WO2017037254A1 - Method for treating industrial wastewater containing organic compounds - Google Patents

Method for treating industrial wastewater containing organic compounds Download PDF

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Publication number
WO2017037254A1
WO2017037254A1 PCT/EP2016/070758 EP2016070758W WO2017037254A1 WO 2017037254 A1 WO2017037254 A1 WO 2017037254A1 EP 2016070758 W EP2016070758 W EP 2016070758W WO 2017037254 A1 WO2017037254 A1 WO 2017037254A1
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WO
WIPO (PCT)
Prior art keywords
permeate
membrane separation
nanofiltration
cooling
stream
Prior art date
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PCT/EP2016/070758
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German (de)
French (fr)
Inventor
Holger Thielert
Kerstin STENZEL
Original Assignee
Thyssenkrupp Industrial Solutions Ag
Thyssenkrupp 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 Thyssenkrupp Industrial Solutions Ag, Thyssenkrupp Ag filed Critical Thyssenkrupp Industrial Solutions Ag
Priority to CN201680051319.4A priority Critical patent/CN108367955B/en
Publication of WO2017037254A1 publication Critical patent/WO2017037254A1/en

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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/029—Multistep processes comprising different kinds of membrane processes selected from reverse osmosis, hyperfiltration or nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/16—Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/12—Addition of chemical agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2649—Filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2676—Centrifugal separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2688—Biological processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/025—Permeate series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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    • 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
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C02F11/127—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering by centrifugation
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • C02F2101/101—Sulfur compounds
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/166—Nitrites
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • 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
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    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • 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
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/14—NH3-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/15—N03-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/046—Recirculation with an external loop
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/22—Activated sludge processes using circulation pipes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • C02F3/302—Nitrification and denitrification treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention relates to a process for the treatment of industrial wastewater containing organic compounds.
  • the industrial waste water is subjected to a biological purification, in which in the industrial wastewater containing impurities are decomposed by bacteria.
  • sludge is separated from the biologically at least partially purified or pre-cleaned wastewater using at least one membrane separation plant.
  • the membrane separation plant can be a plant for ultrafiltration.
  • WO 2012/139917 A2 deals with such a generic method, in which coking effluent, which is loaded, inter alia, with nitrogen compounds, cyanides, phenols and sulfides, is purified in multiple stages by biological and chemical processes.
  • the coking plant effluent is largely freed from pollutants that inhibit nitrification in the multi-stage biological purification in a detoxification reactor. This is followed by a first membrane filtration whose permeate stream is purified by nitrification and subsequent denitrification and post-aeration.
  • suitable detoxification reactor or nitrification reactor is described in DE 198 42 332 B4.
  • the permeate stream of the first membrane filtration is purified by nitrification and subsequent denitrification and subsequent aeration, wherein a second ultrafiltration takes place on the denitrification in a clarifier.
  • the permeate obtained as part of the second ultrafiltration can be discharged into water in accordance with the limits of the German "Ordinance on the requirements for the discharge of waste water into waters - Appendix 46 Coal Coking (BGBl I 2004, 1 167-1 168)".
  • WO 94/03402 A1 describes a method for the biological treatment of wastewater, in which three stages are provided for the reduction of solid fractions, wherein liquid from the third stage of degradation is usable as flushing liquid for toilets.
  • the present invention has for its object to provide a method for the treatment of industrial waste water containing organic compounds, which is characterized by a particularly low environmental impact.
  • the second ultrafiltration, permeate is not derived as purified water and discharged in liquid form to the environment, but a material use is supplied and so a wastewater-free process management is carried out the withdrawn from the membrane separation plant permeate is at least partially fed to a metal production and / or metal processing process and to Cooling of slag is used, wherein at least a portion of the residual substances contained in the permeate remain after cooling on the slag.
  • the permeate withdrawn from the membrane separation plant can be used for different purposes and for this purpose also by means of further membrane separation processes, e.g. Nanofiltration, reverse osmosis, etc. can be divided into different pure or provided with different pollutants streams.
  • the entire permeate withdrawn from the membrane separation plant to a metal production and / or metal processing process in which slag is formed and the optionally further divided and treated permeate is used to cool the slag, at least a portion of which contained in the permeate Residuals remain on the slag after cooling.
  • the slag is then disposed of together with the residues deposited thereon as a solid, and depending on the nature and degree of impurities in addition to a landfill of slag and a technical use can be considered.
  • At least a partial stream of the withdrawn from the membrane separation plant permeate is subjected to a further treatment. It is provided according to a preferred embodiment of the invention that the withdrawn from the membrane separation plant permeate is at least partially subjected to reverse osmosis and divided into a reverse osmosis permeate stream and a reverse osmosis retentate, wherein the reverse osmosis permeate a has high purity and can be used for relatively demanding industrial purposes due to the low level of pollutants.
  • the reverse osmosis permeate stream can be used, for example, as treated process water (make-up water).
  • the treated process water can be used for gas scrubbing, whereby subsequently the industrial waste water to be treated is produced and a total cycle takes place.
  • the high-purity reverse osmosis permeate stream as cooling water in an open cooling water system, in which case no excessive contamination of the cooling water system or excessive concentration of pollutants can be observed even if the cooling water evaporates.
  • membranes is provided according to a preferred embodiment of the invention that the withdrawn from the membrane separation plant permeate added before performing the reverse osmosis to reduce the pH with acid becomes.
  • sulfuric acid may be added in an appropriate amount to the permeate stream withdrawn from the membrane separation plant.
  • the reverse osmosis With the reverse osmosis, inter alia oxidizable organic ingredients (COD fraction), nitrogen components and salts such as chlorides are retained, so that the reverse osmosis permeate stream can be used as described.
  • the enriched reverse osmosis retentate stream is provided with a correspondingly higher proportion of oxidizable organic ingredients (COD) nitrogen and chlorides than the previously withdrawn from the membrane separation plant permeate. It is therefore expedient to supply the reverse osmosis retentate stream to a further division.
  • the reverse osmosis retentate stream is subjected to nanofiltration and split into a nanofiltration permeate stream and a nanofiltration retentate stream.
  • the nano Filtration permeate stream can be used, for example, as previously described for cooling slag.
  • the oxidizable organic ingredients (COD) and the nitrogen components can be retained to a large extent.
  • chlorides and other salts enter the nanofiltration permeate stream, with the preferred use of the nanofiltration permeate stream for cooling slag leaving the chloride-containing salt residues on the slag.
  • the slag with the salt residues can easily be disposed of or used again.
  • the nanofiltration-retentate stream can be fed to a flocculation, precipitation and activated carbon.
  • a flocculation and precipitation step for example, oxidizable organic ingredients (COD) can be removed to a large extent, even if they could not previously be degraded by the biological purification.
  • COD oxidizable organic ingredients
  • the remaining after the flocculation, precipitation and activated carbon stage water can be supplied to the upstream biological purification.
  • the sludge produced in the precipitation and activated carbon treatment is preferably collected in a sedimentation tank, in which case a liquid phase accumulating in the sedimentation tank can be withdrawn.
  • the liquid phase can be supplied, for example, to the nanofiltration permeate stream, again to the flocculation, precipitation and activated carbon stage or to the upstream biological purification.
  • the sludge deposited in the sedimentation tank is preferably fed to a centrifuge to effect further dewatering.
  • different sludges can be treated in each case by associated centrifuges or alternatively by a common centrifuge in the entire process, in the latter case the material flows are expediently separated by switching from each other.
  • the centrifuge concentrate can be returned to the sedimentation tank.
  • the resulting sludge can be added together with the feed coal into the coke oven batteries in order to achieve a further chemical reaction in a largely closed cycle.
  • the present invention can be carried out following a biological purification process consisting of detoxification, first membrane filtration (eg ultrafiltration), nitrification, denitrification, post-aeration and second membrane filtration (eg ultrafiltration) with a nitrification and a denitrification, as is from WO 2012/139917 A2 is known.
  • a biological purification process consisting of detoxification, first membrane filtration (eg ultrafiltration), nitrification, denitrification, post-aeration and second membrane filtration (eg ultrafiltration) with a nitrification and a denitrification, as is from WO 2012/139917 A2 is known.
  • As industrial wastewater then coking plant wastewater is fed which contains, among other nitrogen compounds, cyanides, phenols and sulfides.
  • the coking plant effluent is then fed to a multistage biological purification, for which the nitrification-inhibiting pollutants are at least partially removed in a detoxification reactor, followed by a first membrane filtration and wherein the permeate stream of the first membrane filtration is purified by nitrification and subsequent denitrification.
  • the content of ammonium and / or nitrate and / or nitrite is determined with a measuring probe between two successive process steps, wherein this process step generally has a fundamental independent inventive significance in connection with a biological purification.
  • the invention is based in this context on the finding that at various points in the biological purification a sufficiently low sludge content is present, which allows a probe measurement. This is especially true for the industrial wastewater fed to the biological purification before it is mixed with a bacteria-containing sludge. Furthermore, a measurement with probes may also be possible in particular if, after a purification step, a membrane-technical sludge separation has taken place.
  • the ammonium content can be carried out with a potentiometric measurement by means of ion-selective electrons.
  • the nitrate and nitrite content can be determined, for example, with a probe according to the two-beam UV adsorption process.
  • the industrial wastewater may in particular be coking wastewater, which is contaminated inter alia with nitrogen compounds, cyanides, phenols and sulfides. Other oxidizable organic ingredients may be included.
  • the industrial wastewater is via a collection tank 1 via an inlet line 2 of a biological purification fed.
  • a supply device 3 for a gaseous oxidizing agent, for example air, is provided.
  • a detoxification reactor 4 which may be, for example, a jet zone loop reactor (SZR reactor).
  • SZR reactor jet zone loop reactor
  • the detoxification reactor 4 has an upper reaction zone, a lower mass transport zone and a recirculation device 5 for returning liquid.
  • a pipe is arranged in each case. This serves in each case to support the formation of a fluid circulation of the loop flow.
  • a two-fluid nozzle is further provided, is mixed in the fluid from the return device 5 and the supply line 2 with the air taken from the feeder 3 and turbulently turbulent.
  • the detoxification reactor 4 is followed by a first ultrafiltration unit 6. With the first filtration plant 6, the sludge contained in the stream withdrawn from the detoxification reactor 4 is separated and recycled, while the permeate of the first ultrafiltration plant 6 is fed via an intermediate tank 7 to a nitrification reactor 8 as a second stage of biological purification.
  • the wastewater stream then passes through a basin 9, which is divided into denitrification and post-ventilation, to a second ultrafiltration plant 10.
  • the after-aeration is aerated with air.
  • the sludge deposited as the retentate of the second ultrafiltration unit 10 is passed back to the nitrification reactor 8, the sludge from the second ultrafiltration system 10 withdrawn permeate first in a mixing tank 1 1 with acid, for example, sulfuric acid (H 2 SO 4 ) and subsequently passed to a reverse osmosis system 12.
  • acid for example, sulfuric acid (H 2 SO 4 )
  • a reverse osmosis system 12 salts such as chlorides, oxidizable organic ingredients and nitrogen components are retained.
  • the withdrawn from the reverse osmosis system 12 reverse osmosis permeate stream 13 has a high purity and can be used for example as make-up water for an open cooling system or otherwise as process water (make-up water).
  • the enriched reverse osmosis retentate stream 14 is fed to a nanofiltration plant 15 and split into a nanofiltration permeate stream 16 and a nanofiltration retentate stream 17.
  • oxidizable organic ingredients (COD components) and nitrogen components can be retained.
  • Salts such as chlorides enter the nanofiltration permeate stream 16 so that the nanofiltration permeate stream 16 has a high chloride content.
  • slag cooling may preferably be provided in a steel mill. The salt residues remain on the slag. The slag with the salt residues can then be easily disposed of and reused.
  • the nanofiltration retentate stream 17 is fed to a flocculation, precipitation and activated carbon stage 18.
  • the purified in the flocculation, precipitation and activated carbon stage 18 water can then be supplied via a connecting line 19 of the upstream biological purification, in particular the nitrification reactor 8.
  • the resulting in the flocculation and precipitation stage sludge is transferred into a sedimentation potion 20, wherein a resulting liquid phase via a corresponding line 21 a, 21 b, 21 c the nanofiltration permeate 16 and / or the flocculation and precipitation stage 18 and / or the connection line 19 can be supplied.
  • the resulting in the entire process sludge can be dehydrated by centrifuges 22 in a known manner.
  • a common centrifuge 22 can be used, which is then to switch between the streams.
  • the sponges dewatered by the centrifuge may be added together with the feed coal of a coke oven battery.
  • the ammonium and nitrite content can be determined at suitable locations with a simple measuring probe. Measurement by means of measuring probes is possible if previously a separation of sludge took place in a membrane separation process. The use of such a measuring probe is possible, for example, in the collecting tank 1, the intermediate tank 7, the mixing tank 11, the reverse osmosis permeate stream 13, the reverse osmosis retentate stream 14, the nanofiltration permeate stream 16 and the nanofiltration retentate stream 17.

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Abstract

The invention relates to a method for treating industrial wastewater containing organic compounds. The industrial wastewater undergoes a biological purification process (4, 8) in which impurities contained in the industrial wastewater are decomposed using bacteria, and subsequently sludge is separated from the wastewater which has been at least partly biologically purified using at least one membrane separation system (6, 10, 12, 15). According to the invention, permeate drawn from the membrane separation system (6, 10, 12, 15) is not discharged as purified water and dispensed in liquid form into the environment but rather supplied for utilization, whereby a wastewater-free process is carried out. The permeate drawn from the membrane separation system (6, 10, 12, 15) is at least partly supplied to a metal production and/or metal machining process and used for cooling slag. At least one part of the residual material contained in the permeate remains on the slag after the cooling process.

Description

Verfahren zur Behandlung von organische Verbindungen enthaltendem  Process for the treatment of organic compounds containing
Industrieabwasser  industrial wastewater
Beschreibung description
TECHNISCHES GEBIET TECHNICAL AREA
Die Erfindung betrifft ein Verfahren zur Behandlung von organische Verbindungen enthaltendem Industrieabwasser. Dabei wird das Industrieabwasser einer biologischen Reinigung unterzogen, bei der in dem Industrieabwasser enthaltende Verunreinigungen durch Bakterien zersetzt werden. Nachfolgend wird aus dem biologisch zumindest teilweise gereinigten bzw. vorgereinigten Abwasser Schlamm unter Einsatz zumindest einer Membrantrennanlage abgetrennt. Bei der Membrantrennanlage kann es sich um eine Anlage zur Ultrafiltration handeln. Bezüglich der Begriffsdefinition sowie der Charakterisierung und Unterscheidung verschiedener Membrantrennverfahren wird auf die Veröffentlichung W. Samhaber "Erfahrungen und Anwendungspotential der Nanofiltration", VDI Wissensforum „Membrantechnik in der Prozessindustrie", Hannover, November 2007, verwiesen.  The invention relates to a process for the treatment of industrial wastewater containing organic compounds. The industrial waste water is subjected to a biological purification, in which in the industrial wastewater containing impurities are decomposed by bacteria. Subsequently, sludge is separated from the biologically at least partially purified or pre-cleaned wastewater using at least one membrane separation plant. The membrane separation plant can be a plant for ultrafiltration. With regard to the definition of terms as well as the characterization and differentiation of different membrane separation processes, reference is made to the publication W. Samhaber "Experiences and Application Potential of Nanofiltration", VDI Wissensforum "Membrane Technology in the Process Industry", Hannover, November 2007.
HINTERGRUND BACKGROUND
In Industrieanlagen wie Kokereien, Stahlwerken und Chemiebetrieben fallen hochbelastete Abwässer an. Bei Kokereien entstehen solche hochbelasteten Kokereiabwässer beispielsweise bei der Gasbehandlung.  Industrial plants such as coking plants, steelworks and chemical plants generate highly contaminated wastewater. For coking plants, such highly polluted coking plant effluents are produced, for example, during gas treatment.
Die WO 2012/139917 A2 beschäftigt sich mit einem solchen gattungsgemäßen Verfahren, bei dem Kokereiabwasser, welches unter anderem mit Stickstoffverbindungen, Cyaniden, Phenolen und Sulfiden belastet ist, mehrstufig durch biologische und chemische Prozesse gereinigt wird. Das Kokereiabwasser wird bei der mehrstufigen biologischen Reinigung in einem Entgiftungsreaktor größtenteils von Schadstoffen befreit, die die Nitrifikation hemmen. Nachfolgend erfolgt eine erste Membranfiltration dessen Permeatstrom durch Nitrifikation und nachfolgende Denitrifikation sowie Nachbelüftung gereinigt wird. Die bevorzugte Ausgestaltung eines für das bekannte Verfahren geeigneten Entgiftungsreaktors bzw. Nitrifikationsreaktors ist in der DE 198 42 332 B4 beschrieben. WO 2012/139917 A2 deals with such a generic method, in which coking effluent, which is loaded, inter alia, with nitrogen compounds, cyanides, phenols and sulfides, is purified in multiple stages by biological and chemical processes. The coking plant effluent is largely freed from pollutants that inhibit nitrification in the multi-stage biological purification in a detoxification reactor. This is followed by a first membrane filtration whose permeate stream is purified by nitrification and subsequent denitrification and post-aeration. The preferred embodiment of one for the known method suitable detoxification reactor or nitrification reactor is described in DE 198 42 332 B4.
Bei dem aus der WO 2012/139917 A2 bekannten gattungsgemäßen Verfahren wird der Permeatstronn der ersten Membranfiltration durch Nitrifikation und nachfolgende Denitrifikation und Nachbelüftung gereinigt, wobei auf die Denitrifikation in einem Klärbecken eine zweite Ultrafiltration erfolgt. Das im Rahmen der zweiten Ultrafiltration gewonnene Permeat kann gemäß den Grenzwerten der deutschen„Verordnung über Anforderungen an das Einleiten von Abwasser in Gewässer - Anhang 46 Steinkohleverkokung (BGBl I 2004, 1 167-1 168)" - in Gewässer eingeleitet werden. In the generic method known from WO 2012/139917 A2, the permeate stream of the first membrane filtration is purified by nitrification and subsequent denitrification and subsequent aeration, wherein a second ultrafiltration takes place on the denitrification in a clarifier. The permeate obtained as part of the second ultrafiltration can be discharged into water in accordance with the limits of the German "Ordinance on the requirements for the discharge of waste water into waters - Appendix 46 Coal Coking (BGBl I 2004, 1 167-1 168)".
Die WO 94/03402 A1 beschreibt ein Verfahren zur biologischen Behandlung von Abwasser, bei welchem drei Stufen zum Abbau von Feststoffanteilen vorgesehen sind, wobei Flüssigkeit aus der dritten Abbaustufe als Spülflüssigkeit für Toiletten verwendbar ist. WO 94/03402 A1 describes a method for the biological treatment of wastewater, in which three stages are provided for the reduction of solid fractions, wherein liquid from the third stage of degradation is usable as flushing liquid for toilets.
BESCHREIBUNG DER ERFINDUNG DESCRIPTION OF THE INVENTION
Vor diesem Hintergrund liegt der vorliegenden Erfindung die Aufgabe zugrunde, ein Verfahren zur Behandlung von organische Verbindungen enthaltendem Industrieabwasser anzugeben, welches sich durch eine besonders geringe Umweltbelastung auszeichnet.  Against this background, the present invention has for its object to provide a method for the treatment of industrial waste water containing organic compounds, which is characterized by a particularly low environmental impact.
Gegenstand der Erfindung und Lösung der Aufgabe ist ein Verfahren gemäß Patentanspruch 1 . Object of the invention and solution of the problem is a method according to claim 1.
Ausgehend von einem gattungsgemäßen Verfahren ist erfindungsgemäß vorgesehen, dass das aus der Membrantrennanlage, der zweiten Ultrafiltration, abgezogene Permeat nicht als gereinigtes Wasser abgeleitet und in flüssiger Form an die Umgebung abgegeben wird, sondern einer stofflichen Nutzung zugeführt wird und so eine abwasserfreie Verfahrensführung erfolgt, wobei das aus der Membrantrennanlage abgezogene Permeat zumindest teilweise einem Metallerzeugungs- und/oder Metallverarbeitungsprozess zugeführt wird und zur Kühlung von Schlacke eingesetzt wird, wobei zumindest ein Teil der in dem Permeat enthaltenden Reststoffe nach der Kühlung auf der Schlacke verbleiben. Starting from a generic method is provided according to the invention that the withdrawn from the membrane separation plant, the second ultrafiltration, permeate is not derived as purified water and discharged in liquid form to the environment, but a material use is supplied and so a wastewater-free process management is carried out the withdrawn from the membrane separation plant permeate is at least partially fed to a metal production and / or metal processing process and to Cooling of slag is used, wherein at least a portion of the residual substances contained in the permeate remain after cooling on the slag.
Ausgehend vom Grundkonzept der stofflichen Nutzung können verschiedene Ansätze verfolgt werden, wobei das aus der Membrantrennanlage, der zweiten Ultrafiltration, abgezogene Permeat zu unterschiedlichen Zwecken genutzt werden kann und dafür auch mit Hilfe weiterer Membrantrennverfahren, z.B. Nanofiltration, Umkehrosmose etc. in unterschiedlich reine bzw. mit unterschiedlichen Schadstoffen versehene Stoffströme aufgeteilt werden kann. Starting from the basic concept of material use, various approaches can be followed, wherein the permeate withdrawn from the membrane separation plant, the second ultrafiltration, can be used for different purposes and for this purpose also by means of further membrane separation processes, e.g. Nanofiltration, reverse osmosis, etc. can be divided into different pure or provided with different pollutants streams.
Beispielsweise ist es auch möglich, das gesamte aus der Membrantrennanlage abgezogene Permeat einem Metallerzeugungs- und/oder Metallverarbeitungsprozess zuzuführen, bei dem Schlacke entsteht und das gegebenenfalls weiter aufgeteilte und behandelte Permeat zur Kühlung der Schlacke eingesetzt wird, wobei zumindest ein Teil der in dem Permeat enthaltenden Reststoffe nach der Kühlung auf der Schlacke verbleiben. Die Schlacke wird dann zusammen mit den darauf abgeschiedenen Reststoffen als Feststoff entsorgt, wobei je nach Art und Grad der Verunreinigungen neben einer Deponierung der Schlacke auch eine technische Nutzung in Erwägung gezogen werden kann. For example, it is also possible to supply the entire permeate withdrawn from the membrane separation plant to a metal production and / or metal processing process in which slag is formed and the optionally further divided and treated permeate is used to cool the slag, at least a portion of which contained in the permeate Residuals remain on the slag after cooling. The slag is then disposed of together with the residues deposited thereon as a solid, and depending on the nature and degree of impurities in addition to a landfill of slag and a technical use can be considered.
Wenn das gesamte Permeat in der beschriebenen Weise zur Kühlung von Schlacke eingesetzt wird, ergibt sich eine besonders einfache Verfahrensführung. If the entire permeate is used in the manner described for the cooling of slag, results in a particularly simple process.
Gemäß einer alternativen Ausgestaltung der Erfindung wird zumindest ein Teilstrom des von der Membrantrennanlage abgezogenen Permeates einer weiteren Behandlung unterzogen. Dabei ist gemäß einer bevorzugten Ausgestaltung der Erfindung vorgesehen, dass das aus der Membrantrennanlage abgezogene Permeat zumindest teilweise einer Umkehrosmose unterzogen und in einen Umkehrosmose-Permeatstrom und einen Umkehrosmose- Retentatstrom aufgeteilt wird, wobei der Umkehrosmose-Permeatstrom eine hohe Reinheit aufweist und aufgrund des nur noch geringen Anteils an Schadstoffen auch für relativ anspruchsvolle industrielle Zwecke eingesetzt werden kann. Der Umkehrosmose-Permeatstronn kann beispielsweise als aufbereitetes Prozesswasser (Make-up-Wasser) genutzt werden. Beispielsweise kann in einer Kokereianlage das aufbereitete Prozesswasser für eine Gaswäsche eingesetzt werden, wobei nachfolgend das zu behandelnde Industrieabwasser entsteht und insgesamt ein Kreislauf erfolgt. Darüber hinaus ist es beispielsweise auch möglich, den eine hohe Reinheit aufweisenden Umkehrosmose- Permeatstronn als Kühlwasser in einem offenen Kühlwassersystem einzusetzen, wobei dann auch bei einem Verdampfen des Kühlwassers keine übermäßige Verschmutzung des Kühlwassersystems oder eine übermäßige Aufkonzentrierung von Schadstoffen beobachtet werden kann. According to an alternative embodiment of the invention, at least a partial stream of the withdrawn from the membrane separation plant permeate is subjected to a further treatment. It is provided according to a preferred embodiment of the invention that the withdrawn from the membrane separation plant permeate is at least partially subjected to reverse osmosis and divided into a reverse osmosis permeate stream and a reverse osmosis retentate, wherein the reverse osmosis permeate a has high purity and can be used for relatively demanding industrial purposes due to the low level of pollutants. The reverse osmosis permeate stream can be used, for example, as treated process water (make-up water). For example, in a coking plant, the treated process water can be used for gas scrubbing, whereby subsequently the industrial waste water to be treated is produced and a total cycle takes place. Moreover, it is also possible, for example, to use the high-purity reverse osmosis permeate stream as cooling water in an open cooling water system, in which case no excessive contamination of the cooling water system or excessive concentration of pollutants can be observed even if the cooling water evaporates.
Hinsichtlich der sich insbesondere bei Kokereiabwässern ergebenden chemischen Zusammensetzung und der für eine Umkehrosmose im Rahmen der Erfindung vorgesehenen Membranen ist gemäß einer bevorzugten Weiterbildung der Erfindung vorgesehen, dass das aus der Membrantrennanlage abgezogene Permeat vor der Durchführung der Umkehrosmose zur Reduzierung des pH-Wertes mit Säure versetzt wird. Beispielsweise kann dem aus der Membrantrennanlage abgezogenen Permeatstrom Schwefelsäure in einer geeigneten Menge zugegeben werden. With regard to the resulting in particular in coking plant effluent chemical composition and provided for a reverse osmosis in the invention membranes is provided according to a preferred embodiment of the invention that the withdrawn from the membrane separation plant permeate added before performing the reverse osmosis to reduce the pH with acid becomes. For example, sulfuric acid may be added in an appropriate amount to the permeate stream withdrawn from the membrane separation plant.
Mit der Umkehrosmose werden u.a. oxidierbare organische Inhaltstoffe (CSB- Anteil), Stickstoffkomponenten und Salze wie beispielsweise Chloride zurückgehalten, so dass der Umkehrosmose-Permeatstrom wie beschrieben verwendet werden kann. Der angereicherte Umkehrosmose-Retentatstrom ist mit einem entsprechend höheren Anteil an oxidierbaren organischen Inhaltstoffen (CSB) Stickstoff und Chloriden versehen als das zuvor aus der Membrantrennanlage abgezogene Permeat. Es ist deshalb zweckmäßig, dem Umkehrosmose-Retentatstrom einer weiteren Aufteilung zuzuführen. Dazu ist gemäß einer bevorzugten Ausgestaltung vorgesehen, dass der Umkehrosmose-Retentatstrom einer Nanofiltration unterzogen und in einen Nanofiltration- Permeatstrom und einen Nanofiltration-Retentatstrom aufgeteilt wird. Der Nano- filtrations-Permeatstronn kann beispielsweise wie zuvor beschrieben zur Kühlung von Schlacke verwendet werden. With the reverse osmosis, inter alia oxidizable organic ingredients (COD fraction), nitrogen components and salts such as chlorides are retained, so that the reverse osmosis permeate stream can be used as described. The enriched reverse osmosis retentate stream is provided with a correspondingly higher proportion of oxidizable organic ingredients (COD) nitrogen and chlorides than the previously withdrawn from the membrane separation plant permeate. It is therefore expedient to supply the reverse osmosis retentate stream to a further division. For this purpose, according to a preferred embodiment, the reverse osmosis retentate stream is subjected to nanofiltration and split into a nanofiltration permeate stream and a nanofiltration retentate stream. The nano Filtration permeate stream can be used, for example, as previously described for cooling slag.
Mit der Nanofiltration können insbesondere die oxidierbaren organischen Inhaltstoffe (CSB) sowie die Stickstoffkomponenten zu einem großen Teil zurückgehalten werden. Chloride und andere Salze gelangen dagegen in den Nano- filatration-Permeatstrom, wobei bei der bevorzugten Nutzung des Nanofiltration- Permeatstroms zur Kühlung von Schlacke die chloridhaltigen Salzrückstände auf der Schlacke zurückbleiben. Die Schlacke mit den Salzrückständen kann ohne weiteres entsorgt oder weiter verwendet werden. With nanofiltration, in particular, the oxidizable organic ingredients (COD) and the nitrogen components can be retained to a large extent. On the other hand, chlorides and other salts enter the nanofiltration permeate stream, with the preferred use of the nanofiltration permeate stream for cooling slag leaving the chloride-containing salt residues on the slag. The slag with the salt residues can easily be disposed of or used again.
Der Nanofiltration-Retentatstrom kann einer Flockungs-, Fällungs- und Aktivkohle zugeführt werden. Mit einer solchen Flockungs- und Fällungsstufe können beispielsweise oxidierbare organische Inhaltstoffe (CSB) zu einem großen Teil entfernt werden, auch wenn diese zuvor nicht durch die biologische Reinigung abgebaut werden konnten. The nanofiltration-retentate stream can be fed to a flocculation, precipitation and activated carbon. With such a flocculation and precipitation step, for example, oxidizable organic ingredients (COD) can be removed to a large extent, even if they could not previously be degraded by the biological purification.
Das nach der Flockungs-, Fällungs- und Aktivkohlestufe zurückbleibende Wasser kann der vorgelagerten biologischen Reinigung zugeführt werden. The remaining after the flocculation, precipitation and activated carbon stage water can be supplied to the upstream biological purification.
Der bei der Fällung und Aktivkohlebehandlung entstehende Schlamm wird vorzugsweise in einem Sedimentationstank gesammelt, wobei dann eine in dem Sedimentationstank anfallende Flüssigphase abgezogen werden kann. Die Flüssigphase kann beispielsweise dem Nanofiltration-Permeatstrom, erneut der Flockungs-, Fällungs- und Aktivkohlestufe oder der vorgelagerten biologischen Reinigung zugeführt werden. The sludge produced in the precipitation and activated carbon treatment is preferably collected in a sedimentation tank, in which case a liquid phase accumulating in the sedimentation tank can be withdrawn. The liquid phase can be supplied, for example, to the nanofiltration permeate stream, again to the flocculation, precipitation and activated carbon stage or to the upstream biological purification.
Der in dem Sedimentationstank abgesetzte Schlamm wird vorzugsweise einer Zentrifuge zugeführt, um eine weitere Entwässerung zu bewirken. Grundsätzlich können bei der gesamten Verfahrensführung unterschiedliche Schlämme jeweils durch zugeordnete Zentrifugen oder alternativ durch eine gemeinsame Zentrifuge behandelt werden, wobei im letzten Fall die Stoffströme zweckmaßigerweise durch ein Umschalten voneinander zu trennen sind. Das Zentrifugenzentrat kann in den Sedimentationstank zurückgeführt werden. The sludge deposited in the sedimentation tank is preferably fed to a centrifuge to effect further dewatering. In principle, different sludges can be treated in each case by associated centrifuges or alternatively by a common centrifuge in the entire process, in the latter case the material flows are expediently separated by switching from each other. The centrifuge concentrate can be returned to the sedimentation tank.
Wenn die Industrieabwässer als Kokereiabwässer in einer Kokerei gebildet werden, können die anfallenden Schlämme gemeinsam mit der Einsatzkohle in die Koksofenbatterien gegeben werden, um in einem weitgehend geschlossenen Kreislauf eine weitere chemische Umsetzung zu erreichen. When the industrial wastewater is produced as coke oven effluent in a coking plant, the resulting sludge can be added together with the feed coal into the coke oven batteries in order to achieve a further chemical reaction in a largely closed cycle.
Die vorliegende Erfindung kann insbesondere im Anschluss an ein biologisches Reinigungsverfahren bestehend aus Entgiftung, erste Membranfiltration (z. B. Ultrafiltration), Nitrifikation, Denitrifikation, Nachbelüftung und zweiter Membranfiltration (z. B. Ultrafiltration) mit einer Nitrifikation und einer Denitrifikation erfolgen, wie es aus der WO 2012/ 139917 A2 bekannt ist. Als Industrieabwasser wird dann Kokereiabwasser zugeführt, welches unter anderem Stickstoffverbindungen, Cyanide, Phenole und Sulfide enthält. Das Kokereiabwasser wird dann einer mehrstufigen biologischen Reinigung zugeführt, wozu in einem Entgiftungsreaktor zumindest teilweise die eine Nitrifikation hemmenden Schadstoffe entfernt werden, wobei nachfolgend eine erste Membranfiltration erfolgt und wobei der Permeatstrom der ersten Membranfiltration durch Nitrifikation und nachfolgende Denitrifikation gereinigt wird. The present invention can be carried out following a biological purification process consisting of detoxification, first membrane filtration (eg ultrafiltration), nitrification, denitrification, post-aeration and second membrane filtration (eg ultrafiltration) with a nitrification and a denitrification, as is from WO 2012/139917 A2 is known. As industrial wastewater then coking plant wastewater is fed, which contains, among other nitrogen compounds, cyanides, phenols and sulfides. The coking plant effluent is then fed to a multistage biological purification, for which the nitrification-inhibiting pollutants are at least partially removed in a detoxification reactor, followed by a first membrane filtration and wherein the permeate stream of the first membrane filtration is purified by nitrification and subsequent denitrification.
Gemäß einem weiteren Aspekt der vorliegenden Erfindung wird zwischen zwei aufeinanderfolgenden Prozessschritten der Gehalt an Ammonium und/oder Nitrat und/oder Nitrit mit einer Messsonde bestimmt, wobei diesem Verfahrensschritt im Zusammenhang mit einer biologischen Reinigung allgemein eine grundlegende eigenständige erfinderische Bedeutung zukommt. According to a further aspect of the present invention, the content of ammonium and / or nitrate and / or nitrite is determined with a measuring probe between two successive process steps, wherein this process step generally has a fundamental independent inventive significance in connection with a biological purification.
Bisher wurden in Bioreaktoren zur biologischen Reinigung und in nachfolgenden Prozessschritten aufwändige nasschemische Analysen zur Bestimmung des Ammonium- und Nitratgehaltes durchgeführt. Dazu wird ein Teilstrom ausgeschleust und analysiert. Neben hohen Anschaffungs- und Fertigungskosten für die speziellen Anpassungen an die örtlichen Gegebenheiten ergeben sich auch hohe Betriebsmittel- und Wartungskosten. Until now, complex biological wet-chemical analyzes and subsequent process steps have been carried out in bioreactors to determine the ammonium and nitrate content. For this purpose, a partial flow is discharged and analyzed. In addition to high acquisition and Production costs for the special adaptations to the local conditions also result in high operating and maintenance costs.
Im Gegensatz zu einer nasschemischen Analyse ist im Rahmen der Erfindung eine Bestimmung des Ammonium- und/oder Nitratgehaltes mit Messsonden vorgesehen, so dass keine weiteren Chemikalien notwendig sind, und keine weiteren Kosten für Betriebsmittel anfallen. In contrast to a wet-chemical analysis, a determination of the ammonium and / or nitrate content with measuring probes is provided within the scope of the invention, so that no further chemicals are necessary, and no further costs for resources are incurred.
Der Erfindung liegt in diesem Zusammenhang die Erkenntnis zugrunde, dass an verschiedenen Stellen der biologischen Reinigung ein ausreichend geringer Schlammgehalt vorhanden ist, der eine Sondenmessung ermöglicht. Dies gilt insbesondere für das der biologischen Reinigung zugeführte Industrieabwasser, bevor dieses mit einem Bakterien enthaltenden Schlamm gemischt ist. Des Weiteren ist eine Messung mit Sonden auch nachfolgend insbesondere dann möglich, wenn nach einer Reinigungsstufe eine membrantechnische Schlammabtrennung erfolgt ist. Beispielsweise kann der Ammoniumgehalt mit einer potentiometrischen Messung mittels ionenselektiver Elektronen erfolgen. Der Nitrat- sowie der Nitritgehalt kann beispielsweise mit einer Sonde nach dem Zweistrahl-UV-Adsorptionsverfahren bestimmt werden. The invention is based in this context on the finding that at various points in the biological purification a sufficiently low sludge content is present, which allows a probe measurement. This is especially true for the industrial wastewater fed to the biological purification before it is mixed with a bacteria-containing sludge. Furthermore, a measurement with probes may also be possible in particular if, after a purification step, a membrane-technical sludge separation has taken place. For example, the ammonium content can be carried out with a potentiometric measurement by means of ion-selective electrons. The nitrate and nitrite content can be determined, for example, with a probe according to the two-beam UV adsorption process.
FIGURENBESCHREIBUNG DESCRIPTION OF THE FIGURES
Die Erfindung wird nachfolgend anhand einer lediglich ein Ausführungsbeispiel darstellenden Zeichnung erläutert. Die einzige Figur zeigt ein Anlagen- und Verfahrensschema zur Behandlung von organische Verbindungen enthaltendem Industrieabwasser.  The invention will be explained below with reference to a purely illustrative drawing. The sole figure shows a plant and process scheme for the treatment of industrial wastewater containing organic compounds.
DETAILLIERTE BESCHREIBUNG DER FIGUR DETAILED DESCRIPTION OF THE FIGURE
Bei dem Industrieabwasser kann es sich insbesondere um Kokereiabwasser handeln, welches unter anderem mit Stickstoffverbindungen, Cyaniden, Phenolen und Sulfiden belastet ist. Auch weitere oxidierbare organische Inhaltstoffe können enthalten sein. Das Industrieabwasser wird über einen Sammeltank 1 über eine Einlassleitung 2 einer biologischen Reinigung zugeführt. Des Weiteren ist eine Zuführeinrichtung 3 für ein gasförmiges Oxidationsmittel, beispielsweise Luft, vorgesehen. The industrial wastewater may in particular be coking wastewater, which is contaminated inter alia with nitrogen compounds, cyanides, phenols and sulfides. Other oxidizable organic ingredients may be included. The industrial wastewater is via a collection tank 1 via an inlet line 2 of a biological purification fed. Furthermore, a supply device 3 for a gaseous oxidizing agent, for example air, is provided.
Von der Einlassleitung 2 wird das Industrieabwasser einem Entgiftungsreaktor 4 zugeleitet, bei dem es sich beispielsweise um einen Strahlzonen- Schlaufenreaktor (SZR-Reaktor) handeln kann. Der grundlegende Aufbau eines solchen SZR-Reaktors wird in der DE 198 42 332 B4 beschrieben. From the inlet line 2, the industrial waste water is fed to a detoxification reactor 4, which may be, for example, a jet zone loop reactor (SZR reactor). The basic structure of such an SZR reactor is described in DE 198 42 332 B4.
Der Entgiftungsreaktor 4 weist eine obere Reaktionszone, eine untere Stofftransportzone und eine Rückführeinrichtung 5 zur Rückführung von Flüssigkeit auf. In der Reaktionszone und der Stofftransportzone des Entgiftungsreaktors 4 ist jeweils ein Rohr angeordnet. Dieses dient jeweils zur Unterstützung der Ausbildung einer Flüssigkeitszirkulation der Schlaufenströmung. Zwischen den beiden Zonen ist ferner eine Zweistoffdüse vorgesehen, in der Flüssigkeit aus der Rückführeinrichtung 5 sowie der Zuleitung 2 mit der aus der Zuführeinrichtung 3 entnommenen Luft vermischt und turbulent verwirbelt wird. The detoxification reactor 4 has an upper reaction zone, a lower mass transport zone and a recirculation device 5 for returning liquid. In the reaction zone and the mass transport zone of the detoxification reactor 4, a pipe is arranged in each case. This serves in each case to support the formation of a fluid circulation of the loop flow. Between the two zones, a two-fluid nozzle is further provided, is mixed in the fluid from the return device 5 and the supply line 2 with the air taken from the feeder 3 and turbulently turbulent.
Durch in dem Entgiftungsreaktor 4 vorhandene Bakterien werden Cyanide und andere eine Nitrifikation hemmende Schadstoffe biologisch abgebaut. By present in the detoxification reactor 4 bacteria cyanides and other nitrification inhibiting pollutants are biodegraded.
Dem Entgiftungsreaktor 4 ist eine erste Ultrafiltrationsanlage 6 nachgeschaltet. Mit der ersten Filtrationsanlage 6 wird der in dem aus dem Entgiftungsreaktor 4 abgezogenen Strom enthaltende Schlamm abgeschieden und zurückgeführt, während das Permeat der ersten Ultrafiltrationsanlage 6 über einen Zwischentank 7 einem Nitrifikationsreaktor 8 als zweite Stufe der biologischen Reinigung zugeführt wird. The detoxification reactor 4 is followed by a first ultrafiltration unit 6. With the first filtration plant 6, the sludge contained in the stream withdrawn from the detoxification reactor 4 is separated and recycled, while the permeate of the first ultrafiltration plant 6 is fed via an intermediate tank 7 to a nitrification reactor 8 as a second stage of biological purification.
Von dem Nitrifikationsreaktor 8 gelangt der Abwasserstrom dann über ein Becken 9, welches in Denitrifikation und Nachbelüftung unterteilt ist, zu einer zweiten Ultrafiltrationsanlage 10. Die Nachbelüftung wird mit Luft begast. Während der als Retentat der zweiten Ultrafiltrationsanlage 10 abgeschiedene Schlamm zurück zu dem Nitrifikationsreaktor 8 geleitet wird, wird das aus der zweiten Ultrafiltrationsanlage 10 abgezogene Permeat zunächst in einem Mischtank 1 1 mit Säure, beispielsweise Schwefelsäure (H2SO4) versetzt und nachfolgend zu einer Umkehrosmoseanlage 12 geleitet. In der Umkehrosmoseanlage 12 werden Salze wie beispielsweise Chloride, oxidier- bare organische Inhaltsstoffe und Stickstoffkomponenten zurückgehalten. Der aus der Umkehrosmose-Anlage 12 abgezogene Umkehrosmose-Permeatstrom 13 weist eine hohe Reinheit auf und kann beispielsweise als Zusatzwasser für ein offenes Kühlsystem oder auch anderweitig als Prozesswasser (Make-Up- Wasser) genutzt werden. From the nitrification reactor 8, the wastewater stream then passes through a basin 9, which is divided into denitrification and post-ventilation, to a second ultrafiltration plant 10. The after-aeration is aerated with air. While the sludge deposited as the retentate of the second ultrafiltration unit 10 is passed back to the nitrification reactor 8, the sludge from the second ultrafiltration system 10 withdrawn permeate first in a mixing tank 1 1 with acid, for example, sulfuric acid (H 2 SO 4 ) and subsequently passed to a reverse osmosis system 12. In the reverse osmosis system 12 salts such as chlorides, oxidizable organic ingredients and nitrogen components are retained. The withdrawn from the reverse osmosis system 12 reverse osmosis permeate stream 13 has a high purity and can be used for example as make-up water for an open cooling system or otherwise as process water (make-up water).
Der angereicherte Umkehrosmose-Retentatstrom 14 wird dagegen einer Nanofiltrationsanlage 15 zugeführt und in einen Nanofiltration-Permeatstrom 16 und eine Nanofiltration-Retentatstrom 17 aufgeteilt. Mit der Nanofiltrationsanlage 15 können oxidierbare organische Inhaltsstoffe (CSB-Komponenten) sowie Stickstoffkomponenten zurückgehalten werden. Salze wie beispielsweise Chloride gelangen in den Nanofiltration-Permeatstrom 16, so dass der Nanofiltration- Permeatstrom 16 einen hohen Chloridgehalt aufweist. Als Senke für den salzhaltigen bzw. chloridhaltigen Nanofiltration-Permeatstrom 16 kann vorzugsweise eine Schlackekühlung in einem Stahlwerk vorgesehen sein. Dabei bleiben die Salzrückstände auf der Schlacke zurück. Die Schlacke mit den Salzrückständen kann dann problemlos entsorgt und weiterverwendet werden. In contrast, the enriched reverse osmosis retentate stream 14 is fed to a nanofiltration plant 15 and split into a nanofiltration permeate stream 16 and a nanofiltration retentate stream 17. With the nanofiltration system 15 oxidizable organic ingredients (COD components) and nitrogen components can be retained. Salts such as chlorides enter the nanofiltration permeate stream 16 so that the nanofiltration permeate stream 16 has a high chloride content. As a sink for the salt-containing or chloride-containing nanofiltration permeate stream 16, slag cooling may preferably be provided in a steel mill. The salt residues remain on the slag. The slag with the salt residues can then be easily disposed of and reused.
Der Nanofiltration-Retentatstrom 17 wird einer Flockungs-, Fällungs- und Aktivkohlestufe 18 zugeführt. Das in der Flockungs-, Fällungs- und Aktivkohlestufe 18 gereinigte Wasser kann dann über eine Verbindungsleitung 19 der vorgelagerten biologischen Reinigung, insbesondere dem Nitrifikationsreaktor 8 zugeführt werden. The nanofiltration retentate stream 17 is fed to a flocculation, precipitation and activated carbon stage 18. The purified in the flocculation, precipitation and activated carbon stage 18 water can then be supplied via a connecting line 19 of the upstream biological purification, in particular the nitrification reactor 8.
Der in der Flockungs- und Fällungsstufe anfallende Schlamm wird dagegen in einen Sedimentationstrank 20 überführt, wobei eine anfallende Flüssigphase über eine entsprechende Leitung 21 a, 21 b, 21 c dem Nanofiltration- Permeatstrom 16 und/oder der Flockungs- und Fällungsstufe 18 und/oder der Verbindungsleitung 19 zugeleitet werden kann. Die in den gesamten Verfahren anfallenden Schlämme können in bekannter Weise durch Zentrifugen 22 entwässert werden. Alternativ kann auch eine gemeinsame Zentrifuge 22 eingesetzt werden, welche dann zwischen den Stoffströmen umzuschalten ist. Die durch die Zentrifuge entwässerten Schwämme können beispielsweise gemeinsam mit der Einsatzkohle einer Koksofenbatterie zugegeben werden. In contrast, the resulting in the flocculation and precipitation stage sludge is transferred into a sedimentation potion 20, wherein a resulting liquid phase via a corresponding line 21 a, 21 b, 21 c the nanofiltration permeate 16 and / or the flocculation and precipitation stage 18 and / or the connection line 19 can be supplied. The resulting in the entire process sludge can be dehydrated by centrifuges 22 in a known manner. Alternatively, a common centrifuge 22 can be used, which is then to switch between the streams. For example, the sponges dewatered by the centrifuge may be added together with the feed coal of a coke oven battery.
Bei dem erfindungsgemäßen Verfahren kann der Ammonium- und Nitritgehalt an geeigneten Stellen mit einer einfachen Messsonde bestimmt werden. Eine Messung mittels Messsonden ist möglich, wenn zuvor eine Abtrennung von Schlamm in einem Membrantrennverfahren erfolgte. Der Einsatz einer solchen Messsonde ist beispielsweise in dem Sammeltank 1 , dem Zwischentank 7, dem Mischtank 1 1 , dem Umkehrosmose-Permatstrom 13, dem Umkehrosmose- Retentatstrom 14, dem Nanofiltration-Permeatstrom 16 und dem Nanofiltration- Retentatstrom 17 möglich. In the method according to the invention, the ammonium and nitrite content can be determined at suitable locations with a simple measuring probe. Measurement by means of measuring probes is possible if previously a separation of sludge took place in a membrane separation process. The use of such a measuring probe is possible, for example, in the collecting tank 1, the intermediate tank 7, the mixing tank 11, the reverse osmosis permeate stream 13, the reverse osmosis retentate stream 14, the nanofiltration permeate stream 16 and the nanofiltration retentate stream 17.

Claims

Patentansprüche claims
1 . Verfahren zur Behandlung von organische Verbindungen enthaltendem Industrieabwasser, wobei das Industrieabwasser einer biologischen Reinigung unterzogen wird, bei der in dem Industrieabwasser enthaltende Verunreinigungen durch Bakterien zersetzt werden, und wobei nachfolgend aus dem biologisch zumindest teilweise gereinigten Abwasser Schlamm unter Einsatz zumindest einer Membrantrennanlage abgetrennt wird, d a d u r c h g e k e n n z e i c h n e t, dass das aus der Membrantrennanlage abgezogene Permeat nicht als gereinigtes Wasser abgeleitet und in flüssiger Form an die Umgebung abgegeben wird, sondern einer stofflichen Nutzung zugeführt wird und so eine abwasserfreie Verfahrensführung erfolgt, wobei das aus der Membrantrennanlage abgezogene Permeat zumindest teilweise einem Metallerzeugnis- und/oder Metallverarbeitungsprozess zugeführt wird und zur Kühlung von Schlacke eingesetzt wird, wobei zumindest ein Teil der in dem Permeat enthaltenen Reststoffe nach der Kühlung auf der Schlacke verbleiben. 1 . Process for the treatment of industrial waste water containing organic compounds, wherein the industrial waste water is subjected to a biological purification, in which contaminants contained in the industrial waste water are decomposed by bacteria, and subsequently sludge is separated from the biologically at least partially purified waste water using at least one membrane separation plant in that the permeate withdrawn from the membrane separation plant is not discharged as purified water and is released into the environment in liquid form, but is sent for material use, so that an effluent-free process is carried out, wherein the permeate withdrawn from the membrane separation plant at least partially corresponds to a metal product and / or or metal processing process is supplied and is used for cooling of slag, wherein at least a portion of the residual substances contained in the permeate after cooling on the Sc remain.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das aus der Membrantrennanlage abgezogene Permeat vollständig dem Metallerzeugnis- und/oder Metallverarbeitungsprozess zugeführt wird und zur Kühlung von Schlacke eingesetzt wird, wobei zumindest ein Teil der in dem Permeat enthaltenen Reststoffe nach der Kühlung auf der Schlacke verbleiben. 2. The method according to claim 1, characterized in that the withdrawn from the membrane separation plant permeate is completely supplied to the metal product and / or metal processing process and is used for cooling slag, wherein at least a portion of the residual substances contained in the permeate after cooling on the Slag remain.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das aus der Membrantrennanlage abgezogene Permeat zumindest teilweise einer Umkehrosmose unterzogen und in einen Umkehrosmose-Permeatstrom (13) und einen Umkehrosmose-Retentatstrom (14) aufgeteilt wird, wobei der Um- kehrosmose-Permeatstronn (13) als aufbereitetes Prozesswasser oder als Kühlwasser in einem offenen Kühlwassersystem eingesetzt wird. 3. The method according to claim 1 or 2, characterized in that the withdrawn from the membrane separation plant permeate is at least partially subjected to a reverse osmosis and in a reverse osmosis permeate stream (13) and a reverse osmosis retentate stream (14) is divided, the Um- kehrosmose permeate stream (13) is used as treated process water or as cooling water in an open cooling water system.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass das aus der Membrantrennanlage abgezogene Permeat vor der Durchführung der Um- kehrosmose zur Reduzierung des pH-Wertes mit Säure versetzt wird. 4. The method according to claim 3, characterized in that the withdrawn from the membrane separation plant permeate is added to reduce the pH with acid before performing the kehrosmose.
5. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, dass der Um- kehrosmose-Retentatstrom (14) einer Nanofiltration unterzogen und in einem Nanofiltration-Permeatstrom (16) und einen Nanofiltration-Retentatstrom (17) aufgeteilt wird. 5. The method according to claim 3 or 4, characterized in that the reverse ketoose retentate stream (14) subjected to a nanofiltration and in a nanofiltration permeate stream (16) and a nanofiltration retentate (17) is divided.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass der Nanofiltration-Retentatstrom (17) einer Aktivkohle enthaltenden Flockungs- und Fällungsstufe (18) zugeführt wird. 6. The method according to claim 5, characterized in that the nanofiltration-retentate stream (17) of an activated carbon-containing flocculation and precipitation stage (18) is supplied.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das in der Flockungs-, Fällungs- und Aktivkohlestufe (18) gereinigte Wasser der biologischen Reinigung zugeführt wird. 7. The method according to claim 6, characterized in that in the flocculation, precipitation and activated carbon stage (18) purified water is fed to the biological purification.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass der in der Flockungs-, Fällungs- und Aktivkohlestufe (18) anfallende Schlamm in einen Sedimentationstank (20) überführt wird, wobei eine in den Sedimentationstank anfallende Flüssigphase dem Nanofiltration-Permeatstrom (16) oder der Flockungs-, Fällungs- und Aktivkohlestufe (18) oder der biologischen Reinigung zugeführt wird. 8. The method according to claim 7, characterized in that in the flocculation, precipitation and activated carbon stage (18) resulting sludge is transferred into a sedimentation tank (20), wherein a resulting in the sedimentation tank liquid phase the nanofiltration permeate stream (16) or the flocculation, precipitation and activated carbon stage (18) or biological purification is supplied.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass als organische Verbindungen enthaltendes Industrieabwasser Kokereiabwasser, welches unter anderem mit Stickstoffverbindungen, Cyaniden, Phenolen und Sulfiden belastet ist, zugeführt wird, wobei das Kokereiabwasser bei der mehrstufigen biologischen Reinigung in einem Entgiftungsreaktor größtenteils von Schadstoffen befreit wird, die die Nitrifikation hemmen. 9. The method according to any one of claims 1 to 8, characterized in that as organic compounds containing industrial effluent coke oven wastewater, which is loaded, inter alia, with nitrogen compounds, cyanides, phenols and sulfides, is supplied to the coking effluent in multi-stage biological purification in a detoxification reactor is largely freed of pollutants that inhibit nitrification.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass zwischen zwei aufeinanderfolgenden Prozessschritten der Gehalt an Ammonium und/oder Nitrit mit einer Messsonde bestimmt wird. 10. The method according to any one of claims 1 to 9, characterized in that between two successive process steps, the content of ammonium and / or nitrite is determined with a measuring probe.
PCT/EP2016/070758 2015-09-04 2016-09-02 Method for treating industrial wastewater containing organic compounds WO2017037254A1 (en)

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