EP0406389A1 - Procede et dispositif de separation du mercure contenu dans un milieu aqueux - Google Patents

Procede et dispositif de separation du mercure contenu dans un milieu aqueux

Info

Publication number
EP0406389A1
EP0406389A1 EP90901803A EP90901803A EP0406389A1 EP 0406389 A1 EP0406389 A1 EP 0406389A1 EP 90901803 A EP90901803 A EP 90901803A EP 90901803 A EP90901803 A EP 90901803A EP 0406389 A1 EP0406389 A1 EP 0406389A1
Authority
EP
European Patent Office
Prior art keywords
immobilized
biomass
microorganisms
mercury
aqueous medium
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Withdrawn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
EP90901803A
Other languages
German (de)
English (en)
Inventor
Anja Frischmuth
Peter Weppen
Wolf-Dieter Deckwer
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.)
Helmholtz Zentrum fuer Infektionsforschung HZI GmbH
Original Assignee
Helmholtz Zentrum fuer Infektionsforschung HZI GmbH
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 Helmholtz Zentrum fuer Infektionsforschung HZI GmbH filed Critical Helmholtz Zentrum fuer Infektionsforschung HZI GmbH
Publication of EP0406389A1 publication Critical patent/EP0406389A1/fr
Withdrawn legal-status Critical Current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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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
    • C22B43/00—Obtaining mercury
    • 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

  • heavy metal ions tend to be bound by microbial cell material.
  • the high accumulation capacity of biomass for heavy metal ions is shown in Table 1.
  • the bioconcentration factors given there were measured on resting microorganisms in the GBF and represent distribution constants at a total metal concentration of 1 ppm.
  • Nakajima and Sakaguchi [13 - 15] examined 83 different microorganisms (bacteria, yeasts, fungi and actinomycetes) for their heavy metal accumulation and the selective enrichment from metal ion mixtures. Uranyi, mercury and lead cations were easily absorbed by all the microorganisms examined. Actinomycetes and fungi differ from many bacteria and most yeasts in their selective accumulation of uranium and mercury. Investigations [14, 15] with various immobilized microorganisms in a fixed bed reactor likewise showed a high concentration of uranium. The adsorbed uranium can be almost completely desorbed with sodium carbonate solution and the immobilized cells can be used repeatedly.
  • Advanced Mineral Technologies Inc. (AMT, Golden, Colorado, USA) has patented a process for the treatment of microorganisms (preferably Bacillus subtiiis) with alkali and their use for biosorption (US 4690894, Sept. 1, 1987).
  • a technical process for the separation of heavy metals with sewage sludge was presented by the GDR at the Biotechn ⁇ ca trade fair (Institute for Biotechnology, Academy of Sciences, Leipzig, GDR). The extent to which patent protection in the Federal Republic or a European patent is available is not known.
  • Ion exchange resins can be used in a wide pH range (1-14) and at temperatures up to 80 ° C. It is clear that such a wide range of applications with biomass is not possible. The higher sensitivity, especially against extreme pH values, is not only important for use, but also for regeneration. While metal ions from an ion exchange resin with 10 - 30% acid can be poured in quickly and in a concentrated form, this is not possible with bioabsorbers. Much milder conditions are required here, and this leads to a much lower concentrated solution in the eluate compared to the ion exchange. Concentration factors of 10 2 - 10 3 can be achieved with biomasses, while for ion exchangers they are 10 4 - 10 5 .
  • an ion exchange resin has a ten times higher volume-related capacity than immobilized biomass and the metal ions are therefore also present in ten times the concentration.
  • a decisive disadvantage is therefore not only that a bioadsorber has to be designed much larger, but also that a much lower concentrated metal solution is obtained in the elution.
  • the price for ion exchange resins is 15 - 20 DM / L resin corresponding to 60 DM / kg. If one takes into account that immobilized biomass with a service life of 1/10 is that of an ion exchanger, the price for the biomass used as adsorption material may not exceed 6 DM / kg. This price must include fermentation, processing and immobilization. Such a low price for fermentation-derived and immobilized biomass cannot be realized. For this reason, only waste biomass and possibly appear at the moment Algae extracted from the sea can be used economically. Apart from sewage sludge, which can hardly be used since it is already pre-loaded with heavy metals, there are hardly any waste biomass available or are not available as such on the market for various reasons.
  • assimilating microorganisms are capable of a number of interactions with heavy metal ions, e.g. active transport, intracellular deposits, discharge processes, reduction and totalization, resistance phenomena etc. It would be desirable to find microorganisms which are capable of specific interactions with heavy metals and which, when used, also have special effects with regard to the retention and separation of Heavy metals occur from process streams which, if appropriate, permit a method of removing heavy metals from aqueous media which is more effective and less expensive than the heavy metal sorption on non-assimilating biomass.
  • the object on which the invention is based is achieved by a method for separating mercury from an aqueous medium by means of active absorption and / or separation processes, which is characterized in that
  • Microorganisms which carry out active absorption and / or separation processes can grow on the immobilized biomass in the presence of an aqueous medium containing mercury and
  • the mercury-depleted aqueous medium passes over the biomass provided with their growth.
  • a further embodiment of the invention relates to a method for separating mercury from an aqueous medium by means of active absorption and / or separation processes, which is characterized in that
  • biomass which has been immobilized in the presence of microorganisms which carry out active absorption and / or separation processes the biomass being obtainable by -
  • the grown microorganisms are immobilized together with the biomass or the grown microorganisms are separated from the biomass in a manner known per se and immobilized with other biomass and
  • the aqueous medium to be depleted of mercury passes over the biomass immobilized in the presence of the microorganisms.
  • a further embodiment of the invention relates to a method for separating mercury from an aqueous medium by means of active absorption and / or separation processes, which is characterized in that
  • microorganisms which carry out active absorption and / or separation processes and have been immobilized, the microorganisms being obtainable by
  • microorganisms in the presence of a mercury-containing aqueous medium grow on (possibly immobilized) biomass and
  • the aqueous medium to be depleted of mercury is passed over the immobilized microorganisms, the aqueous medium containing nutrient salts and a carbon source to supply the microorganisms.
  • a further embodiment of the invention relates to a method for separating mercury from an aqueous medium by means of active absorption and / or separation processes, which is characterized in that
  • microorganisms which carry out active absorption and / or separation processes on the carrier material in the presence of the aqueous medium or a mercury-containing aqueous medium with an additional content of nutrient salts and carbon and -
  • the aqueous medium to be depleted of mercury passes over the carrier material provided with its growth.
  • the carrier material can be porous carrier material.
  • pelletizing and / or extrusion can have been immobilized by inclusion, for example in alginate, carageenan, polyacrylamide and / or polyurethane.
  • the immobilized biomass and / or the immobilized microorganisms can be used in the form of a fixed bed or fluidized bed.
  • the microorganisms can be immobilized as biomass in the presence of yeast, such as baker's yeast, mushrooms, other bacteria and / or waste biomass.
  • yeast such as baker's yeast, mushrooms, other bacteria and / or waste biomass.
  • a pH in the range 5.5 to 8 and preferably 6.0 to 7.5 and in particular about 7 can be used.
  • the object on which the invention is based is finally achieved by a device for carrying out the method according to the invention, which is characterized by a bed with immobilized biomass and / or immobilized microorganisms, the bed being designed to be at rest or swirled up by the flow.
  • a device for carrying out the method according to the invention which is characterized by a bed with immobilized biomass and / or immobilized microorganisms, the bed being designed to be at rest or swirled up by the flow.
  • This invention demonstrates
  • the yeast Saccharo ⁇ myces cerevisiae was used as a substrate for the sought organisms in anionic polymers, such as.
  • anionic polymers such as.
  • Alginate included and the Immobilisatperlen of 1 - 3 cm in diameter arranged in a tube as a fixed bed and the bed of a mercury-containing solution (mercury as Hgcy flows vertically.
  • Typical throughputs for an immobilized mass of 11.5 g (beads 1.3 mm in diameter) and a bed height of 10 cm are 2-12 L solution per hour and kg of gel corresponding to a metal load of 0.2-120 mg Hg per hour and kg of gel, preferably at 4 - 8 L / kg.h or 0.4 - 80 mg Hg / kg. H.
  • Example 2 shows two runs in which yeast was used enclosed in alginate beads.
  • the input concentration of the mercury was set to 1 mg / L.
  • Run 2a was stopped without problems after 58 hours and run 2b after 240 hours.
  • the mercury profile in the fixed bed was examined and Hg-Biianze ⁇ created.
  • the mercury balances for runs 2a and 2b can be regarded as consistent.
  • the time course of the Hg bed exit concentration can be described as the same or at least as similar for both runs.
  • the Hg starting concentration at relatively short operating times (about 10-20 hours) has relatively high values, which drop significantly again later, which cannot be explained by any conventional sorption behavior.
  • the Hg initial concentration at the end of the bed is less than 1% of the Hg initial concentration, especially during long operating times.
  • Example 3 a very high Hg concentration of 10 mg / L is used.
  • the course over time of the Hg concentration at the exit initially shows that the process according to the invention can also be used effectively in the solution even at high Hg use concentrations.
  • the Hg concentration at the inlet drops from 10 mg / L to approximately 0.02 mg / L at the outlet with a bed height of 10 cm.
  • Example 3 now also shows the bacterial count densities which were determined after the end of the run in the individual sections after the bed had been dismantled. As the table in Example 3 shows bacterial count densities> 10 7/9 humid gel were determined. However, the originally introduced yeast cells could not be detected, instead new strains of bacteria have appeared in the bed and have settled there in high density.
  • yeasts capable of forming colony could no longer be isolated from the yeast immobilizates originally used.
  • at least twelve different bacterial species have been differentiated according to their colony manifestation, seven of which have been identified by the DSM. These strains are summarized in Table 2. Most isolates grow in the presence of high Hg concentrations (HgCl 2 between 10 and 100 mg / L). Three strains of the genus microbacterium were also found which, according to the DSM, have not yet been described. At least some of the strains listed in Table 2 contain the plasmid-encoded Resiste ⁇ zge ⁇ mer-A, which induces the enzymatic reduction of Hg 2+ to Hg 0 .
  • Table 2 Microorganisms isolated from the yeast immobilized bed and identified by DSM, which enter into active processes with Hg
  • Example 4 shows two fixed bed runs with immobilized S. cerevisiae, which were started under monoseptic conditions at a feed concentration of 1 ppm. In the first few days, there is a steady increase in the Hg concentration at the exit of the bed, which is a kind of breakthrough. After 11 days, a suspension of Microbacterium sp. Inoculated HGS3 or Alkaligenes eutrophus HGS4.
  • the viability of the HGS bacteria is necessary for active Hg uptake or removal from the aqueous medium. In the previous examples, this was ensured in that killed yeast lines served as the substrate source.
  • the substrate supply can also take place via the feed stream, in this example the strain HG62 (Aeromonas hydrophiia) immobilized with alginate under sterile conditions, the feed stream containing not only Hg (1 ppm) but also nutrient salts and acetate as the carbon source. In this run too, the Hg concentration in the bed flow remained consistently low ( ⁇ 0.1 ppm) and the run was stopped after 44 days of operation.
  • the isolated HGS isolates were also examined for their mercury absorption capacity in the quiescent state.
  • the microorganisms were exposed at 30 ° C. and pH 7 with a solution which contained mercury chloride, 5 mmoi pipes buffer and 10 mmol CaCl 2 , and the total and free mercury concentration were determined after 6 hours of equilibration.
  • the bioconcentration factors calculated from these data (in mg Hg / kg BTM per mg Hg / kg solution) are summarized in Table 3 for some microorganisms.
  • the calculated bioconcentration factors can be described as modest (cf. e.g. Table 1) and make it very clear that sorption effects on the cell wall cannot be responsible for the high mercury retention that has been described.
  • the immobilized bed was divided into 4 or 5 sections of approximately the same size and weighed out (as a control). The individual sections were thoroughly mixed and examined for their mercury content by digesting 200 mg immobilist with 1 ml of 14 m HNO 3 and 1 ml of 9 m H 2 SO 4 at 120 ° C. in closed vessels and then analyzing for mercury by means of atomic absorption spectroscopy . The following results were achieved:
  • yeast immobilisate alginate
  • Protein content g protein / kg wet weight 19.5
  • Example 2 the bed was divided into 5 sections (each 2 cm bed height) and analyzed for Hg as described. It resulted
  • Immobilized beads 200 mg of the bed, which was divided into 5 sections of approximately the same size, were briefly treated with sterile phosphate buffer (10 ml) to destroy the alginate grid. Excluding the entry of foreign germs, the most probable number of germs was determined for the individual sections by dilution series (the phosphate buffer solution) (MPN method). The results of the MPN determination are given in the table.
  • Freshly prepared yeast (S. cerevisiae) was immobilized in a sterile manner and put into operation in a fixed bed in a sterile manner and treated with aqueous HgCl 2 solution (+ 10 mmol CaCl 2 + 5 mmol pes-Puf fei).
  • the conditions are summarized in the following table.
  • Hg feed was suspended and instead a bacterial suspension (> 10 9 germs / ml) of HGS3 or HGS4 was continuously fed to the bed for 36 h at a flow rate of 39 ml / h. Then it was switched back to Hg feed. After 50 days, the Hg feed stream was used to add chloramphenicol (1 g / L) over a period of 8 days. The course of the Hg concentration at the bed exit is shown in Fig. 2 for the entire test period of 20 days.
  • Feed concentration mg Hg / L of dry solids, g / kg of fresh gel protein, g / kg of fresh gel particle diameter, mm
  • HGS2 Heeromonas hydrophiia
  • alginate approximately 50 g HGS2 / kg wet gel
  • the feed stream contained the following additional nutrients: Na ⁇ HPO, »(0.93 mg / L), KH 2 P0 4 (0.46 mg / L ), Na acetate (0.5 g / L), NH 4 CI (0.25 g / L), MgSO 4 (0.2 g / L) and a common trace element solution (1 ml / L).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

Procédé et dispositif de séparation du mercure contenu dans un milieu aqueux par des procédés actifs d'absorption et/ou de séparation.
EP90901803A 1989-01-17 1990-01-16 Procede et dispositif de separation du mercure contenu dans un milieu aqueux Withdrawn EP0406389A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3901217 1989-01-17
DE3901217 1989-01-17

Publications (1)

Publication Number Publication Date
EP0406389A1 true EP0406389A1 (fr) 1991-01-09

Family

ID=6372235

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90901803A Withdrawn EP0406389A1 (fr) 1989-01-17 1990-01-16 Procede et dispositif de separation du mercure contenu dans un milieu aqueux

Country Status (3)

Country Link
EP (1) EP0406389A1 (fr)
CA (1) CA2020467A1 (fr)
WO (1) WO1990008108A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1236689A1 (fr) * 2001-02-22 2002-09-04 Realco 2001 S.A./N.V. Procédé pour le traitement d'un effluent aqueux
ITRM20080183A1 (it) * 2008-04-07 2009-10-08 Univ Milano Bicocca Rimozione microbiologica di mercurio da materiali contaminati.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923597A (en) * 1974-08-01 1975-12-02 Gen Electric Mercury concentration by the use of microorganisms
US4690894A (en) * 1985-09-20 1987-09-01 Advanced Mineral Technologies, Inc. Treatment of microorganisms with alkaline solution to enhance metal uptake properties
US4728427A (en) * 1986-10-14 1988-03-01 Revis Nathaniel W Reduction of trace elements to the elemental form by microorganisms

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9008108A1 *

Also Published As

Publication number Publication date
CA2020467A1 (fr) 1990-07-18
WO1990008108A1 (fr) 1990-07-26

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