WO2014196477A1 - Procédé et dispositif de traitement d'une eau contenant des substances organiques difficilement biodégradables - Google Patents

Procédé et dispositif de traitement d'une eau contenant des substances organiques difficilement biodégradables Download PDF

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WO2014196477A1
WO2014196477A1 PCT/JP2014/064479 JP2014064479W WO2014196477A1 WO 2014196477 A1 WO2014196477 A1 WO 2014196477A1 JP 2014064479 W JP2014064479 W JP 2014064479W WO 2014196477 A1 WO2014196477 A1 WO 2014196477A1
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sludge
water
added
alkali
biodegradable organic
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PCT/JP2014/064479
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English (en)
Japanese (ja)
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友時 安池
英之 小森
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栗田工業株式会社
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Priority to CN201480029877.1A priority Critical patent/CN105246840B/zh
Priority to KR1020157033584A priority patent/KR20160014606A/ko
Publication of WO2014196477A1 publication Critical patent/WO2014196477A1/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
    • 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
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/305—Endocrine disruptive agents
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Definitions

  • the present invention relates to a treatment method and a treatment apparatus for water containing hardly biodegradable organic matter, which efficiently treats water containing hardly biodegradable organic matter by Fenton oxidation treatment.
  • Fenton oxidation treatment which is a method for treating difficult biodegradable organic substances
  • OH radicals which are powerful oxidants, are generated by the reaction of iron chemicals and hydrogen peroxide, and these radicals oxidize and decompose organic substances.
  • the Fenton oxidation treatment has two steps of an oxidation step and a subsequent aggregation step because it is necessary to remove the added iron agent.
  • Patent Document 1 in order to solve the first problem, Fenton oxidation treatment is performed by reacting at a pH of 1.0 to 2.0 for 3 to 8 hours with a small amount of iron agent added. Biological treatment without forming sludge by forming complex salt of organic matter. However, according to the study by the present inventors, the COD decomposition rate is very slow at a pH of 1.0 to 2.0, and sludge is finally produced after biological treatment.
  • Patent Documents 2 and 3 in order to solve the second problem, an alkali mixed sludge obtained by adding an alkali agent to a part of the coagulated separation sludge is added to the waste water as a coagulant in the coagulation treatment of the waste water.
  • the metal salt is returned to the agglomeration reaction tank so that the amount of metal is, for example, 2 to 50 times the amount of the metal salt.
  • the required amount of the flocculant is reduced, the amount of generated sludge is reduced, and the sludge dewaterability is improved.
  • this method is applied to Fenton oxidation treatment to reduce the amount of iron agent added, the sludge dewaterability is not improved.
  • Patent Document 4 a divalent iron chemical is added to oxidation-treated water to produce a mixed sludge of divalent and trivalent iron (green last and iron ferrite), and the separated sludge is returned.
  • this method it is necessary to generate sludge having a ratio of divalent iron to total iron of 0.4 to 0.8, and the amount of divalent iron chemical added is large and the chemical cost is excessive.
  • the present invention solves the above-mentioned conventional problems, and in the Fenton oxidation treatment of water containing hardly biodegradable organic matter, reduces the amount of iron agent used and the amount of sludge generated, improves the dewaterability of sludge, and is good It is an object of the present invention to provide a treatment method and a treatment apparatus for water containing hardly biodegradable organic matter that can obtain treated water of high quality.
  • the present inventors have conducted hydrogen peroxide and hydrogen peroxide addition amount of 0.1% in the oxidation step in the Fenton oxidation treatment of water containing a hardly biodegradable organic substance. After adding 005 to 0.2 molar amount of iron drug and reacting under pH 2 to 4 conditions for 1 hour or longer to obtain oxidized water, a part of the sludge obtained by solid-liquid separation is used. The present inventors have found a method of adding an alkali mixed sludge to which an alkaline agent has been added to the oxidation-treated water.
  • the present invention has been achieved on the basis of such knowledge, and the gist thereof is as follows.
  • the solid content of the alkali mixed sludge added to the insolubilization step is 20 to 500 times the amount of the insolubilized product generated by the reaction of the oxidized water and the alkali agent.
  • the insolubilization step adjusts the oxidation-treated water to pH 3.5 to 4.5 and the pre-neutralization treatment water to pH 5 to 12. And a neutralizing step.
  • an apparatus for Fenton oxidation treatment of water containing a non-biodegradable organic substance the water containing the non-biodegradable organic substance is added to hydrogen peroxide and 0.005-0.2 mol times the hydrogen peroxide addition amount.
  • Fenton oxidation means that reacts for 1 hour or more under the condition of pH 2 to 4 by adding an amount of iron agent, and insolubilization that generates an insolubilized product by adding an alkaline agent to the oxidized water obtained by the oxidation means
  • an alkali mixing means for adding and mixing an alkaline agent to a part of the separated sludge obtained by the solid-liquid separation means, and a solid-liquid separation means for solid-liquid separation of the generated insolubilized material.
  • An apparatus for adding water containing hardly biodegradable organic matter comprising: means for adding alkali mixed sludge as at least part of an alkali agent added to oxidation-treated water by the insolubilizing means.
  • the solid content of the alkali mixed sludge added to the insolubilization means is 20 to 500 times the amount of the insolubilized product produced by the reaction of the oxidized water and the alkali agent.
  • the insolubilization means adjusts the pre-neutralization tank for adjusting the oxidation-treated water to pH 3.5 to 4.5 and the pre-neutralization-treated water to pH 5 to 12.
  • an alkaline agent is added to a part of the solid-liquid separation sludge after controlling the pH, the amount of iron agent added and the reaction time in Fenton oxidation. Add the added alkaline sludge to the oxidized water. Thereby, while obtaining a favorable treated water quality, the amount of iron chemical
  • medical agents can be reduced, the production amount of iron sludge can be reduced, and the concentrated iron sludge with high dewaterability can be obtained.
  • alkali mixed sludge it becomes possible to decompose and remove hydrogen peroxide remaining in the oxidation treatment.
  • the water containing hardly biodegradable organic substances to be treated in the present invention is dimethyl sulfoxide (DMSO), ethylenediaminetetraacetic acid (EDTA), phenols, organochlorine compounds, environmental hormones, surfactants, biometabolites, etc.
  • DMSO dimethyl sulfoxide
  • EDTA ethylenediaminetetraacetic acid
  • phenols phenols
  • organochlorine compounds phenols
  • environmental hormones e.g., proliferatives, etc.
  • a water containing sex organics usually the organic content is about 50 ⁇ 1,000 mg / L at COD Cr concentration.
  • the pH of these hardly biodegradable organic substance-containing water is about 1 to 9.
  • a hardly biodegradable organic substance-containing water when such a hardly biodegradable organic substance-containing water is used as a raw water, a predetermined amount of hydrogen peroxide and an iron agent are added, and an acid such as sulfuric acid is added if necessary.
  • the pH is adjusted and the hardly biodegradable organic substance is oxidatively decomposed by a Fenton oxidation reaction under a predetermined pH condition, and the oxidized water is neutralized to generate an insolubilized product, and the insolubilized product is separated into solid and liquid.
  • a part of the separated sludge obtained by solid-liquid separation is added to the oxidation-treated water in the neutralization treatment as an alkali mixed sludge obtained by adding and mixing an alkali agent to this sludge.
  • the Fenton oxidation treatment includes an oxidation process and an aggregation process.
  • the present inventors determined that it is not preferable to set a large amount of iron addition to shorten the reaction time.
  • the amount of iron agent added is 0.005 to 0.2 mole times the amount of hydrogen peroxide added, which is less than conventional, thereby suppressing hydrogen peroxide self-decomposition.
  • the amount of hydrogen peroxide added can also be reduced as compared with the prior art.
  • the reaction time is 1 hour or more, preferably 1 to 3 hours.
  • the amount of iron agent added is particularly preferably 0.02 to 0.1 mole times the amount of hydrogen peroxide added.
  • Iron agents added to raw water include ferrous sulfate (Fe (II)) compounds such as ferrous sulfate and ferrous chloride, ferric sulfate such as ferric sulfate and ferric chloride (Fe (III) )
  • Fe (II) ferrous sulfate
  • ferric sulfate such as ferric sulfate and ferric chloride
  • the iron agent to be added is either Fe (II) compound or Fe (III) compound. Is also possible.
  • the OH radical used for oxidative decomposition is generated by reaction with divalent iron, it is preferably a divalent iron compound.
  • the amount of hydrogen peroxide added is preferably 0.5 to 3 mol times, particularly 0.7 to 2 mol times with respect to COD Cr of raw water.
  • the pH in the oxidation process is 2-4. If the pH is less than 2, the amount of iron dissolved is large, but the reactivity with hydrogen peroxide is poor, and if it exceeds 4, iron precipitates.
  • iron needs to be in an ionic state at the entrance of the solid-liquid separation step after the oxidation step, and therefore the optimum pH is determined based on the reaction time, iron concentration, water temperature, and raw water composition.
  • ⁇ Alkaline agent is added to the oxidized water obtained in the above oxidation step to insolubilize it, and the insolubilized material is separated into solid and liquid.
  • an alkali agent is added to a part of the separated sludge obtained by the solid-liquid separation to obtain an alkali mixed sludge, and the alkali mixed sludge is added to the oxidation-treated water for insolubilization treatment.
  • the process of returning part of the separated sludge is a known process as described in Patent Documents 2 and 3, but the sludge return method is used for Fenton-oxidized water having a low iron concentration. It was found that even when applied, the dewaterability of sludge was not improved.
  • the amount of sludge returned in Patent Documents 2 and 3 is such that the amount of metal in the returned sludge is 2 to 50 times, preferably 15 to 40 times the amount of metal added as a flocculant.
  • the sludge was not densified or the solid-liquid separation was unstable.
  • the solid content of sludge added to the oxidized water is determined based on the amount of insolubilized product produced by the reaction of the oxidized water and the alkaline agent (only the alkaline agent is added to the oxidized water to be insolubilized. 20 to 500 times, preferably 50 to 200 times the amount of the insolubilized product produced when the slag is formed, the aggregate floc size is coarse and sludge having excellent dewatering properties is obtained. It has been found that liquid separation can be stabilized.
  • the amount of returned sludge is less than 20 times the amount, the amount of returned sludge is small, so precipitation of iron ions on the sludge surface does not proceed, and the sludge tends not to be densified. Since the sludge concentration is high, the sludge is not enlarged and is in a dispersed state, and is liable to leak from the solid-liquid separation settling tank.
  • the insolubilization step in the present invention is preferably performed by a two-stage treatment of preliminary neutralization and neutralization. That is, it is preferable to carry out in a first-stage neutralization tank and a second-stage neutralization tank.
  • the oxidation-treated water contains an acid component such as an organic acid
  • iron may not be sufficiently precipitated and may be partially dissolved.
  • the alkali mixed sludge may be added to the preliminary neutralization tank or may be added to the neutralization tank.
  • the following neutralization treatment forms can be employed.
  • the return amount of the sludge is 20% of the amount of insolubilized matter generated by the reaction between the oxidized water and the alkaline agent as the solid content of the returned sludge added to the oxidized water. It is preferable that the amount be up to 500 times.
  • the ratio of the solid content of the returned sludge to the amount of insolubilized product generated by the reaction between the oxidized water and the alkaline agent is referred to as “sludge return ratio”.
  • sludge return ratio the ratio of the solid content of the returned sludge to the amount of insolubilized product generated by the reaction between the oxidized water and the alkaline agent.
  • the ratio of the solid content of the sludge added to the pre-neutralization tank and the neutralization tank there are no particular restrictions.
  • the return sludge is preferably added at least to the preliminary neutralization tank.
  • 20-80% of the returned sludge is pre-neutralized tank.
  • the concentration of the separated sludge is usually a high concentration of 10 to 30%.
  • Caustic soda sodium hydroxide
  • slaked lime etc.
  • Caustic soda sodium hydroxide
  • slaked lime etc.
  • the treatment in the pre-neutralization tank is preferably carried out at a pH of 3.5 to 4.5, particularly 3.8 to 4.2.
  • the residence time of the preliminary neutralization tank is preferably about 5 to 20 minutes.
  • hydrogen peroxide remaining in the oxidation process is also decomposed.
  • Hydrogen peroxide is decomposed by hydroxide and iron (Reference 1: Paper-Paper Technology Association Vol. 49, No. 4, the following reaction formula 3). Accordingly, in the present invention, it is considered that hydrogen peroxide is decomposed by the high concentration alkaline agent adsorbed on the iron and sludge surface contained in the sludge by setting the sludge return ratio as high as 20 to 500 times. It is done.
  • a reducing agent such as sodium bisulfite can be supplementarily added to the preliminary neutralization tank or the neutralization tank.
  • the treatment in the neutralization tank after the preliminary neutralization is preferably performed at pH 5-12.
  • iron may not be sufficiently precipitated and may partially dissolve. In this case, crystallization is promoted by adding separated sludge or alkali mixed sludge to the neutralization tank. Can do. Even when metals other than iron are contained in the wastewater, it is possible to select the optimum pH according to the metal components in the wastewater and add the separated sludge or the alkali mixed sludge.
  • the treatment in the neutralization tank is preferably carried out at a pH of 6.0 to 8.5.
  • the residence time of this neutralization tank is preferably about 5 to 20 minutes.
  • the above neutralized water is then subjected to agglomeration treatment by adding a flocculant to form agglomerated floc.
  • a polymer flocculant As the flocculant, a polymer flocculant is used. Depending on the properties of the raw water, anionic polymers, cationic polymers, amphoteric polymers, and nonionic polymers can be used alone or in combination of two or more, but anionic polymers are preferred. The addition amount of these flocculants is usually 1 to 5 mg / L.
  • the coagulated treated water is then solid-liquid separated to separate the treated water and sludge.
  • Any solid-liquid separation means may be used as long as it can perform solid-liquid separation, and a precipitation tank, a membrane separation device, a filter, and the like can be applied.
  • Part of the separated sludge is sent to a preliminary neutralization tank, a neutralization tank, or an alkali mixing tank, and the remainder is discharged out of the system as excess sludge.
  • the sludge is mixed with an alkali agent to form an alkali mixed sludge.
  • the alkali mixed sludge may be continuously overflowed from the alkali mixing tank.
  • the amount of the alkali agent added to the alkali mixing tank is controlled based on the pH fluctuation of the preliminary neutralizing tank or the neutralizing tank.
  • 1 to 4 are system diagrams showing an example of an embodiment of a treatment apparatus for water containing hardly biodegradable organic substances according to the present invention.
  • 1 is a Fenton oxidation reaction tank
  • 2 is a pre-neutralization tank
  • 3 is a neutralization tank
  • 4 is a coagulation tank
  • 5 is a precipitation tank
  • 6, 6A and 6B are alkali mixing tanks.
  • hydrogen agent, an iron agent such as ferrous sulfate (FeSO 4 ), and an acid such as sulfuric acid (H 2 O 2 ) are added to the raw water as necessary in the Fenton oxidation reaction tank 1.
  • Fenton oxidation is carried out for 1 hour or more under the condition of pH 2-4.
  • the oxidized water in the Fenton oxidation reaction tank 1 is then neutralized sequentially in the preliminary neutralization tank 2 and the neutralization tank 3.
  • the neutralized water is subjected to agglomeration treatment by adding a polymer flocculant (polymer) in the agglomeration tank 4, and the agglomerated water is solid-liquid separated in the precipitation tank 5.
  • Part of the separated sludge is fed to one of the preliminary neutralization tank 2, the neutralization tank 3, and the alkali mixing tank 6, 6A, 6B, and the alkali mixed sludge or the separated sludge is supplied to the preliminary neutralization tank 2 and / or neutralization.
  • Fig. 1 shows the sludge return mode of (1) above.
  • a part of the separated sludge is transferred to the pre-neutralization tank 2, the other part is transferred to the alkali mixing tank 6, and the alkali mixing sludge in which an alkali agent such as NaOH is added and mixed in the alkali mixing tank 6 is medium.
  • an alkali agent such as NaOH is added and mixed in the alkali mixing tank 6 is medium.
  • Japanese tank 3 Added to Japanese tank 3.
  • Fig. 2 shows the sludge return mode of (2) above.
  • a part of the separated sludge is transferred to the neutralization tank 3, and the other part is transferred to the alkali mixing tank 6, and the alkali mixed sludge in which an alkali agent such as NaOH is added and mixed in the alkali mixing tank 6 is in reserve.
  • an alkali agent such as NaOH is added and mixed in the alkali mixing tank 6 is in reserve.
  • Japanese tank 1 Added to Japanese tank 1.
  • FIG. 3 shows the sludge return mode of (3) above.
  • a part of the separated sludge is transferred to the alkali mixing tank 6, and the alkali mixed sludge to which the alkali agent is added and mixed in the alkali mixing tank 6 is added to the preneutralization tank 1. Etc. are added.
  • Fig. 4 shows the sludge return mode of (4) above.
  • a part of the separated sludge is transferred to the alkali mixing tank 6A, and the other part is transferred to the alkali mixing tank 6B.
  • the alkali mixed sludge in which an alkali agent such as NaOH is added and mixed in each of the alkali mixing tanks 6A and 6B is added to the preliminary neutralizing tank 2 and the neutralizing tank 3, respectively.
  • the amount of iron chemical added to the Fenton oxidation reaction tank, the pH condition, and the reaction time are controlled, and a part of the separated sludge obtained by solid-liquid separation is used as alkali mixed sludge to treat Fenton oxidation treated water.
  • the required amount of iron chemicals is reduced, and at the same time, the amount of sludge produced is reduced, a concentrated sludge with high dewatering property is obtained, and further, by adding alkali mixed sludge, the remaining peroxidation in the Fenton oxidation treatment Hydrogen can also be decomposed.
  • treatment was performed using simulated raw water prepared as described below as the raw material containing hardly biodegradable organic matter-containing water.
  • ⁇ Preparation of simulated raw water> After biologically treating synthetic wastewater containing 100 mg / L of isopropyl alcohol (IPA), dimethyl sulfoxide (DMSO), and tetramethylammonium hydroxide (TMAH), concentrated water obtained by coagulation treatment and reverse osmosis membrane separation treatment is used. Furthermore, COD Cr 600 mg / L water containing hardly biodegradable organic matter was prepared by evaporating and concentrating.
  • IPA isopropyl alcohol
  • DMSO dimethyl sulfoxide
  • TMAH tetramethylammonium hydroxide
  • the COD Cr of treated water obtained in the following examples, comparative examples and reference examples was measured after decomposing residual hydrogen peroxide with sodium bisulfite. Further, the hydrogen peroxide concentration of the treated water was measured with a hydrogen peroxide test paper “Checkle KS” (measurement lower limit 3 mg / L) manufactured by Kurita Kogyo Co., Ltd.
  • Example 1 Continuous water treatment with a water flow rate of 1 L / hr was performed with the apparatus shown in FIG.
  • the separated sludge from the sedimentation tank 5 was returned and added in the preliminary neutralization tank 2, and NaOH was added so that the pH was 4.2 ⁇ 0.1.
  • the residence time in the preliminary neutralization tank 2 was 0.2 hours.
  • the alkali mixed sludge from the alkali mixing tank 6 was added so that the pH was 8.0 ⁇ 0.1.
  • the residence time of this neutralization tank was 0.4 hours.
  • the return sludge concentration at this time was 12%.
  • the return sludge ratio was 80, and the sludge was returned to the preliminary neutralization tank 2 and the alkali mixing tank 6. That is, since the SS concentration generated from the oxidized water is 190 mg / L in terms of Fe (OH) 3 , the return ratio is 80, and the sludge is returned at a sludge return rate of 127 mL / hr (sludge concentration 12%). In addition, it adjusted so that 70% might be added to the preliminary
  • aggregating tank 4 3 mg / L of an anionic polymer “PA331” manufactured by Kurita Kogyo Co., Ltd., a polymer aggregating agent, was added, and the agitation was performed at 100 rpm and agglomeration was performed for a residence time of 0.1 hour. .
  • PA331 an anionic polymer manufactured by Kurita Kogyo Co., Ltd.
  • Table 1 shows the water content of the dewatered sludge obtained by dewatering the sludge discharged from the settling tank 5.
  • Example 2 The treated water was obtained under the same reaction time, chemical injection conditions, and sludge return conditions as in Example 1 with continuous water flow of 1 L / hr with the apparatus of FIG. Table 1 shows the analysis results of the treated water and the moisture content of the dewatered sludge.
  • Example 3 The treated water was obtained under the same reaction time, chemical injection conditions, and sludge return conditions as in Example 1 with continuous water flow of 1 L / hr with the apparatus of FIG. However, the return sludge was added to the preliminary neutralization tank 2 in its entirety as alkali mixed sludge. Table 1 shows the analysis results of the treated water and the moisture content of the dewatered sludge.
  • Example 4 The treated water was obtained under the same reaction time, chemical injection conditions, and sludge return conditions as in Example 1 with continuous water flow of 1 L / hr with the apparatus of FIG. Table 1 shows the analysis results of the treated water and the moisture content of the dewatered sludge.
  • Comparative Example 2 The test was carried out in the same manner as in Comparative Example 1 except that the ferrous sulfate addition amount in Fenton oxidation was 100 mg / L as Fe, and the reaction time was 2 hours, and the supernatant water obtained by sedimentation separation was compared. The treated water of Example 2 was used. Table 1 shows the analysis results of the treated water and the moisture content of the dewatered sludge.
  • Table 1 shows the following.
  • Comparative Example 1 the amount of iron agent added is 200 mg-Fe / L, which is twice that of Examples 1 to 4, so that hydrogen peroxide self-decomposes in the Fenton oxidation reaction, the treated water COD Cr is high, Sludge has poor dewaterability.
  • Comparative Example 2 since Comparative Example 2 has the same amount of iron chemical addition as Example 1, the treated water COD Cr concentration is equivalent, but since the sludge is not densified, the moisture content of the dewatered sludge is 79%. high.
  • Reference Example 1 performs sludge return for densification as in Example 1, and the treated water COD Cr is slightly higher than Example 1, but the sludge return ratio is as low as 20.
  • the density of the sludge is insufficient, and the moisture content of the dewatered sludge is as high as 68%. Moreover, since the sludge return ratio is low and the reaction between the alkali mixed sludge and hydrogen peroxide is insufficient, hydrogen peroxide remains in the treated water.
  • the moisture content of the dewatered sludge is as low as 51 to 56%, and in particular, in Example 4 where alkali mixed sludge is added to the preliminary neutralization tank and the neutralization tank, respectively, the moisture content is the lowest. High density sludge can be obtained.
  • the Fenton oxidation reaction is carried out with a small amount of iron agent added, the alkali agent is added to the sludge obtained by solid-liquid separation, and the alkali mixed sludge is returned. It can be seen that water quality can be obtained, iron agent addition amount, sludge generation amount, sludge dewaterability can be improved, and residual hydrogen peroxide can be decomposed and removed.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Treatment Of Sludge (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

L'invention concerne un procédé de traitement d'une eau qui contient des substances organiques difficilement biodégradables par oxydation de Fenton, selon lequel l'utilisation d'un agent chimique à base de fer et la production de boue peuvent être l'une et l'autre réduites, la propriété de déshydratation de la boue peut être améliorée et une eau traitée présentant une bonne qualité d'eau peut être obtenue. Le procédé susmentionné comprend : l'ajout, à une eau contenant des substances organiques difficilement biodégradables, de peroxyde d'hydrogène et d'un agent chimique à base de fer, ledit agent chimique à base de fer étant ajouté en une quantité molaire équivalant à 0,005 à 0,2 fois la quantité de peroxyde d'hydrogène, et la réaction libre du mélange résultant pendant 1 heure ou plus à un pH de 2-4 ; l'ajout, à l'eau ainsi oxydée, d'un agent alcalin de façon à former des matières insolubles ; puis une séparation solide-liquide des matières insolubles ainsi formées. Selon ce procédé, un mélange alcali-boue, qui est obtenu en ajoutant un agent alcalin à une partie de la boue séparée obtenue dans l'étape de séparation solide-liquide et en mélangeant, est ajouté au moins en tant que partie de l'agent alcalin à ajouter à l'eau oxydée dans l'étape d'insolubilisation.
PCT/JP2014/064479 2013-06-04 2014-05-30 Procédé et dispositif de traitement d'une eau contenant des substances organiques difficilement biodégradables WO2014196477A1 (fr)

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CN201480029877.1A CN105246840B (zh) 2013-06-04 2014-05-30 含生物难分解性有机物的水的处理方法和处理装置
KR1020157033584A KR20160014606A (ko) 2013-06-04 2014-05-30 생물 난분해성 유기물 함유수의 처리 방법 및 처리 장치

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JP2013117984A JP5720722B2 (ja) 2013-06-04 2013-06-04 難生物分解性有機物含有水の処理方法及び処理装置

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CN105246840A (zh) 2016-01-13
TW201509828A (zh) 2015-03-16
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