WO2014158058A1 - Procédé de production d'un engrais phosphoré provenant d'un résidu vaseux des stations d'épuration et de traitement et engrais obtenu par ce procédé - Google Patents

Procédé de production d'un engrais phosphoré provenant d'un résidu vaseux des stations d'épuration et de traitement et engrais obtenu par ce procédé Download PDF

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Publication number
WO2014158058A1
WO2014158058A1 PCT/RU2014/000148 RU2014000148W WO2014158058A1 WO 2014158058 A1 WO2014158058 A1 WO 2014158058A1 RU 2014000148 W RU2014000148 W RU 2014000148W WO 2014158058 A1 WO2014158058 A1 WO 2014158058A1
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WO
WIPO (PCT)
Prior art keywords
wws
pyrolysis
additives
sludge
phosphorus
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PCT/RU2014/000148
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English (en)
Russian (ru)
Inventor
Леонид Витальевич ЗЮБИН
Михаил Михайлович БУТУСОВ
Original Assignee
Общество С Ограниченной Ответственностью "Активил"
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Publication of WO2014158058A1 publication Critical patent/WO2014158058A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/13—Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating

Definitions

  • the invention relates to methods for the disposal of domestic and industrial waste, namely, low-waste disposal of sludge formed during wastewater treatment at urban wastewater treatment plants (WWS).
  • WWS urban wastewater treatment plants
  • WWS is a material characterized by high humidity, a high content of organic components (about 55% of the dry weight of WWS) and a high proportion (about 45%) of mineral components, including toxic elements - a number of heavy metals (HM) and their compounds.
  • EU waste management directives WWS processing methods are preferred that allow the disposal of both organic and mineral WWS components, i.e. to produce products on their basis for further use.
  • the optimal direction for the disposal of the organic component is most often thermal processing with energy generation.
  • the mineral residue remaining after thermal processing concentrates, among other mineral substances, practically all inorganic toxic elements and compounds. In this regard, its further use, as a rule, is impossible without special measures, such as:
  • a method of composting WWS consisting of preparing a mixture of WWS with neutral organic substances (for example, sawdust as proposed in US Pat. US Pat. No. 4,659,472) and prolonged exposure to this mixture under special conditions, as a result of which the average concentration of HM in the final product decreases , and the humates formed in compost block part of the TM compounds and prevent them from penetrating the soil.
  • Direct mixing of WWS with lignohumates is also possible (application 20120174638 for a US patent, published 12.07.2012);
  • the process of the company "CAMBI” described in patent EPO784504 consists in applying thermal hydrolysis to the WWS with a dry matter content of 13-14%, in which the destruction of such components of the WWS as microorganisms (bacteria, viruses) and biotoxic compounds occurs.
  • the process consists of three stages:
  • a possible application of the mineral component of WWS can be the manufacture of artificial gravel for building materials.
  • the toxicity of building materials is determined not by the mobility of toxic components, but by their concentration, which puts a barrier to most such applications, not to mention the high cost of this product.
  • the resulting phosphorus-containing material is free from heavy metals to an extent sufficient for use as a fertilizer.
  • - ash as the starting material of the process, has a pulverized structure with an average grain volume of 10 to 500 microns. It is very difficult to work with such material because of the high losses associated with the formation of dust both at the preparatory stage (transportation and transshipment), and in the processing process itself.
  • vitlokite Ca 3 (P0 4 ) 2 which is one of the most stable phosphates and poorly gives off phosphate ions in the processes of interaction with soil structures;
  • the present invention is aimed at eliminating most of the aforementioned disadvantages of the prototype, while the technical result achieved by the implementation of the claimed group of inventions consists in eliminating the formation of intermediate substances that are difficult to redistribute, in eliminating the formation of a large amount of exhaust gases requiring expensive purification systems. Accordingly, the overall production costs and capital investments are reduced. Moreover, the amount of phosphorus-containing product at the output of the process is comparable to that for the prototype, and the energy generation is higher (or less need for additional energy sources).
  • the novelty of the proposed method lies in the fact that the thermal processing of pre-dehydrated sludge is carried out in two stages: at the first stage, the thermal processing is carried out by pyrolysis with limited air intake and well-controlled temperatures, selected depending on the ratio of components in the processed sludge; the maximum pyrolysis temperature T p is maintained within 450 ° C ⁇ T p ⁇ 850 ° C; at the second stage, carbon is burned from the solid pyrolysis products - coked sludge - in an air stream; in this case, gaseous combustion products and a mineral phosphorus-containing product are obtained.
  • Pyrolysis of WWS is carried out in a standard type thermal reactor (for example, a multi-hearth furnace, a rotary furnace, or other types of reactors) with direct or indirect heating and control of the main conditions of pyrolysis - temperature and heating rate.
  • the pyrolysis conditions are selected based on the following requirements:
  • the heating rate and the temperature limit in the reactor provide insignificant, in comparison with the MPC requirements, concentrations of chlorine-containing gases at the outlet of the pyrolysis reactor and, therefore, subsequent combustion of pyrolysis gases allows the installation of simple gas cleaning systems (without the use of wet filters and similar expensive devices).
  • the energy necessary for the OSW pyrolysis process is provided by burning additional fuel in a standard type burner that maintains the required temperatures in the reactor, and / or by returning part of the obtained pyrolysis gas to power the burner.
  • - heavy metals in WWS are in less bound states than in the ash obtained after WWS combustion in fluidized bed furnaces.
  • Lead is present mainly in the form of organic salts, zinc in the form of mineral (often water-soluble) salts. These compounds are less stable compared to the heavy metal oxides contained in the ash from the burning of WWS according to the prototype, and in principle require less energy and substantially less chlorinating additives, such as calcium chloride and the like, used in the prototype for their destruction;
  • the claimed process also allows for additional improvements in its general framework.
  • the proposed method can be improved by the fact that, during processing, sludge is mixed with additives, the composition of which includes (but is not limited to) mineral donors of chlorides (in the form of a powder or concentrated solution of salts of alkali or alkaline earth metals or mixtures thereof).
  • additives the composition of which includes (but is not limited to) mineral donors of chlorides (in the form of a powder or concentrated solution of salts of alkali or alkaline earth metals or mixtures thereof).
  • This operation involves the use of standard devices that are technically no different from the devices used in the second prototype process. Mixing is carried out using standard devices (for example, intensive mixers).
  • the introduction of chlorides into WWS facilitates the subsequent separation of heavy metals from the final product and their concentration in a small amount of gas treatment waste.
  • the composition of additives also includes a group of additives based on some carbonate rocks of fine grinding (for example, chalk, limestone, dolomite, magnesite, etc.). Carbonate additives provide absorption of sulfur
  • the relative composition of the sludge and additives in the mixture is maintained in the following ranges: sludge 80-95% by dry weight, chlorine salts 3-20% by dry weight, carbonate additives - 0-15% by dry weight.
  • the specified amount of chlorine-containing salts ensures the presence in the material of a sufficient amount of chlorides for the formation of volatile chlorides of heavy metals and the partial formation of chlorapatite.
  • the specified amount of carbonate additives provides the absorption of most of the sulfur compounds in the processing of WWS, containing up to 2% sulfur in the organic mass. The presence of such amounts of sulfur in the final product increases the effectiveness of the product as fertilizer. Large quantities of additives become unreasonably costly because they do not give an additional effect.
  • the sludge and additives, after mixing are aggregated using one of the known technically acceptable methods (granulate, pelletize, compact, etc.) into compact formations (hereinafter - granules) with an average transverse size of 3-50 mm.
  • Granulation is carried out on standard granulators of dish-shaped, rotary, screw types, or, alternatively, granulator-mixers are used as devices performing both operations (mixing and granulation) simultaneously.
  • Obtaining granular material of a homogeneous controlled composition improves the quality of the final product as fertilizer, and also reduces the entrainment of dust particles by gas flows in the subsequent stages of the technological process.
  • the granular material (hereinafter referred to as the granulate) is dried before thermal processing using known devices to a residual moisture content of not more than 20%.
  • Pre-drying reduces steam content in pyrolysis gases and thereby reduces the volume of gases requiring cleaning and increases the value of pyrolysis gases as fuel.
  • Drying OSV includes the use of standard devices (tape, drum dryers and the like) that use thermal energy to heat the WWS.
  • Gaseous pyrolysis products carry most of the calorific value of WWS; they are fuel that can be used in devices of known design, for example, burning them in the furnace of a steam boiler to produce thermal energy. Thus, the process can be made energy efficient.
  • Part of the energy obtained by burning pyrolysis products can be used to dry the granulate.
  • low-grade heat is used for drying the granulate, for example, the heat of the flue gases generated by the combustion of pyrolysis products.
  • the coked silt sludge is sprayed with a hydrochloric acid solution.
  • This can be used for the formation of heavy metal chlorides in the case when hydrochloric acid (for example, captured during gas cleaning) is cheaper than chloride donor additives.
  • the maximum gasification temperature T t is preferably maintained within the range of 950 ° C T m ⁇ 1150 ° C. At temperatures below the specified limit does not occur with sufficient intensity of the release of heavy metals from the coked silt sediment; at temperatures above the specified limit, excessive sintering of the material occurs and its value as fertilizer decreases.
  • the burning of carbon from a coked silt sludge (gasification) is preferably carried out in a dense layer in countercurrent flow of a coked silt sludge and an oxidizing air in a known device, for example, in a shaft gasifier described, for example, in patent GB1435088 (C10J 3/02, publ. 1976- 05-12). Such organization of flows ensures that the solid product discharged from the gasifier is cooled by the incoming air; this facilitates the subsequent handling of the finished product.
  • Carrying out gasification of the coked ODS in a countercurrent air-oxidizer in which the syngas is taken out of the gasifier countercurrent to the loaded coked silt sludge allows the process to be carried out in such a way that the syngas discharged from the gasifier is cooled by the supplied granulate.
  • Partially chilled syngas can be sent to a device of a known type, for example, an irrigated scrubber, and it can be cleaned of dust and acid emissions. Since the volume of syngas is much smaller than the total volume of flue gas during direct burning of WWS, such an organization of the process provides an opportunity to reduce the cost of gas cleaning.
  • the purified syngas is preferably sent to combustion in an energy device together with pyrolysis gas.
  • a mineral phosphorus-containing product having a high (at least 25%) porosity is obtained from a sludge from wastewater treatment at the outlet of the gasifier;
  • the phosphorus-containing component in the product is represented, but not limited to, by the following main mineral phases: stenfieldite Ca 4 MD 5 (P0 4 ) 6 , farringtonite Md 3 (P0 4 ) 2, vitlokite Ca 3 (P0 4 ) 2, chlorapatite Ca 5 (P0 4 ) sCl (1.
  • the product does not contain residual carbon, and the content of heavy metals in it meets the standards for phosphate fertilizers: copper - less than 200 mg / kg (MPC for mineral fertilizers for Austria - 778, for the Netherlands - 214 mg / kg), lead - less than 30 mg / kg (MPC for Austria - 100, Holland - 285 mg / kg); zinc - less than 200 mg / kg (MPC for Austria - 3,000, G holland - 857 mg / kg), cadmium - less than 2 mg / kg (MPC for Austria-11, Holland-3.5 mg / kg).
  • Heavy metals in WWS are in less bound states than in ash after its burning in fluidized bed furnaces.
  • Lead is present mainly in the form of organic salts, zinc in the form of mineral (often water-soluble) salts. These compounds are less stable compared to oxides and, in principle, require less energy and significantly less chlorinating additives, such as calcium chloride and the like, used in the prototype for their destruction.
  • Granulation of WWS together with a carbonate mineral has a twofold purpose.
  • calcium carbonate serves as a reliable way to retain hydrogen chloride and prevent its evaporation into the atmosphere of the pyrolysis reactor, even if temperatures are reached at which the dissociation of part of the alkali or alkaline earth metal chlorides, which are also part of the granules, begins. Chlorides are held in granules until they enter the gasifier.
  • carbonate additives can bind the sulfur contained in organic mass of WWS, which reduces the content of sulfur oxides in flue gases generated during the subsequent combustion of pyrolysis gases.
  • gas flow from the gasifier associated with the pyrolyzer is, in turn, 5-6 times less than from the previous pyrolyzer and is not as saturated with chloride gases as in the prototype, since the initial amount of the required chlorine-containing additives in the granules is less .
  • gas purification in the proposed method significantly simpler than the prototype and will require significantly lower capital and production costs.
  • dolomite or magnesite flour as a carbonate additive will increase the magnesium content in the final product and increase the proportion of calcium-magnesium phosphates, which, as shown by numerous experiments, provide better absorption of phosphate ions by plants from the soil compared to tricalcium phosphate (vitlokite).
  • Sludge composition (by dry weight): ash content - 35%, organic mass - 65%.
  • the precipitate was mechanically dehydrated to a moisture content of 65%.
  • calcium chloride and dolomite flour were added to the precipitate (10% each, calculated on the dry weight of the precipitate).
  • granules of about 5 mm in size were formed from a mixture of precipitate with additives and the granules were dried in an oven to a residual moisture content of 10%.
  • the dried granules were pyrolyzed for 35 minutes at a temperature of 450 ° C in a container that did not allow access of air during external heating.
  • the pyrolysis gases generated by heating the precipitate were burned in a flare.
  • Oxidized granules had a composition - ash content of 64%, coke - 36%.
  • the composition of the mineral part of the granules is shown in table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Sludge (AREA)
  • Fertilizers (AREA)
  • Processing Of Solid Wastes (AREA)
  • Gasification And Melting Of Waste (AREA)

Abstract

L'invention concerne des procédés de recyclage des résidus ménagers et industriels et notamment le recyclage à faible production de déchets des résidu vaseux des stations d'épuration (RV STEP). Le procédé de production d'un produit minéral phosphoré pour fertiliser les sols provenant d'un résidu vaseux des stations d'épuration (RV STEP) comprend deux opérations réalisées l'une après l'autre : élimination préliminaire d'humidité dans RV STEP et traitement thermique de RV STEP. L'invention concerne également le produit obtenu à l'aide du procédé de l'invention. Le résultat intermédiaire consiste à exclure la formation de substances intermédiaires qui se prêtent mal à une transformation ultérieure, à empêcher la formation d'une grande quantité de gaz sortants qui nécessitent des systèmes de purification coûteux.
PCT/RU2014/000148 2013-03-27 2014-03-05 Procédé de production d'un engrais phosphoré provenant d'un résidu vaseux des stations d'épuration et de traitement et engrais obtenu par ce procédé WO2014158058A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2013113685 2013-03-27
RU2013113685/05A RU2532198C1 (ru) 2013-03-27 2013-03-27 Способ получения фосфорсодержащего удобрения из илового осадка городских водоочистных сооружений и удобрение, полученное таким способом

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WO2014158058A1 true WO2014158058A1 (fr) 2014-10-02

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3037395A1 (fr) * 2014-12-23 2016-06-29 TSP GmbH Procédé et dispositif de production d'un produit contenant du phosphore sous une forme facile à utiliser pour les plantes provenant d'un produit en vrac d'origine au moins partiellement organique
CN113441513A (zh) * 2021-05-25 2021-09-28 中国地质大学（武汉） 一种稳定化处理重金属废渣的有机-无机复合材料及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2704398C1 (ru) * 2019-03-25 2019-10-28 Общество С Ограниченной Ответственностью "Научно-Технический Центр "Экопромтех" Способ остеклования илового осадка или других органических шламов и отходов и устройство для его реализации

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AT503073A1 (de) * 2006-05-03 2007-07-15 Ash Dec Umwelt Ag Verfahren zur abtrennung von schwermetallen und ascheagglomerat
RU75654U1 (ru) * 2008-04-09 2008-08-20 Валерий Григорьевич Лурий Комплекс для переработки биомассы
CN101708938A (zh) * 2009-11-06 2010-05-19 杭鹏志 污泥或有机垃圾高低温耦合热解方法

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JP4399394B2 (ja) * 2004-06-21 2010-01-13 協同組合ぐんま環境技術コンソーシアム 肥料の製造方法及び製造システム
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RU2046013C1 (ru) * 1993-02-24 1995-10-20 Товарищество с ограниченной ответственностью "Экос" Композиционный карбоминеральный сорбент "карбосиаллит"
RU2079051C1 (ru) * 1994-06-23 1997-05-10 Институт химической физики в Черноголовке РАН Способ переработки твердых бытовых отходов
AT503073A1 (de) * 2006-05-03 2007-07-15 Ash Dec Umwelt Ag Verfahren zur abtrennung von schwermetallen und ascheagglomerat
RU75654U1 (ru) * 2008-04-09 2008-08-20 Валерий Григорьевич Лурий Комплекс для переработки биомассы
CN101708938A (zh) * 2009-11-06 2010-05-19 杭鹏志 污泥或有机垃圾高低温耦合热解方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3037395A1 (fr) * 2014-12-23 2016-06-29 TSP GmbH Procédé et dispositif de production d'un produit contenant du phosphore sous une forme facile à utiliser pour les plantes provenant d'un produit en vrac d'origine au moins partiellement organique
CN113441513A (zh) * 2021-05-25 2021-09-28 中国地质大学（武汉） 一种稳定化处理重金属废渣的有机-无机复合材料及其制备方法
CN113441513B (zh) * 2021-05-25 2022-07-19 中国地质大学（武汉） 一种稳定化处理重金属废渣的有机-无机复合材料及其制备方法

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RU2013113685A (ru) 2014-10-10

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