CN110902956A - Coking wastewater treatment method - Google Patents

Coking wastewater treatment method Download PDF

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Publication number
CN110902956A
CN110902956A CN201911239169.1A CN201911239169A CN110902956A CN 110902956 A CN110902956 A CN 110902956A CN 201911239169 A CN201911239169 A CN 201911239169A CN 110902956 A CN110902956 A CN 110902956A
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wastewater
filler
coking
biochemical reaction
suspended
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CN201911239169.1A
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钟华文
李霞
刘洋
林培喜
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Guangdong University of Petrochemical Technology
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Guangdong University of Petrochemical Technology
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • C02F2101/345Phenols
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/08Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic processes

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biological Treatment Of Waste Water (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

A process for treating the coking sewage includes such steps as introducing the coking sewage into Fe-C-H reactor2O2Carrying out micro-electrolysis and Fenton reagent oxidation pretreatment, wherein nascent hydrogen generated by Fe-C micro-electrolysis and organic components in the wastewater have redox effect, and simultaneously, the generated Fe2+With addition of H2O2A Fenton reagent is formed to further oxidize various pollutants in the wastewater, so that the aim of pretreatment of the coking wastewater is fulfilled; then, the pretreated wastewater enters a suspended filler biochemical reaction tank for aerobic/anoxic biochemical reaction, the suspended filler biochemical reaction tank adopts a plastic filler in a wheel shape, the filler is suspended in the tank, and microorganisms are fixedly grown on the filler; and finally, the wastewater enters a biological ceramsite fixed bed filter for advanced treatment, so that the wastewater can reach better water quality. The invention has good treatment effect and simple flow andthe system occupies small area.

Description

Coking wastewater treatment method
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method for treating coking wastewater.
Background
Coking wastewater is wastewater generated in the processes of coal coking, gas purification, chemical product recovery and chemical product refining. The pollutants contained in the coking wastewater comprise phenols, polycyclic aromatic hydrocarbons, heterocyclic compounds containing nitrogen, oxygen and sulfur and the like, and are typical industrial wastewater containing refractory organic compounds. Coking wastewater is harmful, and polycyclic aromatic hydrocarbon in the wastewater is not only difficult to degrade, but also is a strong carcinogen, so that the environment is seriously polluted and human health is directly threatened.
At present, the domestic coking enterprises generally adopt a method of combining a biological denitrification process and an advanced treatment technology for treating coking wastewater. The biological denitrification process comprises A-O process and A2an-O process, an SBR process, an oxidation ditch process and the like, wherein the processes mainly aim at the denitrification treatment of urban sewage with easily degradable organic matters; for some industrial wastewater, especially for organic wastewater which is difficult to biodegrade, such as coking wastewater, the organic wastewater directly enters a biological denitrification process, and organic carbon is difficult to directly utilize, so that the biological denitrification effect is influenced. The technology of the invention aims at that the coking wastewater which is difficult to biodegrade is firstly effectively pretreated before entering the biological denitrification, and then the biological denitrification is carried out, and the selected biological denitrification process also abandons the processes of long flow. Therefore, the technology of the invention not only has effective denitrification effect, but also has compact flow of the whole treatment system, small occupied area and construction cost saving.
Disclosure of Invention
The invention aims to overcome the defects of insufficient treatment depth, excessive ammonia nitrogen and large occupied area of a treatment system in the conventional coking wastewater treatment technology.
The invention is realized by the following technical scheme:
a coking wastewater treatment method comprises the following steps:
step one, Fe-C-H2O2Pretreatment: the coking wastewater from the regulating reservoir of the coking plant enters an iron-carbon micro-electrolysis cell for reaction, and H is added into the effluent2O2Micro-electrolysis of Fe-C with H2O2Combined into a Fenton reagent, and utilizes ferrous ions and H in the system2O2The generated hydroxyl free radicals (. OH) are mixed to oxidize pollutants in the wastewater to obtain primary wastewater;
step two, treating the suspended filler in a biochemical reaction tank: the primary wastewater enters a suspended filler biochemical reaction tank to carry out aerobic/anoxic biochemical reaction to obtain secondary wastewater;
step three, deep treatment of a fixed bed biological filter: and finally, the secondary wastewater enters a fixed bed biological filter taking biological ceramsite as a filter material to carry out aerobic biological and filtration advanced treatment.
According to the invention, iron-carbon balls are loaded into a micro-electrolyzer, coking wastewater with the pH value adjusted to 3-4 enters an iron-carbon micro-electrolysis cell, nascent hydrogen generated by electrolysis and organic components in water are subjected to redox action, organic functional groups are changed, and wastewater containing ferrous ions is obtained; the reaction time of Fe-C micro-electrolysis is 30-40 min, and the pH value is increased to about 5; followed by addition of H to the water2O2The Fenton reagent is formed by ferrous ions in the system to continue the oxidation reaction, H2O2The amount of H added is 30% for each 1g of COD cut2O21.0-1.5 mL, the oxidation reaction time of the Fenton reagent is 40-60 min, and the pH value is increased to more than 6 after the reaction is finished.
In the invention, the biochemical reaction tank of the suspended filler adopts the wheel-shaped filler, the diameter of the filler is 2.0-3.0 cm, the thickness of the filler is 0.5-1.0 cm, the filler is suspended in the tank, microorganisms are fixedly grown on the filler, and the filling rate is 30-50%. Regulation of Fe-C-H2O2The pH value of the pretreated effluent is 6.5-8.0, the effluent enters a suspended filler biochemical reaction tank for treatment, the concentration of Dissolved Oxygen (DO) is controlled to be 1.5-2.5 mg/L, and the Hydraulic Retention Time (HRT) is controlled to be 12-18 h.
In the invention, the fixed bed biological filter adopts a biological ceramsite filter material, the filter material is spherical, the diameter of the filter material is 10-20 mm, and the stacking thickness of the filter material layer is 1.8-2.5 m. And (3) treating the effluent from the suspended filler biochemical reaction tank, and treating the effluent in a fixed bed filter, wherein the concentration of Dissolved Oxygen (DO) is controlled to be 2.0-2.5 mg/L, and the Hydraulic Retention Time (HRT) is controlled to be 5-8 h.
The invention has great advantages in the aspects of the treatment depth of the coking wastewater, the occupied area of a treatment system and the like, and has good application prospect.
Detailed Description
Example (b):
Fe-C-H2O2pretreatment: adding coking wastewater after oil adjustment in coking plant into iron-carbon micro-electrolysis cell for 35min while adjusting pH to 3.5, and adding 30% of H for each 1g of COD2O21.3 mL, adding a defined amount of H to the effluent2O2Forming a Fenton reagent, oxidizing pollutants in water to obtain pretreated wastewater; wherein, the iron-carbon spheres are filled in a micro-electrolyzer, the iron-carbon spheres in the iron-carbon micro-electrolyzer are directly adopted as the iron-carbon spheres in the market, and the Fenton reagent reaction time is 50 min.
Treating a suspended filler biochemical reaction tank: the pH value of the pretreated wastewater is adjusted to 7.0, and then the pretreated wastewater enters a suspended filler biochemical reaction tank for aerobic/anoxic biochemical reaction, wherein the biochemical reaction tank adopts a wheel-shaped filler, the diameter of the filler is 2.5cm, the thickness of the filler is 0.8cm, the filler is suspended in the tank, and the filling rate is 40%. After the wastewater enters a suspended filler biochemical reaction tank, controlling the DO concentration to be 1.8-2.0 mg/L and the HRT to be 16 h.
Advanced treatment of a fixed bed biological filter: the effluent is treated by a biochemical reaction tank with suspended fillers and finally enters a fixed bed biological filter taking biological ceramsite as a filter material to carry out aerobic biological and filtration advanced treatment, so that various residual pollutants in the wastewater are further reduced. The fixed bed biological filter adopts a biological ceramsite filter material, a spherical filter material with the diameter of 15 mm is selected; the stacking thickness of the filter material layer is 2.0 m. And controlling the DO concentration of the fixed bed biological filter to be 2.0-2.5 mg/L and the HRT to be 6.0 h.
Application example:
the technique of the invention takes the coking wastewater of a certain coking plant in Guangdong province for experimental study, the coking wastewater is treated according to the method of the embodiment, and the treatment results of the water sample for spot check are shown in Table 1.
TABLE 1 sample treatment results of spot check
Figure 466255DEST_PATH_IMAGE001
After coking wastewater subjected to experimental research is treated by the patented technology, the discharge standard of pollutants in the coking chemical industry can be met (GB 16171-2012).
Compared with the prior art for treating the coking wastewater, the technical and economic indexes of the technology of the invention are shown in the table 2.
TABLE 2 comparison of the technical and economic indicators of the two treatment techniques
Figure 245992DEST_PATH_IMAGE002
The invention has certain advantages in the aspect of treating the coking wastewater by combining the comparison of the two technologies in the aspects of treatment effect, system complexity, occupied area and the like.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (4)

1. A coking wastewater treatment method is characterized by comprising the following steps:
step one, Fe-C-H2O2Pretreatment: the coking wastewater from the regulating reservoir of the coking plant enters an iron-carbon micro-electrolysis cell for reaction, and H is added into the effluent2O2Micro-electrolysis of Fe-C with H2O2Combined into a Fenton reagent, and utilizes ferrous ions and H in the system2O2Oxidizing pollutants in the wastewater by using the hydroxyl radicals generated by mixing to obtain primary wastewater;
step two, treating the suspended filler in a biochemical reaction tank: the primary wastewater enters a suspended filler biochemical reaction tank to carry out aerobic/anoxic biochemical reaction to obtain secondary wastewater;
step three, deep treatment of a fixed bed biological filter: and finally, the secondary wastewater enters a fixed bed biological filter taking biological ceramsite as a filter material to carry out aerobic biological and filtration advanced treatment.
2. The coking wastewater treatment method of claim 1, characterized in that in the step one, iron-carbon balls are loaded into a micro-electrolyzer, and the waste to be treated is treatedAdjusting the pH value of water to 3-4 by using 2M sulfuric acid, and then reacting in a Fe-C micro-electrolyzer for 30-40 min; then, 30% H was added2O2The amount of H added is 30% for each 1g of COD cut2O21.0-1.5 mL, and the oxidation reaction time of the Fenton reagent is 40-60 min.
3. The method for treating the coking wastewater according to the claim 1, wherein in the second step, the biochemical reaction tank adopts wheel-shaped filler with the diameter of 2.0-3.0 cm and the thickness of 0.5-1.0 cm, the filler is suspended in the tank, and the filling rate is 30-50%; adjusting the pH value of the primary wastewater to 6.5-8.0, and then treating the primary wastewater in a suspended filler biochemical reaction tank, wherein the concentration of dissolved oxygen is controlled to be 1.5-2.5 mg/L, and the hydraulic retention time is controlled to be 12-18 h.
4. The coking wastewater treatment method according to claim 1, characterized in that in step three, a biological ceramsite filter material is adopted in the fixed bed biological filter, the filter material is spherical, the diameter of the filter material is 10-20 mm, and the stacking thickness of the filter material layer is 1.8-2.5 m; the dissolved oxygen concentration of the fixed bed biological filter is controlled to be 2.0-2.5 mg/L, and the hydraulic retention time is controlled to be 5-8 h.
CN201911239169.1A 2019-12-06 2019-12-06 Coking wastewater treatment method Pending CN110902956A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113772881A (en) * 2021-08-28 2021-12-10 北京百灵天地环保科技股份有限公司 Oxidation treatment method of phenol-cyanogen wastewater

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CN103553282A (en) * 2013-11-18 2014-02-05 攀枝花钢城集团瑞天安全环保有限公司 Deep treatment process of coking wastewater
CN103936225A (en) * 2014-03-24 2014-07-23 同济大学 Coke wastewater advanced treatment method utilizing catalytic internal electrolysis technology and coupled two-stage bio-filter
CN104016547A (en) * 2014-06-19 2014-09-03 中冶建筑研究总院有限公司 Advanced treatment and zero emission process for coking wastewater
CN104016548A (en) * 2014-06-19 2014-09-03 中冶建筑研究总院有限公司 Biochemical treatment process of coking wastewater
CN105417894A (en) * 2016-01-05 2016-03-23 宜兴市永创环保科技有限公司 Treatment method for high-concentration wastewater difficult to degrade
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CN107344798A (en) * 2016-05-06 2017-11-14 上海宝钢化工有限公司 A kind of apparatus for treating carbonized waste water and its processing method
CN107487966A (en) * 2017-10-09 2017-12-19 山东龙安泰环保科技有限公司 A kind of coking distilled ammonia wastewater deep treatment method
CN107555701A (en) * 2016-06-30 2018-01-09 鞍钢股份有限公司 Low-cost coking wastewater treatment method
CN108892309A (en) * 2018-06-25 2018-11-27 河钢股份有限公司 A kind of high-efficient treatment method being suitble to coking wastewater difficult to degrade
CN109231715A (en) * 2018-11-09 2019-01-18 鞍钢股份有限公司 Method for treating chemical ammonia distillation wastewater

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553282A (en) * 2013-11-18 2014-02-05 攀枝花钢城集团瑞天安全环保有限公司 Deep treatment process of coking wastewater
CN103936225A (en) * 2014-03-24 2014-07-23 同济大学 Coke wastewater advanced treatment method utilizing catalytic internal electrolysis technology and coupled two-stage bio-filter
CN104016547A (en) * 2014-06-19 2014-09-03 中冶建筑研究总院有限公司 Advanced treatment and zero emission process for coking wastewater
CN104016548A (en) * 2014-06-19 2014-09-03 中冶建筑研究总院有限公司 Biochemical treatment process of coking wastewater
CN106277555A (en) * 2015-05-27 2017-01-04 鞍钢股份有限公司 High-efficiency low-cost treatment method and system for coking wastewater
CN105417894A (en) * 2016-01-05 2016-03-23 宜兴市永创环保科技有限公司 Treatment method for high-concentration wastewater difficult to degrade
CN107344798A (en) * 2016-05-06 2017-11-14 上海宝钢化工有限公司 A kind of apparatus for treating carbonized waste water and its processing method
CN107555701A (en) * 2016-06-30 2018-01-09 鞍钢股份有限公司 Low-cost coking wastewater treatment method
CN107487966A (en) * 2017-10-09 2017-12-19 山东龙安泰环保科技有限公司 A kind of coking distilled ammonia wastewater deep treatment method
CN108892309A (en) * 2018-06-25 2018-11-27 河钢股份有限公司 A kind of high-efficient treatment method being suitble to coking wastewater difficult to degrade
CN109231715A (en) * 2018-11-09 2019-01-18 鞍钢股份有限公司 Method for treating chemical ammonia distillation wastewater

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113772881A (en) * 2021-08-28 2021-12-10 北京百灵天地环保科技股份有限公司 Oxidation treatment method of phenol-cyanogen wastewater

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Application publication date: 20200324