CN112794577A - Remove SO42-And Cr (VI) - Google Patents

Remove SO42-And Cr (VI) Download PDF

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Publication number
CN112794577A
CN112794577A CN202011634138.9A CN202011634138A CN112794577A CN 112794577 A CN112794577 A CN 112794577A CN 202011634138 A CN202011634138 A CN 202011634138A CN 112794577 A CN112794577 A CN 112794577A
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China
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srb
activated sludge
alpha
concentration
supernatant
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CN202011634138.9A
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Chinese (zh)
Inventor
周天旭
运正菲
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Tianyuan Kangyu Tianjin Environmental Protection Technology Co ltd
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Tianyuan Kangyu Tianjin Environmental Protection Technology Co ltd
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Priority to CN202011634138.9A priority Critical patent/CN112794577A/en
Publication of CN112794577A publication Critical patent/CN112794577A/en
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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
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • 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
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1263—Sequencing batch reactors [SBR]
    • 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

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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)
  • Activated Sludge Processes (AREA)

Abstract

The invention relates to SO removal4 2‑And Cr (VI), in particular to a method for utilizing SRB activated sludge-alpha-Fe2O3Coupling process for removing SO from industrial wastewater4 2‑And Cr (VI). The invention has the beneficial effects that: SO that the SO in the effluent of the invention4 2‑Cr (VI) andthe concentration of S (-II) reaches the national emission standard. Furthermore, since Cu2The adsorption of O can also recover the sulfur generated in the water. Meanwhile, a large amount of chemical reagents are not needed to be added, and only carbon sources are needed to be added to maintain the normal growth and metabolism process of the SRB activated sludge, so that the investment cost of the chemical reagents is reduced; the process is carried out at normal temperature and normal pressure, so that the energy consumption required by heating and pressurizing equipment is saved; meanwhile, the process belongs to a natural biological process, and secondary pollution cannot be generated. Therefore, the process is an environment-friendly wastewater treatment technology.

Description

Remove SO42-And Cr (VI)
Technical Field
The invention relates to SO removal4 2-And Cr (VI), in particular to a methodUtilizing SRB activated sludge-alpha-Fe2O3Coupling process for removing SO from industrial wastewater4 2-And Cr (VI).
Background
A large amount of waste water is generated in the electroplating industry and the mining industry of China every year, and the waste water contains organic pollutants and SO4 2-And Cr (VI), etc. After a large amount of organic pollutants are discharged into a natural receiving water body, a large amount of dissolved oxygen in the water can be consumed, at the moment, the organic pollutants can be converted into an anaerobic putrefaction state to generate H2S, methane and other gases cause a great amount of death of animals and plants in the water, and the water body becomes black and muddy and generates foul smell. SO (SO)4 2-When the water-soluble sulfate is discharged into the environment, water acidification can be caused, the growth of aquatic animals and plants is influenced, and meanwhile, insoluble sulfate precipitates can be formed in soil around the water, so that soil hardening is caused. And Cr (VI) is more than 100 times as toxic as Cr (III) due to its high mutagenicity, carcinogenicity and teratogenicity, and the strong oxidizing property of Cr (VI) can destroy the cells of the organism.
The traditional treatment process of organic pollutants in wastewater mainly comprises advanced oxidation, coagulating sedimentation and biochemical processes, wherein the advanced oxidation process and the coagulating sedimentation process have the problems of high medicament cost, secondary pollution, high energy consumption and the like, and in addition, the high SO content is caused4 2-The inhibition effect on microorganisms in the general activated sludge causes the reduction of the removal rate of organic pollutants. On the other hand, conventional Cr (VI) and SO4 2-The removal process comprises coagulating sedimentation, ion exchange, membrane separation, adsorption and the like, but the removal process has the problems of high cost, high energy consumption, secondary pollution and the like. Therefore, it is necessary to develop a method for removing organic pollutants and SO in wastewater synchronously with high efficiency, low energy consumption, low cost and no secondary pollution4 2-And cr (vi).
Organic pollutants and SO in traditional wastewater4 2-And the Cr (VI) removing process comprises advanced oxidation, coagulating sedimentation and common biochemical processes, and has the following defects:
(1) the dosage of the medicament is large, the treatment cost is high, and the energy consumption is high;
(2) chemical excess sludge can be generated, and secondary pollution is caused;
(3) the common biochemical process has low tolerance to toxic pollutants.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a method for utilizing SRB activated sludge-alpha-Fe2O3Coupling process for removing SO from industrial wastewater4 2-And Cr (VI).
The invention is realized by the following technical scheme:
SRB activated sludge-alpha-Fe utilization method2O3Coupling process for removing SO from industrial wastewater4 2-And cr (vi), comprising the steps of:
(1) culturing SRB activated sludge in a 10L sequencing batch reactor at room temperature in Postgate's B culture medium with inoculation of SRB activated sludge with mass fraction of 13 wt% and SO4 2-Initial concentration is 1000mg/L, and SO in the culture medium is detected4 2-When the concentration of SO is4 2-When the concentration is less than 150mg/L, the supernatant is discharged after the reactor is stood still, and simultaneously, the culture is continued by adding an equal volume of fresh culture medium, and then, each time SO is added4 2-When the concentration is lower than 150mg/L, the operation is carried out in the way, and the obtained sludge suspension is precipitated and the supernatant is discharged to obtain concentrated SRB activated sludge;
(2) will contain SO4 2-And Cr (VI) with concentrated SRB activated sludge and adding alpha-Fe thereto2O3Removal of SO4 2-And Cr (VI), simultaneously adding sodium lactate to provide enough COD to maintain the biological activity of the SRB activated sludge, wherein the concentration of the SRB activated sludge is 7g/L, and the added alpha-Fe2O3The scale is 30nm, the dosage is 500mg/L, wherein, SO4 2-Cr (VI), COD and alpha-Fe2O3Initial concentrations (scale 30nm) were 2000, 60, 4000 and 500mg/L, respectively, operating under the following conditions: the initial pH value is 2.0-9.0, the stirring speed is 50-100 r/min, and the reaction temperature isThe temperature is 15-35 ℃, the total reaction time is 5-15 days, and after the reaction is finished, the reactor is kept stand for solid-liquid separation;
(3) mixing the supernatant treated in the step (2) with H2O2Mixing the solution and adding catalyst nano-Cu2O (scale 50nm) to remove the remaining S (-II) in the supernatant, operating conditions were: h2O2The mol ratio of the catalyst to S (-II) is 1: 2-2: 1, and the catalyst Cu2The adding amount of O is 0.5-2 g/L, and the reaction time is 1-6 h.
According to the technical scheme, preferably, in the step (2), the initial pH of the wastewater is 6.0, the stirring speed is 75 revolutions per minute, the reaction temperature is 25 ℃, and the total reaction time is 10 days.
According to the technical scheme, preferably, the molar ratio of H2O2 to S (-II) in the step (3) is 1: 1, the dosage of the catalyst Cu2O is 1g/L, and the reaction time is 3 hours.
The invention has the beneficial effects that: the invention relates to a method for removing SO from mine wastewater4 2-And Cr (VI), and removing SO from mine wastewater by adopting SRB activated sludge-zero-valent iron coupling process4 2-And cr (vi). Compared with the traditional method, the SO of the invention4 2-And Cr (VI) removal rate can reach more than 90% and 99%, respectively, and H passes through2O2And Cu2The catalytic oxidation reaction between O can quickly and completely remove SO in water4 2-S (-II) generated in the biological reduction process enables SO in the effluent of the invention4 2-The concentrations of Cr (VI) and S (-II) all reach the national emission standard. Furthermore, since Cu2The adsorption of O can also recover the sulfur generated in the water. Meanwhile, a large amount of chemical reagents are not needed to be added, and only carbon sources are needed to be added to maintain the normal growth and metabolism process of the SRB activated sludge, so that the investment cost of the chemical reagents is reduced; the process is carried out at normal temperature and normal pressure, so that the energy consumption required by heating and pressurizing equipment is saved; meanwhile, the process belongs to a natural biological process, and secondary pollution cannot be generated. Therefore, the process is an environment-friendly wastewater treatment technology.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.
The invention relates to a method for preparing activated sludge-alpha-Fe by using SRB2O3Coupling process for removing SO from industrial wastewater4 2-And cr (vi), comprising the steps of:
(1) SRB activated sludge was cultured in a batch mode of operation in a 10L sequencing batch reactor using a self-prepared modified Postgate's B medium at room temperature. Daily detection of SO in culture Medium4 2-When the concentration of SO is4 2-When the concentration is lower than 150mg/L, the supernatant is discharged after the reactor is stood, and meanwhile, the culture is continued by adding the same volume of fresh culture medium. Thereafter whenever SO4 2-When the concentration is lower than 150mg/L, the operation is carried out in the way, and the obtained sludge suspension is precipitated and the supernatant is discharged to obtain the concentrated SRB activated sludge.
(2) Will contain SO4 2-And Cr (VI) with concentrated SRB activated sludge and adding alpha-Fe thereto2O3Removal of SO4 2-And cr (vi), while sodium lactate is added to provide sufficient COD to maintain the biological activity of the SRB activated sludge. Wherein, SO4 2-Cr (VI), COD and alpha-Fe2O3The initial concentrations (scale 30nm) were 2000, 60, 4000 and 500mg/L, respectively. The operating conditions were: the initial pH is 2.0-9.0, the stirring speed is 50-100 r/min, the reaction temperature is 15-35 ℃, and the total reaction time is 5-15 days. And (3) after the reaction is finished, standing the reactor for solid-liquid separation.
(3) Mixing the supernatant treated in the step (2) with H2O2Mixing the solution and adding catalyst nano-Cu2O (size 50nm) for the purpose of rapidly removing the remaining S (-II) in the supernatant. The operating conditions were: h2O2The mol ratio of the catalyst to S (-II) is 1: 2-2: 1, and the catalyst Cu2The adding amount of O is 0.5-2 g/L, and the reaction time is 1-6 h.
Preferably, 13 wt% of SRB activated sludge in the step (1) is inoculated into the culture medium, SO4 2-The initial concentration was 1000 mg/L.
Preferably, in the step (2), the initial pH of the wastewater is 6.0, the stirring speed is 75 revolutions per minute, the reaction temperature is 25 ℃, the total reaction time is 10 days, the concentration of SRB activated sludge is 7g/L respectively, and the added alpha-Fe2O3The scale is 30nm, and the adding amount is 500 mg/L.
Preferably, H in said step (3)2O2The mol ratio of the catalyst to S (-II) is 1: 1, and the catalyst Cu2The adding amount of O is 1g/L, the reaction time is 3 hours, wherein the catalyst Cu2The O dimension is 50 nm.
The invention has the beneficial effects that: the invention relates to a method for removing SO from mine wastewater4 2-And Cr (VI), and removing SO from mine wastewater by adopting SRB activated sludge-zero-valent iron coupling process4 2-And cr (vi). Compared with the traditional method, the SO of the invention4 2-And Cr (VI) removal rate can reach more than 90% and 99%, respectively, and H passes through2O2And Cu2The catalytic oxidation reaction between O can quickly and completely remove SO in water4 2-S (-II) generated in the biological reduction process enables SO in the effluent of the invention4 2-The concentrations of Cr (VI) and S (-II) all reach the national emission standard. Furthermore, since Cu2The adsorption of O can also recover the sulfur generated in the water. Meanwhile, a large amount of chemical reagents are not needed to be added, and only carbon sources are needed to be added to maintain the normal growth and metabolism process of the SRB activated sludge, so that the investment cost of the chemical reagents is reduced; the process is carried out at normal temperature and normal pressure, so that the energy consumption required by heating and pressurizing equipment is saved; meanwhile, the process belongs to a natural biological process, and secondary pollution cannot be generated. Therefore, the process is an environment-friendly wastewater treatment technology.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (3)

1. SRB activated sludge-alpha-Fe utilization method2O3Coupling process for removing SO from industrial wastewater4 2-And cr (vi), characterized by comprising the steps of:
(1) culturing SRB activated sludge with Postgate's B culture medium comprising KH2PO40.5g/L, NH4Cl 1.0.0 g/L, MgSO 4.7H 2O 0.06.06 g/L, CaSO41.0g/L, FeSO 4.7H 2O 0.01g/L, Na2SO44.5g/L, CaCl 2.H 2O 0.06.06 g/L, sodium lactate 3.5g/L in a 10L sequencing batch reactor at room temperature, inoculating SRB activated sludge with a mass fraction of 13 wt%, and inoculating SRB activated sludge with SO4 2-Initial concentration is 1000mg/L, and SO in the culture medium is detected4 2-When the concentration of SO is4 2-When the concentration is less than 150mg/L, the supernatant is discharged after the reactor is stood still, and simultaneously, the culture is continued by adding an equal volume of fresh culture medium, and then, each time SO is added4 2-When the concentration is lower than 150mg/L, the operation is carried out in the way, and the obtained sludge suspension is precipitated and the supernatant is discharged to obtain concentrated SRB activated sludge;
(2) will contain SO4 2-And Cr (VI) with concentrated SRB activated sludge and adding alpha-Fe thereto2O3Removal of SO4 2-And Cr (VI), simultaneously adding sodium lactate to provide enough COD to maintain the biological activity of the SRB activated sludge, wherein the concentration of the SRB activated sludge is 7g/L, and the added alpha-Fe2O3The scale is 30nm, the dosage is 500mg/L, wherein, SO4 2-Cr (VI), COD and alpha-Fe2O3Initial concentrations (scale 30nm) were 2000, 60, 4000 and 500mg/L, respectively, operating under the following conditions: the initial pH is 2.0-9.0, the stirring speed is 50-100 r/min, the reaction temperature is 15-35 ℃, the total reaction time is 5-15 days, and after the reaction is finished, the reactor is kept stand for solid-liquid separation;
(3) mixing the supernatant treated in the step (2) with H2O2The solution is mixed and addedCatalyst nano-scale Cu2O (scale 50nm) to remove the remaining S (-II) in the supernatant, operating conditions were: h2O2The mol ratio of the catalyst to S (-II) is 1: 2-2: 1, and the catalyst Cu2The adding amount of O is 0.5-2 g/L, and the reaction time is 1-6 h.
2. The SRB-utilizing activated sludge-alpha-Fe as claimed in claim 12O3Coupling process for removing SO from industrial wastewater4 2-And cr (vi), characterized in that: in the step (2), the initial pH value of the wastewater is 6.0, the stirring speed is 75 revolutions per minute, the reaction temperature is 25 ℃, and the total reaction time is 10 days.
3. The SRB-utilizing activated sludge-alpha-Fe as claimed in claim 12O3Coupling process for removing SO from industrial wastewater4 2-And cr (vi), characterized in that: in the step (3), the molar ratio of H2O2 to S (-II) is 1: 1, the dosage of the catalyst Cu2O is 1g/L, and the reaction time is 3 hours.
CN202011634138.9A 2020-12-31 2020-12-31 Remove SO42-And Cr (VI) Pending CN112794577A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115432890A (en) * 2022-09-21 2022-12-06 无锡市道格环保科技有限公司 Treatment device and method for reducing pollutant discharge in chromium-containing metal ion wastewater

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105036447A (en) * 2015-01-07 2015-11-11 天津工业大学 Method of removing sulfate radical and hexavalent chromium from industrial waste water through sulfate reducting bacteria activated sludge-[alpha]-Fe2O3 coupling process
WO2018184391A1 (en) * 2017-04-05 2018-10-11 同济大学 Method for synchronously removing complex heavy metal and organic substance by magnetic separation
CN111099784A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Treatment method of desulfurization wastewater

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105036447A (en) * 2015-01-07 2015-11-11 天津工业大学 Method of removing sulfate radical and hexavalent chromium from industrial waste water through sulfate reducting bacteria activated sludge-[alpha]-Fe2O3 coupling process
WO2018184391A1 (en) * 2017-04-05 2018-10-11 同济大学 Method for synchronously removing complex heavy metal and organic substance by magnetic separation
CN111099784A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Treatment method of desulfurization wastewater

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115432890A (en) * 2022-09-21 2022-12-06 无锡市道格环保科技有限公司 Treatment device and method for reducing pollutant discharge in chromium-containing metal ion wastewater
CN115432890B (en) * 2022-09-21 2024-01-23 无锡市道格环保科技有限公司 Treatment device and method for reducing pollutant emission in chromium-containing metal ion wastewater

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