammonium persulfate or potassium hydrogen persulfate, and can also be used.
  • ultrasound it can also be combined with ultrasound and advanced oxidation of hydroxyl radicals.
  • FIG. 1 is a diagram showing the removal of orange-yellow IV by a different amount of a Fenton-like catalytic membrane prepared in the eleventh embodiment, wherein the area of the Fenton-like catalytic membrane is 3.8 ⁇ 10 -3 m 2 , and ⁇ represents a Fenton-like catalytic membrane. The area is 1.9 ⁇ 10 -3 m 2 , ⁇ indicates that the area of the Fenton-like catalytic membrane is 5.7 ⁇ 10 -3 m 2 ; FIG. 2 is the different amount of the Fenton-like catalytic membrane prepared by the specific embodiment 11 for hydrogen peroxide.
  • FIG. 1 is the effect of the repeated use of the Fenton-like catalytic membrane prepared in the eleventh embodiment on the degradation of Orange IV, ⁇ indicates repeated use once, ⁇ indicates repeated use 2 times, ⁇ indicates Repeated use 3 times, ⁇ means repeated use 4 times;
  • FIG. 6 is an XRD pattern of a pure PVDF film
  • FIG. 7 is a Fe 3+ / TiO 2 powder XRD pattern
  • Figure 8 is a SEM photograph of a pure PVDF film
  • Figure 9 is a SEM photograph of a PVDF/Fe 3+ -TiO 2 catalyst film doped with 4% (mass ratio) Fe 3+ /TiO 2 sol
  • Figure 10 is a blend SEM photograph of a PVDF/Fe 3+ -TiO 2 catalytic membrane of 21% (mass ratio) Fe 3+ /TiO 2 sol.
  • the sample of the pure PVDF film (Fig. 6) has diffraction peaks at 2 ⁇ , 20.5 °, 36.5 °, 40.8 °, while the PVDF/Fe 3+ -TiO 2 composite film (Fig. 5)
  • the sample also has a diffraction characteristic peak of Fe 3+ /TiO 2 powder (Fig. 7). This indicates that the butyl titanate undergoes hydrolysis to form TiO 2 crystals during the preparation of the PVDF / Fe 3+ -TiO 2 catalytic membrane. It can be seen from Fig. 8 to Fig.
  • the catalyst prepared by the method of the present embodiment can efficiently and rapidly catalyze hydrogen peroxide, and the decomposition rate of hydrogen peroxide increases with the addition of the catalytic membrane, up to 98%, and has good adsorption and oxidation functions for organic substances in water, and The pH value of the polluted water is not high, and the hydrogen peroxide treatment is catalyzed in the range of pH 3 ⁇ 11 and reused.
  • the prepared Fenton-like catalytic membrane oxidatively degrades organic pollutants by catalyzing the generation of hydroxyl radicals by H 2 O 2 .
  • Fe 3+ doping can introduce defect sites or change crystallinity in the sodium TiO 2 lattice, thereby reducing the recombination of photogenerated electrons and holes and improving the catalytic efficiency. Therefore, the Fenton-like catalytic membrane prepared by the invention combines hydroxyl radicals with holes, so that the catalytic degradation effect is more remarkable.
  • Embodiment 2 This embodiment differs from Embodiment 1 in that the iron compound in the third step is iron sulfate, iron chloride or iron nitrate.
  • the other steps and parameters are the same as in the first embodiment.
  • This embodiment differs from the specific embodiment one or two in that the solvent in step four is N, N- Dimethylacetamide, dimethyl sulfoxide, trimethyl phosphate, tetramethyl urea, N,N-dimethylformamide, hexamethylaminophosphorus or triethyl phosphate.
  • the solvent in step four is N, N- Dimethylacetamide, dimethyl sulfoxide, trimethyl phosphate, tetramethyl urea, N,N-dimethylformamide, hexamethylaminophosphorus or triethyl phosphate.
  • Other steps and parameters are the same as those of the specific embodiment one or two.
  • Specific Embodiment 4 This embodiment differs from one of the specific embodiments 1 to 3 in that the additive in the fourth step is polyvinylpyrrolidone, polyethylene glycol, lithium chloride, ammonium chloride, sodium nitrate or tetrahydrofuran.
  • the other steps and parameters are the same as one of the specific embodiments one to three.
  • This embodiment differs from one of the specific embodiments 1 to 4 in that the film forming process in the fifth step is a coating method or a spinning method.
  • the other steps and parameters are the same as one of the specific embodiments one to four.
  • the coating method is as follows: after the static defoaming, the casting solution is poured onto a glass plate to scrape the film or the casting solution is applied to the support layer, and is stationary in the air. After 30s ⁇ 1min, it is placed in a constant temperature gel bath (using ethanol-water solution or deionized water) to form a film. The prepared film is immersed in a coagulation bath for 24 to 48 hours and then soaked to 15%. The glycerin aqueous solution was air-dried for 24 h or rinsed and placed in distilled water containing 1% formaldehyde.
  • the spinning method is as follows: PVDF hollow fiber yarn spun from a hollow fiber spinning machine in a constant temperature gel bath (using ethanol - Aqueous solution or deionized water) film formation.
  • the prepared hollow fiber filaments are dried in a coagulation bath for 24 ⁇ 48h, then 15% glycerin aqueous solution is dried 24h or rinsed and then added to contain 1%.
  • the preparation method of the Fenton-like catalytic membrane in the present embodiment is carried out according to the following steps: 1. Dissolving 20 mL of n-butyl titanate In 100 mL of absolute ethanol, then add 5 mL of diethanolamine and stir at room temperature to obtain solution A. 2. Dissolve the iron compound in 20 mL of absolute ethanol and 4 mL.
  • the concentration of the compound of iron is 0.01 ⁇ 10mol/L, and then the concentrated nitric acid is added to the solution B to adjust the pH value to 3 to obtain the solution C; At a rate of 300 rd/min, the solution C was added dropwise to the solution A at a rate of 1 drop/second to obtain a sol. 4.
  • the PVDF powder and the additive were 10 ⁇ 8:1.
  • the mass ratio is mixed, and the molar ratio of the moles of the PVDF powder to the iron compound and the n-butyl titanate is 1:0.05 ⁇ 4, and then the PVDF powder and the solvent are used.
  • a mass ratio of 7:35 to 45 is added to the solvent to obtain a casting solution; and the casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
  • the catalyst prepared by the method can efficiently and rapidly catalyze hydrogen peroxide, and the decomposition rate of hydrogen peroxide increases with the addition of the catalytic membrane, up to 98%, and has good adsorption and oxidation functions for organic substances in water, and pollution.
  • the pH of the water is not high, and the hydrogen peroxide treatment is catalyzed in the pH range of 3 ⁇ 11 and reused.
  • the prepared Fenton-like catalytic membrane oxidatively degrades organic pollutants by catalyzing the generation of hydroxyl radicals by H 2 O 2 .
  • Fe 3+ doping can introduce defect sites or change crystallinity in the sodium TiO 2 lattice, thereby reducing the recombination of photogenerated electrons and holes and improving the catalytic efficiency. Therefore, the Fenton-like catalytic membrane prepared by the invention combines hydroxyl radicals with holes, so that the catalytic degradation effect is more remarkable.
  • This embodiment differs from the specific implementation of the sixth embodiment in that the iron compound in the third step is iron sulfate, iron chloride or iron nitrate. Others are the same as in the sixth embodiment.
  • Embodiment 8 This embodiment differs from the sixth or seventh embodiment in that: the solvent in step 4 is N, N- Dimethylacetamide, dimethyl sulfoxide, trimethyl phosphate, tetramethyl urea, N,N-dimethylformamide, hexamethylaminophosphorus or triethyl phosphate. Other steps and parameters are the same as in the sixth or seventh embodiment.
  • This embodiment differs from one of Embodiments 6 to 8 in that the additive in the fourth step is polyvinylpyrrolidone, polyethylene glycol, lithium chloride, ammonium chloride, sodium nitrate or tetrahydrofuran.
  • the additive in the fourth step is polyvinylpyrrolidone, polyethylene glycol, lithium chloride, ammonium chloride, sodium nitrate or tetrahydrofuran.
  • the other steps and parameters are the same as one of the specific embodiments 6 to 8.
  • This embodiment differs from one of Embodiments 6 to 9 in that the film forming process in the fifth step is a coating method or a spinning method.
  • the other steps and parameters are the same as one of the specific embodiments 6 to 9.
  • the coating method is as follows: after the static defoaming, the casting solution is poured onto a glass plate to scrape the film or the casting solution is applied to the support layer, and is stationary in the air. After 30s ⁇ 1min, it is placed in a constant temperature gel bath (using ethanol-water solution or deionized water) to form a film. The prepared film is immersed in a coagulation bath for 24 to 48 hours and then soaked to 15%. The (mass) aqueous solution of glycerin was naturally dried or rinsed and stored in distilled water containing 1% by mass of formaldehyde.
  • the spinning method is as follows: PVDF hollow fiber yarn spun from a hollow fiber spinning machine in a constant temperature gel bath (using ethanol - Aqueous solution or deionized water) film formation.
  • the prepared hollow fiber filaments are immersed in a coagulation bath in a coagulation bath for 24 to 48 hours, and then immersed in a 15% (mass) aqueous glycerin solution for 24 hours. Dry naturally or rinse and store in distilled water containing 1% by mass of formaldehyde.
  • the solution C is added dropwise to the solution A at a rate of 1 drop/second to obtain a sol. 4.
  • the PVDF powder is chlorinated. Lithium 8:1 mass ratio mixing, adding sol, the molar ratio of PVDF powder to the total molar ratio of Fe(NO 3 ) 3 and n-butyl titanate is 1:0.1, and then according to PVDF powder and N, N- Methaneacetamide mass ratio of 7:42 was added to N,N-dimethylacetamide to obtain a casting solution; fifth, the casting solution prepared in the fourth step was subjected to film formation treatment to obtain a Fenton-like catalytic membrane.
  • the coating process of the present embodiment adopts a coating method, and the specific operation is as follows: after the static defoaming, the casting solution is poured onto a glass plate to scrape the film or the casting solution is sprayed on the support layer, and is kept in the air for 30 seconds. It was then placed in a gel bath (deionized water) of constant temperature to form a film. The prepared film was immersed in a coagulation bath for 36 hours and then immersed in a 15% (mass) aqueous glycerin solution for 24 hours. Dry naturally or rinse and store in distilled water containing 1% by mass of formaldehyde.
  • Test 1 Effect of catalytic membrane dosage on Orange IV degradation and H 2 O 2 decomposition.
  • Test 3 Effect of initial pH on Orange IV degradation and H 2 O 2 decomposition
  • Reaction conditions initial concentration of Orange IV: 0.4 mmol/L, concentration of H 2 O 2 : 15 mmol/L, temperature: 20 ° C, catalytic membrane area: 1.90 ⁇ 10 -3 m 2 .
  • This embodiment differs from the eleventh embodiment in that Fe(NO 3 ) 3 is replaced with ferric chloride.
  • the other steps and parameters are the same as in the eleventh embodiment.
  • the preparation method of the Fenton-like catalytic membrane in the present embodiment is carried out according to the following steps: 1. Dissolving 20 mL of n-butyl titanate In 100 mL of absolute ethanol, then add 5 mL of diethanolamine and stir at room temperature to obtain solution A. 2. Dissolve the iron compound in 20 mL of absolute ethanol and 4 mL. In the double distilled water, the concentration of the compound of iron is 1.0 mol/L, and then the concentrated nitric acid is added to the solution B to adjust the pH value to 3 to obtain the solution C; 3.
  • the solution C is added dropwise to the solution A at a rate of 1 drop/second to obtain a sol; 4.
  • the PVDF powder and the lithium chloride are mixed at a mass ratio of 8:1, and the sol, PVDF is added.
  • the molar ratio of the powder to the total mole ratio of the iron compound to the n-butyl titanate is 1:0.2, and then the mass ratio of the PVDF powder to the N,N-dimethylacetamide is 7:42.
  • Dimethylacetamide is used to obtain a casting solution; 5.
  • the casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.

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Abstract

A method for preparing an Fenton-like catalytic membrane involves the following steps: mixing n-butyl titanate, anhydrous ethanol and glacial acetic acid to obtain solution A; mixing an iron compound with anhydrous ethanol to obtain solution C; dropping solution C into solution A under stirring to obtain a sol; preparing a casting solution; film-forming with the resulting casting solution. The method has a simple process and is easy to control. The Fenton-like membrane prepared by the method can catalyze oxidation reaction of hydrogen peroxide at faster speed and with higher efficiency, and can be reused.

Description

类芬顿催化膜的制备方法  Method for preparing Fenton-like catalytic membrane 技术领域Technical field
本发明属于水处理领域。  The invention belongs to the field of water treatment.
背景技术Background technique
Fenton 氧化处理技术是一种有前景的水处理技术，是近十几年来高级氧化技术研究中最为活跃和引人注目的领域。 虽然 Fenton 氧化技术具有较好的处理水中的难降解有机污染物的效果，但在实际应用中存在以下不足：① H2O2 利用率不高，有机物降解不完全； ②简单的 Fenton 反应必须在 pH 值 ＜ 3 的酸性介质中进行，实际废水的酸度一般不超过 3 ，极低的酸度要求增加了水处理成本。 Fenton Oxidation Technology is a promising water treatment technology and the most active and eye-catching area in advanced oxidation technology research for more than a decade. Although Fenton oxidation technology has a good effect on the treatment of refractory organic pollutants in water, it has the following disadvantages in practical applications: 1 H 2 O 2 utilization rate is not high, organic matter degradation is incomplete; 2 simple Fenton reaction must be When the pH value is <3, the acidity of the actual wastewater is generally not more than 3, and the extremely low acidity requirement increases the water treatment cost.
技术问题technical problem
本发明要解决现有 Fenton 氧化技术 存在 H2O2 利用率低、二次污染、应用范围小的技术问题；而提供了类芬顿催化膜的制备方法。 The invention solves the technical problem that the existing Fenton oxidation technology has low utilization rate of H 2 O 2 , secondary pollution and small application range, and provides a preparation method of the Fenton-like catalytic membrane.
技术解决方案Technical solution
本发明中第一种类芬顿催化膜的制备方法是按下述步骤进行的：一、将 22mL 钛酸正丁酯、 22mL 无水乙醇和 12mL 冰乙酸混合，然后用 HNO3 调节 pH 值 =3 ，得到溶液 A ；二、配制铁的化合物浓度为 0.01~10mol/L 的溶液 B ，然后将 10mL 溶液 B 与 10mL 无水乙醇混合，再用 HNO3 调节 pH 值 =3 ，得到溶液 C ；三、在 300r/min 速度搅拌条件下，以 1 滴 / 秒速度将溶液 C 滴加到溶液 A 中，得到溶胶；四、将 PVDF 粉末 与添加剂按 10~8:1 的质量比混合，加入溶胶， PVDF 粉末 的摩尔数 与 铁的化合物 和 钛酸正丁酯的总摩尔数比为 1:0.05~4 ，再按 PVDF 粉末与 溶剂为 7:35~45 的质量比加入溶剂，得到铸膜液；五、将步骤四制得的铸膜液进行成膜处理，即得到了类 Fenton 催化膜。 The preparation method of the first kind of Fenton catalytic membrane in the invention is carried out according to the following steps: 1. Mixing 22 mL of n-butyl titanate, 22 mL of absolute ethanol and 12 mL of glacial acetic acid, and then adjusting the pH value with HNO 3 = 3 , to obtain a solution A; second, the preparation of iron compound concentration of 0.01 ~ 10mol / L of solution B, then 10mL of solution B and 10mL of absolute ethanol mixed, and then adjust the pH value of 3 with HNO 3 = 3, to obtain a solution C; At a rate of 300 r/min, the solution C was added dropwise to the solution A at a rate of 1 drop/second to obtain a sol. 4. The PVDF powder and the additive were mixed at a mass ratio of 10 to 8:1, and the sol, PVDF was added. The molar ratio of the powder to the total molar ratio of the iron compound and the n-butyl titanate is 1:0.05-4, and then the solvent is added according to the mass ratio of the PVDF powder to the solvent of 7:35-45 to obtain a casting solution; The casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
本发明中第二种类芬顿催化膜的制备方法还可按下述步骤进行的：一、将 20mL 钛酸正丁酯溶于 100mL 无水乙醇中，然后加入 5mL 二乙醇胺，室温搅拌，得到溶液 A ；二、将铁的化合物溶解于 20mL 无水乙醇和 4mL 二次蒸馏水中得到铁的化合物浓度为 0.01~10mol/L 的溶液 B ，然后向溶液 B 中加入浓硝酸调 pH 值 =3 ，得到溶液 C ；三、在 300r/min 速度搅拌条件下，以 1 滴 / 秒速度将溶液 C 滴加到溶液 A 中，得到溶胶；四、将 PVDF 粉末 与添加剂按 10~8:1 的质量比混合，加入溶胶， PVDF 粉末 的摩尔数 与 铁的化合物 和 钛酸正丁酯的总摩尔数比为 1:0.05~4 ，按 PVDF 粉末与 溶剂质量比为 7:35~45 再加入溶剂，得到铸膜液；五、将步骤四制得的铸膜液进行成膜处理，即得到了类 Fenton 催化膜。  The preparation method of the second kind of Fenton catalytic membrane in the invention can also be carried out according to the following steps: 1. Dissolving 20 mL of n-butyl titanate In 100 mL of absolute ethanol, then add 5 mL of diethanolamine and stir at room temperature to obtain solution A. 2. Dissolve the iron compound in 20 mL of absolute ethanol and 4 mL. In the double distilled water, the concentration of the compound of iron is 0.01~10mol/L, and then the concentrated nitric acid is added to the solution B to adjust the pH value to 3 to obtain the solution C; Under the condition of 300r/min speed stirring, the solution C is added dropwise to the solution A at a rate of 1 drop/second to obtain a sol; 4. The PVDF powder and the additive are 10~8:1. The mass ratio is mixed, and the molar ratio of the moles of the PVDF powder to the iron compound and the n-butyl titanate is 1:0.05~4, and the mass ratio of the PVDF powder to the solvent is 7:35~45, the solvent is added to obtain a casting solution; 5. The casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
有益效果Beneficial effect
第一种方法制备的催化剂能高效快速的催化过氧化氢，过氧化氢分解率随催化膜加入量的增加而增加，最高可达 98% ，对水中的有机物具有良好的吸附和氧化功能，而且对污染水质 pH 值 要求不高，在 pH 值 3~11 范围内催化过氧化氢处理，并且重复使用。该制备方法步骤简单，易于控制。本发明的制备方法易于实现，可以实现工业化生产，产品在水处理行业有广阔的应用前景，经济效益可观。上述方法 采用改性膜固定催化剂的改性类 Fenton 氧化技术，通过 溶胶 - 凝胶原位共混法制备了 新型类 Fenton 催化膜 ，可经济高效地催化降解 染料废水 ，并可防止常规 Fenton 工艺的催化剂沉淀和流失等问题，实现催化剂的高效利用，而且 具有制备工艺简单、 成本低和 反应容易控制的优点。 The catalyst prepared by the first method can efficiently and rapidly catalyze hydrogen peroxide, and the decomposition rate of hydrogen peroxide increases with the addition of the catalytic membrane, and the highest 98%, it has good adsorption and oxidation functions for organic matter in water, and the pH value of polluted water is not high, at pH 3~11 Hydrogen peroxide treatment is catalyzed in the range and reused. The preparation method has simple steps and is easy to control. The preparation method of the invention is easy to realize, and can realize industrial production, and the product has broad application prospects in the water treatment industry, and the economic benefit is considerable. Above method A novel Fenton-like catalytic membrane was prepared by sol-gel in-situ blending using a modified Fenton oxidation technique using a modified membrane-fixed catalyst to efficiently and efficiently catalyze the degradation of dye wastewater. It can prevent the precipitation and loss of catalyst in the conventional Fenton process, achieve efficient use of the catalyst, and has the advantages of simple preparation process, low cost and easy control of reaction.
第二种方法制备的催化剂能高效快速的催化过氧化氢，过氧化氢分解率随催化膜加入量的增加而增加，最高可达 98% ，对水中的有机物具有良好的吸附和氧化功能，而且对污染水质 pH 值要求不高，在 pH 值 3~11 范围内催化过氧化氢处理，并且重复使用。该方法具有制备工艺简单、 成本低、 催化效率高、重复利用率高和反应容易控制的优点。本发明的制备方法易于实现，可以实现工业化生产，产品在水处理行业有广阔的应用前景，经济效益可观。该方法制备的类芬顿催化膜与氧化剂联用，用于水处理，氧化剂为过氧化氢、臭氧，可与过硫酸钠、过硫酸钾、过硫酸铵或过硫酸氢钾联用，还可以与超声联用，还可以与超声及产生羟基自由基的高级氧化的结合。  The catalyst prepared by the second method can efficiently and rapidly catalyze hydrogen peroxide, and the decomposition rate of hydrogen peroxide increases with the addition of the catalytic membrane, and the highest 98%, it has good adsorption and oxidation functions for organic matter in water, and the pH value of polluted water is not high, at pH 3~11 Hydrogen peroxide treatment is catalyzed in the range and reused. The method has the advantages of simple preparation process and low cost. The advantages of high catalytic efficiency, high recycling efficiency and easy control of the reaction. The preparation method of the invention is easy to realize, and can realize industrial production, and the product has broad application prospects in the water treatment industry, and the economic benefit is considerable. The Fenton-like catalytic membrane prepared by the method is combined with an oxidizing agent for water treatment, and the oxidizing agent is hydrogen peroxide and ozone, and can be combined with sodium persulfate, potassium persulfate, ammonium persulfate or potassium hydrogen persulfate, and can also be used. In combination with ultrasound, it can also be combined with ultrasound and advanced oxidation of hydroxyl radicals.
附图说明DRAWINGS
图1是具体实施方式十一制备的类芬顿催化膜不同用量对橙黄Ⅳ去除图，图中●表示类芬顿催化膜的面积为3.8×10-3m2，■表示类芬顿催化膜的面积为1.9×10-3m2，▲表示类芬顿催化膜的面积为5.7×10-3m2；图2是具体实施方式十一制备的类芬顿催化膜不同用量对过氧化氢分解率图，图中●表示类芬顿催化膜的面积为3.8×10-3m2，■表示类芬顿催化膜的面积为1.9×10-3m2，▲表示类芬顿催化膜的面积为5.7×10-3m2；图3是具体实施方式十一制备的类芬顿催化膜重复使用对OrangeIV降解的影响图，■表示重复使用1次，◆表示重复使用2次，▲表示重复使用3次，▼表示重复使用4次；图4是具体实施方式十一制备的类芬顿催化膜在不同pH值下的污染物去除效果图，■表示pH值=3，●表示pH值=4，▲表示pH值=5，▼表示pH值=6，◆表示pH值=7，表示pH值=9，表示pH值=11；图5是掺杂21%（质量比）Fe3+/TiO2溶胶的PVDF/Fe3+-TiO2催化膜的XRD图谱；图6是纯PVDF膜的XRD图谱；图7是Fe3+/TiO2粉的XRD图谱；图8是纯PVDF膜的SEM照片；图9掺杂4%（质量比）Fe3+/TiO2溶胶的PVDF/Fe3+-TiO2催化膜的SEM照片，图10是掺杂21%（质量比）Fe3+/TiO2溶胶的PVDF/Fe3+-TiO2催化膜的SEM照片。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the removal of orange-yellow IV by a different amount of a Fenton-like catalytic membrane prepared in the eleventh embodiment, wherein the area of the Fenton-like catalytic membrane is 3.8 × 10 -3 m 2 , and ■ represents a Fenton-like catalytic membrane. The area is 1.9×10 -3 m 2 , ▲ indicates that the area of the Fenton-like catalytic membrane is 5.7×10 -3 m 2 ; FIG. 2 is the different amount of the Fenton-like catalytic membrane prepared by the specific embodiment 11 for hydrogen peroxide. Decomposition rate diagram, where the area of the Fenton-like catalytic membrane is 3.8 × 10 -3 m 2 , ■ indicates that the area of the Fenton-like catalytic membrane is 1.9 × 10 -3 m 2 , and ▲ indicates the Fenton-like catalytic membrane. The area is 5.7×10 -3 m 2 ; Figure 3 is the effect of the repeated use of the Fenton-like catalytic membrane prepared in the eleventh embodiment on the degradation of Orange IV, ■ indicates repeated use once, ◆ indicates repeated use 2 times, ▲ indicates Repeated use 3 times, ▼ means repeated use 4 times; Figure 4 is the effect of pollutant removal at different pH values of the Fenton-like catalytic membrane prepared in the eleventh embodiment, ■ indicates pH = 3, ● indicates pH = 4, ▲ indicates pH = 5, ▼ indicates pH = 6, ◆ indicates pH = 7, indicating pH = 9, indicating pH = 11; Doped with 21% (mass ratio) Fe 3+ / TiO 2 sol PVDF / Fe 3+ -TiO XRD pattern of the catalyst film 2; FIG. 6 is an XRD pattern of a pure PVDF film; FIG. 7 is a Fe 3+ / TiO 2 powder XRD pattern; Figure 8 is a SEM photograph of a pure PVDF film; Figure 9 is a SEM photograph of a PVDF/Fe 3+ -TiO 2 catalyst film doped with 4% (mass ratio) Fe 3+ /TiO 2 sol, Figure 10 is a blend SEM photograph of a PVDF/Fe 3+ -TiO 2 catalytic membrane of 21% (mass ratio) Fe 3+ /TiO 2 sol.
本发明的实施方式Embodiments of the invention
具体实施方式一：本实施方式中类芬顿催化膜的制备方法是按下述步骤进行的：一、将 22mL 钛酸正丁酯、 22mL 无水乙醇和 12mL 冰乙酸混合，然后用浓 HNO3 调节 pH 值 =3 ，得到溶液 A ；二、配制铁的化合物浓度为 0.01~10mol/L 的溶液 B ，然后将 10mL 溶液 B 与 10mL 无水乙醇混合，再用 HNO3 调节 pH 值 =3 ，得到溶液 C ；三、在 300r/min 速度搅拌条件下，以 1 滴 / 秒速度将溶液 C 滴加到溶液 A 中，得到溶胶；四、将 PVDF 粉末 与添加剂按 10~8:1 的质量比混合，加入溶胶， PVDF 粉末 的摩尔数 与 铁的化合物 和 钛酸正丁酯的总摩尔数比为 1:0.05~4 ，再按 PVDF 粉末与 溶剂为 7:35~45 的质量比加入溶剂，得到铸膜液；五、将步骤四制得的铸膜液进行成膜处理，即得到了类 Fenton 催化膜。 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the preparation method of the Fenton-like catalytic membrane in the present embodiment is carried out according to the following steps: 1. Mixing 22 mL of n-butyl titanate, 22 mL of absolute ethanol and 12 mL of glacial acetic acid, and then using concentrated HNO 3 Adjust pH = 3 to obtain solution A; 2. Prepare solution B with a concentration of 0.01 to 10 mol/L of iron, then mix 10 mL of solution B with 10 mL of absolute ethanol, and adjust pH = 3 with HNO 3 to obtain Solution C; Third, at a rate of 300r / min, the solution C is added dropwise to the solution A at a rate of 1 drop / sec to obtain a sol; Fourth, the PVDF powder and the additive are mixed at a mass ratio of 10 to 8:1. Adding sol, the molar ratio of the PVDF powder to the total molar ratio of the iron compound and the n-butyl titanate is 1:0.05~4, and then adding the solvent according to the mass ratio of the PVDF powder to the solvent of 7:35-45, Casting solution; V. The casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
由图 5- 图 7 可知， 纯 PVDF 膜（图 6 ） 的样品在 2 θ为 20.5 °、 36.5 °、 40.8 °时有衍射峰，而 PVDF/Fe3+-TiO2 复合膜（图 5 ） 的样品除了纯 PVDF 膜的衍射特征峰外，还明显有 Fe3+/TiO2 粉（图 7 ） 的衍射特征峰。这表明在 PVDF / Fe3+-TiO2 催化膜 的制备过程中钛酸丁酯经过水解反应生成了 TiO2 晶体。由图 8- 图 10 可知，对照纯 PVDF 膜（图 8 ），图 9 和图 10 的 PVDF/Fe3+-TiO2 催化膜（图 9 和图 10 ）的非对称结构随着 Fe3+/TiO2 溶胶量的增加逐渐减弱，皮层变厚，亚层内的指状孔减少，网络孔略显增多，这表明掺 Fe3+ 纳米 TiO2 溶胶的加入，改变了铸膜液固有的性能，减缓了相转移的速率，阻碍了指状孔的形成和发展，进而提高和改善了分离膜的应用性能和形态结构。 It can be seen from Fig. 5 - Fig. 7 that the sample of the pure PVDF film (Fig. 6) has diffraction peaks at 2θ, 20.5 °, 36.5 °, 40.8 °, while the PVDF/Fe 3+ -TiO 2 composite film (Fig. 5) In addition to the diffraction characteristic peak of the pure PVDF film, the sample also has a diffraction characteristic peak of Fe 3+ /TiO 2 powder (Fig. 7). This indicates that the butyl titanate undergoes hydrolysis to form TiO 2 crystals during the preparation of the PVDF / Fe 3+ -TiO 2 catalytic membrane. It can be seen from Fig. 8 to Fig. 10 that the asymmetric structure of the PVDF/Fe 3+ -TiO 2 catalyst film (Figs. 9 and 10) of Fig. 9 and Fig. 10 with Fe 3+ / is compared with the pure PVDF film (Fig. 8). The increase of TiO 2 sol content gradually weakened, the cortex became thicker, the finger pores in the sublayer decreased, and the network pores increased slightly. This indicates that the addition of Fe 3+ nano TiO 2 sol changed the inherent properties of the casting solution. The rate of phase transfer is slowed down, hindering the formation and development of finger pores, thereby improving and improving the application properties and morphological structure of the separation membrane.
本实施方式方法制备的催化剂能高效快速的催化过氧化氢，过氧化氢分解率随催化膜加入量的增加而增加，最高可达 98% ，对水中的有机物具有良好的吸附和氧化功能，而且对污染水质 pH 值要求不高，在 pH 值 3~11 范围内催化过氧化氢处理，并且重复使用。所制备的类 Fenton 催化膜通过催化 H2O2 产生 羟基自由基来氧化降解有机污染物。 Fe3+ 掺杂，可在钠米 TiO2 晶格中引入缺陷位置或改变结晶度，从而减少光生电子与空穴的复合，提高催化效率。因此 本发明制备的类芬顿催化膜 将羟基自由基与空穴结合，使催化降解效果更显著。The catalyst prepared by the method of the present embodiment can efficiently and rapidly catalyze hydrogen peroxide, and the decomposition rate of hydrogen peroxide increases with the addition of the catalytic membrane, up to 98%, and has good adsorption and oxidation functions for organic substances in water, and The pH value of the polluted water is not high, and the hydrogen peroxide treatment is catalyzed in the range of pH 3~11 and reused. The prepared Fenton-like catalytic membrane oxidatively degrades organic pollutants by catalyzing the generation of hydroxyl radicals by H 2 O 2 . Fe 3+ doping can introduce defect sites or change crystallinity in the sodium TiO 2 lattice, thereby reducing the recombination of photogenerated electrons and holes and improving the catalytic efficiency. Therefore, the Fenton-like catalytic membrane prepared by the invention combines hydroxyl radicals with holes, so that the catalytic degradation effect is more remarkable.
具体实施方式二：本实施方式与具体实施方式一不同的是：步骤三所述铁的化合物为硫酸铁、氯化铁或硝酸铁。其它步骤和参数与具体实施方式一相同。 Specific Embodiment 2: This embodiment differs from Embodiment 1 in that the iron compound in the third step is iron sulfate, iron chloride or iron nitrate. The other steps and parameters are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二不同的是：步骤四所述溶剂为 N,N- 二甲基乙酰胺、二甲基亚砜、磷酸三甲酯、四甲基脲、 N,N- 二甲基甲酰胺、六甲基氨基磷或磷酸三乙酯。其它步骤和参数与具体实施方式一或二相同。 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 3: This embodiment differs from the specific embodiment one or two in that the solvent in step four is N, N- Dimethylacetamide, dimethyl sulfoxide, trimethyl phosphate, tetramethyl urea, N,N-dimethylformamide, hexamethylaminophosphorus or triethyl phosphate. Other steps and parameters are the same as those of the specific embodiment one or two.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是：步骤四所述添加剂为聚乙烯吡咯烷酮、聚乙二醇、氯化锂、氯化铵、硝酸钠或四氢呋喃。其它步骤和参数与具体实施方式一至三之一相同。 Specific Embodiment 4: This embodiment differs from one of the specific embodiments 1 to 3 in that the additive in the fourth step is polyvinylpyrrolidone, polyethylene glycol, lithium chloride, ammonium chloride, sodium nitrate or tetrahydrofuran. The other steps and parameters are the same as one of the specific embodiments one to three.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是：步骤五所述成膜处理采用的是涂布法或纺丝法。其它步骤和参数与具体实施方式一至四之一相同。 BEST MODE FOR CARRYING OUT THE INVENTION V: This embodiment differs from one of the specific embodiments 1 to 4 in that the film forming process in the fifth step is a coating method or a spinning method. The other steps and parameters are the same as one of the specific embodiments one to four.
涂布法的如下：静止脱泡后将铸膜液倾倒在玻璃板上刮膜或将铸膜液涂刮在了支撑层上，在空气中静止 30s~1min 后放入温度恒定的凝胶浴中 ( 采用乙醇 - 水溶液或去离子水 ) 成膜。将制得的膜在凝固浴中 24~48h 之后浸泡到 15% 的甘油水溶液中 24h 自然晾干或经淋洗后放入到含有 1% 甲醛的蒸馏水中保存。 The coating method is as follows: after the static defoaming, the casting solution is poured onto a glass plate to scrape the film or the casting solution is applied to the support layer, and is stationary in the air. After 30s~1min, it is placed in a constant temperature gel bath (using ethanol-water solution or deionized water) to form a film. The prepared film is immersed in a coagulation bath for 24 to 48 hours and then soaked to 15%. The glycerin aqueous solution was air-dried for 24 h or rinsed and placed in distilled water containing 1% formaldehyde.
纺丝法如下：将中空纤维纺丝机纺出的 PVDF 中空纤维丝在温度恒定的凝胶浴中 ( 采用乙醇 - 水溶液或去离子水 ) 成膜。将制得的中空纤维丝在凝固浴中 24~48h 之后 15% 的甘油水溶液 24h 自然晾干或经淋洗后放入到含有 1% 甲醛的蒸馏水中保存。 The spinning method is as follows: PVDF hollow fiber yarn spun from a hollow fiber spinning machine in a constant temperature gel bath (using ethanol - Aqueous solution or deionized water) film formation. The prepared hollow fiber filaments are dried in a coagulation bath for 24~48h, then 15% glycerin aqueous solution is dried 24h or rinsed and then added to contain 1%. Store in distilled water of formaldehyde.
具体实施方式六：本实施方式中类芬顿催化膜的制备方法是按下述步骤进行的：一、将 20mL 钛酸正丁酯溶于 100mL 无水乙醇中，然后加入 5mL 二乙醇胺，室温搅拌，得到溶液 A ；二、将铁的化合物溶解于 20mL 无水乙醇和 4mL 二次蒸馏水中得到铁的化合物浓度为 0.01~10mol/L 的溶液 B ，然后向溶液 B 中加入浓硝酸调 pH 值 =3 ，得到溶液 C ；三、在 300rd/min 速度搅拌条件下，以 1 滴 / 秒速度将溶液 C 滴加到溶液 A 中，得到溶胶；四、将 PVDF 粉末 与添加剂 10~8:1 的质量比混合，加入溶胶， PVDF 粉末 的摩尔数 与 铁的化合物 和 钛酸正丁酯的总摩尔数比为 1:0.05~4 ，再按 PVDF 粉末与 溶剂为 7:35~45 的质量比加入溶剂，得到铸膜液；五、将步骤四制得的铸膜液进行成膜处理，即得到了类 Fenton 催化膜。 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 6: The preparation method of the Fenton-like catalytic membrane in the present embodiment is carried out according to the following steps: 1. Dissolving 20 mL of n-butyl titanate In 100 mL of absolute ethanol, then add 5 mL of diethanolamine and stir at room temperature to obtain solution A. 2. Dissolve the iron compound in 20 mL of absolute ethanol and 4 mL. In the double distilled water, the concentration of the compound of iron is 0.01~10mol/L, and then the concentrated nitric acid is added to the solution B to adjust the pH value to 3 to obtain the solution C; At a rate of 300 rd/min, the solution C was added dropwise to the solution A at a rate of 1 drop/second to obtain a sol. 4. The PVDF powder and the additive were 10~8:1. The mass ratio is mixed, and the molar ratio of the moles of the PVDF powder to the iron compound and the n-butyl titanate is 1:0.05~4, and then the PVDF powder and the solvent are used. A mass ratio of 7:35 to 45 is added to the solvent to obtain a casting solution; and the casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
该方法制备的催化剂能高效快速的催化过氧化氢，过氧化氢分解率随催化膜加入量的增加而增加，最高可达 98% ，对水中的有机物具有良好的吸附和氧化功能，而且对污染水质 pH 值要求不高，在 pH 值 3~11 范围内催化过氧化氢处理，并且重复使用。所制备的类 Fenton 催化膜通过催化 H2O2 产生 羟基自由基来氧化降解有机污染物。 Fe3+ 掺杂，可在钠米 TiO2 晶格中引入缺陷位置或改变结晶度，从而减少光生电子与空穴的复合，提高催化效率。因此 本发明制备的类芬顿催化膜 将羟基自由基与空穴结合，使催化降解效果更显著。The catalyst prepared by the method can efficiently and rapidly catalyze hydrogen peroxide, and the decomposition rate of hydrogen peroxide increases with the addition of the catalytic membrane, up to 98%, and has good adsorption and oxidation functions for organic substances in water, and pollution. The pH of the water is not high, and the hydrogen peroxide treatment is catalyzed in the pH range of 3~11 and reused. The prepared Fenton-like catalytic membrane oxidatively degrades organic pollutants by catalyzing the generation of hydroxyl radicals by H 2 O 2 . Fe 3+ doping can introduce defect sites or change crystallinity in the sodium TiO 2 lattice, thereby reducing the recombination of photogenerated electrons and holes and improving the catalytic efficiency. Therefore, the Fenton-like catalytic membrane prepared by the invention combines hydroxyl radicals with holes, so that the catalytic degradation effect is more remarkable.
具体实施方式七：本实施方式与具体实施六不同的是：步骤三所述铁的化合物为硫酸铁、氯化铁或硝酸铁。其它与具体实施方式六相同。 BEST MODE FOR CARRYING OUT THE INVENTION Seventh Embodiment: This embodiment differs from the specific implementation of the sixth embodiment in that the iron compound in the third step is iron sulfate, iron chloride or iron nitrate. Others are the same as in the sixth embodiment.
具体实施方式八：本实施方式与具体实施方式六或七不同的是：步骤四所述溶剂为 N,N- 二甲基乙酰胺、二甲基亚砜、磷酸三甲酯、四甲基脲、 N,N- 二甲基甲酰胺、六甲基氨基磷或磷酸三乙酯。其它步骤和参数与具体实施方式六或七相同。 Embodiment 8: This embodiment differs from the sixth or seventh embodiment in that: the solvent in step 4 is N, N- Dimethylacetamide, dimethyl sulfoxide, trimethyl phosphate, tetramethyl urea, N,N-dimethylformamide, hexamethylaminophosphorus or triethyl phosphate. Other steps and parameters are the same as in the sixth or seventh embodiment.
具体实施方式九：本实施方式与具体实施方式六至八之一不同的是：步骤四所述添加剂为聚乙烯吡咯烷酮、聚乙二醇、氯化锂、氯化铵、硝酸钠或四氢呋喃。其它步骤和参数与具体实施方式六至八之一相同。 BEST MODE FOR CARRYING OUT THE INVENTION Nine: This embodiment differs from one of Embodiments 6 to 8 in that the additive in the fourth step is polyvinylpyrrolidone, polyethylene glycol, lithium chloride, ammonium chloride, sodium nitrate or tetrahydrofuran. The other steps and parameters are the same as one of the specific embodiments 6 to 8.
具体实施方式十：本实施方式与具体实施方式六至九之一不同的是：步骤五所述成膜处理采用的是涂布法或纺丝法。其它步骤和参数与具体实施方式六至九之一相同。 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 10: This embodiment differs from one of Embodiments 6 to 9 in that the film forming process in the fifth step is a coating method or a spinning method. The other steps and parameters are the same as one of the specific embodiments 6 to 9.
涂布法的如下：静止脱泡后将铸膜液倾倒在玻璃板上刮膜或将铸膜液涂刮在了支撑层上，在空气中静止 30s~1min 后放入温度恒定的凝胶浴中 ( 采用乙醇 - 水溶液或去离子水 ) 成膜。将制得的膜在凝固浴中浸泡 24~48h 之后浸泡到 15% （质量）的甘油水溶液中 24h 自然晾干或经淋洗后放入到含有 1% （质量）甲醛的蒸馏水中保存。 The coating method is as follows: after the static defoaming, the casting solution is poured onto a glass plate to scrape the film or the casting solution is applied to the support layer, and is stationary in the air. After 30s~1min, it is placed in a constant temperature gel bath (using ethanol-water solution or deionized water) to form a film. The prepared film is immersed in a coagulation bath for 24 to 48 hours and then soaked to 15%. The (mass) aqueous solution of glycerin was naturally dried or rinsed and stored in distilled water containing 1% by mass of formaldehyde.
纺丝法如下：将中空纤维纺丝机纺出的 PVDF 中空纤维丝在温度恒定的凝胶浴中 ( 采用乙醇 - 水溶液或去离子水 ) 成膜。将制得的中空纤维丝在凝固浴将制得的膜在凝固浴中浸泡 24~48h 之后浸泡到 15% （质量）的甘油水溶液 24h 自然晾干或经淋洗后放入到含有 1% （质量）甲醛的蒸馏水中保存。 The spinning method is as follows: PVDF hollow fiber yarn spun from a hollow fiber spinning machine in a constant temperature gel bath (using ethanol - Aqueous solution or deionized water) film formation. The prepared hollow fiber filaments are immersed in a coagulation bath in a coagulation bath for 24 to 48 hours, and then immersed in a 15% (mass) aqueous glycerin solution for 24 hours. Dry naturally or rinse and store in distilled water containing 1% by mass of formaldehyde.
具体实施方式十一：本实施方式中类芬顿催化膜的制备方法是按下述步骤进行的：一、将 22mL 钛酸正丁酯、 22mL 无水乙醇（溶剂）和 12mL 冰乙酸（抑制剂）混合，然后用 HNO3 调节 pH 值 =3 ，得到溶液 A ；二、配制 Fe(NO3)3 浓度为 0.75mol/L 的溶液 B ，然后将 10mL 溶液 B 与 10mL 无水乙醇混合，再用 HNO3 调节 pH 值 =3 ，得到溶液 C ；三、在 300r/min 速度搅拌条件下，以 1 滴 / 秒速度将溶液 C 滴加到溶液 A 中，得到溶胶；四、将 PVDF 粉末 与氯化锂 8:1 的质量比混合，加入溶胶， PVDF 粉末 的摩尔数 与 Fe(NO3)3 和 钛酸正丁酯的总摩尔数比为 1:0.1 ，再按 PVDF 粉末与 N,N- 二甲基乙酰胺质量比为 7:42 加入 N,N- 二甲基乙酰胺 ，得到铸膜液；五、将步骤四制得的铸膜液进行成膜处理，即得到了类 Fenton 催化膜。BEST MODE FOR CARRYING OUT THE INVENTION Eleven: The preparation method of the Fenton-like catalytic membrane in the present embodiment is carried out according to the following steps: 1. 22 mL of n-butyl titanate, 22 mL of absolute ethanol (solvent) and 12 mL of glacial acetic acid (inhibitor) Mixing, then adjusting the pH value with HNO 3 = 3 to obtain solution A; 2. Preparing solution B with a concentration of Fe(NO 3 ) 3 of 0.75 mol/L, then mixing 10 mL of solution B with 10 mL of absolute ethanol, and then using HNO 3 adjusts the pH value to 3 to obtain solution C. 3. At a rate of 300 r/min, the solution C is added dropwise to the solution A at a rate of 1 drop/second to obtain a sol. 4. The PVDF powder is chlorinated. Lithium 8:1 mass ratio mixing, adding sol, the molar ratio of PVDF powder to the total molar ratio of Fe(NO 3 ) 3 and n-butyl titanate is 1:0.1, and then according to PVDF powder and N, N- Methaneacetamide mass ratio of 7:42 was added to N,N-dimethylacetamide to obtain a casting solution; fifth, the casting solution prepared in the fourth step was subjected to film formation treatment to obtain a Fenton-like catalytic membrane.
本实施方式成膜处理采用的是涂布法，具体操作如下：静止脱泡后将铸膜液倾倒在玻璃板上刮膜或将铸膜液涂刮在了支撑层上，在空气中静止 30s 后放入温度恒定的凝胶浴（去离子水 ) 中成膜。将制得的膜在凝固浴中浸泡 36h 之后浸泡到 15% （质量）的甘油水溶液中 24h 自然晾干或经淋洗后放入到含有 1% （质量）甲醛的蒸馏水中保存。 The coating process of the present embodiment adopts a coating method, and the specific operation is as follows: after the static defoaming, the casting solution is poured onto a glass plate to scrape the film or the casting solution is sprayed on the support layer, and is kept in the air for 30 seconds. It was then placed in a gel bath (deionized water) of constant temperature to form a film. The prepared film was immersed in a coagulation bath for 36 hours and then immersed in a 15% (mass) aqueous glycerin solution for 24 hours. Dry naturally or rinse and store in distilled water containing 1% by mass of formaldehyde.
采用下述试验验证本发明的效果： The effects of the present invention were verified by the following tests:
试验一：催化膜用量对 Orange IV 降解以及 H2O2 分解的影响。Test 1: Effect of catalytic membrane dosage on Orange IV degradation and H 2 O 2 decomposition.
反应条件： Orange IV 初始浓度： 0.4mmol/L ， H2O2 浓度： 15mmol/L ， pH 值 =3.17 ，温度： 20 ℃。Reaction conditions: Orange IV initial concentration: 0.4 mmol/L, H 2 O 2 concentration: 15 mmol/L, pH = 3.17, temperature: 20 °C.
该试验结果见图 1 和 2 ，由此可知，本实施方式方法制备的催化剂能高效快速的催化过氧化氢，过氧化氢分解率随催化膜加入量的增加而增加，最高可达 98% ，对水中的有机物具有良好的吸附和氧化功能。 The test results are shown in Figures 1 and 2. It can be seen that the catalyst prepared by the method of the present embodiment can efficiently and rapidly catalyze hydrogen peroxide, and the decomposition rate of hydrogen peroxide increases with the increase of the amount of the catalytic membrane, up to 98%. It has good adsorption and oxidation functions for organic substances in water.
试验二：催化膜重复使用对OrangeIV降解的影响Test 2: Effect of repeated use of catalytic membrane on the degradation of Orange IV
反应条件：OrangeIV初始浓度：0.4mmol/L，H2O2浓度：15mmol/L，pH值=3.16，温度：20℃，催化膜面积：1.90×10-3m2。Reaction conditions: initial concentration of Orange IV: 0.4 mmol/L, concentration of H 2 O 2 : 15 mmol/L, pH = 3.16, temperature: 20 ° C, catalytic membrane area: 1.90 × 10 -3 m 2 .
该试验结果见图3，由此可知，可多次使用。The results of this test are shown in Fig. 3, from which it can be seen that it can be used multiple times.
试验三：初始pH值对OrangeIV降解以及H2O2分解的影响Test 3: Effect of initial pH on Orange IV degradation and H 2 O 2 decomposition
反应条件：OrangeIV初始浓度：0.4mmol/L，H2O2浓度：15mmol/L，温度：20℃，催化膜面积：1.90×10-3m2。Reaction conditions: initial concentration of Orange IV: 0.4 mmol/L, concentration of H 2 O 2 : 15 mmol/L, temperature: 20 ° C, catalytic membrane area: 1.90 × 10 -3 m 2 .
该试验结果见图4。由图4可知，对污染水质pH值要求不高。The test results are shown in Figure 4. It can be seen from Fig. 4 that the pH value of the polluted water quality is not high.
具体实施方式十二：本实施方式与具体实施方式十一不同的是：采用硫酸铁替换 Fe(NO3)3 。其它步骤和参数与具体实施方式十一相同。BEST MODE FOR CARRYING OUT THE INVENTION Twelve: This embodiment differs from the eleventh embodiment in that Fe(NO 3 ) 3 is replaced with iron sulfate. The other steps and parameters are the same as in the eleventh embodiment.
具体实施方式十三：本实施方式与具体实施方式十一不同的是：采用氯化铁替换 Fe(NO3)3 。其它步骤和参数与具体实施方式十一相同。BEST MODE FOR CARRYING OUT THE INVENTION Thirteen: This embodiment differs from the eleventh embodiment in that Fe(NO 3 ) 3 is replaced with ferric chloride. The other steps and parameters are the same as in the eleventh embodiment.
具体实施方式十四：本实施方式中类芬顿催化膜的制备方法是按下述步骤进行的：一、将 20mL 钛酸正丁酯溶于 100mL 无水乙醇中，然后加入 5mL 二乙醇胺，室温搅拌，得到溶液 A ；二、将铁的化合物溶解于 20mL 无水乙醇和 4mL 二次蒸馏水中得到铁的化合物浓度为 1.0 mol/L 的溶液 B ，然后向溶液 B 中加入浓硝酸调 pH 值 =3 ，得到溶液 C ；三、在 300r/min 速度搅拌条件下，以 1 滴 / 秒速度将溶液 C 滴加到溶液 A 中，得到溶胶；四、将 PVDF 粉末 与氯化锂按 8:1 的质量比混合，加入溶胶， PVDF 粉末 的摩尔数 与 铁的化合物 和 钛酸正丁酯的总摩尔数比为 1:0.2 ，再按 PVDF 粉末与 N,N- 二甲基乙酰胺质量比为 7:42 加入 N,N- 二甲基乙酰胺，得到铸膜液；五、将步骤四制得的铸膜液进行成膜处理，即得到了类 Fenton 催化膜。 DETAILED DESCRIPTION OF THE INVENTION Fourteenth embodiment: The preparation method of the Fenton-like catalytic membrane in the present embodiment is carried out according to the following steps: 1. Dissolving 20 mL of n-butyl titanate In 100 mL of absolute ethanol, then add 5 mL of diethanolamine and stir at room temperature to obtain solution A. 2. Dissolve the iron compound in 20 mL of absolute ethanol and 4 mL. In the double distilled water, the concentration of the compound of iron is 1.0 mol/L, and then the concentrated nitric acid is added to the solution B to adjust the pH value to 3 to obtain the solution C; 3. At 300 r/min Under the condition of speed stirring, the solution C is added dropwise to the solution A at a rate of 1 drop/second to obtain a sol; 4. The PVDF powder and the lithium chloride are mixed at a mass ratio of 8:1, and the sol, PVDF is added. The molar ratio of the powder to the total mole ratio of the iron compound to the n-butyl titanate is 1:0.2, and then the mass ratio of the PVDF powder to the N,N-dimethylacetamide is 7:42. Dimethylacetamide is used to obtain a casting solution; 5. The casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
具体实施方式十五：本实施方式与具体实施方式十四不同的是：采用硫酸铁替换 Fe(NO3)3 。其它步骤和参数与具体实施方式十四相同。BEST MODE FOR CARRYING OUT THE INVENTION Fifteen: This embodiment differs from the fourteenth embodiment in that Fe(NO 3 ) 3 is replaced with iron sulfate. The other steps and parameters are the same as in the fourteenth embodiment.
具体实施方式十六：本实施方式与具体实施方式十四不同的是：采用氯化铁替换 Fe(NO3)3 。其它步骤和参数与具体实施方式十四相同。BEST MODE FOR CARRYING OUT THE INVENTION Sixteenth embodiment: This embodiment differs from the fourteenth embodiment in that Fe(NO 3 ) 3 is replaced with ferric chloride. The other steps and parameters are the same as in the fourteenth embodiment.

Claims (10)

  1. 类芬顿催化膜的制备方法，其特征在于类芬顿催化膜的制备方法是按下述步骤进行的：一、将22mL钛酸正丁酯、22mL无水乙醇和12mL冰乙酸混合，然后用HNO3调节pH值=3，得到溶液A；二、配制铁的化合物浓度为0.01~10mol/L的溶液B，然后将10mL溶液B与10mL无水乙醇混合，再用HNO3调节pH值=3，得到溶液C；三、在300r/min速度搅拌条件下，以1滴/秒速度将溶液C滴加到溶液A中，得到溶胶；四、将PVDF粉末与添加剂按10~8:1的质量比混合，加入溶胶，PVDF粉末的摩尔数与铁的化合物和钛酸正丁酯的总摩尔数比为1:0.05~4，再按PVDF粉末与溶剂为7:35~45的质量比加入溶剂，得到铸膜液；五、将步骤四制得的铸膜液进行成膜处理，即得到了类Fenton催化膜。A method for preparing a Fenton-like catalytic membrane, characterized in that the method for preparing a Fenton-like catalytic membrane is carried out according to the following steps: 1. Mixing 22 mL of n-butyl titanate, 22 mL of absolute ethanol and 12 mL of glacial acetic acid, and then using HNO 3 adjusts the pH value to 3 to obtain the solution A; 2. prepares the solution B of the compound having an iron concentration of 0.01 to 10 mol/L, and then mixes 10 mL of the solution B with 10 mL of absolute ethanol, and then adjusts the pH value with HNO 3 = 3 , to obtain a solution C; three, at a rate of 300r / min speed, the solution C is added dropwise to the solution A at a rate of 1 drop / sec to obtain a sol; Fourth, the PVDF powder and the additive according to the quality of 10 ~ 8:1 Compared with the mixing, adding the sol, the molar ratio of the PVDF powder to the total molar ratio of the iron compound and the n-butyl titanate is 1:0.05-4, and then adding the solvent according to the mass ratio of the PVDF powder to the solvent of 7:35-45. The casting solution is obtained. 5. The casting solution prepared in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
  2. 根据权利要求1所述的类芬顿催化膜的制备方法，其特征在于步骤三所述铁的化合物为硫酸铁、氯化铁或硝酸铁。The method for preparing a Fenton-like catalytic membrane according to claim 1, wherein the compound of iron in the third step is iron sulfate, iron chloride or iron nitrate.
  3. 根据权利要求2所述的类芬顿催化膜的制备方法，其特征在于步骤四所述溶剂为N,N-二甲基乙酰胺、二甲基亚砜、磷酸三甲酯、四甲基脲、N,N-二甲基甲酰胺、六甲基氨基磷或磷酸三乙酯。The method for preparing a Fenton-like catalytic membrane according to claim 2, wherein the solvent in the fourth step is N,N-dimethylacetamide, dimethyl sulfoxide, trimethyl phosphate, tetramethylurea , N,N-dimethylformamide, hexamethylaminophosphorus or triethyl phosphate.
  4. 根据权利要求1、2或3所述的类芬顿催化膜的制备方法，其特征在于步骤四所述添加剂为聚乙烯吡咯烷酮、聚乙二醇、氯化锂、氯化铵、硝酸钠或四氢呋喃。The method for preparing a Fenton-like catalytic membrane according to claim 1, 2 or 3, wherein the additive in the fourth step is polyvinylpyrrolidone, polyethylene glycol, lithium chloride, ammonium chloride, sodium nitrate or tetrahydrofuran. .
  5. 据权利要求4所述的类芬顿催化膜的制备方法，其特征在于步骤五所述成膜处理采用的是涂布法或纺丝法。A method of producing a Fenton-like catalytic film according to claim 4, wherein the film forming treatment in the fifth step is a coating method or a spinning method.
  6. 芬顿催化膜的制备方法，其特征在于类芬顿催化膜的制备方法是按下述步骤进行的：一、将20mL钛酸正丁酯溶于100mL无水乙醇中，然后加入5mL二乙醇胺，室温搅拌，得到溶液A；二、将铁的化合物溶解于20mL无水乙醇和4mL二次蒸馏水中得到铁的化合物浓度为0.01~10mol/L的溶液B，然后向溶液B中加入浓硝酸调节pH值=3，得到溶液C；三、在300r/min速度搅拌条件下，以1滴/秒速度将溶液C滴加到溶液A中，得到溶胶；四、将PVDF粉末与添加剂按10~8:1的质量比混合，加入溶胶，PVDF粉末的摩尔数与铁的化合物和钛酸正丁酯的总摩尔数比为1:0.05~4，再按PVDF粉末与溶剂为7:35~45的质量比加入溶剂，得到铸膜液；五、将步骤四制得的铸膜液进行成膜处理，即得到了类Fenton催化膜。A method for preparing a Fenton catalytic membrane, characterized in that the method for preparing a Fenton-like catalytic membrane is carried out according to the following steps: 1. Dissolving 20 mL of n-butyl titanate in 100 mL of absolute ethanol, and then adding 5 mL of diethanolamine. Stirring at room temperature to obtain a solution A; 2. Dissolving the iron compound in 20 mL of absolute ethanol and 4 mL of twice-distilled water to obtain a solution B of iron having a compound concentration of 0.01 to 10 mol/L, and then adding concentrated nitric acid to the solution B to adjust the pH. Value = 3, to obtain a solution C; 3. At a rate of 300 r / min, the solution C is added dropwise to the solution A at a rate of 1 drop / sec to obtain a sol; 4. The PVDF powder and the additive are 10 to 8: The mass ratio of 1 is mixed, the sol is added, the molar ratio of the PVDF powder to the total molar ratio of the iron compound and the n-butyl titanate is 1:0.05-4, and then the PVDF powder and the solvent are 7:35-45. The casting solution is obtained by adding a solvent; and the casting solution obtained in the fourth step is subjected to a film forming treatment to obtain a Fenton-like catalytic film.
  7. 据权利要求6所述的类芬顿催化膜的制备方法，其特征在于步骤三所述铁的化合物为硫酸铁、氯化铁或硝酸铁。A method of producing a Fenton-like catalytic membrane according to claim 6, wherein the compound of iron in the third step is iron sulfate, iron chloride or iron nitrate.
  8. 根据权利要求7所述的类芬顿催化膜的制备方法，其特征在于步骤四所述溶剂为N,N-二甲基乙酰胺、二甲基亚砜、磷酸三甲酯、四甲基脲、N,N-二甲基甲酰胺、六甲基氨基磷或磷酸三乙酯。The method for preparing a Fenton-like catalytic membrane according to claim 7, wherein the solvent in the fourth step is N,N-dimethylacetamide, dimethyl sulfoxide, trimethyl phosphate, tetramethylurea , N,N-dimethylformamide, hexamethylaminophosphorus or triethyl phosphate.
  9. 根据权利要求6、7或8所述的类芬顿催化膜的制备方法，其特征在于步骤四所述添加剂为聚乙烯吡咯烷酮、聚乙二醇、氯化锂、氯化铵、硝酸钠或四氢呋喃。The method for preparing a Fenton-like catalytic membrane according to claim 6, 7 or 8, wherein the additive in the fourth step is polyvinylpyrrolidone, polyethylene glycol, lithium chloride, ammonium chloride, sodium nitrate or tetrahydrofuran. .
  10. 根据权利要求9所述的类芬顿催化膜的制备方法，其特征在于步骤五所述成膜处理采用的是涂布法或纺丝法。The method for producing a Fenton-like catalytic film according to claim 9, wherein the film forming treatment in the fifth step is a coating method or a spinning method.
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