WO1998030506A1 - Procede de traitement et valorisation energetique optimisee des boues d'epuration urbaine et industrielle - Google Patents
Procede de traitement et valorisation energetique optimisee des boues d'epuration urbaine et industrielle Download PDFInfo
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- WO1998030506A1 WO1998030506A1 PCT/FR1997/001819 FR9701819W WO9830506A1 WO 1998030506 A1 WO1998030506 A1 WO 1998030506A1 FR 9701819 W FR9701819 W FR 9701819W WO 9830506 A1 WO9830506 A1 WO 9830506A1
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- Prior art keywords
- sludge
- dryer
- energy
- treatment
- thin
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- 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
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- 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
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such processes
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- 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
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/127—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering by centrifugation
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- 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
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F3/00—Fertilisers from human or animal excrements, e.g. manure
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/12—Bioreactors or fermenters specially adapted for specific uses for producing fuels or solvents
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
- C12M47/14—Drying
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
- C12M47/18—Gas cleaning, e.g. scrubbers; Separation of different gases
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B23/00—Heating arrangements
- F26B23/02—Heating arrangements using combustion heating
- F26B23/022—Heating arrangements using combustion heating incinerating volatiles in the dryer exhaust gases, the produced hot gases being wholly, partly or not recycled into the drying enclosure
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B7/00—Drying solid materials or objects by processes using a combination of processes not covered by a single one of groups F26B3/00 and F26B5/00
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2201/00—Pretreatment
- F23G2201/20—Dewatering by mechanical means
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2900/00—Special features of, or arrangements for incinerators
- F23G2900/50007—Co-combustion of two or more kinds of waste, separately fed into the furnace
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2900/00—Special features of, or arrangements for incinerators
- F23G2900/50208—Biologic treatment before burning, e.g. biogas generation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/12—Heat utilisation in combustion or incineration of waste
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/145—Feedstock the feedstock being materials of biological origin
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- 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
- Y02W10/20—Sludge processing
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- 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
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- 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
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/918—Miscellaneous specific techniques
- Y10S210/919—Miscellaneous specific techniques using combined systems by merging parallel diverse waste systems
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/918—Miscellaneous specific techniques
- Y10S210/92—Miscellaneous specific techniques using combined systems of sequential local and regional or municipal sewage systems
Definitions
- the present invention relates to a process for the treatment and energy recovery of sludge produced in wastewater treatment plants of urban and industrial origin.
- the process which is the subject of claim 1 is characterized by an unprecedented combination of means known and experienced separately, making it possible to "release" the energy contained in the sewage sludge and to obtain a positive energy balance, equal to ⁇ 5.7 tonnes of oil equivalent / year / 1000 population equivalent.
- the process which is the subject of claim 1 completely addresses the problem posed by the elimination of sewage sludge without transfer of nuisance, by protecting the soil, groundwater and the environment against bacteriological and olfactory pollution and that of heavy metals; it is characterized in that:
- the landfill of sewage sludge is expected to disappear due to its ban announced for 2002.
- the agricultural spreading of sewage sludge which is increasingly practiced today, is characterized by the fact that the high content of P205 sludge and the relatively low need of plants for phosphorous fertilizers include phosphorus as a limiting element and identify the sludge at a "delay" fertilizer slowly releasing the nutrients.
- the process which is the subject of the present invention makes it possible to remedy these drawbacks; it provides for the "energy recovery” of sludges previously thermally dried up to 92% of dry matter, as "supplementary fuel” easily storable and automatically dosable in the ovens of incineration plants for household waste, equipped with recovery of energy and smoke purification installation separating the heavy metals, which undergo a treatment in accordance with the protection of soil and groundwater.
- the tonnage of this dried sludge represents, on average, in France, "4.5%" of that of household waste for the same number of equivalent inhabitants.
- Their use as an additional fuel will fill the "hollow” thermal load of furnaces-boilers due to the variability of the humidity rate of household waste and their composition, therefore their PCI (lower calorific value), and d '' ensure a “constant” steam production and equal as far as possible to their nominal capacity, thanks to the adequate storage and automatic dosing equipment for the dried sludge which is part of the process of the invention, and which will be installed on the site of the household waste incineration plant closest to that of the wastewater treatment plant.
- Figure 1 shows the equipment relating to the first five functions of the process.
- FIG. 3 represents a "variant" of the realization of functions 1 and 2 of the method.
- Figure 4 shows the application of the process to the complete treatment of slurry and its transformation into granulated fertilizer.
- Anaerobic digestion (1) of fresh liquid sludge which "releases" part of the energy of the sludge in the form of biogas. After treatment with drying and filtration, it is stored for use.
- the biogas PCI is around 5500 Kcal / Nm3 or 6.395 kwh / Nm3.
- the anaerobic digestion is carried out at the temperature of 35 ° C sheltered from air for approximately 20 days in a single conventional reactor. Heating of the fresh liquid sludge is carried out through the heat exchanger (1a) using the hot water produced by the heat of condensation of the drying mist.
- a small electric boiler (1b) will use the heat exchanger (1a) to heat the sludge for the first time.
- the conventional anaerobic digestion can be replaced in the method according to the invention, by anaerobic digestion with separation of the two phases of acidogenesis hydrolysis and methanization, or by aerobic stabilization ther ophile followed by a anaerobic digestion.
- the first device (4a) is a "rotary thin-film dryer" of the indirect type, with a double jacket heated by circulation of thermal oil itself heated in the above-mentioned recovery boiler (3a) thanks to the circulation pump (4d).
- the recovery boiler (3a) can produce, in the process according to the invention, saturated steam under pressure, which will be used as heating fluid in the jacket of the thin-layer dryer instead thermal oil.
- the heat exchange takes place through the internal envelope on which the sludge to be dried is spread in a thin layer.
- the heat transfer coefficient is high due to the thinness of the thin layer of mud, the renewal of which in contact with the wall is intense thanks to the strong turbulence of the thin layer created by a linear speed of the ends of the neighboring blades. 8 m / s.
- the mmce layer dryer is a proven dryer which allows sewage sludge to be dried with variable dryness at the inlet, without recycling of dried sludge, providing the sludge at the outlet with the desired dryness without fear of the extremely viscous phase and sticky, called the plastic phase, which the sewage sludge crosses during thermal drying beyond a dryness close to 50% DM (% of dry matter), which limit is variable depending on the nature of the sludge.
- the rotor of the dryer is equipped with adjustable and removable blades which are at the origin of the great flexibility of the dryer, and ensure the spreading of the sludge in a thin layer and its continuous advancement until the outlet of the dryer at around 64% of dry matter, that is to say beyond the plastic phase of the sludge, in granulated form thanks to the internal device for granulating the dryer.
- the incoming sludge is first heated to a temperature of around 100 ° C., then the water evaporates at this temperature. contained in sludge; due to the elevation of their temperature to 100 ° C during drying, the sludge is hygienized and its bacteriological pollution is almost entirely eliminated. Evaporation of the water contained in the sludge continues in the second drying apparatus (see below) until a dryness of approximately 92% DM with the production of stable granules free of dust; due to the reduction in the humidity of the sludge at the end of drying, to a value well below 15% of water, the risk of resumption of fermentation of the dried sludge with the formation of bad odors is eliminated.
- the thin layer dryer can be replaced in the process according to the invention, by any other type of dryer.
- the second device (4b) is a vibrated fluidized bed dryer / cooler which ensures the end of the drying of the sludge from 64% DM to around 92% DM by convection by means of hot gases through recovery boiler outlet (3a) a fixed perforated sole.
- the same vibrated dryer (4b) comprises at its end a partitioned zone through which circulates fresh air, by means of fans (4e) and (4f) serving to cool the dried sludge to 92% DM to a temperature below 50 ° C, compatible with its subsequent storage.
- the vibrated dryer / cooler (4b) does not have rotating blades which grind the sludge producing fine dust of dried sludge; the sludge granules previously formed in the thin-layer dryer are therefore not destroyed in the vibrated dryer / cooler, only their size is slightly reduced due to the reduction in their water content. This results in the absence of dust in the final dry product and in the hot exhaust gases; a cyclone (4g) is however installed on the hot gas outlet circuit for safety.
- the cooled dried sludge is brought by a conveyor belt (4h) with a translucent cover, and a bucket elevator (4i) in a storage silo (4j) equipped with a telescopic chute (4k), before being transported by truck equipped with a pneumatic system for discharging dried sludge on the site of the nearest household waste incineration plant.
- the vibrated fluidized bed dryer can be replaced in the process according to the invention, by any other type of dryer, likewise the safety cyclone can be either removed or replaced by any other device such as a filter sleeve .
- This energy recovery from steam in the form of hot water is used to heat fresh liquid sludge before their anaerobic digestion, and to heat the premises of the treatment plant.
- the condenser by mixture (5b) is used by injection of purified water, to condense any excess of mist and is dimensioned to condense if applicable, all of the mist from the thin-layer dryer.
- the volatile compounds contained in the sludge such as: mercaptans, formaldehyde and hydrogen sulfide, are found entrained in the fumes from the indirect thin-layer dryer where the sludge is pre-dried up to about 64% DM; at this stage, all the smelly volatile compounds are evaporated and entrained by the fumes towards the condensers; the noncondensable gases leaving the condensers represent a low flow rate and are sucked through a droplet separator (5c), by a fan (5d) and discharged towards the hearth of the gas turbine to be burned and thus thermally deodorized; thus, the 64% DM pre-dried sludge is freed from foul-smelling volatile compounds and can be dried in the vibrated fluidized bed dryer using hot gases without the risk of transmitting significant olfactory pollution to them, so that the deodorization of the hot gases leaving the vibrated dryer / cooler is not necessary, which considerably simplifies the method according to the invention.
- the deodorization of the incondensable gases leaving the condensers can be carried out chemically or biologically, and the vibrated dryer / cooler can be equipped in the process according to the invention, 'an installation for the deodorization of hot exhaust gases.
- the dried sludge representing a small volume is transported by truck to the site of the nearest household waste incineration plant where it will be installed, as part of the method of the invention, a suitable storage silo (6a) of the dried sludge as well as automatic metering equipment (6b) of the flow of the dried sludge.
- a household waste incineration plant is declared capable of burning dry sludge, if it is equipped, in addition to energy recovery, with a smoke purification installation (8) in accordance with the regulations in force with a view to the protection of soil, groundwater and the environment, in particular concerning the elimination of heavy metals from household waste and dried sludge.
- the elimination of heavy metals from the dried sludge will entail a “marginal” additional cost, to be determined and compared to case by case with the benefit of the recovery of the energy contained in the dried sludge.
- the destination of the dried sludge can be in the process according to the invention, different from that set out above such as any other incineration plant.
- connection, measurement and regulation equipment, handling and storage of sludge, etc. is characterized in that it will be chosen at the cutting edge of technology on the date of each implementation of the process according to the invention; the schematic representations of this material appearing on the attached process diagram are not limiting.
- the process according to the invention reduces the tonnage of sewage sludge, during the treatment stages, as indicated in the table below:
- the “variant”, object of claim 4, of the method object of the invention is characterized in that the functions 3, 4 and 6 of the method are unchanged, and that the anointings 1, 2 and 5 can be produced, in an unprecedented manner within the framework of the process, as follows: the fresh liquid sludges are heated to the temperature of 55-60 ° C. in the condenser (5e) of the vapors from the thin-layer dryer, then dehydrated continuously by centrifugation (2a) with prior addition of polymers; the quantity of polymers used is lower and the dryness of the fresh dehydrated sludge is higher, due to the elevation of the temperature of the sludge to 55-60 ° C.
- the electric boiler (1b) and the heat exchanger (1a) which, if necessary, would serve as a backup.
- the dehydrated sludge with 28-30% dry matter feed directly by gravity through a chute (1c), the horizontal thermophilic anaerobic digester (1), equipped with an agitator ensuring the mixing of the sludge during its digestion and a optimal degassing; the volume of the digester is much reduced due to the increase in the dryness of the incoming fresh sludge to 28-30% DM instead of 4-5% DM, resulting in a reduction of the volume of the digester by approximately 6 times for a unchanged length of stay.
- the digested sludge is continuously extracted at the end of the horizontal reactor, and is dosed using a special pump (2d) directly, without an intermediate storage silo, to the thermal drying of the digested sludge.
- the horizontal digester is dimensioned with a reserve of sufficient volume to compensate for an untimely stoppage of the thermal drying of the sludge.
- the duration of the sludge stay in the reactor is close to 20 days.
- Functions 3, 4 and 6 of the process are then carried out without change.
- the “application”, object of claim 5, of the method object of the invention, to the treatment of “slurry”, is characterized in that the functions 1, 2, 3 and 4 of the method are unchanged, and that functions 5 and 6 can be performed, in an unprecedented way within the framework of the process, as follows:
- the condensation of the fumes from the indirect thin-layer dryer takes place on the one hand in the tubular condenser (5a), producing hot water for heating the anaerobic digester, and on the other hand in an evaporator.
- the incondensable gases leaving the condensers represent a low flow rate and are sucked through a droplet separator (5c), by a fan (5d) and discharged towards the hearth of the gas turbine to be burned and thus thermally
- Dried slurry is valued as a granulated “farm” fertilizer, bagged using the bagging machine (6a); it is rich in nutritive elements and will be in priority used according to the needs of the plants, without overdose, in the same way as a commercial fertilizer.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1997603975 DE69703975T3 (de) | 1997-01-06 | 1997-10-13 | Optimierte methode zur behandlung und energielieferten verwertung von kommunalem und industriellem klärschlamm |
AT97909392T ATE198873T1 (de) | 1997-01-06 | 1997-10-13 | Optimierte methode zur behandlung und energielieferten verwertung von kommunalem und industriellem klärschlamm |
US09/142,195 US6171499B1 (en) | 1997-01-06 | 1997-10-13 | Optimised method for the treatment and energetic upgrading of urban and industrial sludge purifying plants |
CA 2254724 CA2254724C (fr) | 1997-01-06 | 1997-10-13 | Procede de traitement et valorisation energetique optimisee des boues d'epuration urbaine et industrielle |
EP19970909392 EP0906248B2 (fr) | 1997-01-06 | 1997-10-13 | Procede de traitement et valorisation energetique optimisee des boues d'epuration urbaine et industrielle |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9700050A FR2758100B1 (fr) | 1997-01-06 | 1997-01-06 | Procede de traitement et valorisation energetique optimisee des boues de stations d'epuration urbaine et industrielle |
FR97/00050 | 1997-01-06 |
Publications (1)
Publication Number | Publication Date |
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WO1998030506A1 true WO1998030506A1 (fr) | 1998-07-16 |
Family
ID=9502387
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR1997/001819 WO1998030506A1 (fr) | 1997-01-06 | 1997-10-13 | Procede de traitement et valorisation energetique optimisee des boues d'epuration urbaine et industrielle |
Country Status (7)
Country | Link |
---|---|
US (1) | US6171499B1 (fr) |
EP (1) | EP0906248B2 (fr) |
AT (1) | ATE198873T1 (fr) |
CA (1) | CA2254724C (fr) |
DE (1) | DE69703975T3 (fr) |
FR (1) | FR2758100B1 (fr) |
WO (1) | WO1998030506A1 (fr) |
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CN108298788A (zh) * | 2018-03-29 | 2018-07-20 | 天津大学 | 一种低浓度污泥消化干化过程中沼气梯级利用系统 |
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CN116854319B (zh) * | 2023-05-29 | 2023-11-24 | 山东驰盛新能源设备有限公司 | 一种污泥处理方法及其处理装置 |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2240890A1 (en) * | 1973-08-17 | 1975-03-14 | Anstett Alfred | Desiccation and pasteurisation of liq. and solid farm manure - using combustion heat of fermentation gas |
EP0564298A1 (fr) * | 1992-04-01 | 1993-10-06 | Ngk Insulators, Ltd. | Procédé pour le traitement des boues organiques |
DE19502856A1 (de) * | 1995-01-30 | 1996-08-01 | Vit Robert | Vorrichtung und Verfahren zur Verminderung der Schlammproduktion in Kläranlagen |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH476949A (de) * | 1968-07-08 | 1969-08-15 | Von Roll Ag | Verfahren zur gemeinsamen Verbrennung von festen Abfallstoffen, insbesondere Stadtmüll, und wässrigem Klärschlamm, insbesondere aus kommunalen Kläranlagen, sowie Einrichtung zur Ausführung des Verfahrens |
US3702596A (en) * | 1971-02-24 | 1972-11-14 | John L Winther | Incinerator sludge concentrator combination |
US3954069A (en) * | 1975-03-10 | 1976-05-04 | Myrens Verksted A/S | Process and apparatus for the incineration of aqueous sewage sludge |
US4753181A (en) * | 1984-07-20 | 1988-06-28 | Leon Sosnowski | Incineration process |
DE3842446C1 (fr) * | 1988-12-16 | 1990-10-04 | Still Otto Gmbh, 4630 Bochum, De | |
MC2073A1 (fr) * | 1989-09-21 | 1990-10-03 | Baria Guy | Injecteur de boues baria |
DE4121968A1 (de) * | 1991-06-28 | 1993-01-14 | Noell K & K Abfalltech | Verfahren zur kombinierten klaerschlamm- und muellverbrennung |
DE4138036C2 (de) * | 1991-11-19 | 1999-07-08 | Rothemuehle Brandt Kritzler | Verfahren und Vorrichtung zur Behandlung eines zu einem Dickschlamm entwässerten Klärschlammes |
FR2724008B1 (fr) * | 1994-08-29 | 1997-05-09 | Degremont | Procede d'incineration auto-thermique de boues et eventuellement en outre d'ordures menageres |
-
1997
- 1997-01-06 FR FR9700050A patent/FR2758100B1/fr not_active Expired - Fee Related
- 1997-10-13 DE DE1997603975 patent/DE69703975T3/de not_active Expired - Fee Related
- 1997-10-13 CA CA 2254724 patent/CA2254724C/fr not_active Expired - Fee Related
- 1997-10-13 EP EP19970909392 patent/EP0906248B2/fr not_active Expired - Lifetime
- 1997-10-13 US US09/142,195 patent/US6171499B1/en not_active Expired - Fee Related
- 1997-10-13 WO PCT/FR1997/001819 patent/WO1998030506A1/fr active IP Right Grant
- 1997-10-13 AT AT97909392T patent/ATE198873T1/de not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2240890A1 (en) * | 1973-08-17 | 1975-03-14 | Anstett Alfred | Desiccation and pasteurisation of liq. and solid farm manure - using combustion heat of fermentation gas |
EP0564298A1 (fr) * | 1992-04-01 | 1993-10-06 | Ngk Insulators, Ltd. | Procédé pour le traitement des boues organiques |
DE19502856A1 (de) * | 1995-01-30 | 1996-08-01 | Vit Robert | Vorrichtung und Verfahren zur Verminderung der Schlammproduktion in Kläranlagen |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001056715A1 (fr) * | 2000-02-07 | 2001-08-09 | Daniel Friedli | Procede de traitement |
DE10152751A1 (de) * | 2001-10-29 | 2003-05-15 | Hans-Joachim Auerbach | Verfahren zur Aufbereitung von Biofiltraten aus biotechnologisch behandelten Substraten und Anordnung zur Durchführung des Verfahrens |
Also Published As
Publication number | Publication date |
---|---|
DE69703975D1 (de) | 2001-03-01 |
DE69703975T3 (de) | 2004-06-03 |
CA2254724C (fr) | 2002-10-29 |
FR2758100A1 (fr) | 1998-07-10 |
EP0906248B2 (fr) | 2003-11-12 |
DE69703975T2 (de) | 2001-11-15 |
ATE198873T1 (de) | 2001-02-15 |
US6171499B1 (en) | 2001-01-09 |
FR2758100B1 (fr) | 1999-02-12 |
CA2254724A1 (fr) | 1998-07-16 |
EP0906248A1 (fr) | 1999-04-07 |
EP0906248B1 (fr) | 2001-01-24 |
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