WO2013123926A2 - Method for utilizing phosphorous-containing wastes - Google Patents

Method for utilizing phosphorous-containing wastes Download PDF

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Publication number
WO2013123926A2
WO2013123926A2 PCT/DE2013/000088 DE2013000088W WO2013123926A2 WO 2013123926 A2 WO2013123926 A2 WO 2013123926A2 DE 2013000088 W DE2013000088 W DE 2013000088W WO 2013123926 A2 WO2013123926 A2 WO 2013123926A2
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WIPO (PCT)
Prior art keywords
phosphorus
plants
melt gasification
containing waste
fuel gas
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PCT/DE2013/000088
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German (de)
French (fr)
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WO2013123926A4 (en
WO2013123926A3 (en
Inventor
Joachim Mallon
Michael Schaaf
Klaus Scheidig
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Joachim Mallon
Michael Schaaf
Klaus Scheidig
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Application filed by Joachim Mallon, Michael Schaaf, Klaus Scheidig filed Critical Joachim Mallon
Priority to EP13716180.8A priority Critical patent/EP2817564A2/en
Publication of WO2013123926A2 publication Critical patent/WO2013123926A2/en
Publication of WO2013123926A3 publication Critical patent/WO2013123926A3/en
Publication of WO2013123926A4 publication Critical patent/WO2013123926A4/en

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • 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
    • C02F11/06—Treatment of sludge; Devices therefor by oxidation
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/44—Details; Accessories
    • F23G5/46—Recuperation of heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/001—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals for sludges or waste products from water treatment installations
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2204/00—Supplementary heating arrangements
    • F23G2204/10—Supplementary heating arrangements using auxiliary fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2206/00—Waste heat recuperation
    • F23G2206/10—Waste heat recuperation reintroducing the heat in the same process, e.g. for predrying
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2900/00—Special features of, or arrangements for incinerators
    • F23G2900/50007—Co-combustion of two or more kinds of waste, separately fed into the furnace
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2900/00—Special features of, or arrangements for incinerators
    • F23G2900/508—Providing additional energy for combustion, e.g. by using supplementary heating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2900/00—Special features of, or arrangements for incinerators
    • F23G2900/70—Incinerating particular products or waste
    • F23G2900/7004—Incinerating contaminated animal meals
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • 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
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
    • 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
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation

Definitions

  • the invention relates to a process for the recovery of phosphorus-containing waste in plants for their exclusive energy recovery, such as mono-incineration plants for sewage sludge and / or animal meal, co-incineration in power plants or in
  • Sewage sludge is a significant energetic and material resource that has not been exploited so far (Lehrmann: Klärschlamm-Entsorgung in Europa, lecture: VDI conference "Sewage Sludge Treatment", Heidelberg, 16/17 Nov. 2011) (Mono / co-incineration) and recycling (fertilization, P-recycling) mutually largely because, for example, in the co-incineration of sewage sludge in a coal power plant introduced with the sewage sludge P 2 C> 5 share by the resulting ash during coal combustion so strong is diluted, that a P recycling economically no longer makes sense.
  • thermochemical or metallurgical processes seem to be suitable for such phosphorus recycling.
  • the heavy metal Entfrachtung is achieved by a chlorinating roasting at 1000 ° C in the rotary kiln oven (Adam: Technical possibilities of
  • the Mephrec process which is tested for P recycling from sewage sludge and animal meal as well as from the mono-combustion ashes of these materials, is a metallurgical one
  • Citric acid solubility of phosphorus similar to Thomas flour used in agriculture in the past for phosphorus fertilization, and a metal alloy producing a fuel gas which is processed for thermal afterburning or energy recovery, e.g. is suitable for generating electricity in the CHP.
  • the disadvantage is that in the melt gasification of mono-combustion ashes alone the calorific value of this gas for an economic
  • the invention is therefore based on the object, a recycling by P recycling of phosphorus-containing waste in plants for their exclusive energy recovery, such as mono-incinerators for sewage sludge and / or animal meal, co-incineration in power plants or additional firing in furnaces of the cement industry or comparable ovens of other industries.
  • the object is achieved by integrating a plant for the melt gasification of substances containing P in existing or newly constructed plants for exclusive
  • Sewage sludge and / or animal meal in co-incineration in power plants or in
  • Another advantage is that the invention for both existing mono-combustion plants for
  • Sewage sludge and / or animal meal for co-incineration plants of sewage sludge and / or other P-containing substances with high organic content such as power plants, kilns in the cement industry or comparable ovens other industries and in the construction of such facilities is applicable and at the same time the economics of the melt gasification Improved feedstocks with increased organically poor ash content.
  • a mono-combustion capacity of 100,000 ta TS in the fluidized-bed furnace is considered, which generates 50,000 1 a of ash during normal operation.
  • sewage sludge incineration capacity is only 80% utilized, producing only 40,000 t / a ash.
  • Half of produced ash (20,000 t / a) is mixed with the remaining sewage sludge (20,000 t / a TS) and briquetted.
  • the wet briquettes produced (45,000 t / a) are fed to the melt gasification in the Mephrec reactor, with the remaining ash (20,000 t / a) being blown into the reactor in a dust-like manner via the nozzles.
  • Fluidized bed furnace and Mephrec reactor work in parallel.
  • the blast furnace gas produced in the melt gasification is fed directly to the combustion zone of the fluidized bed furnace and there supports the combustion process.
  • the volume of exhaust gas to be cleaned from the fluidized-bed furnace is only insignificantly greater in this mode of operation than during normal combustion of 100,000 t / a TS.
  • the melt gasification in the Mephrec reactor can thus take place without additional gas purification capacities.
  • slag can be used as a P fertilizer or used as a precursor for multi-nutrient fertilizer.

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Treatment Of Sludge (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to a method for utilizing phosphorous-containing wastes in facilities for the exclusive energy recovery of said wastes, such as mono-incinerators for sewage sludge and/or animal meal, during the co-incineration in power plants or during additional firings in cement industry furnaces or comparable furnaces of other branches of industry, in which method an installation for melt gasification of P-containing substances is integrated into existing or new facilities of said kind. Depending on the composition of the P-containing substance, said installation generates a metal melt, a lime-silico-phosphate-containing slag low in heavy metals, and a fuel gas, and the fuel gas is supplied as fuel to the facilities for the exclusive energy recovery.

Description

Beschreibung  description
Verfahren zur Verwertung von phosphorhaltigen Abfällen  Process for recycling phosphorus-containing waste
[001] Die Erfindung betrifft ein Verfahren zur Verwertung von phosphorhaltigen Abfällen in Anlagen für ihre ausschließlich energetische Verwertung, wie Monoverbrennungsanlagen für Klärschlamm und/oder Tiermehl, bei der Mitverbrennung in Kraftwerken oder bei  The invention relates to a process for the recovery of phosphorus-containing waste in plants for their exclusive energy recovery, such as mono-incineration plants for sewage sludge and / or animal meal, co-incineration in power plants or in
Zusatzfeuerungen in Brennöfen der Zementindustrie oder vergleichbaren Öfen anderer Additional firing in furnaces of the cement industry or comparable furnaces of others
Industriezweige. Industries.
[002] Steigende Energie- und Rohstoff-Preise zwingen zunehmend zu hoher Ressourcen- Effizienz in allen Bereichen der Wirtschaft und hat der Recycling-Industrie neue Märkte und Entwicklungsmöglichkeiten eröfmet. Beispielhaft wird in diesem Zusammenhang auf die in den vergangenen Jahren entwickelten P-Recycling- Verfahren verwiesen, deren Bedeutung darauf basiert, dass das Element Phosphor eine besondere Bedeutung für alle biologischen Prozesse besitzt und hierfür durch kein anderes Element ersetzt werden kann. Mangels eigener abbauwürdiger Phosphat-Lagerstätten sind Deutschland wie auch viele andere Länder abhängig vom Import von P-Erzen und P-Düngemitteln. Ein großer Teil dieser Phosphat-Importe könnte aber durch ein wirtschaftliches Recycling der in den Abfallstoffen wie beispielsweise  Increasing energy and raw material prices are increasingly forcing resource efficiency in all areas of the economy and has opened up new markets and development opportunities for the recycling industry. By way of example, reference is made in this connection to the P recycling process developed in recent years, the significance of which is based on the fact that the element phosphorus has a special significance for all biological processes and can not be replaced by any other element for this purpose. Due to the lack of own phosphate deposits that can be mined Germany as well as many other countries are dependent on the import of P-ores and P-fertilizers. However, a large part of these phosphate imports could be due to an economic recycling of waste materials such as
Klärschlamm und Tiermehl enthaltenen Phosphate ersetzt werden (Pinnekamp u. Everding, Schlusspräsentation der durch das BMBF geförderten Vorhaben. Vorträge. Berlin, 14. Sept. 2011; veröff. in Gewässerschutz- Wasser-Abwasser 228, Aachen 2011, ISBN 978-3-938996-34- 8). Pinnekamp and Everding, final presentation of the project funded by the BMBF Lectures: Berlin, Sept. 14, 2011, published in Wasserschutz- Wasser-Abwasser 228, Aachen 2011, ISBN 978-3-938996 -34- 8).
[003] Mit Heizwerten von 10-12 MJ/kg TS, 2-6 % Phosphor in der Trockensubstanz (TS) und ca. 2 Mio. t/a TS in Deutschland bzw. fast 12 Mio. t/a TS in Europa stellt insbesondere  With calorific values of 10-12 MJ / kg TS, 2-6% phosphorus in the dry matter (TS) and about 2 million t / a TS in Germany or almost 12 million t / a TS in Europe especially
Klärschlamm eine bedeutsame energetische und stoffliche Ressource dar, deren Verwertung bisher unzureichend ist (Lehrmann: Klärschlamm-Entsorgung in Europa. Vortrag. VDI- Fachkonferenz„Klärschlammbehandlung". Heidelberg, 16/17. Nov. 2011). Praktisch schließen sich bis heute energetische Nutzung (Mono/Mitverbrennung) und stoffliche Verwertung (Düngung, P-Recycling) gegenseitig weitgehend aus, da beispielsweise bei der Mitverbrennung von Klärschlamm in einem Kohlekraftwerk der mit dem Klärschlamm eingebrachte P2C>5-Anteil durch die bei der Kohleverbrennung anfallende Asche so stark verdünnt wird, dass ein P- Recycling wirtschaftlich nicht mehr sinnvoll ist. Sewage sludge is a significant energetic and material resource that has not been exploited so far (Lehrmann: Klärschlamm-Entsorgung in Europa, lecture: VDI conference "Sewage Sludge Treatment", Heidelberg, 16/17 Nov. 2011) (Mono / co-incineration) and recycling (fertilization, P-recycling) mutually largely because, for example, in the co-incineration of sewage sludge in a coal power plant introduced with the sewage sludge P 2 C> 5 share by the resulting ash during coal combustion so strong is diluted, that a P recycling economically no longer makes sense.
[004] Im Gegensatz zur Mitverbrennung weist die bei der Monoverbrennung von Klärschlamm anfallende Asche erhöhte P205-Gehalte auf, die im Bereich von 7 - 25 % liegen (Petzet und Cornel:„Neue Wege des Phosphorrecyclings aus Klärschlammaschen", KA-Korrespondenz Abwasser, Abfall 2010 (57) Nr.4, S. 357-365; vergl. auch Lehrmann, s.o.). Nachteilig ist, dass der in der Asche enthaltene Phosphor in einer Bindungsform vorliegt, die nur eine geringe Pflanzenverfugbarkeit besitzt und deshalb durch die erforderlichen höheren Düngemittelgaben bei Asche-Düngung eine Schwermetall-Anreicherung des Bodens auch dann zu erwarten ist, wenn die genannten Grenzwerte der DüMV eingehalten werden (Perez: Phosphorus dynamics in soil and plant availibility of fertilizers. Diss. Universität Göttingen, Juli 2010, S. 128-131). In contrast to co-incineration, the ash produced in the mono-combustion of sewage sludge has increased P 2 O 5 contents, which are in the range of 7 - 25% (Petzet and Cornel: "New ways of phosphorus recycling from sewage sludge ash", KA- Correspondence waste water, waste 2010 (57) No. 4, P. 357-365, see also Lehrmann, so.) The disadvantage is that the phosphorus contained in the ash is present in a binding form, which has only a low Pflanzenverfugbarkeit and therefore by the required higher fertilizer inputs in ash fertilization, a heavy metal accumulation of the soil is to be expected even if the said limits of DüMV observed (Perez : Phosphorus Dynamics in Soil and Plant Availability of Fertilizers, Diss. Universität Göttingen, July 2010, pp. 128-131).
[005] Die mit dem Ziel entwickelten Verfahren, die Pflanzenverfügbarkeit des in der Asche enthaltenen Phosphors zu erhöhen und die Asche gleichzeitig von Schwermetallen zu entfrachten lassen sich zur Zeit noch nicht wirtschaftlich darstellen (vergl. Pinnekamp u. Everding). The process developed with the aim of increasing the plant availability of the phosphorus contained in the ash and to remove the ash from heavy metals at the same time can not yet be economically represented (compare Pinnekamp and Everding).
[006] Jedoch scheinen unter wirtschaftlichen Aspekten betrachtet, speziell thermochemische bzw. metallurgische Verfahren für ein solches Phosphorrecycling geeignet zu sein. However, from an economic point of view, especially thermochemical or metallurgical processes seem to be suitable for such phosphorus recycling.
[007] Bei dem durch die AshDec GmbH angebotenen Verfahren für Aschen aus Mono- Verbrennungsanlagen wird die Schwermetall-Entfrachtung durch eine chlorierende Röstung bei 1000°C im Drehrohr-Ofen erreicht (Adam: Technische Möglichkeiten der In the method offered by the AshDec GmbH for ashes from mono-incineration plants, the heavy metal Entfrachtung is achieved by a chlorinating roasting at 1000 ° C in the rotary kiln oven (Adam: Technical possibilities of
Phosphorrückgewinnung aus Klärschlamm-Aschen. VDI Fachkonferenz„Klärschlamm- Behandlung". Offenbach, 27728. Okt. 2010). Unter den gewählten Reaktions-Bedingungen entstehen Bindungsformen des Phosphors, die eine hohe Pflanzenverfugbarkeit gewährleisten. Die Nachteile des Verfahrens liegen im Energie- Verbrauch des fremdbeheizten Drehrohr-Ofens, in der Anlagen-Verfügbarkeit beim Dauerbetrieb mit heißen chlorhaltigen Gasen und beim Aufwand zur Regeneration der eingesetzten chloridhaltigen Additive. Phosphorus recovery from sewage sludge ash. Offenbach, 27728. Oct. 2010) Under the chosen reaction conditions, forms of binding of the phosphor arise, which ensure a high plant availability.The disadvantages of the method lie in the energy consumption of the externally heated rotary kiln furnace, in the plant availability in continuous operation with hot chlorine-containing gases and the effort to regenerate the used chloride-containing additives.
[008] Das Mephrec- Verfahren, für das P-Recycling aus Klärschlamm und Tiermehl wie auch aus den Monoverbrennungs- Aschen dieser Materialien erprobt, ist ein metallurgisches  [008] The Mephrec process, which is tested for P recycling from sewage sludge and animal meal as well as from the mono-combustion ashes of these materials, is a metallurgical one
Verfahren, bei dem eine gleichzeitige stoffliche und energetische Verwertung von Process in which a simultaneous material and energy recovery of
phosphorhaltigen Abfällen realisiert wird (Scheidig, Mallon, Schaaf: Zulainftsfähige Phosphorus-containing waste is realized (Scheidig, Mallon, Schaaf: Zulinftsfähige
Klärschlamm-Verwertung. KA - Korrespondenz Abwasser, Abfall 57 (2010) Nr. 9, S. 902-915). Bei dieser Sauerstoff- Schmelzvergasung von organik- und phosphorhaltigen Abfallen wie bspw. Klärschlamm wird neben der schwermetallarmen Schlacke mit einer hohen Sludge recycling. KA - correspondence waste water, Waste 57 (2010) No. 9, pp. 902-915). In this oxygen melt gasification of organic and phosphorus-containing waste such as. Sewage sludge is in addition to the low-heavy metal slag with a high
Zitronensäurelöslichkeit des Phosphors, ähnlich dem in der Vergangenheit in der Landwirtschaft zur Phosphordüngung eingesetztem Thomasmehl, und einer Metalllegierung ein Brenngas erzeugt, das aufbereitet zur thermischen Nachverbrennung oder zur energetischen Verwertung, z.B. zur Stromerzeugung im BHKW geeignet ist. Nachteilig ist, dass bei der Schmelzvergasung von Monoverbrennungs-Asche allein der Heizwert dieses Gases für eine wirtschaftliche Citric acid solubility of phosphorus, similar to Thomas flour used in agriculture in the past for phosphorus fertilization, and a metal alloy producing a fuel gas which is processed for thermal afterburning or energy recovery, e.g. is suitable for generating electricity in the CHP. The disadvantage is that in the melt gasification of mono-combustion ashes alone the calorific value of this gas for an economic
Verstromung nicht ausreicht. Das wirkt sich insgesamt nachteilig für das Mephrec-Verfahren zum Phosphorrecycling und stofflichen Verwertung von Aschen aus, welches durch den im Mephrec-Reaktor notwendigen Einsatz von metallurgischem Koks verfahrenspezifisch relativ hohe Betriebs-Kosten aufweist. Power generation is insufficient. This has a disadvantageous overall for the Mephrec process for phosphorus recycling and recycling of ashes, which by the im Mephrec reactor necessary use of metallurgical coke process-specific relatively high operating costs.
[009] Der Erfindung liegt deshalb die Aufgabe zugrunde, eine stoffliche Verwertung durch P- Recycling aus phosphorhaltigen Abfällen in Anlagen für ihre ausschließlich energetische Verwertung, wie Monoverbrennungsanlagen für Klärschlamm und/oder Tiermehl, bei der Mitverbrennung in Kraftwerken oder bei Zusatzfeuerungen in Brennöfen der Zementindustrie oder vergleichbaren Öfen anderer Industriezweige zu schaffen.  The invention is therefore based on the object, a recycling by P recycling of phosphorus-containing waste in plants for their exclusive energy recovery, such as mono-incinerators for sewage sludge and / or animal meal, co-incineration in power plants or additional firing in furnaces of the cement industry or comparable ovens of other industries.
[010] Die Aufgabe wird durch die Integrierung einer Anlage zur Schmelzvergasung von P- haltigen Stoffen in bestehende oder neu zu errichtende Anlagen zur ausschließlichen  [010] The object is achieved by integrating a plant for the melt gasification of substances containing P in existing or newly constructed plants for exclusive
energetischen Verwertung von P-haltigen Stoffen, wie Monoverbrennungsanlagen für energetic utilization of P-containing substances, such as mono-incineration plants for
Klärschlamm und/oder Tiermehl, bei der Mitverbrennung in Kraftwerken oder bei Sewage sludge and / or animal meal, in co-incineration in power plants or in
Zusatzfeuerungen in Brennöfen der Zementindustrie oder vergleichbaren Öfen anderer Additional firing in furnaces of the cement industry or comparable furnaces of others
Industriezweige entsprechend den Merkmalen der Patentansprüche gelöst. Industries solved according to the features of the claims.
[011] Vorteilhafterweise werden die nach dem Stand der Technik anerkannten wirtschaftlichen und verfahrenstechnischen Vorteile von Anlagen für die ausschließlich energetische Verwertung von phosphorhaltigen Abfällen, wie Monoverbrennungsanlagen für Klärschlamm und/oder Tiermehl, bei der Mitverbrennung in Kraftwerken oder bei Zusatzfeuerungen in Brennöfen der Zementindustrie oder vergleichbaren Öfen anderer Industriezweige mit der Sauerstoff- Schmelzvergasung von organik- und phosphorhaltigen Abfallen wie bspw. Klärschlamm verbunden, bei dem neben der schwermetallarmen Schlacke mit einer hohen Advantageously, the recognized by the prior art economic and procedural advantages of plants for the exclusive energetic utilization of phosphorus-containing waste, such as mono-incinerators for sewage sludge and / or animal meal, co-incineration in power plants or additional firing in kilns in the cement industry or comparable Furnaces of other industries associated with the oxygen melt gasification of organic and phosphorus-containing waste such as. Sewage sludge, in addition to the low-heavy metal slag with a high
Zitronensäurelöslichkeit des Phosphors ähnlich dem in der Vergangenheit in der Landwirtschaft zur Phosphordüngung eingesetztem Thomasmehl und einer Metalllegierung ein Brenngas erzeugt wird, das aufbereitet zur thermischen Nachverbrennung und/oder alternativ zur energetischen Verwertung, z.B. zur Stromerzeugung im BHKW geeignet ist. Weiter vorteilhaft ist, dass die Erfindung sowohl für alle bestehenden Monoverbrennungs-Anlagen für Citric acid solubility of phosphorus similar to Thomas flour used in the past in agriculture for phosphorus fertilization and a metal alloy to produce a fuel gas which is processed for thermal afterburning and / or alternatively for energy recovery, e.g. is suitable for generating electricity in the CHP. Another advantage is that the invention for both existing mono-combustion plants for
Klärschlamm und/oder Tiermehl, für Anlagen zur Mitverbrennung von Klärschlamm und/oder anderen P-haltigen Stoffen mit hohen organischen Anteil wie Kraftwerke, Brennöfen der Zementindustrie oder vergleichbaren Öfen anderer Industriezweige als auch beim Neubau solcher Anlagen anwendbar ist und gleichzeitig die Wirtschaftlichkeit der Schmelzvergasung bei Einsatzmaterialien mit erhöhten organikarmen Ascheanteilen verbessert. Sewage sludge and / or animal meal, for co-incineration plants of sewage sludge and / or other P-containing substances with high organic content such as power plants, kilns in the cement industry or comparable ovens other industries and in the construction of such facilities is applicable and at the same time the economics of the melt gasification Improved feedstocks with increased organically poor ash content.
[012] Nachfolgend wird die Erfindung an einem Ausfuhrungsbeispiel erläutert, wobei eine Monoverbrennungs-Kapazität von 100.000 t a TS im Wirbelschicht-Ofen betrachtet wird, die im Normalbetrieb 50.000 1 a Asche erzeugt. Beispielhaft wird die Verbrennungs-Kapazität für Klärschlamm nur zu 80 % genutzt, sodass nur 40.000 t/a Asche erzeugt werden. Die Hälfte der erzeugten Asche (20.000 t/a) wird zusammen mit dem verbleibenden Klärschlamm (20.000 t/a TS) gemischt und brikettiert. Die erzeugten feuchten Briketts (45.000 t/a) werden der Schmelzvergasung im Mephrec-Reaktor zugeführt, wobei die restliche Asche (20.000 t/a) dem Reaktor staubförmig über die Düsen eingeblasen werden. Wirbelschicht-Ofen und Mephrec- Reaktor arbeiten parallel. Das bei der Schmelzvergasung erzeugte Gichtgas wird der Verbrennungszone des Wirbelschicht-Ofens direkt zugeführt und unterstützt dort den Verbrennungs- Vorgang. Das zu reinigende Abgasvolumen aus dem Wirbelschicht-Ofen ist bei dieser Fahrweise nur unwesentlich größer als im Normalbetrieb bei der Verbrennung von 100.000 t/a TS. Die Schmelzvergasung im Mephrec-Reaktor kann somit ohne zusätzliche Gasreinigungs-Kapazitäten erfolgen. Anstelle von 50.000 t/a Klärschlamm-Asche aus der Monoverbrennung von Klärschlamm werden 55.000 t/a schwermetallarme Mephrec-Schlacke erzeugt, deren P-Gehalt in einer gut pflanzenverfügbaren Form vorliegt. Die Schlacke kann als P-Dünger eingesetzt oder als Vorprodukt für Mehrnährstoff-Dünger verwendet werden. The invention is explained below using an exemplary embodiment, wherein a mono-combustion capacity of 100,000 ta TS in the fluidized-bed furnace is considered, which generates 50,000 1 a of ash during normal operation. By way of example, sewage sludge incineration capacity is only 80% utilized, producing only 40,000 t / a ash. Half of produced ash (20,000 t / a) is mixed with the remaining sewage sludge (20,000 t / a TS) and briquetted. The wet briquettes produced (45,000 t / a) are fed to the melt gasification in the Mephrec reactor, with the remaining ash (20,000 t / a) being blown into the reactor in a dust-like manner via the nozzles. Fluidized bed furnace and Mephrec reactor work in parallel. The blast furnace gas produced in the melt gasification is fed directly to the combustion zone of the fluidized bed furnace and there supports the combustion process. The volume of exhaust gas to be cleaned from the fluidized-bed furnace is only insignificantly greater in this mode of operation than during normal combustion of 100,000 t / a TS. The melt gasification in the Mephrec reactor can thus take place without additional gas purification capacities. Instead of 50,000 t / a sewage sludge ash from the mono-incineration of sewage sludge, 55,000 t / a of low-Mephrec slag with a P content in good plant-available form is produced. The slag can be used as a P fertilizer or used as a precursor for multi-nutrient fertilizer.

Claims

Patentansprüche claims
1. Verfahren zur Verwertung von phosphorhaltigen Abfallen in Anlagen für ihre 1. Method of recycling phosphorus-containing waste in plants for their
ausschließlich energetische Verwertung, wie Monoverbrennungsanlagen für Klärschlamm und/oder Tiermehl, bei der Mitverbrennung in Kraftwerken oder bei Zusatzfeuerungen in Brennöfen der Zementindustrie oder vergleichbaren Öfen anderer Industriezweige, dadurch gekennzeichnet, dass in die Anlagen zur ausschließlich energetischen Verwertung eine Anlage zur Schmelzvergasung von P-haltigen Stoffen integriert wird, die exclusively energy recovery, such as mono-incineration plants for sewage sludge and / or animal meal, co-incineration in power plants or auxiliary furnaces in furnaces of the cement industry or comparable ovens other industries, characterized in that the plants for exclusively energy recovery a plant for the melt gasification of P-containing Is integrated, which
abhängig von der Zusammensetzung der P-haltigen Stoffe eine Metallschmelze, eine depending on the composition of the P-containing substances a molten metal, a
schwermetallarme Kalk-Silico-Phosphat-haltige Schlacke und ein Brenngas erzeugt und das Brenngas in die Anlagen für die ausschließlich energetische Verwertung als Brennstoff zugeführt wird. produced low-lime lime-silico-phosphate-containing slag and a fuel gas and the fuel gas is fed into the plants for the exclusive use of energy as fuel.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die in die Anlage zur Schmelzvergasung von P-haltigen Stoffen eingebrachten Stoffe anorganisch und/oder organisch zusammengesetzte phosphorhaltige Abfalle sind, die stückig und/oder brikettiert und/oder staubförmig der Schmelzvergasung zugeführt werden. 2. The method according to claim 1, characterized in that the introduced into the plant for the melt gasification of P-containing substances inorganically and / or organically composed phosphorus-containing waste, the lumpy and / or briquetted and / or dust-like are fed to the melt gasification.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die anorganisch und/oder organisch zusammengesetzten phosphorhaltigen Abfalle Einsatzmaterialien oder Reststoffe der Anlagen für die ausschließlich energetische Verwertung phosphorhaltiger Abfalle und/oder Mischungen davon sind. 3. The method according to claim 2, characterized in that the inorganic and / or organically combined phosphorus-containing waste are feed materials or residues of the plants for the exclusive energetic utilization of phosphorus-containing waste and / or mixtures thereof.
4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass staubförmige 4. The method according to claim 2, characterized in that dust-like
phosphorhaltige Abfalle in die Hochtemperaturzone der Schmelzvergasung allein oder als Mischung mit einem Brenngas oder mit Luft und/oder Sauerstoff und/oder einem körnigen bis staubförmigen Brennstoff zugeführt werden. phosphorus-containing waste in the high-temperature zone of the melt gasification alone or as a mixture with a fuel gas or with air and / or oxygen and / or a granular to dust-like fuel are supplied.
5. Verfahren nach Anspruch 1 bis 4, gekennzeichnet dadurch, dass die Schmelzvergasung in einem Schacht-Schmelz- Vergaser wie dem Mephrec-Reaktor oder einem Schacht-Schmelz- Ofen wie dem Kupolofen erfolgt. 5. The method of claim 1 to 4, characterized in that the melt gasification takes place in a shaft melting gasifier such as the Mephrec reactor or a shaft melting furnace such as the cupola.
PCT/DE2013/000088 2012-02-22 2013-02-19 Method for utilizing phosphorous-containing wastes WO2013123926A2 (en)

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