CA2877061A1 - Method and plant for recovering material and/or energy from phosphorus-containing waste - Google Patents
Method and plant for recovering material and/or energy from phosphorus-containing waste Download PDFInfo
- Publication number
- CA2877061A1 CA2877061A1 CA 2877061 CA2877061A CA2877061A1 CA 2877061 A1 CA2877061 A1 CA 2877061A1 CA 2877061 CA2877061 CA 2877061 CA 2877061 A CA2877061 A CA 2877061A CA 2877061 A1 CA2877061 A1 CA 2877061A1
- Authority
- CA
- Canada
- Prior art keywords
- phosphorus
- air
- dust
- energy
- metallurgical
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/04—Calcareous fertilisers from blast-furnace slag or other slags containing lime or calcium silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- 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
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B5/00—Thomas phosphate; Other slag phosphates
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
- F23J15/022—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
-
- 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
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
-
- 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
Abstract
The invention relates to a method and a plant for recovering material and energy from phosphorus-containing waste by means of an air-assisted smelting-gasification and/or oxygen-assisted smelting-gasification process in metallurgical shaft furnaces. In said method, the phosphorus and/or phosphorous compounds reaching the gas phase in metallurgical shaft furnaces during the method-specific recovery of material and energy from phosphorus-containing waste by means of air-assisted and/or oxygen-assisted smelting-gasification can be easily separated and be used for metallurgical material recycling processes without having to go through a complex wet gas purification process combined with an integrated quenching step to obtain cooling to about 5°C, e.g. because of organic residues contained in the waste.
Description
= 2 Method And Plant For Recovering Material And/Or Energy From Phosphorus-Containing Waste The invention relates to a method and to a plant for recovering material and energy from phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces.
The recycling industry is increasingly pursuing the objective of reducing the consumption of finite natural resources, including phosphorus, or of using such resources more efficiently ["Kreislaufwirtschaft Pflanzennahrstoffe, insbesondere Phosphor" (Closed loop recycling management of plant nutrients, in particular phosphorus) funding initiative, final presentation, Berlin on 09/14/2011 , Dohmann, Conference Paper 1]. Phosphorus is essential for all biological processes and plays a key role in the transfer and storage of energy and in the synthesis of amino acids and proteins, cannot be substituted, and is the limiting factor for many growth processes. It is not consumed, but is diluted, making enrichment increasingly economically complex. The most important source for phosphorus recovery is animal and human excretions (sewage sludge).
When fully recycled, sewage sludge (66,000 Mg P/a) as well as animal and bone meal (23,700 Mg P/a) allow approximately 75% of Germany's mineral fertilizer imports (on average, 120,000 Mg P/a) to be saved ["Kreislaufwirtschaft Pflanzennahrstoffe, insbesondere Phosphor" (Closed loop recycling management of plant nutrients, in particular phosphorus) funding initiative, final presentation, Berlin on 09/14/2011 , Pinnekamp, Conference Paper Introductory Remarks].
According to the prior art, the following process-based / plant-based solutions for recycling sewage sludge, animal meal and their ashes from the respective mono-incineration processes are considered to be particularly promising ["Kreislaufwirtschaft Pflanzennahrstoffe, . 3 insbesondere Phosphor" (Closed loop recycling management of plant nutrients, in particular phosphorus) funding initiative, final presentation, Berlin on 09/14/2011 , Rosckosch, Conference Paper German Federal Environmental Agency].
- ASH DEC - thermochemical process Product: phosphate fertilizer (raw product, optionally multi-nutrient fertilizer) made of sewage sludge ashes by heating in a rotary kiln while adding additives - Mephrec - metallurgical process Product: lime phosphate fertilizer from sewage sludge, sewage sludge ashes and other phosphorus-containing waste by way of air and/or oxygen melt gasification in a fixed bed reactor - PhosRec - special sintering process Product: phosphate fertilizer or phosphate resource from animal meal by incineration in a rotary kiln, while simultaneously utilizing the recovered energy.
Previously, only the Mephrec process achieved the simultaneous material and energy recovery from organic, phosphorus-containing waste having varying degrees of calorific values and/or feed materials in one method step, by generating a phosphorus-containing slag , which is comparable to the well-known fertilizer "Thomas meal" and has high solubility in citric acid of the lime silicophosphates formed in the slag matrix, an iron metal alloy, which acts in a method-specific manner as a heavy metal drain, and a fuel gas, which has varying degrees of calorific ' 4 values and is suitable after purification for direct energy generation via gas motors or units comparable to these.
Such a metallurgical method for recovering energy and material from inorganic and/or organic waste having a high calorific value and for minimizing the necessary method-related, plant-related, production organizational and therefore financial expenditures for processing the feed materials into formed bodies or briquettes is claimed according to DE 10 2008 045 289, in which the waste that has a high calorific value and/or is rich in recyclable fractions and brings about material binding is mixed, either as a binding agent alone or in combination with a hydraulic binding agent content and/or an opening material, with further inorganic and/or organic waste that has a high calorific value and/or is rich recyclable fractions, thereafter formed and/or pressed or extruded to obtain formed bodies or briquettes and/or is compacted or formed into briquettes by other method steps, stored, and subsequently used for the simultaneous recovery of energy and material in a single method step, utilizing known metallurgical procedure techniques in cupola melting furnaces, oxygen cupola melting furnaces, shaft melt gasifiers, high-temperature oxygen melt gasifiers or similar metallurgical units as bulk material. As the bulk material, which, in total, is composed of coke and/or coke substitutes, mineral and/or metallic aggregates added, or not added, based on melting and gasification aspects, and the molded bodies and/or briquettes, moves downward, it is dried in the furnace shaft, heated, gasified and subsequently melted, wherein, depending on the composition of the molded bodies or briquettes forming the bulk material, at the same time a furnace gas that has a high calorific value, which is to say that has not been spent, a liquid slag that is high in recyclable fractions, and a liquid metal alloy are created in the reduction zone that exists in the metallurgical unit.
The waste that has a high calorific value and/or is rich in recyclable fractions and brings about the material binding can also be bone meal and/or animal meal. Cement and/or cement substitutes are claimed as hydraulically acting binding agents. The opening materials, which are added in particular to waste that has a high calorific value and/or is rich in recyclable fractions and high in moisture, are in particular ashes and/or slags and/or mineral and/or metallic and/or oxidic granular or pulverulent substances that are high in recyclable fractions and/or rich in phosphorus. Further inorganic and/or organic waste that has a high calorific value and/or is rich in recyclable fractions can be mixtures of sewage sludge and/or further organic and/or inorganic phosphorus-containing substances and/or substances that increase the calorific value.
The method is characterized in that a furnace gas that has a high calorific value, which is to say that has not been spent, a liquid slag that is rich in recyclable fractions, which is to say rich in phosphorus, and a liquid metal alloy acting as a heavy metal drain are created simultaneously in the metallurgical unit.
The disadvantage is that, in a way that is specific to the method, a furnace gas that has a high calorific value and has not been spent is generated, which prior to the energetic use for power generation necessitates a complex, wet gas purification process that is combined with an integrated quenching step for the purpose of cooling to approximately 5 C, due to organic residues that are present.
It is further disadvantageous that, in a way that is specific to the method, phosphorus and/or phosphorus compounds reaching the gas phase require technically and technologically complex separation in the gas purification process, and therefore cannot be used for the metallurgical material recycling.
DE 000002952642 Al describes a method for the dry hot purification of gases containing harmful substances, such as process gases and waste gases from thermal treatment plants, which are created during the pyrolysis of waste substances by heating them to the decomposition temperature, for example, in which the harmful substance-containing raw gas is caused to react at an elevated temperature with the additives that are added to the raw gas, and the harmful substances are thus removed from the raw gas.
The disadvantage is that the dust separated during gas purification contains reaction products of harmful substance and additives, which result in undesirable accumulations during the recirculation into the thermal treatment plants.
It is therefore the object of the invention to create a method and a plant for recovering material and energy from phosphorus-containing waste, in which, without the use of a complex, wet gas purification process that is combined with an integrated quenching step for the purpose of cooling to approximately 5 C, for example due to organic residues that are present, the phosphorus and/or phosphorus compounds reaching the gas phase, in a way specific to the method, during the material and energy recovery of phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces can be easily separated and rendered usable for metallurgical material recycling.
The object is achieved by integrating a post-incineration chamber, which is integrated in or directly on the metallurgical shaft furnace, as an integral part of a graduated gas purification process, comprising a dry dedusting step without adding additives for binding and removing gaseous harmful substances by a dedusting device having integrated dust recirculation into the melting and superheating zone of the metallurgical shaft furnace, without adding additives for binding and removing gaseous harmful substances according to the features of the claims.
Advantageously, the apparatus-related, economical and process-related advantages recognized according to the prior art of metallurgical shaft furnaces with direct post-incineration of furnace gases are combined with the air and/or oxygen melt gasification of organic matter-and phosphorus-containing waste, such as sewage sludge, by directly post-incinerating the fuel gas, which has a high calorific value and is directly generated in the furnace for air and/or oxygen melt gasification, with an excess of incineration material ( X.> 1) to obtain a dust-laden, completely spent offgas, without binding gaseous harmful substances by way of additives.
In in-house examinations, it was surprisingly found that the phosphorus and/or the phosphorus compounds reaching the gas phase largely as aerosols, due to the nature of the method, can basically be fully converted into an oxide, hereafter referred to as phosphate, separated after cooling to below the melting temperature of P205, which is to say below 340 C, as a dust component from the first stage of simple, dry dedusting according to the prior art, and recirculated into the melting and superheating zone of the furnace for air and/or oxygen melt gasification. In a second stage then, gaseous harmful substances, such as S
and Cl compounds, are easily separated from the gas, likewise according to the prior art, for example by adding additives and/or by integrating scrubbers.
During the recirculation of the dust from the first stage of dry dedusting, an accumulation of highly volatile heavy metals may occur in the dust that is removed with the fully post-incinerated gas, depending on the content of these heavy metals. Depending on the level of accumulation, this is counteracted by outwardly transferring portions of the separated dust.
The invention will be described in more detail hereafter based on two exemplary embodiments for separating phosphorus-containing dust from the first stage of the graduated gas purification process. The experiments were carried out using a metallurgical shaft furnace for air and oxygen melt gasification, having an inner shaft diameter of 400 mm, a usable shaft height of 2 m, and post-incineration provided directly over the charging opening. The average batch weight was 19.5 kg. The feed amounts and the briquette components for each experiment are illustrated in Table I.
ir 9 Table 1 Feed material and charging Mixture II IV
Components in the briquette Sewage slude % 60 49 Ashes from sewage slude mono- % 40 incineration % 15 Cement % 47 Animal meal % 4 Sawdust Feed amount per experiment Briquette kg 335 315 Iron kg 9.3 15.3 Batch coke kg 89.5 31.5 Limestone kg 6.3 Table 2 shows the average furnace parameters that were set.
Table 2 Furnace parameters Mixture II
IV
Melting [Batch 1 to end of batch] kg/h 248 capacity Oxygen Quantity 0 Nm3/h 25 4Ir 10 Air Quantity 0 Nm3/h 251 Air Temperature 0 C 236 Upper fire [estimated visually] normal strong Corresponding to the composition having a high calorific value composed of 47%
animal meal, 49% sewage sludge, and 4% sawdust as opening material, a strong upper fire developed in Experiment IV compared to Experiment IL
Slag granules having the following oxide analysis (Table 3) were generated.
Table 3 Oxides Si02 A1203 CaO MgO FeO + Fe203 Femee % % % % % % %
II 27.6 19.9 32.5 3.8 3.3 0.2 10.6 IV 28.7 20.5 33.8 3.3 1.3 1.3 3.8 Table 4 Chemical dust analysis Mixture II
IV
P205 total % mass 17.3 19.8 S03 total % mass 0.16 0.08 ZnO total % mass 1.25 1.79 TiO2 % maa 0.56 0.19 Fe2O3 % mass 11.5 35.9 A1203 % mass 14.9 3.47 S102 % mass 25.9 19.3 Na20 % mass 0.83 1.92 K20 % mass 1.77 3.76 CaO % mass 24.5 10.0 MgO % mass 2.85 1.38 MnO % mass 0.15 0.46 The dust separated from the completely post-incinerated furnace gas contained a significant amount of P205, in addition the customary ash components according to Table 4.
The phosphate content according to Table 5 forms a Ce-Fe phosphate (Ca9Fe(PO4)7), which represents a stoichiometric mixture of Fe203, CaCO3 and Ca2P207 (Solid State Sciences 6(2004) 186].
Table 5 Mineralogical dust analysis Mixture II IV
Quartz Si02 S102 Ca-Fe phosphate Ca9Fe(PO4)7 Ca9Fe(PO4)7 Hematite Fe203 Maghemite Fe203 = 12 Calcium aluminate (C3A) Ca3A1206 Ca3A1206 Magnesite MgCO3 Calcite CaCO3 Meionite (Ca, Na)2(Si, A1)6012(CO3)o 5 K-Fe oxide KFe02 Picromerite K2Mg(SO4)2*6H20 Jarosite (K, H30)Fe3(SO4)2(0F1)6
The recycling industry is increasingly pursuing the objective of reducing the consumption of finite natural resources, including phosphorus, or of using such resources more efficiently ["Kreislaufwirtschaft Pflanzennahrstoffe, insbesondere Phosphor" (Closed loop recycling management of plant nutrients, in particular phosphorus) funding initiative, final presentation, Berlin on 09/14/2011 , Dohmann, Conference Paper 1]. Phosphorus is essential for all biological processes and plays a key role in the transfer and storage of energy and in the synthesis of amino acids and proteins, cannot be substituted, and is the limiting factor for many growth processes. It is not consumed, but is diluted, making enrichment increasingly economically complex. The most important source for phosphorus recovery is animal and human excretions (sewage sludge).
When fully recycled, sewage sludge (66,000 Mg P/a) as well as animal and bone meal (23,700 Mg P/a) allow approximately 75% of Germany's mineral fertilizer imports (on average, 120,000 Mg P/a) to be saved ["Kreislaufwirtschaft Pflanzennahrstoffe, insbesondere Phosphor" (Closed loop recycling management of plant nutrients, in particular phosphorus) funding initiative, final presentation, Berlin on 09/14/2011 , Pinnekamp, Conference Paper Introductory Remarks].
According to the prior art, the following process-based / plant-based solutions for recycling sewage sludge, animal meal and their ashes from the respective mono-incineration processes are considered to be particularly promising ["Kreislaufwirtschaft Pflanzennahrstoffe, . 3 insbesondere Phosphor" (Closed loop recycling management of plant nutrients, in particular phosphorus) funding initiative, final presentation, Berlin on 09/14/2011 , Rosckosch, Conference Paper German Federal Environmental Agency].
- ASH DEC - thermochemical process Product: phosphate fertilizer (raw product, optionally multi-nutrient fertilizer) made of sewage sludge ashes by heating in a rotary kiln while adding additives - Mephrec - metallurgical process Product: lime phosphate fertilizer from sewage sludge, sewage sludge ashes and other phosphorus-containing waste by way of air and/or oxygen melt gasification in a fixed bed reactor - PhosRec - special sintering process Product: phosphate fertilizer or phosphate resource from animal meal by incineration in a rotary kiln, while simultaneously utilizing the recovered energy.
Previously, only the Mephrec process achieved the simultaneous material and energy recovery from organic, phosphorus-containing waste having varying degrees of calorific values and/or feed materials in one method step, by generating a phosphorus-containing slag , which is comparable to the well-known fertilizer "Thomas meal" and has high solubility in citric acid of the lime silicophosphates formed in the slag matrix, an iron metal alloy, which acts in a method-specific manner as a heavy metal drain, and a fuel gas, which has varying degrees of calorific ' 4 values and is suitable after purification for direct energy generation via gas motors or units comparable to these.
Such a metallurgical method for recovering energy and material from inorganic and/or organic waste having a high calorific value and for minimizing the necessary method-related, plant-related, production organizational and therefore financial expenditures for processing the feed materials into formed bodies or briquettes is claimed according to DE 10 2008 045 289, in which the waste that has a high calorific value and/or is rich in recyclable fractions and brings about material binding is mixed, either as a binding agent alone or in combination with a hydraulic binding agent content and/or an opening material, with further inorganic and/or organic waste that has a high calorific value and/or is rich recyclable fractions, thereafter formed and/or pressed or extruded to obtain formed bodies or briquettes and/or is compacted or formed into briquettes by other method steps, stored, and subsequently used for the simultaneous recovery of energy and material in a single method step, utilizing known metallurgical procedure techniques in cupola melting furnaces, oxygen cupola melting furnaces, shaft melt gasifiers, high-temperature oxygen melt gasifiers or similar metallurgical units as bulk material. As the bulk material, which, in total, is composed of coke and/or coke substitutes, mineral and/or metallic aggregates added, or not added, based on melting and gasification aspects, and the molded bodies and/or briquettes, moves downward, it is dried in the furnace shaft, heated, gasified and subsequently melted, wherein, depending on the composition of the molded bodies or briquettes forming the bulk material, at the same time a furnace gas that has a high calorific value, which is to say that has not been spent, a liquid slag that is high in recyclable fractions, and a liquid metal alloy are created in the reduction zone that exists in the metallurgical unit.
The waste that has a high calorific value and/or is rich in recyclable fractions and brings about the material binding can also be bone meal and/or animal meal. Cement and/or cement substitutes are claimed as hydraulically acting binding agents. The opening materials, which are added in particular to waste that has a high calorific value and/or is rich in recyclable fractions and high in moisture, are in particular ashes and/or slags and/or mineral and/or metallic and/or oxidic granular or pulverulent substances that are high in recyclable fractions and/or rich in phosphorus. Further inorganic and/or organic waste that has a high calorific value and/or is rich in recyclable fractions can be mixtures of sewage sludge and/or further organic and/or inorganic phosphorus-containing substances and/or substances that increase the calorific value.
The method is characterized in that a furnace gas that has a high calorific value, which is to say that has not been spent, a liquid slag that is rich in recyclable fractions, which is to say rich in phosphorus, and a liquid metal alloy acting as a heavy metal drain are created simultaneously in the metallurgical unit.
The disadvantage is that, in a way that is specific to the method, a furnace gas that has a high calorific value and has not been spent is generated, which prior to the energetic use for power generation necessitates a complex, wet gas purification process that is combined with an integrated quenching step for the purpose of cooling to approximately 5 C, due to organic residues that are present.
It is further disadvantageous that, in a way that is specific to the method, phosphorus and/or phosphorus compounds reaching the gas phase require technically and technologically complex separation in the gas purification process, and therefore cannot be used for the metallurgical material recycling.
DE 000002952642 Al describes a method for the dry hot purification of gases containing harmful substances, such as process gases and waste gases from thermal treatment plants, which are created during the pyrolysis of waste substances by heating them to the decomposition temperature, for example, in which the harmful substance-containing raw gas is caused to react at an elevated temperature with the additives that are added to the raw gas, and the harmful substances are thus removed from the raw gas.
The disadvantage is that the dust separated during gas purification contains reaction products of harmful substance and additives, which result in undesirable accumulations during the recirculation into the thermal treatment plants.
It is therefore the object of the invention to create a method and a plant for recovering material and energy from phosphorus-containing waste, in which, without the use of a complex, wet gas purification process that is combined with an integrated quenching step for the purpose of cooling to approximately 5 C, for example due to organic residues that are present, the phosphorus and/or phosphorus compounds reaching the gas phase, in a way specific to the method, during the material and energy recovery of phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces can be easily separated and rendered usable for metallurgical material recycling.
The object is achieved by integrating a post-incineration chamber, which is integrated in or directly on the metallurgical shaft furnace, as an integral part of a graduated gas purification process, comprising a dry dedusting step without adding additives for binding and removing gaseous harmful substances by a dedusting device having integrated dust recirculation into the melting and superheating zone of the metallurgical shaft furnace, without adding additives for binding and removing gaseous harmful substances according to the features of the claims.
Advantageously, the apparatus-related, economical and process-related advantages recognized according to the prior art of metallurgical shaft furnaces with direct post-incineration of furnace gases are combined with the air and/or oxygen melt gasification of organic matter-and phosphorus-containing waste, such as sewage sludge, by directly post-incinerating the fuel gas, which has a high calorific value and is directly generated in the furnace for air and/or oxygen melt gasification, with an excess of incineration material ( X.> 1) to obtain a dust-laden, completely spent offgas, without binding gaseous harmful substances by way of additives.
In in-house examinations, it was surprisingly found that the phosphorus and/or the phosphorus compounds reaching the gas phase largely as aerosols, due to the nature of the method, can basically be fully converted into an oxide, hereafter referred to as phosphate, separated after cooling to below the melting temperature of P205, which is to say below 340 C, as a dust component from the first stage of simple, dry dedusting according to the prior art, and recirculated into the melting and superheating zone of the furnace for air and/or oxygen melt gasification. In a second stage then, gaseous harmful substances, such as S
and Cl compounds, are easily separated from the gas, likewise according to the prior art, for example by adding additives and/or by integrating scrubbers.
During the recirculation of the dust from the first stage of dry dedusting, an accumulation of highly volatile heavy metals may occur in the dust that is removed with the fully post-incinerated gas, depending on the content of these heavy metals. Depending on the level of accumulation, this is counteracted by outwardly transferring portions of the separated dust.
The invention will be described in more detail hereafter based on two exemplary embodiments for separating phosphorus-containing dust from the first stage of the graduated gas purification process. The experiments were carried out using a metallurgical shaft furnace for air and oxygen melt gasification, having an inner shaft diameter of 400 mm, a usable shaft height of 2 m, and post-incineration provided directly over the charging opening. The average batch weight was 19.5 kg. The feed amounts and the briquette components for each experiment are illustrated in Table I.
ir 9 Table 1 Feed material and charging Mixture II IV
Components in the briquette Sewage slude % 60 49 Ashes from sewage slude mono- % 40 incineration % 15 Cement % 47 Animal meal % 4 Sawdust Feed amount per experiment Briquette kg 335 315 Iron kg 9.3 15.3 Batch coke kg 89.5 31.5 Limestone kg 6.3 Table 2 shows the average furnace parameters that were set.
Table 2 Furnace parameters Mixture II
IV
Melting [Batch 1 to end of batch] kg/h 248 capacity Oxygen Quantity 0 Nm3/h 25 4Ir 10 Air Quantity 0 Nm3/h 251 Air Temperature 0 C 236 Upper fire [estimated visually] normal strong Corresponding to the composition having a high calorific value composed of 47%
animal meal, 49% sewage sludge, and 4% sawdust as opening material, a strong upper fire developed in Experiment IV compared to Experiment IL
Slag granules having the following oxide analysis (Table 3) were generated.
Table 3 Oxides Si02 A1203 CaO MgO FeO + Fe203 Femee % % % % % % %
II 27.6 19.9 32.5 3.8 3.3 0.2 10.6 IV 28.7 20.5 33.8 3.3 1.3 1.3 3.8 Table 4 Chemical dust analysis Mixture II
IV
P205 total % mass 17.3 19.8 S03 total % mass 0.16 0.08 ZnO total % mass 1.25 1.79 TiO2 % maa 0.56 0.19 Fe2O3 % mass 11.5 35.9 A1203 % mass 14.9 3.47 S102 % mass 25.9 19.3 Na20 % mass 0.83 1.92 K20 % mass 1.77 3.76 CaO % mass 24.5 10.0 MgO % mass 2.85 1.38 MnO % mass 0.15 0.46 The dust separated from the completely post-incinerated furnace gas contained a significant amount of P205, in addition the customary ash components according to Table 4.
The phosphate content according to Table 5 forms a Ce-Fe phosphate (Ca9Fe(PO4)7), which represents a stoichiometric mixture of Fe203, CaCO3 and Ca2P207 (Solid State Sciences 6(2004) 186].
Table 5 Mineralogical dust analysis Mixture II IV
Quartz Si02 S102 Ca-Fe phosphate Ca9Fe(PO4)7 Ca9Fe(PO4)7 Hematite Fe203 Maghemite Fe203 = 12 Calcium aluminate (C3A) Ca3A1206 Ca3A1206 Magnesite MgCO3 Calcite CaCO3 Meionite (Ca, Na)2(Si, A1)6012(CO3)o 5 K-Fe oxide KFe02 Picromerite K2Mg(SO4)2*6H20 Jarosite (K, H30)Fe3(SO4)2(0F1)6
Claims (7)
1.) A
method for recovering material and/or energy from phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces, characterized in that - the fuel gas, which has a high calorific value and is generated during the air and/or oxygen shaft melt gasification, and the gaseous phosphorus contained in the fuel gas and/or the phosphorus compounds and/or aerosols contained in the fuel gas and the oxidizable highly volatile heavy metals and the compounds thereof are directly and completely post-incinerated, with an excess of incineration material ( .lambda.> 1);
- the dust contained in the completely spent fuel gas and the oxide compounds formed of the gaseous phosphorus and/or phosphorus compounds and/or aerosols are cooled to temperatures below the melting temperature of P2O5;
- the dust contained in the completely spent fuel gas and the oxide compounds formed of the gaseous phosphorus and/or phosphorus compounds and/or aerosols and/or highly volatile heavy metals and the compounds thereof are separated in dry form in the first stage of the gas purification process, without adding additives that bind gaseous harmful substances;
- the separated dust is recirculated together with the oxide compounds into the melting and superheating zone of the metallurgical shaft furnaces having air and/or oxygen melt gasification; and - starting at a second stage, gaseous harmful substances are separated from the gas by adding additives that bind gaseous harmful substances and/or by integrating scrubbers.
method for recovering material and/or energy from phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces, characterized in that - the fuel gas, which has a high calorific value and is generated during the air and/or oxygen shaft melt gasification, and the gaseous phosphorus contained in the fuel gas and/or the phosphorus compounds and/or aerosols contained in the fuel gas and the oxidizable highly volatile heavy metals and the compounds thereof are directly and completely post-incinerated, with an excess of incineration material ( .lambda.> 1);
- the dust contained in the completely spent fuel gas and the oxide compounds formed of the gaseous phosphorus and/or phosphorus compounds and/or aerosols are cooled to temperatures below the melting temperature of P2O5;
- the dust contained in the completely spent fuel gas and the oxide compounds formed of the gaseous phosphorus and/or phosphorus compounds and/or aerosols and/or highly volatile heavy metals and the compounds thereof are separated in dry form in the first stage of the gas purification process, without adding additives that bind gaseous harmful substances;
- the separated dust is recirculated together with the oxide compounds into the melting and superheating zone of the metallurgical shaft furnaces having air and/or oxygen melt gasification; and - starting at a second stage, gaseous harmful substances are separated from the gas by adding additives that bind gaseous harmful substances and/or by integrating scrubbers.
2.) The method for recovering material and energy from phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces according to claim 1, characterized in that, prior to entering the first stage of the gas purification process, the fully spent fuel gas is cooled to temperatures higher than the condensation temperature of water vapor and lower than the melting temperature of P2O5.
3.) A method for recovering material and energy from phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces according to claim 1 and claim 2, characterized in that, prior to entering the first stage of the gas purification process, the fully spent fuel gas is cooled to temperatures lower than 300°C, and preferably to 150°C.
4.) A method for recovering material and energy from phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces according to claim 1 to claim 3, characterized in that the amount of dust recirculated into the melting and superheating zone of the metallurgical shaft furnaces having air and/or oxygen melt gasification is the total amount, or a partial amount, of the amount of dust that is separated in dry form in the first stage of the gas purification process, without adding additives that bind gaseous harmful substances.
5.) The method for recovering material and energy from phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces according to claim 4, characterized in that the partial amount of the dust recirculated into the melting and superheating zone of the metallurgical shaft furnaces having air and/or oxygen melt gasification is determined by the content of highly volatile heavy metals and the compounds thereof, and results in no significant accumulation of the highly volatile heavy metals and of the compounds thereof in the dust that is contained in the fully spent fuel gas during the recirculation into the melting and superheating zone of the metallurgical shaft furnace.
6.) A plant for recovering material and energy from phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces, characterized in that a post-incineration chamber is provided in or directly on the metallurgical shaft furnace as an integral part of a graduated gas purification process, comprising the first stage as dry dedusting having no addition device for additives and having a removal device for dust, having an integrated dust recirculation device to the melting and superheating zone of the metallurgical shaft furnace, and the second stage as a gas treatment device, comprising dry dedusting having an addition device for additives and a removal device for dust and/or by integrating scrubbers.
7.) The plant for recovering material and energy from phosphorus-containing waste by way of air and/or oxygen melt gasification in metallurgical shaft furnaces according to claim 6, characterized in that the first stage of the dry dedusting is an electric filter.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102012014357.5 | 2012-07-19 | ||
| DE201210014357 DE102012014357B3 (en) | 2012-07-19 | 2012-07-19 | Process and plant for the material and / or energetic utilization of phosphorus-containing waste |
| PCT/DE2013/000354 WO2014036983A2 (en) | 2012-07-19 | 2013-07-03 | Method and plant for recovering material and/or energy from phosphorus-containing waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2877061A1 true CA2877061A1 (en) | 2014-03-13 |
Family
ID=48953296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2877061 Abandoned CA2877061A1 (en) | 2012-07-19 | 2013-07-03 | Method and plant for recovering material and/or energy from phosphorus-containing waste |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2874763B1 (en) |
| CA (1) | CA2877061A1 (en) |
| DE (1) | DE102012014357B3 (en) |
| DK (1) | DK2874763T3 (en) |
| ES (1) | ES2647616T3 (en) |
| PL (1) | PL2874763T3 (en) |
| WO (1) | WO2014036983A2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014013813A1 (en) | 2014-09-23 | 2016-03-24 | Bma Braunschweigische Maschinenbauanstalt Ag | Process and arrangement for wastewater treatment |
| DE102018105059A1 (en) | 2018-03-06 | 2019-09-12 | Klärschlammverwertung Region Nürnberg GmbH | Process for the utilization of valuable, in particular phosphorus-containing waste materials by means of melt gasification |
| DE102020001989A1 (en) | 2020-03-30 | 2021-09-30 | Grenzebach Bsh Gmbh | Process and device for the production of phosphorus from sewage sludge |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2952642C2 (en) * | 1979-12-28 | 1985-06-05 | Deutsche Kommunal-Anlagen Miete GmbH, 8000 München | Method and device for dry hot cleaning of gases containing pollutants |
| DE4324699C2 (en) * | 1993-07-23 | 1995-06-22 | Hans Ulrich Dipl Ing Feustel | Method and device for the complete afterburning of process gases in a coke-heated shaft furnace |
| DE10217956B4 (en) * | 2002-07-18 | 2008-04-17 | Joachim Mallon | Process for phosphorus recovery |
| DE102008045289A1 (en) * | 2008-09-02 | 2010-03-04 | Mallon, Joachim, Dipl.-Phys. | Use of waste materials to form briquettes which are used as a charge in a metallurgical process |
| AT510273B1 (en) * | 2011-03-17 | 2012-03-15 | Siemens Vai Metals Tech Gmbh | METHOD FOR HEATING CONTROL FOR EXHAUST GASES FROM REPRODUCTION OR SYNTHESEGAS PLANTS |
-
2012
- 2012-07-19 DE DE201210014357 patent/DE102012014357B3/en not_active Expired - Fee Related
-
2013
- 2013-07-03 ES ES13747778.2T patent/ES2647616T3/en active Active
- 2013-07-03 WO PCT/DE2013/000354 patent/WO2014036983A2/en active Application Filing
- 2013-07-03 DK DK13747778.2T patent/DK2874763T3/en active
- 2013-07-03 CA CA 2877061 patent/CA2877061A1/en not_active Abandoned
- 2013-07-03 EP EP13747778.2A patent/EP2874763B1/en not_active Not-in-force
- 2013-07-03 PL PL13747778T patent/PL2874763T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK2874763T3 (en) | 2017-12-04 |
| WO2014036983A2 (en) | 2014-03-13 |
| WO2014036983A3 (en) | 2014-05-08 |
| ES2647616T3 (en) | 2017-12-22 |
| EP2874763A2 (en) | 2015-05-27 |
| DE102012014357B3 (en) | 2013-09-05 |
| PL2874763T3 (en) | 2018-01-31 |
| EP2874763B1 (en) | 2017-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2817124C (en) | Procede de traitement de dechets organiques | |
| Das et al. | An overview of utilization of slag and sludge from steel industries | |
| CN103614562B (en) | A kind of melting furnace process Steel Plant solid waste processing method | |
| CN112442589B (en) | Method and system for co-processing waste incineration fly ash and zinc-containing dust and mud of iron and steel plant | |
| US5198190A (en) | Method of recycling hazardous waste | |
| DE102011008008A1 (en) | Heavy metal poor, modifiable, phosphate containing, fertilizing soil substrate, useful as powder and/or as pellet for soil improvement in agriculture and horticulture, comprises producing soil substrate made of heavy metal-containing waste | |
| KR20030055357A (en) | An apparatus and method for recycling dust and sludge containing iron ironmaking process using coal and fine ore | |
| BR102014023373B1 (en) | PROCESS AND SYSTEM FOR THE ELIMINATION OF THE EXPANSIBILITY OF THE LD E LE SHIELD SLAG | |
| CN107828974A (en) | A kind of waste printed circuit board combined treatment process | |
| CN101532068B (en) | Blast furnace ironmaking production process by cyclically utilizing steel slag and iron slag in metallurgy and chemical industry | |
| CN105695731A (en) | Method for producing nickel iron fine powder and zinc oxide through rotary kiln | |
| AU2012397402B2 (en) | Reduced-iron production method and production device | |
| SK281417B6 (en) | Process for utilizing iron-containing wastes or residues | |
| CN102344981A (en) | Separation and direct reduction process of iron and boron in boron-containing iron ore concentrate | |
| CA2877061A1 (en) | Method and plant for recovering material and/or energy from phosphorus-containing waste | |
| Khojiev et al. | The technology for the reduction of metal oxides using waste polyethylene materials | |
| CN103805771B (en) | Sulfate slag produces the method for ferrum | |
| KR101493968B1 (en) | Process for recovering valuable metals from wastes produced during the manufacture and the processing of stainless steel | |
| CN106544457A (en) | Based on the CO that blast furnace slag waste heat recovery and slag charge are utilized2Emission-reducing system and method | |
| KR20060104255A (en) | Pig iron manufacture method of material and device that do waste tire to heat soure and contains ferrite oxide | |
| JP2005111394A (en) | Disposal method for organic waste | |
| JP2015529539A (en) | Process and plant for separating heavy metals from phosphorus-containing starting materials | |
| RU2487952C1 (en) | Method of making pellets for metallurgy | |
| KR101088183B1 (en) | Synthetic method of portland cement by using the heat and elements of the fused blast furnace slag and portland cement manufactured with this | |
| JP4268439B2 (en) | Method for producing highly functional calcium ferrite using waste gypsum board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |
Effective date: 20190703 |
|
| FZDE | Discontinued |
Effective date: 20190703 |
|
| FZDE | Discontinued |
Effective date: 20190703 |
|
| FZDE | Discontinued |
Effective date: 20190703 |