EP0484352A1 - Verfahren zur biologischen behandlung von abwasser und anlage sowie reaktor zur durchführung des verfahrens - Google Patents

Verfahren zur biologischen behandlung von abwasser und anlage sowie reaktor zur durchführung des verfahrens

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Publication number
EP0484352A1
EP0484352A1 EP90910545A EP90910545A EP0484352A1 EP 0484352 A1 EP0484352 A1 EP 0484352A1 EP 90910545 A EP90910545 A EP 90910545A EP 90910545 A EP90910545 A EP 90910545A EP 0484352 A1 EP0484352 A1 EP 0484352A1
Authority
EP
European Patent Office
Prior art keywords
reactor
activated sludge
solution
nitrification
denitrification
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Withdrawn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
EP90910545A
Other languages
German (de)
English (en)
French (fr)
Inventor
Eberhard Kuhn
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP0484352A1 publication Critical patent/EP0484352A1/de
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic processes
    • C02F3/308Biological phosphorus removal
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/006Regulation methods for biological treatment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/06Aerobic processes using submerged filters
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/08Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/15N03-N
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/16Total nitrogen (tkN-N)
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/18PO4-P
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/21Dissolved organic carbon [DOC]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/08Aerobic processes using moving contact bodies
    • C02F3/082Rotating biological contactors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/902Materials removed
    • Y10S210/903Nitrogenous

Definitions

  • the invention relates to the purification of waste water by means of a continuous biotechnological process.
  • the treatment of wastewater to be cleaned comprises the basic procedural operations of conversion and separation of substances.
  • Four areas of activity can be distinguished from each other: removal of organic substances (carbon degradation), oxidative conversion of the inorganic nitrogen compounds ammonium and nitrite to nitrate (nitrification), conversion of the nitrate and nitrite to gaseous nitrogen compounds (denitrification) and biological elimination of phosphorus without the use of external chemical precipitants.
  • microorganisms are used that have the special skills required for converting substances.
  • these specialized microorganisms should be available in as large a number as possible, so that high material conversion rates and thus efficient wastewater purification are achieved.
  • the activated sludge which contains the necessary microorganisms in common, are kept in a biologically closed system.
  • the aeration basin is preceded by an anaerobic mixing basin for raw sewage and recycled activated sludge separated from the cleaned sewage solution.
  • phosphate is redissolved, in order to subsequently be taken up more by the bacteria in the aerated aeration tank and to be removed from the system with the excess sludge.
  • the customary methods also include a stage in which nitrogen is broken down.
  • Characteristic values for such biotechnological processes for wastewater treatment are the following sum parameters, which each record a subset of the pollution contained in the wastewater:
  • Total Kjeldahl Nitrogen the sum of organically bound nitrogen fixed in ammonium.
  • the object of the present invention is to provide a further developed method for biological wastewater treatment, which is characterized by a higher denitrification capacity, a reduced concentration of nitrogen and phosphate in the discharge and a lower critical ratio BOD5 / TKN.
  • the devices necessary for carrying out the improved method are also to be made available.
  • the ravage is solved by the method for biological treatment of waste water specified in claim 1.
  • Process steps a) and b) and e) to h) are already known per se.
  • the proposed process differs fundamentally from the main processes known to date in that the solution is separated from the activated sludge following the anaerobic precursor, the separate nitrification of the separated solution by means of a second, chemitrophotrophic biocenosis and the subsequent remixing of the nitrified Solution with the Bele ⁇ islamm, whose chemoorganotrophic biocenosis has not been subjected to nitrification.
  • the denitrification stage is downstream.
  • the aeration of the denitrifying biocenosis takes place either after the denitrification in a separate, subsequent process step or already in the denitrification stage itself, for example by means of a NOx-controlled interval ventilation, and additionally in a subsequent further process step.
  • the method according to the invention is based on the following functional principle:
  • the incoming raw wastewater is first brought into contact with a chemoorganotrophic first biocenosis under anaerobic conditions. Hydrolyzing and fermentative bacteria produce lower fatty acids from poly- and monomeric carbon compounds. Phosphate-redissolving bacteria store these fatty acids inside with the release of phosphate. This results in a selective separation of the waste water, the organically bound carbon (DOC) contained in the solution being largely reduced, while the nitrogen content is reduced and the phosphate content increases sharply.
  • DOC organically bound carbon
  • the solution is separated from the activated sludge and thus also from the first biocenosis.
  • the separated solution is nitrified separately by means of a second, chemolithotrophic biocenosis.
  • the course of the nitrification stage is then brought back into contact with the first, chemoorganotrophic biocenosis.
  • the denitrified mixture of solution and activated sludge is aerated, so that an anaerobic environment is established. Further phosphate is removed from the solution.
  • the process ends with the separation of the cleaned wastewater from the activated sludge, which is returned to the anaerobic precursor.
  • the nitrification of the solution separated according to the invention in connection with the downstream denitrification leads to a significant increase in the denitrification performance in comparison to the previously known main stream processes with simultaneous or upstream denitrification. This has the consequence that the effluent wastewater contains significantly smaller amounts of nitrogen and the critical ratio BOD5 / TKN is lower.
  • the costs of the aeration required for carbon oxidation can also be minimized.
  • the proposed method can be used if extensive elimination of carbon in the anaerobic precursor is guaranteed.
  • the prerequisite for this is that the BOD5 value for the incoming raw wastewater is not too high, since the capacity for storing carbon of the P-redissolving microorganisms is limited.
  • the dirt concentrations usually found in municipal wastewater should be within the permissible range.
  • the temporal distribution of the inflow loads should not show excessive peaks, since otherwise easily degradable carbon compounds will penetrate into the nitrification stage. Since, according to the invention, the nitrification stage is arranged before the denitrification stage and the aeration stage, the incoming raw sewage must have sufficient buffer capacity.
  • the task aimed at specifying a corresponding device for carrying out the proposed method is solved by the four-stage system for the biological treatment of waste water specified in claim 3.
  • the use of anaerobic pre-tanks, intermediate settling tanks, nitrification reactors, denitrification reactors, secondary settling tanks, aeration devices and a sludge recirculation are known, taken on their own.
  • the critical ratio BSB5 / TKN is relatively low, since the cascade-like arrangement of the individual components means that the reflux ratio is small and high denitrification rates can be achieved.
  • the splitting of the volume flows in the intermediate clarifier is characteristic of the plant according to the invention.
  • the ratio between the volume flows of the solution fed to the nitrification stage and the activated sludge passed through the sludge bypass should be as large as possible, since then a high percentage of the nitrogen in the form of nitrate for the subsequent denitrification in the downstream Denitrification level is available.
  • the ratio that can be achieved in practical operation is determined by the settling behavior of the activated sludge in the intermediate clarifier.
  • a ventilation device for example, a terminal aeration basin comes into question, which can also be integrated with the denitrification reactor in a common structural unit.
  • the ventilation required for the temporary creation of an aerobic environment can also be carried out by means of a NOx-controlled oxygen interval ventilation.
  • a simultaneous denitrification reactor can be provided instead of the denitrification reactor, in which a simultaneous denitrification / residual nitrification of the mixture of solution and activated sludge takes place in an alternating aerobic and anoxic environment.
  • a fixed bed reactor for example a trickling filter, has proven itself as the nitrification reactor; However, this can also be designed as an aeration stage with its own intermediate clarifier and sludge return.
  • the denitrification reactor is expediently designed as a stirred tank reactor.
  • the invention has created a specially designed reactor specifically for the technical implementation of the proposed method in small plants.
  • This, in the patent say 10 circumscribed reactor allows the settlement of the first chemoorganotrophic biocenosis on a submerged disc diving body, so that it can be referred to as a three-phase submerged reactor.
  • Characteristic of the three-phase submerged reactor according to the invention is the division of its reactor vessel into a first compartment, into which the inlet for the raw sewage flows, and into a second compartment that is as well separated from the flow as possible, into which a return for re-introducing the separately nitrified solution opens .
  • Another essential feature is the arrangement of a ventilation device in the second compartment, by means of which an aerobic environment can be set locally or for a limited time.
  • the incoming raw wastewater is fed into the lower area of the first anaerobic compartment and flows upwards between the disks of the submerged disk submersible.
  • the vegetation on the disc diving body which represents the first chemoorganotrophic biocenosis, produces lower fatty acids from dissolved carbon compounds and stores them with the release of phosphate.
  • This first compartment thus corresponds to the anaerobic antechamber in a conventional system with stirred tank reactors.
  • the supernatant solution leaves the first anaerobic compartment via the outlet above and is fed to a separate nitrification.
  • the nitrification stage located half of the three-phase submerged reactor is then returned from below to the second anoxic compartment.
  • Denitrification and phosphate uptake now take place here by means of the carbon compound stored in the anaerobic part and the reduction equivalents contained in the primary sludge.
  • the thus denitrified wastewater solution flows upward within the second compartment and reaches its upper region, in which the aeration device is arranged.
  • the oxygen entered there is used by the biocenosis located on the panes of the submersible body for the oxidation of stored carbon compounds, coupled with an absorption of phosphate.
  • the cleaned wastewater leaves the reactor through the outlet provided in the upper part of the second compartment and can, if necessary, be subjected to a clarification.
  • the three-phase submerged reactor proposed by the invention is distinguished by the following advantageous properties: it enables a P-resolving biocenosis to settle on solid surfaces, namely on the disks of the disc diving body.
  • the energy input is relatively low in comparison to other systems.
  • the primary sludge is used to optimize P elimination and denitrification. There is no need for complex sludge cycles.
  • the separating device is designed as separating rods which run essentially vertically and are arranged between the disks of the disk immersion body. These separating rods are expediently each with their upper end in one upper partition and anchored with its lower end in a lower partition.
  • the film of biomass that forms on the separating rods and the disks of the disk immersion body not only serves for the biochemical conversion within the reactor, but also simultaneously seals the two compartments. A high quality of the compartmentalization is necessary, since the critical ratio BSB5 / TKN depends on it.
  • a sludge channel is provided between the lower partition, in which the separating rods are anchored, and the bottom of the reactor vessel, through which primary sludge and excess sludge get from the first anaerobic compartment into the second anoxic compartment in a controlled manner.
  • a sludge barrier on the inner wall of the reactor vessel below the inlet for raw waste water has proven itself. This mud barrier should reach close to the circumference of the diving body.
  • the ventilation device is a rotating, semi-submersible submersible body, the disks of which are partially arranged between the disks of the submerged submersible body. Due to the rotation of the additional disc diving body, oxygen is introduced into the upper region of the second compartment, which is coupled with the biocenosis which is located on the discs of the diving body for the oxidation of stored carbon compounds Ingestion of phosphate.
  • the submerged-lying disc diving body and the semi-submerged additional diving body have the same direction of rotation, whereby the additional diving body rotates many times faster than the very slowly rotating, submerged-lying diving body.
  • Excess sludge formed during wastewater treatment can be removed from the reactor if an additional outlet for excess sludge is provided at the bottom of the reactor vessel.
  • the system specified in claim 20 also serves to carry out the method according to claim 1 for the biological treatment of waste water.
  • This plant contains the three-phase submerged reactor described above as a core and represents an alternative to the technical implementation specified in claim 3 with conventional individual components.
  • the pretreatment of the incoming raw sewage takes place by contacting the first chemoorganotrophic biocoenosis in the first compartment, which represents the anaerobic precursor, and the subsequent separation of the solution from the activated sludge.
  • the nitrification reactor connected between the outflow of the first compartment and the return flow into the second compartment contains the second, chemolithotrophic biocenosis by means of which the separated solution is nitrified separately.
  • the subsequent common denitrification of the solution mixed again with the activated sludge takes place in the second compartment of the three-phase submerged reactor.
  • Figure 1 shows a method for the biological treatment of waste water, in a schematic diagram
  • FIG. 2 shows a first plant for the biological treatment of waste water, in a schematic representation
  • FIG. 3 shows a three-phase submerged reactor for the biological treatment of waste water, in a vertical section
  • Figure 4 shows the colonization of the reactor of Figure 3 with microorganisms
  • Figure 5 shows the milieu zoning within the reactor of Figure 3;
  • FIG. 6 shows the reactor of FIG. 3 as part of a second alternative plant for the biological ⁇ treatment of waste water, in a schematic representation.
  • FIG. 1 the inventive method for the biological treatment of waste water is shown in a schematic diagram. It is a main flow process.
  • the incoming raw waste water is mixed in an anaerobic preliminary stage with activated sludge, which contains a first chemoorganotrophic biocenosis I.
  • the solution is then separated from the activated sludge.
  • the separated solution is brought into contact with a second chemolithotrophic biocenosis II in a subsequent nitrification stage in which the aerobic environment prevails.
  • the activated sludge is led past this nitrification stage.
  • the separately nitrified solution is mixed again with the activated sludge which contains the biocoenosis I.
  • a common denitrification of the mixture of solution and activated sludge now takes place in an anoxic environment. This is followed by a simultaneous denitrification stage in which aerobic and anoxic environments are alternately set by interval ventilation. A residual nitrification or denitrification thus takes place simultaneously.
  • the cleaned wastewater is separated from the activated sludge and leaves the system as a drain.
  • the activated sludge, and thus the biocoenosis I, is returned to the anaerobic preliminary stage.
  • the plant shown schematically in FIG. 2 represents a first alternative of a technical implementation of the method explained above with reference to FIG. 1 using conventional reactors.
  • the incoming raw sewage is first placed in a fully mixed anaerobic basin AVB, which is designed as a stirred tank reactor, and mixed there with the first chemoorganotrophic biocenosis I.
  • the activated sludge settles in a subsequent intermediate clarifier ZKB.
  • the supernatant solution flows into a pump sump PS and from there is passed into a nitrification reactor NIR.
  • a fixed bed reactor is used here as the nitrification reactor NIR, for example, a trickling filter on which the second chemolithothrophic biocenosis II is located. This is followed by a denitrification reactor DER, into which the separately nitrified solution is passed.
  • the activated sludge deposited at the bottom of the intermediate clarification basin ZKB is pumped through a sludge bypass bypass, ie bypassing the nitrification reactor NIR, into the denitrification reactor DER.
  • the biocenosis II is aerated in a downstream terminal aeration tank TBB.
  • the aeration device can also be integrated in the form of a NOx-controlled oxygen interval ventilation (not shown) in the denitrification reactor DER, which thus becomes a simultaneous denitrification reactor with an alternating aerobic and anoxic environment.
  • the final stage is a secondary clarifier NKB, in which the solution is separated from the activated sludge again.
  • the cleaned wastewater leaves the plant via the outlet, while the activated sludge that is deposited is pumped back into the anaerobic antechamber AVB via a sludge return Scotland and thus remains largely in the plant.
  • Excess sludge US is withdrawn from the plant via a drain at the secondary clarifier NKB.
  • FIG. 3 shows a specially designed three-phase submerged reactor 3PSR, which is used to carry out the method for biological treatment of waste water described with reference to FIG.
  • a submerged disc immersion body 2 is rotatably mounted about its axis of rotation 3.
  • the inside of the reactor vessel 1 is vertically between the Discs of the disc diving body 2 extending T-rods 4 divided into a first compartment KI and a second compartment KII.
  • the dividing bars 4 are each anchored in an upper dividing wall 5 and a lower dividing wall 6.
  • An inlet 7 for raw waste water opens into the lower part of the first compartment KI.
  • a first drain 8 is provided for the solution.
  • a return line 9 opens into the lower part of the second compartment KII for reintroduction of the solution nitrified separately outside the reactor.
  • a second outlet 10 is provided for the cleaned waste water.
  • an outlet 11 for excess sludge is arranged at the bottom of the reactor vessel 1.
  • a sludge barrier 12 is arranged below the inlet 7, which reaches close to the circumference of the disc diving body 2.
  • the mixing of the wastewater to be cleaned and the activated sludge suspended in this in the lower part of the reactor are carried out by mixing shafts 14 and 15, which are arranged horizontally below the disc immersion body 2.
  • an additional disc diving body 16 is arranged in the upper part of the second compartment KII. Its axis of rotation 17 runs parallel to the axis of rotation 3 of the submerged immersion body 2 and is arranged approximately at the level of the reactor vessel 1.
  • the discs of this additional disc The diving body 16 are thus semi-submerged and partially overlap with the disks of the submerged disc diving body 2.
  • the semi-submerged additional diving body 16 and the submerged disc diving body 2 both rotate in the same counterclockwise direction. While the disc diving body ⁇ * only makes one revolution about every 8 hours, the additional disc diving body 16 rotates comparatively quickly at one to two revolutions per minute.
  • the first chemoorganotrophic biocenosis I is located on the submerged disc immersion body 2 - compare FIG. 4. Primary and excess sludge settles in the lower region of the reactor. A third fining biocenosis III is located on the discs of the additional disc diving body 16.
  • the division of the interior of the reactor by means of the separating rods 4, between which the disks of the disk immersion body 2 rotate, serves for environmental zoning, as is shown in FIG. 5.
  • Anaerobic environment prevails in the first compartment KI.
  • the chemoorganotrophic biocenosis I is subject to a cyclic change from anaerobic (approx. 3 hours), anoxic (approx. 3 hours) and aerobic (approx. 2 Hours) conditions.
  • FIG. 1 A second technical implementation of the method for biological treatment of waste water shown in FIG. 1 is shown in FIG.
  • the core of this plant is the three-phase submerged reactor 3PSR described above with reference to FIGS. 3, 4 and 5.
  • the plant comprises a conventional fixed bed nitrification reactor NIR 1 , which serves as a nitrification stage, and a secondary settling tank NKB '.
  • NIR 1 a conventional fixed bed nitrification reactor
  • NKB ' secondary settling tank
  • the incoming raw wastewater reaches the lower region of the anaerobic first comparator KII of the 3PSR reactor via the inlet 7 (cf. FIG. 3) and flows upwards between the disks of its disc immersion body 2.
  • the wastewater comes into contact with the biocenosis I under anaerobic conditions.
  • the cleaned wastewater solution leaves the 3PSR reactor through its second outlet 10 above.

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  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (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)
EP90910545A 1989-07-28 1990-07-24 Verfahren zur biologischen behandlung von abwasser und anlage sowie reaktor zur durchführung des verfahrens Withdrawn EP0484352A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3925091 1989-07-28
DE19893925091 DE3925091A1 (de) 1989-07-28 1989-07-28 Verfahren zur biologischen behandlung von abwasser und anlage sowie reaktor zur durchfuehrung des verfahrens

Publications (1)

Publication Number Publication Date
EP0484352A1 true EP0484352A1 (de) 1992-05-13

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EP90910545A Withdrawn EP0484352A1 (de) 1989-07-28 1990-07-24 Verfahren zur biologischen behandlung von abwasser und anlage sowie reaktor zur durchführung des verfahrens

Country Status (9)

Country Link
US (1) US5281335A (xx)
EP (1) EP0484352A1 (xx)
JP (1) JPH04506926A (xx)
AU (1) AU632154B2 (xx)
CA (1) CA2059638A1 (xx)
DD (1) DD296668A5 (xx)
DE (1) DE3925091A1 (xx)
HU (1) HUT69504A (xx)
WO (1) WO1991001948A1 (xx)

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CA2059638A1 (en) 1991-01-29
DE3925091C2 (xx) 1993-09-23
HU905462D0 (en) 1992-06-29
US5281335A (en) 1994-01-25
AU6031490A (en) 1991-03-11
JPH04506926A (ja) 1992-12-03
DE3925091A1 (de) 1991-01-31
AU632154B2 (en) 1992-12-17
WO1991001948A1 (de) 1991-02-21
DD296668A5 (de) 1991-12-12
HUT69504A (en) 1995-09-28

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