CN106673359A - 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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CN106673359A
CN106673359A CN201611259337.XA CN201611259337A CN106673359A CN 106673359 A CN106673359 A CN 106673359A CN 201611259337 A CN201611259337 A CN 201611259337A CN 106673359 A CN106673359 A CN 106673359A
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waste water
sedimentation tank
coal tar
manganese powder
reactor
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龙炳清
邓其娟
聂付江
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Sichuan Normal University
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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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • 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
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • 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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • 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
    • C02F2101/34—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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/16—Total nitrogen (tkN-N)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/18—PO4-P
    • 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
    • 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
    • C02F3/28—Anaerobic digestion processes
    • 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
    • C02F3/34—Biological 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锰粉还原、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，将清洁锰粉加入反应器，并通入工业CO2进行反应，锰粉的粒度小于180目，每升废水加入锰粉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，分离出的锰粉返回反应器。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，煤焦油废水进入锰粉还原反应器后，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）通过锰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的目的是维持锰粉还原合适的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），经锰粉还原（20min、40℃、CO2压力0.6MPa、每升废水加入锰粉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 78mg/L、NH3-N 8.7mg/L、挥发酚0.4mg/L、CN-0.15mg/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），经锰粉还原（40min、25℃、CO2压力0.1MPa、每升废水加入锰粉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 75mg/L、NH3-N6.9mg/L、挥发酚0.4mg/L、CN-0.13mg/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，将清洁锰粉加入反应器，并通入工业CO2进行反应，锰粉的粒度小于180目，每升废水加入锰粉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，分离出的锰粉返回反应器，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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