WO2017177656A1 - 一种非溶性氧化还原介体型生物载体及其制备方法 - Google Patents

一种非溶性氧化还原介体型生物载体及其制备方法 Download PDF

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WO2017177656A1
WO2017177656A1 PCT/CN2016/103243 CN2016103243W WO2017177656A1 WO 2017177656 A1 WO2017177656 A1 WO 2017177656A1 CN 2016103243 W CN2016103243 W CN 2016103243W WO 2017177656 A1 WO2017177656 A1 WO 2017177656A1
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redox mediator
graphene oxide
soluble redox
base material
rule
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全燮
毛彦俊
权伍哲
陈硕
于洪涛
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Dalian University of Technology
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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/105—Characterized by the chemical composition
    • C02F3/106—Carbonaceous materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/105—Characterized by the chemical composition
    • C02F3/107—Inorganic materials, e.g. sand, silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties
    • 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention relates to a non-soluble redox mediator type biological carrier and a preparation method thereof, which are applied to biological treatment of environmental pollutants, and is especially suitable for biological treatment of sewage, and belongs to the field of biological treatment and functional materials of pollutants.
  • Refractory organic pollutants are those organic compounds that are hardly degraded by microorganisms or that take a long time to degrade, which are easily accumulated in natural media such as water and soil, and thus cause harm to the environment, such as halogenated compounds and single rings.
  • Their environmental hazards have received widespread attention from all over the world. Controlling refractory organic pollutants is an important issue in the field of water pollution prevention and control. Recent studies have shown that the addition of artificial redox mediators can accelerate the biodegradation rate of refractory organic pollutants and shorten the degradation time. Therefore, redox mediators have potential application value and are receiving more and more attention at home and abroad.
  • the so-called redox mediator transfers electrons through its own redox ability, mainly involved in the extracellular electron transport process of microorganisms, in order to accelerate the electron transfer rate, and the degradation rate of pollutants is significantly improved.
  • Graphene-like substances both with ⁇ -
  • the ⁇ -conjugated system is insoluble, and a part of its edge group can provide an active site for electron-depleting ability, such as a carbonyl group.
  • the low relative content of these active sites limits their use as redox mediators in sewage treatment. Therefore, the surface functional groups of graphenes need to be carbonylated to provide a large number of active sites for electron-depleting ability, thereby improving their performance as redox mediators.
  • directly as a redox mediator there will be problems of loss, so there will also be problems such as increasing the cost of addition and secondary pollution to the environment. Based on this, the object of the present invention is to develop a novel non-soluble redox mediator type biological carrier by supporting a non-soluble redox mediator in a base material of a biological carrier.
  • the present invention aims to provide a novel non-soluble redox mediator type biological carrier and a preparation method thereof.
  • An insoluble redox mediator type biological carrier comprising a non-soluble redox mediator functional material and a base material; the non-soluble redox mediator functional material is graphene oxide and/or Or carbonylation-modified graphene oxide; the base material is extrusion grade polyethylene particles or extrusion grade polypropylene particles.
  • the mass percentage of the non-soluble redox mediator functional material to the base material is not more than 40%.
  • a method for preparing a non-soluble redox mediator type biological carrier the steps are as follows:
  • step 2) The N-GO obtained in step 1) Add water, ultrasonically make it fully dispersed; add oxidant under acidic and ice water bath conditions, stir well for not less than 3h; dry to obtain carbonylation modified graphene oxide, recorded as Q-GO; GO
  • the mass ratio of water, acid and oxidant is 1 : 50-150 : 20-60 : 3-8 ;
  • the non-soluble redox mediator functional material is graphene oxide and / Or carbonylation modified graphene oxide;
  • the acid is H 2 SO 4 or HNO 3 ; the above oxidizing agent is dichromate.
  • the solvent is water, ethanol or dimethylformamide.
  • the invention has the beneficial effects that the preparation method provided by the invention has the advantages of simple process, flexible and controllable method, strong adaptability, large-scale production, and high efficiency of removing refractory organic pollutants.
  • the temperature of the reaction extruder barrel is 135 °C in the barrel, 145 °C in the barrel 2, 155 °C in the barrel, and 130 in the head section. °C.
  • the melt-mixed and extruded material is stripped, cooled, drawn, and pelletized through a die head to obtain a columnar carrier.
  • a moving bed reactor using activated sludge method (no loading) and different types of carriers are used.
  • methyl orange MO
  • the azo dye wastewater is the target, the carrier dosage ratio is 30%, and the hydraulic retention time is 8 hours.
  • the decolorization and COD are compared. Removal effect.
  • the adsorption experiments of methyl orange in water by different carriers were carried out in the absence of microorganisms. The results showed that polyethylene carrier, unmodified graphene oxide carrier and carbonylation modified graphene oxide carrier adsorbed methyl orange. The effect is not obvious, the removal rate is less than 1% .
  • the average removal rate of COD is 63% (activated sludge), 68% (polyethylene carrier), 70% (unmodified graphene oxide carrier), 85% ( Carbonylated modified graphene oxide biocarriers).
  • the carbonylation-modified graphene oxide biocarrier can significantly accelerate the extracellular electron transport of microorganisms on its surface.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Biological Treatment Of Waste Water (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)

Abstract

一种非溶性氧化还原介体型生物载体，包括非溶性氧化还原介体功能材料和基础原料；非溶性氧化还原介体功能材料为氧化石墨烯、羰基化改性氧化石墨烯中的一种或组合；所述的基础原料为为挤出级聚乙烯颗粒或挤出级聚丙烯颗粒。还公开了非溶性氧化还原介体型生物载体的制备方法。

Description

一种非溶性氧化还原介体型生物载体及其制备方法
技术领域
本发明涉及一种非溶性氧化还原介体型生物载体及其制备方法，应用于环境污染物的生物处理，尤其适用于污水的生物处理中，属于污染物的生物处理及功能性材料领域。
背景技术
难降解有机污染物是指几乎不能被微生物降解，或降解所需时间非常长，它们容易在水体、土壤等自然介质中积累，进而对环境造成危害的那些有机化合物，如卤代化合物、单环芳香化合物、酚类、邻苯二甲酸酯、多环芳香烃、氮代化合物、多氯联苯、有机氯杀虫剂、有机磷杀虫剂、氨基甲酸酯杀虫剂和除草剂等，它们对环境的危害已受到世界各国的普遍重视。控制难降解有机污染物，是水污染防治领域中面临的重要课题。最近相关研究表明人工氧化还原介体的加入可加速难降解有机污染物的生物降解速度，缩短降解时间。因此，氧化还原介体具有潜在的应用价值而越来越受到国内外的广泛关注。
所谓氧化还原介体是通过自身的氧化还原能力来传递电子，主要参与到微生物的胞外电子传递过程，以加速电子传递速率，污染物的降解速率得到显著提高。目前，通常用到的氧化还原介体主要是一些醌、吩嗪、酞菁等。这类物质都具有π - π共轭体系，并且具有得失电子能力的活性位点，如羰基（ C=O ）。然而这些物质都具有可溶性，而且在生物水处理过程中，需要定期的投加，这样就存在处理成本高，对环境造成二次污染等问题。石墨烯类物质，既具有π - π共轭体系，又具有非溶性，而且其边缘的部分基团可以提供得失电子能力的活性位点，类如羰基。然而这些活性位点的相对含量低制约了其作为氧化还原介体在生污水处理中的应用。 因此，需要对石墨烯类物质表面官能团进行羰基化改性，以提供大量的得失电子能力的活性位点，进而改善其作为氧化还原介体的性能。然而直接将其作为氧化还原介体，又会存在流失的问题，因而同样会存在增加投加成本和对环境造成二次污染等问题。基于此，本发明的目的是将非溶性氧化还原介体负载于生物载体的基础原料中，开发出一种新型非溶性氧化还原介体型生物载体。
发明内容
针对生物水处理技术中，由于受到电子传递速率的限制，对水体中难降解有机物的处理速率慢的问题， 本发明旨在提供一种新型非溶性的氧化还原介体型生物载体及其制备方法。
本发明的技术方案：
一种非溶性氧化还原介体型生物载体，其包括非溶性氧化还原介体功能材料和基础原料；非溶性氧化还原介体功能材料为氧化石墨烯和 / 或羰基化改性氧化石墨烯；所述的基础原料为挤出级聚乙烯颗粒或挤出级聚丙烯颗粒。
所述的非溶性氧化还原介体功能材料与基础原料的质量百分比不超过 40% 。
一种非溶性氧化还原介体型生物载体的制备方法，步骤如下：
(1) 氧化石墨烯的羰基化改性方法
1) 用氨水调节氧化石墨烯分散液的 pH 至 8-12 ， 60-100 ℃ 条件下 水热反应 3-9 小时，冷却，在不大于 60 ℃条件下烘干，所得固体记为 N-GO ；
2) 将步骤 1) 所得 N-GO 加入水中，超声使其充分分散；在酸性及冰水浴条件下加入氧化剂，充分搅拌，时间不少于 3h ；烘干即得羰基化改性氧化石墨烯，记为 Q-GO ；其中， N-GO 、水、酸与氧化剂的质量比为 1 ： 50-150 ： 20-60 ： 3-8 ；
(2) 非溶性氧化还原介体型生物载体的制备方法
1) 将非溶性氧化还原介体功能材料在溶剂中超声使其充分分散，再添加基础原料，浸泡 1-4 小时，每半小时搅拌一次，使其与基础原料充分接触； 60-80 ℃下烘干所得固体混合物待用；所述的非溶性氧化还原介体功能材料为氧化石墨烯和 / 或羰基化改性氧化石墨烯；
2) 利用螺杆挤出机对上述固体混合物进行熔融挤出，螺杆挤出机各段的加工温度为 120 ℃ ~190 ℃，保证基础原料在熔融状态下与非溶性氧化还原介体功能材料充分混合以及定型。
所述的酸为 H2SO4 或 HNO3 ；上述的氧化剂为重铬酸盐。
所述的溶剂为水、乙醇或二甲基甲酰胺。
本发明的有益效果：本发明所提出的制备方法，工艺简单，方法灵活可控，适应性强，可规模化生产，具有高效的对难降解有机污染物的去除效率。
具体实施方式
以下结合技术方案详细叙述本发明的具体实施方式。
实施例 1
羰基化改性氧化石墨烯功能性材料的制备：氧化石墨烯分散液，用氨水调其 pH 为 10 ， 90 ℃水热 6 小时；冷却； 60 ℃烘干，所得固体记为 N-GO ；将 0.2gN-GO 加入 20mL 水中，超声使其充分分散，在冰水浴条件下，加入 5ml H2SO4 ，及 1.2g 重铬酸钾，充分搅拌，反应 3 小时， 60 ℃烘干。所得羰基化改性氧化石墨烯（ Q-GO ）。
利用 X 射线衍射对氧化石墨烯在改性前后的基团及相对含量变化做了分析。结果表明：氧化石墨烯表面主要含有羰基（ C=O ），羟基（ -OH ），羧基（ -COOH ）及醚（ -O- ）等。对 C=O 、 C-O 及 C-OH 的峰面积积分得到的相对百分含量。分析结果为： C=O 的相对含量由改性前的 8% 升高到 50% ， C-O 及 C-OH 由改性前的 63% 和 30% ，分别降低到 30% 和 20% 。说明羟基化改性后的氧化石墨烯 C=O 含量增加显著。
实施例 2
非溶性氧化还原介体生物载体的制备及对甲基橙染料废水的处理效果对比实验。将羰基化改性氧化石墨烯功能料在水中超声使其充分分散，聚乙烯颗粒基础原料加入到分散液中，非溶性氧化还原介体功能材料与基础原料的质量比为 1:100 ；浸泡 2h ，每半小时搅拌一次，使水中的功能料能够充分与高密度聚乙烯颗粒接触； 80 ℃烘干，待用。利用螺杆挤出机对物料进行熔融挤出，所使用的反应挤出机螺筒温度为：机筒一区 135 ℃，机筒二区 145 ℃，机筒三区 155 ℃，机头区 130 ℃。熔融混合挤出的物料经过模具头成条、冷却、牵引、切粒得到柱状载体。
分别采用活性污泥法（不投加载体），和投加不同类型载体（分别为聚乙烯载体，未改性氧化石墨烯载体，及羰基化改性氧化石墨烯载体）的移动床反应器，以甲基橙（ MO ）偶氮染料废水为目标物，载体投加比为 30% ，水力停留时间为 8 小时的条件下，对比考察了其脱色及 COD 的去除效果。在无微生物存在下，进行了不同载体对水体中甲基橙的吸附实验，结果表明：聚乙烯载体，未改性氧化石墨烯载体，及羰基化改性氧化石墨烯载体对甲基橙的吸附作用不明显，去除率均不到 1% 。甲基橙的生物降解实验对比结果表明：当进水甲基橙浓度为 786-808 mg/L ，稳定运行阶段，不同反应器的出水甲基橙浓度为 324-337mg/L （活性污泥）， 226-237 mg/L （聚乙烯载体）， 127-133 mg/L （未改性氧化石墨烯载体）， 10-12 mg/L （羰基化改性的氧化石墨烯生物载体）。平均去除率分别为 59% （活性污泥）， 71% （聚乙烯载体）， 84% （未改性氧化石墨烯载体）， 98% （羰基化改性的氧化石墨烯生物载体）。脱色能力羰基化改性的氧化石墨烯生物载体＞未改性氧化石墨烯载体＞聚乙烯载体＞活性污泥。当进水 COD 浓度为 1167-1239mg/L ，其 COD 的平均去除率分别为 63% （活性污泥）， 68% （聚乙烯载体）， 70% （未改性氧化石墨烯载体）， 85% （ 羰基化改性的氧化石墨烯生物载体）。说明，装有羰基化改性的氧化石墨烯生物载体的反应器具有更强的 COD 去除能力。因此，羰基化改性的氧化石墨烯生物载体能够显著加速微生物在其表面的胞外电子传递过程。

Claims (6)

  1. [根据细则26改正26.12.2016]
    1. 一种非溶性氧化还原介体型生物载体，其特征在于，非溶性氧化还原介体型生物载体包括非溶性氧化还原介体功能材料和基础原料；非溶性氧化还原介体功能材料为氧化石墨烯、羰基化改性氧化石墨烯中的一种或组合；所述的基础原料为为挤出级聚乙烯颗粒或挤出级聚丙烯颗粒。
  2. [根据细则26改正26.12.2016]　
    2. 根据权利要求 1 所述的非溶性氧化还原介体型生物载体，其特征在于，所述的非溶性氧化还原介体功能材料和基础原料的质量百分比不超过 40% 。
  3. [根据细则26改正26.12.2016]　
    3. 权利要求 1 或 2 所述的非溶性氧化还原介体型生物载体的制备方法，其特征在于，步骤如下：(1) 氧化石墨烯的羰基化改性方法1) 用氨水调节氧化石墨烯分散液的 pH 至 8-12 ， 60-100 ℃ 条件下 水热反应 3-9 小时，冷却，在不大于 60 ℃条件下烘干，所得固体记为 N-GO ；2) 将步骤 1) 所得 N-GO 加入水中，超声使其充分分散；在酸性及冰水浴条件下加入氧化剂，充分搅拌，时间不少于 3h ；烘干即得羰基化改性氧化石墨烯，记为 Q-GO ；其中， N-GO 、水、酸与氧化剂的质量比为 1 ： 50-150 ： 20-60 ： 3-8 ；(2) 非溶性氧化还原介体型生物载体的制备方法1) 将非溶性氧化还原介体功能材料在溶剂中超声使其充分分散，再添加基础原料，浸泡 1-4 小时，每半小时搅拌一次，使其与基础原料充分接触； 60-80 ℃下烘干所得固体混合物待用；所述的非溶性氧化还原介体功能材料为氧化石墨烯和 / 或羰基化改性氧化石墨烯；2) 利用螺杆挤出机对上述固体混合物进行熔融挤出，螺杆挤出机各段的加工温度为 120 ℃ ~190 ℃，保证基础原料在熔融状态下与非溶性氧化还原介体功能材料充分混合以及定型。
  4. [根据细则26改正26.12.2016]　
    4. 根据权利要求 3 所述的制备方法，其特征在于，所述的酸为 H2SO4 或 HNO3 ；所述的氧化剂为重铬酸盐。
  5. [根据细则26改正26.12.2016]　
    5. 根据权利要求 3 所述的制备方法，其特征在于，所述的溶剂为水、乙醇或二甲基甲酰胺。
  6. [根据细则26改正26.12.2016]　
    6. 根据权利要求 4 所述的制备方法，其特征在于，所述的溶剂为水、乙醇或二甲基甲酰胺。
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