WO2021232600A1 - 一种可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法 - Google Patents

一种可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法 Download PDF

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WO2021232600A1
WO2021232600A1 PCT/CN2020/109989 CN2020109989W WO2021232600A1 WO 2021232600 A1 WO2021232600 A1 WO 2021232600A1 CN 2020109989 W CN2020109989 W CN 2020109989W WO 2021232600 A1 WO2021232600 A1 WO 2021232600A1
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wastewater
visible light
clo
oxidation
organic pollutants
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李倩
苏瑞典
苏园
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山东大学
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/39—
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • 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
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2305/10—Photocatalysts

Definitions

  • the invention relates to a method for efficiently removing organic pollutants in wastewater by combined use of visible light catalysis and ClO 2 oxidation, and belongs to the chemical and environmental technical fields of organic wastewater treatment.
  • Photocatalytic oxidation technology mostly uses semiconductors as catalysts and sunlight as driving energy to produce oxidizing active substances (such as hydroxyl radicals, superoxide radicals, etc.), which convert organic pollutants into non-toxic or low-toxic substances. It is a highly oxidizing, energy-saving, highly efficient and thorough pollutant removal technology.
  • photocatalytic oxidation technology represented by visible light catalytic technology often appears in wastewater treatment processes such as industrial organic wastewater and antibiotic pharmaceutical wastewater.
  • wastewater treatment processes such as industrial organic wastewater and antibiotic pharmaceutical wastewater.
  • the electron-hole recombination rate is high, the photon utilization rate is low, and the catalytic efficiency often cannot reach the theoretical value.
  • the active materials produced in the photocatalytic oxidation process have a very short lifespan and are easily quenched during the mass transfer process.
  • the oxidative degradation of pollutants is also limited to the solid-liquid interface of the catalyst, which restricts the improvement of pollutant removal efficiency and interaction with light. Large-scale industrial application of catalytic technology.
  • ClO 2 oxidation technology As a common effluent disinfection technology, is widely used in water treatment processes such as medical wastewater oxidation treatment, drinking water sterilization and disinfection, and ClO 2 has strong oxidation and durability. It has the advantages of long, high efficiency and few disinfection by-products.
  • the traditional ClO 2 generation method mostly uses chlorite as the raw material, and adopts ozone oxidation, strong acid oxidation and strong ultraviolet oxidation to convert chlorite into ClO 2 gas and store it, and its conversion efficiency is relatively low, and It is possible to bring unreacted chlorite ions into the effluent water.
  • the present invention provides a visible light photocatalytic oxidation -ClO 2 associated method for efficiently removing organic pollutants with wastewater.
  • the oxidative degradation of organic pollutants of the present invention is carried out in a quartz reactor containing a double-walled cooling circulating water interlayer, a visible light-responsive catalyst is used as a catalyst, chlorate is used as a ClO 2 precursor, and a xenon lamp with a certain optical power density is used as a light source. Construct a visible light catalysis-ClO 2 oxidation combined system to carry out catalytic oxidative degradation treatment of wastewater containing organic matter to achieve high-efficiency removal of organic pollutants in the wastewater.
  • a method for the combined use of visible light catalysis and ClO 2 oxidation to efficiently remove organic pollutants in wastewater includes the following steps:
  • step (2) Turn on the xenon lamp light source, adjust the distance between the light source and the liquid surface of the wastewater treated in step (1), add chlorate to the system, keep the reaction temperature constant, and fully stir to achieve the degradation of organic pollutants.
  • the pH is 3-11, and an acidic regulator or an alkaline regulator is used to adjust the pH.
  • step (1) the pH is 5-9.
  • the acid regulator is hydrochloric acid, acetic acid or nitric acid, and the alkali regulator is NaOH or ammonia.
  • the visible light responsive catalyst is one of Ag/TiO 2 , BiVO 4 , WO 3 , and Cu 2 O.
  • the visible light responsive catalyst is BiVO 4 .
  • the addition amount of the visible light responsive catalyst is 10-50 mg/L.
  • the organic matter in the wastewater is one or a mixture of two or more of norfloxacin, sulfadiazine, bisphenol A, and imidacloprid.
  • the wastewater body is tap water, surface river water, domestic sewage, printing and dyeing wastewater, medical wastewater, aquaculture wastewater or seawater.
  • the optical power density of the light source is 100-300 mW/cm 2 , and the distance from the liquid surface is 10-50 cm.
  • the chlorate is one of hypochlorite, chlorite, chlorate or perchlorate.
  • the chlorate is added in an amount such that its concentration reaches 0.1-1.0 mmol/L.
  • the stirring adsorption time is 30-60 min.
  • the reaction temperature is 25-45°C.
  • the treatment process of the present invention is not affected by inorganic substances and organic substances.
  • the present invention still has higher treatment efficiency, and the treatment process of the present invention is more stable.
  • the present invention adopts the combined process of visible light catalysis and ClO 2 oxidation to remove organic pollutants in wastewater.
  • the active substances produced in the photocatalytic process are used as oxidants to transfer electrons with chlorate radicals to generate ClO 2 and other chlorine-containing active substances. It can continue to oxidize and degrade organic pollutants with strong oxidizing ability and long duration, avoiding the short life of photobioactive substances and short mass transfer distance in the photocatalytic process, and effectively improving the degradation rate of pollutants.
  • ClO 2 has a tendency to specifically attack compounds containing phenol, aniline and other structures, and further degrade pollutants that cannot be completely degraded by photocatalysis, which is beneficial to increase the mineralization rate and reduce biological toxicity.
  • the treatment process of the present invention uses the active material produced in the photocatalytic process as an oxidant to oxidize the chlorate to generate ClO 2 and other chlorine-containing active materials, avoiding the strong oxidant, strong acid or strong light in the traditional ClO 2 production method.
  • the use reduces the cost of raw materials and production risks, and is conducive to the safe and orderly implementation of the actual water treatment process.
  • the treatment process of the present invention produces ClO 2 by adding solid chlorate medicaments in the photocatalytic system.
  • the operation is safe and simple, and the dosage is controllable. It can occur simultaneously and at the same time as the photocatalytic technology, which greatly reduces The cost of production and storage equipment and the cost of off-site transportation in the traditional ClO 2 production method also reduce the potential risks in the entire production process and enhance the safety and controllability of the reaction.
  • the dosage level of the chlorate is far lower than the dosage level of various chlorine-containing substances in the ClO 2 oxidation technology in the current industrial production, and meets the limit standard for the concentration of chlorate in the water body.
  • ClO 2 is partially converted into chlorate, and continues to participate in the new ClO 2 conversion process, which improves the utilization efficiency of ClO 2 and extends the combined use of visible light catalysis and ClO 2 oxidation. Catalytic lifetime in the system.
  • the photocatalyst used in the treatment process of the present invention has visible light responsiveness. Compared with ultraviolet light photocatalysts, this type of photocatalyst can more efficiently use sunlight and carry out organic pollutants for the photocatalytic technology driven by sunlight. The degradation provides the possibility to reduce energy consumption.
  • the treatment process of the present invention is not affected by inorganic substances and organic substances. In the case of inorganic substances and organic substances in the water body, it still has a higher treatment efficiency and the treatment process is more stable.
  • Figure 1 is a schematic diagram of a double-walled sandwich reactor used in the present invention
  • Figure 2 is a comparison diagram of the effect of the combined process of visible light catalysis-ClO 2 oxidation composed of different types of visible light responsive photocatalysts in the treatment of norfloxacin antibiotic organic wastewater in Examples 1, 2, 3, and 4 of the present invention; in the figure, a Where the visible light catalyst is bismuth vanadate, b is the visible light catalyst being Cu 2 O, c is the visible light catalyst being WO 3 , and d is the visible light catalyst being Ag/TiO 2 ;
  • FIG. 3 is a diagram showing the treatment effect of the combined process of visible light catalysis and ClO 2 oxidation composed of different concentrations of sodium hypochlorite precursors described in Examples 5, 6, and 7 of the present invention on norfloxacin antibiotic organic wastewater;
  • FIG. 4 is a comparison diagram of the effect of pH in the water body on the treatment of norfloxacin antibiotic organic wastewater by the combined process of visible light catalysis-ClO 2 oxidation in the embodiment 8 of the present invention
  • Fig. 6 is a comparison diagram of the effect of the combined visible light catalysis-ClO 2 oxidation process described in Examples 14, 15, 16, 17, 18, and 19 of the present invention in treating norfloxacin antibiotic organic wastewater in actual water bodies.
  • the double-wall sandwich reactor used in the embodiment includes a reactor body, the body includes an inner wall and an outer wall, the inner wall encloses a reaction cavity, the inner wall and the outer wall are sandwiched, the air inlet and the air outlet on the inner wall, and the air inlet Connect the air inlet pipe, the air inlet pipe extends to the bottom of the reaction cavity, the inner wall is also provided with a liquid inlet and a collection port, the liquid inlet and the collection port respectively pass through the outer wall, and a circulating cooling liquid inlet and a circulating cooling liquid are provided on the outer wall
  • the outlet, the circulating cooling liquid inlet and the circulating cooling liquid outlet are communicated with the interlayer, and the open end of the inner wall is provided with a sealing cover.
  • a method for the combined use of visible light catalysis and ClO 2 oxidation to efficiently remove organic pollutants in wastewater the steps are as follows:
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that the visible light catalyst is Cu 2 O, and the rest are exactly the same as in Example 1.
  • Example 1 the visible light catalysis-ClO 2 oxidation combined use method to efficiently remove organic pollutants in wastewater, the difference is that the visible light catalyst is WO 3 , and the rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that the visible light catalyst is Ag/TiO 2 , and the rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that the ClO 2 precursor is sodium chlorite, and the rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that the ClO 2 precursor is sodium chlorate, and the rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that the ClO 2 precursor is sodium perchlorate, and the rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is: before adding the bismuth vanadate catalyst, the pH of the wastewater is adjusted to 3, 5, and 5, respectively. 7, 9, 11, and the rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is: while adding the ClO 2 precursor, the concentration of 10.0mmol/L Cl - solution is added, The rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is: while adding ClO 2 precursor, the concentration of 1.0mmol/L SO 4 2- The solution and the rest are exactly the same as in Example 1.
  • Example 1 -ClO 2 oxide The visible light of the catalyst in Example 1 -ClO 2 oxide on the method of efficient removal of organic pollutants in waste water, except that: the addition of ClO 2 precursor simultaneously, added at a concentration 10.0mmol / L HCO 3 - solution , And the rest are exactly the same as in Example 1.
  • Example 1 -ClO 2 oxide The visible light of the catalyst in Example 1 -ClO 2 oxide on the method of efficient removal of organic pollutants in waste water, except that: the addition of ClO 2 precursor simultaneously added at a concentration of 1.0mmol / L ClO 3 - solution , And the rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is: while adding the ClO 2 precursor, add a fulvic acid solution with a concentration of 1.0 mg/L , And the rest are exactly the same as in Example 1.
  • the oxidative degradation experiment was carried out with norfloxacin simulated wastewater.
  • the oxidative degradation experiment was carried out in a double-walled sandwich reactor.
  • the initial concentration of norfloxacin in the simulated wastewater of norfloxacin was 10mg/L and the initial volume was 100mL.
  • Constant-temperature cooling circulating water is passed into the interlayer of the wall interlayer reactor to maintain the reactor temperature at about 25°C.
  • the treatment method of the application embodiment is used to degrade the simulated wastewater of norfloxacin.
  • a photocatalytic control group without hypochlorite was established. In the process of oxidative degradation of norfloxacin, samples are taken at a fixed time.
  • the sampling time is 2h, namely 0min, 5min, 10min, 30min, and 1mL at 60min.
  • Figure 4 shows the effect of water pH on the treatment of norfloxacin antibiotic organic wastewater by the combined process of visible light catalysis and ClO 2 oxidation.
  • the present invention also conducts single-factor experiments on the effect of inorganic substances and organic substances on the treatment effect of the visible light catalysis-ClO 2 oxidation combined process, and evaluates the degradation ability and anti-interference ability of the process in actual water bodies.
  • said inorganic substance is Cl -, Br -, ClO 3 -, NO 3 -, SO 4 2-, CO 3 2- or HCO 3 - in one or several ,
  • the concentration is 0.01-1.00 mmol/L;
  • the organic substance is fulvic acid, palm humic acid or black humic acid, and the concentration is 0.1-1.0 mg/L.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that the organic solution is prepared with tap water, and the rest are completely the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that surface river water is used to prepare an organic solution, and the rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that the organic solution is prepared with tap water, and the rest are completely the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that domestic sewage is used to prepare an organic solution, and the rest are exactly the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that the printing and dyeing wastewater is used to prepare an organic solution, and the rest are completely the same as in Example 1.
  • Example 1 The visible light catalysis-ClO 2 oxidation combined method described in Example 1 to efficiently remove organic pollutants in wastewater, the difference is that seawater is used to prepare an organic solution, and the rest are exactly the same as in Example 1.

Abstract

本发明涉及一种可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，方法包括：(1)将含有有机物的废水调节至恒定pH，添加可见光响应催化剂后置于暗处，充分搅拌吸附直至达到吸附平衡；(2)打开氙灯光源，调节光源与液面间的距离，向体系中加入含氯酸盐，保持反应温度恒定，充分搅拌实现有机污染物的降解。本发明采用可见光催化-ClO 2氧化联用工艺去除废水中有机污染物，光催化过程中产生的活性物质作为氧化剂，与含氯酸根发生电子转移，进而生成ClO 2等含氯活性物质，能够继续氧化降解有机污染物，氧化能力强且持续时间长，避免了光催化过程中光生活性物质寿命较短、传质距离短等问题，有效地提高了污染物降解速率。

Description

一种可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法 技术领域
本发明涉及一种可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，属于有机废水处理的化学及环境技术领域。
背景技术
随着工业发展水平的提高和生产生活条件的改善，有机废水日益成为生态安全和人体健康的潜在威胁。目前，除了吸附、混凝以及膜过滤等传统废水处理技术，光催化、ClO 2氧化等高级氧化技术应用于有机污染物的降解逐渐成为研究热点。光催化氧化技术多以半导体为催化剂，以太阳光为驱动能量，产生氧化性的活性物质(如羟基自由基、超氧自由基等)，将有机污染物转化为无毒或低毒物质，是一类氧化性强、节约能源、高效彻底的污染物去除技术。目前，以可见光催化技术为代表的光催化氧化技术常出现在工业有机废水、抗生素制药废水等废水处理工艺中。但是，在传统的光催化技术应用过程中，电子-空穴复合率高，光子利用率低，催化效率往往不能达到理论值。此外，光催化氧化过程中产生的活性物质寿命极短，在传质过程中容易发生猝灭，污染物的氧化降解也局限在催化剂的固液界面，制约着污染物去除效率的提高和与光催化技术的大规模工业化应用。
目前虽有光催化技术与其他技术联用来处理废水，但仍然无法解决光催化氧化过程中产生的活性物质寿命极短，在传质过程中容易发生猝灭的问题，污染物去除效率仍然得不到有效的提高，如中国专利文献CN105016526A公开的一种难降解有机废水的光催化-吸附絮凝联用技术。
除光催化氧化技术之外，ClO 2氧化技术作为一种常见的出水消毒技术，被广泛应用在医疗废水氧化处理、饮用水杀菌消毒等水处理工艺中，而且ClO 2具有氧化性强、持久性长、效率高以及消毒副产物少等优点。传统的ClO 2发生方式多以亚氯酸盐为原料，采用臭氧氧化、强酸氧化以及强紫外线氧化等方式，将亚氯酸盐转化为ClO 2气体并进行储存，其转化效率相对较低，并且有可能将未反应的亚氯酸根离子带入出水中。同时，由于很多国家和组织对水体中亚氯酸根离子的浓度提出了限制标准，ClO 2氧化技术产生的亚氯酸盐、氯酸盐等无机消毒副产物，成为了威胁人体健康的潜在风险。因此，ClO 2氧化技术在提高污染物氧化降解效率和降低消毒副产物超标风险之间进退两难。
针对现有光催化技术存在着光子利用率较低、活性物质寿命较短等缺点，而ClO 2氧化技术工艺复杂、操作繁琐，能耗大且无机消毒副产物难以消除等缺点，亟需提出一种绿色、高效、节能、环保的有机废水处理的新技术。
发明内容
针对现有光催化技术以及ClO 2氧化技术存在的缺陷，本发明提出了一种可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法。
发明概述：
本发明有机污染物的氧化降解在含有双壁冷却循环水夹层的石英反应器中进行，以可见光响应的催化剂为催化剂，含氯酸盐为ClO 2前驱体，一定光功率密度的氙灯为光源，构建可见光催化-ClO 2氧化联用体系，对含有有机物的废水进行催化氧化降解处理，实现对废水中有机污染物的高效去除。
发明详述：
本发明是通过如下技术方案实现的，
一种可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，包括步骤如下：
(1)将含有有机物的废水调节至恒定pH，添加可见光响应催化剂后置于暗处，充分搅拌吸附直至达到吸附平衡；
(2)打开氙灯光源，调节光源与步骤(1)处理后废水的液面间的距离，向体系中加入含氯酸盐，保持反应温度恒定，充分搅拌实现有机污染物的降解。
根据本发明优选的，步骤(1)中，所述的pH为3-11，采用酸性调节剂或碱性调节剂进行调节pH。
进一步优选的，步骤(1)中，所述的pH为5-9。
进一步优选的，酸性调节剂为盐酸、醋酸或硝酸，碱性调节剂为NaOH或氨水。
根据本发明优选的，步骤(1)中，所述的可见光响应催化剂为Ag/TiO 2、BiVO 4、WO 3、Cu 2O中的一种。
进一步优选的，所述的可见光响应催化剂为BiVO 4。
根据本发明优选的，步骤(1)中，可见光响应催化剂的添加量为10-50mg/L。
根据本发明优选的，步骤(1)中，废水中有机物为诺氟沙星、磺胺嘧啶、双酚A、吡虫啉中的一种或两种以上混合。
根据本发明优选的，步骤(1)中，废水水体为自来水、地表河水、生活污水、印染废水、医疗废水、养殖废水或海水。
根据本发明优选的，步骤(2)中，所述的光源光功率密度为100-300mW/cm 2，与液面间的距离为10-50cm。
根据本发明优选的，步骤(2)中，所述的含氯酸盐为次氯酸盐、亚氯酸盐、氯酸盐或高氯酸盐中的一种。
根据本发明优选的，步骤(2)中，含氯酸盐的添加量使使其浓度达到0.1-1.0mmol/L。
根据本发明优选的，步骤(2)中，所述的搅拌吸附时间为30-60min。
根据本发明优选的，步骤(2)中，所述的反应温度为25-45℃。
本发明的处理工艺不受无机物质、有机物质的影响，在水体中存在无机物质、有机物质的情况下，本发明仍具有较高的处理效率，本发明的处理工艺更稳定。
与现有技术相比，本发明的有益效果为：
1、本发明采用可见光催化-ClO 2氧化联用工艺去除废水中有机污染物，光催化过程中产生的活性物质作为氧化剂，与含氯酸根发生电子转移，进而生成ClO 2等含氯活性物质，能够继续氧化降解有机污染物，氧化能力强且持续时间长，避免了光催化过程中光生活性物质寿命较短、传质距离短等问题，有效地提高了污染物降解速率。此外，ClO 2对含有苯酚、苯胺等结构的化合物具有特异性攻击的趋势，对光催化不能够完全降解的污染物进一步降解，有利于提高矿化率和降低生物毒性。
2、本发明的处理工艺，利用光催化过程中产生的活性物质作为氧化剂，氧化含氯酸根生成ClO 2等含氯活性物质，避免了传统的ClO 2产生方式中强氧化剂、强酸或强光的使用，降低了原料成本和生产风险，有利于实际水处理工艺的安全有序进行。
3、本发明的处理工艺，通过在光催化系统中以固体含氯酸盐药剂投加的方式产生ClO 2，操作安全简便且剂量可控，可以与光催化技术同时同地发生，大大降低了传统ClO 2生产方式中的生产及贮存设备成本和异地运输成本，同时降低了整个生产过程中潜在的风险，增强了反应的安全性和可控性。
4、本发明的处理工艺，含氯酸盐的使用剂量水平远低于目前工业生产中ClO 2氧化技术中的各种含氯物质的剂量水平，满足水体中含氯酸根浓度的限制标准。此外，理论上，ClO 2在完成污染物氧化后，部分转化为含氯酸根，继续参与到新的ClO 2转化过程中，提高了ClO 2的利用效率，延长了可见光催化-ClO 2氧化联用系统中的催化寿命。
5、本发明的处理工艺采用的光催化剂具有可见光响应能力，相比于紫外光光催化剂，该类光催化剂能够更加高效地利用太阳光，为太阳光的驱动下的光催化技术进行有机污染物的降解提供可能，降低能源消耗。
6、本发明的处理工艺不受无机物质、有机物质的影响，在水体中存在无机物质、有机物质的情况下，仍具有较高的处理效率，处理工艺更稳定。
附图说明
图1为本发明所使用双壁夹层反应器示意图；
图中，1、光源，2、密封盖，3、出气口，4、进液口，5、收集口，6、循环冷却水进口，7、进气口，8循环冷却水出口，9、废水，10、催化剂。
图2为本发明实施例1、2、3、4所述不同种类可见光响应光催化剂组成的可见光催化-ClO 2氧化联用工艺处理诺氟沙星抗生素有机废水的效果对比图；图中，a为可见光催化剂为钒酸铋，b为可见光催化剂为Cu 2O，c为可见光催化剂为WO 3，d为可见光催化剂为Ag/TiO 2；
图3为本发明实施例5、6、7所述不同浓度次氯酸钠前驱体组成的可见光催化-ClO 2氧化联用工艺对诺氟沙星抗生素有机废水的处理效果图；
图4为本发明实施例8所述的水体中的pH对可见光催化-ClO 2氧化联用工艺的处理诺氟沙星抗生素有机废水的效果对比图；
图5为本发明实施例9、10、11、12、13所述的水体中的无机物质、有机物质对可见光催化-ClO 2氧化联用工艺处理诺氟沙星抗生素有机废水的效果对比图；
图6本发明实施例14、15、16、17、18、19所述的可见光催化-ClO 2氧化联用工艺在实际、水体中处理诺氟沙星抗生素有机废水的效果对比图。
具体实施方式
下面通过具体实施例并结合附图对本发明做进一步说明，但本发明的保护范围不限于下述实施例。
如无特殊说明，实施例中使用的原料均为常规市购产品。
实施例中使用的双壁夹层反应器，包括反应器本体，本体包括内壁和外壁，内壁围成反应空腔，内壁与外壁之间为夹层，在内壁上进气口和出气口，进气口连接进气管，进气管延伸至反应空腔底部，在内壁上还设置有进液口和收集口，进液口和收集口分别穿过外壁，在外壁上设置有循环冷却液进口和循环冷却液出口，循环冷却液进口和循环冷却液出口与夹层连通，在内壁的开口端设置有密封盖。
实施例1、
一种可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，步骤如下：
(1)将含有有机物的废水调节pH＝7，添加30mg的可见光催化剂钒酸铋催化剂并置于暗处，充分搅拌吸附60min直至达到吸附平衡；
(2)打开氙灯光源，调节光源与液面间相距30cm，向体系中加入ClO 2前驱体次氯酸钠使其浓度达到1.0mmol/L，保持反应温度恒定，充分搅拌实现有机污染物的降解。
实施例2、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：可见光催化剂为Cu 2O，其余均与实施例1完全相同。
实施例3、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：可见光催化剂为WO 3，其余均与实施例1完全相同。
实施例4、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：可见光催化剂为Ag/TiO 2，其余均与实施例1完全相同。
实施例5、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：ClO 2前驱体为亚氯酸钠，其余均与实施例1完全相同。
实施例6、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：ClO 2前驱体为氯酸钠，其余均与实施例1完全相同。
实施例7、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：ClO 2前驱体为高氯酸钠，其余均与实施例1完全相同。
实施例8、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：在投加钒酸铋催化剂之前，将废水的pH分别调节至3、5、7、9、11，其余均与实施例1完全相同。
实施例9、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：在加入ClO 2前驱体的同时，加入浓度为10.0mmol/L Cl -溶液，其余均与实施例1完全相同。
实施例10、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：在加入ClO 2前驱体的同时，加入浓度为1.0mmol/L SO 4 2-溶液，其余均与实施例1完全相同。
实施例11、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：在加入ClO 2前驱体的同时，加入浓度为10.0mmol/L HCO 3 -溶液，其余均与实施例1完全相同。
实施例12、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：在加入ClO 2前驱体的同时，加入浓度为1.0mmol/L ClO 3 -溶液，其余均与实施例1完全相同。
实施例13、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：在加入ClO 2前驱体的同时，加入浓度为1.0mg/L黄腐酸溶液，其余均与实施例1完全相同。
应用实验例：
采用诺氟沙星模拟废水进行氧化降解实验，氧化降解实验在双壁夹层反应器中进行，诺氟沙星模拟废水中诺氟沙星的初始浓度为10mg/L，初始体积为100mL，向双壁夹层反应器的夹层中通入恒温冷却循环水，使反应器温度维持在25℃左右。应用实施例的处理方法对诺氟沙星模拟废水进行降解。同时，设立不加次氯酸盐的光催化对照组。在诺氟沙星的氧化降解过程中，在固定时间取样，取样时间为2h，即0min，5min，10min，30min，60min时取样1mL，经0.22μm滤膜过滤后使用高效液相色谱测定诺氟沙星溶液浓度的变化。
实验例1：
不同种类可见光响应光催化剂组成的可见光催化-ClO 2氧化联用工艺对诺氟沙星抗生素有机废水的处理效果见图2所示。
实验例2：
不同浓度次氯酸钠前驱体组成的可见光催化-ClO 2氧化联用工艺对诺氟沙星抗生素有机废水的处理效果见图3所示。
实验例3：
水体pH对可见光催化-ClO 2氧化联用工艺的处理诺氟沙星抗生素有机废水效果见图4。
实验例4：
本发明还进行无机物质、有机物质对可见光催化-ClO 2氧化联用工艺的处理效果的影响的单因素实验，并对该工艺在实际水体中的降解能力和抗干扰能力进行评估。在达到吸附平衡后的有机物溶液中加入一定浓度的干扰物质，包括实际水体中的无机物质和有机物质，并在同一反应器中加入一定浓度的含氯酸盐，通过夹套冷却水控制反应温度恒定，充分搅拌进行污染物的降解；所述的无机物质为Cl -，Br -，ClO 3 -，NO 3 -，SO 4 2-，CO 3 2-或HCO 3 -中的一种或几种，浓度为0.01-1.00mmol/L；所述的有机物质为黄腐酸、棕腐酸或黑腐酸，浓度为0.1-1.0mg/L。
在水体中存在无机物质、有机物质的情况下，可见光催化-ClO 2氧化联用工艺的处理诺氟沙星抗生素有机废水效果见图5。
实施例14、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：使用自来水配制有机物溶液，其余均与实施例1完全相同。
实施例15、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：使用地表河水配制有机物溶液，其余均与实施例1完全相同。
实施例16、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：使用自来水配制有机物溶液，其余均与实施例1完全相同。
实施例17、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：使用生活污水配制有机物溶液，其余均与实施例1完全相同。
实施例18、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：使用印染废水配制有机物溶液，其余均与实施例1完全相同。
实施例19、
如实施例1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，所不同的是：使用海水配制有机物溶液，其余均与实施例1完全相同。

Claims (10)

  1. 一种可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，包括步骤如下：
    (1)将含有有机物的废水调节至恒定pH，添加可见光响应催化剂后置于暗处，充分搅拌吸附直至达到吸附平衡；
    (2)打开氙灯光源，调节光源与步骤(1)处理后废水的液面间的距离，向体系中加入含氯酸盐，保持反应温度恒定，充分搅拌实现有机污染物的降解。
  2. 根据权利要求1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，其特征在于，步骤(1)中，所述的pH为3-11，采用酸性调节剂或碱性调节剂进行调节pH，优选的，所述的pH为5-9。
  3. 根据权利要求1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，其特征在于，酸性调节剂为盐酸、醋酸或硝酸，碱性调节剂为NaOH或氨水。
  4. 根据权利要求1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，其特征在于，步骤(1)中，所述的可见光响应催化剂为BiVO 4、Cu 2O、WO 3、Ag/TiO 2中的一种；优选的，所述的可见光响应催化剂为BiVO 4。
  5. 根据权利要求1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，其特征在于，步骤(1)中，可见光响应催化剂的添加量为10-50mg/L。
  6. 根据权利要求1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，其特征在于，步骤(1)中，废水中有机物为诺氟沙星、磺胺嘧啶、双酚A、吡虫啉中的一种或两中以上混合；废水水体为自来水、地表河水、生活污水、印染废水、医疗废水、养殖废水或海水。
  7. 根据权利要求1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，其特征在于，步骤(2)中，所述的光源光功率密度为100-300mW/cm 2，与液面间的距离为10-50cm。
  8. 根据权利要求1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，其特征在于，步骤(2)中，所述的含氯酸盐为次氯酸盐、亚氯酸盐、氯酸盐或高氯酸盐中的一种。
  9. 根据权利要求1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，其特征在于，步骤(2)中，含氯酸盐的添加量使使其浓度达到0.1-1.0mmol/L。
  10. 根据权利要求1所述的可见光催化-ClO 2氧化联用高效去除废水中有机污染物的方法，其特征在于，步骤(2)中，所述的搅拌吸附时间为30-60min，所述的反应温度为25-45℃。
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