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    • 专利摘要:
    Method for Gasifying Carbonaceous Material and a Gasification System The present invention relates to a method for gasifying carbonaceous material. The method comprises a first step of pyrolyzing and partially gasifying the carbonaceous material to produce volatiles and carbon. volatiles and carbon are then separated and subsequently carbon is carbonated and volatiles are reformed. The crude gaseous product is then cleaned with carbon or carbon supported catalysts or other catalysts.
    公开号:BR112013001807B1
    申请号:R112013001807-0
    申请日:2011-07-26
    公开日:2019-05-21
    发明作者:Chun Zhu Li
    申请人:Curtin University Of Technology；
    IPC主号:
    专利说明:

    Field of the invention [001] The present invention relates to a method for gasifying carbonaceous material and a gasification system.
    Background of the invention [002] Gasification refers to the conversion of a solid or liquid material, such as a carbonaceous material, into a gaseous fuel. Gasification is of interest to many low-emission technologies in the chemical and energy industries.
    [003] The gasification of a carbonaceous material can be conceptually divided into two stages although a clear distinction between the two stages is not possible. When the carbonaceous (solid) material is heated, a mixture of gas and steam (“volatiles”), including moisture from the carbonaceous material, is released from the carbonaceous material, leaving a solid residue (“carbon”). The volatiles and carbon then react with gasifying agents such as H2O and O2 to form a gaseous product.
    [004] Low-grade carbonaceous fuels such as brown coal (lignite), peat, biomass and solid waste are particularly suitable for gasification due to their high gasification reactivity. However, these low-grade fuels have several specific properties, which must be considered when designing and operating a gasifier to gasify these low-grade fuels.
    [005] First, low-grade fuels generally have a high production of volatiles, for example, 80% by weight or more (on a dry basis) for some types of biomass. The complete overhaul of the volatile tar components is one of the most important considerations in the design of a gasifier because tar removal is complex and costly.
    [006] Second, low-grade fuels often contain well-dispersed alkali and alkaline earth metal (AAEM) species that can easily volatize during pyrolysis and gasification. The AAEM species volatilized in the gasification of the gaseous product can cause the corrosion / erosion of turbine / engine components. Volatilized AAEM species can also react with bed materials (eg sand)
    Petition 870180138532, of 10/07/2018, p. 24/54 / 25 in a fluidized bed gasifier, resulting in the agglomeration and fluidization of the bed materials. On the other hand, if these AAEM species are retained in carbon, they can be excellent catalysts for carbon gasification.
    [007] Third, low-grade carbon and volatile fuels are very reactive. The interaction between carbon and volatiles can increase the volatilization of their inherent metallic species (eg Na in brown coal and K in biomass), disable the carbon structure and thus reduce carbon reactivity. In the worst case, volatile-carbon interactions can practically end carbon gasification. In the presence of volatile-carbon interactions, increasing the gasification temperature does not always lead to a significant improvement in gasification rates. In fact, volatile-carbon interactions impact almost every aspect of gasification.
    [008] Oxygen consumption is an important consideration in the design and operation of a gasifier to achieve high efficiency. In many gasifiers, volatiles, being more reactive than carbon, tend to react preferentially with O2, leaving the carbon less reactive to be slowly aerated with steam and other aerating agents. A more preferable situation would be for the less reactive carbon to react with O2 allowing the more reactive volatiles to be reformed with steam and other gasifying agents.
    [009] The crude gaseous product may contain traces of tar, volatilized inorganic species (eg alkali) and pollutant-forming species (eg NH3, HCN and H2S). It normally needs to be cleaned before being used, for example, as a gaseous fuel in a turbine / engine or as a charge for chemical synthesis. The removal of various undesirable components such as tar materials, AAEM vapor, particulates and H2S / NH3 / HCI from the gasification of the gaseous product normally adds complexity to the total gasification process and forms an important part of the total gasification capital and operating costs. When these unwanted species are removed by washing with liquid (eg water), a stream of liquid waste is generated which must then be treated at high cost.
    Petition 870180138532, of 10/07/2018, p. 25/54 / 25
    Various conventional catalysts can be used to reform tar. However, these catalysts often deactivate easily.
    [010] Consequently, there is a need for technological advancement. Summary of the invention [011] In accordance with an aspect of the present invention, a method is provided for gasifying a carbonaceous material, the method comprising the steps of:
    pyrolyze the carbonaceous material to produce volatiles and carbon;
    separate carbon and volatiles;
    carbonize carbon;
    reforming volatiles to produce a gaseous product; and, passing partially reformed volatiles and / or gaseous product through a gaseous product cleaning zone, as well as a catalyst bed.
    [012] Passing the partially reformed volatiles and / or gaseous product through a catalyst bed results in several effects including removing tar residues and other impurities such as inorganic contaminants, and increasing the hydrogen content of the gaseous product by carrying out the reaction of displacement of water and gas, thus producing a clean gaseous product.
    [013] The catalyst bed may comprise a moving carbon bed or catalyst supported on carbon. The moving bed can be a moving bed of non-isothermal carbon or catalyst supported on carbon. Carbon or carbon-supported catalysts can be prepared from pyrolysis and / or partial gasification of the carbonaceous material (including that loaded with catalytic species). In one example, the process comprises the step of discharging spent carbon or carbon supported catalyst from the catalyst bed and gasifying the spent carbon or carbon supported catalyst to recover its energy values. The spent or partially spent carbon or catalysts supported on carbon can also be returned to the field as an organic soil corrector, a source of nutrients and / or for carbon bio-sequestration.
    [014] In another embodiment, the catalyst bed is one of a series of catalyst beds.
    Petition 870180138532, of 10/07/2018, p. 26/54 / 25 [015] In one embodiment of the invention, the step of pyrolyzing the carbonaceous material comprises pyrolyzing the carbonaceous material for a period of time that is long enough to convert substantially all of the carbonaceous material to volatiles and carbon.
    [016] In one embodiment, the step of pyrolyzing the carbonaceous material comprises heating the carbonaceous material with a counter-current flow of hot gas. Hot gas can be produced from carbon gasification. The carbonaceous material can undergo simultaneous pyrolysis and (partial) gasification.
    [017] In one embodiment, the step of carbonizing the carbon comprises reacting the carbon with an aerating agent. The step of carbonizing the carbon comprises reacting the carbon with a controlled amount of oxygen-containing gas. The gasification step can be performed in isolation from the step of reforming the volatiles to minimize volatile-carbon interactions.
    [018] In accordance with another aspect of the present invention, a method is provided for treating the crude gaseous product produced from the gasification of low-grade carbonaceous materials, in which the crude gaseous product contains partially reformed volatiles, tar residues and contaminants , the method comprising passing the crude gaseous product through a bed of catalyst.
    [019] In one embodiment, the method for treating the crude gaseous product comprises passing the crude gaseous product through a catalyst bed that comprises a moving carbon bed or carbon supported catalyst. Tar residues and other impurities such as inorganic contaminants are removed from the crude gaseous product. In addition, the hydrogen content of the treated gaseous product compared to that of the crude gaseous product is increased by effecting the displacement reaction of water and gas.
    [020] The method may comprise the step of drying the carbonaceous material before pyrolyzing the carbonaceous material. For representations in which the method comprises the step of drying the carbonaceous material, the steam produced from the drying step can be used in the step of reforming the volatiles.
    Petition 870180138532, of 10/07/2018, p. 27/54
    5/25 [021] In accordance with another aspect of the present invention, a gasification system is provided to gasify a carbonaceous material, the gasification system comprising:
    a reform zone to reform volatiles to produce a gaseous product;
    a carbon gasification zone to carbonize carbon;
    a pyrolysis zone to pyrolyze carbonaceous material, the pyrolysis zone being in fluid communication with the reform zone and the carbon gasification zone, in an arrangement whereby the volatiles and carbon formed in the pyrolysis zone are separated and directed the reform zone and the carbon gasification zone, respectively; and, a gaseous product cleaning zone in fluid communication with the reforming zone in an arrangement whereby partially reformed volatiles and / or the gaseous product can be passed through the gaseous product cleaning zone.
    [022] In this way, the gasification system of the present invention reduces and typically minimizes volatile carbon interactions.
    [023] In a representation, the pyrolysis zone is placed in the middle of the reform zone and the carbon gasification zone.
    [024] In one embodiment, the gaseous product cleaning zone comprises a catalyst bed. It should be understood that the catalyst bed can comprise more than one catalyst bed arranged in series.
    [025] In pyrolysing the carbonaceous material involves introductions of the invention, the gasification system can be provided with an entrance for the introduction of carbonaceous material in the pyrolysis zone, and one or more entries for the introduction of gasifying agents, such as steam and oxygen-containing gas in the carbon gasification zone. The gasification system can also be provided with an outlet for removing the gaseous product from the catalyst bed.
    [026] In one representation, the gasification system comprises a gasification reactor having the zones of reform, carbon gasification and pyrolysis defined in it.
    Petition 870180138532, of 10/07/2018, p. 28/54 / 25 [027] In a representation of the invention, the carbon gasification zone is placed in a lower part of the gasification reactor. The reform zone can be placed on top of the gasification reactor.
    [028] In one representation, the carbon gasification zone is also provided with an ash discharge device, as well as a closed hopper, operatively connected to an outlet placed at the bottom of the gasification reactor.
    [029] In one embodiment of the invention, the pyrolysis zone is configured to retain the carbonaceous material in the pyrolysis zone for a residence time long enough to convert substantially all of the carbonaceous material to volatiles and carbon.
    [030] The pyrolysis zone can be provided with a pyrolyzer adapted to retain the carbonaceous material in the pyrolysis zone for a residence time long enough to convert substantially all of the carbonaceous material into volatiles and carbon.
    [031] In one representation, a portion of the carbon formed in the pyrolysis zone is separated from the remaining carbonaceous material as a gas cleaning catalyst and directed to the gas product cleaning zone.
    [032] In one representation, the gasification system comprises a separate reactor, such as a moving bed reactor, for pyrolyzing and / or partially gasifying a carbonaceous material in order to prepare carbon catalysts or supported on carbon, the system being prepared in accordance with in order to allow the pyrolysed and / or partially carbonated carbonaceous material to be discharged into the product cleaning zone to act as the catalysts for cleaning the gaseous product. The carbonaceous material can be the main load for gasification.
    [033] The gas product cleaning zone can coincide with the carbon gasification zone, which can be configured and operated under conditions under which the carbon can undergo partial or complete gasification. The carbon gasification zone can also be a separate reactor, including carbon deposit.
    [034] In accordance with another aspect of the present invention, an apparatus is provided for pyrolyzing and partially gasifying carbonaceous materials, the apparatus comprising:
    Petition 870180138532, of 10/07/2018, p. 29/54 / 25 at least one element having a surface arranged so that, when the apparatus receives the carbonaceous material, the received carbonaceous material is in contact with the surface for a sufficiently long period of time for the pyrolysis of the carbonaceous material;
    wherein the apparatus is arranged in such a way that the surface receives heat for pyrolysis and partial gasification of the carbonaceous material.
    [035] In a representation, the surface has a downward sloping part arranged to assist the contact of the carbonaceous material with the surface during the period of time.
    [036] The apparatus may comprise a plurality of surfaces, each surface being arranged to receive carbonaceous material so that the received carbonaceous material is in contact with the respective surface for a sufficiently long period of time for the pyrolysis of the carbonaceous material, each surface being prepared to receive heat to pyrolyze and partially gasify the carbonaceous material. The plurality of surfaces can be in a cascade arrangement and the apparatus can be arranged so that the carbonaceous material is transferred to the successive surfaces of the cascade arrangement after a period of time sufficient to carry out the pyrolysis of the carbonaceous material .
    [037] In one embodiment, the apparatus comprises a stirrer associated with at least one element, the stirrer being arranged to stir the carbonaceous material in contact with the surface in order to transfer the carbonaceous material to a region below the surface.
    [038] In representations in which the apparatus comprises the plurality of surfaces in the cascade arrangement, the agitator may be arranged so as to transfer the carbonaceous material to a successive surface of the cascade arrangement.
    [039] In one representation, the apparatus comprises a plurality of agitators, each agitator being associated with a respective element having a respective surface, each agitator being arranged in order to transfer the carbonaceous material to a successive surface of the cascade arrangement or, in the case of one last surface of the cascading arrangement, to a region below the last surface of the cascading arrangement.
    Petition 870180138532, of 10/07/2018, p. 30/54 / 25 [040] The plurality of surfaces can be arranged in a vertical cascade arrangement and the apparatus can comprise a rotary axis that extends vertically through the plurality of surfaces on which the agitators associated with the respective surfaces are driven by means of rotation of the rotary axis.
    [041] Each successive surface of the vertical cascade arrangement may have a downward sloping part that is complementary to the surface above.
    Brief description of Figures [042] Representations of the present invention will now be described, by way of example only, with reference to the attached Figures, in which:
    Figure 1 is a schematic diagram of a method for gasifying a carbonaceous material according to a representation of the present invention;
    Figure 2 is a schematic diagram of a gasification system according to a representation of the present invention;
    Figure 3 is a schematic diagram of a representation of an apparatus for pyrolyzing a carbonaceous material that can be used in the gasification system shown in Figure 2; and,
    Figure 4 is a schematic diagram of a gasification system for gasifying a carbonaceous material in order to produce carbon and a gaseous product according to a representation of the present invention. Detailed description [043] Representations of the present invention refer to a method 10 for gasifying a carbonaceous material, a gasification system 20, 40, and an apparatus 30 for pyrolyzing carbonaceous material as described with reference to Figures 1 to 4.
    [044] It should be noted that method 10 can be carried out in a gasification reactor having in itself integrally defined a pyrolysis zone to pyrolyze carbonaceous material, a carbon gasification zone to gasify carbon with steam and a gas containing oxygen , a reform zone to reform volatiles with steam to produce a gaseous product, and a gas cleaning zone to clean the gaseous product. A representation of the gasification reactor according to the present invention will be described in greater detail on later pages of the report.
    Petition 870180138532, of 10/07/2018, p. 31/54 / 25 [045] In its broadest form, and as shown in Figure 1, the gasification method 10 comprises the steps of pyrolyzing 12 the carbonaceous material to produce volatiles and carbon, separating 14 the carbon and the volatiles, gasifying 16 carbon, reform 18 volatiles to produce a gaseous product, and clean 19 the gaseous product.
    [046] The term “carbonaceous material” is used in its broadest meaning throughout this report and includes, but is not limited to, coal such as anthracite, bituminous coal, sub-bituminous coal, brown coal, lignite and peat, biomass, rubber waste including but not limited to vehicle tires, waste plastic materials, agricultural waste, their mixtures and mixtures of said carbonaceous materials with other substances. The method and system of the representations of the present invention described with reference to Figures 1 to 4 are particularly suitable for use with low-grade carbonaceous material having high volatile matter production and high moisture content. The system described with reference to Figure 4 is especially suitable for use with biomass having high production of volatile matter and high moisture content.
    [048] In representations in which the moisture content of the carbonaceous material is high, it is preferable to dry the carbonaceous material before pyrolyzing the carbonaceous material. The advantages of pre-drying the carbonaceous material are twofold. Pre-drying minimizes the agglomeration of particles of carbonaceous material in storage hoppers and gasification reactors.
    [049] Additionally, while it is preferable that a certain amount of moisture is inherently introduced into the gasification reactor with the carbonaceous material, and subsequently converted to steam for use in the reforming area, an excessive amount of moisture would increase the requirements of energy inside the gasification reactor to convert moisture into steam and would result in decreased efficiency.
    [050] Therefore, in one embodiment, method 10 comprises a step of drying the carbonaceous material before pyrolyzing the carbonaceous material.
    [051] In a form of the invention, drying the carbonaceous material comprises contacting the carbonaceous material with the gaseous product of the
    Petition 870180138532, of 10/07/2018, p. 32/54 / 25 process in an indirect heat exchange mechanism. The indirect exchange of heat with the gaseous product can be achieved by passing the carbonaceous material through a conventional indirect dryer, known to those skilled in the art. In this way, the sensitive heat of the gaseous product can be efficiently used in method 10.
    [052] In a representation of method 10, pyrolyzing the carbonaceous material involves introducing a continuous flow of the carbonaceous material into a pyrolysis zone of a gasification reactor. To facilitate a continuous flow of carbonaceous material into the pyrolysis zone and to minimize particle agglomeration, it is preferable to control the moisture content of the carbonaceous material, as described above, and the particle size of the carbonaceous material.
    [053] Pyrolysing the carbonaceous material comprises heating the carbonaceous material, preferably by directly heating the carbonaceous material with a hot gas. The hot gas can be produced in the carbon gasification zone of the gasification reactor and is directed in a direct heat exchange against current with the continuous flow of the carbonaceous material in the pyrolysis zone. The temperature of the hot gas depends on the type of carbonaceous material, and can be in a temperature range of about 900 ° C to about 1200 ° C. The carbonaceous material can undergo simultaneous pyrolysis and partial gasification through reactions with the flow of hot gas.
    [054] In a preferred embodiment, the continuous flow of carbonaceous material progressively descends through the pyrolysis zone over a period long enough to substantially ensure the complete pyrolysis of the carbonaceous material in volatiles and carbon. In one representation, the continuous flow of carbonaceous material descends progressively through the pyrolysis zone by gravity. In an alternative representation, the continuous flow of carbonaceous material descends progressively through the pyrolysis zone by means of a transfer medium, as well as a auger, a screw, a moving bed or a stirring medium associated with a pyrolyzer, as will be described for example with reference to Figure 3.
    [055] After pyrolysis, the volatiles ascend to an aerator reform zone while the carbon descends to an aerator gasification zone. Advantageously, the complete pyrolysis of the carbonaceous material in
    Petition 870180138532, of 10/07/2018, p. 33/54 / 25 volatiles and carbon allows the best separation of volatiles and carbon for the reform zone and carbon gasification zone, respectively, thus minimizing the interactions between volatiles and carbon in the carbon gasification zone. Consequently, the substantial absence of volatiles in the carbon gasification zone facilitates a relative increase in the carbon gasification index compared to state of the art processes. In the substantial absence of volatiles, oxygen is mainly consumed by carbon, facilitating the rapid gasification of carbon, which is normally the determining step of the index. Thus, representations of the present invention increase gasification rates with minimal amounts of oxygen to achieve high gasification efficiency.
    [056] Gasifying carbon comprises introducing gasifying agents, such as steam and an oxygen-containing gas, into the carbon gasification zone and reacting the carbon with the vapor and the oxygen-containing gas.
    [057] In one embodiment of the invention, the oxygen-containing gas introduced into the coal gasification zone may comprise air, pure oxygen or diluted oxygen. Exothermic reactions between oxygen and carbon can be represented with the following simplified reactions:
    C + 1 AO2 CO (1)
    C + O2 CO2 (2) [058] The endometric reaction between steam and carbon can be shown with a simplified reaction:
    C + H2O CO + H2 (3) [059] The amount of gas containing oxygen and / or steam introduced into the carbon gasification zone can be varied, respectively, to control the operating temperature of the carbon gasification zone.
    [060] The required operating temperature can be determined based on the energy balance within the gasification reactor between several
    Petition 870180138532, of 10/07/2018, p. 34/54 / 25 zones, including the catalyst bed for cleaning the gaseous product. In order to achieve high gasification efficiency, the oxygen supply index in the carbon gasification zone is preferably as low as possible.
    [061] In one representation, carbon is substantially consumed in the carbon gasification zone, resulting in the production of hot gas and ash. The ash can be discharged from the carbon gasification zone of the gasification reactor using an ash discharge device, as well as a closed hopper.
    [062] The hot gas resulting from carbon gasification provides a heating source to heat and pyrolyze carbonaceous material in the pyrolysis zone of the gasification reactor, to reform volatiles in the reform zone and to clean the gaseous product in the gas cleaning zone. .
    [063] It should be noted that, in the case of insufficient carbon to balance heat demand, including the start-up mode, part of the gaseous product produced in method 10 could be recycled and burned in the carbon gasification zone or burned in the zone reform.
    [064] Hot gas flows from the carbon gasification zone to the pyrolysis zone and passes in direct heat exchange against the current with the carbonaceous material as it progressively moves through the pyrolysis zone and is pyrolyzed. When the hot gas passes through the pyrolysis zone, the hot gas mixes with the volatiles (including steam) released from the carbonaceous material and flows into the reform zone. In this way, the hot gas helps to separate the volatiles from the carbon produced in the pyrolysis zone.
    [065] Hot gas also satisfies the energy demand for volatile reform endothermic reactions in the reform zone. In the reform zone, volatiles and steam react endothermically to produce a gaseous product. In one representation, the reforming of volatiles with steam in the reform zone is carried out at a temperature ranging from about 700 ° C to about 1000 ° C. Advantageously, therefore, part of the sensitive heat of the hot gas produced in the carbon gasification zone is recovered in chemical energy in the form of the gaseous product.
    Petition 870180138532, of 10/07/2018, p. 35/54 / 25 [066] The excess of gasifying agents in the aforementioned hot gas would come into contact and react with the pyrolizing charge, its volatiles and carbon when they flow upwards.
    [068] The gaseous product produced in the reform zone may contain organic and inorganic contaminants. Examples of contaminants include, but are not limited to, tar residues, NH3, HCN, H2S, and volatilized inorganic AAEM species. A gaseous product that contains contaminants is often called a "crude gaseous product".
    [069] Method 10 conveniently removes organic and inorganic contaminants from the gaseous product.
    [070] In one embodiment of the invention, method 10 further comprises passing the partially reformed volatiles and / or gaseous product through a catalyst bed.
    [071] In one embodiment, the catalyst bed comprises a moving bed of non-isothermal catalyst. In another embodiment, the catalyst bed is a plurality of fluidly interconnected beds arranged in series.
    [072] In one embodiment, the catalyst comprises a transition metal catalyst supported on a substrate of carbonaceous material. This can be produced from pyrolysis and / or partial gasification of the carbonaceous material containing or being impregnated with the metal. Alternatively, the metal can be loaded / impregnated with carbon following methods commonly known to those skilled in the art. In a preferred embodiment, the catalyst comprises Fe and / or Ni supported on carbon. In another representation, the catalyst can be carbon itself. Advantageously, the carbon produced from the biomass pyrolysis contains abundant inherent catalytic species, particularly AAEM species, which are well dispersed within the carbon. Consequently, the carbon produced from the pyrolysis can be used to catalyze the decomposition of tar residues in the gaseous product. In the case of carbon catalysts or supported on carbon, the catalysts can be produced from the pyrolysis of a carbonaceous material in a reactor (eg, moving bed) and then fed into a gas cleaning zone. The carbonaceous material can be the filler (eg, biomass) to be gasified. In another representation
    Petition 870180138532, of 10/07/2018, p. 36/54 / 25 is preferable, the catalyst comprises a steel core (treated) such as ilmenite.
    [073] The catalyst bed can be integral with the gasification reactor and in fluid communication with the reform zone. In certain embodiments in which the catalyst comprises a carbon or carbon-supported catalyst, the spent catalyst can be discharged into the carbon gasification zone of the gasification reactor and subsequently gasified. Thus, no flow of solid or liquid waste arises from the treatment of the contaminated gaseous product as described above.
    [074] Passing partially reformed volatiles and / or the gaseous product through a catalyst bed removes inorganic contaminants from them. Volatilized AAEMs condense on the surface of the solid catalyst at an appropriate temperature, and the particulates are also trapped by the catalyst bed. Other inorganic contaminants such as NH3, H2S and other compounds containing N, CI or S are decomposed or absorbed through contact with the solid catalyst. In this way, inorganic contaminants like AAEMs are captured in the catalyst. Advantageously, AAEMs increase carbon reactivity in the carbon gasification zone. Therefore, method 10 provides a means by which volatile inorganic contaminants generated from low-grade carbonaceous materials can be conveniently used to increase carbon gasification. AAEMs subsequently report to ash.
    [075] Passing partially reformed volatiles and / or gaseous product through the catalyst bed also removes organic contaminants, such as tar residues, by catalyzed reform reactions, eg with steam. This advantageously recovers thermal energy (sensitive heat) in the chemical energy of the reform products. Some tar residues are also removed by coke forming on the surface of the solid catalyst. In addition, the hydrogen content of the gaseous product can be increased by passing the gaseous product through the catalyst bed (s), because at the lower temperature end of the catalyst bed a water displacement reaction and gas (CO + H2O CO2 + H2) is favored.
    Petition 870180138532, of 10/07/2018, p. 37/54 / 25 [076] The passage of partially reformed volatiles and / or gaseous product through the catalyst bed can be carried out at a temperature limit of about 1000 ° C to about 200 ° C. Preferably, the temperature of the catalyst bed decreases progressively to about 200 ° C in the direction of the gas flow.
    [078] The gasification system 20 and an apparatus 30 for pyrolyzing carbonaceous material for use in the gasification system 20 will now be described with reference to Figures 2 and 3.
    [079] The gasification system 20 comprises a gasification reactor 21 having four reaction zones integrally defined therein, namely a pyrolysis zone 22, a carbon gasification zone 23, a reform zone 25, and a catalyst bed 26. The pyrolysis zone 22 is in fluid communication with the carbon gasification zone 23 and the reform zone 25.
    [080] In general the gasification reactor 21 is a vertical side reactor having a substantially constant cross-sectional area and substantially along its entire length and / or along a direction of material and / or fluid flow. Where it is advantageous to vary the residence time of the material and / or fluid in the reactor 21, and depending on the compositional characteristics of the carbonaceous material, the cross-sectional area of the reactor 21 can be varied along its length and / or along the direction material and / or fluid flow. Preferably, reactor 21 is coated with refractory.
    [081] An upper part of the gasification reactor 21 is provided with an inlet 28a for the introduction of a continuous flow of carbonaceous material such as biomass through a feeder 28. The feeder 28 is in fluid communication with the inlet 28a of the reactor, and preferably comprises a rotary feeder to minimize blocking problems. The feeder 28 preferably also comprises a stirrer associated with a hopper for storing biomass. The agitator is positioned to minimize the potential for biomass binding in the hopper.
    [082] The pyrolysis zone 22 is provided with an apparatus 30 (see Figure 3) for pyrolyzing carbonaceous material. Any suitable pyrolyzer such as those already known to those skilled in the art can be employed.
    Petition 870180138532, of 10/07/2018, p. 38/54 / 25
    Illustrative examples of suitable pyrolyzers include, but are not limited to, mobile beds, screw / auger / oven pyrolysers, and a combination thereof.
    [083] Apparatus 30 can be configured to facilitate the transfer of carbonaceous material progressively through the pyrolyzer to the carbon gasification zone, either by gravity or by mechanical transfer. Preferably, apparatus 30 is adapted to retain the carbonaceous material in the pyrolysis zone for a sufficiently long period to substantially convert the carbonaceous material to carbon and volatiles.
    [084] In the representation shown in Figure 2, the pyrolysis zone 22 is provided with the apparatus 30 to heat carbonaceous material with a heated gas derived from the carbon gasification zone 23 to produce volatiles and carbon. Apparatus 30 is shown in more detail in Figure 3.
    [085] In a preferred form, the apparatus 30 is spaced from the carbon gasification zone 23 and the reform zone 25 to facilitate the effective separation of the carbon and resulting volatiles produced in the apparatus 30.
    [086] Apparatus 30 includes three pairs of conical surfaces 32, 34, 36. It should be noted that the number of these conical surfaces can vary. The pairs of conical surfaces 32, 34, 36 are spaced from each other and placed in longitudinal alignment spaced along the length of a rotary axis 31. Each pair of conical surfaces 32, 34, 36 comprises an upper inverted conical surface 32a, 34a .36a spaced from an opposing lower vertical tapered surface 32b, 34b, 36b.
    [087] Preferably the pairs of conical surfaces 32, 34, 36 comprise perforated metal sheets suitable for the passage of heat, and in particular hot gas through them. The metal sheets also function as effective heat conductors for direct heating of the carbonaceous material.
    [088] The lower vertical tapered surfaces 32b, 34b, 36b are provided with an opening 32c, 34c, 36c concentrically arranged around axis 31. The purpose of opening 32c, 34c, 36c is to provide the passage of the carbonaceous material from the tapered surfaces lower vertical
    Petition 870180138532, of 10/07/2018, p. 39/54 / 25
    32b, 34b, 36b for the upper inverted conical surfaces 34a, 36a and the carbon gasification zone 23 disposed immediately below.
    [089] Additionally, the diameter of the upper inverted conical surface 32a, 34a, 36a is less than the diameter of the opposite lower vertical conical surface 32b, 34b, 36b. In this way, the carbonaceous materials residing on the upper inverted conical surface 32a, 34a, 36a can slide off the edge of said surface and fall on the opposite lower vertical conical surface 32b, 34b, 36b disposed immediately below.
    [090] Apparatus 30 also includes one or more stirring means 32d, 34d, 36d associated with each respective pair of conical surfaces 32, 34, 36. It should be noted that the number of stirring means need not be equal to the number of pairs of conical surfaces. The stirring means 32d, 34d, 36d in this particular embodiment are rotating arms. The rotating arms are spaced a short distance (eg, 2-5 mm) above the upper inverted conical surfaces 32a, 34a, 36a and / or above the lower opposite vertical conical surfaces 32b, 34b, 36b. The stirring means 32d, 34d, 36d are operable by rotating the rotary axis 31. The rotational speed of the axis 31 can vary, depending on the characteristics of the carbonaceous material, to control the residence time of the particle in the pyrolysis zone. In one example, the rotating arms rotate at a speed of 12 rpm.
    [091] The rotation of the rotary axis 31 causes the stirring means 32d, 34d, 36d to disassemble particles of carbonaceous material residing on the lower vertical conical surfaces 32b, 34b, 36b and causes them to pass through the respective openings 32c, 34c , 36c for the respective openings 32c, 34c, 36c for the inverted conical surfaces immediately below them. Similarly, the rotation of the rotary axis causes the agitation means 32d, 34d, 36d to disassemble particles of carbonaceous material residing on the upper inverted conical surfaces 32a, 34a, 36a and causes them to slide and fall off the edge of said surfaces and are collected on the lower vertical tapered surface 32b, 34b, 36b immediately below them.
    [092] The rotation speed of the shaft can be changed to vary the residence time of the carbonaceous material residing on the conical surfaces
    Petition 870180138532, of 10/07/2018, p. Upper inverted 40/54 / 25 32a, 34a, 36a and lower vertical tapered surfaces 32b, 34b, 36b. In this way, the residence time of the carbonaceous material in the apparatus 30 can be controlled to allow a sufficient period for the carbonaceous material to be substantially converted into carbon and volatiles.
    [093] The slope of the conical surfaces can be varied to control the length of time that the particles of carbonaceous material reside on said surfaces. Alternatively, the conical surfaces can be rotated with respect to the stirring means.
    [094] Other suitable means already known to control the residence time of the carbonaceous material in the apparatus 30 to substantially promote the complete pyrolysis of the carbonaceous carbon and volatile material can also be employed in the process and apparatus of the present invention. In addition to the pyrolysis reactions, the charge may also undergo some gasification extensions inside the device 30.
    [095] The carbon gasification zone 23 is placed in a lower part of the reactor 21. The carbon gasification zone 23 can be supplied with one or more fixed beds or mobile beds with grids to support the carbon at the same time allows oxygen-containing gas and steam to pass through the moving bed (s) and react with the carbon. Alternatively, the carbon gasification zone 23 can be provided with a bubbling fluidized bed and a gas distributor to supply gas containing oxygen and steam.
    [096] In the representation shown in Figure 2, the carbon is gasified in a fixed bed with a conical shape. The reactor 21 is provided with an oxygen-containing gas inlet 23a and a steam inlet 23b. It is anticipated that air would generally be used for small scale applications, as well as biomass gasification, and that pure or diluted oxygen would be used for large scale applications, as well as carbon gasification, particularly when capturing and storing dioxide. carbon dioxide are intended or when the gaseous product is used to synthesize liquid fuels and chemicals.
    [097] The carbon gasification zone 23 is also provided with an ash discharge device 24, as well as a closed hopper.
    Petition 870180138532, of 10/07/2018, p. 41/54 / 25 [098] The reform zone 25 is placed in an upper part of the reactor 21 and comprises a void defined by the upper part of the reactor 21 in which the gas reform reactions between volatiles and steam can happen.
    [099] Reform zone 25 is in fluid communication with a catalyst bed 26. Preferably the catalyst bed 26 is a solid catalyst moving bed or a series of catalyst beds. In one embodiment, the arrangement of the moving bed is such that the spent catalyst is discharged into reactor 21. Therefore, the catalyst bed 26 is provided with a solid catalyst discharge device 26a to continuously replenish the moving solid catalyst bed at the as the catalyst is discharged from the catalyst bed 26. The catalyst bed 26 is provided with an outlet 27 for the removal of the gaseous product.
    [100] The solid catalyst in the catalyst bed can take many forms. Transition metal catalysts (eg, Fe and / or Ni) supported on carbon are preferable representations, which can be produced by the pyrolysation and partial gasification of a carbonaceous material (eg, biomass or brown coal) loaded with transition metals ( Fe and / or Ni). Carbon itself, without charged metals, can be the catalyst. Alternatively, ilmenite, an iron ore, can also be used as the solid catalyst.
    [101] Figure 4 shows a representation of a system 40 for producing gaseous and carbon product from a carbonaceous material, in particular biomass. System 40 is for use with representations of method 10 which comprises the additional step of exposing the partially reformed gaseous and / or volatile product to carbon. The carbon produced by method 10 can be used as activated carbon or as an organic soil corrector and / or for fixing carbon.
    [102] In this example, a load of carbonaceous material with a moisture content of up to 60% in storage 50 is fed into a dryer 52 where the moisture in the load is reduced, preferably to a moisture content below 20%. The heat produced by other process steps can be used as a heating medium for the dryer 52.
    Petition 870180138532, of 10/07/2018, p. 42/54 / 25 [103] The partially dried cargo is then fed into the pyrolyzer 54 where the cargo is heated to produce carbon and volatiles. The inventors have demonstrated that pyrolysis of the dry charge at a moderate temperature, as well as from about 450 ° C to about 550 ° C, would release a substantial part of the volatile potentials of the load. In addition, under moderate pyrolysis temperatures, inorganic species, as well as AAEM species, tend to get trapped in carbon. The retention of inorganic species in carbon is particularly beneficial because it increases the catalytic activity of carbon and facilitates the recycling of inorganic nutrients back to the soil in instances where biomass can be used as the filler and the resulting carbon is used as an organic corrective from soil.
    [104] Pyrolyzer 54 can be configured to facilitate the transfer of carbon from pyrolyzer 54 to a reactor 60, either by gravity or mechanical transfer means.
    [105] Before transferring the carbon to reactor 60, the carbon can be transferred and temporarily held in a storage chamber (not shown) that is in fluid communication with reactor 60. The storage chamber can be supplied with a control means to control a carbon flow rate to reactor 60.
    [106] After pyrolysis, the volatiles are directed to a gas reformer 56. The gas reformer 56 is heated and a desired amount of steam generated in the dryer 52 is introduced together with a gas containing oxygen (O2), as well as oxygen or air, in the gas reformer 56 through respective inlets 56a and 56b where volatiles undergo gas reform reactions to produce a crude gaseous product largely comprising CO and H2.
    [107] A portion of the crude gas and / or carbon product can be directed, as indicated by dotted lines 54a and 56c, to a combustion 58 for combustion to produce a high temperature gas that can be used to heat the gas reformer 56 and reactor 60.
    [108] The crude gaseous product produced in gas reformer 56 is introduced into reactor 60 which also retains the carbon produced in pyrolyzer 54. Reactor 60 is heated to a temperature of up to 900 ° C and the carbon in it behaves like a solid catalyst to decompose
    Petition 870180138532, of 10/07/2018, p. 43/54 / 25 catalytically tar residues contained in the crude gaseous product to form CO, H2 and other combustible gases. Some tar residues are also removed by the formation of coke on the carbon surface. Other inorganic contaminants are also removed from the crude gaseous product by carbon. For example, species released from AAEM and inorganic particulates can also be apprehended by carbon and other inorganic contaminants such as NH3, H2S and other compounds containing N, CI or S are decomposed or absorbed through contact with carbon. In this way, inorganic contaminants like AAEMs are captured in the carbon. Advantageously, AAEMs increase carbon reactivity.
    [109] The crude gaseous product may contain excessive steam and the operating conditions in reactor 60 are such that when the crude gaseous product is brought into contact with the carbon in reactor 60, the carbon may be partially gasified.
    [110] Partial carbon gasification in reactor 60 should preferably be carried out at a temperature of about 700 ° C to about 900 ° C. Advantageously, these temperatures promote the formation of catalytically active sites on carbon for the decomposition of tar residues and carbon activation.
    [111] After partial gasification, the spent carbon produced by the process of the present invention has a large surface area, typically above 700 m2 per gram of carbon. Some possible pollutants (eg, organic) on carbon are also removed in the partial gasification process. Importantly, above this temperature limit, the AAEM species inherent in carbon are transformed into more leachable forms, which facilitates the recycling of inorganic nutrients to the field.
    [112] The spent carbon discharged from reactor 60 is stored in a container 64. The spent carbon contains abundant species of AAEM and other inorganic nutrients, and can be easily returned to the soil as an organic soil corrective. Recycling carbon in this way has two important advantages: (1) the return of inorganic nutrients in carbon to the field, and (2) the sequestration of carbon, thus reducing carbon emissions in relation to power generation. These factors are important for the
    Petition 870180138532, of 10/07/2018, p. 44/54 / 25 long-term sustainable development of rural and regional communities.
    [113] The relative amounts of carbon and gas product produced by method 40 (i.e., carbon-to-gas product index) can be varied. In one embodiment, reactor 60 comprises a partial gasification zone and a complete gasification zone. The partial gasification zone of reactor 60 is operated under conditions in which carbon is partially gasified to produce gaseous product and spent carbon, while the complete gasification zone of reactor 60 is operated under conditions in which carbon is carbonated to produce gas. and ashes. Where a large volume of clean gaseous product is required, a greater relative proportion of carbon needs to be transferred to the complete gasification zone of reactor 60. Alternatively, where a greater volume of spent carbon is required, a greater relative proportion of carbon may be transferred to the partial gasification zone of reactor 60.
    [114] System 20 or 40 can be provided with means to establish, maintain and / or vary the temperature distribution inside the gasification reactor. Such means may include controllers to control the feed rates for gas containing oxygen and / or steam. For example, in order to increase the temperature in the carbon gasification zone, more gas containing oxygen can be supplied to promote exothermic reactions with carbon in it.
    [115] In some representations, system 20 or 40 further comprises a plurality of sensors and probes for sampling gas and solids.
    [116] As described in detail above, representations of the present invention provide an efficient method of gasification, especially for low-grade carbonaceous materials, to manufacture relatively high-quality gaseous products for purposes such as electricity generation, heat production and chemical synthesis.
    [117] Representations of the present invention also provide solid catalysts capable of removing tar residues, other contaminants and pollutant-forming species from the gaseous product stream as well as capable of increasing the hydrogen content in the gaseous product.
    Petition 870180138532, of 10/07/2018, p. 45/54 / 25 [118] It can be seen that the sensitive heat of the gaseous product can be efficiently used in an indirect heat exchange with other process flows in the present invention, such as steam, before these flows are introduced into the carbon gasification. Alternatively, the sensitive heat of the gaseous product can be used to dry the carbonaceous material before undergoing gasification.
    [119] In some representations, particularly in the mode of initialization of the gasification method 10, the gaseous product may be subjected to combustion in the carbon gasification zone to raise the operating temperature therein and / or subjected to combustion in the reform zone to raise the temperature in it.
    [120] It can also be noted that while the previous description refers to specific sequences of steps in the method, parts of systems, mechanisms and equipment and their configuration are provided for illustrative purposes only and are not intended to limit the scope of the present invention to any form.
    [121] Representations of the present invention could increase the efficiency of gasification. The technology can be used appropriately in, for example, energy and chemical industries. In particular, the inventors propose that representations of the present invention are suitable for generating distributed force using relatively wide particle size distribution biomass.
    [122] Advantageously, method 10 integrates pyrolysis, volatile reform, carbon gasification and the cleaning of the gaseous product to give a compact gasifier configuration to improve the efficiency and economy of the process.
    [123] It is clear to any person skilled in the art that some representations of the present invention can provide advantages over the state of the art including, but not limited to, the following:
    - provide a gasification process, especially for gasifying low-quality carbonaceous materials that can be carried out in a single gasification reactor integrating gasification and cleaning with hot gas;
    Petition 870180138532, of 10/07/2018, p. 46/54 / 25
    - minimize the interactions between volatiles and carbon during carbon gasification, leading to a higher carbon gasification index;
    - minimize direct oxygen consumption by volatiles and their reform products;
    - promote the direct reaction of carbon with oxygen in the carbon gasification zone to generate the heat necessary for various reactions inside the gasification reactor, thus recovering the thermal energy of the carbon gasification products in the form of chemical energy as the gaseous product ;
    - minimize total oxygen consumption to maximize gasification efficiency;
    - minimize the amount of tar residues in the gaseous product, a problem that commonly arises in the gasification of low-quality carbonaceous materials, reforming tar residues with a catalyst;
    - minimize the volatilization of inorganic species, in particular AAEMs, which are common in low-grade carbonaceous materials;
    - removing volatile AAEMs and pollutant-forming impurities such as NH3, HCN and H2S with the catalyst;
    - the spent catalyst must be discharged, as a form of disposal, into the carbon gasification zone and oxidized gasification, thus contributing to the production of thermal energy in the reactor without generating an additional flow of liquid or solid waste;
    - the catalyst can be used to promote the reaction of displacement of water and gas thus increasing the hydrogen content of the final product without the conventional problems associated with deactivation, regeneration and disposal of the catalyst.
    [124] Numerous variations and modifications will appear to specialists in the field, in addition to those already described, without departing from the basic inventive concepts. All such variations and modifications must be considered within the scope of the present invention, the nature of which must be determined from the previous description. For example, it should be noted that representations of this invention are capable of being practiced and performed in a variety of ways both on a small (few megawatts or less) and large (a few hundred megawatts) scale.
    Petition 870180138532, of 10/07/2018, p. 47/54 / 25 [125] In describing this invention, except where the context requires otherwise due to the express language or necessary implication, the terms "understand" or variations like "understand" or "understanding" are used in an inclusive sense, ie, to specify the presence of established aspects, but not to prevent the presence or addition of other aspects in various representations of the invention.
    权利要求:
    Claims (21)
    [1]
    1. Method for aerating carbonaceous material (10), the method comprising the steps of:
    pyrolysis of carbonaceous material to produce volatile and carbon products (12);
    separating carbon and volatiles (14);
    gasifying carbon (16);
    reforming volatiles to produce a gaseous product (18); and, passing partially reformed volatiles and / or gaseous product (19) through a gaseous product cleaning zone;
    characterized by at least the steps of pyrolysis of the carbonaceous material (12), carbon gasification (16), and reforming of the volatiles to produce a gaseous product (18) are carried out in a reactor (21) that has a pyrolysis zone (22) , a carbon gasification zone (23), and a reform zone (25), so that after pyrolysis (12), the volatiles go up to the reform zone (25) and the coal goes down to the gasification zone ( 23);
    whereby the gaseous product cleaning zone comprises at least one catalyst bed (26); and, therefore, the gaseous product cleaning zone is in fluid communication with the reforming zone (25) in an arrangement whereby partially reformed volatiles and / or gaseous products pass through the gaseous product cleaning zone.
    [2]
    2/4
    Method (10) according to claim 1, characterized in that the pyrolysis step of carbonaceous material (12) is carried out using a pyrolysis apparatus.
    [3]
    3/4 react the coal with a controlled amount of an oxygen-containing gas.
    Method (10) according to claim 1 or 2, characterized in that the catalyst bed comprises a mobile bed of solid catalyst.
    [4]
    4/4
    Method (10) according to any one of claims 1 to 3, characterized in that the gaseous product cleaning zone comprises a plurality of catalyst beds (26) arranged in series.
    [5]
    Method (10) according to any one of claims 1 to 4, characterized in that the catalyst bed (26) comprises coal, a catalyst supported on coal or ilmenite.
    Petition 870180138532, of 10/07/2018, p. 49/54
    [6]
    Method (10) according to claim 5, characterized in that when the catalyst bed (26) comprises coal or catalyst supported on coal, the coal or catalyst supported on coal is prepared from pyrolysis and / or partial gasification of carbonaceous material.
    [7]
    Method (10) according to claim 5, characterized in that the method (10) further comprises discharging spent coal or coal based catalyst from the catalyst bed (26) and gasifying (16) the spent coal or catalyst based of coal.
    [8]
    Method (10) according to any one of claims 1 to 7, characterized in that the partially reformed volatiles and / or gaseous product pass through the catalyst bed (26) to remove contaminating products therefrom.
    [9]
    Method (10) according to claim 8 characterized in that the inorganic contaminants comprise alkali or alkaline earth metal species or particulates.
    [10]
    Method (10) according to claim 9, characterized in that the contaminants further comprise compounds containing N-, S- or Cl-.
    [11]
    Method (10) according to any one of claims 1 to 10, characterized in that the partially reformed volatiles and / or gaseous products pass through the catalyst bed (26) to remove organic contaminants from it by catalyst reform reactions, where contaminants comprise tar residues.
    [12]
    Method (10) according to any one of claims 1 to 11, characterized in that the pyrolysis step of the carbonaceous material comprises heating the carbonaceous material with a counter-flow of hot gas.
    [13]
    Method (10) according to claim 12, characterized in that the hot gas is produced in the carbon gasification zone (23).
    [14]
    Method (10) according to claim 12, characterized in that the hot gas is produced from the gaseous combustion product in a carbon gasification zone (23) or reform zone (25).
    [15]
    Method (10) according to any one of claims 1 to 14, characterized in that the gasification step of the coal (16) comprises in
    Petition 870180138532, of 10/07/2018, p. 50/54
    [16]
    16. Gasification system (20) for carrying out the method of gasifying a carbonaceous material as defined in claim 1, where the gasification system (20) comprises:
    a reform zone (25) for reforming volatiles to produce a gaseous product (18);
    a coal gasification zone (23) for gasifying coal (16);
    a pyrolysis zone (22) for pyrolysis of carbonaceous material, the reform zone (25) and the coal gasification zone (23) being placed in between, the pyrolysis zone (22) being in fluid communication with the reform zone (25) and the coal gasification zone (23) in an arrangement in which the volatiles and coal formed in the pyrolysis zone (22) are separated and directed so that the volatiles rise into the reform zone (25) and the coal goes down to the coal gasification zone (23), respectively; and, a gaseous product cleaning zone in fluid communication with the reform zone (25), in an arrangement in which the partially reformed volatiles and / or gaseous product pass through the gaseous product cleaning zone;
    characterized in that the gasification system (20) comprises a reactor (21) having the reform (25), coal gasification (23), and pyrolysis (22) zones defined therein, and the gaseous product cleaning zone at least one catalyst bed (26).
    [17]
    System (20) according to claim 15, characterized in that the pyrolysis zone (22) comprises a pyrolysis apparatus.
    [18]
    System (20) according to claim 16 or 17, characterized in that the coal gasification zone (23) is arranged in a lower portion of the gasification reactor (21).
    [19]
    System (20) according to any one of claims 16 to 18, characterized in that the reforming area (25) is arranged in an upper portion of the gasification reactor (21).
    Petition 870180138532, of 10/07/2018, p. 51/54
    [20]
    System (20) according to any one of claims 16 to 19, characterized in that a part of the coal formed in the pyrolysis zone (22) is separated from the remaining carbonaceous material as a gas cleaning catalyst and directed to the cleaning of gaseous product.
    [21]
    21. System (20) according to one of claims 16 to 20, characterized in that the gasification system (20) is provided with a carbon storage zone arranged between the pyrolysis zone (22) and the product cleaning zone gas, and a control system associated with it, the control system being arranged, in use, to control the flow rate of coal to the cleaning zone of the gaseous product.
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    同族专利:
    公开号 | 公开日
    CA2806344A1|2012-02-02|
    CN103119135A|2013-05-22|
    SG187594A1|2013-03-28|
    CN103119135B|2017-06-30|
    BR112013001807A2|2016-05-31|
    JP6321375B2|2018-05-09|
    AU2011284780A1|2013-03-14|
    CN107254332A|2017-10-17|
    NZ607367A|2015-03-27|
    AU2011284780B2|2015-06-18|
    US20130306913A1|2013-11-21|
    US20150191664A1|2015-07-09|
    WO2012012823A1|2012-02-02|
    CN107254332B|2020-06-26|
    CA2806344C|2019-03-12|
    JP2013532742A|2013-08-19|
    ES2708356T3|2019-04-09|
    EP2598616A4|2014-04-09|
    US10144887B2|2018-12-04|
    EP2598616A1|2013-06-05|
    EP2598616B1|2018-10-31|
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    法律状态:
    2018-07-10| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-04-02| B09A| Decision: intention to grant|
    2019-05-21| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/07/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/07/2011, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    AU2010903348A|AU2010903348A0|2010-07-27|Method and Apparatus for Gasification|
    AU2010903348|2010-07-27|
    AU2010905356|2010-12-06|
    AU2010905356A|AU2010905356A0|2010-12-06|Process and apparatus for the gasification of carbonaceous material|
    PCT/AU2011/000936|WO2012012823A1|2010-07-27|2011-07-26|A method of gasifying carbonaceous material and a gasification system|
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