CN106746322A - 煤焦油废水的处理方法 - Google Patents

煤焦油废水的处理方法 Download PDF

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CN106746322A
CN106746322A CN201611259339.9A CN201611259339A CN106746322A CN 106746322 A CN106746322 A CN 106746322A CN 201611259339 A CN201611259339 A CN 201611259339A CN 106746322 A CN106746322 A CN 106746322A
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sedimentation basin
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龙炳清
崔伟
陈刚
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Sichuan Normal University
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    • C02F9/00Multistage treatment of water, waste water or sewage
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    • C02F1/34Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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    • C02F1/70Treatment of water, waste water, or sewage by reduction
    • C02F1/705Reduction by metals
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2001/007Processes including a sedimentation step
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2003/001Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
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    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F2003/001Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • C02F2003/003Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
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    • C02F2101/30Organic compounds
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/30Organic compounds
    • C02F2101/40Organic compounds containing sulfur
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    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
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    • C02F2303/24Separation of coarse particles, e.g. by using sieves or screens
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    • C02F3/02Aerobic processes
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used

Abstract

本发明介绍的煤焦油废水的处理方法包括CO2加压并在超声波作用下铁铝锌复合粉还原、厌氧、好氧和生物滤塔处理等工序,处理后的废水可稳定达标排放。

Description

煤焦油废水的处理方法
技术领域
本发明涉及煤焦油加工和储存过程产生的废水的一种处理方法。
背景技术
煤焦油是生产化学品的重要原料之一,其加工和储存过程产生的废水中污染物COD浓度高,成分复杂,毒性大,并含有大量持久性有机污染物(含苯环和(或)杂环等的有机物),处理难度大。该废水若不处理直接排入环境,将对环境造成严重污染。目前煤焦油废水的处理方法主要有焚烧法和生物处理法。焚烧法处理成本高,而且产生大气污染。生物处理法需要先进行高级氧化(如铁碳微电解、金属粉还原、Fenton法等)预处理,然后生物处理。在高级氧化预处理过程中,需要加入硫酸,导致后续生物处理(如厌氧、水解酸化)过程中产生H2S,产生较严重的二次污染;同时由于SO4 2-对微生物的生长有明显的抑制作用,影响生物处理效果,废水难以稳定达标排放。开发二次污染小、处理成本低、能稳定达标排放的煤焦油废水的处理方法具有较大实用价值。
发明内容
针对目前煤焦油废水处理方法的问题,本发明的目的是寻找二次污染小、能稳定达标排放的煤焦油废水的处理方法,其特征在于将经调节池调节后的煤焦油废水送入耐压反应器,将清洁铁铝锌复合粉加入反应器,并通入工业CO2进行反应。铁铝锌复合粉的粒度小于180目,铁铝锌复合粉中每种金属的含量不低于5%(返回使用的铁铝锌复合粉不受此限制),每升废水加入铁铝锌复合粉10g~50g,机械搅拌并在超声波作用下的反应时间为20min~40min,反应温度为25℃~60℃,每立方米废水输入超声波的功率为2kW~8kW, CO2的压力为0.1MPa~1.0MPa。反应后的废水进行液固分离,分离出的铁铝锌复合粉返回反应器。液固分离后的废水用石灰乳或其他碱性物质调节其pH值到6.8~8.5,然后进入沉淀池沉淀1h~3h,不定期从沉淀池中抽出污泥进行过滤,滤饼作危险固体废弃物处置,滤液返回沉淀池。沉淀池的上清废水送厌氧反应器。废水在厌氧反应器中停留24h~120h,厌氧温度为25℃~55℃。厌氧后的废水进入生物好氧池常温处理,好氧处理时间为8h~16h。好氧处理后的废水进入沉淀池沉淀1h~3h,不定期从沉淀池中抽出污泥进行过滤,滤饼作危险固体废弃物处置,滤液返回好氧池。沉淀池的上清废水送多层生物滤塔处理。生物滤塔的填料为活性炭或多孔陶粒,每层厚度为1.0m~2.0m,总厚度为2m~6m。生物滤塔的优势菌种为光合细菌中的红假单胞菌(Rhodopseudomonas)。生物滤塔的水力负荷为30 m3/m2.d~90m3/m2.d。生物滤塔的出水达标排放或回用。
本发明的目的是这样实现的,煤焦油废水进入铁铝锌复合粉还原反应器后,废水中的大分子有机物,特别是持久性有机污染物(含苯环和(或)杂环等的有机物)通过铁铝锌复合粉还原产生的强还原自由基的作用而破坏,为后续生化处理创造有利条件。通入压力CO2的目的是维持铁铝锌复合粉还原合适的pH值(2.0~5.0),输入超声波可以加快反应的传质过程。还原后的废水用石灰乳或其他碱性物质调节其pH值,以满足后续厌氧和好氧过程的要求。经前述处理的废水在厌氧过程中,通过微生物的作用,大分子有机物进一步变成小分子有机物,为后续生物氧化创造更有利条件。通过生物氧化处理,剩余的大多数有机物被去除,同时去除氮等污染物。废水最后进入活性炭或多孔陶粒生物滤塔,在微生物,特别是红假单胞菌的作用下,进一步去除有机物和氮等污染物,保证处理后的废水稳定达标排放。
相对于现有方法(铁碳微电解、金属粉还原、Fenton法等),本发明的突出优点是采用CO2代替目前广泛使用的硫酸作酸化剂,不引入SO4 2-离子,基本消除了产生H2S的物质基础(煤焦油废水含有少量S),从而大大减轻了H2S的污染,同时也避免了SO4 2-对厌氧和好氧过程中微生物的抑制作用,大大提高生物处理的效率;煤焦油加工厂都建有燃烧装置,燃料燃烧产生的CO2废气可充分利用,不仅可降低处理成本,而且可以减少碳排放;处理后的废水能稳定达标排放,具有明显的经济效益和环境效益。
具体实施方法
实施例1:日处理1立方米煤焦油废水(挥发酚2400mg/L、COD15500mg/L、CN-25.5mg/L、NH3-N57mg/L),经铁铝锌复合粉还原(20min、40℃、CO2压力0.6MPa、每升废水加入铁铝锌复合粉40g、每立方米废水输入的超声波功率4kW)、厌氧(pH8.5、72h、25℃~35℃)、好氧(12h)和生物滤塔(多孔陶粒填料层总厚度4m、水力负荷35m3/m2.d)处理后出水的污染物浓度分别为CODCr 53mg/L、NH3-N 7.0mg/L、挥发酚0.3mg/L、CN-0.10mg/L。
实施例2:日处理3立方米煤焦油废水(挥发酚920mg/L,COD8700mg/L,CN-17mg/L、NH3-N48mg/L),经铁铝锌复合粉还原(40min、25℃、CO2压力0.1MPa、每升废水加入铁铝锌复合粉10g、每立方米废水输入的超声波功率2kW)、厌氧(pH6.8、24h、35℃~55℃)、好氧(8h)和生物滤塔(活性炭填料层总厚度2m、水力负荷90m3/m2.d)处理后出水的污染物浓度分别为CODCr 45mg/L、NH3-N 6.3mg/L、挥发酚0.2mg/L、CN-0.06mg/L。

Claims (1)

1. 一种煤焦油废水的处理方法,其特征在于将经调节池调节后的煤焦油废水送入耐压反应器,将清洁铁铝锌复合粉加入反应器,并通入工业CO2进行反应,铁铝锌复合粉的粒度小于180目,铁铝锌复合粉中每种金属的含量不低于5%,每升废水加入铁铝锌复合粉10g~50g,机械搅拌并在超声波作用下的反应时间为20min~40min,反应温度为25℃~60℃,每立方米废水输入超声波的功率为2kW~8kW, CO2的压力为0.1MPa~1.0MPa,反应后的废水进行液固分离,分离出的铁铝锌复合粉返回反应器,液固分离后的废水用石灰乳或其他碱性物质调节其pH值到6.8~8.5,然后进入沉淀池沉淀1h~3h,不定期从沉淀池中抽出污泥进行过滤,滤饼作危险固体废弃物处置,滤液返回沉淀池,沉淀池的上清废水送厌氧反应器,废水在厌氧反应器中停留24h~120h,厌氧温度为25℃~55℃,厌氧后的废水进入生物好氧池常温处理,好氧处理时间为8h~16h,好氧处理后的废水进入沉淀池沉淀1h~3h,不定期从沉淀池中抽出污泥进行过滤,滤饼作危险固体废弃物处置,滤液返回好氧池,沉淀池的上清废水送多层生物滤塔处理,生物滤塔的填料为活性炭或多孔陶粒,填料总厚度为2m~6m,生物滤塔的优势菌种为光合细菌中的红假单胞菌,生物滤塔的水力负荷为30 m3/m2.d~90m3/m2.d,生物滤塔的出水达标排放或回用。
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