WO2020258931A1 - Method for treating organic dye in waste water - Google Patents

Method for treating organic dye in waste water Download PDF

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Publication number
WO2020258931A1
WO2020258931A1 PCT/CN2020/080333 CN2020080333W WO2020258931A1 WO 2020258931 A1 WO2020258931 A1 WO 2020258931A1 CN 2020080333 W CN2020080333 W CN 2020080333W WO 2020258931 A1 WO2020258931 A1 WO 2020258931A1
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Prior art keywords
sponge
photocatalyst
composite sponge
nano
modified graphene
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PCT/CN2020/080333
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French (fr)
Chinese (zh)
Inventor
童裳慧
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童裳慧
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Publication of WO2020258931A1 publication Critical patent/WO2020258931A1/en

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

Definitions

  • the invention relates to a method for treating waste water, in particular to a method for treating organic dyes in waste water.
  • Graphene oxide is the precursor for the preparation of graphene by redox method. It not only has the structural characteristics of graphene, but also has oxygen-containing functional groups such as hydroxyl and carboxyl on the surface. It has good water solubility and also has a high specific surface area. The polar functional group is easy to form strong interaction with some molecules, which is beneficial to composite with other materials.
  • CN108997608A discloses a method for preparing graphene hydrophobic oil-absorbing sponge.
  • the sponge prepared by this method has poor regeneration ability and cannot meet the requirement of repeated use of the adsorbent material.
  • CN108384049A discloses a method for preparing titanium dioxide-graphene composite sponge.
  • Water, graphene oxide and titanium dioxide are mixed to obtain a mixed liquid; the mixed liquid is mixed with a reducing agent to obtain a reaction liquid; the sponge is immersed in the reaction liquid, and a reduction reaction is performed under a sealed condition to obtain a titanium dioxide-graphene composite sponge.
  • the titanium dioxide-graphene composite sponge prepared by the method has poor adsorption capacity for wastewater organic dyes, low photocatalytic degradation rate of organic dyes in the adsorption material, and poor regeneration capacity of the adsorption material.
  • the purpose of the present invention is to provide a method for treating organic dyes in wastewater, which can effectively adsorb organic dyes in wastewater.
  • the photocatalytic degradation rate of organic dyes in the adsorption material is high.
  • the adsorption material can be reused.
  • the present invention provides a method for treating organic dyes in wastewater, including the following steps:
  • the concentration of graphene oxide in the graphene oxide suspension emulsion is 2-15 mg/ml.
  • the nano-level photocatalyst is nano titanium dioxide, nano zinc oxide or nano tin oxide.
  • the reducing agent is hydrazine hydrate, ascorbic acid or ammonia.
  • the mass ratio of the nano-scale photocatalyst to the reducing agent is 1:5-30.
  • the concentration of nano-scale photocatalyst is 0.2-1 mg/ml, and the concentration of reducing agent is 2-10 mg/ml.
  • the sponge is selected from one of polyurethane sponge, melamine sponge, polyester sponge, polyether sponge or polyvinyl alcohol sponge.
  • step (2) the wastewater containing organic dyes is subjected to 3 or more stages of adsorption treatment.
  • the organic dye is selected from one or more of methyl orange, methylene blue, rhodamine B, methyl violet, and neutral red.
  • the sponge undergoes ultrasonic cleaning, washing and drying before soaking.
  • the invention first prepares the graphene oxide composite sponge, and then reacts the graphene oxide composite sponge with the mixed solution of the nano-level photocatalyst and the reducing agent to prepare the photocatalyst modified graphene composite sponge.
  • This can make the photocatalyst evenly distributed on the graphene oxide, reduce the agglomeration of the photocatalyst, give full play to the surface effect and small size effect of the nano-level photocatalyst, and effectively increase the specific surface area and the surface area of the nano-level photocatalyst modified graphene composite sponge. Adsorption capacity.
  • Graphene's two-dimensional structure, high conductivity, and covalent bonds formed with nano-level photocatalysts enhance the activity of the photocatalyst, reduce the energy gap difference of the photocatalyst, and enable the adsorbed organic dyes to complete the photocatalysis in the visible light region
  • Degradation makes the nano-level photocatalyst modified graphene composite sponge easy to regenerate and realizes the reuse of adsorption materials.
  • the method for treating organic dyes in wastewater of the present invention includes the following steps: (1) preparation of adsorption materials; (2) adsorption of organic dyes; (3) regeneration of adsorption materials.
  • the sponge may be one of polyurethane sponge, melamine sponge, polyester sponge, polyether sponge or polyvinyl alcohol sponge.
  • the sponge is a polyurethane sponge or a melamine sponge.
  • the sponge is a polyurethane sponge.
  • the volume of the sponge is 20 ⁇ 500cm 3 .
  • the volume of the sponge is 100-400 cm 3 .
  • the volume of the sponge is 150-300 cm 3 .
  • the shape of the sponge can be a cuboid or a cube.
  • the shape of the sponge is a rectangular parallelepiped. In this way, the graphene oxide can be better coated on the sponge, so that the prepared photocatalyst modified graphene composite sponge has stronger adsorption capacity and higher photocatalytic degradation performance.
  • the sponge can be ultrasonically cleaned, washed and dried before being soaked.
  • the lotion for ultrasonic cleaning can be water or alcohol solution.
  • the alcohol solution is ethanol.
  • the sponge is ultrasonically cleaned twice, the first washing liquid is absolute ethanol, and the second washing liquid is deionized water.
  • the washing liquid used in the washing process can be water or alcohol solvent.
  • the lotion is water or ethanol. More preferably, the lotion is water.
  • the washing process is to soak the washing sponge with distilled water.
  • the drying temperature is 50-100°C.
  • the drying temperature is 60 to 80°C. More preferably, the drying temperature is 60 to 70°C. In this way, the sponge can achieve a better coating effect, and the prepared photocatalyst modified graphene composite sponge has stronger adsorption capacity and higher photocatalytic degradation performance.
  • the sheet diameter of graphene oxide may be 1-50 ⁇ m; preferably 5-35 ⁇ m; more preferably 20-25 ⁇ m.
  • the oxygen to carbon molar ratio of graphene oxide may be 0.3 to 0.8, preferably 0.5 to 0.7, and more preferably 0.6 to 0.7.
  • Examples of graphene oxide include, but are not limited to, graphene oxide of Changzhou Sixth Element Material Technology Co., Ltd.
  • the graphene oxide sheet diameter is 20-25 ⁇ m, and the oxygen-carbon molar ratio is 0.6.
  • the concentration of graphene oxide in the graphene oxide suspension emulsion is 2-15 mg/ml.
  • the concentration of graphene oxide is 2-10 mg/ml. More preferably, the concentration of oxidized graphene is 3 to 5 mg/ml.
  • the nano-level photocatalyst is nano-titanium dioxide, nano-zinc oxide or nano-tin oxide.
  • the nano-level photocatalyst is nano-titanium dioxide or nano-zinc oxide.
  • the nano-level photocatalyst is nano-titanium dioxide. In this way, the nano-level photocatalyst can be better distributed on the graphene oxide, so that the prepared photocatalyst modified graphene composite sponge has stronger adsorption capacity and higher photocatalytic degradation performance.
  • the reducing agent is hydrazine hydrate, ascorbic acid or ammonia.
  • the reducing agent is hydrazine hydrate or ascorbic acid. More preferably, the reducing agent is ascorbic acid.
  • the mass ratio of the nano-level photocatalyst to the reducing agent is 1:5-30.
  • the mass ratio of the nano-level photocatalyst to the reducing agent is 1:10-30. More preferably, the mass ratio of the nano-scale photocatalyst to the reducing agent is 1:15-25.
  • the concentration of the nano-level photocatalyst is 0.2-1 mg/ml, and the concentration of the reducing agent is 2-10 mg/ml.
  • the concentration of the nano-level photocatalyst is 0.2-0.7 mg/ml. More preferably, the concentration of the nano-level photocatalyst is 0.2-0.5 mg/ml.
  • the concentration of the reducing agent is 5-10 mg/ml. More preferably, the concentration of the reducing agent is 5-7 mg/ml. In this way, the prepared photocatalyst modified graphene composite sponge can have stronger adsorption capacity and higher photocatalytic degradation performance.
  • the reaction temperature of the graphene oxide composite sponge and the mixture of nano-level photocatalyst and reducing agent is 50-150°C.
  • the reaction temperature is 70 to 120°C. More preferably, the reaction temperature is 70-100°C.
  • the reaction time is 8-20h. Preferably, the reaction time is 10-18h. More preferably, the reaction time is 10-15h. In this way, the nano-level photocatalyst can be better distributed on the graphene oxide, and the prepared photocatalyst-modified graphene composite sponge has stronger adsorption capacity and higher photocatalytic degradation performance.
  • the washing liquid for washing the photocatalyst modified graphene composite sponge hydrogel is an ethanol aqueous solution.
  • the ethanol concentration of the ethanol aqueous solution is 1-20 vol%. More preferably, the ethanol concentration of the ethanol aqueous solution is 3-10 vol%.
  • the washing time is 15 ⁇ 36h.
  • the washing time is 20 to 36 hours. More preferably, the washing time is 24 to 36 hours.
  • the temperature for drying the photocatalyst modified graphene composite sponge hydrogel is 50-100°C.
  • the drying temperature is 50-80°C. More preferably, the drying temperature is 60 to 75°C.
  • the drying time is 5-20h.
  • the drying time is 10-20h. More preferably, the drying time is 15-20h. In this way, the prepared photocatalyst modified graphene composite sponge can have stronger adsorption capacity and higher photocatalytic degradation performance.
  • the weight of nanometer titanium dioxide in the photocatalyst modified graphene composite sponge is 0.1-5 wt% of the total weight of the composite sponge.
  • the weight of the nano titanium dioxide is 1 to 5 wt% of the total weight of the composite sponge. More preferably, the weight of the nano titanium dioxide is 2 to 4 wt% of the total weight of the composite sponge.
  • the wastewater containing organic dyes is passed through an adsorption reactor equipped with a photocatalyst modified graphene composite sponge to adsorb the organic dyes in the wastewater.
  • the wastewater containing organic dyes is subjected to 3 or more adsorption treatments.
  • the wastewater containing organic dyes is subjected to 5 or more adsorption treatments.
  • the waste water containing organic dyes is treated by adsorption of more than 7 levels.
  • the adsorption treatment can be 7-10 levels. This can more fully adsorb the organic dyes in the wastewater.
  • the organic dye can be selected from one or more of methyl orange, methylene blue, rhodamine B, methyl violet, and neutral red.
  • the organic dye can be selected from one or more of methyl orange, methylene blue, and rhodamine B. More preferably, the organic dye is methylene blue.
  • the photocatalyst modified graphene composite sponge can be made into an adsorption fitting and loaded into the adsorption reactor.
  • the photocatalyst modified graphene composite sponge is fixed in a stretchable network barrier and loaded into an adsorption reactor.
  • the adsorbed saturated photocatalyst modified graphene composite sponge is taken out, and the organic dye is catalytically decomposed under light to obtain a regenerated photocatalyst modified graphene composite sponge.
  • the photocatalyst modified graphene composite sponge when the difference between the concentration of organic dyes in the wastewater at the inlet and the outlet of the adsorption reactor is less than 50 mg/ml, the photocatalyst modified graphene composite sponge is adsorbed saturated, and a new photocatalyst modified graphene composite sponge is replaced. Saturated photocatalyst modified graphene composite sponge for regeneration.
  • photocatalysis can be performed under natural light.
  • the time of photocatalysis is 36 ⁇ 80h.
  • the time for photocatalysis is 36-60h. More preferably, the time for photocatalysis is 48-60h. This can increase the photocatalytic degradation rate of organic dyes.
  • the graphene oxide of the following examples and comparative examples was purchased from Changzhou Sixth Element Material Technology Co., Ltd., with a sheet diameter of 20-25 ⁇ m, and an oxygen-carbon molar ratio of 0.6.
  • the polyurethane sponge with a volume of 10cm ⁇ 10cm ⁇ 2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning.
  • the polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C.
  • the dried polyurethane sponge is soaked in a graphene oxide suspension emulsion with a concentration of 2 mg/ml, squeezed and soaked several times, and then centrifuged to obtain a graphene oxide composite sponge.
  • the graphene oxide composite sponge is placed in a mixture of nano-titanium dioxide and ascorbic acid (the concentration of nano-titanium dioxide is 0.2mg/ml, and the concentration of ascorbic acid is 5mg/ml) and reacted at 80°C for 12 hours to obtain photocatalytically modified graphene Composite sponge hydrogel.
  • the photocatalyst modified graphene composite sponge hydrogel was immersed and washed with 1 vol% ethanol aqueous solution for 24 hours, and dried at 65°C for 10 hours to prepare a photocatalyst modified graphene composite sponge.
  • the photocatalyst modified graphene composite sponge was , The weight of nano titanium dioxide is 1.4wt% of the total weight of the composite sponge.
  • the photocatalyst modified graphene composite sponge is fixed in the stretchable network compartment to make an adsorption accessory, and the adsorption accessory is put into the adsorption reactor.
  • the waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
  • the photocatalyst modified graphene composite sponge is saturated with adsorption and replaced with a new photocatalyst Modified graphene composite sponge.
  • the adsorbed saturated photocatalyst modified graphene composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated photocatalyst modified graphene composite sponge.
  • the polyurethane sponge with a volume of 10cm ⁇ 10cm ⁇ 2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning.
  • the polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C.
  • the dried polyurethane sponge is soaked in a graphene oxide suspension emulsion with a concentration of 4 mg/ml, squeezed and soaked several times, and then centrifuged to obtain a graphene oxide composite sponge.
  • the graphene oxide composite sponge is placed in a mixture of nano-titanium dioxide and ascorbic acid (the concentration of nano-titanium dioxide is 0.2mg/ml, and the concentration of ascorbic acid is 5mg/ml) and reacted at 80°C for 12 hours to obtain photocatalytically modified graphene Composite sponge hydrogel.
  • the photocatalyst modified graphene composite sponge hydrogel was immersed and washed with 1 vol% ethanol aqueous solution for 24 hours, and dried at 65°C for 10 hours to prepare a photocatalyst modified graphene composite sponge.
  • the photocatalyst modified graphene composite sponge was The weight of the nano titanium dioxide is 2.6% by weight of the total weight of the composite sponge.
  • the photocatalyst modified graphene composite sponge is fixed in the stretchable network compartment to make an adsorption accessory, and the adsorption accessory is put into the adsorption reactor.
  • the waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
  • the photocatalyst modified graphene composite sponge is saturated with adsorption and replaced with a new photocatalyst Modified graphene composite sponge.
  • the adsorbed saturated photocatalyst modified graphene composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated photocatalyst modified graphene composite sponge.
  • the polyurethane sponge with a volume of 10cm ⁇ 10cm ⁇ 2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning.
  • the polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C.
  • the dried polyurethane sponge is soaked in a graphene oxide suspension emulsion with a concentration of 5 mg/ml, squeezed and soaked for several times, and then centrifuged to obtain a graphene oxide composite sponge.
  • the graphene oxide composite sponge is placed in a mixture of nano-titanium dioxide and ascorbic acid (the concentration of nano-titanium dioxide is 0.2mg/ml, and the concentration of ascorbic acid is 5mg/ml) and reacted at 80°C for 12 hours to obtain photocatalytically modified graphene Composite sponge hydrogel.
  • the photocatalyst modified graphene composite sponge hydrogel was immersed and washed with 1 vol% ethanol aqueous solution for 24 hours, and dried at 65°C for 10 hours to prepare a photocatalyst modified graphene composite sponge.
  • the photocatalyst modified graphene composite sponge was The weight of the nano titanium dioxide is 3.1 wt% of the total weight of the composite sponge.
  • the photocatalyst modified graphene composite sponge is fixed in the stretchable network compartment to make an adsorption accessory, and the adsorption accessory is put into the adsorption reactor.
  • the waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
  • the photocatalyst modified graphene composite sponge is saturated with adsorption and replaced with a new photocatalyst Modified graphene composite sponge.
  • the adsorbed saturated photocatalyst modified graphene composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated photocatalyst modified graphene composite sponge.
  • the polyurethane sponge with a volume of 10cm ⁇ 10cm ⁇ 2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning.
  • the polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C.
  • the dried polyurethane sponge is soaked in a graphene oxide suspension emulsion with a concentration of 5 mg/ml, squeezed and soaked several times, and then centrifuged to obtain a graphene oxide composite sponge.
  • the graphene oxide composite sponge is placed in a mixture of nano-titanium dioxide and ascorbic acid (the concentration of nano-titanium dioxide is 0.5mg/ml, the concentration of ascorbic acid is 5mg/ml), and the reaction is carried out at 80°C for 12h to obtain photocatalytically modified graphene Composite sponge hydrogel.
  • the photocatalyst modified graphene composite sponge hydrogel was immersed and washed with 1 vol% ethanol aqueous solution for 24 hours, and dried at 65°C for 10 hours to prepare a photocatalyst modified graphene composite sponge.
  • the photocatalyst modified graphene composite sponge was The weight of the nano titanium dioxide is 4.1 wt% of the total weight of the composite sponge.
  • the photocatalyst modified graphene composite sponge is fixed in the stretchable network compartment to make an adsorption accessory, and the adsorption accessory is put into the adsorption reactor.
  • the waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
  • the photocatalyst modified graphene composite sponge is saturated with adsorption and replaced with a new photocatalyst Modified graphene composite sponge.
  • the adsorbed saturated photocatalyst modified graphene composite sponge was exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated photocatalyst modified graphene composite sponge.
  • the polyurethane sponge with a volume of 10cm ⁇ 10cm ⁇ 2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning.
  • the polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C. Soak the dried polyurethane sponge in the graphene oxide suspension emulsion with a concentration of 5mg/ml, squeeze and soak for several times, take out the centrifugation, soak and wash the centrifugal composite sponge with 1vol% ethanol aqueous solution for 24h, at 65°C After drying for 10 hours, a graphene oxide composite sponge was prepared.
  • the graphene oxide composite sponge is fixed in the stretchable network compartment to form an adsorption accessory, and the adsorption accessory is installed in the adsorption reactor.
  • the waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
  • the graphene oxide composite sponge is saturated with adsorption and replaced with a new graphene oxide composite sponge .
  • the saturated graphene oxide composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated graphene oxide composite sponge.
  • the graphene oxide is mixed with water to obtain 100 ml of a graphene oxide dispersion with a concentration of 5 mg/ml; 0.5 mg of hydrophilic titanium dioxide is added to the graphene oxide dispersion and ultrasonicated for 60 minutes to obtain a mixed solution.
  • the polyurethane sponge was immersed in the reaction solution, and the reduction reaction was carried out at 80°C for 8 hours under a sealed condition, and the obtained sponge was dried at 100°C for 12 hours to obtain a titanium dioxide-graphene composite sponge.
  • the polyurethane sponge is ultrasonically cleaned with ethanol, acetone, and deionized water for 15 minutes before use, and then dried at 100° C. for 12 hours.
  • the titanium dioxide-graphene composite sponge is fixed in the stretchable network compartment to form an adsorption accessory, and the adsorption accessory is loaded into the adsorption reactor.
  • the waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
  • the titanium dioxide-graphene composite sponge is saturated with adsorption and replaced with a new titanium dioxide-graphene Composite sponge.
  • the saturated titanium dioxide-graphene composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated titanium dioxide-graphene composite sponge.
  • the photocatalytic degradation rate test is as follows:

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Abstract

Disclosed is a method for treating an organic dye in waste water, comprising the following steps: (1) soaking a sponge in a graphene oxide suspension emulsion to obtain a graphene oxide composite sponge; placing the graphene oxide composite sponge in a nanoscale mixture of a photocatalyst and a reducing agent to obtain a photocatalyst-modified graphene composite sponge hydrogel; and washing and drying the photocatalyst-modified graphene composite sponge hydrogel to prepare a photocatalyst-modified graphene composite sponge; (2) passing the waste water containing the organic dye through an adsorption reactor equipped with the photocatalyst-modified graphene composite sponge, so as to adsorb the organic dye in the waste water; (3) taking out the adsorbing saturated photocatalyst-modified graphene composite sponge, and catalytically decomposing the organic dye under illumination to obtain a regenerated photocatalyst-modified graphene composite sponge. The method can effectively adsorb an organic dye in waste water, and the used adsorption material is easy to be regenerated.

Description

废水中有机染料的处理方法Treatment method of organic dyes in wastewater 技术领域Technical field
本发明涉及一种废水的处理方法，特别是废水中有机染料的处理方法。The invention relates to a method for treating waste water, in particular to a method for treating organic dyes in waste water.
背景技术Background technique
氧化石墨烯是氧化还原法制备石墨烯的前驱体，不仅具有石墨烯的结构特点，而且表面具有羟基、羧基等含氧官能团，具有良好的水溶性，同时也具有较高的比表面积，其表面的极性官能团易与一些分子形成强的相互作用，利于与其他材料复合。Graphene oxide is the precursor for the preparation of graphene by redox method. It not only has the structural characteristics of graphene, but also has oxygen-containing functional groups such as hydroxyl and carboxyl on the surface. It has good water solubility and also has a high specific surface area. The polar functional group is easy to form strong interaction with some molecules, which is beneficial to composite with other materials.
CN108997608A公开了一种石墨烯疏水吸油海绵的制备方法。制备氧化石墨烯悬浮液；将聚氨酯海绵分别用乙醇和纯水超声洗涤；向氧化石墨烯悬浮液中加入水合肼还原剂和洁净聚氨酯海绵，置于微波化学反应器，加热还原反应；将聚氨酯海绵置于超声清洗器超声分散，洗掉多余石墨烯；将清洗后的聚氨酯海绵干燥，浸入二甲基硅氧烷溶液中，挤干残余液体、干燥，得到石墨烯疏水吸油海绵。由该方法制备得到的海绵再生能力不强，不能达到吸附材料重复利用的要求。CN108997608A discloses a method for preparing graphene hydrophobic oil-absorbing sponge. Prepare graphene oxide suspension; ultrasonically wash polyurethane sponge with ethanol and pure water; add hydrazine hydrate reducing agent and clean polyurethane sponge to graphene oxide suspension, place it in a microwave chemical reactor, and heat the reduction reaction; the polyurethane sponge Place it in an ultrasonic cleaner for ultrasonic dispersion to wash off excess graphene; dry the cleaned polyurethane sponge, immerse it in a dimethylsiloxane solution, squeeze the remaining liquid, and dry to obtain a graphene hydrophobic oil-absorbing sponge. The sponge prepared by this method has poor regeneration ability and cannot meet the requirement of repeated use of the adsorbent material.
CN108384049A公开了一种二氧化钛-石墨烯复合海绵的制备方法。将水、氧化石墨烯和二氧化钛混合，得到混合液；将混合液与还原剂混合，得到反应液；将海绵浸渍在反应液中，在密封条件下进行还原反应，得到二氧化钛-石墨烯复合海绵。该方法制备得到的二氧化钛-石墨烯复合海绵对废水有机染料的吸附能力差，吸附材料中的有机染料光催化降解率低，吸附材料再生能力差。CN108384049A discloses a method for preparing titanium dioxide-graphene composite sponge. Water, graphene oxide and titanium dioxide are mixed to obtain a mixed liquid; the mixed liquid is mixed with a reducing agent to obtain a reaction liquid; the sponge is immersed in the reaction liquid, and a reduction reaction is performed under a sealed condition to obtain a titanium dioxide-graphene composite sponge. The titanium dioxide-graphene composite sponge prepared by the method has poor adsorption capacity for wastewater organic dyes, low photocatalytic degradation rate of organic dyes in the adsorption material, and poor regeneration capacity of the adsorption material.
发明内容Summary of the invention
有鉴于此，本发明的目的在于提供一种废水中有机染料的处理方法，该方法能够有效吸附废水中的有机染料。吸附材料中的有机染料光催化降解率高。吸附材料可以重复利用。In view of this, the purpose of the present invention is to provide a method for treating organic dyes in wastewater, which can effectively adsorb organic dyes in wastewater. The photocatalytic degradation rate of organic dyes in the adsorption material is high. The adsorption material can be reused.
本发明提供一种废水中有机染料的处理方法，包括如下步骤：The present invention provides a method for treating organic dyes in wastewater, including the following steps:
(1)将海绵浸泡于氧化石墨烯悬乳液中，得到氧化石墨烯复合海绵；将氧化石墨烯复合海绵置于纳米级光催化剂和还原剂的混合液中，得到光催化剂改性石墨烯复合海绵水凝胶；将光催化剂改性石墨烯复合海绵水凝胶洗涤、干燥，制得光催化剂改性石墨烯复合海绵；(1) Soak the sponge in the graphene oxide suspension emulsion to obtain a graphene oxide composite sponge; place the graphene oxide composite sponge in a mixture of nano-level photocatalyst and reducing agent to obtain a photocatalyst modified graphene composite sponge Hydrogel; washing and drying the photocatalyst modified graphene composite sponge hydrogel to prepare the photocatalyst modified graphene composite sponge;
(2)将含有机染料的废水通过装有光催化剂改性石墨烯复合海绵的吸附反应器，吸附废水中的有机染料；(2) Pass the wastewater containing organic dyes through an adsorption reactor equipped with a photocatalyst modified graphene composite sponge to absorb the organic dyes in the wastewater;
(3)将吸附饱和的光催化剂改性石墨烯复合海绵取出，在光照下催化分解有机染料，得到再生的光催化剂改性石墨烯复合海绵。(3) Take out the saturated photocatalyst modified graphene composite sponge, and decompose the organic dye under light to obtain a regenerated photocatalyst modified graphene composite sponge.
根据本发明的处理方法，优选地，氧化石墨烯悬乳液中氧化石墨烯的浓度为2～15mg/ml。According to the treatment method of the present invention, preferably, the concentration of graphene oxide in the graphene oxide suspension emulsion is 2-15 mg/ml.
根据本发明的处理方法，优选地，纳米级光催化剂为纳米二氧化钛、纳米氧化锌或纳米氧化锡。According to the treatment method of the present invention, preferably, the nano-level photocatalyst is nano titanium dioxide, nano zinc oxide or nano tin oxide.
根据本发明的处理方法，优选地，还原剂为水合肼、抗坏血酸或氨水。According to the treatment method of the present invention, preferably, the reducing agent is hydrazine hydrate, ascorbic acid or ammonia.
根据本发明的处理方法，优选地，纳米级光催化剂与还原剂的质量比为1:5～30。According to the treatment method of the present invention, preferably, the mass ratio of the nano-scale photocatalyst to the reducing agent is 1:5-30.
根据本发明的处理方法，优选地，纳米级光催化剂和还原剂的混合液中，纳米级光催化剂的浓度为0.2～1mg/ml，且还原剂的浓度为2～10mg/ml。According to the treatment method of the present invention, preferably, in the mixture of nano-scale photocatalyst and reducing agent, the concentration of nano-scale photocatalyst is 0.2-1 mg/ml, and the concentration of reducing agent is 2-10 mg/ml.
根据本发明的处理方法，优选地，海绵选自聚氨酯海绵、三聚氰胺海绵、聚酯海绵、聚醚海绵或聚乙烯醇海绵中的一种。According to the treatment method of the present invention, preferably, the sponge is selected from one of polyurethane sponge, melamine sponge, polyester sponge, polyether sponge or polyvinyl alcohol sponge.
根据本发明的处理方法，优选地，步骤(2)中，含有机染料的 废水经过3级以上吸附处理。According to the treatment method of the present invention, preferably, in step (2), the wastewater containing organic dyes is subjected to 3 or more stages of adsorption treatment.
根据本发明的处理方法，优选地，有机染料选自甲基橙、亚甲基蓝、罗丹明B、甲基紫、中性红中的一种或多种。According to the treatment method of the present invention, preferably, the organic dye is selected from one or more of methyl orange, methylene blue, rhodamine B, methyl violet, and neutral red.
根据本发明的处理方法，优选地，步骤(1)中，海绵在浸泡之前，经过超声清洗、洗涤和干燥。According to the treatment method of the present invention, preferably, in step (1), the sponge undergoes ultrasonic cleaning, washing and drying before soaking.
本发明先制备得到氧化石墨烯复合海绵，再将氧化石墨烯复合海绵与纳米级光催化剂和还原剂的混合液反应制备得到光催化剂改性石墨烯复合海绵。这样可以使光催化剂均匀分布在氧化石墨烯上，减少光催化剂的团聚现象，充分发挥纳米级光催化剂的表面效应与小尺寸效应，有效增加纳米级光催化剂改性石墨烯复合海绵的比表面积和吸附能力。石墨烯的二维结构、高导电性以及与纳米级光催化剂形成的共价键，增强了光催化剂的活性，降低了光催化剂的能隙差，可以使吸附的有机染料在可见光区域完成光催化降解，使纳米级光催化剂改性石墨烯复合海绵易于再生，实现吸附材料的重复利用。The invention first prepares the graphene oxide composite sponge, and then reacts the graphene oxide composite sponge with the mixed solution of the nano-level photocatalyst and the reducing agent to prepare the photocatalyst modified graphene composite sponge. This can make the photocatalyst evenly distributed on the graphene oxide, reduce the agglomeration of the photocatalyst, give full play to the surface effect and small size effect of the nano-level photocatalyst, and effectively increase the specific surface area and the surface area of the nano-level photocatalyst modified graphene composite sponge. Adsorption capacity. Graphene's two-dimensional structure, high conductivity, and covalent bonds formed with nano-level photocatalysts enhance the activity of the photocatalyst, reduce the energy gap difference of the photocatalyst, and enable the adsorbed organic dyes to complete the photocatalysis in the visible light region Degradation makes the nano-level photocatalyst modified graphene composite sponge easy to regenerate and realizes the reuse of adsorption materials.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.
本发明的废水中有机染料的处理方法，包括如下步骤：(1)吸附材料的制备；(2)有机染料的吸附；(3)吸附材料的再生。The method for treating organic dyes in wastewater of the present invention includes the following steps: (1) preparation of adsorption materials; (2) adsorption of organic dyes; (3) regeneration of adsorption materials.
<吸附材料的制备步骤><Preparation steps of adsorption material>
将海绵浸泡于氧化石墨烯悬乳液中，得到氧化石墨烯复合海绵；将氧化石墨烯复合海绵置于纳米级光催化剂和还原剂的混合液中，得到光催化剂改性石墨烯复合海绵水凝胶；将光催化剂改性石墨烯复合 海绵水凝胶洗涤、干燥，制得光催化剂改性石墨烯复合海绵。Soak the sponge in the graphene oxide suspension emulsion to obtain a graphene oxide composite sponge; place the graphene oxide composite sponge in a mixture of nano-level photocatalyst and reducing agent to obtain a photocatalyst modified graphene composite sponge hydrogel ; The photocatalyst modified graphene composite sponge hydrogel is washed and dried to prepare a photocatalyst modified graphene composite sponge.
在本发明中，海绵可以为聚氨酯海绵、三聚氰胺海绵、聚酯海绵、聚醚海绵或聚乙烯醇海绵中的一种。优选地，海绵为聚氨酯海绵或三聚氰胺海绵。根据本发明的一个具体的实施方式，海绵为聚氨酯海绵。海绵的体积为20～500cm 3。优选地，海绵的体积为100～400cm 3。更优选地，海绵的体积为150～300cm 3。海绵的形状可以为长方体或立方体。优选地，海绵的形状为长方体。这样可以使氧化石墨烯更好的涂覆在海绵上，使制备得到的光催化剂改性石墨烯复合海绵具有更强的吸附能力，更高的光催化降解性能。 In the present invention, the sponge may be one of polyurethane sponge, melamine sponge, polyester sponge, polyether sponge or polyvinyl alcohol sponge. Preferably, the sponge is a polyurethane sponge or a melamine sponge. According to a specific embodiment of the present invention, the sponge is a polyurethane sponge. The volume of the sponge is 20～500cm 3 . Preferably, the volume of the sponge is 100-400 cm 3 . More preferably, the volume of the sponge is 150-300 cm 3 . The shape of the sponge can be a cuboid or a cube. Preferably, the shape of the sponge is a rectangular parallelepiped. In this way, the graphene oxide can be better coated on the sponge, so that the prepared photocatalyst modified graphene composite sponge has stronger adsorption capacity and higher photocatalytic degradation performance.
在本发明中，海绵在浸泡之前，可以经过超声清洗、洗涤和干燥。超声清洗的洗液可以为水或醇溶液。优选地，醇溶液为乙醇。根据本发明的一个具体的实施方式，海绵经过两次超声清洗，第一次的洗液为无水乙醇，第二次的洗液为去离子水。洗涤过程中所使用的洗液可以为水或醇溶剂。优选地，洗液为水或乙醇。更优选地，洗液为水。根据本发明地一个具体实施方式，洗涤过程为用蒸馏水浸泡洗涤海绵。干燥温度为50～100℃。优选地，干燥温度为60～80℃。更优选地，干燥温度为60～70℃。这样可以使海绵达到更好地涂覆效果，使制备得到的光催化剂改性石墨烯复合海绵具有更强的吸附能力，更高的光催化降解性能。In the present invention, the sponge can be ultrasonically cleaned, washed and dried before being soaked. The lotion for ultrasonic cleaning can be water or alcohol solution. Preferably, the alcohol solution is ethanol. According to a specific embodiment of the present invention, the sponge is ultrasonically cleaned twice, the first washing liquid is absolute ethanol, and the second washing liquid is deionized water. The washing liquid used in the washing process can be water or alcohol solvent. Preferably, the lotion is water or ethanol. More preferably, the lotion is water. According to a specific embodiment of the present invention, the washing process is to soak the washing sponge with distilled water. The drying temperature is 50-100°C. Preferably, the drying temperature is 60 to 80°C. More preferably, the drying temperature is 60 to 70°C. In this way, the sponge can achieve a better coating effect, and the prepared photocatalyst modified graphene composite sponge has stronger adsorption capacity and higher photocatalytic degradation performance.
在本发明中，氧化石墨烯的片径可以为1～50μm；优选为5～35μm；更优选为20～25μm。氧化石墨烯的氧碳摩尔比可以为0.3～0.8，优选为0.5～0.7，更优选为0.6～0.7。氧化石墨烯的实例包括但不限于常州第六元素材料科技股份有限公司的氧化石墨烯。氧化石墨烯片径为20～25μm，氧碳摩尔比为0.6。In the present invention, the sheet diameter of graphene oxide may be 1-50 μm; preferably 5-35 μm; more preferably 20-25 μm. The oxygen to carbon molar ratio of graphene oxide may be 0.3 to 0.8, preferably 0.5 to 0.7, and more preferably 0.6 to 0.7. Examples of graphene oxide include, but are not limited to, graphene oxide of Changzhou Sixth Element Material Technology Co., Ltd. The graphene oxide sheet diameter is 20-25 μm, and the oxygen-carbon molar ratio is 0.6.
在本发明中，氧化石墨烯悬乳液中氧化石墨烯的浓度为2～15mg/ml。优选地，氧化石墨烯的浓度为2～10mg/ml。更优选地，氧 化石墨烯的浓度为3～5mg/ml。In the present invention, the concentration of graphene oxide in the graphene oxide suspension emulsion is 2-15 mg/ml. Preferably, the concentration of graphene oxide is 2-10 mg/ml. More preferably, the concentration of oxidized graphene is 3 to 5 mg/ml.
在本发明中，纳米级光催化剂为纳米二氧化钛、纳米氧化锌或纳米氧化锡。优选地，纳米级光催化剂为纳米二氧化钛或纳米氧化锌。根据本发明的一个具体的实施方式，纳米级光催化剂为纳米二氧化钛。这样可以使纳米级光催化剂更好地分布在氧化石墨烯上，使制备得到的光催化剂改性石墨烯复合海绵具有更强的吸附能力，更高的光催化降解性能。In the present invention, the nano-level photocatalyst is nano-titanium dioxide, nano-zinc oxide or nano-tin oxide. Preferably, the nano-level photocatalyst is nano-titanium dioxide or nano-zinc oxide. According to a specific embodiment of the present invention, the nano-level photocatalyst is nano-titanium dioxide. In this way, the nano-level photocatalyst can be better distributed on the graphene oxide, so that the prepared photocatalyst modified graphene composite sponge has stronger adsorption capacity and higher photocatalytic degradation performance.
在本发明中，还原剂为水合肼、抗坏血酸或氨水。优选地，还原剂为水合肼或抗坏血酸。更优选地，还原剂为抗坏血酸。这样可以使纳米级光催化剂更好地分布在氧化石墨烯上，使制备得到的光催化剂改性石墨烯复合海绵具有更强的吸附能力，更高的光催化降解性能。In the present invention, the reducing agent is hydrazine hydrate, ascorbic acid or ammonia. Preferably, the reducing agent is hydrazine hydrate or ascorbic acid. More preferably, the reducing agent is ascorbic acid. In this way, the nano-level photocatalyst can be better distributed on the graphene oxide, so that the prepared photocatalyst modified graphene composite sponge has stronger adsorption capacity and higher photocatalytic degradation performance.
在本发明中，纳米级光催化剂与还原剂的质量比为1:5～30。优选地，纳米级光催化剂与还原剂的质量比为1:10～30。更优选地，纳米级光催化剂与还原剂的质量比为1:15～25。In the present invention, the mass ratio of the nano-level photocatalyst to the reducing agent is 1:5-30. Preferably, the mass ratio of the nano-level photocatalyst to the reducing agent is 1:10-30. More preferably, the mass ratio of the nano-scale photocatalyst to the reducing agent is 1:15-25.
在本发明中，纳米级光催化剂和还原剂的混合液中，纳米级光催化剂的浓度为0.2～1mg/ml，且还原剂的浓度为2～10mg/ml。优选地，纳米级光催化剂的浓度为0.2～0.7mg/ml。更优选地，纳米级光催化剂的浓度为0.2～0.5mg/ml。优选地，还原剂的浓度为5～10mg/ml。更优选地，还原剂的浓度为5～7mg/ml。这样可以使制备得到的光催化剂改性石墨烯复合海绵具有更强的吸附能力，更高的光催化降解性能。In the present invention, in the mixed solution of the nano-level photocatalyst and the reducing agent, the concentration of the nano-level photocatalyst is 0.2-1 mg/ml, and the concentration of the reducing agent is 2-10 mg/ml. Preferably, the concentration of the nano-level photocatalyst is 0.2-0.7 mg/ml. More preferably, the concentration of the nano-level photocatalyst is 0.2-0.5 mg/ml. Preferably, the concentration of the reducing agent is 5-10 mg/ml. More preferably, the concentration of the reducing agent is 5-7 mg/ml. In this way, the prepared photocatalyst modified graphene composite sponge can have stronger adsorption capacity and higher photocatalytic degradation performance.
在本发明中，氧化石墨烯复合海绵与纳米级光催化剂和还原剂的混合液的反应温度为50～150℃。优选地，反应温度为70～120℃。更优选地，反应温度为70～100℃。反应时间为8～20h。优选地，反应时间为10～18h。更优选地，反应时间为10～15h。这样可以使纳米级光催化剂更好地分布在氧化石墨烯上，使制备得到的光催化剂 改性石墨烯复合海绵具有更强的吸附能力，更高的光催化降解性能。In the present invention, the reaction temperature of the graphene oxide composite sponge and the mixture of nano-level photocatalyst and reducing agent is 50-150°C. Preferably, the reaction temperature is 70 to 120°C. More preferably, the reaction temperature is 70-100°C. The reaction time is 8-20h. Preferably, the reaction time is 10-18h. More preferably, the reaction time is 10-15h. In this way, the nano-level photocatalyst can be better distributed on the graphene oxide, and the prepared photocatalyst-modified graphene composite sponge has stronger adsorption capacity and higher photocatalytic degradation performance.
在本发明中，洗涤光催化剂改性石墨烯复合海绵水凝胶的洗液为乙醇水溶液。优选地，乙醇水溶液的乙醇浓度为1～20vol％。更优选地，乙醇水溶液的乙醇浓度为3～10vol％。洗涤时间为15～36h。优选地，洗涤时间为20～36h。更优选地，洗涤时间为24～36h。干燥光催化剂改性石墨烯复合海绵水凝胶的温度为50～100℃。优选地，干燥温度为50～80℃。更优选地，干燥温度为60～75℃。干燥时间为5～20h。优选地，干燥时间为10～20h。更优选地，干燥时间为15～20h。这样可以使制备得到的光催化剂改性石墨烯复合海绵具有更强的吸附能力，更高的光催化降解性能。In the present invention, the washing liquid for washing the photocatalyst modified graphene composite sponge hydrogel is an ethanol aqueous solution. Preferably, the ethanol concentration of the ethanol aqueous solution is 1-20 vol%. More preferably, the ethanol concentration of the ethanol aqueous solution is 3-10 vol%. The washing time is 15～36h. Preferably, the washing time is 20 to 36 hours. More preferably, the washing time is 24 to 36 hours. The temperature for drying the photocatalyst modified graphene composite sponge hydrogel is 50-100°C. Preferably, the drying temperature is 50-80°C. More preferably, the drying temperature is 60 to 75°C. The drying time is 5-20h. Preferably, the drying time is 10-20h. More preferably, the drying time is 15-20h. In this way, the prepared photocatalyst modified graphene composite sponge can have stronger adsorption capacity and higher photocatalytic degradation performance.
在本发明中，光催化剂改性石墨烯复合海绵中纳米二氧化钛的重量为复合海绵总重量的0.1～5wt％。优选地，纳米二氧化钛的重量为复合海绵总重量的1～5wt％。更优选地，纳米二氧化钛的重量为复合海绵总重量的2～4wt％。In the present invention, the weight of nanometer titanium dioxide in the photocatalyst modified graphene composite sponge is 0.1-5 wt% of the total weight of the composite sponge. Preferably, the weight of the nano titanium dioxide is 1 to 5 wt% of the total weight of the composite sponge. More preferably, the weight of the nano titanium dioxide is 2 to 4 wt% of the total weight of the composite sponge.
<有机染料的吸附步骤><The adsorption step of organic dye>
将含有机染料的废水通过装有光催化剂改性石墨烯复合海绵的吸附反应器，吸附废水中的有机染料。The wastewater containing organic dyes is passed through an adsorption reactor equipped with a photocatalyst modified graphene composite sponge to adsorb the organic dyes in the wastewater.
在本发明中，含有机染料的废水经过3级以上吸附处理。优选地，含有机染料的废水经过5级以上吸附处理。更优选地，含有机染料的废水经7级以上吸附处理。例如，吸附处理可以为7～10级。这样可以更充分地吸附废水中的有机染料。In the present invention, the wastewater containing organic dyes is subjected to 3 or more adsorption treatments. Preferably, the wastewater containing organic dyes is subjected to 5 or more adsorption treatments. More preferably, the waste water containing organic dyes is treated by adsorption of more than 7 levels. For example, the adsorption treatment can be 7-10 levels. This can more fully adsorb the organic dyes in the wastewater.
在本发明中，有机染料可以选自甲基橙、亚甲基蓝、罗丹明B、甲基紫、中性红中的一种或多种。优选地，有机染料可以选自甲基橙、亚甲基蓝、罗丹明B中的一种或多种。更优选地，有机染料为亚甲基蓝。In the present invention, the organic dye can be selected from one or more of methyl orange, methylene blue, rhodamine B, methyl violet, and neutral red. Preferably, the organic dye can be selected from one or more of methyl orange, methylene blue, and rhodamine B. More preferably, the organic dye is methylene blue.
在本发明中，光催化剂改性石墨烯复合海绵可以制作成吸附配件装入吸附反应器中。根据本发明的一个具体的实施方式，将光催化剂改性石墨烯复合海绵固定在可伸缩网络隔层中，装入吸附反应器。In the present invention, the photocatalyst modified graphene composite sponge can be made into an adsorption fitting and loaded into the adsorption reactor. According to a specific embodiment of the present invention, the photocatalyst modified graphene composite sponge is fixed in a stretchable network barrier and loaded into an adsorption reactor.
<吸附材料的再生步骤><Regeneration step of adsorbent material>
将吸附饱和的光催化剂改性石墨烯复合海绵取出，在光照下催化分解有机染料，得到再生的光催化剂改性石墨烯复合海绵。The adsorbed saturated photocatalyst modified graphene composite sponge is taken out, and the organic dye is catalytically decomposed under light to obtain a regenerated photocatalyst modified graphene composite sponge.
在本发明中，当吸附反应器入口与出口的废水中有机染料的浓度相差小于50mg/ml时，光催化剂改性石墨烯复合海绵吸附饱和，更换新的光催化剂改性石墨烯复合海绵，吸附饱和的光催化剂改性石墨烯复合海绵进行再生。In the present invention, when the difference between the concentration of organic dyes in the wastewater at the inlet and the outlet of the adsorption reactor is less than 50 mg/ml, the photocatalyst modified graphene composite sponge is adsorbed saturated, and a new photocatalyst modified graphene composite sponge is replaced. Saturated photocatalyst modified graphene composite sponge for regeneration.
在本发明中，光照催化可以在自然光下进行。光照催化的时间为36～80h。优选地，光照催化的时间为36～60h。更优选地，光照催化的时间为48～60h。这样可以提高有机染料的光催化降解率。In the present invention, photocatalysis can be performed under natural light. The time of photocatalysis is 36～80h. Preferably, the time for photocatalysis is 36-60h. More preferably, the time for photocatalysis is 48-60h. This can increase the photocatalytic degradation rate of organic dyes.
以下实施例和比较例的氧化石墨烯购自常州第六元素材料科技股份有限公司，片径为20～25μm，氧碳摩尔比为0.6。The graphene oxide of the following examples and comparative examples was purchased from Changzhou Sixth Element Material Technology Co., Ltd., with a sheet diameter of 20-25 μm, and an oxygen-carbon molar ratio of 0.6.
实施例1Example 1
将体积为10cm×10cm×2cm的聚氨酯海绵先置于无水乙醇中超声清洗，再置于去离子水中超声清洗。将超声清洗后的聚氨酯海绵用蒸馏水浸泡洗涤，并在65℃条件下干燥。将干燥后的聚氨酯海绵浸泡于浓度为2mg/ml的氧化石墨烯悬乳液中，挤压浸泡多次，取出离心，得到氧化石墨烯复合海绵。将氧化石墨烯复合海绵置于纳米二氧化钛和抗坏血酸的混合液(纳米二氧化钛的浓度为0.2mg/ml，抗坏血酸的浓度为5mg/ml)中，在80℃下反应12h，得到光催化改性石墨烯复合 海绵水凝胶。将光催化改性石墨烯复合海绵水凝胶用1vol％的乙醇水溶液浸泡洗涤24h，在65℃下干燥10h，制得光催化剂改性石墨烯复合海绵，该光催化剂改性石墨烯复合海绵中，纳米二氧化钛的重量为复合海绵总重量的1.4wt％。The polyurethane sponge with a volume of 10cm×10cm×2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning. The polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C. The dried polyurethane sponge is soaked in a graphene oxide suspension emulsion with a concentration of 2 mg/ml, squeezed and soaked several times, and then centrifuged to obtain a graphene oxide composite sponge. The graphene oxide composite sponge is placed in a mixture of nano-titanium dioxide and ascorbic acid (the concentration of nano-titanium dioxide is 0.2mg/ml, and the concentration of ascorbic acid is 5mg/ml) and reacted at 80°C for 12 hours to obtain photocatalytically modified graphene Composite sponge hydrogel. The photocatalyst modified graphene composite sponge hydrogel was immersed and washed with 1 vol% ethanol aqueous solution for 24 hours, and dried at 65°C for 10 hours to prepare a photocatalyst modified graphene composite sponge. The photocatalyst modified graphene composite sponge was , The weight of nano titanium dioxide is 1.4wt% of the total weight of the composite sponge.
将光催化剂改性石墨烯复合海绵固定在可伸缩网络隔层中，做成吸附配件，将吸附配件装入吸附反应器中。将含有机染料的废水通过装有吸附配件的吸附反应器，吸附废水中的有机染料，经过3级吸附处理。The photocatalyst modified graphene composite sponge is fixed in the stretchable network compartment to make an adsorption accessory, and the adsorption accessory is put into the adsorption reactor. The waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
检测吸附反应器出水口的废水中有机染料的浓度，当吸附反应器入口与出口废水中有机染料的浓度差小于50mg/ml时，光催化剂改性石墨烯复合海绵吸附饱和，更换新的光催化剂改性石墨烯复合海绵。将吸附饱和的光催化剂改性石墨烯复合海绵，在自然光照下曝晒48h，催化分解有机染料，得到再生光催化剂改性石墨烯复合海绵。Detect the concentration of organic dyes in the wastewater at the outlet of the adsorption reactor. When the concentration difference of the organic dyes in the wastewater at the inlet and outlet of the adsorption reactor is less than 50mg/ml, the photocatalyst modified graphene composite sponge is saturated with adsorption and replaced with a new photocatalyst Modified graphene composite sponge. The adsorbed saturated photocatalyst modified graphene composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated photocatalyst modified graphene composite sponge.
实施例2Example 2
将体积为10cm×10cm×2cm的聚氨酯海绵先置于无水乙醇中超声清洗，再置于去离子水中超声清洗。将超声清洗后的聚氨酯海绵用蒸馏水浸泡洗涤，并在65℃条件下干燥。将干燥后的聚氨酯海绵浸泡于浓度为4mg/ml的氧化石墨烯悬乳液中，挤压浸泡多次，取出离心，得到氧化石墨烯复合海绵。将氧化石墨烯复合海绵置于纳米二氧化钛和抗坏血酸的混合液(纳米二氧化钛的浓度为0.2mg/ml，抗坏血酸的浓度为5mg/ml)中，在80℃下反应12h，得到光催化改性石墨烯复合海绵水凝胶。将光催化改性石墨烯复合海绵水凝胶用1vol％的乙醇水溶液浸泡洗涤24h，在65℃下干燥10h，制得光催化剂改性石墨烯复合海绵，该光催化剂改性石墨烯复合海绵中纳米二氧化钛的重量为复合海绵总重量的2.6wt％。The polyurethane sponge with a volume of 10cm×10cm×2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning. The polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C. The dried polyurethane sponge is soaked in a graphene oxide suspension emulsion with a concentration of 4 mg/ml, squeezed and soaked several times, and then centrifuged to obtain a graphene oxide composite sponge. The graphene oxide composite sponge is placed in a mixture of nano-titanium dioxide and ascorbic acid (the concentration of nano-titanium dioxide is 0.2mg/ml, and the concentration of ascorbic acid is 5mg/ml) and reacted at 80°C for 12 hours to obtain photocatalytically modified graphene Composite sponge hydrogel. The photocatalyst modified graphene composite sponge hydrogel was immersed and washed with 1 vol% ethanol aqueous solution for 24 hours, and dried at 65°C for 10 hours to prepare a photocatalyst modified graphene composite sponge. The photocatalyst modified graphene composite sponge was The weight of the nano titanium dioxide is 2.6% by weight of the total weight of the composite sponge.
将光催化剂改性石墨烯复合海绵固定在可伸缩网络隔层中，做成吸附配件，将吸附配件装入吸附反应器中。将含有机染料的废水通过装有吸附配件的吸附反应器，吸附废水中的有机染料，经过3级吸附处理。The photocatalyst modified graphene composite sponge is fixed in the stretchable network compartment to make an adsorption accessory, and the adsorption accessory is put into the adsorption reactor. The waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
检测吸附反应器出水口的废水中有机染料的浓度，当吸附反应器入口与出口废水中有机染料的浓度差小于50mg/ml时，光催化剂改性石墨烯复合海绵吸附饱和，更换新的光催化剂改性石墨烯复合海绵。将吸附饱和的光催化剂改性石墨烯复合海绵，在自然光照下曝晒48h，催化分解有机染料，得到再生光催化剂改性石墨烯复合海绵。Detect the concentration of organic dyes in the wastewater at the outlet of the adsorption reactor. When the concentration difference of the organic dyes in the wastewater at the inlet and outlet of the adsorption reactor is less than 50mg/ml, the photocatalyst modified graphene composite sponge is saturated with adsorption and replaced with a new photocatalyst Modified graphene composite sponge. The adsorbed saturated photocatalyst modified graphene composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated photocatalyst modified graphene composite sponge.
实施例3Example 3
将体积为10cm×10cm×2cm的聚氨酯海绵先置于无水乙醇中超声清洗，再置于去离子水中超声清洗。将超声清洗后的聚氨酯海绵用蒸馏水浸泡洗涤，并在65℃条件下干燥。将干燥后的聚氨酯海绵浸泡于浓度为5mg/ml的氧化石墨烯悬乳液中，挤压浸泡多次，取出离心，得到氧化石墨烯复合海绵。将氧化石墨烯复合海绵置于纳米二氧化钛和抗坏血酸的混合液(纳米二氧化钛的浓度为0.2mg/ml，抗坏血酸的浓度为5mg/ml)中，在80℃下反应12h，得到光催化改性石墨烯复合海绵水凝胶。将光催化改性石墨烯复合海绵水凝胶用1vol％的乙醇水溶液浸泡洗涤24h，在65℃下干燥10h，制得光催化剂改性石墨烯复合海绵，该光催化剂改性石墨烯复合海绵中纳米二氧化钛的重量为复合海绵总重量的3.1wt％。The polyurethane sponge with a volume of 10cm×10cm×2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning. The polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C. The dried polyurethane sponge is soaked in a graphene oxide suspension emulsion with a concentration of 5 mg/ml, squeezed and soaked for several times, and then centrifuged to obtain a graphene oxide composite sponge. The graphene oxide composite sponge is placed in a mixture of nano-titanium dioxide and ascorbic acid (the concentration of nano-titanium dioxide is 0.2mg/ml, and the concentration of ascorbic acid is 5mg/ml) and reacted at 80°C for 12 hours to obtain photocatalytically modified graphene Composite sponge hydrogel. The photocatalyst modified graphene composite sponge hydrogel was immersed and washed with 1 vol% ethanol aqueous solution for 24 hours, and dried at 65°C for 10 hours to prepare a photocatalyst modified graphene composite sponge. The photocatalyst modified graphene composite sponge was The weight of the nano titanium dioxide is 3.1 wt% of the total weight of the composite sponge.
将光催化剂改性石墨烯复合海绵固定在可伸缩网络隔层中，做成吸附配件，将吸附配件装入吸附反应器中。将含有机染料的废水通过装有吸附配件的吸附反应器，吸附废水中的有机染料，经过3级吸附处理。The photocatalyst modified graphene composite sponge is fixed in the stretchable network compartment to make an adsorption accessory, and the adsorption accessory is put into the adsorption reactor. The waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
检测吸附反应器出水口的废水中有机染料的浓度，当吸附反应器入口与出口废水中有机染料的浓度差小于50mg/ml时，光催化剂改性石墨烯复合海绵吸附饱和，更换新的光催化剂改性石墨烯复合海绵。将吸附饱和的光催化剂改性石墨烯复合海绵，在自然光照下曝晒48h，催化分解有机染料，得到再生光催化剂改性石墨烯复合海绵。Detect the concentration of organic dyes in the wastewater at the outlet of the adsorption reactor. When the concentration difference of the organic dyes in the wastewater at the inlet and outlet of the adsorption reactor is less than 50mg/ml, the photocatalyst modified graphene composite sponge is saturated with adsorption and replaced with a new photocatalyst Modified graphene composite sponge. The adsorbed saturated photocatalyst modified graphene composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated photocatalyst modified graphene composite sponge.
实施例4Example 4
将体积为10cm×10cm×2cm的聚氨酯海绵先置于无水乙醇中超声清洗，再置于去离子水中超声清洗。将超声清洗后的聚氨酯海绵用蒸馏水浸泡洗涤，并在65℃条件下干燥。将干燥后的聚氨酯海绵浸泡于浓度为5mg/ml的氧化石墨烯悬乳液中，挤压浸泡多次，取出离心，得到氧化石墨烯复合海绵。将氧化石墨烯复合海绵置于纳米二氧化钛和抗坏血酸的混合液(纳米二氧化钛的浓度为0.5mg/ml，抗坏血酸的浓度为5mg/ml)中，在80℃下反应12h，得到光催化改性石墨烯复合海绵水凝胶。将光催化改性石墨烯复合海绵水凝胶用1vol％的乙醇水溶液浸泡洗涤24h，在65℃下干燥10h，制得光催化剂改性石墨烯复合海绵，该光催化剂改性石墨烯复合海绵中纳米二氧化钛的重量为复合海绵总重量的4.1wt％。The polyurethane sponge with a volume of 10cm×10cm×2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning. The polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C. The dried polyurethane sponge is soaked in a graphene oxide suspension emulsion with a concentration of 5 mg/ml, squeezed and soaked several times, and then centrifuged to obtain a graphene oxide composite sponge. The graphene oxide composite sponge is placed in a mixture of nano-titanium dioxide and ascorbic acid (the concentration of nano-titanium dioxide is 0.5mg/ml, the concentration of ascorbic acid is 5mg/ml), and the reaction is carried out at 80°C for 12h to obtain photocatalytically modified graphene Composite sponge hydrogel. The photocatalyst modified graphene composite sponge hydrogel was immersed and washed with 1 vol% ethanol aqueous solution for 24 hours, and dried at 65°C for 10 hours to prepare a photocatalyst modified graphene composite sponge. The photocatalyst modified graphene composite sponge was The weight of the nano titanium dioxide is 4.1 wt% of the total weight of the composite sponge.
将光催化剂改性石墨烯复合海绵固定在可伸缩网络隔层中，做成吸附配件，将吸附配件装入吸附反应器中。将含有机染料的废水通过装有吸附配件的吸附反应器，吸附废水中的有机染料，经过3级吸附处理。The photocatalyst modified graphene composite sponge is fixed in the stretchable network compartment to make an adsorption accessory, and the adsorption accessory is put into the adsorption reactor. The waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
检测吸附反应器出水口的废水中有机染料的浓度，当吸附反应器入口与出口废水中有机染料的浓度差小于50mg/ml时，光催化剂改性石墨烯复合海绵吸附饱和，更换新的光催化剂改性石墨烯复合海绵。将吸附饱和的光催化剂改性石墨烯复合海绵，在自然光照下曝晒48h， 催化分解有机染料，得到再生光催化剂改性石墨烯复合海绵。Detect the concentration of organic dyes in the wastewater at the outlet of the adsorption reactor. When the concentration difference of the organic dyes in the wastewater at the inlet and outlet of the adsorption reactor is less than 50mg/ml, the photocatalyst modified graphene composite sponge is saturated with adsorption and replaced with a new photocatalyst Modified graphene composite sponge. The adsorbed saturated photocatalyst modified graphene composite sponge was exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated photocatalyst modified graphene composite sponge.
比较例1Comparative example 1
将体积为10cm×10cm×2cm的聚氨酯海绵先置于无水乙醇中超声清洗，再置于去离子水中超声清洗。将超声清洗后的聚氨酯海绵用蒸馏水浸泡洗涤，并在65℃条件下干燥。将干燥后的聚氨酯海绵浸泡于浓度为5mg/ml的氧化石墨烯悬乳液中，挤压浸泡多次，取出离心，将离心后的复合海绵用1vol％的乙醇水溶液浸泡洗涤24h，在65℃下干燥10h，制得氧化石墨烯复合海绵。The polyurethane sponge with a volume of 10cm×10cm×2cm was first placed in absolute ethanol for ultrasonic cleaning, and then placed in deionized water for ultrasonic cleaning. The polyurethane sponge after ultrasonic cleaning was soaked and washed with distilled water, and dried at 65°C. Soak the dried polyurethane sponge in the graphene oxide suspension emulsion with a concentration of 5mg/ml, squeeze and soak for several times, take out the centrifugation, soak and wash the centrifugal composite sponge with 1vol% ethanol aqueous solution for 24h, at 65℃ After drying for 10 hours, a graphene oxide composite sponge was prepared.
将氧化石墨烯复合海绵固定在可伸缩网络隔层中，做成吸附配件，将吸附配件装入吸附反应器中。将含有机染料的废水通过装有吸附配件的吸附反应器，吸附废水中的有机染料，经过3级吸附处理。The graphene oxide composite sponge is fixed in the stretchable network compartment to form an adsorption accessory, and the adsorption accessory is installed in the adsorption reactor. The waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
检测吸附反应器出水口的废水中有机染料的浓度，当吸附反应器入口与出口废水中有机染料的浓度差小于50mg/ml时，氧化石墨烯复合海绵吸附饱和，更换新的氧化石墨烯复合海绵。将吸附饱和的氧化石墨烯复合海绵，在自然光照下曝晒48h，催化分解有机染料，得到再生氧化石墨烯复合海绵。Detect the concentration of organic dyes in the wastewater at the outlet of the adsorption reactor. When the concentration difference of the organic dyes in the wastewater from the inlet and outlet of the adsorption reactor is less than 50mg/ml, the graphene oxide composite sponge is saturated with adsorption and replaced with a new graphene oxide composite sponge . The saturated graphene oxide composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated graphene oxide composite sponge.
比较例2Comparative example 2
将氧化石墨烯与水混合，得到100ml浓度为5mg/ml的氧化石墨烯分散液；向所述氧化石墨烯分散液中加入0.5mg亲水性二氧化钛，超声60min，得到混合液。The graphene oxide is mixed with water to obtain 100 ml of a graphene oxide dispersion with a concentration of 5 mg/ml; 0.5 mg of hydrophilic titanium dioxide is added to the graphene oxide dispersion and ultrasonicated for 60 minutes to obtain a mixed solution.
在500rpm的搅拌速率下，以1滴/秒的滴加速率，向所述混合液中滴加0.5g抗坏血酸，得到反应液。Under a stirring rate of 500 rpm, 0.5 g of ascorbic acid was added dropwise to the mixed solution at a dropping rate of 1 drop/sec to obtain a reaction solution.
将聚氨酯海绵浸渍在所述反应液中，在密封条件下，于80℃进行还原反应8h，将所得到的海绵100℃下干燥12h，得到二氧化钛-石墨 烯复合海绵。其中，所述聚氨酯海绵在使用前依次用乙醇、丙酮和去离子水分别超声清洗15min，然后100℃下干燥12h。The polyurethane sponge was immersed in the reaction solution, and the reduction reaction was carried out at 80°C for 8 hours under a sealed condition, and the obtained sponge was dried at 100°C for 12 hours to obtain a titanium dioxide-graphene composite sponge. Wherein, the polyurethane sponge is ultrasonically cleaned with ethanol, acetone, and deionized water for 15 minutes before use, and then dried at 100° C. for 12 hours.
将二氧化钛-石墨烯复合海绵固定在可伸缩网络隔层中，做成吸附配件，将吸附配件装入吸附反应器中。将含有机染料的废水通过装有吸附配件的吸附反应器，吸附废水中的有机染料，经过3级吸附处理。The titanium dioxide-graphene composite sponge is fixed in the stretchable network compartment to form an adsorption accessory, and the adsorption accessory is loaded into the adsorption reactor. The waste water containing organic dyes is passed through an adsorption reactor equipped with adsorption accessories to absorb the organic dyes in the waste water and undergoes a three-stage adsorption treatment.
检测吸附反应器出水口的废水中有机染料的浓度，当吸附反应器入口与出口废水中有机染料的浓度差小于50mg/ml时，二氧化钛-石墨烯复合海绵吸附饱和，更换新的二氧化钛-石墨烯复合海绵。将吸附饱和的二氧化钛-石墨烯复合海绵，在自然光照下曝晒48h，催化分解有机染料，得到再生二氧化钛-石墨烯复合海绵。Detect the concentration of organic dyes in the wastewater at the outlet of the adsorption reactor. When the concentration difference of the organic dyes in the wastewater at the inlet and outlet of the adsorption reactor is less than 50mg/ml, the titanium dioxide-graphene composite sponge is saturated with adsorption and replaced with a new titanium dioxide-graphene Composite sponge. The saturated titanium dioxide-graphene composite sponge is exposed to natural light for 48 hours to catalyze the decomposition of organic dyes to obtain a regenerated titanium dioxide-graphene composite sponge.
实验例1Experimental example 1
对实施例1～4和比较例1～2制备得到的样品以及纯聚氨酯海绵样品对亚甲基蓝的饱和吸附量进行测试，测试方法如下：The samples prepared in Examples 1 to 4 and Comparative Examples 1 to 2 and the pure polyurethane sponge samples were tested for their saturated adsorption capacity of methylene blue. The test methods are as follows:
将300mg/ml的亚甲基蓝溶液通过装有体积为10cm×10cm×2cm样品的吸附反应器，测量反应器出口的亚甲基蓝浓度，当反应器入口与出口的溶液中，亚甲基蓝的浓度差小于50mg/ml时，样品即达到吸附饱和。计算达到吸附饱和时，反应器处理的总溶液体积和处理后溶液中亚甲基蓝的浓度，从而计算出样品对亚甲基蓝的饱和吸附量。亚甲基蓝的浓度，采用紫外分光光度计在660nm波长测亚甲基蓝溶液的吸光度而计算得到。结果如表1所示。Pass the 300mg/ml methylene blue solution through an adsorption reactor with a sample volume of 10cm×10cm×2cm, and measure the methylene blue concentration at the outlet of the reactor. When the concentration difference between the inlet and outlet of the reactor is less than 50mg/ml , The sample reaches adsorption saturation. When the adsorption saturation is reached, the total solution volume processed by the reactor and the concentration of methylene blue in the treated solution are calculated, so as to calculate the saturated adsorption capacity of the sample for methylene blue. The concentration of methylene blue is calculated by measuring the absorbance of the methylene blue solution at a wavelength of 660 nm using an ultraviolet spectrophotometer. The results are shown in Table 1.
实验例2Experimental example 2
光催化降解率的测试，测试方法如下：The photocatalytic degradation rate test, the test method is as follows:
将实验例1中吸附饱和的样品置于阳光下暴晒48h，取0.25g暴晒后的样品放置于100ml纯水中，超声30min，使样品中残余的亚甲 基蓝脱附到水中，通过紫外分光光度计在660nm波长测水溶液的吸光度而计算得到水中亚甲基蓝的浓度，从而计算出亚甲基蓝的光催化降解率。结果如表1所示。Place the sample saturated with adsorption in experimental example 1 in the sun for 48 hours, take 0.25 g of the exposed sample and place it in 100 ml of pure water, and ultrasonicate for 30 minutes to desorb the residual methylene blue in the sample into the water. Measure the absorbance of the aqueous solution at a wavelength of 660nm to calculate the concentration of methylene blue in the water, thereby calculating the photocatalytic degradation rate of methylene blue. The results are shown in Table 1.
表1Table 1
检测样品Test sample 亚甲基蓝的饱和吸附量mg/gSaturated adsorption capacity of methylene blue mg/g 光催化降解率％Photocatalytic degradation rate%
实施例1Example 1 237237 7070
实施例2Example 2 245245 7777
实施例3Example 3 252252 8686
实施例4Example 4 239239 7979
比较例1Comparative example 1 225225 3939
比较例2Comparative example 2 215215 5858
纯聚氨酯海绵Pure polyurethane sponge 5050 88
本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。The present invention is not limited to the above-mentioned embodiments. Without departing from the essence of the present invention, any modifications, improvements, and replacements that can be imagined by those skilled in the art fall within the scope of the present invention.

Claims (10)

  1. 一种废水中有机染料的处理方法，其特征在于，包括如下步骤：A method for treating organic dyes in wastewater, which is characterized in that it comprises the following steps:
    (1)将海绵浸泡于氧化石墨烯悬乳液中，得到氧化石墨烯复合海绵；将氧化石墨烯复合海绵置于纳米级光催化剂和还原剂的混合液中，得到光催化剂改性石墨烯复合海绵水凝胶；将光催化剂改性石墨烯复合海绵水凝胶洗涤、干燥，制得光催化剂改性石墨烯复合海绵；(1) Soak the sponge in the graphene oxide suspension emulsion to obtain a graphene oxide composite sponge; place the graphene oxide composite sponge in a mixture of nano-level photocatalyst and reducing agent to obtain a photocatalyst modified graphene composite sponge Hydrogel; washing and drying the photocatalyst modified graphene composite sponge hydrogel to prepare the photocatalyst modified graphene composite sponge;
    (2)将含有机染料的废水通过装有光催化剂改性石墨烯复合海绵的吸附反应器，吸附废水中的有机染料；(2) Pass the wastewater containing organic dyes through an adsorption reactor equipped with a photocatalyst modified graphene composite sponge to adsorb the organic dyes in the wastewater;
    (3)将吸附饱和的光催化剂改性石墨烯复合海绵取出，在光照下催化分解有机染料，得到再生的光催化剂改性石墨烯复合海绵。(3) Take out the saturated photocatalyst modified graphene composite sponge, and decompose the organic dye under light to obtain a regenerated photocatalyst modified graphene composite sponge.
  2. 根据权利要求1所述的处理方法，其特征在于，所述的氧化石墨烯悬乳液中氧化石墨烯的浓度为2～15mg/ml。The processing method according to claim 1, wherein the concentration of graphene oxide in the graphene oxide suspension emulsion is 2-15 mg/ml.
  3. 根据权利要求1所述的处理方法，其特征在于，所述的纳米级光催化剂为纳米二氧化钛、纳米氧化锌或纳米氧化锡。The processing method according to claim 1, wherein the nano-level photocatalyst is nano-titanium dioxide, nano-zinc oxide or nano-tin oxide.
  4. 根据权利要求1所述的处理方法，其特征在于，所述的还原剂为水合肼、抗坏血酸或氨水。The treatment method according to claim 1, wherein the reducing agent is hydrazine hydrate, ascorbic acid or ammonia.
  5. 根据权利要求1所述的处理方法，其特征在于，纳米级光催化剂与还原剂的质量比为1:5～30。The processing method according to claim 1, wherein the mass ratio of the nano-scale photocatalyst to the reducing agent is 1:5-30.
  6. 根据权利要求1所述的处理方法，其特征在于，纳米级光催化剂和还原剂的混合液中，纳米级光催化剂的浓度为0.2～1mg/ml，且还原剂的浓度为2～10mg/ml。The processing method according to claim 1, wherein in the mixture of nano-scale photocatalyst and reducing agent, the concentration of nano-scale photocatalyst is 0.2-1 mg/ml, and the concentration of reducing agent is 2-10 mg/ml .
  7. 根据权利要求1所述的处理方法，其特征在于，所述的海绵选自聚氨酯海绵、三聚氰胺海绵、聚酯海绵、聚醚海绵或聚乙烯醇海绵中的一种。The processing method according to claim 1, wherein the sponge is selected from one of polyurethane sponge, melamine sponge, polyester sponge, polyether sponge or polyvinyl alcohol sponge.
  8. 根据权利要求1所述的处理方法，其特征在于，步骤(2)中，含有机染料的废水经过3级以上吸附处理。The treatment method according to claim 1, characterized in that, in step (2), the wastewater containing organic dyes is subjected to 3 or more stages of adsorption treatment.
  9. 根据权利要求1所述的处理方法，其特征在于，所述的有机染料选自甲基橙、亚甲基蓝、罗丹明B、甲基紫、中性红中的一种或多种。The processing method according to claim 1, wherein the organic dye is selected from one or more of methyl orange, methylene blue, rhodamine B, methyl violet, and neutral red.
  10. 根据权利要求1～9任一项所述的处理方法，其特征在于，步骤(1)中，海绵在浸泡之前，经过超声清洗、洗涤和干燥。The processing method according to any one of claims 1-9, wherein in step (1), the sponge is ultrasonically cleaned, washed and dried before soaking.
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