EP3500529A1 - Système de récupération de sels de phosphate et procédé pour faire fonctionner ce système - Google Patents

Système de récupération de sels de phosphate et procédé pour faire fonctionner ce système

Info

Publication number
EP3500529A1
EP3500529A1 EP17764518.1A EP17764518A EP3500529A1 EP 3500529 A1 EP3500529 A1 EP 3500529A1 EP 17764518 A EP17764518 A EP 17764518A EP 3500529 A1 EP3500529 A1 EP 3500529A1
Authority
EP
European Patent Office
Prior art keywords
reactor
recirculation
plant
phosphate
phosphate salts
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Withdrawn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
EP17764518.1A
Other languages
German (de)
English (en)
Inventor
Siegfried Egner
Iosif Mariakakis
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP3500529A1 publication Critical patent/EP3500529A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46176—Galvanic cells
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • 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
    • C02F3/1205—Particular type of activated sludge processes
    • C02F3/1215—Combinations of activated sludge treatment with precipitation, flocculation, coagulation and separation of phosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B9/00—Fertilisers based essentially on phosphates or double phosphates of magnesium
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • C02F2001/4619—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only cathodic or alkaline water, e.g. for reducing
    • 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
    • C02F2101/105—Phosphorus compounds
    • 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • 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 plant for the production of
  • Phosphate salts especially MAP or KMP
  • phosphate-containing liquids such as process or effluents with one or more reactors, each comprising two electrodes of opposite polarity and the one reaction space between them
  • each reactor having an inlet and a drain.
  • the elements nitrogen, potassium, and phosphorus are essential substances among other elements for plant growth. These are usually contained as ions in solid or liquid organic waste or wastewater. to Treatment of this waste or waste water, eg municipal wastewater, these substances must be removed on the one hand to protect the environment (eutrophication). On the other hand, it is also important in terms of sustainability, this
  • Phosphate salts such as magnesium ammonium phosphate (MAP) or potassium magnesium phosphate (KMP) are high quality
  • the spontaneous precipitation of MAP or KMP is limited by the usually low magnesium concentration.
  • the addition of magnesium hydroxide, magnesium oxide or water-soluble magnesium salts to MAP precipitation is known.
  • magnesium hydroxide or magnesium oxides e.g. to wastewater or other organic substances to be treated
  • the optimum pH for precipitating MAP is 8.5-9, for KMP the value is even higher.
  • the number of reactors arranged in series ie the length of the system and thus the minimum residence time of the liquid in the reactor, must be selected accordingly in order to supply sufficient magnesium ions.
  • a disadvantage is that the number of series-connected reactors of this Minimum speed or the degraded phosphate load depends and thus the operation is not flexible.
  • the invention solves this problem by a system with one or more reactors, each comprising two electrodes of opposite polarity and spanning a reaction space between them, each reactor having an inlet and a drain and wherein the flow into a recirculation and in a Downstream divides and the recirculation part of the liquid of the
  • the liquid is passed several times through a reactor and passes through the electrochemical process several times until the amount of magnesium ions required for the degradation of the phosphate
  • Raising the pH preferably at least 8 or even at least 8.5 or even increase to 9.5 or more and so the precipitation of MAP and / or KMP is possible or supported.
  • the number of series-connected reactors advantageously from the
  • Salt crystals are transported by the flow and do not sediment.
  • the discharge of salt crystals from the system (plant) can be done early, especially after each reactor, yet high conversion rate and efficiency, since the recoverable in each reactor amount of MAP or KMP is increased compared to the tubular reactor construction according to the prior art.
  • the crystals can also be deposited only after several series-connected reactors or after each reactor.
  • outlet of one or more reactors opens into a storage container, from which in turn the recirculation branches off.
  • the removal device can be on the suction or the
  • a crystal separation unit such as a sedimentation tank or a filter, can be provided as removal device.
  • ammonia formed becomes volatile and can be sent to further use together with or separately from the released hydrogen. Because ammonium is usually around one
  • both substances are formed simultaneously and preferably also separated simultaneously.
  • the reactor the effluent and / or the recirculation to comprise a unit for collecting and separating off gases
  • ammonia together with hydrogen for material and / or energetic utilization either in the course and / or the recirculation of e.g. in combination with the crystal separation or directly via one in the reactor
  • the system in addition to the required flow velocity to avoid to be unwanted settling of crystals and in order to be independent of the supplied and degraded phosphate load in terms of the number of reactors, so that the system feed rate (flow) (Q D ) and the
  • Recirculation amount (Q R ) are set to one another so that the pH at a desired location a value pH> 8, especially pH> 8.5 preferably> 9 and thus promotes the demixing of ammonia in addition to the particularly efficient crystallization of phosphate salts is, in particular by the reaction space of
  • reactors are connected in parallel. It also combinations are possible. For example, two or more reactors may be connected in parallel to be arranged in series with other reactors. In this case, the recirculation and optionally also the gas or crystal separation can be arranged so that it is provided for each individual reactor. But it can also be, for example
  • Reactors may be arranged in parallel or in series, wherein the recirculation leads to the inlet of the first or a previous series-connected reactor or feeds the inlet of several parallel-connected reactors.
  • the required pH increase of a reactor can be individually set or achieved or the pH increase of several
  • Reactors jointly influenced.
  • the flow of supplied liquid in the inlet to the flow in the recirculation is designed so that at least as much recirculation as inlet the
  • Reactor is fed.
  • the flow rate of the recirculation is greater than the flow rate of the inlet.
  • Ammonia which can also be processed into fertilizer. It can be provided as in the prior art that one of the electrodes is a sacrificial electrode, in particular of magnesium-containing material, so that MAP or KMP can be formed.
  • the invention relates to a method for
  • phosphate-containing liquids such as process or wastewater, in particular MAP and KMP
  • a drain stream is separated into a downstream and a recirculation (recirculation) and the
  • the pH preferably be set to> 8, in particular to> 8.5 and preferably to> 9, so that In addition to a preferred high flow rate, a particularly efficient phosphate salt precipitation takes place, if appropriate, hydrogen and also volatile ammonia can be separated off and recovered or utilized for the fertilizer industry.
  • Such a method and such a device can be used particularly advantageously in the context of municipal sewage treatment plants and other biological sewage treatment plants.
  • the invention therefore also relates to the implementation, ie use of the process in a biological wastewater treatment plant and the biological treatment plant comprising a biological stage, a biomass separation and downstream of the biomass separation
  • the sewage sludge is in particular supplied to a sludge dewatering and there is a Filtratwasserstrom, which is fed back to the inlet of the biological stage.
  • Filtrate water flow is usually loaded with phosphorus and nitrogen.
  • Phosphorus in the process water of a biological treatment plant (eg municipal) is not in the filtrate water
  • an anaerobic treatment step may be used between the biomass separation and the drainage
  • This anaerobic stage liberates phosphorus and ammonium present in the biomass, so that compared to a sewage treatment plant without this anaerobic stage, the cargo at N and P in the filtrate water is increased.
  • Wastewater treatment plant the biological stage is usually aerobic, this is atmospheric oxygen through the ventilation
  • nitrogen is also an important plant adjuvant
  • Filtrate water stream is therefore according to the invention a plant for recovering phosphate salts from phosphate-containing
  • Liquids as described above comprising one or more electrolytic reactors, each comprising two electrodes of opposite polarity and spanning a reaction space between them, each reactor having an inlet and a drain.
  • the sequence splits after a Kristallabtrenn worn or a storage container in a recirculation and in an effluent and the recirculation thus leads a portion of the liquid of the flow of the reactor to the inlet of the same or another reactor again.
  • Phosphate salts and a unit for collecting and
  • the invention relates to a method for
  • the filtrate is fed via an inlet to the at least one reactor and this flows through it through a flow again and precipitated phosphate salts and volatile ammonia are withdrawn via removal devices ,
  • ammonia, phosphate salts and the resulting hydrogen takes place in particular in one plant and in particular simultaneously.
  • the system and the method for operating the system can be designed as described above.
  • FIG. 2 shows an alternative embodiment of the system
  • FIG. 4 shows a cascade connection of the system
  • FIG. 5 shows a scheme for the electrolytic reaction
  • Figure 6 is a schematic representation of a biological
  • FIG. 1 shows a system according to a first embodiment, which is provided in its entirety by the reference numeral 10.
  • the plant comprises a reactor 12 with an inlet 14 and an outlet 16.
  • the reactor 12 is an electrolytic reactor in which the consumption of a sacrificial anode of magnesium phosphorus
  • phosphorus-containing liquids to particular MAP or KMP can crystallize. This can be done purely galvanic or by applying a current. It is the
  • the pH of liquids, in particular wastewaters, and other phosphorus-containing liquids is about 5 to 7. Owing to the electrolytic reaction in the reactor (see Figure 5), OH " ions are released, so that the pH in the reactor The pH before the reactor 12 is therefore lower than behind the reactor 12.
  • the process 16 now leads into a storage container 18, to which a crystal separator 20 connects, via which the phosphate salts can be withdrawn.
  • a partial flow of the effluent 16 is then recombined as the recirculation 22 with the inlet 14 and the reactor 12 again fed.
  • the flow in the recirculation 22 is designated Q R.
  • Q R > 5 x Q D.
  • Another part of the process 16 is taken as effluent 24 of the system 10, wherein here measurements of the pH by means of a probe 26 and the phosphorus with a probe 28 and the outflow has a flow of Q D again.
  • the pH at the effluent 24 is 8 8 to 9.5 or above.
  • the flow rate can be so
  • Storage tank 18 may also be a deposit
  • pumps 23 and 15 are provided in the recirculation 22 and in the inlet 14.
  • FIG. 2 shows a system 10 'in which n reactors 12 are connected in parallel.
  • the process 16 all
  • Reactors 12 is supplied to a storage container 18, from which the recirculation 22 feeds, which in turn is fed to the inlet 14 of the system 10 '. In this way, the overall performance of the system 10 'can be increased without having to vary the individual reactors 12.
  • FIG. 3 shows a further embodiment of the invention, wherein here, in a modification of FIG. 2, the reactors 12 of the system 10 "are connected not only in parallel but also in series, with a series consisting of up to n reactors 12 and up to m Reactors are connected in parallel.
  • the sequence 16 of the n is arranged in series
  • Reactors then each supplied to the buffer container 18, which in turn feeds the recirculation 22 from this buffer container 18.
  • FIG. 4 shows a cascade connection.
  • each one is
  • Cascade stage 40 constructed analogously to Figure 2.
  • the outflow 24 of a cascade stage 40 is at the same time the inflow of the next cascade stage.
  • FIG. 6 shows the basic principle of a biological
  • a sewage treatment plant comprising a biological stage 100, wherein the leaving the biological stage liquid of a
  • Biomass separation 102 is supplied, in particular to withhold the biomass.
  • the biomass (sludge) leaving the biomass separation 102 is then separated in a stage 104 (sludge dewatering) into a filtrate water stream 108 and as well as dewatered biomass (106).
  • stage 104 sludge dewatering
  • Filtratwasserstrom 108 which still contains nitrogen and phosphate, is fed to a plant 10 described above for the production of phosphate salts and gaseous ammonia, wherein in the system 10 is preferably
  • MAP 120 Magnesium ammonium phosphate (MAP) 120 and ammonium in the form of liberated ammonia 122 is recovered.
  • This effluent 24 of the system 10 is then fed back to the feedstream 132 of the biological stage 100
  • Circulation is not burdened by phosphorus and nitrogen and in particular energy to remove nitrogen as N 2 (respiration) and phosphate is no longer needed.
  • Phosphate salts and preferably also from ammonia
  • Exposure of the fluid can be the
  • Reaction chamber 12 increases. In this way, facilities can be provided which enable a particularly cost-efficient, if not profitable, implementation of wastewater, in particular sewage from agriculture, but also from municipal water management. Therefore, the implementation in a biological sewage treatment plant is particularly preferred.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
  • Removal Of Specific Substances (AREA)
  • Mechanical Engineering (AREA)

Abstract

La présente invention concerne un système (10) pour séparer le phosphate à partir de liquides contenant du phosphate et récupérer les sels de phosphate avec un ou plusieurs réacteurs (12) qui comprennent respectivement deux électrodes de polarité opposée et forment entre eux un espace de réaction, chaque réacteur (12) présentant une arrivée (14) et une évacuation (16) et dans lequel l'évacuation (16) se scinde en une recirculation (22) et en un effluent (24), la recirculation (22) amenant une partie du liquide de l'évacuation (16) du réacteur (12) jusqu'à l'arrivée du même réacteur ou d'un autre réacteur (12). L'invention concerne également un procédé prévu à cet effet et un système d'épuration biologique ainsi qu'un procédé pour la faire fonctionner.
EP17764518.1A 2016-08-22 2017-08-22 Système de récupération de sels de phosphate et procédé pour faire fonctionner ce système Withdrawn EP3500529A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016115554.3A DE102016115554A1 (de) 2016-08-22 2016-08-22 Anlage zur Gewinnung von Phosphatsalzen und biologische Kläranlage sowie Verfahren zum Betreiben dieser Anlagen
PCT/EP2017/071132 WO2018037008A1 (fr) 2016-08-22 2017-08-22 Système de récupération de sels de phosphate et procédé pour faire fonctionner ce système

Publications (1)

Publication Number Publication Date
EP3500529A1 true EP3500529A1 (fr) 2019-06-26

Family

ID=59829333

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17764518.1A Withdrawn EP3500529A1 (fr) 2016-08-22 2017-08-22 Système de récupération de sels de phosphate et procédé pour faire fonctionner ce système

Country Status (5)

Country Link
US (1) US20190177189A1 (fr)
EP (1) EP3500529A1 (fr)
CA (1) CA3034541A1 (fr)
DE (1) DE102016115554A1 (fr)
WO (1) WO2018037008A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109336344B (zh) * 2018-11-21 2021-11-09 刘兴海 可防止污水二次污染的污泥处理装置
CN113354231B (zh) * 2021-07-02 2022-09-02 江西科技学院 一种水库底泥中重金属的处理装置及处理方法
GB202113793D0 (en) * 2021-09-27 2021-11-10 Arvia Water Tech Limited Improved liquid treatment
CN113880200A (zh) * 2021-10-29 2022-01-04 杭州回水科技股份有限公司 多反应槽组合的电絮凝设备
CN114130637B (zh) * 2021-11-26 2023-05-12 西安西热水务环保有限公司 一种晶种高效分级分离装置

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000176482A (ja) * 1998-12-18 2000-06-27 Matsushita Electric Works Ltd 汚水処理装置
DE10112934B4 (de) 2001-03-12 2004-08-26 Berliner Wasserbetriebe Anstalt des öffentlichen Rechts Verfahren zur Vermeidung und Beseitigung von Inkrustationen bei der Förderung und Ableitung von Flüssigkeiten
DE102005034138A1 (de) 2005-07-19 2007-01-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Reaktor zur Gewinnung von Magnesiumammoniumphosphat und Verfahren zur Gewinnung von Magnesiumammoniumphosphat aus Gülle oder ammoniumhaltigen Abgasen
DE102010050691B3 (de) 2010-11-06 2012-03-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren Rückgewinnung von Phospatsalzen aus einer Flüssigkeit
DE102010050692B3 (de) 2010-11-06 2012-03-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Reaktor zur Rückgewinnung von Phosphatsalzen aus einer Flüssigkeit

Also Published As

Publication number Publication date
US20190177189A1 (en) 2019-06-13
DE102016115554A1 (de) 2018-02-22
CA3034541A1 (fr) 2018-03-01
WO2018037008A1 (fr) 2018-03-01

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