EP1986964A1 - Process for eliminating organic matter and for generating energy - Google Patents

Process for eliminating organic matter and for generating energy

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Publication number
EP1986964A1
EP1986964A1 EP07730999A EP07730999A EP1986964A1 EP 1986964 A1 EP1986964 A1 EP 1986964A1 EP 07730999 A EP07730999 A EP 07730999A EP 07730999 A EP07730999 A EP 07730999A EP 1986964 A1 EP1986964 A1 EP 1986964A1
Authority
EP
European Patent Office
Prior art keywords
organic material
oxidant
process according
combustion
organic matter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07730999A
Other languages
German (de)
French (fr)
Other versions
EP1986964B1 (en
Inventor
Stéphane BARBATI
Maurice Ambrosio
Virginie Fontanier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aix Marseille Universite
Original Assignee
Universite de Provence Aix Marseille I
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Universite de Provence Aix Marseille I filed Critical Universite de Provence Aix Marseille I
Publication of EP1986964A1 publication Critical patent/EP1986964A1/en
Application granted granted Critical
Publication of EP1986964B1 publication Critical patent/EP1986964B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2201/00—Pretreatment
    • F23G2201/80—Shredding
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2202/00—Combustion
    • F23G2202/30—Combustion in a pressurised chamber
    • 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
    • F23G2900/70—Incinerating particular products or waste
    • F23G2900/7002—Animal fat, e.g. lard, tallow, stearin
    • 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
    • F23G2900/70—Incinerating particular products or waste
    • F23G2900/7003—Incinerating litter from animals, e.g. poultry litter
    • 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
    • F23G2900/70—Incinerating particular products or waste
    • F23G2900/7004—Incinerating contaminated animal meals
    • 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
    • F23G2900/70—Incinerating particular products or waste
    • F23G2900/7009—Incinerating human or animal corpses or remains

Definitions

  • the present invention relates to a new process for the removal of organic matter and energy production.
  • the waste to be disposed of can be solid or non-solid.
  • the raw product is first transformed into a solid waste called animal meal, which is then destroyed by incineration, that is to say by combustion with the flame at temperature. higher than 850 0 C. But the incineration produces dioxins, and it must be carried out on flour generating dust which can be toxic.
  • This process is essentially based on a flameless combustion at a relatively low temperature, and under pressure, in the presence of an oxidant such as air.
  • an oxidant such as air.
  • the present application relates to a method for destroying organic material, wherein is installed in a reactor said organic matter in comminuted form and is carried at its combustion without a flame at a temperature of 240-400 0 C., under a pressure of 100 to 300 bar, in the presence of an oxygenated oxidant, for at least 20 minutes, while stirring the medium.
  • organic matter refers to the carbonaceous material from living or non living beings, plants or animals. More precisely, it is about materials able to decompose. This notion should not be confused with that of "organic compound”, a family to which belong in particular plastics and polymers and more particularly PCBs (PolyChloro-Biphenyls), also called, especially in Quebec,
  • PCBs Polychlorinated biphenyls as well as polychlorinated terphenyls, monomethyl tetrachlorodiphenylmethane, monomethyl dichlorodiphenylmethane and monomethyl dibromodiphenylmethane, which are assimilated thereto.
  • the treated organic materials do not need to be in solid form. They are obviously in a form that can be milled (that is to say minced in the case of meat or fish for example).
  • raw products are processed. They are especially not degreased.
  • organic materials there may be mentioned those of animal origin (including humans) including animal by-products including poultry by-products and fisheries and animal waste.
  • Mention may in particular be made of organic materials of animal origin, such as those derived from cattle, pigs, goats, poultry, equines, rodents such as rabbits and hares. It is also possible to mention in particular the waste exiting the slaughterhouse or rendering animals, for example carcasses of cattle, poultry, pigs, sheep, and animal fats from the preparation of meat. Another example is slurry and fishery waste.
  • Some of these materials may be in the form of corpses or carcasses. It can also be animal parts like the blood, feet, head, horns, muzzle, tonsils / pharyngeal lymphatic ring, penis, tail, lungs, kidneys, esophagus, liver, heart, diaphragm, spleen, pre-stomachs, stomach, testes, trachea, larynx, extralobular bronchi, gallbladder, bile, fat, intestine, mesentery anus, female genitalia, udders, fetuses , the spinal cord and the hard mother, the spine, the sacrum, the tendons, the ligaments, the nervous tissues, the lymphatic tissues, the blood vessels, the meat not intended for food. It can also be metabolic waste. We can also treat waste of any kind from the pharmaceutical industry or veterinary hospitals or hospitals, for example as cottons, linens or compresses soiled, anatomical waste of human or animal origin as those mentioned above.
  • Waste water also called waste water
  • domestic sewage consists of toilet flushing gates, greywater evacuation kitchens and bathrooms. Waste in these dirty waters consists of degradable organic matter and mineral matter. These substances are in dissolved or suspended form.
  • wastewater networks lead to treatment plants where the water is treated and where most of the organic matter is in the form of sludge.
  • animal by-products not intended for human consumption categories 1 2 and 3 according to the regulation of October 3, 2002 establishing in France the sanitary rules applicable to animal by-products not intended for human consumption.
  • the waste is used in the reduced form process.
  • reduced form is meant that the pieces of organic material or containing organic material are small. They come for example in the form of a slurry.
  • the particle size of at least preferably 50%, preferably 80%, especially 90% of the pieces is advantageously less than 20 mm, preferably less than 15 mm, especially less than 10 mm, more particularly less than 5 mm (evaluation by sieving ).
  • the condition of the products (solid, slurry, etc.) is classically indicated for normal temperature and pressure conditions.
  • the process of the invention can be carried out between 240 and 400 ° C., preferably between 250 and 350 ° C., particularly between 280 and 320 ° C.
  • the process of the invention is carried out under a pressure of 100 to 300 bar, preferably between 150 and 250 bar, preferably between 180 and 230 bar, particularly about 200 bar.
  • Oxidizing compounds that may be mentioned include oxygenates.
  • oxygen is used, in particular in the form of air optionally mixed with one or more other gases.
  • oxygenates are used from waste or by-products of the industry, such as, for example, nitrous oxide.
  • COD chemical oxygen demand
  • a catalyst especially based on (Cu, Pt, Pd, Ru, Rh, Ti, especially on different supports such as oxides of aluminum, cerium or silicon.
  • the catalyst will for example be a metal oxide, such as selenium oxide, rhenium or hafnium, or those mentioned in the examples.
  • the catalyst may for example be used at a rate of approximately 2 g / l. It can especially be used at a pH of about 12.
  • a zeolite will be used.
  • the reaction time depends on the amount of organic material introduced initially.
  • the reaction time can vary from 20 minutes. at 120 min. for carbon concentrations of between 5 g and 40 g per liter, preferably 20 to 120 min, preferably 60 to 100 min, most preferably 75 to 90 min.
  • the initial heating can be interrupted as soon as the set temperature is reached.
  • one or more of the inlet effluents are heated, for example the oxidizer or the additional organic materials to be treated in the case of a semi-continuous implementation. , or continuous, thanks to the energy produced by the implementation of the process.
  • the heat energy produced by the reaction is removed using a particularly aqueous fluid, such as using industrial effluents, and more particularly using slaughterhouse effluents for the on-site treatment of raw animal material.
  • the agitation system may be a conventional blade system.
  • the oxidizer preferably air, serves or in particular contributes to the agitation of the treated organic material.
  • the oxidizer preferably air, serves or in particular contributes to the agitation of the treated organic material.
  • it is advantageously injected under pressure in the organic material.
  • the process of the invention may be carried out batchwise, semi-continuously, or continuously.
  • the reactor will be adapted to the form of implementation of the process. It is generally any suitable enclosure capable of withstanding high temperature and pressure.
  • the mineral phase is an ultimate waste
  • the process of the invention is endowed with remarkable qualities. It effectively destroys treated organic materials, especially proteins, and especially the prion. It makes it possible to transform this organic matter essentially into mineral matter, water and carbon dioxide.
  • the method further has the advantage of being autothermal.
  • the combustion is started, it is indeed no longer necessary to provide additional energy. Even an excess energy is obtained which allows, for example, to heat inlet effluents, for example the oxidant or the additional organic materials to be treated.
  • the effluents are brought to the reaction temperature.
  • the quantity of water needed to evacuate the heat energy produced by the reaction can be provided by industrial effluents, and more particularly effluents from slaughterhouses for the on-site treatment of raw animal materials. This energy produced can also be used to produce or complete district heating.
  • the method of the invention allows not only to work on animal meal, as is the case of incinerators, but also on raw products.
  • the invention can be implemented simply in a reactor capable of withstanding the above pressures, for example by using a reactor equipped with a heating system, a system for introducing the oxidizer, an organic material introduction system, a stirring system, a gas evacuation system, a low output for the mineral material, and preferably water and bath probes.
  • the present application also relates to a method for producing energy which is installed in a reactor an organic material in comminuted form, is carried at its flameless combustion at a temperature of 240-400 0 C under a pressure of 100 to 300 bar, in the presence of an oxygenated oxidant, for at least 20 minutes, while stirring the medium and recovering the energy produced by the combustion.
  • the recovery of the energy produced by the combustion can in particular be obtained by using one or more heat exchangers, in particular brazed plate and fin exchangers.
  • the energy thus produced and recovered for example in the form of hot fluid for example hot water, can be used conventionally.
  • Figure 1 describes a type of equipment and assembly used for the implementation of the invention, used for the realization of the following examples which illustrate the present application.
  • Example 1 Treatment of a batch of raw animal materials
  • a batch of (batch system) 20 grams of substrate is manually introduced into a hot oxidative treatment reactor, and sealed.
  • the hot oxidative treatment reactor used is a 450-mL volume autoclave made of a stainless steel crucible and a Hastelloy C276 lid, operating under subcritical conditions.
  • the equipment is designed to withstand a maximum temperature of 400 0 C and a maximum pressure of 30 MPa.
  • the reactor is heated using an electric oven with a power of 4500W, placed around the autoclave.
  • the system is also equipped with a mechanical stirrer and a manometer. The safety of the assembly is ensured by a solenoid valve and a rupture disc.
  • the reactor also has two feed lines / liquid and gaseous withdrawal.
  • the treated substrate consists of 20 g of raw animal material (8 g dry weight), not defatted, in the form of a brown pasty slurry with a characteristic odor and a particle size less than 5 mm.
  • the optimal hydrothermal oxidation reaction produces a liquid effluent.
  • This effluent contains 1.6 g / L of TOC (including 0.8 g of acetic acid) and 1.6 g / L of ammonia.
  • the destruction of organic matter represents an abatement of more than 99%.
  • the solid phase contains about 400 mg of inorganic and inert material, which represents a reduction of 95% of the solids. This solid phase contains a negligible amount of organic matter.
  • the gaseous effluents produced are separated and collected using a condenser and then trapped in an acid solution (HCl) and then basic (NaOH).
  • Example 2 Treatment of raw animal materials The procedure is as indicated above in Example 1, but adding 2 g / L to pH 12 of platinum catalyst on alumina. The TOC value of the outlet effluent is only 60 mg / L.
  • the method of the invention is therefore effective to eliminate in particular the prion, both in organic materials than in animal meal.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Process for destroying organic matter, in which said organic matter in ground form is introduced into a reactor and subjected to flameless combustion at a temperature of 240 to 400°C under a pressure of 100 to 300 bar, in the presence of an oxygen-containing oxidizer for at least 20 minutes, while stirring the medium, and process for generating energy, in which the energy generated by the combustion is furthermore recovered.

Description

Procédé d'élimination de matières organiques et de production d'énergie Process for removing organic matter and producing energy
La présente invention a pour objet un nouveau procédé d'élimination de matières organiques et de production d'énergie.The present invention relates to a new process for the removal of organic matter and energy production.
Dans la société actuelle, l'élimination des déchets et en particulier des matières organiques notamment d'origine animale, revêt une importance de plus en plus grande.In today's society, the disposal of waste, particularly organic matter, particularly of animal origin, is of increasing importance.
En outre, l'apparition de certains facteurs de maladies comme le prion, implique une destruction radicale de beaucoup de matières organiques.In addition, the appearance of certain disease factors, such as the prion, involves a radical destruction of many organic materials.
Les déchets à éliminer peuvent être solides, ou non solides.The waste to be disposed of can be solid or non-solid.
On sait par exemple déjà éliminer certains déchets par pyrolyse, c'est-à-dire par combustion à haute température dans un four.For example, it is already possible to eliminate certain wastes by pyrolysis, that is to say by combustion at high temperature in an oven.
En ce qui concerne plus particulièrement par exemple les carcasses animales, on transforme tout d'abord le produit brut en un déchet solide appelé farines animales, qui sont ensuite détruites par incinération, c'est-à-dire par combustion à la flamme à température supérieure à 8500C. Mais l'incinération produit des dioxines, et elle doit être réalisée sur des farines génératrices de poussières qui peuvent être toxiques.With particular reference for example to animal carcasses, the raw product is first transformed into a solid waste called animal meal, which is then destroyed by incineration, that is to say by combustion with the flame at temperature. higher than 850 0 C. But the incineration produces dioxins, and it must be carried out on flour generating dust which can be toxic.
Il serait donc souhaitable de trouver une technique efficace d'élimination des matières organiques, permettant de travailler directement sur le produit brut, ne produisant pas de toxines et permettant d'éviter la formation de poussières potentiellement toxiques.It would therefore be desirable to find an effective technique for the removal of organic matter, which makes it possible to work directly on the raw product, which does not produce toxins and which makes it possible to avoid the formation of potentially toxic dusts.
Il serait également souhaitable de trouver un procédé qui ne soit pas demandeur en énergie et même si possible qui produise de l'énergie plutôt qu'en consommer.It would also be desirable to find a process that does not demand energy and even if possible that produces energy rather than consuming it.
Après de longues recherches, les demandeurs ont trouvé un procédé donnant satisfaction.After extensive research, the applicants have found a satisfactory process.
Ce procédé est essentiellement fondé sur une combustion sans flamme à température relativement basse, et sous pression, en présence d'un comburant tel que l'air. C'est pourquoi la présente demande a pour objet un procédé de destruction d'une matière organique, dans lequel on installe dans un réacteur ladite matière organique sous forme broyée, et on procède à sa combustion sans flamme à une température de 240 à 400 0C, sous une pression de 100 à 300 bars, en présence d'un comburant oxygéné, pendant au moins 20 minutes, tout en procédant à l'agitation du milieu.This process is essentially based on a flameless combustion at a relatively low temperature, and under pressure, in the presence of an oxidant such as air. This is why the present application relates to a method for destroying organic material, wherein is installed in a reactor said organic matter in comminuted form and is carried at its combustion without a flame at a temperature of 240-400 0 C., under a pressure of 100 to 300 bar, in the presence of an oxygenated oxidant, for at least 20 minutes, while stirring the medium.
Rappelons que le terme « matière organique » désigne la matière carbonée provenant des êtres vivants ou non, végétaux ou animaux. Plus précisément il s'agit de matières capables de se décomposer. Cette notion ne doit pas être confondue avec celle de « composé organique », famille à laquelle appartiennent notamment les plastiques et les polymères et plus particulièrement les PCB (PolyChloro-Biphényles), également appelés, notamment au Québec,Remember that the term "organic matter" refers to the carbonaceous material from living or non living beings, plants or animals. More precisely, it is about materials able to decompose. This notion should not be confused with that of "organic compound", a family to which belong in particular plastics and polymers and more particularly PCBs (PolyChloro-Biphenyls), also called, especially in Quebec,
BPC (Biphényles PolyChlorés) ainsi que les polychloroterphényles, le monométhyl tétrachlorodiphénylméthane, le monométhyl dichlorodiphénylméthane et le monométhyl dibromodiphénylméthane qui y sont assimilés.PCBs (Polychlorinated biphenyls) as well as polychlorinated terphenyls, monomethyl tetrachlorodiphenylmethane, monomethyl dichlorodiphenylmethane and monomethyl dibromodiphenylmethane, which are assimilated thereto.
Selon la présente invention, les matières organiques traitées n'ont pas besoin d'être sous forme solide. Elles se trouvent évidemment sous une forme susceptible d'être broyée (c'est-à-dire hachée dans le cas de viande ou poisson par exemple).According to the present invention, the treated organic materials do not need to be in solid form. They are obviously in a form that can be milled (that is to say minced in the case of meat or fish for example).
Dans des conditions préférentielles de mise en œuvre de l'invention, on traite des produits bruts. Ils sont notamment non dégraissés.Under preferred conditions of implementation of the invention, raw products are processed. They are especially not degreased.
A titre de matières organiques, on peut citer celles d'origine animale (y compris l'homme) notamment les sous-produits animaux dont les sous- produits avicoles et de pêcherie et les déchets animaux.As organic materials, there may be mentioned those of animal origin (including humans) including animal by-products including poultry by-products and fisheries and animal waste.
On peut citer en particulier les matières organiques d'origine animale comme ceux provenant de bovins, porcins, caprins, volailles, équidés, rongeurs comme les lapins et lièvres. On peut citer aussi en particulier les déchets en sortie d'abattoir ou d'équarrissage des animaux, par exemple, des carcasses de boeufs, de volailles, de cochons, de moutons, et des graisses animales provenant de la préparation des viandes. On peut citer encore les lisiers et les déchets de pêcherie.Mention may in particular be made of organic materials of animal origin, such as those derived from cattle, pigs, goats, poultry, equines, rodents such as rabbits and hares. It is also possible to mention in particular the waste exiting the slaughterhouse or rendering animals, for example carcasses of cattle, poultry, pigs, sheep, and animal fats from the preparation of meat. Another example is slurry and fishery waste.
Certaines de ces matières peuvent se présenter sous la forme de cadavres ou de carcasses. Il peut aussi s'agir de parties animales comme le sang, les pieds, la tête, les cornes, le mufle, les amygdales/anneau lymphatique pharyngien, le pénis, la queue, les poumons, les reins, l'œsophage, le foie, le cœur, le diaphragme, la rate, les pré-estomacs, l'estomac, les testicules, la trachée, le larynx, les bronches extralobulaires, la vésicule biliaire, la bile, la graisse, l'intestin, le mésentère les anus, les organes génitaux femelles, les mamelles, les fœtus, la moelle épinière et la dure mère, la colonne vertébrale, le sacrum, les tendons, les ligaments, les tissus nerveux, les tissus lymphatiques, les vaisseaux sanguins, la viande non destinée à l'alimentation. Il peut aussi s'agir de déchets métaboliques. On peut également traiter des déchets de toute sorte provenant de l'industrie pharmaceutique ou des hôpitaux ou hôpitaux vétérinaires par exemple comme des cotons, linges ou compresses souillés, des déchets anatomiques d'origine humaine ou animale comme ceux précités.Some of these materials may be in the form of corpses or carcasses. It can also be animal parts like the blood, feet, head, horns, muzzle, tonsils / pharyngeal lymphatic ring, penis, tail, lungs, kidneys, esophagus, liver, heart, diaphragm, spleen, pre-stomachs, stomach, testes, trachea, larynx, extralobular bronchi, gallbladder, bile, fat, intestine, mesentery anus, female genitalia, udders, fetuses , the spinal cord and the hard mother, the spine, the sacrum, the tendons, the ligaments, the nervous tissues, the lymphatic tissues, the blood vessels, the meat not intended for food. It can also be metabolic waste. We can also treat waste of any kind from the pharmaceutical industry or veterinary hospitals or hospitals, for example as cottons, linens or compresses soiled, anatomical waste of human or animal origin as those mentioned above.
On peut encore citer en particulier les matières organiques en suspension ou solution dans les eaux usées (encore appelées eaux résiduaires) ou de lavage. Les eaux usées domestiques se composent des eaux vannes d'évacuation des toilettes, des eaux ménagères d'évacuation des cuisines et salles de bains. Les déchets présents dans ces eaux souillées sont constitués par des matières organiques dégradables et des matières minérales. Ces substances sont sous forme dissoute ou en suspension. Pour rappel les réseaux d'eaux usées aboutissent à des stations d'épuration où les eaux sont traitées et où l'essentiel des matières organiques se retrouve sous forme de boues.Mention may also be made in particular of organic materials in suspension or solution in wastewater (also called waste water) or washing. Domestic sewage consists of toilet flushing gates, greywater evacuation kitchens and bathrooms. Waste in these dirty waters consists of degradable organic matter and mineral matter. These substances are in dissolved or suspended form. As a reminder, the wastewater networks lead to treatment plants where the water is treated and where most of the organic matter is in the form of sludge.
On peut traiter aussi bien les boues primaires, dépôts récupérés par simple décantation des eaux usés et présentant des concentrations élevées en matières minérales (sables, terre...) mais aussi en matière organique, que les boues physico-chimiques, boues ressemblant aux boues primaires mais auxquelles il a été rajouté un réactif (sels de fer, d'aluminium, ou autres agents floculants) pour agglomérer les particules fines et améliorer la décantation, que les boues biologiques encore appelées boues secondaires, et provenant d'une épuration biologique des eaux (boues activées, lits bactériens...). On peut citer aussi les boues mixtes constituées d'un mélange de boues primaires et biologiques et les boues d'aération prolongée obtenues sans décantation primaire avec des matières polluantes intensivement aérées. On peut encore citer les sous-produits animaux non destinés à la consommation humaine de catégories 1 2 et 3 selon le règlement du 3 octobre 2002 établissant en France les règles sanitaires applicables aux sous-produits animaux non destinés à la consommation humaine. Dans des conditions préférentielles de mise en œuvre de l'invention, les déchets sont mis en oeuvre dans le procédé sous forme réduite.It is possible to treat both primary sludge, deposits recovered by simple decantation of waste water and having high concentrations of mineral matter (sands, earth ...) but also organic matter, that physicochemical sludge, sludge-like sludge but to which a reagent (salts of iron, aluminum, or other flocculating agents) has been added to agglomerate the fine particles and to improve the settling, that the biological sludge still called secondary sludge, and coming from a biological purification of waters (activated sludge, bacterial beds ...). Mixed sludge consisting of a mixture of primary and biological sludge and prolonged aeration sludge obtained without primary settling with highly aerated pollutants can also be mentioned. We can also mention animal by-products not intended for human consumption categories 1 2 and 3 according to the regulation of October 3, 2002 establishing in France the sanitary rules applicable to animal by-products not intended for human consumption. Under preferred conditions of implementation of the invention, the waste is used in the reduced form process.
Par "forme réduite" l'on entend que les morceaux de matières organiques ou contenant des matières organiques sont de petite taille. Ils se présentent par exemple sous forme d'une bouillie pâteuse. La granulométrie d'au moins avantageusement 50%, de préférence 80%, notamment 90% des morceaux est avantageusement inférieure à 20 mm, de préférence inférieure à 15 mm, notamment inférieure à 10 mm, tout particulièrement inférieure à 5 mm (évaluation par tamisage).By "reduced form" is meant that the pieces of organic material or containing organic material are small. They come for example in the form of a slurry. The particle size of at least preferably 50%, preferably 80%, especially 90% of the pieces is advantageously less than 20 mm, preferably less than 15 mm, especially less than 10 mm, more particularly less than 5 mm (evaluation by sieving ).
On opère avantageusement sur une bouillie de la matière organique que l'on souhaite traiter.It is advantageous to operate on a slurry of the organic material that it is desired to treat.
L'état des produits (solide, bouillie, etc.) est indiqué classiquement pour des conditions normales de température et de pression.The condition of the products (solid, slurry, etc.) is classically indicated for normal temperature and pressure conditions.
Le procédé de l'invention peut être mis en oeuvre entre 240 et 4000C, de préférence entre 250 et 3500C, particulièrement entre 280 et 3200C. Le procédé de l'invention est mis oeuvre sous une pression de 100 à 300 bars, de préférence entre 150 et 250 bars, de préférence entre 180 et 230 bars, particulièrement environ 200 bars.The process of the invention can be carried out between 240 and 400 ° C., preferably between 250 and 350 ° C., particularly between 280 and 320 ° C. The process of the invention is carried out under a pressure of 100 to 300 bar, preferably between 150 and 250 bar, preferably between 180 and 230 bar, particularly about 200 bar.
A titre de comburant, on peut citer les composés oxygénés.Oxidizing compounds that may be mentioned include oxygenates.
Dans des conditions préférentielles de mise en oeuvre de l'invention, on utilise de l'oxygène, notamment sous forme d'air éventuellement en mélange avec un ou plusieurs autres gaz.Under preferred conditions of implementation of the invention, oxygen is used, in particular in the form of air optionally mixed with one or more other gases.
Dans encore d'autres conditions préférentielles de mise en oeuvre, on utilise des composés oxygénés provenant de déchets ou sous produits de l'industrie, comme par exemple l'oxyde de diazote. On procède avantageusement en présence d'un excès de comburant.In still other preferred conditions of implementation, oxygenates are used from waste or by-products of the industry, such as, for example, nitrous oxide. Advantageously proceed in the presence of an excess of oxidant.
A cette fin, on peut préalablement déterminer la demande chimique en oxygène (DCO) de la matière organique que l'on souhaite traiter. Rappelons que la DCO exprime la quantité d'oxygène nécessaire pour oxyder la matière organique (biodégradable ou non) à l'aide d'un oxydant, le bichromate de potassium.For this purpose, the chemical oxygen demand (COD) of the organic material which it is desired to treat can be determined beforehand. Remember that COD expresses the amount of oxygen needed to oxidize matter organic (biodegradable or not) using an oxidant, potassium dichromate.
Dans encore d'autres conditions préférentielles de mise en oeuvre de l'invention, on opère en présence d'un catalyseur, notamment à base de (Cu, Pt, Pd, Ru, Rh, Ti, notamment sur différents supports comme les oxydes d'aluminium, de cérium ou de silicium.In still other preferred conditions of implementation of the invention, it operates in the presence of a catalyst, especially based on (Cu, Pt, Pd, Ru, Rh, Ti, especially on different supports such as oxides of aluminum, cerium or silicon.
Le catalyseur sera par exemple un oxyde métallique, comme l'oxyde de sélénium, de rhénium ou d'hafnium, ou ceux cités dans les exemples.The catalyst will for example be a metal oxide, such as selenium oxide, rhenium or hafnium, or those mentioned in the examples.
Le catalyseur peut être par exemple utilisé à raison de 2 g/L environ. II peut notamment être mis en oeuvre à pH d'environ 12.The catalyst may for example be used at a rate of approximately 2 g / l. It can especially be used at a pH of about 12.
Dans encore d'autres conditions préférentielles, on utilisera une zéolite.In still other preferred conditions, a zeolite will be used.
Le temps de la réaction dépend de la quantité de matière organique introduite au départ. Le temps de réaction peut varier de 20 min. à 120 min. pour des concentrations en carbone comprises entre 5 g et 40 g par litre, avantageusement de 20 à 120 min, de préférence de 60 à 100 min, tout particulièrement de 75 à 90 min.The reaction time depends on the amount of organic material introduced initially. The reaction time can vary from 20 minutes. at 120 min. for carbon concentrations of between 5 g and 40 g per liter, preferably 20 to 120 min, preferably 60 to 100 min, most preferably 75 to 90 min.
Le procédé de l'invention étant autotherme, le chauffage initial peut être interrompu dès que la température fixée est atteinte. Dans d'autres conditions préférentielles de mise en œuvre de l'invention, on chauffe un ou plusieurs des effluents d'entrée, par exemple le comburant ou les matières organiques supplémentaires à traiter dans le cas d'une mise en oeuvre en semi-continu, ou continu, grâce à l'énergie produite par la mise en œuvre du procédé. Dans encore d'autres conditions préférentielles de mise en œuvre de l'invention, on évacue l'énergie calorifique produite par la réaction à l'aide d'un fluide notamment aqueux, comme à l'aide d'effluents industriels, et plus particulièrement à l'aide d'effluents de centres d'abattage pour le traitement sur place des matières animales crues. Le système d'agitation peut être un système classique à pales.The method of the invention being autothermal, the initial heating can be interrupted as soon as the set temperature is reached. In other preferred conditions of implementation of the invention, one or more of the inlet effluents are heated, for example the oxidizer or the additional organic materials to be treated in the case of a semi-continuous implementation. , or continuous, thanks to the energy produced by the implementation of the process. In still other preferred conditions of implementation of the invention, the heat energy produced by the reaction is removed using a particularly aqueous fluid, such as using industrial effluents, and more particularly using slaughterhouse effluents for the on-site treatment of raw animal material. The agitation system may be a conventional blade system.
Dans des conditions préférentielles de mise en oeuvre, le comburant, de préférence l'air, sert ou notamment contribue à l'agitation de la matière organique traitée. Pour cela, il est avantageusement injecté sous pression au sein de la matière organique.Under preferred conditions of use, the oxidizer, preferably air, serves or in particular contributes to the agitation of the treated organic material. For this, it is advantageously injected under pressure in the organic material.
Le procédé de l'invention peut être mis en oeuvre de manière discontinue, semi-continue, ou continue. Le réacteur sera adapté à la forme de mise en œuvre du procédé. C'est de manière générale toute enceinte adaptée capable de supporter de hautes température et pression.The process of the invention may be carried out batchwise, semi-continuously, or continuously. The reactor will be adapted to the form of implementation of the process. It is generally any suitable enclosure capable of withstanding high temperature and pressure.
En fin de mise en oeuvre de procédé, on obtient une suspension aqueuse contenant essentiellement des minéraux.At the end of the process, an aqueous suspension containing essentially minerals is obtained.
Celle-ci, selon sa composition, peut être retraitée ou rejetée directement dans la nature ou transférée dans une station d'épuration.Depending on its composition, it can be reprocessed or rejected directly in the wild or transferred to a treatment plant.
La phase minérale est un déchet ultimeThe mineral phase is an ultimate waste
Le procédé de l'invention est doté de remarquables qualités. Il permet de détruire efficacement les matières organiques traitées, en particulier les protéines, et tout particulièrement le prion. II permet de transformer cette matière organique essentiellement en des matières minérales, de l'eau et du gaz carbonique.The process of the invention is endowed with remarkable qualities. It effectively destroys treated organic materials, especially proteins, and especially the prion. It makes it possible to transform this organic matter essentially into mineral matter, water and carbon dioxide.
Le procédé en outre offre l'avantage d'être autotherme. Lorsque la combustion est entamée, il n'est en effet plus nécessaire d'apporter d'énergie supplémentaire. On obtient même une énergie excédentaire qui permet par exemple de chauffer des effluents d'entrée par exemple le comburant ou les matières organiques supplémentaires à traiter. De préférence on amène les effluents à température de réaction.The method further has the advantage of being autothermal. When the combustion is started, it is indeed no longer necessary to provide additional energy. Even an excess energy is obtained which allows, for example, to heat inlet effluents, for example the oxidant or the additional organic materials to be treated. Preferably, the effluents are brought to the reaction temperature.
La quantité d'eau nécessaire pour évacuer l'énergie calorifique produite par la réaction peut être apportée par des effluents industriels, et plus particulièrement des effluents de centres d'abattage pour le traitement sur place des matières animales crues. On peut utiliser cette énergie produite également pour réaliser ou compléter un chauffage urbain.The quantity of water needed to evacuate the heat energy produced by the reaction can be provided by industrial effluents, and more particularly effluents from slaughterhouses for the on-site treatment of raw animal materials. This energy produced can also be used to produce or complete district heating.
Le procédé de l'invention permet non seulement de travailler sur des farines animales, comme c'est le cas des incinérateurs, mais également sur des produits bruts.The method of the invention allows not only to work on animal meal, as is the case of incinerators, but also on raw products.
L'invention peut être mis en oeuvre simplement dans un réacteur capable de supporter les pressions ci-dessus, par exemple en utilisant un réacteur muni d'un système de chauffage, d'un système d'introduction du comburant, d'un système d'introduction de matières organiques, un système d'agitation, un système d'évacuation de gaz, une sortie basse pour la matière minérale, et de préférence des sondes eaux et bains.The invention can be implemented simply in a reactor capable of withstanding the above pressures, for example by using a reactor equipped with a heating system, a system for introducing the oxidizer, an organic material introduction system, a stirring system, a gas evacuation system, a low output for the mineral material, and preferably water and bath probes.
Les propriétés ci-dessus sont illustrées ci-après dans la partie expérimentale. Elles justifient l'utilisation des procédés ci-dessus décrits, dans la fabrication d'énergie.The above properties are illustrated hereinafter in the experimental section. They justify the use of the processes described above in the manufacture of energy.
C'est pourquoi la présente demande a aussi pour objet un procédé de production d'énergie dans lequel on installe dans un réacteur une matière organique sous forme broyée, on procède à sa combustion sans flamme à une température de 240 à 400 0C, sous une pression de 100 à 300 bars, en présence d'un comburant oxygéné, pendant au moins 20 minutes, tout en procédant à l'agitation du milieu et on récupère l'énergie produite par la combustion.This is why the present application also relates to a method for producing energy which is installed in a reactor an organic material in comminuted form, is carried at its flameless combustion at a temperature of 240-400 0 C under a pressure of 100 to 300 bar, in the presence of an oxygenated oxidant, for at least 20 minutes, while stirring the medium and recovering the energy produced by the combustion.
La récupération de l'énergie produite par la combustion peut notamment être obtenue par utilisation d'un ou plusieurs échangeurs de chaleur, notamment des échangeurs à plaques et ailettes brasés.The recovery of the energy produced by the combustion can in particular be obtained by using one or more heat exchangers, in particular brazed plate and fin exchangers.
L'énergie ainsi produite et récupérée par exemple sous forme de fluide chaud, par exemple eau chaude, peut être utilisée classiquement.The energy thus produced and recovered for example in the form of hot fluid, for example hot water, can be used conventionally.
Les conditions préférentielles de mise en œuvre des procédés de destruction d'une matière organique ci-dessus décrites s'appliquent également aux autres objets de l'invention visés ci-dessus, notamment aux procédés de production d'énergie.The preferred conditions of implementation of the organic material destruction processes described above also apply to the other objects of the invention referred to above, especially to energy production processes.
La figure 1 décrit un type d'appareillage et montage utilisable pour la mise en œuvre de l'invention, utilisé pour la réalisation des exemples qui suivent et qui illustrent la présente demande.Figure 1 describes a type of equipment and assembly used for the implementation of the invention, used for the realization of the following examples which illustrate the present application.
Exemple 1 : Traitement d'un lot de matières animales cruesExample 1: Treatment of a batch of raw animal materials
On introduit manuellement un lot de (système batch) 20 grammes de substrat dans un réacteur de traitement oxydatif à chaud, et fermé hermétiquement.A batch of (batch system) 20 grams of substrate is manually introduced into a hot oxidative treatment reactor, and sealed.
Le réacteur de traitement oxydatif à chaud utilisé est un autoclave de volume utile de 450 mL formé d'un creuset en acier inoxydable et d'un couvercle en Hastelloy C276, fonctionnant en régime sous-critique. L'appareillage est conçu pour supporter une température maximale de 4000C et une pression maximale de 30 MPa. Le chauffage du réacteur se fait grâce à un four électrique d'une puissance de 4500W, placé autour de l'autoclave. Le système est également muni d'un agitateur mécanique et d'un manomètre. La sécurité de l'ensemble est assurée par une électrovanne et un disque de rupture. Le réacteur possède également deux lignes d'alimentation / prélèvement liquide et gazeux.The hot oxidative treatment reactor used is a 450-mL volume autoclave made of a stainless steel crucible and a Hastelloy C276 lid, operating under subcritical conditions. The equipment is designed to withstand a maximum temperature of 400 0 C and a maximum pressure of 30 MPa. The reactor is heated using an electric oven with a power of 4500W, placed around the autoclave. The system is also equipped with a mechanical stirrer and a manometer. The safety of the assembly is ensured by a solenoid valve and a rupture disc. The reactor also has two feed lines / liquid and gaseous withdrawal.
Le substrat traité est constitué de 20 g de matières animales crues (8 g en poids sec), non dégraissées, se présentant sous forme d'une bouillie pâteuse brune avec une odeur caractéristique et une granulométrie inférieure à 5 mm.The treated substrate consists of 20 g of raw animal material (8 g dry weight), not defatted, in the form of a brown pasty slurry with a characteristic odor and a particle size less than 5 mm.
La composition des échantillons donnée ci-dessous a été déterminée par rapport aux matières sèches.The sample composition given below was determined in relation to dry matter.
Composition moyenne des matières animales crues :Average composition of raw animal materials:
MS = Matières SèchesMS = dry matter
COT = Carbone Organique TotalTOC = Total Organic Carbon
Une agitation mécanique est maintenue en continu à 500 tr/min. Le four est ensuite mis en marche et le thermostat réglé pour atteindre une température à l'intérieur du réacteur de 2800C.Mechanical agitation is continuously maintained at 500 rpm. The oven is then turned on and the thermostat set to reach a temperature inside the reactor of 280 ° C.
À la température fixée, de l'air est injecté et la pression est fixée à 200 bars. Le thermostat s'arrête. Un flux continu d'air est assuré à l'aide d'une micro fuite en sortie du réacteur. On laisse réagir pendant 60 min. On évacue l'énergie calorifique produite par la réaction à l'aide d'eau.At the set temperature, air is injected and the pressure is set at 200 bar. The thermostat stops. A continuous flow of air is provided by means of a micro leak at the outlet of the reactor. Allowed to react for 60 min. The heat energy produced by the reaction is evacuated with water.
La réaction d'oxydation hydrothermale optimale produit un effluent liquide. Cet effluent contient 1 ,6 g/L de COT (dont 0,8 g d'acide acétique) et 1 ,6 g/L d'ammoniaque. La destruction de la matière organique représente un abattement supérieur à 99 %. En fin de réaction, la phase solide contient environ 400 mg de matière minérale et inerte, ce qui représente une réduction de 95% des matières sèches. Cette phase solide contient une quantité négligeable de matière organique. Les effluents gazeux produits sont séparés et collectés à l'aide d'un condenseur puis piégés dans une solution acide (HCI) puis basique (NaOH).The optimal hydrothermal oxidation reaction produces a liquid effluent. This effluent contains 1.6 g / L of TOC (including 0.8 g of acetic acid) and 1.6 g / L of ammonia. The destruction of organic matter represents an abatement of more than 99%. At the end of the reaction, the solid phase contains about 400 mg of inorganic and inert material, which represents a reduction of 95% of the solids. This solid phase contains a negligible amount of organic matter. The gaseous effluents produced are separated and collected using a condenser and then trapped in an acid solution (HCl) and then basic (NaOH).
Exemple 2: Traitement de matières animales crues On opère comme indiqué ci-dessus à l'exemple 1 , mais en ajoutant 2 g/L à pH 12 de catalyseur de platine sur alumine. La valeur COT de l'effluent de sortie n'est plus que de 60 mg/L.Example 2 Treatment of raw animal materials The procedure is as indicated above in Example 1, but adding 2 g / L to pH 12 of platinum catalyst on alumina. The TOC value of the outlet effluent is only 60 mg / L.
Exemple 3: Traitement de matières animales cruesExample 3 Treatment of raw animal materials
On opère comme indiqué ci-dessus à l'exemple 1 , mais en ajoutantOne operates as indicated above in example 1, but adding
2 g/L à pH 12 de catalyseur de palladium sur alumine. La valeur de la concentration d'ammoniaque n'est plus que de 32 mg/L.2 g / L at pH 12 of palladium catalyst on alumina. The value of the ammonia concentration is only 32 mg / L.
Pour les trois exemples, il n'a pas été possible de détecter la présence de protéines dans le milieu final par la technique de détermination utilisée.For the three examples, it was not possible to detect the presence of proteins in the final medium by the determination technique used.
Le procédé de l'invention est donc efficace pour éliminer notamment le prion, tant dans les matières organiques que dans des farines animales. The method of the invention is therefore effective to eliminate in particular the prion, both in organic materials than in animal meal.

Claims

REVENDICATIONS
1. Un procédé de destruction d'une matière organique, dans lequel on installe dans un réacteur ladite matière organique sous forme broyée, et on procède à sa combustion sans flamme à une température de 240 à 400 0C, sous une pression de 100 à 300 bars, en présence d'un comburant oxygéné, pendant au moins 20 minutes, tout en procédant à l'agitation du milieu.1. A method of destroying an organic material, wherein is installed in a reactor said organic material in ground form, and proceeds to its combustion without flame at a temperature of 240 to 400 0 C under a pressure of 100 to 300 bars, in the presence of an oxygenated oxidant, for at least 20 minutes, while stirring the medium.
2. Un procédé selon la revendication 1, caractérisé en ce que la matière organique est d'origine animale. 2. A process according to claim 1, characterized in that the organic material is of animal origin.
3. Un procédé selon la revendication 1 ou 2, caractérisé en ce que la matière organique est une matière organique provenant de celles en suspension ou solution dans les eaux usées (eaux résiduaires).3. A method according to claim 1 or 2, characterized in that the organic material is an organic material from those suspended or solution in wastewater (wastewater).
4. Un procédé selon l'une des revendications 1 à 3, caractérisé en ce que la granulométrie d'au moins 50%, des morceaux de la matière organique est inférieure à 20 mm.4. A method according to one of claims 1 to 3, characterized in that the particle size of at least 50%, pieces of the organic material is less than 20 mm.
5. Un procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'il est mis en oeuvre entre 250 et 3500C.5. A method according to one of claims 1 to 4, characterized in that it is carried out between 250 and 350 0 C.
6. Un procédé selon l'une des revendications 1 à 5, caractérisé en ce qu'il est mis en oeuvre entre 150 et 250 bars. 6. A process according to one of claims 1 to 5, characterized in that it is carried out between 150 and 250 bar.
7. Un procédé selon l'une des revendications 1 à 6, caractérisé en ce que le comburant oxygéné comprend de l'air.7. A process according to one of claims 1 to 6, characterized in that the oxygenated oxidant comprises air.
8. Un procédé selon l'une des revendications 1 à 7, caractérisé en ce qu'il est mis en oeuvre en présence d'un excès de comburant.8. A process according to one of claims 1 to 7, characterized in that it is carried out in the presence of an excess of oxidant.
9. Un procédé selon l'une des revendications 1 à 8, caractérisé en ce qu'il est mis en oeuvre en présence d'un catalyseur, par exemple à base de Cu,9. A process according to one of claims 1 to 8, characterized in that it is carried out in the presence of a catalyst, for example based on Cu,
Pt, Pd, Ru, Rh, Ti.Pt, Pd, Ru, Rh, Ti.
10. Un procédé selon l'une des revendications 1 à 9, caractérisé en ce que l'on chauffe un ou plusieurs des effluents d'entrée, par exemple le comburant ou les matières organiques supplémentaires à traiter dans le cas d'une mise en oeuvre en semi-continu, ou continu, grâce à l'énergie produite par la mise en œuvre du procédé.10. A process according to one of claims 1 to 9, characterized in that one or more of the input effluents is heated, for example the oxidant or the additional organic materials to be treated in the case of an implementation. works in semi-continuous, or continuous, thanks to the energy produced by the implementation of the process.
11. Un procédé selon l'une des revendications 1 à 10, caractérisé en ce que le comburant est injecté sous pression au sein de la matière organique pour l'agiter. 11. A method according to one of claims 1 to 10, characterized in that the oxidant is injected under pressure in the organic material for stirring.
12. Un procédé de production d'énergie dans lequel on installe dans un réacteur une matière organique sous forme broyée, on procède à sa combustion sans flamme comme défini à l'une des revendications 1 à 11 et on récupère l'énergie produite par la combustion. 12. A method of producing energy in which is installed in a reactor an organic material in milled form, it is proceeded to its combustion without flame as defined in one of claims 1 to 11 and recovering the energy produced by the combustion.
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