EP1044167A1 - Entfernung von schwermetallionen aus wässrigen medien - Google Patents

Entfernung von schwermetallionen aus wässrigen medien

Info

Publication number
EP1044167A1
EP1044167A1 EP98966413A EP98966413A EP1044167A1 EP 1044167 A1 EP1044167 A1 EP 1044167A1 EP 98966413 A EP98966413 A EP 98966413A EP 98966413 A EP98966413 A EP 98966413A EP 1044167 A1 EP1044167 A1 EP 1044167A1
Authority
EP
European Patent Office
Prior art keywords
sulfide
heavy metal
mercury
metal ions
wet oxidation
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP98966413A
Other languages
German (de)
English (en)
French (fr)
Inventor
Holger Heidenreich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of EP1044167A1 publication Critical patent/EP1044167A1/de
Withdrawn legal-status Critical Current

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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/025—Thermal hydrolysis
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/911—Cumulative poison
    • Y10S210/912—Heavy metal
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/911—Cumulative poison
    • Y10S210/912—Heavy metal
    • Y10S210/914—Mercury

Definitions

  • the invention relates to a method for removing heavy metal ions, in particular mercury and silver ions, from aqueous media.
  • Waste water containing organic compounds can be cleaned in various ways.
  • One possibility is that the waste water is concentrated and then the residue is burned.
  • Another possibility is to subject the wastewater to an oxidative treatment (so-called wet oxidation) (H. Perkow, R. Steiner, H. Vollmüller, Chem.-Ing.-Tech. 52
  • the present invention was therefore based on the object of providing an improved process for removing heavy metal ions from aqueous media.
  • a process has now been found for removing heavy metal ions, in particular mercury and silver ions from aqueous media, which is characterized in that sulfide precipitation is carried out in the presence of iron oxide to precipitate the heavy metal ions.
  • the heavy metal ions to be precipitated are dissolved heavy metal salts which are precipitated in the form of their sulfides during sulfide precipitation.
  • a water-soluble sulfide is preferably used for the sulfide precipitation, water-soluble preferably being understood to mean a solubility in water at 20 ° C. of greater than or equal to 100 g / 1, in particular greater than 300 g / 1.
  • particularly preferred sulfides are hydrogen sulfide, alkali sulfide, in particular sodium sulfide, alkali hydrogen sulfide, in particular sodium hydrogen sulfide or mixtures thereof.
  • the sulfide used for the sulfide precipitation is preferably used stoichiometrically or in a stoichiometric excess, based on the heavy metal cation to be precipitated.
  • the sulfide precipitation is preferably carried out at a temperature of 20 to 155 ° C. It can be carried out at normal pressure or at elevated pressure, preferably at 1 to 6 bar.
  • the process according to the invention is preferably carried out in the presence of an iron oxide compound from the group FeO, Fe 2 ⁇ 3 and Fe 2 ⁇ 4 or mixtures thereof.
  • the amount by weight of iron oxide is preferably 5 to 500, in particular 5 to 100 mg / l of waste water.
  • the wet oxidation product of iron and heavy metal is used as the aqueous medium.
  • the content of inorganic salts is preferably 0 to 15% by weight, based on the iron-containing water.
  • the iron content of the water supplied to the wet oxidation is preferably - the iron is preferably in the form of iron sulfate - 5 to 500 mg / 1, particularly preferably 10 to 100 mg / 1.
  • the aqueous medium generally has a pH of 0.5 to 2.5.
  • the waste water is preferably pumped with a high-pressure pump through a heat exchanger, in which it is preheated by the cleaned waste water in countercurrent.
  • the temperature should be sufficiently high that the oxidation, which is preferably carried out with air, starts. From a TOC content of 10,000 to 20,000 mg / 1, the oxidation can proceed autothermally without the use of additional energy. Since oxidation in the gas phase generally proceeds very slowly under the temperature conditions of the wet oxidation, it is preferably ensured by setting a pressure which is above the saturated steam pressure at the corresponding temperature that at least part of the water in the reactor is preferably present in liquid form.
  • a catalyst is preferably added to accelerate the reaction.
  • Metals from the subgroups are used in particular as catalysts.
  • preferred catalysts are understood to be divalent catalytic copper ions, copper sulfate or copper sulfide being preferably used.
  • the copper catalyst is preferably used in an amount of 100 to 1000 mg / 1, particularly preferably from 200 to 700 mg / 1.
  • the wet oxidation is carried out at a temperature of 240 to 280 ° C., it being advantageous to set a pressure of 100 to 200 bar.
  • the cleaned waste water and the low-oxygen exhaust gas are preferably separated from one another in a liquid separator.
  • the catalyst is preferably precipitated as sulfide, separated and returned to the wet oxidation process, where it is in turn oxidized to copper sulfate.
  • reaction products of the wet oxidation are carbon dioxide and water with small proportions of anoxidized, low molecular weight fragments of poorly degradable organic compounds.
  • the nitrogen content of organic compounds is largely converted into ammonia, which is stripped from the cleaned, acidic wastewater after pH adjustment.
  • iron oxide required for sulfide precipitation comes from the wet oxidation stage of an iron-containing aqueous medium, it may be advantageous to remove this solution or suspension after the wet oxidation, i.e. Add polyelectrolytes before or preferably after sulfide precipitation.
  • salts are, for example
  • Polyphosphoric acid, polyvinylsulfuric acid, polyvinylsulfonic acid, polyvinylphosphonic acid, polyacrylic acid, polyethyleneimines, polyvinylamines, polyvinylpyridines etc. are to be mentioned.
  • the polyelectrolytes can be used, for example, in an amount of 0.0001 to 0.1% by weight, based on the suspension or solution.
  • the aqueous medium used for the wet oxidation has, in particular, a pH of 5.5 to 8.0.
  • Heavy metal ion-reduced wastewater obtained by the process according to the invention preferably has a residual heavy metal content of less than 1 mg / kg copper or silver and less than 0.005 mg / kg mercury.
  • mercury ions are separated off in the presence of copper ions by sulfide precipitation, characterized in that the water-soluble sulfide is present in a stoichiometric amount or in excess, preferably from 1.0 to 2.0 molar equivalents, preferably 1.0 to 1.5 molar equivalents per equivalent of mercury ions.
  • Mercury sulfide is preferably precipitated, with the large amount of copper ions remaining in solution.
  • the precipitated mercury sulfide can then be separated off together with the iron oxide.
  • the separated copper sulfide can then, for example, be used again as a catalyst in the wet oxidation process, where it is then oxidized to the soluble copper sulfate.
  • composition 15,000 mg / 1 TOC
  • the waste water purified to a residual TOC content of 350 mg / l (degree of purification of 97.6%) is cooled while preheating the reaction feed, depressurized under high pressure - separation of the purified waste water and the low-oxygen exhaust gas - and the finely divided Iron oxide continuously separated using a sand filter and filter press.
  • the acidic wastewater pH approx. 2.0
  • a 30% sodium hydrogen sulfide solution approximatelyx. 37 1 / h; end point detection via redox potential measurement
  • Copper is decanted to return it as a catalyst suspension for the wet oxidation process before the reactor.
  • Partially distributed mercury sulfide that co-precipitates under these conditions is thus partly returned to the catalyst cycle and concentrated therein without being able to be discharged, and partly remains finely divided in the waste water (concentration of mercury in the purified waste water 0.2 mg / kg ).
  • Example 2 30 m 3 / h of neutralized wastewater of the following composition are continuously oxidized with air in a high-pressure wet oxidation reactor at 250 ° C. and 150 bar pressure.
  • composition 15,000 mg / 1 TOC
  • the wastewater (pH 2.0), which has been cleaned to a residual TOC content of 350 mg / l (degree of purification of 97.6%), is cooled with preheating of the reactor feed, depressurized - separation of the cleaned wastewater and of the low-oxygen exhaust gas - and continuously via one
  • Fine flow metering pump with 14 ml / h of a 30% sodium hydrogen sulfide solution. After a residence time of approx. 1 hour, the precipitated mercury sulfide is continuously separated off together with the finely divided iron oxide using a sand filter and filter press. Then the filtrate, largely cleaned of mercury, is removed with a 30% solution for the purpose of separating the copper catalyst
  • the waste water from Example 2 is wet-oxidized as described above and a 30% sodium hydrogen sulfide solution is added to precipitate the mercury.
  • the water with 30 1 / h of an aqueous 0.1% mixture of a cationic high molecular weight polyacrylamide copolymer.
  • the iron oxide which can now be readily filtered, is separated off together with the precipitated mercury sulfide, as described above.
  • the catalyst removal is then continued, as set out in Example 2. After the HgS / CuS separation, the cleaned wastewater contains ⁇ 1 mg / kg copper and ⁇ 0.002 mg / kg mercury.

Landscapes

  • 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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Removal Of Specific Substances (AREA)
EP98966413A 1998-01-10 1998-12-29 Entfernung von schwermetallionen aus wässrigen medien Withdrawn EP1044167A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19800699A DE19800699A1 (de) 1998-01-10 1998-01-10 Entfernung von Schwermetallionen aus wäßrigen Medien
DE19800699 1998-01-10
PCT/EP1998/008488 WO1999035094A1 (de) 1998-01-10 1998-12-29 Entfernung von schwermetallionen aus wässrigen medien

Publications (1)

Publication Number Publication Date
EP1044167A1 true EP1044167A1 (de) 2000-10-18

Family

ID=7854308

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98966413A Withdrawn EP1044167A1 (de) 1998-01-10 1998-12-29 Entfernung von schwermetallionen aus wässrigen medien

Country Status (8)

Country Link
US (1) US6342162B1 (id)
EP (1) EP1044167A1 (id)
JP (1) JP2002500103A (id)
CN (1) CN1285807A (id)
AU (1) AU2276499A (id)
DE (1) DE19800699A1 (id)
ID (1) ID26830A (id)
WO (1) WO1999035094A1 (id)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6238570B1 (en) * 1999-02-25 2001-05-29 General Electric Company Method for treating aqueous composition contaminants
CN1295165C (zh) * 2005-03-17 2007-01-17 周石来 一种含汞废水的处理方法
US8236185B2 (en) 2006-03-23 2012-08-07 J.I. Enterprises, Inc. Methods for using sulfidized red mud
US8231711B2 (en) 2006-03-23 2012-07-31 J. I. Enterprises, Inc. Sorption processes
US8382991B2 (en) * 2006-03-23 2013-02-26 J. I. Enterprises, Inc. Method of sorbing discolored organic compounds from water
US7763566B2 (en) * 2006-03-23 2010-07-27 J.I. Enterprises, Inc. Method and composition for sorbing toxic substances
CN102001734B (zh) * 2010-12-01 2013-06-12 新疆天业（集团）有限公司 处理含汞废水的重金属沉降剂
CN102145930B (zh) * 2011-02-21 2012-08-29 李开明 一种含汞废水的处理方法
WO2013040658A1 (en) * 2011-09-21 2013-03-28 Alcoa Of Australia Limited Method for controlling emissions
US11213784B2 (en) * 2018-04-18 2022-01-04 Clairion Ltd. Process for separation of heavy metals and/or sulfur species from ionic liquids
WO2020199382A1 (zh) * 2019-03-29 2020-10-08 中国瑞林工程技术股份有限公司 利用气体连续净化污水的方法和系统
CN112897752A (zh) * 2021-01-26 2021-06-04 北京师范大学 生活饮用水的处理方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873581A (en) * 1971-10-21 1975-03-25 Toms River Chemical Corp Process for reducing the level of contaminating mercury in aqueous solutions
US4705638A (en) * 1984-05-03 1987-11-10 The University Of Toronto Innovations Foundation Waste water treatment
US5154833A (en) 1992-01-08 1992-10-13 Connaught Laboratories Inc. Removal of mercury from waste streams
DE4229662C2 (de) 1992-09-04 1996-08-14 Steag Ag Verfahren zur Entfernung von Quecksilber aus aus Rauchgaswäschern stammenden Abwässern
GB9220269D0 (en) 1992-09-25 1992-11-11 Bio Separation Ltd Separation of heavy metals from aqueous media
US6153108A (en) * 1998-06-11 2000-11-28 Texaco Inc. Method for removal of heavy metals from water

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9935094A1 *

Also Published As

Publication number Publication date
US6342162B1 (en) 2002-01-29
JP2002500103A (ja) 2002-01-08
WO1999035094A1 (de) 1999-07-15
DE19800699A1 (de) 1999-07-15
AU2276499A (en) 1999-07-26
CN1285807A (zh) 2001-02-28
ID26830A (id) 2001-02-15

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