Method for treating phosphate-containing ashes from waste incineration plants using wet chemical decomposition to extract aluminum, calcium, phosphorus and nitrogen compounds

Abstract

The invention relates to a method for treating phosphate-containing waste, in particular phosphate-containing ashes from waste incineration plants, by wet-chemical digestion to obtain aluminum, calcium, phosphorus and nitrogen compounds.

Description

[0001] The invention relates to a process for treating phosphate-containing waste, in particular phosphate-containing ash from waste incineration plants, by wet chemical digestion to obtain aluminium, calcium, phosphorus and nitrogen compounds.

[0002] Phosphate rocks are needed for the production of fertilizers. To replace these finite phosphate rocks, it is generally known that European industrialized countries are pursuing the recovery of phosphorus and phosphates from waste and wastewater (see patent DE 10 2012 015 065 B3). This is also advisable because phosphate rocks are increasingly contaminated with heavy metals such as cadmium and uranium, and these contaminants are found in fertilizers and groundwater.

[0003] A significant phosphate resource in Europe is wastewater from municipal and industrial sewage treatment plants. In Germany alone, approximately 50,000 metric tons of phosphorus enter wastewater annually. The vast majority of this phosphorus is precipitated as metal salts using precipitating agents such as iron or aluminum salts and removed with the sewage sludge. Today, phosphate-containing sewage sludge is mostly incinerated, and the resulting ash is either landfilled or otherwise misappropriated (e.g., for road construction or mine backfilling), as the phosphorus it contains is not recovered—with a few exceptions in pilot plants.

[0004] Similar to other industrial recycling processes, such as the recovery of iron from scrap, the recovery of paper from waste paper, and the recovery of copper and other metals from electrical appliances, the industrial recovery of phosphorus from waste is also possible. A key requirement for this is that the phosphorus-containing residues have a sufficiently high phosphorus concentration and low levels of impurities, essentially corresponding to currently used raw phosphates, ideally without harmful uranium and cadmium impurities.

[0005] Phosphates are produced from raw phosphate (rock, with a phosphorus content of approximately 30% P2O5) by Acid digestionPhosphate is obtained preferably with sulfuric acid, producing phosphoric acid and / or calcium phosphate fertilizer (so-called "superphosphate"). The ash from incinerated sewage sludge or animal waste such as animal meal contains up to 35 wt.% P₂O₅, but, depending on the precipitating agent, also up to 25 wt.% iron, aluminum, or calcium oxide. This high metal oxide content, which can be up to ten times higher than in raw phosphate, significantly limits the use of sewage sludge ash as an alternative raw phosphate in industrial processes. A solution to this problem is presented in patent DE 10 2012 015 065 B3, in which phosphates are bound by aluminum salts during wastewater treatment and subsequently converted to calcium phosphate, so that when the sewage sludge is subsequently incinerated, the remaining ash preferably contains calcium phosphate and as few aluminum and iron compounds as possible.The calcium phosphate-rich ash is suitable for use as raw phosphate for the production of fertilizers, but always in combination with accompanying impurities from the ash.

[0006] Ashes produced from the combustion of sewage sludge, organic waste, biodegradable waste, animal waste, etc., such as animal meal, contain various valuable materials. The following table shows the main components (calculated as oxides) and the valuable material content of some ashes produced during sewage sludge combustion: Ash A Ash B Ash C % Fe 2 O 3 21,9 3,1 11,9 % Al 2 O 3 9,3 21,5 12,4 % CaO 15,2 14,5 11,4 % P 2 O 5 21,0 23,0 20,5 % SiO2 18,2 27,0 23,0

[0007] The special value of ash is due to its content of P 2 O 5 , CaO and Al 2 O 3.

[0008] Currently, it is not possible to efficiently and cost-effectively recover the various valuable materials from such ashes as marketable products. The invention described here describes a optional multi-stage process with which not only calcium phosphate-containing fertilizers, but also higher-value phosphates such as pure calcium phosphate and / or calcium nitrate phosphate or phosphoric acid and / or nitrous phosphoric acid, as well as calcium sulfate (gypsum) and aluminum hydroxophosphate can be obtained from ashes.

[0009] The inventive process is based on converting the valuable materials from the ash into different products by fractional dissolution in mineral acids and by adding suitable reactants, in particular into products from the group consisting of calcium nitrate (CaNO 3 ), calcium phosphate (Ca 3 (PO 4 ) 2 ), calcium sulfate (CaSO 4 ), and aluminum hydroxophosphate (Al(OH) 3 x AlPO 4 ).

[0010] The inventive method is described in Figure 1 schematically represented.

[0011] When extracting valuable materials from phosphate-containing ash in stage 1, hydrochloric acid or other hydrohalic acids are explicitly not used, as is sometimes the state of the art today.

[0012] If ashes with hydrochloric acid When treated, iron, aluminum, and calcium salts dissolve, preferably their phosphates. While different fractions of aluminum compounds and / or calcium phosphate can be obtained from the combined digestion solution, the disadvantage lies in the chloride component. Because all the chlorides in question are readily soluble, they ultimately leave the process as wastewater or can only be recovered with great difficulty, e.g., by evaporation.

[0013] This significant disadvantage is impressively overcome by the invention in an (optionally) multi-stage process in which, in the first stage, dilute nitric acid and / or dilute phosphoric acid are used instead of dilute hydrochloric acid to treat the ash (the dissolution process in acid). The salts of these acids, such as calcium phosphate or calcium nitrate, are considerably more valuable than, for example, sodium or calcium chloride. Therefore, the salts, especially calcium phosphate and calcium nitrate, can be recovered through precipitation and evaporation processes, and their marketing—primarily as NP fertilizers (NP = nitrogen-phosphorus fertilizer)—makes the entire recycling process economically viable.

[0014] The first stage can essentially be described by the following equations: Ca 3 PO 4 2 + 6 HNO 3 = 3 Ca NO 3 2 + 2 H 3 PO 4 AlPO 4 + 3 HNO 3 = Al NO 3 3 + H 3 PO 4

[0015] From the solids, e.g., the ash, primarily calcium and aluminum ions dissolve, while iron ions dissolve only in small quantities and remain in the residue along with the also sparingly soluble silicates (SiO2). According to the state of the art, the insoluble components are separated from the acidic digestion solution by filtration, e.g., using a decanter, a vacuum belt filter, or a filter press. Preferably, to reduce losses, the residue in the filter units is washed with water, and the wash water is returned to the first process stage as dilution water for the digestion acid.

[0016] Following stage 1, calcium sulfate (CaSO₄; gypsum) can be precipitated by adding sulfuric acid (H₂SO₄) to the resulting filtrate or supernatant from stage 1. This takes place in the acidic, filtered digestion solution in the second stage according to the chemical equation

[0017] To reduce the need for nitric acid and make the process more economical, an important step in the multi-stage process is the recovery of nitric or phosphoric acid. Thus, almost complete recovery of the nitric or phosphoric acid is possible if sulfuric acid diluted in a stoichiometric ratio to the calcium content is added, whereby precipitation to calcium sulfate (gypsum) surprisingly occurs even at a pH of under 1 is possible. The sum of the two steps results in the following chemical equation:

[0018] The calcium sulfate precipitate (gypsum) is filtered, dewatered, and washed with water in a known manner. Preferably, this acidic wash water is also recycled as dilution water into the first process stage. The dewatered gypsum can be further processed in subsequent steps outside the process chain described here, e.g., by calcination to anhydrite or by chemical reaction according to patent DE 196 11 454 A1.

[0019] Through multiple recirculations, the concentration of phosphoric acid is continuously increased by further dissolving phosphate from the ash. It could be raised to a concentration of over 30% H₃PO₄ if it weren't for the interfering aluminum ions, which are also dissolved. Depending on the Al₂O₃ content of the ash, the Al concentration in the digestion acid can rise above 5%, making it unmarketable. According to the invention, this problem is solved in a third stage solved by precipitating aluminium ions as aluminium hydroxophosphate by adding preferably calcium oxide.

[0020] Due to the high salt concentration in the acid used for digestion, the precipitation of aluminum hydroxophosphate is surprisingly possible with the addition of only small amounts of hydroxyl ions, resulting in only a slight increase in the otherwise strongly acidic pH from approximately 1 to 1.5 to approximately 2.0 to 2.5. This is preferably achieved by adding calcium oxide (CaO), but also by adding calcium hydroxide, calcium carbonate, calcium silicate (calcium silicate), sodium hydroxide, or sodium silicate. The aluminum hydroxophosphate precipitate is separated or recovered by filtration according to the state of the art, e.g., using a decanter, a vacuum belt filter, or a filter press.

[0021] The process of third stage can be described by the following equation:

[0022] While Ca phosphate and Ca nitrate remain in solution, the Al salts precipitate out at pH values ​​of approximately 2.

[0023] After the removal (depletion) of calcium and aluminum ions in process stages two and three, a phosphoric acid or nitrous phosphoric acid with only slight impurities is obtained. This can be concentrated by evaporation and used as phosphoric acid or nitrous phosphoric acid for the production of fertilizers, whereby mineral raw phosphates can be digested with this acid, which is state of the art.

[0024] Furthermore, the purified phosphoric acid or nitrous phosphoric acid can be recycled and, according to the invention, used in the first stage to dissolve ingredients from the ash.

[0025] In a preferred variant of the process, in which nitrous phosphoric acid is produced, the following occurs in the fourth stageThe nitrous phosphoric acid is neutralized with limestone (calcium carbonate) or quicklime (calcium oxide) and the precipitate is evaporated, resulting in a mixture of calcium phosphate and calcium nitrate. 2 H 3 PO 4 + 2 HNO 3 + 2 CaO = Ca NO 3 2 + Ca H 2 PO 4 2 + 2 H 2 O

[0026] This blended product is a preferred NP fertilizer.

[0027] The Figure 2 shows the process steps in an overview.

[0028] If all four stages 1-4 are carried out one after the other, the valuable substances calcium nitrate (CaNO 3 ), calcium phosphate (Ca 3 (PO 4 ) 2 ), calcium sulfate (CaSO 4 ), and aluminum hydroxophosphate ((Al(OH) 3 x AlPO 4 ) can be obtained simultaneously from phosphate-containing solids, e.g. ashes, in a single process.

[0029] It is evident that not all four stages of the process necessarily have to be carried out. It is also possible, for example, to obtain only calcium phosphate and calcium sulfate (gypsum) (stages 1, 2, 4). Alternatively, only stages 1, 3, and 4 can be carried out.

[0030] Interestingly, stages 2 and 3 can also be skipped, so that stage 4 can be carried out directly after stage 1.

[0031] Furthermore, the sequence can be varied by, for example, performing stage 3 after stage 1, then stages 2 and subsequently 4.

[0032] As described in detail above, the phosphoric acid (H3PO4) or nitrous phosphoric acid (HNO3 / H3PO4) produced can be recycled after stage 2 and stage 3 for use in the treatment of the ash in stage 1. This recycling of the Al- and Ca-depleted acid enables a significant cost reduction because less fresh acid is required to dissolve the ash.

[0033] In a first Aspect A1 The present invention thus relates to a process for obtaining (producing) precipitates selected from the group consisting of calcium nitrate (CaNO₃), calcium phosphate (Ca₃(PO₄)₂), calcium sulfate (CaSO₄), and aluminum hydroxophosphate (Al(OH)₃ x AlPO₄), from phosphate-containing ash from waste incineration plants, the process comprising at least the obtaining (producing) of calcium phosphate (Ca₃(PO₄)₂) and calcium nitrate (CaNO₃), characterized in that a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) optionally the filtrate or supernatant is at least partially recycled for use in step a), d) optionally the filtrate or supernatant is concentrated, preferably by evaporation, to obtain phosphoric acid or nitrous phosphoric acid (HNO₃ / H₃PO₄), e) optionally calcium phosphate precipitate and calcium nitrate precipitate are obtained and separated by adding calcium oxide or calcium carbonate to the filtrate or supernatant. preferably steps a), b) and e) are carried out.

[0034] In another alternative embodiment of aspect A1, steps a), b) and d) are preferably carried out.

[0035] In another alternative embodiment of aspect A1, steps a), b), c) and d) are preferably carried out.

[0036] In another alternative embodiment of aspect A1, steps a), b), c) and e) are preferably carried out.

[0037] If step c) is carried out in an embodiment of aspect A1, preferably at least 10% of the filtrate / supernatant is recycled for use in step a), more preferably at least 20%, more preferably 20% to 80%, and most preferably 40% to 60%, based on the total amount of filtrate obtained.

[0038] In a second Aspect A2The present invention relates to a process for obtaining (producing) precipitates selected from the group consisting of calcium nitrate (CaNO₃), calcium phosphate (Ca₃(PO₄)₂), calcium sulfate (CaSO₄), and aluminum hydroxophosphate (Al(OH)₃·AlPO₄); from phosphate-containing ash from waste incineration plants, the process comprising at least the obtaining (producing) of calcium sulfate (CaSO₄), characterized in that a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) a pH value <1 is adjusted by adding sulfuric acid to the filtrate or supernatant, and calcium sulfate precipitate is obtained and separated.

[0039] Optionally, in a preferred embodiment of aspect A2, following the recovery / deposition of the calcium sulfate according to step c) of aspect A2, the optional steps c)-e) of aspect A1 can follow, as described herein, wherein preferably Step c) is carried out.

[0040] Optionally, in a preferred embodiment of aspect A2, following the recovery / deposition of the calcium sulfate according to step c) of aspect A2, the optional steps c)-e) of aspect A1 can be carried out as described herein, preferably with step e) being performed.

[0041] Optionally, in an alternative embodiment of aspect A2, following the recovery / deposition of the calcium sulfate according to step c) of aspect A2, the optional steps c)-e) of aspect A1 can be carried out as described herein, preferably steps c) and d).

[0042] Optionally, in an alternative embodiment of aspect A2, following the recovery / deposition of the calcium sulfate according to step c) of aspect A2, the optional steps c)-e) of aspect A1 can be carried out as described herein, preferably steps c) and e).

[0043] In an embodiment of aspect A2, if step c) of aspect A1 is carried out, preferably at least 10% of the filtrate / supernatant is recycled for use in step a), more preferably at least 20%, more preferably 20% to 80%, and most preferably 40% to 60%, based on the total amount of filtrate obtained.

[0044] In a third Aspect A3The present invention relates to a process for obtaining (producing) precipitates selected from the group consisting of calcium nitrate (CaNO3), calcium phosphate (Ca3(PO4)2), calcium sulfate (CaSO4), and aluminum hydroxophosphate (Al(OH)3 x AlPO4) from ashes from waste incineration plants, the process comprising at least the obtaining (producing) of aluminum hydroxophosphate (Al(OH)3 x AlPO4), characterized in that a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) by raising the pH value in the filtrate or supernatant the dissolved aluminium is obtained and separated as aluminium hydroxophosphate precipitate.

[0045] Optionally, in a preferred embodiment of aspect A3, following the recovery / deposition of the aluminium hydroxophosphate precipitate according to step c) of aspect A3, the optional steps c)-e) of aspect A1 can be carried out as described herein, preferably with step e) being performed.

[0046] Optionally, in a preferred embodiment of aspect A3, following the recovery / deposition of the aluminium hydroxophosphate precipitate according to step c) of aspect A3, the optional steps c)-e) of aspect A1 can be carried out as described herein, preferably with step d) being performed.

[0047] Optionally, in an alternative embodiment of aspect A3, following the recovery / deposition of the aluminium hydroxophosphate precipitate according to step c) of aspect A3, optional steps c)-e) of aspect A1 may be carried out as described herein, preferably steps c) and d).

[0048] Optionally, in an alternative embodiment of aspect A3, following the recovery / deposition of the aluminium hydroxophosphate precipitate according to step c) of aspect A3, the optional steps c)-e) of aspect A1 can be carried out as described herein, preferably steps c) and e).

[0049] In an embodiment of aspect A3, if step c) of aspect A1 is carried out, preferably at least 10% of the filtrate / supernatant is recycled for use in step a), more preferably at least 20%, more preferably 20% to 80%, and most preferably 40% to 60%, based on the total amount of filtrate obtained.

[0050] In a fourth Aspect A4 The present invention relates to a process for obtaining (producing) precipitates selected from the group consisting of calcium nitrate (CaNO₃), calcium phosphate (Ca₃(PO₄)₂), calcium sulfate (CaSO₄), and aluminum hydroxophosphate (Al(OH)₃·AlPO₄); from phosphate-containing ashes from waste incineration plants, characterized in that a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) calcium sulfate precipitate is obtained and separated by adding sulfuric acid to the filtrate or supernatant, d) the dissolved aluminum is obtained and separated as aluminum hydroxophosphate precipitate by raising the pH of the filtrate or supernatant, e) optionally, the filtrate or supernatant is recycled, at least partially, for use in step a), f) optionally, the filtrate or supernatant is concentrated by evaporating water to obtain phosphoric acid or nitrous phosphoric acid (HNO₃ / H₃PO₄), or g) optionally, calcium nitrate precipitate and / or calcium phosphate precipitate are obtained and separated by adding calcium oxide or calcium carbonate to the filtrate or supernatant, or, alternatively,concentrated by evaporation or spray drying, where, of the optional steps e)-g, step g) is preferably carried out.

[0051] Optionally, in a preferred embodiment of aspect A4, of the optional steps e)-g), preferably steps e) and g) are carried out.

[0052] Optionally, in a preferred embodiment of aspect A4, of the optional steps e)-g), preferably steps e), f) and g) are carried out.

[0053] Optionally, in a further preferred embodiment of aspect A4, of the optional steps e)-g), preferably steps e) and f) are carried out.

[0054] If step e) is carried out in an embodiment of aspect A4, preferably at least 10% of the filtrate / supernatant is recycled for use in step a), particularly preferably at least 20%, even more preferably 20% to 80%, and most preferably 40% to 60%, based on the total amount of filtrate obtained.

[0055] As already described herein, in the process according to the present invention the sequence of steps 2 and 3 (precipitation of calcium sulfate, precipitation of aluminum hydroxyphosphate) in this order is not mandatory, so that step 1 can also be followed by step 3 (and subsequently by step 2).

[0056] In a fifth Aspect A5The present invention thus relates to a process for obtaining (producing) precipitates selected from the group consisting of calcium nitrate (CaNO₃), calcium phosphate (Ca₃(PO₄)₂), calcium sulfate (CaSO₄), and aluminum hydroxophosphate (Al(OH)₃·AlPO₄); from phosphate-containing ashes from waste incineration plants, characterized in that a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) the dissolved aluminum is recovered and separated as aluminum hydroxophosphate precipitate by raising the pH of the filtrate or supernatant, d) calcium sulfate precipitate is recovered and separated by adding sulfuric acid to the filtrate or supernatant, e) optionally, the filtrate or supernatant is recycled, at least partially, for use in step a), f) optionally, the filtrate or supernatant is concentrated by evaporating water to obtain phosphoric acid or nitrous phosphoric acid (HNO₃ / H₃PO₄), or g) optionally, calcium nitrate precipitate and / or calcium phosphate precipitate are recovered and separated by adding calcium oxide or calcium carbonate to the filtrate or supernatant, or, alternatively,concentrated by evaporation or spray drying, where, of the optional steps e)-g, at least step g) is preferably carried out.

[0057] Optionally, in a preferred embodiment of aspect A5, of the optional steps e)-g), preferably steps e) and g) are carried out.

[0058] Optionally, in a preferred embodiment of aspect A5, of the optional steps e)-g), preferably steps e), f) and g) are carried out.

[0059] Optionally, in a further preferred embodiment of aspect A5, of the optional steps e)-g), preferably steps e) and f) are carried out.

[0060] In an embodiment of aspect A5, if step e) is carried out, preferably at least 10% of the filtrate / supernatant is recycled for use in step a), more preferably at least 20%, more preferably 20% to 80%, and most preferably 40% to 60%, based on the total amount of filtrate obtained.

[0061] As described in detail herein, phosphoric acid (H 3 PO 4) is also produced in processes according to the above aspects, so that these processes can of course also be understood as processes for the optional production of phosphoric acid (H 3 PO 4), and corresponding embodiments are part of the present invention.

[0062] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The phosphate-containing ash is obtained by burning sewage sludge, biodegradable waste, organic waste and / or animal waste.

[0063] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above,The phosphate-containing ash is obtained by burning sewage sludge, biodegradable waste, biowaste and / or animal waste in a waste incineration plant.

[0064] The term "Precipitate" For the purposes of the invention, the term "precipitate" refers to the precipitation of a dissolved substance as a solid from a solution, usually triggered by the addition of suitable substances (precipitating agents). In particular, the term encompasses any completely or partially insoluble precipitate in the form of flakes, droplets, or crystalline material, in any microcrystalline, crystalline, or amorphous form. The term "precipitate" expressly includes any further processing, modification, refining, etc., of the precipitates obtained in the process according to the invention into powders, dusts, bulk materials, granular materials, grits, etc.

[0065] The term "Calcium phosphate"within the meaning of the invention comprises Ca 3 (PO 4 ) 2 ), CaHP04 and Ca(H 2 PO 4 ) 2 .

[0066] The term "Ash" For the purposes of the invention, "ash" refers to any solid residue from the combustion of organic material, for example, sewage sludge, biodegradable waste, biowaste and / or animal waste, slaughterhouse waste, e.g., animal meal. Ash consists primarily of oxides and (bi)carbonates of various metals, e.g., Al₂O₃, CaO, Fe₂O₃, MgO, MnO, P₂O₅, P₄O₁₀, K₂O, SiO₂, Na₂CO₃, NaHCO₃, etc.

[0067] The term "phosphate-containing ash" For the purposes of the invention, 'as' refers to ashes, as defined herein, containing at least one phosphate, as defined herein.

[0068] The term "Phosphates"For the purposes of the invention, the term "phosphates" refers, firstly, to P₂O₅ and P₄O₁₀. Furthermore, the term "phosphates" refers to the salts and esters of orthophosphoric acid (H₃PO₄) and expressly includes the condensates (polymers) of orthophosphoric acid and their esters. In particular, the term "phosphates" refers to metallic salts of phosphoric acid with the general formula X(Y)m(PO₄)n, where X and optionally Y are metals selected from the group consisting of aluminum, beryllium, bismuth, lead, cadmium, chromium, iron, gallium, indium, potassium, cobalt, copper, magnesium, manganese, molybdenum, sodium, nickel, osmium, palladium, rhodium, ruthenium, strontium, titanium, vanadium, tungsten, zinc, and tin.

[0069] The term "Waste incineration plants" For the purposes of the invention, this refers to all systems, equipment and the like that are suitable for burning the atmospherically combustible components of any type of waste.

[0070] The term "sewage sludge" For the purposes of the invention, this refers to any suspension of finely dispersed particles of a solid substance in a liquid.

[0071] In a preferred embodiment, the liquid in which the particles are suspended is a wastewater as defined herein.

[0072] The term "Wastewater" For the purposes of this invention, "wastewater" refers to all liquids of an aqueous and / or organic nature, or mixtures thereof, that do not meet the drinking water quality standards defined by the German Drinking Water Ordinance (TrinkwV) and / or national and / or international drinking water standards (e.g., DIN 2000 in Germany). The term "wastewater" further includes all wastewater as defined in Section 54 Paragraph 1 of the German Water Resources Act (WHG).

[0073] In a preferred embodiment, the wastewater referred to in the invention is water that has been contaminated through use or whose properties or composition have been altered. Furthermore, the term "wastewater" as used in the invention includes water whose properties have been altered through domestic, commercial, agricultural, or other use, and the water that flows off with it during dry weather (sewage), as well as rainwater collected from built-up or paved areas and flowing off from precipitation (stormwater). Liquids escaping from and collected in facilities for the treatment, storage, and disposal of waste are also considered sewage.

[0074] Wastewater includes domestic wastewater from toilets (fecal or blackwater), sanitary facilities, kitchens, and washing machines (washing or greywater), as well as wastewater from businesses that discharge into the public sewer system (commercial or industrial wastewater). Heated water from cooling systems is also considered wastewater. Wastewater generated during various cleaning and treatment processes in water treatment plants is also considered wastewater within the meaning of the invention.

[0075] In a particularly preferred embodiment, the sewage sludge is present as primary sludge, raw sludge, excess sludge, as treated and / or stabilized sewage sludge (aerobic / anaerobic).

[0076] The term "Organic waste"For the purposes of this invention, "organic waste" refers to all organic waste of animal or plant origin that arises in a household or business and can be broken down by microorganisms, soil organisms, or enzymes. This includes, for example, food scraps and grass clippings. Organic waste is generally collected separately via the so-called organic waste bin and treated separately through composting and fermentation. The resulting compost and digestate are often returned to the environment, for example, in horticulture and agriculture. The term "organic waste" encompasses waste as defined in the EU Waste Framework Directive, including garden and park waste as well as food and kitchen waste (from households, restaurants, catering businesses, retail outlets, and food processing companies).

[0077] The term "biodegradable waste"For the purposes of the invention, in addition to biowaste as defined herein, the term also includes all organic waste of animal or plant origin from agriculture and forestry that can be degraded by microorganisms, soil organisms, or enzymes. In particular, this term includes all organic waste of animal or plant origin from agriculture and forestry that further contains at least one of the following biodegradable materials selected from the list consisting of wood, paper, and cardboard.

[0078] The term "Animal waste" For the purposes of the invention, this includes animal carcasses of deceased, dead or stillborn large or domestic animals - or parts thereof - as well as slaughter waste, spoiled food of animal origin, and animal by-products such as milk, eggs, confiscated items, but also intestinal contents and manure, as well as all other products and products.

[0079] In particular, the term "animal waste" as used in the invention includes meat and animal by-products from domestic animals, wild animals, or farm animals that were killed or died due to illness, especially TSE-infected animal carcasses, as well as animals contaminated with chemicals or prohibited substances and laboratory animals. It also includes meat and by-products that carry the risk of other, non-communicable diseases.

[0080] The term "animal waste" as used in the invention also includes killed, i.e., unslaughtered, animals, animal by-products (e.g., milk), and any animal products containing drug residues. It also expressly includes all waste and by-products from slaughterhouses, kitchen and food waste, food of animal origin no longer suitable for human consumption, raw milk, fresh fish, or fresh fish by-products. In particular, the following are included: Kitchen and food waste of any kind, fish or other marine animals, as well as fish waste of any kind, former animal food products that are no longer intended for human consumption due to other, non-harmful consequences, e.g., packaging defects, carcass parts, raw milk, shells, hatchery by-products and cracked egg by-products, hair, fur, horns, etc., animal waste from the food industry, hides, hooves and horns, pig bristles and feathers, expired meat, inferior meat, meat from animals under significant stress, blood from animals (not ruminants) that have been slaughtered after inspection in a slaughterhouse, animal carcass parts and by-products that have arisen in the production of products intended for human consumption, defatted bones and greaves, as well as animal meal.

[0081] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above,The combustion of sewage sludge, biodegradable waste, biowaste and / or animal waste takes place in a waste incineration plant at 600° to 1,200°C, preferably at 800° to 900°C.

[0082] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The reaction of the solids (ash) with nitric acid takes place.

[0083] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The reaction of the solids (ash) with phosphoric acid takes place.

[0084] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The reaction of the solids (ash) takes place with a mineral acid mixture of phosphoric acid and nitric acid and contains no hydrohalic acids. In particular, the mineral acid mixture does not contain hydrochloric acid.

[0085] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The mineral acid mixture is present in an aqueous dilution at a concentration of 5 wt.% to 50 wt.%, preferably 10 wt.% to 30 wt.%.

[0086] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The phosphate-containing ash is mixed with the mineral acid mixture in a reactor, wherein the proportion of ash is 5 wt.% to 50 wt.%, preferably 20 wt.% to 30 wt.% based on the diluted mineral acid.

[0087] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The mineral acid mixture contains at least phosphoric and nitric acid.

[0088] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, In addition to phosphoric and nitric acid, the mineral acid mixture also contains sulfuric acid.

[0089] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The reaction time between acid and ash is 2 to 300 minutes, preferably 10 to 60 minutes.

[0090] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The reaction temperature is 20°C to 90°C, preferably 60°C to 80°C.

[0091] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The acid-insoluble part of the solids is separated by mechanical filtration and / or dehydration processes.

[0092] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The separation of the acid-insoluble part of the solids is carried out using dewatering units (e.g. vacuum belt filter, chamber filter press, membrane filter press, sieve belt press, centrifuge).

[0093] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The separation of the acid-insoluble part of the solids is carried out using a vacuum belt filter.

[0094] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, After the acid-insoluble part of the solids has been separated, the residue in the filter units is washed with water and the wash water is returned to the first process stage.

[0095] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above,Sulfuric acid is added in a dilution of 10 to 98 wt.%, preferably 40 to 80 wt.%.

[0096] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above, The sulfuric acid is added in a molar ratio corresponding to the dissolved calcium concentration of 0.5 Ca to 1.5 SO 4 (sulfate), preferably 1.0 Ca to 1.0 SO 4 (sulfate).

[0097] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above, The addition of sulfuric acid takes place in a stirred reactor.

[0098] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above, The residence time in the stirred reactor after the addition of sulfuric acid is 5 to 60 minutes, preferably 10 to 30 minutes.

[0099] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above, The reaction temperature (precipitation of calcium sulfate after addition of sulfuric acid) in the stirred reactor is 20° to 90°C, preferably 60° to 90°C.

[0100] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above,The calcium sulfate precipitate is separated by mechanical filtration and / or dehydration processes.

[0101] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above, The separation of the calcium sulfate precipitate is carried out using dewatering units (e.g. vacuum belt filter, chamber filter press, membrane filter press, sieve belt press, centrifuge).

[0102] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above, The calcium sulfate precipitate is separated using a vacuum belt filter.

[0103] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above, After the calcium sulfate precipitate has been separated, the residue in the filter units is washed with water and the wash water is returned to the first process stage.

[0104] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above,After separation of the calcium sulfate precipitate, the obtained filtrate (diluted mineral acid mixture) is at least partially reused for the digestion of the solids.

[0105] In preferred embodiments of the Aspects A2, A4 and A5, as well as the corresponding embodiments described above, The proportion of the filtrate being recycled is at least 10%, preferably at least 20%, more preferably 20% to 80%, and most preferably 40% to 60%, based on the total amount of filtrate obtained.

[0106] In preferred embodiments of the Aspects A3, A4 and A5, as well as the corresponding embodiments described above, After separation of the acid-insoluble part of the ash or after separation of the calcium sulfate precipitate, the pH of the filtrate or supernatant is increased with alkali or alkaline earth hydroxides or oxides, preferably with sodium hydroxide, potassium hydroxide, sodium silicate solution, calcium hydroxide or calcium carbonate.

[0107] In preferred embodiments of the Aspects A3, A4 and A5, as well as the corresponding embodiments described above,The pH value in a stirred reactor is adjusted to 2.0 to 3.0, preferably to 2.0 to 2.5.

[0108] In preferred embodiments of the Aspects A3, A4 and A5, as well as the corresponding embodiments described above, The residence time in the stirred reactor is 5 to 60 minutes, preferably 10 to 30 minutes.

[0109] In preferred embodiments of the Aspects A3, A4 and A5, as well as the corresponding embodiments described above, The aluminum hydroxophosphate is separated or obtained by mechanical filtration and / or dehydration processes.

[0110] In preferred embodiments of the Aspects A3, A4 and A5, as well as the corresponding embodiments described above, The separation / recovery of the aluminium hydroxophosphate precipitate is carried out using dewatering units (e.g. vacuum belt filter, chamber filter press, membrane filter press, sieve belt press, centrifuge).

[0111] In preferred embodiments of the Aspects A3, A4 and A5, as well as the corresponding embodiments described above, The separation / recovery of the aluminium hydroxophosphate precipitate is carried out using a filter press.

[0112] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above,The filtrate or supernatant containing nitric acid (HNO3) and / or phosphoric acid (H3PO4), optionally obtained after deposition of Fe silicate and / or calcium sulfate, and / or aluminum hydroxophosphate, is concentrated by evaporation to an acid content of 30 wt.% to 70 wt.%, preferably 40 wt.% to 60 wt.%.

[0113] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The pH of the filtrate or supernatant containing nitric acid (HNO3) and / or phosphoric acid (H3PO4), optionally obtained after deposition of Fe silicate and / or calcium sulfate, and / or aluminum hydroxophosphate, is adjusted to 4 to 12, preferably 6 to 9, by the addition of calcium oxide or calcium carbonate, forming calcium precipitates.

[0114] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above,Calcium oxide or calcium carbonate is added to the filtrate or supernatant containing nitric acid (HNO3) and / or phosphoric acid (H3PO4), optionally obtained after separation of Fe silicate and / or calcium sulfate, and / or aluminum hydroxophosphate, in a stirred reactor, forming calcium precipitates.

[0115] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, After the formation of calcium precipitates, the solid suspension is evaporated by the addition of heat or spray-dried to such an extent that a solid with a residual moisture content of 0 wt.% to 25 wt.%, preferably of 2 wt.% to 10 wt.%, is obtained.

[0116] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The precipitate(s) is present as a completely or partially insoluble precipitate in the form of flakes, droplets or crystalline material, in any microcrystalline, crystalline or amorphous form.

[0117] In preferred embodiments of the Aspects A1 to A5, as well as the corresponding embodiments listed above, The precipitate(s) is further processed, modified, refined, etc. into powders, dusts, bulk materials, granular materials, grits, etc. Examples

[0118] The entire process is described by the following experimental procedure: The starting material is ash from a sewage sludge incineration plant. The main components were analyzed as follows: wt. % P2O5 25,0 wt. % CaO 17,5 wt. % Fe2O3 26,9 wt. % Al2O3 6,7 wt. % SiO2 19,5

[0119] 100 g of ash are treated in a beaker with 300 g of dilute acid. The dilute acid consists of: 70 wt.% water; 15 wt.% HNO₃; and 15 wt.% H₃PO₄. The suspension is stirred for 30 minutes at 40°C and then filtered through a vacuum filter basket. The filter cake is then weighed and subsequently dried at 100°C. Wet filter cake = 122g Dried filter cake = 72g

[0120] This means that 72g of 100g of ash did not dissolve in the acid, while 28g (28%) were acid-soluble. A total of 275g of filtrate was weighed back and subsequently analyzed. The analytical results in the following table are compared with theoretical values ​​that would result if the main ash components had dissolved completely (in the filtrate and the wet fraction of the filter cake): (100%) (is) acid-soluble wt. % P2O5 17,78* 13,68 88,7% wt. % CaO 5,37 4,80 89,4% wt. % Fe2O3 8,25 0,47 5,7% wt. % Al2O3 2,06 1,56 75,7% wt. % SiO2 5,98 0,02 0,3% *7.69% P 2 O 5 result from the ash, 10.09% P 2 O 5 from the added phosphoric acid.

[0121] The results show that high redissolution rates of phosphate, calcium, and aluminum are achieved, while iron is only slightly dissolved and silicon, as expected, is almost insoluble as SiO₂. The concentration of H₃PO₄ has increased from 15 wt% to 13.68 x 1.37 = 18.7 kgThe concentration is increased by a factor of 1.37 (the conversion factor for P₂O₅ to H₃PO₄). Evaporation by this factor of 2 yields an acid with 37.4% H₃PO₄ and 30% HNO₃. This acid can be used to produce fertilizers or can be neutralized with CaO and then evaporated, resulting in a double salt of Ca(NO₃)₂ * Ca(H₂PO₄)₂.

[0122] This process has the disadvantage that, on the one hand, considerable quantities of nitric and phosphoric acid are required, and on the other hand, impurities of iron and aluminum salts degrade the product quality. The process would be economically marginal and would severely limit the added value of the end products.

[0123] These problems, which are particularly severe with higher Al concentrations in the sewage sludge ash (which can exceed 20% Al 2 O 3), are solved by the multi-stage process according to the invention in stage 2 and stage 3 as follows: The filter cake (122 g wet weight) from the first stage (the ash dissolution process) is washed with 100 g of hot water (70–90°C). The resulting wash filtrate is mixed with 200 g of filtrate from the first stage (dilute sulfuric acid) and 25 g of sulfuric acid (48% w / w) in a beaker (total weight = 100 + 200 + 25 = 325 g). After a few minutes, white calcium sulfate precipitates according to the reaction described above. After 30 minutes, the precipitate is filtered through a vacuum filter. 280 g of filtrate and 43 g of gypsum wet filter cake are obtained. The filtrate is analyzed.

[0124] The analysis results in the following table are compared with values ​​obtained from a parallel experiment in which filtrate of the first stage plus wash water were analyzed in the above-mentioned ratios: Filtrate + WW after Ca precipitation PH value 1,9 0,9 wt. % P2O5 9,58 9,43 wt. % CaO 3,70 1,45 wt. % Fe2O3 0,32 0,33 wt. % Al2O3 0,98 1,01

[0125] The data clearly show that the calcium content is reduced, as is the pH value, because additional hydrogen ions were able to form. The acidic filtrate from the second stage can now be used to dissolve the ash, eliminating the need for dosing H₃PO₄, as new phosphoric acid is constantly formed from the phosphate-containing ash. This stage is particularly noteworthy in the multi-stage process because the use of sulfuric acid reduces overall acid costs (sulfuric acid is the most cost-effective acid in terms of efficiency), and because gypsum is also recovered.

[0126] Using the recycled filtrate (low-calcium dilute acid), the first-stage formula is now as follows: 100 g of ash are treated in a beaker with 300 g of dilute acid. The dilute acid consists of 270 g of recycled material and 20 g of HNO₃. The suspension is stirred for 30 minutes at 40°C and then filtered through a vacuum filter press. The filter cake is then weighed and subsequently dried at 100°C. Wet filter cake = 130g Dried filter cake = 75g

[0127] This means that 75g of 100g of ash did not dissolve in the acid, i.e., 25g (25%) are acid-soluble. A total of 258g of filtrate (dilute acid) was weighed back and subsequently analyzed. The analytical results essentially correspond to the results of the first initial stage, except that the CaO content was slightly higher at 5.8% (because additional calcium was introduced via the recycled material), while the Al₂O₃ content increased further from 1.5% to 2.6%. In a third stage, the aluminum concentration in the dilute acid is reduced by adding small amounts of calcium oxide. For this, 150g of dilute acid is mixed with 1g of CaO at room temperature. A precipitate formed, which was filtered after 15 minutes using a vacuum filter press. 123g of filtrate and 25g of wet filter cake were obtained. The filtrate was analyzed.

[0128] The analysis results in the following table are compared with values ​​obtained from a parallel experiment in which the dilute acid was analyzed before the addition of CaO. dilute acid after AI precipitation PH value 0,9 2,2 wt. % P2O5 9,35 8,95 wt. % CaO 5,84 6,42 wt. % Fe2O3 0,54 0,48 wt. % Al2O3 2,61 0,84

[0129] A slight increase in pH resulted in the formation of an Al-PO4 precipitate, as evidenced by the decreased values ​​for P₂O₅ and Al₂O₃. The precipitation was intentionally reduced only slightly to prevent excessive accumulation of Al ions. The precipitate, washed with water and dried, was analyzed as follows: wt. % P2O5 31,3 wt. % CaO 1,1 wt. % Fe2O3 3,5 wt. % Al2O3 56,1

[0130] The precipitate was further processed in a further experiment according to patent DE 10 2012 015 065 B3 2013.07.18 and converted to sodium aluminate solution and a calcium phosphate precipitate.

[0131] The process steps described here can be adapted depending on the concentration of Ca and Al ions in the digestion acid (or the corresponding oxide concentrations in the ash). The essence of the invention lies in the fact that combining the process steps enables economical process control and, above all, yields low-aluminum end products.

[0132] The purified HNO₃-H₃PO₄ acid is preferably neutralized with CaO to a pH of 6 and concentrated by water evaporation, e.g., by spray drying. A double salt of calcium nitrate and calcium phosphate is formed. According to the invention, a salt with the following composition could be produced: 19.5 wt.% P₂O₅; 28.5 wt.% CaO; 24.3 wt.% NO₃; 0.8 wt.% Al₂O₃; 0.6 wt.% Fe₂O₃.

[0133] Figure 3 The diagram shows the different process flows. Forms of execution

[0134] AF1. Process for the recovery (production) of precipitates selected from the group consisting of calcium nitrate (CaNO3), calcium phosphate (Ca3(PO4)2), calcium sulfate (CaSO4), and aluminum hydroxophosphate (Al(OH)3·AlPO4), from ashes from waste incineration plants, the process comprising at least the recovery (production) of calcium phosphate (Ca3(PO4)2) and calcium nitrate (CaNO3), characterized in that a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) calcium phosphate precipitate and calcium nitrate precipitate are obtained and separated by adding calcium oxide or calcium carbonate to the filtrate or supernatant. AF2. Method according to embodiment AF1, the method additionally comprising the extraction (production) of calcium sulfate (CaSO4), characterized in thatthat a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) calcium sulfate precipitate is obtained and separated by adding sulfuric acid to the filtrate or supernatant, d) calcium phosphate precipitate and calcium nitrate precipitate are obtained and separated by adding calcium oxide or calcium carbonate to the filtrate or supernatant. AF3. Process according to embodiment AF1 or AF2, the process additionally comprising the recovery (production) of aluminum hydroxophosphate (Al(OH)₃·AlPO₄), characterized in that a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) optionally calcium sulfate precipitate is obtained and separated by adding sulfuric acid to the filtrate or supernatant.d) by raising the pH value, the dissolved aluminum is obtained and separated as aluminum hydroxophosphate precipitate; e) by adding calcium oxide or calcium carbonate to the filtrate or supernatant, calcium phosphate precipitate and calcium nitrate precipitate are obtained and separated. AF4. Process according to embodiments AF1 to AF3, the process comprising the recovery (production) of precipitates selected from the group consisting of calcium nitrate (CaNO3), calcium phosphate (Ca3(PO4)2), calcium sulfate (CaSO4), and aluminum hydroxophosphate (Al(OH)3·AlPO4), from phosphate-containing ashes from waste incineration plants, characterized in that a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids; b) the acid-insoluble part of the solids is separated, preferably by a mechanical filtration and / or dewatering process.c) calcium sulfate precipitate is obtained and separated by adding sulfuric acid to the filtrate or supernatant, preferably by a mechanical filtration and / or dehydration process; d) the dissolved aluminum is obtained and separated as aluminum hydroxophosphate precipitate by increasing the pH, preferably by a mechanical filtration and / or dehydration process; e) optionally the filtrate or supernatant is recycled for use in step a); f) optionally the filtrate or supernatant is concentrated, preferably by evaporation; or g) optionally calcium phosphate precipitate and calcium nitrate precipitate are obtained and separated by adding calcium oxide or calcium carbonate to the filtrate or supernatant, preferably by a mechanical filtration and / or dehydration process. AF5. Process according to embodiments AF2 to AF4, characterized in that the sulfuric acid is used in a dilution of 10 to 98 wt.%,preferably 40 to 80 wt.% is added, preferably in a stirred reactor, wherein the sulfuric acid is preferably added in a molar ratio corresponding to the dissolved calcium concentration of 0.5 Ca to 1.5 SO₄ (sulfate), preferably 1.0 Ca to 1.0 SO₄ (sulfate). AF6. Process according to embodiment AF3 or AF4, characterized in that the pH value is adjusted to 2.0 to 3.0, preferably to 2.0 to 2.5, preferably with alkali or alkaline earth hydroxides or oxides, in particular with sodium hydroxide, potassium hydroxide, sodium silicate solution, calcium hydroxide, or calcium carbonate. AF7. Process according to embodiment AF6, characterized in that the phosphate-containing ash is obtained by incinerating phosphate-containing sewage sludge, biodegradable waste, biowaste, and / or animal waste in a waste incineration plant. AF8. Methods according to embodiments AF1 to AF7, characterized in that,that the reaction of the solids with a mineral acid mixture takes place, wherein the mineral acid mixture is present in an aqueous dilution at a concentration of 5 wt.% to 50 wt.%, preferably 10 wt.% to 30 wt.%, and, optionally, the phosphate-containing ash is mixed with the mineral acid mixture in a reactor, wherein the proportion of ash is preferably 5 wt.% to 50 wt.%, preferably 20 wt.% to 30 wt.% based on the diluted mineral acid mixture. AF9. Process according to embodiment AF8, wherein the mineral acid mixture contains at least phosphoric acid (H₃PO₄) and nitric acid (HNO₃), wherein the diluted mineral acid mixture preferably contains 10 wt.% to 50 wt.% HNO₃ and 90 to 50 parts H₃PO₄, based on the total mineral acid content of the aqueous dilution.

Claims

1. A process for the recovery (production) of precipitates selected from the group consisting of calcium nitrate (CaNO3), calcium phosphate (Ca3(PO4)2), calcium sulfate (CaSO4), and aluminum hydroxophosphate (Al(OH)3 x AlPO4); from ashes from waste incineration plants and for the optional production of phosphoric acid (H3PO4), the process comprising at least the recovery (production) of calcium sulfate (CaSO4), characterized by the fact that a) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) a pH value <1 is adjusted by adding sulfuric acid to the filtrate or supernatant, and calcium sulfate precipitate is obtained and separated.

2. Method according to claim 1, characterized by the fact thata) the solids (ash) are reacted with nitric acid or phosphoric acid or a mineral acid mixture of the two acids, b) the acid-insoluble part of the solids is separated, c) a pH value <1 is adjusted by adding sulfuric acid to the filtrate or supernatant and calcium sulfate precipitate is obtained and separated, d) optionally the filtrate or supernatant is at least partially recycled for use in step a), e) optionally the filtrate or supernatant is concentrated, preferably by evaporation, to obtain phosphoric acid or nitrous phosphoric acid (HNO3 / H3PO4), f) optionally calcium phosphate precipitate and calcium nitrate precipitate are obtained and separated by adding calcium oxide or calcium carbonate to the filtrate or supernatant, preferably carrying out steps a), b), c) and d).

3. Method according to claim 2, characterized by the fact that Steps a), b), c) and d) are carried out.

4. Method according to claim 2, characterized by the fact that Steps a), b), c) and f) are carried out.

5. Method according to claim 2, characterized by the fact that Steps a), b), c), d) and e) are carried out.

6. Method according to claim 2, characterized by the fact that Steps a), b), c), d) and f) are carried out.

7. Method according to claims 2, 3, 5 and 6, characterized by the fact that , when step d) is carried out, at least 10% of the filtrate / supernatant is recycled for use in step a), preferably at least 20%, more preferably 20% to 80%, and even more preferably 40% to 60%, based on the total amount of filtrate obtained.

8. Method according to claims 1 to 7, characterized by the fact that It is a process for the production of phosphoric acid (H3PO4).

9. Method according to claims 1 to 8, characterized by the fact thatThe phosphate-containing ash is obtained by burning phosphate-containing sewage sludge, biodegradable waste, biowaste and / or animal waste in a waste incineration plant.

10. Method according to claims 1 to 9, characterized by the fact that the reaction of the phosphate-containing solids (ash) with phosphoric acid takes place in step (a).