EP3009495B1 - Verfahren und vorrichtung zur feuervergasung eines kohlenstoffhaltigen materials, das ein ascheschmelzbad umfasst - Google Patents

Verfahren und vorrichtung zur feuervergasung eines kohlenstoffhaltigen materials, das ein ascheschmelzbad umfasst Download PDF

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EP3009495B1
EP3009495B1 EP15190009.9A EP15190009A EP3009495B1 EP 3009495 B1 EP3009495 B1 EP 3009495B1 EP 15190009 A EP15190009 A EP 15190009A EP 3009495 B1 EP3009495 B1 EP 3009495B1
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Prior art keywords
pyro
molten
bath
carbonaceous material
carbon material
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English (en)
French (fr)
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EP3009495A1 (de
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Serge Ravel
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/06—Continuous processes
    • C10J3/08—Continuous processes with ash-removal in liquid state
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0969—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/1223—Heating the gasifier by burners

Definitions

  • the present invention relates to the general field of renewable energies and, more particularly, the thermochemical treatment of the carbonaceous material to produce synthesis gases.
  • the present invention relates to a process for the preparation of a synthesis gas via the pyro-gasification of a carbonaceous material such as in particular an ash rich carbon material, said method using a melt ash bath.
  • the present invention also relates to a device for implementing such a method.
  • thermochemical pathway of synthesis gas production from this resource that is (the) biomass and / or waste has been studied for a long time.
  • This pathway includes (i) pyrolysis which corresponds to the process of conversion of the resource in the absence of reagents, (ii) gasification which takes place in the presence of reactive gases such as air, oxygen or steam. water and (iii) processes combining pyrolysis and gasification.
  • Gasification makes it possible to obtain a recoverable gas other than to produce heat.
  • this synthesis gas possibly cleaned for eliminating fine particles, alkali metals, tars and others, can replace fossil fuels, as, for example, to supply thermal engines, to synthesize liquid fuels or chemical compounds and / or to supply engines and / or gas turbines for the production of electricity.
  • reactors include fixed-bed reactors, which can be co- or countercurrent, fluidized bed reactors and flow-driven reactors.
  • the problem of pyro-gasification is based on the need to heat very quickly, ie in a few seconds, the resource (biomass and / or waste) at high temperature, which corresponds to a temperature above 1000 ° C, to obtain a yield in maximum gas and a gas with maximum energy power.
  • RFE Driven flow reactors
  • the fluidized bed reactors are already on an industrial scale (2 to 100 MWth). They allow rapid pyrolysis but at a maximum temperature of the order of 850 ° C. Under these conditions, they produce a gas of lower quality than that produced by the RFE with a lower heating value (PCI) and a higher tar content. Fluidized bed reactors are sensitive to the ash content of the resource, which causes bed agglomeration problems. Also, always in order to control the ash agglomeration phenomena making the fluidization of the resource to be treated, this type of reactor operates at a moderate temperature, namely at temperatures below the ash melting temperature. As a result, these reactors are limited in temperature and resource type (wood only).
  • US 3,841,239 discloses a process for converting a carbonaceous material to syngas by pyrolysis plus gasification comprising a step of contacting said carbonaceous material with a melt of ash of pyro-gasified carbonaceous material.
  • the inventors have therefore set themselves the goal of proposing a method and a pyro-gasification device making it possible to solve the problems of reactors with fluidized beds and driven flux, while avoiding the use of a plasma arc or torch.
  • the inventors have also set themselves the goal of proposing a method and a pyro-gasification device that can use any resource to be processed, and particularly the rich ash resources.
  • the invention provides a method and a device for overcoming all or part of the disadvantages and difficulties encountered in the methods and devices of the prior art.
  • the present invention provides a method according to claim 1 and a device according to claim 9 for producing a synthesis gas from a carbon resource and by using a bath of molten ash, said ashes resulting from a process of pyro-gasification of a carbon resource.
  • the carbon resource to be treated does not require prior drying and / or grinding steps since centimetric particles can be treated.
  • the moisture of the carbon resource produces water vapor that participates in the gasification process.
  • centimetric particles makes it possible to guarantee a residence time in the molten ash bath, ie until their total gasification.
  • the carbon resource that can be used in the context of the process and the device according to the present invention can be a resource rich in ash since it is these latter which feed the molten bath.
  • the method and the device according to the present invention allow a pyro-gasification of the carbonaceous resource at a high temperature i.e. higher than 1000.degree.
  • Thermochemical treatment at such a temperature results in a rate of conversion of the carbonaceous resource into fast gas, which improves the gas yield.
  • this high temperature can be obtained by the combustion of a part of the pyro-gasification gas obtained by carrying out the process according to the invention. As a result, this process has, once started, autothermal operation requiring no external source of energy.
  • the ash contained in the carbonaceous material thus treated is ultimately melted in the bed and incorporated into the bath of molten ash.
  • the present invention provides a process for producing, by pyrolysis and gasification, a synthesis gas from a carbonaceous material, comprising at least one step of contacting said carbonaceous material with a carbon ash bath. pyro-gasified melt in the presence of a gasifying agent, whereby synthesis gas is produced.
  • thermochemical process for converting a carbonaceous material into a synthesis gas.
  • This thermochemical process involves pyrolysis followed by gasification and is, therefore, a pyro-gasification process.
  • the gasifying agent or gaseous agent required for the gasification is in particular water vapor and / or carbon dioxide.
  • a gasifying agent is present in an amount sufficient to allow gasification of the carbonaceous material. Such an amount can be readily determined by those skilled in the art by routine work.
  • carbonaceous material is meant a material of which at least one of the constituents is an organic, synthetic or natural compound. Any carbonaceous material known to those skilled in the art can be used in the context of the present invention.
  • the carbonaceous material used in the context of the present invention is an organic material of animal or vegetable origin (also known under the name of "biomass") or an organic material resulting from human activities.
  • the carbonaceous material used in the context of the present invention is chosen from the group consisting of agricultural products such as dedicated productions called "energy” such as alfalfa and silage corn; crop residues such as cereal straw and corn stover; forest production; forest production residues such as residues from wood processing; agricultural residues from livestock farming such as animal meal, manure and slurry; and organic waste.
  • agricultural products such as dedicated productions called "energy” such as alfalfa and silage corn
  • crop residues such as cereal straw and corn stover
  • forest production forest production residues such as residues from wood processing
  • agricultural residues from livestock farming such as animal meal, manure and slurry
  • organic waste organic waste
  • Organic waste includes household organic waste, industrial organic waste, hospital waste, sludges from sewage treatment, sludges from the treatment of industrial liquid effluents, sludge from silo bottoms and mixtures thereof.
  • the industrial organic waste comprises waste from the agri-food or catering industries; packaging such as pallets, crates and plastic containers; production waste such as sawdust, falling and cutting; used products such as paper, out of service equipment and tires; and materials such as cardboard, textiles and plastics.
  • dried sludge means a sludge in the form of a solid sludge or a slurry and whose dry matter mass% relative to the total sludge mass is greater than 30%, especially greater than 40% and, in particular, greater than 50%.
  • the carbonaceous material used in the context of the present invention is in solid form.
  • the present invention makes it possible to use a carbonaceous material which has not undergone a high grinding step i.e. a grinding step to obtain residues having characteristic dimensions, less than 1 mm or even less than or equal to 500 ⁇ m.
  • a high grinding step i.e. a grinding step to obtain residues having characteristic dimensions, less than 1 mm or even less than or equal to 500 ⁇ m.
  • the carbonaceous material used in the context of the present invention has residues of which at least one of the three dimensions characterizing them is greater than 1 mm.
  • the carbonaceous material used in the context of the present invention has a mass ratio of fines with respect to the total mass of carbonaceous material of less than 1%.
  • fines is meant particles whose characteristic dimensions are less than 1 mm. Under these conditions, possible clogging of the recovery pipes of the synthesis gas by the soot obtained by gasification in the atmosphere of the high temperature oven of fine particles forming a cloud of dust.
  • the carbonaceous material used in the present invention may have any ash content.
  • the ash content of this carbonaceous material is between 0.5 and 50% by weight.
  • the ash content of a sample expressed in mass% corresponds to the ratio of the mass of the residue obtained after calcination at a defined temperature and for a given time, to the initial mass of the sample. The ash content is measured by calcination at 550 ° C. according to DIN EN 14775.
  • the carbonaceous material has a high ash content i.e. an ash content of between 10% and 50% by weight.
  • the essential characteristic of the process according to the present invention resides in the use of an ash bath of molten pyro-gasified carbonaceous material. Indeed, it is the ashes of the carbonaceous material i.e. of the treated carbon resource that are used molten to constitute the bath.
  • the ashes of the treated resource are present only in the form of contaminants, for example in baths of nitrates or potassium carbonates and / or molten sodium [4,5 ] , baths of molten glass [6] or baths of molten steel or slag [7,8] .
  • the ashes obtained are generally collected and discharged [2,3] .
  • the ashes of the treated carbonaceous material corresponding to the non-combustible residues of the treated carbonaceous material are the essential constituent of the melt.
  • the elements other than the ashes of molten carbonaceous material that can contain the bath are present in the form of traces ie their quantity by mass relative to the total mass of the melt is less than 10%, especially less than 5% and, in particular, less than 1%.
  • compositions of the ashes can be variable especially according to the resources and, for the same resource, depending on the source or the season, elements can advantageously be added to the ashes to maintain the melting temperature thereof in a range typically located between 1000 and 1600 ° C. This temperature range also limits the degradation of the walls of the gasification furnace.
  • fluxes which are known products and used, especially in foundry and glass, to lower the melting temperature of one or more element (s) or chemical compound (s).
  • a flux such as cullet is used to stabilize the melting temperatures of the ash bath and prevent its solidification.
  • the amount of ash of pyro-gasified carbonaceous material is greater than or equal to 90% relative to the total mass of the melt, in particular greater than or equal to 95%, in particular greater than or equal to 99%.
  • the nature and the composition of the ashes of pyro-carbonified carbonaceous material are variable. They depend in particular on the nature of the carbonaceous material used during the thermochemical treatment process and the oxidizing or reducing conditions used during this process.
  • the ashes of pyro-gasified carbonaceous material comprise one or more element (s) chosen from the group consisting of silicon dioxide (SiO 2 ), calcium oxide (CaO), potassium oxide. (K 2 O), aluminum oxide (Al 2 O 3 ), iron (III) oxide (FeO 3 ), magnesium oxide (MgO) and phosphorus pentoxide (P 2 O 5) ).
  • element (s) chosen from the group consisting of silicon dioxide (SiO 2 ), calcium oxide (CaO), potassium oxide. (K 2 O), aluminum oxide (Al 2 O 3 ), iron (III) oxide (FeO 3 ), magnesium oxide (MgO) and phosphorus pentoxide (P 2 O 5) ).
  • ashes from crop residues such as cereal straw are rich in calcium oxide (CaO) and potassium oxide (K 2 O)
  • those from organic waste as used products and in particular tires are rich in silicon dioxide (SiO 2 ).
  • the ashes of pyro-carbonified carbonaceous material contain all of
  • the ashes of pyro-gasified carbonaceous material are in molten form.
  • they are brought and maintained at a higher temperature or equal to 1000 ° C.
  • This temperature is in particular between 1000 ° C. and 1600 ° C. and, in particular, between 1000 ° C. and 1400 ° C.
  • Synthesis gas means the gas obtained by pyro-gasification of the carbonaceous material used. Such gas is also known as syngaz.
  • the nature and composition of the synthesis gas obtained by carrying out the process according to the present invention depend in particular on the nature of the carbonaceous material used during the thermochemical treatment process and on the oxidizing or reducing conditions used during this process.
  • the synthesis gas produced by the process according to the present invention comprises hydrogen (H 2 ), carbon monoxide (CO) and carbon dioxide (CO 2 ) and optionally one or more other element (s). (s) gaseous, this or these last (s) being advantageously present in the form of traces.
  • the respective proportion of the various elements present in the synthesis gas ie H 2 , CO and CO 2 depends on the nature of the carbonaceous material treated and the thermal conditions in the furnace.
  • Race element means a gaseous element present in a volume percentage relative to the total volume of the synthesis gas of less than 6%, in particular less than 4%, in particular less than 2%, and more particularly less than 1%.
  • methane (CH 4 ) acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), ethane (C 2 H 6 ), inorganic pollutants such as hydrogen sulphide (H 2 S), ammonia (NH 3 ), chloridic acid (HCl), hydrogen cyanide (HCN) and carbon oxysulfide (COS), as well as organic compounds such as benzene (C 6 H 6
  • thermochemical treatment of a particular carbonaceous material it is possible for one or more of these gaseous elements to be present in a percentage by volume relative to the total volume of synthesis gas greater than 6. %, and does not constitute (s) more than one element (s) in the state of traces.
  • the gaseous compounds previously mentioned and produced by the pyro-gasification process are supplemented by residual compounds. Indeed, when the partial combustion of the synthesis gas in the furnace, necessary to provide the energy to maintain the oven temperature and necessary to allow the endothemic gasification reactions is performed with a reactive gas comprising oxygen such as air, oxygen-enriched air or oxygen, the residual nitrogen (N 2 ) of the combustion air and / or the residual oxygen (O 2 ) of the reactive gas and / or the carbon dioxide (CO 2 ) produced by the partial combustion of the synthesis gas and / or the residual carbon dioxide (CO 2 ) if the gasifier is CO 2 and / or the water vapor produced by the combustion and / or by pyrolysis and / or residual steam if the gasifying agent is water vapor are added to the synthesis gas produced by pyro-gasification.
  • a reactive gas comprising oxygen such as air, oxygen-enriched air or oxygen, the residual nitrogen (N 2 ) of the combustion air and / or the residual oxygen (O 2 ) of the
  • step (a) of the process according to the present invention corresponds to the step of starting said process and consists in preparing the heat-transfer reaction medium used during the pyro-gasification and more particularly during the pyrolysis of the carbonaceous material introduced during step (b).
  • step (a) of the method according to the present invention can be envisaged for the implementation of step (a) of the method according to the present invention.
  • step (a) of the process according to the present invention may consist in introducing, into the reaction chamber, a carbonaceous material such as previously defined and subjecting the latter to pyro-gasification, in the presence a fuel and optionally an oxidant, at a temperature greater than or equal to 1000 ° C, in particular between 1000 ° C and 1600 ° C and, in particular, between 1000 ° C and 1400 ° C so as to obtain a molten ash bath.
  • the molten ash thus obtained is ash from the pyro-gasification of the carbonaceous material initially introduced into the reaction chamber.
  • the usable fuel is in particular selected from methane, butane, propane, fuel oil, oil, dihydrogen and a mixture thereof.
  • the oxidant is advantageously a reactive gas comprising oxygen such as air, oxygen-enriched air or oxygen.
  • step (a) of the process according to the present invention may consist in introducing, in the reaction chamber, ash from a previous pyro-gasification process, cold or cooled and subjecting the ashes to a temperature greater than or equal to 1000 ° C, especially between 1000 ° C and 1600 ° C and, in particular, between 1000 ° C and 1400 ° C so as to obtain a melt ash bath.
  • the cold or cooled ashes used in this variant have a temperature of less than 1000 ° C., in particular less than 600 ° C., in particular less than 200 ° C.
  • the ash used is cold ash whose temperature is between 20 ° C and 100 ° C.
  • the melt ash bath thus prepared must have a thickness sufficient to allow the carbonaceous material to float on its surface.
  • Those skilled in the art will be able to determine the most appropriate thickness as a function of the carbonaceous material to be treated and the size of the residues forming this carbonaceous material.
  • the bath of molten ash has a thickness greater than or equal to 9 mm and in particular greater than or equal to 1 cm.
  • the thickness of the melt ash bath is controlled by the temperature. The latter must be adjusted according to the viscosity of the ash which determines the thickness of the layer and the speed of its flow.
  • Step (b) of the process according to the present invention consists in putting the carbonaceous material as defined above in contact with the melt ash bath as defined above.
  • This contacting consists in introducing, by gravity, the carbonaceous material into the molten ash bath.
  • the carbonaceous material to be treated can be brought into contact with the melt ash bath sequentially or continuously.
  • the carbonaceous material to be treated is introduced into the melt bath continuously.
  • the person skilled in the art will be able to determine, without inventive effort, the introduction rate and therefore the mass flow rate best adapted according to the nature of the carbonaceous material.
  • the flow rate of the carbonaceous material is between 300 kg / h and 500 kg / h.
  • the carbonaceous material floats on the surface of the melt ash bath or is incorporated therein, resulting, as previously explained, pyro-gasification of the carbonaceous material.
  • the residence time of the carbonaceous material in the melt ash bath depends on the size of the elements constituting this carbonaceous material. As an illustrative and non-limiting example, when the largest of the three dimensions characterizing these elements is of the order of 3 cm, this residence time is between 3 and 10 min.
  • the pyro-gasification process during step (b) of the process according to the present invention is carried out under atmospheric pressure, the atmosphere in the reaction chamber being that generated by the partial combustion of the gases and by the pyro-gasification of the carbonaceous material.
  • a gasifying agent may also be added in addition to the water vapor from the carbonaceous material and, to gasify, totally or almost completely, the carbonaceous material to be treated.
  • a gasifying agent is advantageously water vapor and / or carbon dioxide.
  • An oxidizer must also be added to allow partial combustion of the synthesis gas necessary to keep the furnace in the correct temperature range and provide the energy needed for gasification.
  • This oxidant is advantageously a reactive gas comprising oxygen such as air, air enriched with oxygen or oxygen.
  • Step (c) of the process according to the present invention consists in recovering or harvesting the synthesis gas produced during the pyro-gasification process.
  • All or part of the recovered synthesis gas can be used as a fuel, in particular for heating the reaction chamber and maintaining, in the latter, the ash of molten pyro-gasified carbonaceous material at a temperature as defined above, ie a temperature greater than or equal to at 1000 ° C, typically between 1000 ° C and 1600 ° C and, in particular, between 1000 ° C and 1400 ° C.
  • a temperature as defined above, typically between 1000 ° C and 1600 ° C and, in particular, between 1000 ° C and 1400 ° C.
  • All or part of the recovered synthesis gas can also be used to yield to a heat transfer fluid the thermal energy that it comprises, to supply heat engines, to synthesize liquid fuels or chemical compounds and / or to supply engines and / or gas turbines for the production of electricity.
  • the process according to the present invention further comprises a step of discharging part of the melt ash continuously or sequentially.
  • the evacuation of the liquid ash is carried out continuously at the outlet of the furnace and thus a current is established causing the carbonaceous material which floats on the ash bed towards the exit of the furnace.
  • the furnace is dimensioned so that this current ensures a residence time sufficient for complete gasification of the carbonaceous material particles.
  • the ashes thus recovered can be cooled or thermally quenched to turn them into an inert vitrified material that can be used as a road sub-layer material (for example).
  • the present invention also relates to a device that can be used in the context of the process for producing a synthesis gas from a carbonaceous material.
  • Such a device comprises (i) a reaction chamber comprising an ash bath of a molten pyro-gasified carbonaceous material, (ii) means opening into said reaction chamber adapted to bring, in the latter, the carbonaceous material to treat, (iii) means adapted to recover the synthesis gas produced and (iv) means adapted to maintain said ash bath in molten form.
  • a reaction chamber comprising an ash bath of a molten pyro-gasified carbonaceous material
  • means opening into said reaction chamber adapted to bring, in the latter, the carbonaceous material to treat
  • means adapted to recover the synthesis gas produced means adapted to maintain said ash bath in molten form.
  • the reaction chamber 1 is the part of the device in which the pyro-gasification process takes place. It comprises, in its lower part, the molten ash bath 2.
  • This reaction chamber may be the internal cavity of any furnace or gasifier or gasifier 3 usually used in the field of pyro-gasification.
  • the reaction chamber corresponds to the internal cavity of a horizontal oven of elongated, cylindrical or parallelepiped shape.
  • this furnace has a length of between 1 m and 6 m and in particular between 1.5 m and 5 m and, in particular, of the order of 3 m (ie 3 m ⁇ 1 m) and a width of between 30 cm and 3 m and in particular between 40 cm and 2 m and, in particular, of the order of 1 m (ie 1 m ⁇ 50 cm).
  • the walls of the reaction chamber are made of a refractory material especially chosen from refractory metals such as, for example, chromium, hafnium, iridium, molybdenum, niobium, rhenium, ruthenium, tantalum, tungsten, vanadium and zirconium; refractory steels; superalloys such as, for example, alloys based on nickel or cobalt; graphite; thermomechanical ceramics such as carbides such as, for example, silicon carbide (SiC), titanium carbide (TiC), boron carbide (B 4 C), zirconium carbide (ZrC) or tungsten carbide (WC), nitrides such as, for example, aluminum nitride (AIN), boron nitride (BN), silicon nitride (Si 3 N 4 ) or titanium nitride (TiN), borides such as, for example, aluminum nitride (AIN),
  • the device according to the present invention comprises means 4 opening into said reaction chamber for bringing into the latter, the carbonaceous material to be treated.
  • These means include in particular 1 ers means adapted to contain the carbonaceous material and 2 nds means adapted to convey said carbonaceous material of these 1 ers means to the molten ash bath. These are the average 2 nds that open into the reaction chamber.
  • the 1 st means are advantageously selected from a reservoir, a tank, a silo, a bin, a hopper and one of their association.
  • association is meant in particular a tank, a tank, a silo or a bucket whose lower part is provided with a hopper.
  • the lower part of these 1 ers means has an opening or discharge opening, possibly obstructible (by for example, by means of a rotary valve) and / or optionally provided with a sieve, said orifice or said discharge opening being adapted for the flow of the carbonaceous material.
  • the 1 st means adapted to contain the carbonaceous material are not directly connected to the reaction chamber, it is not necessary that they be in a material capable of withstanding high temperatures material such as those of the reaction chamber function.
  • any material usually used for tanks, tanks, silos, buckets or hoppers is used in the context of the present invention.
  • these 1 ers means and, more particularly, the opening or discharge opening they present are held above said 2 nds means or connected to said 2 nds means for receiving the carbonaceous material.
  • the latter may be in the form of a pipe or a withdrawal pipe whose distal end is connected to the orifice or the opening discharge means of the 1st and the proximal end opens at the two knots means and advantageously at the upper part of these two means nds, the proximal end can optionally be connected to said means 2 knots.
  • the average 2 nds are chosen among a treadmill, a vibrating belt or a worm conveyor. Since these 2 nds means open into the reaction chamber, it may be necessary for the latter or at least part of these means opening into the reaction chamber to be of a material adapted to withstand the temperatures prevailing in the latter in operation or be coated or covered with such material. Such materials belong to the refractory materials as previously defined and are, in particular, selected from nickel-based refractory steels. These 2 nds means open into the reaction chamber at an opening in the wall of the reaction chamber and in particular the upstream portion of the reaction chamber and therefore the upstream portion of the melt ash bath.
  • the device according to the present invention also comprises means 5 adapted to recover the synthesis gas produced following the pyro-gasification process.
  • These means comprise at least one exhaust duct through which the synthesis gas escapes.
  • the proximal end of this or these evacuation conduit (s) opens into the reaction chamber at the level of the upper wall and / or the lateral walls, and in particular at the level of the downstream part of the reaction chamber and therefore the downstream part of the molten ash bath.
  • This or these ducts (s) can be optionally combined with (s) an extraction device or suction to facilitate the recovery of the synthesis gas.
  • the distal end of the exhaust duct (s) is connected to the means and devices used during the subsequent use of the synthesis gas produced by the process according to the present invention.
  • means for using the synthesis gas as a fuel such as a motor, a burner or an injector, means for exchanging the heat of the synthesis gas as a fuel. boiler, means for cooling the synthesis gas such as a tuyere inducing the freezing of the synthesis gas and means for purifying and / or cleaning the synthesis gas which may comprise a tempering zone and / or means for capturing condensable materials.
  • the device according to the present invention further comprises means 6 for maintaining the ash bath of pyro-carbonified carbonaceous material in molten form.
  • These means are intended to maintain the temperature of the reaction chamber and that of the ash bath at a temperature above 1000 ° C, especially between 1000 ° C and 1600 ° C and, in particular, between 1000 ° C and 1400 ° C .
  • These means comprise at least one burner and in particular a gas burner. When these means comprise several burners, the latter are regularly arranged at the level of the upper wall and / or the side walls of the reaction chamber, in order to obtain a homogeneous temperature in the chamber.
  • the burner (s) is (are) fed by any suitable fuel.
  • the fuel is in particular chosen from methane, butane, propane, fuel oil, oil, dihydrogen, a synthesis gas and a mixture thereof.
  • the fuel is, more particularly, chosen among methane, butane, propane, fuel oil, oil, dihydrogen and a mixture thereof.
  • synthesis gas it is possible either to continue to feed the burner (s) with methane, butane, propane, fuel oil, oil, dihydrogen and one of their mixtures, or use at least a portion of the synthesis gas produced.
  • the distal end of at least one of the means 5 adapted to recover the synthesis gas is connected to at least one gas burner.
  • Means 6 for maintaining the molten pyro-gasified carbonaceous ash bath in melt form may further comprise means for measuring, controlling and / or adjusting the temperature within the reaction chamber.
  • the rectification of the temperature may consist in acting on the burner (s), in particular on the characteristics of the fuel supply of this or these latter (s).
  • the device according to the present invention may further comprise means 7 adapted to evacuate a portion of the ashes of molten pyro-gasified carbonaceous material.
  • the device according to the present invention comprises a tank, a vessel or a vessel fluidly connected to the reaction chamber at its downstream portion. More particularly, this tray, this tank or this overflow container is secured to the external fac of the oven at the downstream part of the reaction chamber and is connected thereto via a duct, possibly obstructible, arranged in the wall of the oven.
  • a duct possibly obstructible, arranged in the wall of the oven.
  • a reaction chamber is used, the upstream portion of which is raised above its downstream part. This elevation is between 1 and 30 ° , especially between 2 and 20 ° and, in particular, of the order of 10 ° (ie 10 ° ⁇ 5 ° ).
  • the gasification furnace forms with the horizontal an angle of between 1 and 30 ° , especially between 2 and 20 ° and, in particular, of the order of 10 ° .
  • the device according to the present invention may also have suitable means for injecting an oxidant capable of promoting gasification.
  • the oxidant is advantageously a reactive gas comprising oxygen such as air, oxygen-enriched air or oxygen.
  • the device according to the present invention has a reaction chamber 1 corresponding to the internal cavity of a furnace 3 made of ceramic or metal refractory material having a sufficient thickness so that the external walls of the cavity do not exceed 50.degree. C. and in particular 30.degree. vs.
  • this parallelepiped-shaped oven has a length of 3 m and a width of 1 m.
  • the lower part of the reaction chamber was previously filled with ashes of pyro-gasified carbonaceous material, heated via burners 6a and 6b located on the walls or on the ceiling of the furnace, fed with a fuel selected from methane, butane propane, oil, oil, dihydrogen and a mixture thereof to a temperature such that the ashes are liquid ie a temperature of between 1000 ° C and 1400 ° C.
  • a fuel selected from methane, butane propane, oil, oil, dihydrogen and a mixture thereof to a temperature such that the ashes are liquid ie a temperature of between 1000 ° C and 1400 ° C.
  • the molten ash bath 2 comprises in particular silicon dioxide (SiO 2 ), calcium oxide (CaO), potassium oxide (K 2 O), aluminum oxide (Al 2 O 3 ), iron (III) oxide (FeO 3 ), magnesium oxide (MgO) and phosphorus pentoxide (P 2 O 5 ).
  • This molten ash bath 2 has a layer of sufficient thickness so that the particles of carbonaceous material to be treated can float there.
  • the molten ash bath must have a minimum thickness of 9 mm so that particles of 3 cm can float.
  • the particles of biomass or advantageously solid waste having a high ash content, especially an ash content greater than 10%, are continuously injected via a hopper 41 and a treadmill or vibrating belt 42 .
  • the hopper 41 placed above the distal portion 42b of the treadmill or vibrating conveyor 42 deposits solid particles therein. These are fed from the distal portion 42b of the treadmill or vibrating to the proximal portion 42a of said belt.
  • the particles fall, from the proximal portion 42a of the treadmill or vibrating, in the oven via an opening 43 opening in the upper upstream of the reaction chamber.
  • the particles fall more particularly at the upstream portion 2a of the molten ash bath 2 .
  • the particles float on the molten ash bath 2 , pyrolyze and gasify while being driven, by gravity and the stream of molten ash, to the downstream portion of the melt 2b .
  • the speed of the stream of the molten ash is adjusted by three parameters: the temperature of the molten ash bath, the addition of a flux (cullet for example) and, optionally, by inclining more or less the oven 3 .
  • the temperature of the bath is regulated by the energy input of the burners 6a and 6b .
  • the objective is (i) to maintain the liquid ash bath in spite of ashes whose composition can vary, in particular because of the variability of the input carbonaceous material and (ii) thus to control a viscosity allowing a controlled flow of ashes downstream.
  • controlled flow is meant a flow neither too slow nor too fast to adjust the residence time of the particles in the bath.
  • a flux (cullet, for example) also makes it possible to keep the bed molten in case the variability of the ashes leads to a melting temperature that is too high, thus risking a solidification of the bed.
  • the angle 31 that forms the furnace relative to the horizontal and therefore that forms the upstream portion 2a relative to the downstream portion of the melt 2b is an additional means to facilitate the flow of ash. It is of the order of 10 ° (ie 10 ° ⁇ 5 ° ).
  • the synthesis gas is collected and recovered at the outlet by a pipe-type recovery duct 5 opening at the top of the furnace 3 .
  • the pyro-gasification gas for wood waste input with air used as an oxidizer to provide the energy necessary for gasification (by partial combustion of the synthesis gas) in addition to the water vapor used as gasifying agent, has the following composition: 50% nitrogen (N 2 ), 15% hydrogen (H 2 ), 15% carbon monoxide (CO), 16% carbon dioxide (CO 2 ), 3 % of methane (CH 4 ) and organic pollutants (volatile organic compounds, and polycyclic aromatic hydrocarbons) and inorganic (sulfur compounds, acid vapors) in an amount of less than 1%, the percentages being expressed by volume relative to total volume of synthesis gas produced.
  • Part 51 of the synthesis gas representing 30% to 40% by volume relative to the total volume of synthesis gas produced is used to heat the reaction chamber 2 via the burners 6a and 6b .
  • the ashes of each particle feed the molten bed of ash. They constitute the motor driving the particles introduced into the device. Part of the ash may be discharged at a duct 71 , possibly clogged, arranged in the wall of the furnace at the downstream portion of the reaction chamber and therefore at the downstream level of the molten ash bath 2b . The excess ash flows via this conduit into a tank, a tank or an unrepresented overflow container.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Claims (10)

  1. Verfahren zum Umwandeln eines kohlenstoffhaltigen Materials in Synthesegas durch Pyrolyse und anschließender Vergasung, umfassend zumindest einen Schritt des Inkontaktbringens des kohlenstoffhaltigen Materials mit einem Schmelzbad von Aschen aus pyrovergastem, kohlenstoffhaltigen Material in einer Reaktionskammer (1) unter Vorhandensein von einem Vergasungsmittel, wodurch Synthesegas erzeugt wird,
    dadurch gekennzeichnet, dass der stromaufwärtige Abschnitt der Reaktionskammer (1) in Bezug auf ihren stromabwärtigen Abschnitt erhöht ausgeführt ist.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das kohlenstoffhaltige Material ausgewählt ist aus der Gruppe bestehend aus landwirtschaftlicher Erzeugungen, Rückständen aus landwirtschaftlichen Erzeugungen, forstwirtschaftlicher Erzeugungen, Rückständen aus forstwirtschaftlichen Erzeugungen, landwirtschaftlichen Rückständen aus Tierhaltung und organischen Abfällen.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die organischen Abfälle ausgewählt sind aus der Gruppe umfassend organische Haushaltsabfälle, industrielle organische Abfälle, Krankenhausabfälle, Schlämme aus der Abwasseraufbereitung, Schlämme aus der Aufbereitung von industriellen Abwässern, Schlämme aus Siloböden und deren Gemische.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Aschen aus pyrovergastem, kohlenstoffhaltigen Material ein oder mehrere Elemente, ausgewählt aus der Gruppe umfassend Siliciumdioxid (SiO2), Calciumoxid (CaO), Kaliumoxid (K2O), Aluminiumoxid (Al2O3), Eisen(III)Oxid (FeO3), Magnesiumoxid (MgO) und Phosphorpentoxid (P2O5), enthalten.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass erzeugte Synthesegas Wasserstoff (H2), Kohlenmonoxid (CO) und Kohlendioxid (CO2) und gegebenenfalls ein oder mehrere weitere gasförmige Elemente enthält.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Verfahren die nachstehenden Schritte umfasst:
    a) Herstellen eines Schmelzbads von Aschen aus pyrovergastem, kohlenstoffhaltigen Material;
    b) Inkontaktbringen des kohlenstoffhaltigen Materials mit dem in Schritt (a) hergestellten Schmelzbad von Aschen aus pyrovergastem, kohlenstoffhaltigen Material unter Vorhandensein eines Vergasungsmittels;
    c) Gewinnen des in Schritt (b) erzeugten Synthesegases.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das gesamte Synthesegas oder ein Teil davon als Brennstoff verwendet wird, um die Schmelzaschen aus pyrovergastem, kohlenstoffhaltigen Material auf einer Temperatur höher oder gleich 1000 °C, typischerweise zwischen 1000 °C und 1600 °C und insbesondere zwischen 1000 °C und 1400 °C, zu halten.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Verfahren ferner einen Schritt des kontinuierlichen oder sequentiellen Ablassens eines Teils der Schmelzaschen umfasst.
  9. Vorrichtung, die im Rahmen eines Verfahrens nach einem der vorangehenden Ansprüche eingesetzt wird, enthaltend (i) eine Reaktionskammer (1), die ein Schmelzbad (2) von Aschen aus pyrovergastem, kohlenstoffhaltigen Material enthält, (ii) Einrichtungen (4), die in die Reaktionskammer münden und dazu ausgelegt sind, in diese das aufzubereitende, kohlenstoffhaltige Material einzuführen, (iii) Einrichtungen (5), die dazu ausgelegt sind, das erzeugte Synthesegas zu gewinnen und (iv) Einrichtungen (6), die dazu ausgelegt sind, das Aschenbad in geschmolzener Form aufrechtzuerhalten, dadurch gekennzeichnet, dass der stromaufwärtige Abschnitt der Reaktionskammer (1) in Bezug auf ihren stromabwärtigen Abschnitt erhöht ausgeführt ist.
  10. Vorrichtung nach Anspruch 9, dadurch gekennzeichnet, dass sie ferner Einrichtungen (7) enthält, die dazu ausgelegt sind, einen Teil der Schmelzachsen aus pyrovergastem, kohlenstoffhaltigen Material abzulassen.
EP15190009.9A 2014-10-15 2015-10-15 Verfahren und vorrichtung zur feuervergasung eines kohlenstoffhaltigen materials, das ein ascheschmelzbad umfasst Not-in-force EP3009495B1 (de)

Applications Claiming Priority (1)

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FR1459881A FR3027311B1 (fr) 2014-10-15 2014-10-15 Procede et dispositif pour la pyro-gazeification d'une matiere carbonee comprenant un bain de cendres en fusion

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EP3009495B1 true EP3009495B1 (de) 2018-11-07

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CN114479952B (zh) * 2020-10-27 2023-07-28 中国石油化工股份有限公司 一种生物质制氢热载体及其制备方法与应用

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US3841239A (en) * 1972-06-17 1974-10-15 Shin Meiwa Ind Co Ltd Method and apparatus for thermally decomposing refuse
US4181504A (en) 1975-12-30 1980-01-01 Technology Application Services Corp. Method for the gasification of carbonaceous matter by plasma arc pyrolysis
US4141694A (en) 1977-08-26 1979-02-27 Technology Application Services Corporation Apparatus for the gasification of carbonaceous matter by plasma arc pyrolysis
EP1148295B1 (de) * 1999-01-27 2011-03-23 Sumitomo Metal Industries, Ltd. Abfallvergasungsschmelzofen und vergasungsschmelzverfahren
US8197566B2 (en) * 2008-12-08 2012-06-12 General Electric Company Gasifier additives for improved refractory life
EP2723832B1 (de) 2011-06-23 2017-06-21 Xylowatt S.A. Gasgenerator, der mit festem kohlenstoffbrennstoff funktioniert
FR2985265B1 (fr) 2011-12-29 2013-12-27 Cogebio Procede et equipement de gazeification en lit fixe
US20150184090A1 (en) * 2012-06-08 2015-07-02 How Jie Ni Waste treatment gasification system

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EP3009495A1 (de) 2016-04-20
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