EP2451905B1 - Verfahren zur wärmebehandlung von material in einem reaktor mit einer wand als selbstschmelztiegel - Google Patents

Verfahren zur wärmebehandlung von material in einem reaktor mit einer wand als selbstschmelztiegel Download PDF

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EP2451905B1
EP2451905B1 EP10728717.9A EP10728717A EP2451905B1 EP 2451905 B1 EP2451905 B1 EP 2451905B1 EP 10728717 A EP10728717 A EP 10728717A EP 2451905 B1 EP2451905 B1 EP 2451905B1
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reactor
temperature
composition
ash
ashes
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EP2451905A2 (de
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Jean-Marie Seiler
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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
    • C10J3/72—Other features
    • C10J3/74—Construction of shells or jackets
    • 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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/485—Entrained flow gasifiers
    • 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
    • C10J3/72—Other features
    • C10J3/723—Controlling or regulating the gasification process
    • 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
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • 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
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/15—Details of feeding means
    • C10J2200/152—Nozzles or lances for introducing gas, liquids or suspensions
    • 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
    • C10J2300/0903—Feed preparation
    • 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
    • C10J2300/0959—Oxygen
    • 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
    • C10J2300/0983—Additives
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
    • C10J2300/1628—Ash post-treatment
    • C10J2300/1634—Ash vitrification
    • 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
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only

Definitions

  • the invention relates to the field of heat treatment of materials in a self-crucible wall reactor, or cold crucible, such as a driven flow reactor.
  • the invention is particularly applicable for carrying out a gasification of biomass, pretreated or otherwise, in an allothermal entrained flow reactor (that is to say using an external energy to the system consisting of the treated materials to ensure the gas conversion ) or autothermal (does not require energy external to the system to ensure the gas conversion).
  • the invention can be used to carry out all types of gasification of materials, for example coal, sewage sludge or any type of liquid and / or solid waste containing organic and inorganic elements in order to produce electricity or biofuels.
  • the invention is also applicable to carry out thermal treatments of materials in other allothermal reactors, for example in plasma reactors or reactors in which a fuel gas is added (hydrogen or methane for example).
  • the invention also relates to the heat treatment of material in all types of industrial fusion reactor, for example an asbestos melting reactor for vitrifying asbestos.
  • the gasification of biomass has mainly been developed for cogeneration-type applications, that is to say, to treat biomass and transform it into thermal energy and electricity.
  • One known technique for carrying out such a gasification consists in contacting fine particles of biomass with oxygen at high temperature in a driven flow reactor, for example described in the documents US 5,620,487 and US 4,680,035 .
  • the documents US 5,968,212 and DE 4,446,803 describe techniques that make it possible to manage refractory zones with double constituents and cooled zones to take into account the thermal stresses.
  • the reactor 1 comprises an inlet orifice 2 through which are introduced the material to be treated 4, for example biomass, and reactant gases 6 such as oxygen and / or methane.
  • the reactor 1 comprises a high temperature chamber 8 (temperature for example between about 1000 ° C. and 1800 ° C.) in which the conversion reactions of the biomass 4 into synthesis gas 10 obtained at a port of output 12 of the high temperature chamber 8.
  • the conversion time of biomass 4 into synthesis gas 10, corresponding to the residence time of the biomass 4 in the high temperature chamber 8, is of the order of a few seconds.
  • the reactor 1 also comprises a burner 22 making it possible to obtain the desired temperature in the chamber 8.
  • the biomass contains organic compounds that can be represented in the form of C 6 H 9 ⁇ 1 O 4 ⁇ 0.5 (elementary representation) making it possible to obtain synthesis gases such as CO, H 2 , CO 2 , H 2 O or CH 4 .
  • the biomass also comprises inorganic compounds formed by all the other elements contained in the biomass (mainly oxides such as CaO, SiO 2 , Al 2 O 3 , FeO or MgO) and which are likely not to turn into synthesis gas. During the operation of gasification of biomass, these compounds are transformed into ashes.
  • Inorganic compounds are non-recoverable elements for the transformation of biomass into fuel (fuel being obtained by recombining CO and H 2 gases to obtain CH 4 ), generate operating problems for treatment plants, environmental problems and require, for certain mineral elements, a re-spreading on the ground. Between about 0.5% and 3% by mass of the biomass is in the form of ashes during a gasification operation of biomass in a driven flow reactor.
  • the reactor 1 can work under a pressurized atmosphere, for example up to about 80 bar.
  • the pressure resistance is supported by a cold wall surrounding the high temperature chamber 8 of the reactor.
  • the wall of the chamber 8 must also be able to withstand the high temperature.
  • a driven flow reactor can therefore operate under severe conditions of temperature and pressure.
  • the biomass particles will pyrolyze very rapidly, releasing partially oxidized vapors taking into account the oxygen present in the chamber 8.
  • a reaction is thus obtained providing the heat necessary for the gasification of the biomass coal and heating the mixture.
  • Residual ash will melt and become deposit mainly on the wall 8 where they will flow.
  • These residual ashes will form a layer of molten ash, or molten ash, and a layer of solid ash acting as thermal insulator between the liquid ash layer and the wall of the chamber 8, also called reactor wall, according to the principle of operation of the reactor in a self-crucible, and forming a so-called self-crucible wall.
  • the wall of the high temperature chamber 8 is isolated from the molten ash by a layer of solid ash of thickness, for example between about 1 mm and a few centimeters, for example. example less than or equal to about 5 cm.
  • This layer of solid ash forms spontaneously in contact with the walls of the chamber which are cooled by a water circulation system.
  • the figure 3 represents the various elements forming the "multilayer" wall of the high temperature chamber 8.
  • Such a multilayer wall is for example described in the document US 2005/0108940 A1 .
  • the outer layer of the wall comprises a forced convection cooling circuit 14.
  • This circuit 14 comprises tubes in which pressurized water circulates. These tubes are provided with fins allowing on the one hand to have good mechanical grip against an intermediate layer 16, and on the other hand to form a heat flow collector from the inside of the chamber 8 to the tubes of the cooling circuit 14.
  • This outer layer is also designed to withstand the pressure in the chamber 8 during the operation of the reactor 1.
  • the multilayer wall also comprises the intermediate layer 16 having a thickness of between about 1 cm and 2 cm of refractory ceramic type, for example based on silicon carbide (SiC).
  • This intermediate layer 16 has good thermal conductivity, thus allowing the heat flow to be well distributed between a third layer 18 of solidified ash and the cooling circuit 14.
  • This intermediate layer 16 also makes it possible to absorb the thermal shocks in the event of a loss. part of the solid ash layer 18 during operation of the reactor 1.
  • the multilayer wall comprises the layer of solidified ash 18 supported by the intermediate layer 16.
  • This layer 18 acts as a heat shield and is based on a material (solid ash) of the same nature as that of molten ash 20 flowing on the inner surface of the wall, against this layer of solid ash 18 (this flow is represented by an arrow on the figure 3 ).
  • the reactor when the reactor operates in a self-crucible, a portion of the ash contained in the hydrocarbon feedstock of the biomass solidifies and forms a refractory material.
  • the other part of the ash is in liquid form and is recovered at the bottom of the reactor (outlet port 12) and quenched with water.
  • the conduct of a driven flow reactor is currently carried out by an empirical approach, based on information providing the operating characteristics of the reactor as a function of known compositions of materials to be treated.
  • the figure 2 represents a curve giving, as a function of the value of a ratio of concentrations of elements present in the material to be treated, the operating temperature of the reactor.
  • the values of the abscissa axis correspond to those of the following concentration ratio: CaO + MgO + Fe 2 O 3 + Na 2 O + K 2 O SiO 2 + Al 2 O 3 + TiO 2
  • the invention is as described in claim 1.
  • An object of the present invention is to propose a method for driving, or controlling, or using, deterministic and non-empirical, a reactor type self-crucible, and a method of heat treatment of materials in a reactor with a high temperature chamber and self-crucible wall, which can be used for all types of resources, or raw materials, even those whose corresponding reactor operating temperatures are not known, and this without damaging the reactor.
  • the present invention proposes a process for the thermal treatment of materials in a high temperature chamber reactor with a self-crucible wall, comprising at least one step for determining the liquidus temperature T liq of the ash resulting from the treated materials.
  • operating temperature of the reactor T dark steady state is then selected as dark> T liq.
  • the operating temperature T f of the reactor designates here and throughout the rest of the document the temperature at the outlet of the high temperature chamber of the reactor, that is to say the temperature of the gas present at the outlet of the high temperature chamber.
  • the liquidus temperature of a mixture corresponds to the temperature from which all the constituents of the mixture become liquid.
  • Such a method makes it possible to solve the problems related to the inorganics present in the treated materials thanks to an optimal operation of the reactor obtained by a choice of the optimal operating temperature of the reactor according to the nature of the treated materials.
  • the method according to the invention therefore makes it possible to achieve optimal thermochemical conversion of the materials to be treated, and more particularly an optimal thermochemical conversion of the inorganics present in these materials, whatever the nature of the materials to be treated.
  • the operating temperature of the reactor is adjusted with respect to the chemical properties of the ash, that is to say with respect to the composition of the ashes of the materials to be used. treated, in a deterministic manner, with the key parameter that represents the liquidus temperature T liq of ash from treated materials.
  • the method according to the invention therefore makes it possible to heat-treat materials even if they have never been treated before.
  • the The invention makes it possible to modify deterministically the characteristics of the ashes in order to render their treatment compatible with the operating constraints of the reactor.
  • this method makes it possible to obtain a thermodynamic equilibrium operation of the reactor, allowing a perfect prediction of the composition of the synthesis gas and a cracking of the methane and the tars.
  • the operating temperature of the reactor can also be controlled according to the chemical reactions of gasification occurring in the reactor during the heat treatment of the materials, that is to say according to the evolution of the composition of the ash from the treated materials. It is therefore possible on the one hand to operate the reactor at a minimum temperature maximizing the conversion to CO and H 2 , and on the other hand to avoid operating the reactor at too high temperatures which would increase heat losses.
  • the minimum temperature may therefore depend on the material to be process, the operating pressure of the reactor and the residence time of the material in the reactor.
  • the operating temperature of the reactor T dark steady state can be chosen such that T dark> T LIQ2.
  • T liq2 of the ash resulting from the modified composition of the heat-treated materials After the determination of the liquidus temperature T liq2 of the ash resulting from the modified composition of the heat-treated materials, it is possible to verify that T liq2 ⁇ T 2 in order to fulfill the condition T 1 ⁇ T liq2 ⁇ T 2 .
  • the invention proposes a quantifiable method thus making it possible to modify this initial composition so that the ash from the modified composition have a liquidus temperature which is compatible and optimal for the operation of the reactor.
  • T func is chosen such that 30 ° C ⁇ (T func - T liq ) ⁇ 100 ° C.
  • T func can be chosen such that 30 ° C ⁇ (T func - T liq2 ) ⁇ 100 ° C.
  • the thermal losses in the reactor and the thickness of the solid ash layer formed on the reactor wall depend in particular on the difference between the operating temperature of the reactor and the liquidus temperature of the ash from the materials to be treated, it is therefore possible to reduce the thermal losses in the reactor, which may be less than about 100 kW / m 2 , by bringing the steady-state reactor operating temperature closer to the liquidus temperature of the ash from the treated materials (difference of less than or equal to about 100 ° C).
  • the initial composition of the treated materials may be modified such that the liquidus temperature T liq2 of the ash resulting from the modified composition of the treated materials may be between about 1200 ° C. and 1800 ° C., for example between about 1400 ° C and 1600 ° C, or between about 1300 ° C and 1500 ° C, or between about 1300 ° C and 1600 ° C, or between about 1450 ° C and 1550 ° C. It will preferably be chosen to modify the initial composition of the treated materials such that the liquidus temperature T liq 2 of the ash resulting from the modified composition of the treated materials may be between about 1400 ° C. and 1600 ° C.
  • this temperature range ([1400 ° C. to 1600 ° C.]) can be increased by a value ranging from about 100 ° C. to 200 ° C.
  • the modification of the initial composition of the treated materials such as liquidus temperature T LIQ2 ash modified on material composition is between about 1400 ° C and 1600 ° C, or between about 1300 ° C and 1500 ° C, or between about 1300 ° C and 1600 ° C, or between about 1450 ° C and 1550 ° C, may comprise at least one step of adding inorganic compounds to the initial composition of the treated materials that can substantially equalize the concentrations of SiO 2 and CaO in the modified composition of the treated materials.
  • the initial composition of the treated materials may be modified by at least one step of adding MgO and / or Fe 2 O 3 and / or K 2 O and / or Na 2 O and / or P 2 O 5 and and / or CaO and / or SiO 2 , depending on the liquidus T liq2 temperature of the ash resulting from the modified composition of the desired treated materials.
  • the additions of fluxing agents (compounds of the K 2 O, Na 2 O, Fe 2 O 3 , MgO or P 2 O 5 type ) to the treated materials can lead to a reduction in the liquidus temperature of the ashes from the treated materials between approximately 50 ° C and 200 ° C.
  • the liquidus temperature of the ashes resulting from the modified composition of the treated materials can be increased.
  • the thickness of the solid ash layer of the self-crucible wall of the reactor may be less than or equal to about 5 cm, or between about 1 cm and 2 cm, and / or be substantially constant during the operation of the reactor. its operating temperature T func .
  • the operating temperature of the reactor T dark may be between about 1000 ° C and 1800 ° C, and for example between about 1400 ° C and 1600 ° C for a biomass treatment.
  • composition of the ash formed on the reactor wall can be analyzed at least once, and preferably several times, during the heat treatment process for a given resource.
  • the self-crucible wall reactor may be of the driven flow type and / or the treated materials may be biomass.
  • the process can be implemented preferably for large capacity reactors, that is to say whose flow of treated materials can be greater than or equal to about 50 tons / hour.
  • the method may use a device for rapidly measuring the content of inorganic compounds and ashes of the treated materials, and a device for automatically adjusting the composition of the treated materials according to the operating temperature of the desired reactor.
  • the liquidus temperature of the ashes from the treated materials can be determined by a software of thermodynamic calculations.
  • the driven flow reactor 1 comprises a high temperature chamber 8 comprising a "multilayer" wall (layers 14, 16, 18 and 20) formed during the self-crucible operation of the reactor 1.
  • thermodynamic modeling of the multilayer wall of the driven flow reactor 1 is described below.
  • the solid ash layer 18 is then formed against the intermediate layer 16 and the heat flux ⁇ which passes through the different layers 20, 18, 16 and 14 of the wall is constant.
  • Ti liner / water is close to the temperature of the water circulating in the cooling circuit 14 (for example about 100 ° C.).
  • a reference heat flow for example equal to about 100 kW / m 2 if it is desired not to exceed this level of thermal losses, with a thermal conductivity characteristic of the intermediate layer 16 of between about 5 W / mK and 10 W / mK, and a thickness of the intermediate layer 16 equal to about 1 cm, a temperature difference of between about 100 ° C and 200 ° C is then obtained. This difference in temperature therefore remains low compared with the difference between the temperature of the gas (for example between about 1400 ° C. and 1600 ° C.) and that of the cooling water (equal to about 100 ° C.).
  • a thickness of the solid ash layer 18 of between about 1 and 2 cm, and for example equal to about 1.5 cm.
  • the interface temperature between the solid ash layer and the liquid ash layer (Ti s / solid ) is derived from "steady state" metallurgical considerations.
  • Reactor steady state operation means that flow rates, compositions, and temperature distributions are established and do not change over time. This means in particular that the flow of liquid ash 20 is established and that the solid ash layer 18 is established and that its thickness no longer varies.
  • the interface temperature between the liquid ash layer and the solid ash layer therefore corresponds to an intrinsic property of the ash, thereby decoupling the temperature in the high temperature chamber from the temperature within the wall.
  • the ashes flowing along the wall of the high temperature chamber i.e. the ashes present in the layer 20 , are completely liquid (no solid).
  • the thickness of the liquid ash layer 20 varies between about 0.5 mm and 2.5 mm for a reference viscosity of about 1 Pa.s.
  • the average flow rate of liquid ash varies between about 2 mm / s and 20 mm / s.
  • the Reynolds number remains very low, for example equal to about 10 -5 , which confirms the laminar flow regime of the liquid ash 20.
  • the thickness of the liquid ash layer increases by a factor of between about 4 and 10, just as the average flow rate decreases by the same factor.
  • the conduction heat resistance associated with the liquid ash layer varies here between about 5.10 -4 and 2.10 -3 KW -1 .m 2 . This means that for an average heat flow of about 100 kW / m 2 , the temperature difference over the thickness of the liquid ash layer is of the order of 50 ° C to 200 ° C. Taking radiation into account makes it possible to reduce this difference in temperature by a factor of between approximately 1.5 and 3. The difference in temperature over the thickness of the liquid ash layer then falls between approximately 30 ° C. and 70 ° C. ° C.
  • the liquidus temperature of the ash is an intrinsic property of the ash.
  • the basic components of an ash are oxides, of which silica (SiO 2 ) and calcium oxide (CaO) are the most important in quantity. These species thus form the reference system for the analysis of the evolution of the liquidus temperature T liqu of ashes according to the composition of these ashes.
  • the variation of Tl l versus the amount of SiO 2 is such that: SiO 2 mass (kg) T liqu 1 1800 1.5 1690 2 1610 3 1620 4 1830
  • low melting oxides such as for example K 2 O or Na 2 O, which are significantly present in the biomass ash (up to 20% by weight), may reduce the T liqu of nearly 200 ° C.
  • SiO 2 (respectively CaO) can play either the role of flux (reducing T liqu ) or refractory (increasing T liqu ) depending on the initial concentration of CaC (respectively SiO) 2 ).
  • the liquidus temperature of an ash can therefore vary between about 1150 ° C. to more than 1600 ° C. depending on the composition of the ash, or even, for an ash rich in calcium oxide, up to a temperature of greater than about 2000 ° C.
  • the operating temperature of the reactor is therefore chosen to be higher than the liquidus temperature of the ash from the treated materials.
  • Ti g / s is equal to T liqu + ⁇ T slag , with ⁇ T slag temperature difference over the thickness of the liquid ash layer.
  • ⁇ T slag is small compared to T liqu .
  • T liqu is a good approximation of Ti g / s .
  • h gas is directly related to gas flow and thermal radiation. It appears that the heat losses are directly proportional to the gap dark T - T liquefied.
  • the heat losses can be reduced by comparing the operating temperature of the reactor with the liquidus temperature of the ash.
  • the operating temperature of the reactor can be chosen higher by about 50 ° C to 100 ° C compared to T liqu .
  • Can preferably be selected as dark T is about 50 ° C ⁇ (func T - T liq) ⁇ 100 ° C.
  • the temperature difference T func - T liqu controls both heat losses and the thickness of the layer of solid ash from the reactor wall.
  • T func - T liqu controls both heat losses and the thickness of the layer of solid ash from the reactor wall.
  • the ash composition will be monitored during the process to ensure that the liquidus temperature does not vary more than about 50 ° C. Maintaining this temperature range therefore amounts to maintaining the proper ash composition range.
  • the initial composition of the treated materials has a liquidus temperature ash from these materials that does not allow to choose an optimum operating temperature, for example when liquidus this temperature is too high
  • it is possible to adjust the composition by modifying it in order to modify the liquidus temperature of the ashes resulting from the modified composition of materials.
  • This modification is, in this case, for example carried out by continuous additions of inorganic compounds melting to the initial composition of treated materials, throughout the heat treatment of these materials.
  • the operating temperature of the reactor may be chosen in particular to allow the reforming of tars and methane. In particular, it is possible to choose an operating temperature of less than about 1500 ° C., for example equal to about 1250 ° C. If it is desired to operate the reactor at this temperature level, it will then be possible to reduce the ash liquidus temperature to about 1150 ° C. if the liquidus temperature of the ashes resulting from the initial composition of the treated materials is greater than this value.
  • the liquidus temperature of the ash can be reduced by incorporating Na 2 O, K 2 O or other low melting point oxides into the initial composition of the treated materials.
  • a modification of the initial composition of the treated materials, thus modifying the composition of ash in the reactor and thus modifying the liquidus temperature of these ashes, by additions of compounds can be preferably carried out when the ash content (i.e. the initial content of inorganic compounds) of the treated materials is low (eg the case of wood).
  • compositions of the ash C1, C2 and C3 are detailed in the table below.
  • the liquidus temperature of the ash from the treated materials is preferably calculated from a thermodynamic calculation software for reasons of cost and speed.
  • a thermodynamic calculation software for reasons of cost and speed.
  • the liquidus temperature of the ashes is determined by means of a modeling software whose models base on experimental data established with ashes of different compositions.
  • a modeling software whose models base on experimental data established with ashes of different compositions.
  • the liquidus temperature can for example be measured by a method of microscopic observations after a quenching of a small amount (for example 40 mg) of ash as a ball initially heated to high temperature in a furnace.
  • the liquidus temperature of the ashes can also be measured in situ by X-ray diffraction at high temperature.
  • the liquidus temperature of the ashes can also be approached by a differential thermal analysis - thermogravimetric analysis (ATD-ATG), a calorimetric method consisting in following the evolution of the temperature difference between the sample studied and a control body. inert.
  • ATTD-ATG differential thermal analysis - thermogravimetric analysis
  • the composition of the ash C2 can also be optimized by reducing the liquidus temperature of these ashes by adding a flux, for example Fe 2 O 3 or MgO (according to the ash compositions, the MgO can have a melting character if it it is added in small quantities).
  • a flux for example Fe 2 O 3 or MgO (according to the ash compositions, the MgO can have a melting character if it it is added in small quantities).
  • the operating temperature of the reactor can be modified in particular by adjusting the flow rate of oxygen (reactant gas) at the inlet of the high temperature chamber.
  • oxygen reactant gas
  • the gasified material in the heat treatment process described here is pretreated biomass, for example in the form of small particles, of a solid suspension in an organic liquid (or "slurry” in English), of char ( biomass coal) using techniques such as fluidized beds, slow pyrolysis, roasting or grinding.
  • the particle size of the treated materials and the addition of fluxing agents are therefore two parameters which make it possible to optimize the yield the reactor by minimizing the need for oxygen for combustion.
  • the cooling carried out by the cooling circuit 14 makes it possible to form the layer of solid ash of sufficient thickness to thermally protect the wall, and particularly the intermediate layer 16.
  • the characteristic time of setting up the solid ash layer 18 is inversely proportional to the flow rate of the reactor 1. For example, in the case of a reactor of industrial size (that is to say, whose flow is greater than or equal to about 50 tons / hour, the solid ash layer 18 may in about six hours, while for a small reactor (flow rate equal to about 50 kg / h), the solid ash layer will be formed after about 5 days.

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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)
  • Physical Or Chemical Processes And Apparatus (AREA)

Claims (12)

  1. Verfahren zur Wärmebehandlung von Materialien (4) in einem Reaktor (1) mit Hochtemperaturkammer (8) und Wand als Selbstschmelztiegel (14, 16, 18, 20), umfassend zumindest einen Schritt des Bestimmens der Liquidus-Temperatur Tliq der aus den behandelten Materialien (4) stammenden Aschen (18, 20), wobei die Betriebstemperatur des Reaktors Tfonc im Dauerbetrieb dann so gewählt wird, dass Tfonc > Tliq und Tfonc so gewählt wird, dass 30 °C ≤ (Tfonc - Tliq) ≤ 100 °C ist.
  2. Verfahren nach Anspruch 1, ferner umfassend die Schritte:
    - Modifizieren der ursprünglichen Zusammensetzung der behandelten Materialien (4) durch Zugabe von anorganischen Verbindungen; dann
    - Bestimmen der Liquidus-Temperatur Tliq2 der aus der modifizierten Zusammensetzung der behandelten Materialien (4) stammenden Aschen (18, 20),
    wobei die Betriebstemperatur des Reaktors Tfonc im Dauerbetrieb dann so gewählt wird, dass Tfonc > Tliq2 ist.
  3. Verfahren nach Anspruch 2, wobei Tfonc so gewählt wird, dass 30 °C ≤ (Tfonc - Tliq2) ≤ 100 °C ist.
  4. Verfahren nach einem der vorangehenden Ansprüche, wobei die ursprüngliche Zusammensetzung der behandelten Materialien (4) so modifiziert wird, dass die Liquidus-Temperatur Tliq2 der aus der modifizierten Zusammensetzung der behandelten Materialien (4) stammenden Aschen (18, 20) zwischen etwa 1000 °C und 1800 °C liegt.
  5. Verfahren nach einem der vorangehenden Ansprüche, wobei die ursprüngliche Zusammensetzung der behandelten Materialien (4) so modifiziert wird, dass die Liquidus-Temperatur Tliq2 der aus der modifizierten Zusammensetzung der behandelten Materialien (4) stammenden Aschen (18, 20) zwischen etwa 1400 °C und 1600 °C liegt.
  6. Verfahren nach Anspruch 5, wobei das Modifizieren der ursprünglichen Zusammensetzung der behandelten Materialien (4) so, dass die Liquidus-Temperatur Tliq2 der aus der modifizierten Zusammensetzung der behandelten Materialien (4) stammenden Aschen (18, 20) zwischen etwa 1400 °C und 1600 °C liegt, zumindest einen Schritt des Zugebens von anorganischen Verbindungen zur ursprünglichen Zusammensetzung der behandelten Materialien (4) umfasst, wodurch die Konzentrationen an SiO2 und an CaO in der modifizierten Zusammensetzung der behandelten Materialien (4) im Wesentlichen gleich gemacht werden.
  7. Verfahren nach einem der vorangehenden Ansprüche, wobei die ursprüngliche Zusammensetzung der behandelten Materialien (4) durch zumindest einen Schritt des Zugebens von MgO und/oder Fe2O3 und/oder K2O und/oder Na2O und/oder P2O5 und/oder CaO und/oder SiO2 in Abhängigkeit von der Liquidus-Temperatur Tliq2 der aus der gewünschten modifizierten Zusammensetzung der behandelten Materialien (4) stammenden Aschen (18, 20) modifiziert wird.
  8. Verfahren nach einem der vorangehenden Ansprüche, wobei die Dicke der Schicht aus festen Aschen (18) der Wand als Selbstschmelztiegel des Reaktors (1) geringer oder gleich etwa 5 cm ist und/oder im Wesentlichen konstant ist während des Betriebs des Reaktors bei seiner Betriebstemperatur Tfonc.
  9. Verfahren nach einem der vorangehenden Ansprüche, wobei die Dicke der Schicht aus festen Aschen (18) der Wand als Selbstschmelztiegel des Reaktors (1) zwischen etwa 1 cm und 2 cm ist und/oder im Wesentlichen konstant ist während des Betriebs des Reaktors bei seiner Betriebstemperatur Tfonc.
  10. Verfahren nach einem der vorangehenden Ansprüche, wobei die Zusammensetzung der an der Wand des Reaktors (1) gebildeten Aschen (18, 20) zumindest einmal im Laufe des Verfahrens zur Wärmebehandlung analysiert wird.
  11. Verfahren nach einem der vorangehenden Ansprüche, wobei der Reaktor (1) mit Wand als Selbstschmelztiegel (14, 16, 18, 20) vom Typ mit Flugstrom ist und/oder die behandelten Materialien (4) Biomasse sind.
  12. Verfahren nach einem der vorangehenden Ansprüche, wobei die Liquidus-Temperatur der aus den behandelten Materialien (4) stammenden Aschen (18, 20) durch eine Software für thermodynamische Berechnungen bestimmt wird.
EP10728717.9A 2009-07-10 2010-07-08 Verfahren zur wärmebehandlung von material in einem reaktor mit einer wand als selbstschmelztiegel Active EP2451905B1 (de)

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FR0903425A FR2947834B1 (fr) 2009-07-10 2009-07-10 Procede de traitement thermique de matieres dans un reacteur a paroi en auto-creuset
PCT/EP2010/059779 WO2011003966A2 (fr) 2009-07-10 2010-07-08 Procede de traitement thermique de matieres dans un reacteur a paroi en auto-creuset

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CN102206516A (zh) * 2010-03-29 2011-10-05 通用电气公司 耐火墙及气化装置和方法
BE1021471B1 (nl) 2012-04-03 2015-11-27 Flooring Industries Limited, Sarl Laminaatpaneel, werkwijze voor het vervaardigen van een laminaatpaneel en perselement om de werkwijze te verwezenlijken
CN102911740A (zh) * 2012-09-28 2013-02-06 上海锅炉厂有限公司 一种两段式气流床气化装置及其气化方法
CN117078112B (zh) * 2023-10-16 2024-01-02 云境商务智能研究院南京有限公司 应用于企业异常用电管理的能耗检测方法及数据分析系统

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FR2947834A1 (fr) 2011-01-14
BR112012000620B1 (pt) 2018-07-17
FR2947834B1 (fr) 2011-09-09
US9181503B2 (en) 2015-11-10
WO2011003966A2 (fr) 2011-01-13
US20120097516A1 (en) 2012-04-26
EP2451905A2 (de) 2012-05-16
WO2011003966A3 (fr) 2011-03-03

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