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WO2006064084A1 - Procede d’extraction du manganese de l’eau - Google Patents

Procede d’extraction du manganese de l’eau Download PDF

Info

Publication number
WO2006064084A1
WO2006064084A1 PCT/FI2005/000532 FI2005000532W WO2006064084A1 WO 2006064084 A1 WO2006064084 A1 WO 2006064084A1 FI 2005000532 W FI2005000532 W FI 2005000532W WO 2006064084 A1 WO2006064084 A1 WO 2006064084A1
Authority
WO
WIPO (PCT)
Prior art keywords
peracetic acid
coagulant
process according
aqueous liquid
manganese
Prior art date
Application number
PCT/FI2005/000532
Other languages
English (en)
Inventor
Kaj Jansson
Heikki Palonen
Eija Laine
Kati MATULA
Original Assignee
Kemira Oyj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kemira Oyj filed Critical Kemira Oyj
Publication of WO2006064084A1 publication Critical patent/WO2006064084A1/fr

Links

Classifications

    • 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
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C22B47/0018—Treating ocean floor nodules
    • C22B47/0045—Treating ocean floor nodules by wet processes
    • C22B47/0081—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C22B47/0018—Treating ocean floor nodules
    • C22B47/009—Treating ocean floor nodules refining, e.g. separation of metals obtained by the above methods
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F2101/203—Iron or iron compound
    • 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
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • 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
    • C02F2103/06—Contaminated groundwater or leachate
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a process for removing manganese from an aqueous liquid by treating the aqueous liquid with an oxidant and optionally with a coagulant.
  • raw water is often colored, as turbid surface water may contain humus as well as iron and manganese.
  • the raw water used by Finnish pulp and paper mills is surface water. Also a remarkable part of the domestic water in Finland is surface water.
  • the main requirements for water quality concern color or humic substances and iron and manganese concentrations.
  • the adverse effect of soluble manganese in drinking water is related to discoloration.
  • the growth of iron and manganese - oxidizing bacteria on water mains can lead to general deterioration of the quality of the water distributed. For these reasons standards have been established for maximum concentrations of soluble manganese in drinking water.
  • Manganese is conventionally removed from water by following scheme: aeration, coagulation, addition of alkali, clarification and sand filtration.
  • the removal of manganese usually requires oxidation of manganese (II) to higher oxidation states in which manganese precipitates as a solid compound.
  • the most common oxidation state is (IV), but also exist (III) and an intermediate oxidation state between (III) and (II) can be as oxidation product.
  • the chemical formulas are mainly manganese oxides or oxyhydrates.
  • DE-A1 -2408051 discloses a process for removing manganese from water. According to the process an oxidant and sodium aluminate are added to the water to be purified so as to precipitate manganese(IV)-oxyhydrate which can be separated by filtration. Disclosed oxidants are air and/or potassium permanganate.
  • DE-B-1517542 discloses a process for removing manganese from water. According to the process a water flow is divided into two parts one of which is oxidized with ozone for oxidizing Mn(II) to Mn(IV).
  • DE-B-1642479 discloses a process comprising oxidizing raw water containing soluble iron and manganese and adding thereto prior to or after or during the oxidation iron(lll)-oxyhydrate and manganese(IV)-oxyhydrat. These added substances catalyze the flocculation process and act as a flocculant.
  • the solid containing iron(lll)-oxyhydrate and manganese(IV)-oxyhydrate precipitate obtained in the flocculation is separated by filtration. A portion of the solid filter precipitate or sludge is recirculated.
  • the oxidation can be carried out by using air, ozone, chlorine or potassium permanganate.
  • WO-A-97/34836 discloses the preparation of a coagulant by subjecting a concentrated aqueous solution of a water treatment chemical containing an iron and/or aluminium compound as the main component and soluble bivalent Mn(II) as an impurity to oxidation by means of an oxidant to convert the soluble Mn(II) to manganese dioxide or permanganate.
  • oxidants are ozone, hydrogen peroxide, chlorine, chlorine dioxide, chlorate, permanganate and ferrite.
  • the coagulant can be used for removing manganese from raw water, the manganese being oxidized to manganese dioxide due to the presence of a surplus of oxidant in the coagulant.
  • JP-2003001272 discloses a process for removing manganese from raw water by adding hydrogen peroxide to the raw water in order to convert soluble manganese to insoluble manganese dioxide and removing the formed manganese dioxide particles by membrane filtration.
  • An object of the present invention is to provide a simple and efficient process for removing manganese from raw water or other aqueous liquids by using an oxidant which also acts as a biocide preventing the growth of bacteria on water mains.
  • a process for removing manganese from an aqueous liquid comprising treating the aqueous liquid with peracetic acid in order to oxidize soluble Mn(II) present in the aqueous liquid to an insoluble manganese compound and optionally with a coagulant, and separating the formed insoluble manganese compound from the treated raw water.
  • the soluble Mn(II) present in the aqueous liquid is oxidized to a higher oxidation state in which manganese precipitates as a solid compound.
  • the oxidation state is preferably (IV), but can also be (III) or an intermediate oxidation state between (III) and (II).
  • mixtures of insoluble manganese compounds can be formed during the oxidation.
  • Preferred insoluble manganese compounds are manganese oxides and manganese oxyhydrates, and especially preferred are manganese(IV) dioxide and manganese(IV) oxyhydrate.
  • the aqueous liquid is treated with a coagulant before the treatment with the peracetic acid.
  • This order of treatment results in good manganese removal.
  • the flocculated substance including organic matter can be removed before the treatment with the peracetic acid.
  • the aqueous liquid is treated with a coagulant after the treatment with the peracetic acid.
  • the coagulant can be an inorganic coagulant, preferably an iron or aluminium compound.
  • the iron compound can be a divalent or trivalent iron compound, preferably a trivalent iron compound, such as ferric sulphate or ferric chloride.
  • a preferred aluminium compound is polyaluminiumchloride. Also other aluminium compounds can be used, such as alum (aluminium sulphate).
  • the precipitated manganese compound can be separated by filtration, such as sand filtration.
  • the peracetic acid can be equilibrium peracetic acid or distilled peracetic acid.
  • Equilibrium peracetic acid is an aqueous solution which preferably contains about 10% to 20% by weight peracetic acid, 13% to 16% by weight hydrogen peroxide and 21 % to 26 % by weight acetic acid.
  • a typical ePAA contains about 13% by weight peracetic acid, 15% by weight hydrogen peroxide and 22% by weight acetic acid.
  • Distilled peracetic acid is an aqueous solution which preferably contains about 20% to 60% by weight peracetic acid, 0.5% to 1.5% by weight hydrogen peroxide and 1% to 3% by weight acetic acid.
  • a typical dPAA contains about 40% by weight peracetic acid, 1 % by weight hydrogen peroxide and 2% by weight acetic acid.
  • the process of the present invention can be carried out at a pH between 5 and 11 , preferably between 7 and 9.
  • the pH of the aqueous liquid after coagulation and before the addition of peracetic acid can be adjusted to 7 or higher, preferably to 8 or higher.
  • the pH after the addition of peracetic acid can be kept at 7 or higher, preferably at 8 or higher. Any suitable alkali can be used for the pH adjustment.
  • the pH of the aqueous liquid before or during peracetic acid treatment can be adjusted to 7 or higher, preferably to 8 or higher. During the subsequent coagulation the pH is lower.
  • the peracetic acid is preferably added in an amount of from 0.1 mg/l to 100 mg/l, more preferably from 1 mg to 10 mg/l.
  • the amount refers to the weight of peracetic acid.
  • the aqueous liquid is preferably raw water including surface water and ground water to be used after the removal of manganese as domestic water including drinking water or as process water for e.g. pulp and paper industry.
  • the maximum concentration of manganese in the raw water to be purified according to the present invention is typically 1 mg/l.
  • the aqueous liquid can also be industrial waste or recirculation water, for example from metal industry or textile industry, or municipal waste water.
  • ePAA equilibrium peracetic acid (aqueous solution containing about 13% by weight peracetic acid, 22% by weight acetic acid and 15% by weight hydrogen peroxide)
  • dPAA distilled peracetic acid (aqueous solution containing about 40% by weight peracetic acid, 1% by weight hydrogen peroxide and 2% by weight acetic acid)
  • NaCIO sodium hypochlorite (as a reference)
  • ePAA was not able to oxidize manganese, when the coagulant (polyaluminium- chloride) was added after oxidant. A higher dose of dPAA was very effective in removing manganese if the addition point was before coagulant. NaCIO, if added before coagulant, was not able to remove manganese. If ePAA was added after coagulation with polyaluminumchloride it was able to remove manganese. A higher dose of dPAA was more affective also in this case. NaCIO was as effective as ePAA in this case.
  • Water sample was surface water taken from a river in western Finland. Because manganese content was enough high for detecting effect of different treatments it was not needed to add any extra manganese.
  • the composition of the water sample is set forth in Table III.
  • the influence of pH on Mn content was studied at various PAA dosages.
  • the results are shown in Tables V-VII.
  • the dosages of dPAA relate to the weight of the PAA solution (the weight of the active substance can be calculated by multiplying the value by 0.4)
  • the first phase is usually chemical precipitation with an inorganic coagulant.
  • ferric sulphate trade name PIX 322
  • PIX 322 ferric sulphate
  • pH was adjusted to desired value, and thereafter PAA was dosed at various amounts with or without additional pH adjustment.
  • Tables VIII-X The dosages of dPAA relate to the weight of the PAA solution (the weight of the active substance can be calculated by multiplying the value by 0.40).
  • Example 3 Additional experiments were carried out as described in Example 3 for another raw water having the composition set forth in Table Xl.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Ocean & Marine Engineering (AREA)
  • Oceanography (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Removal Of Specific Substances (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

La présente invention concerne un procédé d’extraction du manganèse d’un liquide aqueux, comprenant : le traitement du liquide aqueux au moyen d’un acide peracétique en vue d’oxyder le Mn(II) soluble présent dans le liquide aqueux en composé de manganèse insoluble ; le traitement éventuel dudit liquide au moyen d’un agent coagulant ; et la séparation du composé de manganèse insoluble formé du liquide aqueux traité.
PCT/FI2005/000532 2004-12-16 2005-12-15 Procede d’extraction du manganese de l’eau WO2006064084A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20041620A FI117337B (fi) 2004-12-16 2004-12-16 Menetelmä mangaanin poistamiseksi vedestä
FI20041620 2004-12-16

Publications (1)

Publication Number Publication Date
WO2006064084A1 true WO2006064084A1 (fr) 2006-06-22

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2005/000532 WO2006064084A1 (fr) 2004-12-16 2005-12-15 Procede d’extraction du manganese de l’eau

Country Status (2)

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FI (1) FI117337B (fr)
WO (1) WO2006064084A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013098478A3 (fr) * 2011-12-30 2013-08-22 Kemira Oyj Amélioration de l'efficacité de peracides

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2408051A1 (de) * 1974-02-20 1975-08-21 Kronos Titan Gmbh Verfahren zur entfernung von mangan aus wasser
US4419246A (en) * 1982-09-30 1983-12-06 E. I. Du Pont De Nemours & Co. Removal of heavy metal ions
DE3504394A1 (de) * 1984-02-09 1985-09-26 Hubert F. 6000 Frankfurt Neuhausen Verfahren zur reinigung von zur wasserversorgung und -entsorgung dienenden einrichtungen
JPH0422494A (ja) * 1990-05-17 1992-01-27 Komatsu Ltd 排水の分解処理方法
DE4125990A1 (de) * 1991-08-06 1993-02-11 Henkel Kgaa Verfahren zum reinigen tensidhaltiger schmutzwaesser
US5205835A (en) * 1991-02-07 1993-04-27 Fmc Corporation Process to remove manganese dioxide from wet process denim fibers by neutralizing with peracetic acid
US5472619A (en) * 1993-09-03 1995-12-05 Birko Corporation Waste water treatment with peracetic acid compositions
WO1997008381A1 (fr) * 1995-08-30 1997-03-06 Sunds Defibrator Industries Ab Procede pour empecher l'accumulation de metaux dans un processus de blanchiment de pate a papier en circuit ferme
JPH09248576A (ja) * 1996-03-14 1997-09-22 Taiheiyo Kinzoku Kk マグネシュウムを含有するマンガン酸性溶液からのマンガンの優先的除去法
WO1997034836A1 (fr) * 1996-03-18 1997-09-25 Kemira Chemicals Oy Procede permettant d'ameliorer l'applicabilite d'un produit chimique de traitement de l'eau, et coagulant
US6485696B1 (en) * 1998-10-30 2002-11-26 The United States Of America As Represented By The Secretary Of The Interior Recovery/removal of metallic elements from waste water using ozone
JP2003001272A (ja) * 2001-06-26 2003-01-07 Maezawa Ind Inc マンガンの除去方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2408051A1 (de) * 1974-02-20 1975-08-21 Kronos Titan Gmbh Verfahren zur entfernung von mangan aus wasser
US4419246A (en) * 1982-09-30 1983-12-06 E. I. Du Pont De Nemours & Co. Removal of heavy metal ions
DE3504394A1 (de) * 1984-02-09 1985-09-26 Hubert F. 6000 Frankfurt Neuhausen Verfahren zur reinigung von zur wasserversorgung und -entsorgung dienenden einrichtungen
JPH0422494A (ja) * 1990-05-17 1992-01-27 Komatsu Ltd 排水の分解処理方法
US5205835A (en) * 1991-02-07 1993-04-27 Fmc Corporation Process to remove manganese dioxide from wet process denim fibers by neutralizing with peracetic acid
DE4125990A1 (de) * 1991-08-06 1993-02-11 Henkel Kgaa Verfahren zum reinigen tensidhaltiger schmutzwaesser
US5472619A (en) * 1993-09-03 1995-12-05 Birko Corporation Waste water treatment with peracetic acid compositions
WO1997008381A1 (fr) * 1995-08-30 1997-03-06 Sunds Defibrator Industries Ab Procede pour empecher l'accumulation de metaux dans un processus de blanchiment de pate a papier en circuit ferme
JPH09248576A (ja) * 1996-03-14 1997-09-22 Taiheiyo Kinzoku Kk マグネシュウムを含有するマンガン酸性溶液からのマンガンの優先的除去法
WO1997034836A1 (fr) * 1996-03-18 1997-09-25 Kemira Chemicals Oy Procede permettant d'ameliorer l'applicabilite d'un produit chimique de traitement de l'eau, et coagulant
US6485696B1 (en) * 1998-10-30 2002-11-26 The United States Of America As Represented By The Secretary Of The Interior Recovery/removal of metallic elements from waste water using ozone
JP2003001272A (ja) * 2001-06-26 2003-01-07 Maezawa Ind Inc マンガンの除去方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 016, no. 180 (C - 0935) 30 April 1992 (1992-04-30) *
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 01 30 January 1998 (1998-01-30) *
PATENT ABSTRACTS OF JAPAN vol. 2003, no. 05 12 May 2003 (2003-05-12) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013098478A3 (fr) * 2011-12-30 2013-08-22 Kemira Oyj Amélioration de l'efficacité de peracides
CN104105669A (zh) * 2011-12-30 2014-10-15 凯米罗总公司 改善过氧酸的效率

Also Published As

Publication number Publication date
FI20041620A0 (fi) 2004-12-16
FI117337B (fi) 2006-09-15
FI20041620L (fi) 2006-06-17

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