EP0000195B1 - Process for treating sludge or ashes, especially clarified sludge sewage or clarified sewage ashes - Google Patents

Process for treating sludge or ashes, especially clarified sludge sewage or clarified sewage ashes Download PDF

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Publication number
EP0000195B1
EP0000195B1 EP78100246A EP78100246A EP0000195B1 EP 0000195 B1 EP0000195 B1 EP 0000195B1 EP 78100246 A EP78100246 A EP 78100246A EP 78100246 A EP78100246 A EP 78100246A EP 0000195 B1 EP0000195 B1 EP 0000195B1
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Prior art keywords
high temperature
sludge
clarifying
temperature treatment
ash
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German (de)
French (fr)
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EP0000195A1 (en
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Horst Dr.-Ing. Huck
Harald Dr. Dipl. Landwirt Munk
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Saarberg-Fernwarme GmbH
Thomasphosphatfabriken GmbH
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Saarberg-Fernwarme GmbH
Thomasphosphatfabriken GmbH
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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05FORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F7/00Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses

Definitions

  • the invention relates to a method for digesting sludge or ashes, in particular sewage sludge or sewage sludge ash with a proportion of undigested mineral fertilizer components, in particular insoluble phosphate compounds, for fertilizing purposes.
  • sewage treatment plants industrial or municipal wastewater is usually passed through a sand trap, which largely separates coarse particles, sand, quartz and SiO z- containing substances.
  • the wastewater is treated further using the activated sludge process and then contains only small amounts of Si0 2 .
  • the end product is a digested sewage sludge, which is usually either burned, thickened, or composted with household waste.
  • the object of the invention is to develop a method which makes it possible to digest the insoluble phosphate salts present in sewage sludge or sewage sludge ash and thereby to produce high-quality fertilizers from the products mentioned.
  • the plant-available CaNaP0 4 when using Na 2 C0 3 as a disintegrant the plant-available CaNaP0 4 can be obtained from the poorly plant-available iron, calcium and aluminum phosphates.
  • magnesium salts the readily plant-available Mg 3 (PO 4 ) 2 is formed
  • CaO calcium silicophosphates, which are readily available to plants, are formed, since the sewage sludge or its ashes can contain residual amounts of fine-grained Si0 2 .
  • the amount of disintegrating agents to be added varies greatly depending on the composition of the sewage sludge or sewage sludge ash and is generally between 5 and 40%, based on the total amount of the mixture, as the examples given later show.
  • both sewage sludge and sewage sludge ash can be fed to the high-temperature treatment in the presence of the additives Na 2 CO 3 , CaO, Ca (OH) 2 , MgO and / or MgSO 4 .
  • sewage sludge ash is to be understood as meaning both the solid residue which arises during sewage sludge incineration and during sewage sludge gasification to produce a fuel gas.
  • the treatment of the sewage sludge ash can take place in the melt, preferably in a so-called melting chamber furnace, the mass transfer in the melt being higher than in the solid phase, which leads to a shortening of the reaction times.
  • the high-temperature treatment of the sewage sludge or sewage sludge ash can also be carried out in other ovens, for example in rotary drum ovens, rotary tube ovens, muffle ovens or fluidized bed ovens.
  • a further embodiment of the method consists in briquetting the sewage sludge ash to be treated with admixture of disintegrating agents and mixing the briquettes with hot iron slag for high-temperature treatment.
  • the hot slag serves as a source of heat for the chemical reaction in the briquette between mud ash and, for example, soda.
  • the heat content of the slag is transferred to the briquettes, so that the supply of external heat can advantageously be dispensed with.
  • up to 0.7-0.8 t ash briquettes can be brought to a temperature of around 800 ° C with 1 t slag.
  • the cooled product is then ground.
  • a mixture of 80 parts ash and 20 parts soda is formed into briquettes and embedded in a ratio of 25% briquettes + 75% LD slag in hot LD slag and stored for 2 hours.
  • the result is a digested briquette mixture with a content of 19.1% P 2 O 5 at 100% relative Solubility in citric acid.
  • the joint grinding of LD slag and high-temperature treated briquettes gave a content of 9.2% P 2 0, with a relative solubility of 78%.
  • the LD slag alone showed a content of 3.7% P 2 0 5 with a relative solubility of only 46%.
  • Table 1 shows an example of the success of the method according to the invention in the result of two vegetation tests. This shows that a sewage sludge ash digested with soda has the same plant effectiveness as the standard fertilizer Thomas phosphate.
  • the figure shows an example of a schematically illustrated plant for carrying out the digestion process according to the invention.
  • Sewage sludge of any origin which contains mineral fertilizer components not available for plants, such as iron, aluminum and calcium phosphates
  • a mixing system 2 with suitable disintegrating agents, such as Na Z C0 3 or MgO, which are fed to the mixing container via a line 3 and a metering device 4, are mixed.
  • suitable disintegrating agents such as Na Z C0 3 or MgO
  • the mixture of sewage sludge and disintegrant is then conveyed into a fluidized bed furnace 6 by means of a screw conveyor 5 and burned there at a temperature of about 900 ° C.
  • the combustion air is fed to the fluidized bed furnace 6 via a line 7 and a preheater 8 and the required fuel, for example gas or oil, via a line 9.
  • the reaction products occurring in the fluidized bed furnace 6, such as exhaust gas, sand and ash, are drawn off via a line 10, cooled in a heat exchanger 11 or by admixing air and then subjected to a rough separation in a cyclone separator 12.
  • the solids separated in this process essentially sand and ash, are discharged from the cyclone separator 12 via a line 13, while the still slightly contaminated exhaust gas is fed via a line 14 to a filter 15 and is subjected to a fine cleaning therein.
  • the cleaned exhaust gas leaves the filter 15 via a line 16, while the fine ash separated in the filter 15 is drawn off via a line 17.
  • the ashes accumulating in the cyclone separator 12 and in the filter 15 can be reused as high-quality fertilizers after appropriate grinding.

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Treatment Of Sludge (AREA)

Description

Die Erfindung betrifft ein Verfahren zum Aufschließen von Schlämmen oder Aschen, insbesondere von Klärschlämmen oder Klärschlammaschen mit einem Anteil an nicht aufgeschlossenen mineralischen Düngemittelkomponenten, insbesondere an unlöslichen Phosphatverbindungen, für Düngezwecke.The invention relates to a method for digesting sludge or ashes, in particular sewage sludge or sewage sludge ash with a proportion of undigested mineral fertilizer components, in particular insoluble phosphate compounds, for fertilizing purposes.

Industrielle oder kommunale Abwässer werden in Kläranlagen üblicherweise durch einen Sandfang geleitet, welcher grobe Teile, Sand, Quarz und SiOz-enthaltende Substanzen weitgehend abscheidet. Die Abwässer werden nach dem Belebtschlammverfahren weiterbehandelt und enthalten dann nur noch geringe Mengen von Si02. Es fällt als Endprodukt ein ausgefaulter Klärschlamm an, der in der Regel entweder verbrannt, eingedickt oder zusammen mit Hausmüll kompostiert wird. Die Wirksamkeit dieser Klärschlämme oder Klärschlammaschen für Düngezwecke wird dadurch beeinträchtigt, daß die in ihnen enthaltenen mineralischen Düngemittelkomponenten, insbesondere die durch Fällungsmittel ausgefällten Phosphatverbindungen, wie Eisen-, Aluminium- oder Kalziumphosphate, aufgrund ihrer Unlöslichkeit für die Pflanzen als Düngemittel nicht voll verfügbar sind, d.h. die Pflanzenwurzeln sind nur unvollkommen in der Lage, diese nicht aufgeschlossenen Phosphatsalze aufzunehmen.In sewage treatment plants, industrial or municipal wastewater is usually passed through a sand trap, which largely separates coarse particles, sand, quartz and SiO z- containing substances. The wastewater is treated further using the activated sludge process and then contains only small amounts of Si0 2 . The end product is a digested sewage sludge, which is usually either burned, thickened, or composted with household waste. The effectiveness of these sewage sludge or sewage sludge ash for fertilizing purposes is impaired by the fact that the mineral fertilizer components they contain, in particular the precipitated phosphate compounds, such as iron, aluminum or calcium phosphates, are not fully available as fertilizers because of their insolubility for the plants, ie the plant roots are only imperfectly able to absorb these undigested phosphate salts.

Aus der FR - A - 2 237 127 ist es bekannt, aus Flüssen, Häfen und Sedimentationsteichen gewonnenen, hauptsächlich aus Si02 bestehenden Schlamm zu trocknen, das getrocknete Schlammpulver zwecks Schmelzpunkterniedrigung mit einem Natriumsalz oder Kalksalz zu mischen, die Mischung auf 1 200°C oder darüber zu erhitzen und die geschmolzene Masse in Wasser zu einem nichtstaubenden, glasartigen, wasserunlöslichen Granulat erstarren zu lassen. Dieses bekannte Verfahren wandelt Schlämme durch Zumischung der genannten Zuschlagstoffe vor einem Schmelzprozeß in eine wasser- und säureunlösliche Glas- oder Wasserglasmasse um, die sich in Granulat- oder Blockform für den Straßenbau, nicht aber für Düngezwecke eignet.From FR - A - 2 237 127 it is known to dry sludge, mainly consisting of SiO 2 , obtained from rivers, harbors and sedimentation ponds, to mix the dried sludge powder with a sodium salt or lime salt in order to lower the melting point, the mixture to 1200 ° C or heat it over and allow the melted mass to solidify in water to form a non-dusting, glass-like, water-insoluble granulate. This known method converts sludges by admixing the additives mentioned before a melting process into a water- and acid-insoluble glass or water glass mass, which is suitable in granular or block form for road construction, but not for fertilizing purposes.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zu entwickeln, welches es ermöglicht, die in Klärschlämmen oder Klärschlammaschen vorhandenen unlöslichen Phosphatsalze aufzuschließen und dadurch aus den genannten Produkten hochwertige Düngemittel zu erzeugen.The object of the invention is to develop a method which makes it possible to digest the insoluble phosphate salts present in sewage sludge or sewage sludge ash and thereby to produce high-quality fertilizers from the products mentioned.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß die Schlämme oder Aschen, insbesondere die Klärschlämme oder Klärschlammaschen, in Gegenwart einer oder mehrerer der Verbindungen Na2C03, CaO, Ca(OH)2, MgO und/oder MgS04 einer Hochtemperaturbehandlung bis zu 1 200°C unterzogen werden, wobei die schwerlöslichen Phosphate in gut wasser- und/oder zitronensäurelösliche (= pflanzenverfügbare) Phosphatverbindungen umgewandelt werden.This object is achieved in that the sludge or ash, in particular the sewage sludge or sewage sludge ash, in the presence of one or more of the compounds Na 2 CO 3 , CaO, Ca (OH) 2 , MgO and / or MgSO 4, a high-temperature treatment up to 1 200 ° C, the poorly soluble phosphates are converted into water and / or citric acid soluble (= plant-available) phosphate compounds.

Durch die erfindungsgemäße Behandlung des Klärschlammes oder der Klärschlammasche mit einer Verbindung der vorgenannten Art, welche mit den für die Pflanzenwurzeln night verfügbaren Düngemittelkomponenten im Zuge einer Hochtemperaturbehandlung chemisch derart reagiert, daß wasser- und/oder zitronensäurelösliche Substanzen entstehen, welche nunmehr für die Pflanzen als Düngemittel verfügbar sind, gelingt es, aus wenig wertvollem Klärschlamm oder wenig wertvoller Klärschlammasche einen hochwertigen Dünger zu erzeugen.By treating the sewage sludge or the sewage sludge ash according to the invention with a compound of the aforementioned type which chemically reacts with the fertilizer components available for the plant roots at night in the course of a high-temperature treatment in such a way that water- and / or citric acid-soluble substances are formed which are now used as fertilizers for the plants are available, it is possible to produce a high-quality fertilizer from less valuable sewage sludge or less valuable sewage sludge ash.

Im Hinblick auf die im Klärschlamm enthaltenen Phosphatverbindungen, wie z.B. die Eisen-, Calcium- und Aluminiumphosphate, läßt sich bei der Verwendung von Na2C03 als Aufschlußmittel aus den schlecht pflanzenverfügbaren Eisen-, Calcium- und Aluminiumphosphaten das pflanzenverfügbare CaNaP04 gewinnen. Bei Verwendung von Magnesiumsalzen entsteht das gut pflanzenverfügbare Mg3(PO4)2, während bei Verwendung von CaO gut pflanzenverfügbare Calciumsilicophosphate entstehen, da die Klärschlämme bzw. deren Aschen Restmengen an feinkörnigem Si02 enthalten können.With regard to the phosphate compounds contained in the sewage sludge, such as the iron, calcium and aluminum phosphates, when using Na 2 C0 3 as a disintegrant the plant-available CaNaP0 4 can be obtained from the poorly plant-available iron, calcium and aluminum phosphates. When using magnesium salts, the readily plant-available Mg 3 (PO 4 ) 2 is formed , while when using CaO, calcium silicophosphates, which are readily available to plants, are formed, since the sewage sludge or its ashes can contain residual amounts of fine-grained Si0 2 .

Die Menge der zuzusetzenden Aufschlußmittel schwankt stark in Abhängigkeit von der Zusammensetzung des Klärschlammes bzw. der Klärschlammasche und liegt in der Regel zwischen 5 und 40%, bezogen auf die Gesamtmenge der Mischung, wie die später angeführten Beispiele zeigen.The amount of disintegrating agents to be added varies greatly depending on the composition of the sewage sludge or sewage sludge ash and is generally between 5 and 40%, based on the total amount of the mixture, as the examples given later show.

Gemäß dem Verfahren nach der Erfindung kann sowohl Klärschlamm als auch Klärschlammasche der Hochtemperaturbehandlung in Gegenwart von den Zuschlagstoffen Na2C03, CaO, Ca(OH)2, MgO und/oder MgS04 zugeführt werden. Hierbei ist unter Klärschlammasche sowohl der bei der Klärschlammverbrennung als auch der bei Klärschlammvergasung zur Erzeugung eines Brenngases anfallende feste Rückstand zu verstehen. Die Behandlung der Klärschlammasche kann in der Schmelze, vorzugsweise in einem sogenannten Schmelzkammerofen erfolgen, wobei der Stoffaustausch in der Schmelze höher ist als in der festen Phase, was zu einer Verkürzung der Reaktionszeiten führt.According to the method according to the invention, both sewage sludge and sewage sludge ash can be fed to the high-temperature treatment in the presence of the additives Na 2 CO 3 , CaO, Ca (OH) 2 , MgO and / or MgSO 4 . Here, sewage sludge ash is to be understood as meaning both the solid residue which arises during sewage sludge incineration and during sewage sludge gasification to produce a fuel gas. The treatment of the sewage sludge ash can take place in the melt, preferably in a so-called melting chamber furnace, the mass transfer in the melt being higher than in the solid phase, which leads to a shortening of the reaction times.

Es hat sich gezeigt, daß der Wirkungsgrad des Verfahrens nach der Erfindung am größten ist bei Reaktionstemperaturen zwischen 600 und 1 200°C, vorzugsweise bei 900°C.It has been shown that the efficiency of the process according to the invention is greatest at reaction temperatures between 600 and 1200 ° C, preferably at 900 ° C.

Die Hochtemperaturbehandlung des Klärschlammes oder der Klärschlammasche kann auch in anderen Öfen, beispielsweise in Drehtrommelöfen, Drehrohröfen, Muffelöfen oder Wirbelschichtöfen durchgeführt werden.The high-temperature treatment of the sewage sludge or sewage sludge ash can also be carried out in other ovens, for example in rotary drum ovens, rotary tube ovens, muffle ovens or fluidized bed ovens.

Als besonders wirkungsvoll erweist sich dabei die Behandlung des Klärschlammes oder der Klärschlammasche in einem Wirbelschichtofen, in dem alle Reaktionspartner in einem stark turbulenten Bewegungszust and gehalten werden. Sowohl der Stoff- als auch der Wärmeübergang zwischen den Reaktionspartnern ist somit groß, so daß mit relativ kurzen Verweilzeiten (etwa 2-20 sec.) gefahren werden kann.The treatment of the sewage sludge or the sewage sludge ash in a fluidized bed furnace in which all reactants are kept in a highly turbulent state of motion proves to be particularly effective. Both the mass and the heat transfer between the Reaction partners is thus large, so that it can be driven with relatively short dwell times (about 2-20 sec.).

Eine weitere Ausgestaltung des Verfahrens besteht darin, die zu behandelnde Klärschlammasche unter Zumischung von Aufschlußmitteln zu brikettieren und die Briketts zur Hochtemperaturbehandlung mit heißen Eisenhüttenschlacken zu vermengen. Dabei dient die heiße Schlacke als Wärmelieferant für die chemische Umsetzung im Brikett zwischen Schlammasche und beispielsweise Soda. Der Wärmeinhalt der Schlacke wird auf die Briketts übertragen, so daß in vorteilhafter Weise auf die Zufuhr von Fremdwärme verzichtet werden kann. Je nach dem Wärmeverlust der Schlakke, der zum Beispiel durch Abstrahlung bedingt ist, können mittels 1 t Schlacke bis zu 0,7-0,8 t Aschebriketts auf eine Temperatur von etwa 800°C gebracht werden. Das erkaltete Produkt wird anschließend vermahlen.A further embodiment of the method consists in briquetting the sewage sludge ash to be treated with admixture of disintegrating agents and mixing the briquettes with hot iron slag for high-temperature treatment. The hot slag serves as a source of heat for the chemical reaction in the briquette between mud ash and, for example, soda. The heat content of the slag is transferred to the briquettes, so that the supply of external heat can advantageously be dispensed with. Depending on the heat loss of the slag, which is caused, for example, by radiation, up to 0.7-0.8 t ash briquettes can be brought to a temperature of around 800 ° C with 1 t slag. The cooled product is then ground.

Durch diese Verfahrensvariante lassen sich somit zwei umweltrelevante Abfallstoffe mit Hilfe von bisher ungenutzter und daher verlorener Wärmeenergie in hohem Maße zu nutzbaren, für die Landwirtschaft wertvollen Düngemitteln vereinigen.With this process variant, two environmentally relevant waste materials can be combined to a large extent with the help of previously unused and therefore lost heat energy to make usable fertilizers that are valuable for agriculture.

Für die Zugabe von den Aufschlußmittel NaZC03, CaO, Ca(OH)2' MgO und/oder MgS04 zu dem zu behandelnden Klärschlamm bieten sich mehrere Möglichkeiten an:

  • Das Aufschlußmittel kann, falls es wasserunlöslich ist, bereits im Zuge der Reinigung der Abwässer zugegeben werden; es kann aber auch erst später dem bereits eingedickten bzw. ausgeflockten oder thermisch konditionierten Klärschlamm zugemischt werden, oder es wird unmittelbar in die Hochtemperaturbehandlungszone eingeführt. Bei Kläranlagen, die bereits mit einer Verbrennungsanlage für den anfallenden Klärschlamm ausgerüstet sind, erweist es sich als zweckmäßig, das Aufschlußmittel zusätzlich in die Verbrennungsanlage einzuführen und somit die Aufschließung der nicht pflanzenverfügbaren Phosphate an Ort und Stelle durchzuführen. In diesem Falle ist der zusätzliche Investitionsaufwand zur Durchführung des erfindungsgemäßen Verfahrens besonders gering.
There are several options for adding the digesting agents Na Z C0 3 , CaO, Ca (OH) 2 ' MgO and / or MgS0 4 to the sewage sludge to be treated:
  • If it is insoluble in water, the disintegrant can already be added during the purification of the waste water; however, it can also be added to the already thickened or flocculated or thermally conditioned sewage sludge later, or it is introduced directly into the high-temperature treatment zone. In sewage treatment plants that are already equipped with an incineration plant for the sewage sludge that arises, it proves to be expedient to additionally introduce the disintegrant into the incineration plant and thus to carry out the disintegration of the phosphates which are not available to the plant on site. In this case, the additional investment required to carry out the method according to the invention is particularly low.

Nachfolgend wird die Erfindung anhand von Ausführungsbeispielen und einer Zeichnung näher erläutert. Es zeigen

  • - die Beispiele 1-6 mit verschiedenen Aufschlußmitteln durchgeführte Versuche. Dabei ist die angegebene Löslichkeit sowohl der unbehandelten als auch der aufgeschlossenen Klärschlammasche in 2%iger Zitronensäure (pH=3,4) ein Maß für die Pflanzenverfügbarkeit der gewonnenen Düngemittel,
  • - die Tabelle 1 das Ergebnis zweier Vegetationsversuche,
  • - die Figur ein schematisch dargestelltes Ausführungsbeispiel einer bevorzugten Verfahrensvariante zur Durchführung des erfindungsgemäßen Verfahrens.
The invention is explained in more detail below on the basis of exemplary embodiments and a drawing. Show it
  • - Examples 1-6 experiments carried out with different disintegrants. The stated solubility of both the untreated and the digested sewage sludge ash in 2% citric acid (pH = 3.4) is a measure of the plant availability of the fertilizers obtained,
  • - Table 1 the result of two vegetation tests,
  • - The figure shows a schematically illustrated embodiment of a preferred method variant for performing the method according to the invention.

Beispiel 1example 1

85 Teile Klärschlammasche (Löslichkeit in 2%iger Zitronensäure=0,5%) werden mit 15 Teilen Kieserit (MgS04) innig vermischt und in einem Drehrohrofen bei 1 200°C behandelt. Es resultiert eine Aufschlußmasse, die bei einem Gehalt von 21,5% P2O5 eine relative Löslichkeit in Zitronensäure von 71% aufweist.85 parts of sewage sludge ash (solubility in 2% citric acid = 0.5%) are mixed intimately with 15 parts of kieserite (MgS0 4 ) and treated in a rotary kiln at 1200 ° C. The result is a digestion mass which, at a content of 21.5% P 2 O 5, has a relative solubility in citric acid of 71%.

Beispiel 2Example 2

71 Teile Asche werden mit 29 Teilen CaO innig vermischt und in einem Muffelofen bei 1 200°C behandelt. Es resultiert eine Aufschlußmasse, die bei einem Gehalt von 16,1% P20, eine relative Löslichkeit in Zitronensäure von 87% aufweist.71 parts of ashes are intimately mixed with 29 parts of CaO and treated in a muffle furnace at 1200 ° C. The result is a digestion mass which, at a content of 16.1% P 2 0, has a relative solubility in citric acid of 87%.

Beispiel 3Example 3

82 Teile Asche werden mit 18 Teilen Soda innig vermischt und in einem Drehrohrofen bei 900°C behandelt. Es resultiert eine Aufschlußmasse, die bei einem Gehalt von 19,8% P20, eine relative Löslichkeit in Zitronensäure von 95% aufweist.82 parts of ashes are intimately mixed with 18 parts of soda and treated in a rotary kiln at 900 ° C. The result is a digestion mass which, at a content of 19.8% P 2 0, has a relative solubility in citric acid of 95%.

Beispiel 4Example 4

80 Teile Asche werden mit 16 Teilen Soda und 4 Teilen CaO innig vermischt und bei 950°C behandelt. Es resultiert eine Aufschlußmasse, die bei einem Gehalt von 18,9% P2O5 eine relative Löslichkeit in Zitronensäure von 92% aufweist.80 parts of ashes are intimately mixed with 16 parts of soda and 4 parts of CaO and treated at 950 ° C. The result is a digestion mass which, at a content of 18.9% P 2 O 5, has a relative solubility in citric acid of 92%.

Beispiel 5Example 5

50 Teile Klärschlamm mit einem Wassergehalt von 50% und einem P2O5-Gehalt in der Trockenmasse von 7,3% werden mit 1,8 Teilen Soda innig vermischt und bei steigender Temperatur bis 950°C verbrannt. Es resultiert eine chemisch aufgeschlossene Masse, die bei einem Gehalt von 18,7% P2O5 eine relative Löslichkeit in Zitronensäure von 73% aufweist.50 parts of sewage sludge with a water content of 50% and a P 2 O 5 content in the dry matter of 7.3% are mixed intimately with 1.8 parts of soda and burned to 950 ° C with increasing temperature. The result is a chemically digested mass which, at a content of 18.7% P 2 O 5, has a relative solubility in citric acid of 73%.

Beispiel 6Example 6

Eine Mischung aus 80 Teilen Asche und 20 Teilen Soda wird zu Briketts geformt und im Verhältnis 25% Briketts + 75% LD-Schlacke in heißer LD-Schlacke eingebettet und 2 Stunden gelagert. Es resultiert eine aufgeschlossene Brikettmischung mit einem Gehalt von 19,1% P2O5 bei 100% relativer Löslichkeit in Zitronensäure. Die gemeinsame Vermahlung von LD-Schlacke und hochtemperaturbehandelten Briketts ergab einen Gehalt von 9,2% P20, bei einer relativen Löslichkeit von 78%. Die LD-Schlacke allein zeigte einen Gehalt von 3,7% P205 bei einer relativen Löslichkeit von nur 46%.A mixture of 80 parts ash and 20 parts soda is formed into briquettes and embedded in a ratio of 25% briquettes + 75% LD slag in hot LD slag and stored for 2 hours. The result is a digested briquette mixture with a content of 19.1% P 2 O 5 at 100% relative Solubility in citric acid. The joint grinding of LD slag and high-temperature treated briquettes gave a content of 9.2% P 2 0, with a relative solubility of 78%. The LD slag alone showed a content of 3.7% P 2 0 5 with a relative solubility of only 46%.

In der Tabelle 1 ist als Beispiel für den Erfolg des erfindungsgemäßen Verfahrens des Ergebnis zweier Vegetationsversuche dargestellt. Hieraus geht hervor, daß eine mit Soda aufgeschlossene Klärschlammasche die gleiche Pflanzenwirksamkeit entfaltet wie dans Standarddüngemittel Thomasphosphat.Table 1 shows an example of the success of the method according to the invention in the result of two vegetation tests. This shows that a sewage sludge ash digested with soda has the same plant effectiveness as the standard fertilizer Thomas phosphate.

In der Figur ist beispielhaft eine schematisch dargestellte Anlage zur Durchführung des erfindungsgemäßen Aufschlußverfahrens dargestellt. Hierbei wird Klärschlamm beliebiger Herkunft, der mineralische, für Pflanzen nicht verfügbare Düngemittelkomponenten, wie z.B. Eisen-, Aluminium- und Calciumphosphate enthält, über eine Leitung 1 der Anlage zugeführt und in einer Mischanlage 2 intensiv mit geeigneten Aufschlußmittel, wie z.B. NaZC03 oder MgO, welche über eine Leitung 3 und eine Dosiervorrichtung 4 dem Mischbehälter zugeleitet werden, vermischt. Daraufhin wird die Mischung aus Klärschlamm und Aufschlußmittel mittels einer Förderschnecke 5 in einen Wirbelschichtofen 6 gefördert und dort bei einer Temperatur von etwa 900°C verbrannt. Die Verbrennungsluft wird dem Wirbelschichtofen 6 über eine Leitung 7 und einen Vorerhitzer 8 und der erforderliche Brennstoff, z.B. Gas oder Öl, über eine Leitung 9 zugeleitet.The figure shows an example of a schematically illustrated plant for carrying out the digestion process according to the invention. Sewage sludge of any origin, which contains mineral fertilizer components not available for plants, such as iron, aluminum and calcium phosphates, is fed to the system via a line 1 and intensively in a mixing system 2 with suitable disintegrating agents, such as Na Z C0 3 or MgO, which are fed to the mixing container via a line 3 and a metering device 4, are mixed. The mixture of sewage sludge and disintegrant is then conveyed into a fluidized bed furnace 6 by means of a screw conveyor 5 and burned there at a temperature of about 900 ° C. The combustion air is fed to the fluidized bed furnace 6 via a line 7 and a preheater 8 and the required fuel, for example gas or oil, via a line 9.

Durch die Zugabe der genannten Aufschlußmittel zu dem Klärschlamm findet im Zuge der Verbrennung des Schlammes gleichzeitig eine chemische Umwandlung der im Klärschlamm enthaltenen unlöslichen Phosphatverbindungen in wasser- und/oder zitronensäurelösliche Phosphatverbindungen statt, die nunmehr für Pflanzenwurzeln aufnehmbar sind und sich somit in besonderem Maße als Dungemittel eignen.By adding the above-mentioned disintegrants to the sewage sludge, during the course of the combustion of the sludge there is a chemical conversion of the insoluble phosphate compounds contained in the sewage sludge into water- and / or citric acid-soluble phosphate compounds, which can now be absorbed by plant roots and are therefore particularly useful as fertilizers own.

Die im Wirbelschichtofen 6 anfallenden Reaktionsprodukte wie Abgas, Sand und Asche werden über eine Leitung 10 abgezogen, in einem Wärmetauscher 11 oder durch Luftzumischung abgekühlt und dann in einem Zyklonabscheider 12 einer Grobzerlegung unterzogen. Die hierbei abgetrennten Feststoffe, im wesentlichen Sand und Asche, werden über eine Leitung 13 aus dem Zyklonabscheider 12 abgeleitet, während das noch geringfügig verunreinigte Abgas über eine Leitung 14 einem Filter 15 zugeführt und in diesem einer Feinreinigung unterzogen wird. Das gereinigte Abgas verläßt das Filter 15 über eine Leitung 16, während die im Filter 15 abgetrennte Feinasche über eine Leitung 17 abgezogen wird.The reaction products occurring in the fluidized bed furnace 6, such as exhaust gas, sand and ash, are drawn off via a line 10, cooled in a heat exchanger 11 or by admixing air and then subjected to a rough separation in a cyclone separator 12. The solids separated in this process, essentially sand and ash, are discharged from the cyclone separator 12 via a line 13, while the still slightly contaminated exhaust gas is fed via a line 14 to a filter 15 and is subjected to a fine cleaning therein. The cleaned exhaust gas leaves the filter 15 via a line 16, while the fine ash separated in the filter 15 is drawn off via a line 17.

Die im Zyklonabscheider 12 sowie im Filter 15 anfallenden Aschen können nach entsprechender Aufmahlung als hochwertige Düngemittel weiterverwendet werden.

Figure imgb0001
The ashes accumulating in the cyclone separator 12 and in the filter 15 can be reused as high-quality fertilizers after appropriate grinding.
Figure imgb0001

Claims (10)

1. A process for the decomposition of sludges or ashes, in particular clarifying sludges or clarifying sludge ash having a proportion of undecomposed mineral fertilizer components, in particular insoluble phosphate compounds, for fertilizer purposes, characterised in that the sludges or ashes, in particular the clarifying sludges or clarifying sludge ash, are treated at a high temperature up to 1200°C, in the presence of one or more of the compounds Na2CO3, CaO, Ca(OH),, MgO and MgS04, whereby the difficultly-soluble phosphates are converted into phosphate compounds which are highly soluble in water and/or citric acid and which are usable by plants.
2. A process as claimed in Claim 1, characterised in that the high temperature treatment is carried out at temperatures of between 600 and 1200°C, in particular at a temperature of 900°C.
3. A process as claimed in Claim 1 and 2, characterised in that the difficultly-soluble iron phosphates, calcium phosphates and aluminium phosphates are converted by the high temperature treatment and the addition of lime into CaNaP04, which is usable by plants.
4. A process as claimed in Claim 1 and 2, characterised in that by the addition of MgO and/or MgS04, the difficultly-soluble phosphates are converted during the high temperature treatment into Mg3(PO4)2, which is readily usable by plants.
5. A process as claimed in Claim 1 and 2, characterised in that, by the addition of CaO and/or Ca(OM)2 with the co-operation of sand residues which are contained in the sludge or clarifying sludge, calcium silicophosphates are produced, which are readily usable by plants.
6. A process as claimed in one of Claims 1 to 5, characterised in that the Na2C03, CaO, Ca(OH)2, MgO and/or MgS04 are added to the sludge or ash, in particular the clarifying sludge or clarifying sludge ash, before or during the high temperature treatment.
7. A process as claimed in one of Claims 1 to 6, characterised in that the high temperature treatment is effected in a rotary drum furnace, a rotary tube furnace, or a shelved furnace.
8. A process as claimed in one of Claims 1 to 6, characterised in that the high temperature treatment is carried out in a fluidized bed furnace.
9. A process as claimed in one of Claims 1 to 6, characterised in that the high temperature treatment is carried out in a muffle furnace or melting chamber furnace, that the clarifying sludge ash is melted and its treatment with the sodium compounds, calcium compounds and/or magnesium compounds, is effected in the melt.
10. A process as claimed in Claim 1 or 6, characterised in that the clarifying sludge ash and the Na2C03, CaO, Ca(OH)2, MgO and/or MgSO4 are briquetted and the briquettes are subjected to the high temperature treatment by mixing with hot ironworks slag.
EP78100246A 1977-06-29 1978-06-27 Process for treating sludge or ashes, especially clarified sludge sewage or clarified sewage ashes Expired EP0000195B1 (en)

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DE2729277 1977-06-29
DE19772729277 DE2729277A1 (en) 1977-06-29 1977-06-29 METHODS FOR TREATMENT OF SLUDGE OR ASH, IN PARTICULAR OF SEWING SLUDGE OR SEWING SLUDGE ASH

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EP0000195B1 true EP0000195B1 (en) 1982-04-21

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EP1134206B1 (en) 2000-03-16 2013-05-15 GFR Gesellschaft für die Aufbereitung und Verwertung von Reststoffen mbH Use of incineration ashes of sewage sludge as phosphatic fertiliser
DE10243840B4 (en) * 2002-09-13 2004-07-22 BAM Bundesanstalt für Materialforschung und -prüfung Process for the separation of environmentally relevant heavy metals from sewage sludge ash
JP2006001819A (en) * 2004-06-21 2006-01-05 Tokyo Metropolis Method and apparatus for manufacturing phosphorus fertilizer using incineration ash
DE102004059935A1 (en) 2004-12-09 2006-06-14 BAM Bundesanstalt für Materialforschung und -prüfung Process for the separation of heavy metals from sewage sludge ash
DE102009014884B4 (en) 2009-03-25 2014-11-06 Ingeborg Klose Process for the elimination of pollutants from sewage sludge and process for the production of phosphates and phosphate-containing compounds
EP2725001B1 (en) * 2011-06-27 2019-10-02 Taiheiyo Cement Corporation Phosphate fertilizer, and method for producing phosphate fertilizer
JP6021182B2 (en) * 2012-12-14 2016-11-09 太平洋セメント株式会社 Method for producing a bitter earth phosphate fertilizer
KR101782709B1 (en) * 2013-05-03 2017-09-27 오토텍 (핀랜드) 오와이 Process and plant for separating heavy metals from phosphoric starting material
JP6391142B2 (en) * 2014-02-13 2018-09-19 太平洋セメント株式会社 Method for producing phosphate fertilizer
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EP0000195A1 (en) 1979-01-10
AT361414B (en) 1981-03-10
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ATA454078A (en) 1980-07-15
DE2729277A1 (en) 1979-01-04

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