WO2013137322A1 - Procédé de traitement des eaux usées - Google Patents

Procédé de traitement des eaux usées Download PDF

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Publication number
WO2013137322A1
WO2013137322A1 PCT/JP2013/057018 JP2013057018W WO2013137322A1 WO 2013137322 A1 WO2013137322 A1 WO 2013137322A1 JP 2013057018 W JP2013057018 W JP 2013057018W WO 2013137322 A1 WO2013137322 A1 WO 2013137322A1
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WIPO (PCT)
Prior art keywords
anaerobic
wastewater
treatment method
treatment step
waste water
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PCT/JP2013/057018
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English (en)
Japanese (ja)
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李玉友
中手一郎
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株式会社ダイセル
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Priority to JP2014504962A priority Critical patent/JP6029649B2/ja
Priority to CN201380008250.3A priority patent/CN104105671A/zh
Publication of WO2013137322A1 publication Critical patent/WO2013137322A1/fr

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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
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
    • 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
    • C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the present invention relates to a wastewater treatment method. More specifically, the present invention relates to anaerobic treatment of wastewater containing a high concentration of sulfate.
  • an upflow anaerobic sludge bed that stores sludge (granule), which is agglomerated by anaerobic microorganisms mainly composed of methane bacteria, in the tank and supplies treatment liquid from the bottom of the tank.
  • An upflow anaerobic biological treatment apparatus using UASB: Upflow Anaerobic Sludge Bed
  • an expanded sludge bed EVSB: Expanded Granular Sludge Bed
  • This technology temporarily stores the processing liquid inside the processing tank in the storage tank using the gas pressure of the generated biogas by switching the valve, and after reducing the gas pressure in the processing tank, The processing liquid in the processing tank is agitated by the stored liquid by returning the stored liquid in the storage tank to the processing tank (see Patent Document 1).
  • an object of the present invention is to provide a wastewater treatment method capable of reducing the generation of hydrogen sulfide and treating industrial wastewater containing both high-concentration COD and sulfate.
  • the present invention Including an anaerobic treatment step of treating wastewater using anaerobic organisms under anaerobic conditions, and
  • the waste water in the anaerobic treatment step contains sulfuric acid or sulfate, organic acid and alcohol
  • a wastewater treatment method is provided, wherein the weight ratio of the organic acid to the alcohol is 1/99 to 99/1 (the former / the latter).
  • the total amount of organic acid and alcohol is preferably 0.1 to 10% by weight with respect to the whole waste water in the anaerobic treatment step.
  • the organic acid is preferably a carboxylic acid.
  • the alcohol is preferably methanol or ethanol.
  • the chemical oxygen demand of the waste water in the anaerobic treatment step is 900 to 100,000 mg / L.
  • the ratio between the chemical oxygen demand (mg / L) and the SO 4 2 ⁇ concentration (mg / L) is 0.2 to 10 (the former / the latter). preferable.
  • a gas containing hydrogen sulfide is generated, and in the anaerobic treatment step or after the anaerobic treatment step, the gas containing hydrogen sulfide and the oxygen concentration are 0.5% by volume to 2%. It is preferable to contact an oxygen-containing gas that is 0.0 vol%.
  • the anaerobic organism can form an anaerobic bacterial conglomerate in the anaerobic treatment step.
  • the anaerobic organism can generate methane gas in the anaerobic treatment step.
  • the anaerobic organism is preferably one or more bacteria selected from Halothiobacillus neapolitanus and Thioalkalimicrobium sibiricum.
  • an aerobic treatment process for treating wastewater under aerobic conditions.
  • a sludge solubilization step of solubilizing the sludge generated in the anaerobic treatment step to obtain a sludge solubilized solution it is preferable to further include a sludge solubilization step of solubilizing the sludge generated in the anaerobic treatment step to obtain a sludge solubilized solution.
  • waste water treatment method of the present invention generation of hydrogen sulfide can be reduced, and industrial wastewater containing both high-concentration COD and sulfate can be treated, so both high-concentration COD and sulfate are contained. There is an effect that the treatment efficiency of industrial wastewater is remarkably improved.
  • the wastewater treatment method of the present invention is Including an anaerobic treatment step of treating wastewater using anaerobic organisms under anaerobic conditions, and
  • the waste water in the anaerobic treatment step contains sulfuric acid or sulfate, organic acid and alcohol,
  • the weight ratio of the organic acid to the alcohol may be 1/99 to 99/1 (the former / the latter), and is not particularly limited.
  • the weight ratio of the organic acid to the alcohol is preferably 1/50 to 50/1 (the former / the latter), and 1/25 to 10 / 1 (the former / the latter) is more preferable, and 1/1 to 1/5 (the former / the latter) is more preferable.
  • the total amount of the organic acid and the alcohol is preferably 0.1 to 10% by weight with respect to the entire waste water in the anaerobic treatment step. More preferably, it is 1 to 5% by weight, and further preferably 0.2 to 2% by weight.
  • the organic acid is preferably a carboxylic acid, such as a carboxylic acid having 1 to 5 carbon atoms such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.
  • a carboxylic acid having 1 to 5 carbon atoms such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.
  • Preferred are organic acids having 1 to 3 carbon atoms, and particularly preferred is acetic acid.
  • These carboxylic acids can be used alone or in combination of two or more.
  • the alcohol is preferably an aliphatic alcohol having about 1 to 10 carbon atoms such as methanol, ethanol, 1-propanol, 1-butanol, etc., particularly methanol and ethanol. preferable.
  • the said alcohol can be used individually or in mixture of 2 or more types.
  • the chemical oxygen demand of the wastewater in the anaerobic treatment step is preferably 900 to 100,000 mg / L, more preferably 1000 to 100,000 mg / L, and 1000 to 20000 mg / L. More preferably it is.
  • the chemical oxygen demand may be described as “COD” or “CODcr”.
  • the ratio of chemical oxygen demand (mg / L) and SO 4 2 ⁇ concentration (mg / L) is preferably 0.2 to 10 (the former / the latter), It is more preferably 0.2 to 2000, and further preferably 1 to 10.
  • the ratio between the chemical oxygen demand (mg / L) and the SO 4 2 ⁇ concentration (mg / L) may be described as “COD / SO 4 2 ⁇ ” or “COD / S”.
  • a gas containing hydrogen sulfide is generated in the anaerobic treatment step, and the gas containing hydrogen sulfide and oxygen are added in the anaerobic treatment step or after the anaerobic treatment step. It is preferable to contact an oxygen-containing gas having a concentration of 0.5% to 2.0% by volume. Thereby, even when COD / SO 4 2 ⁇ is lower, there is an effect that the anaerobic treatment of the waste water becomes possible.
  • the oxygen-containing gas is not particularly limited, but it is preferable to use air.
  • the wastewater treatment method of the present invention further includes an aerobic treatment step of treating wastewater under aerobic conditions in addition to the anaerobic treatment step.
  • an aerobic treatment step of treating wastewater under aerobic conditions in addition to the anaerobic treatment step.
  • the wastewater treatment method of the present invention preferably further includes a sludge solubilization step of solubilizing sludge generated in the anaerobic treatment step and the like to obtain a sludge solubilized liquid in addition to the anaerobic treatment step.
  • a sludge solubilization step of solubilizing sludge generated in the anaerobic treatment step and the like to obtain a sludge solubilized liquid in addition to the anaerobic treatment step.
  • At least one of the organic acid and the alcohol in the wastewater in the anaerobic treatment step is added to the wastewater before the anaerobic treatment step. Is preferred.
  • sulfuric acid or sulfate may be added to the waste water.
  • caustic soda sodium hydroxide
  • sodium hydroxide sodium hydroxide
  • phosphoric acid may be added to the waste water.
  • waste water it is preferable to use industrial wastewater, and it is more preferable to use industrial wastewater such as papermaking, chemical industry, fishery processing, and leather.
  • the anaerobic organism may be one that can form an anaerobic bacterial conglomerate (granule) in the anaerobic treatment step. preferable.
  • anaerobic organism it is preferable to use one or more bacteria selected from Halothiobacillus neapolitanus and Thioalkalimicrobium sibiricum. In particular, it is desirable to use a mixture of a plurality of bacteria.
  • other sulfur-oxidizing bacteria such as Sulfurimonas denitrifiacans can coexist, and preferred anaerobic organisms include SRB (sulfate such as Desulfovibrio fructosovorans, Desulfovibrio sp., Thermodesulfovibrio yellowstonii).
  • HAB H 2 -producing acetogenic bacteria
  • Clostridium sporogenes Clostridium sp., Syntrophobacter fumaroxidans
  • MPB methane-
  • Methanobacterium sp. producing bacteria methane producing bacteria
  • the anaerobic treatment step includes a UASB (Upflow Anaerobic Sludge Blanket) type methane fermentation tank (hereinafter sometimes referred to as “UASB tank”) or EGSB (Expanded Granule Sludge Bed; developed granular sludge). It is preferably carried out in a floor-type methane fermentation tank (hereinafter sometimes referred to as “EGSB tank”).
  • UASB tank Upflow Anaerobic Sludge Blanket type methane fermentation tank
  • EGSB Extragranule Sludge Bed
  • EGSB tank floor-type methane fermentation tank
  • UASB tank includes a trade name “Biotan” (manufactured by Sumitomo Heavy Industries, Ltd.), and an example of an EGSB tank includes a trade name “Biobed” (manufactured by Sumitomo Heavy Industries, Ltd.).
  • the following experiment was conducted using an apparatus as shown in FIG. Specifically, the effective volume of the UASB reaction tank 1 was 6 L, and the inside of the tank was maintained at a medium temperature (35 ⁇ 0.5 ° C.) with hot water circulating to the water jacket 4. The generated biogas was measured with a gas meter 3.
  • the artificial wastewater used contains 1000 mg / L acetic acid, 1000 mg / L ethanol and sulfate (R1: 3000 mg / L, R2: 150 mg / L).
  • the substrate tank 6 the substrate is stirred by a stirrer, and the substrate is supplied to the UASB reaction tank 1 through a pump.
  • HRT was shortened in 5 steps from 48h to 4h, and a high concentration (R1) and low concentration (R2) sulfate-containing ethanol drainage control experiment was conducted. went. Specifically, in stage I (0-29 days), HRT is 48 h, in stage II (30-48 days), HRT is 24 h, in stage III (49-75 days), HRT is 12 h, and stage VI ( 76-92 days), the HRT was 6 h, and in stage VI (93-100 days), the HRT was 4 h.
  • SS Suspended Solid, that is, the amount of suspended matter in the wastewater
  • VSS Volatile Suspended Solid, that is, the amount of organic substance in the wastewater
  • TS Total Solid
  • TVSS Total VSS, and so on.
  • the following bacteria were alive in the sludge.
  • Desulfovibrio fructosovorans Desulfovibrio sp., Thermodesulfovibrio yellowstonii (above, SRB), Clostridium sporogenes, Clostridium sp., Syntrophobacter fumaroxidans (above, HAB), Methanobacterium sp., ConiMP, coniiMP Further, the bacteria in the sludge formed agglomerates (granule) and retained the agglomerates even after the test of the wastewater treatment performance evaluation described later.
  • the nutrient salts added to the substrate are shown in Table 2 below.
  • Figure 2 (Horizontal axis: days, vertical axis is pH, OLR (volumetric load) (gCOD / L / d), Gas Production (L / L / d), COD removal rate (COD removal) Rate) (%), Gas Compositon (gas composition) (%)) and Fig.
  • Fig. 4 (Horizontal axis: Organic loading rate (gCOD / L / d), vertical axis represents COD removal rate (%), Sulfate removal rate (sulfide removal rate) %), Gas Production Rate (gas production rate) (L / L / d)) shows the influence of COD volumetric load on the gas production rate, COD removal rate and sulfate removal rate in R1. As the COD volumetric load increased, the gas production rate increased linearly. The COD removal rate tended to decrease slightly as the volumetric load in the reaction vessel was increased. The maximum removal rate of sulfate was 43.5% (volume load average 2.88 g-COD / L / d). At higher loads, the sulfate removal rate was about 35%.
  • FIG. 5 (horizontal axis: HRT is 48, 24, 12 hrs in order from the left, vertical axis is COD conversion rate (%), S conversion rate (%) in order from the top) is the COD during the treatment of wastewater containing high concentration sulfate. The mass balance of S is shown.
  • the conversion rates from inflow COD to methane gas and sulfide (hydrogen sulfide gas and sulfide in water) were about 50.8% and 27.3%, respectively.
  • the conversion rates from sulfate in artificial wastewater to hydrogen sulfide gas and sulfide in water were about 3.9% and 36.4%, respectively, and the dissolution rate in water was large.
  • R1 and R2 inflow COD to methane gas were about 47.5% and 86.9%, respectively.
  • R2 was used for methane production and the COD ratio was significantly higher than R1.
  • the conversion from inflow COD to sulfide was only 1.6%.
  • FIG. 7 is a comparison diagram of sulfate mass balance of R1 and R2 in HRT12h.
  • the sulfate reduction rate of R2 was about 62.9%.
  • the conversion rates to hydrogen sulfide gas and sulfide in water were about 45.9% and 16.9%, respectively, and a sulfate reduction rate higher than R1 was achieved.
  • FIG. 8 (horizontal axis: HRT is 12, 6, 4 hrs in order from left, vertical axis is COD conversion rate (%), S conversion rate (%) in order from left) Balance was calculated.
  • the conversion rates from inflow COD to methane gas and sulfide (hydrogen sulfide gas and sulfide in water) were about 50.8% and 27.3%, respectively.
  • the conversion rates from sulfate in artificial wastewater to hydrogen sulfide gas and sulfide in water were about 3.9% and 36.4%, respectively, and the dissolution rate in water was large.
  • wastewater treatment method of the present invention generation of hydrogen sulfide can be reduced, and industrial wastewater containing both high-concentration COD and sulfate can be treated, so that it is particularly useful as a wastewater treatment method for chemical industrial wastewater. It is.

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  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)

Abstract

Ce procédé de traitement des eaux usées est caractérisé en ce qu'il implique une étape de traitement anaérobie pour le traitement des eaux usées utilisant des organismes anaérobies dans des conditions anaérobies, par les eaux usées dans l'étape de traitement anaérobie contenant un acide organique, de l'alcool et de l'acide sulfurique ou des sulfates et par le rapport en poids de l'acide organique et de l'alcool étant de 1/99 à 99/1 (acide organique/alcool). Au moyen de ce procédé de traitement des eaux usées, la génération de sulfure d'hydrogène peut être réduite et des eaux usées industrielles contenant à la fois de la Demande Chimique en Oxygène à concentration élevée et des sulfates peut être traitée.
PCT/JP2013/057018 2012-03-13 2013-03-13 Procédé de traitement des eaux usées WO2013137322A1 (fr)

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JP2014504962A JP6029649B2 (ja) 2012-03-13 2013-03-13 排水処理方法
CN201380008250.3A CN104105671A (zh) 2012-03-13 2013-03-13 废水处理方法

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JP2012-056504 2012-03-13

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CN112877232B (zh) * 2020-12-21 2023-01-10 武汉水之国环保科技有限公司 一株分离的脱硫弧菌及利用其处理污水的方法

Citations (9)

* Cited by examiner, † Cited by third party
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JPS59162997A (ja) * 1983-03-09 1984-09-13 Kurita Water Ind Ltd 有機性汚水の処理方法
JPH01249198A (ja) * 1988-03-30 1989-10-04 Akua Runesansu Gijutsu Kenkyu Kumiai 嫌気性処理における硫酸還元反応抑制方法および硫酸還元菌阻害性物質
JPH0679295A (ja) * 1992-09-07 1994-03-22 Kurita Water Ind Ltd 有機性排水の処理方法
JPH06315697A (ja) * 1990-01-05 1994-11-15 Shell Internatl Res Maatschappij Bv 排水流の処理方法
JPH11689A (ja) * 1997-06-11 1999-01-06 Kurita Water Ind Ltd 有機性排水の処理装置
JP2005103375A (ja) * 2003-09-29 2005-04-21 Fuji Electric Holdings Co Ltd メタン発酵処理方法及び装置
JP2006055769A (ja) * 2004-08-20 2006-03-02 Ebara Corp 有機性汚濁物質の嫌気性処理方法及び装置
JP2007289914A (ja) * 2006-03-31 2007-11-08 Ebara Corp 嫌気性微生物による有機性廃棄物の処理方法及び装置
JP2009299048A (ja) * 2008-05-13 2009-12-24 Nippon Sharyo Seizo Kaisha Ltd 燃料ガスの脱硫方法及び脱硫装置

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Publication number Priority date Publication date Assignee Title
CN1092152C (zh) * 1992-05-26 2002-10-09 帕克斯 除去水中含硫化合物的方法
EP1186571A1 (fr) * 2000-09-12 2002-03-13 Gastec N.V. Procédé d'oxydation sélective de sulfure d'hydrogène à soufre élémentaire
CN1242934C (zh) * 2003-10-23 2006-02-22 哈尔滨工业大学 硫酸盐废水处理中微生物代谢类型调控方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59162997A (ja) * 1983-03-09 1984-09-13 Kurita Water Ind Ltd 有機性汚水の処理方法
JPH01249198A (ja) * 1988-03-30 1989-10-04 Akua Runesansu Gijutsu Kenkyu Kumiai 嫌気性処理における硫酸還元反応抑制方法および硫酸還元菌阻害性物質
JPH06315697A (ja) * 1990-01-05 1994-11-15 Shell Internatl Res Maatschappij Bv 排水流の処理方法
JPH0679295A (ja) * 1992-09-07 1994-03-22 Kurita Water Ind Ltd 有機性排水の処理方法
JPH11689A (ja) * 1997-06-11 1999-01-06 Kurita Water Ind Ltd 有機性排水の処理装置
JP2005103375A (ja) * 2003-09-29 2005-04-21 Fuji Electric Holdings Co Ltd メタン発酵処理方法及び装置
JP2006055769A (ja) * 2004-08-20 2006-03-02 Ebara Corp 有機性汚濁物質の嫌気性処理方法及び装置
JP2007289914A (ja) * 2006-03-31 2007-11-08 Ebara Corp 嫌気性微生物による有機性廃棄物の処理方法及び装置
JP2009299048A (ja) * 2008-05-13 2009-12-24 Nippon Sharyo Seizo Kaisha Ltd 燃料ガスの脱硫方法及び脱硫装置

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CN104105671A (zh) 2014-10-15
JP6029649B2 (ja) 2016-11-24
JPWO2013137322A1 (ja) 2015-08-03

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