method and system for the production of synthesis gas

专利摘要:
METHOD AND SYSTEM FOR THE PRODUCTION OF SYNTHESIS GAS. A method of producing synthesis gas is provided by introducing a feed material to be gasified in a gasification apparatus comprising at least one fluidized component that can be operated as a fluidized bed, wherein the gasification apparatus is configured to convert at least one portion of the feed material in an aerator product gas comprising synthesis gas; and maintaining fluidization of at least one fluidized component by introducing a fluidizing gas therein, wherein the fluidizing gas comprises at least one component other than steam. A system for producing synthesis gas is also provided.
公开号:BR112014009997A2
申请号:R112014009997-9
申请日:2012-10-15
公开日:2020-12-01
发明作者:Weibin Jiang；Bruce E Mccomish；Bryan C Borum；Benjamin H Carryer；Mark D Ibsen；Mark K Robertson；Eric R Elrod；Sim Weeks；Harold A Wright
申请人:Rentech, Inc.；
IPC主号:

专利说明:

[0001] [0001] Not applicable i BACKGROUND: Field of the Invention
[0002] [0002] This description generally relates to the gasification field. More specifically, the description concerns a system and method for the production of synthesis gas by gasifying carbonaceous materials. Even more specifically, the system and method described provide better gasification of carbonaceous materials by incorporating alternative gasifier fluidizing gas in place of, or in addition to, steam. Fundamentals of the Invention
[0003] [0003] Gasification is used to produce process gas suitable for the production of various chemicals, for the production of Fischer-Tropsch liquid hydrocarbons and for the production of energy. Many feed materials can serve as carbonaceous sources for gasification, including, for example, chopped bark, wood chips, sawdust, sludge (for example, sewage sludge), municipal solid waste (MSW), waste-derived fuel (RDF) and a variety of other carbonaceous materials.
[0004] [0004] Fischer-Tropsch synthesis (FT) represents a catalytic method for the creation of synthetic liquid fuels. The reaction occurs by the metal catalysis of an exothermic reaction between carbon monoxide and hydrogen gas in mixtures known as synthesis gas, or "synthesis gas". The liquid product of the reaction is typically refined to produce a range of synthetic fuels, lubricants and waxes. The main metals used as catalysts are cobalt and iron. The supply of synthesis gas having a desired molar ratio of hydrogen to carbon monoxide is necessary for the economical production of Fischer-Tropsch synthesis products.
[0005] [0005] A concern in the production of syngas by means of gasification is its moisture content. For example, excessive amounts - of water vapor in the gas of gasification products can be undesirable for numerous end uses of syngas, such as, but not limited to, Fischer-Tropsch synthesis, power generation and the production of chemicals not Fischer-Tropsch
[0006] [0006] In this way, there is a need in technology for better gasification systems and methods, while gas produced anywhere in gasification can be used as an advantage as a fluidizing gas for a fluidized bed pyrolyzer, thus reducing the amount of vapor required from this. Desirably, such better systems and methods make it possible to use an alternative gasifier fluidization gas that can (for example, exhaust gas) or cannot (for example, product synthesis gas) in any way be considered a waste product. , the use of alternative gas makes it possible to produce additional synthesis gas from it, the use of alternative gas alters the composition (for example, the ratio of hydrogen to carbon monoxide in the synthesis gas produced from it) of the product gas of the resulting gasifier in a desirable manner, or some combination of these. SUMMARY
[0007] [0007] A method of producing synthesis gas is described herein, the method comprising: introducing a feed material to be gasified in a gasification apparatus comprising at least one fluidized component which can be operated as a fluidized bed, in which the apparatus gasification is configured to convert at least a portion of the feed material into an aerator product gas comprising synthesis gas; and maintaining fluidization of at least one fluidized component by introducing a fluidizing gas therein, wherein the fluidizing gas comprises at least one component other than steam. In embodiments, the fluidizing gas comprises less than about 100, 90, 80, 70, 60, 50, 40, 30, 20, or 10 percent by volume of steam. In modalities,. the fluidizing gas substantially comprises vapor volume percent. At least one component can be selected from the group consisting of natural gas, flue gas, synthesis gas, LP flue gas, Fischer-Tropsch exhaust gas, product heavy oil processor synthesis gas, exhaust gas VSA, PSA exhaust gas, exhaust gas, CO2-rich gas, dry wind gas, combustion air, oxygenates and combinations thereof.
[0008] [0008] In modalities, the method still comprises producing at least one component downstream of the gasification apparatus. The method may further comprise conditioning the gas product of the aerator to provide a conditioned synthesis gas having a molar ratio of hydrogen to carbon monoxide that is different from the molar ratio of hydrogen to carbon monoxide in the gas of the aerator product, an amount reduced by at least one component with respect to the amount of the component in the aerator product gas, or both. The method may further comprise separating hydrogen from at least a portion of the conditioned synthesis gas to provide a separate hydrogen stream and a reduced hydrogen gas and using at least a portion of the reduced hydrogen gas as the fluidizing gas. The method may further comprise converting at least a portion of the conditioned synthesis gas to Fischer-Tropsch hydrocarbons by means of Fischer-Tropsch synthesis and updating at least a portion of the Fischer-Tropsch hydrocarbons by reaction with at least a portion of the separate hydrogen stream. In embodiments, conditioning of the aerator product gas comprises introducing at least a portion of the aerator product gas into a synthesis gas conditioner configured to change the molar ratio of hydrogen to carbon monoxide in the aerator product gas. The syngas conditioner may comprise a partial oxidation reactor. The partial oxidation reactor can be configured for operation a. a temperature in the range of about 900 ° C to about 1500 ° C, from about 1000 ° C to about 1300 ° C, or from about 1150 ° C to about 1250 ° C. The method may also comprise producing oxygen-enriched air to introduce into the partial oxidation reactor, while producing oxygen-enriched air produces a nitrogen-rich product and uses at least a portion of the nitrogen-rich product as a gasifier fluidization gas. In modalities, production of oxygen-enriched air comprises adsorption by vacuum oscillation.
[0009] [0009] In embodiments, the method further comprises conditioning the gas product from the aerator to provide a conditioned synthesis gas having a molar ratio of hydrogen to carbon monoxide that is different from the molar ratio of hydrogen to carbon monoxide in the product gas of the gasifier, a reduced amount of at least one component with respect to the amount of the component in the gasifier product gas, or both and conditioning synthesis gas comprises reforming at least a portion of the synthesis gas, thereby producing a conditioned synthesis gas having an altered molar ratio of hydrogen to carbon monoxide with respect to the molar ratio of hydrogen to carbon monoxide in the gas product of the gasifier.
[00010] [00010] In embodiments, the method further comprises conditioning the gas product of the aerator to provide a conditioned synthesis gas having a molar ratio of hydrogen to carbon monoxide that is different from the molar ratio of hydrogen to carbon monoxide in the product gas gasifier, a reduced amount of at least one component with respect to the amount of the component in the gasifier product gas, or both and conditioning synthesis gas comprises extracting a carbon dioxide-rich flue gas from at least a portion of the gas gasifier product and the method further comprises using at least a portion of the flue gas rich in. carbon dioxide as a fluidizing gas. Extraction of a carbon dioxide-rich flue gas from at least a portion of the aerator product gas may comprise introducing at least a portion of the aerator product gas into a carbon dioxide removal unit. The carbon dioxide removal unit can operate through pressure differentiation. In modalities, the carbon dioxide removal unit is a pressure swing adsorption unit (PSA).
[00011] [00011] In modalities, at least one component is produced downstream of the gasification apparatus and the method further comprises converting at least a portion of the synthesis gas into Fischer-Tropsch hydrocarbons by means of Fischer-Tropsch synthesis. The method may further comprise subjecting at least a portion of the Fischer-Tropsch hydrocarbons to heavy product oil processing, wherein heavy product oil processing produces a heavy oil processing exhaust gas from the product and uses at least a portion of the product's exhaust gas from heavy oil processing as a fluidizing gas. In embodiments, at least one fluidized component comprises a fluidized bed gasifier and at least a portion of the product's heavy oil processing exhaust gas is introduced as a gasifier fluidizing gas.
[00012] [00012] In modalities, at least one component is produced downstream of the gasification apparatus, the method still comprises converting at least a portion of the synthesis gas into Fischer-hydrocarbons
[00013] [00013] In modalities, at least one component is produced downstream of the gasification apparatus, the method further comprises converting at least a portion of the synthesis gas into Fischer-Tropsch hydrocarbons by means of Fischer-Tropsch synthesis, the synthesis of Fischer-Tropsch is associated with the production of a Fischer-Tropsch waste water comprising oxygenates and the method further comprises removing oxygenates from at least a portion of the Fischer-Tropsch waste water by contacting it with steam, to produce a steam containing oxygenated and a residual water of Fischer-Tropsch reduced in oxygenated and using at least a portion of the vapor containing oxygenated as a fluidizing gas.
[00014] [00014] In modalities, at least one component is produced downstream of the gasification apparatus and the method still comprises converting. at least a portion of the synthesis gas in Fischer-Tropsch hydrocarbons by means of Fischer-Tropsch synthesis, a hydrocarbon-containing purge gas is extracted during Fischer-Tropsch synthesis and at least a portion of the hydrocarbon-containing purge gas is used as fluidizing gas.
[00015] [00015] In modalities, at least one component is produced upstream of the gasification apparatus. At least one component can comprise natural gas. The method may further comprise drying at least a portion of the feed material to reduce its moisture content prior to introduction into the gasification apparatus. Drying at least a portion of the feed material may further comprise bringing at least a portion of the feed material into contact with a drying medium to provide the gasifier feed material with reduced humidity and a dry wind gas comprising volatile organic compounds (VOC's). The method may further comprise using at least a portion of the dry wind gas as the fluidizing gas. In embodiments, the drying medium comprises superheated steam.
[00016] [00016] In embodiments, the gasification apparatus comprises a double fluidized bed gasifier comprising a fluidized bed pyrolyzer fluidly connected with a fluidized bed combustor, such that a circulating stream comprising a heat transfer material can be continuously circulated between the pyrolyzer, in which the circulating stream temperature is reduced by means of endothermic pyrolysis and the fluidized bed combustion, in which the circulating stream temperature is increased and in which the fluidized bed combustor can be operated to increase the temperature of the circulating stream by combustion of at least coal introduced into it with the circulating stream. In embodiments, combustion in the combustion produces a combustion combustion gas and the method further comprises + using at least a portion of the combustion combustion gas as fluidizing gas. The gasifier feed material can be introduced into the pyrolyzer from a feed box configured for storing gasifier feed material and the method can further comprise introducing at least a portion of the combustion gas from the combustion gas into the feed box, while contacting direct combustion gas from the combustion gas with the gasifier feed material provides a dry gasifier feed material to introduce into the pyrolyzer and a feed gas opening gas and the method may further comprise using at least a portion of the opening gas of the supply box as fluidizing gas. In embodiments, combustion in the combustion is carried out by introducing hot combustion air into it and the method further comprises using a portion of the hot combustion air as a fluidizing gas for at least one other component of the double fluidized bed gasifier in addition to the fluidized bed.
[00017] [00017] In modalities, the gasification apparatus comprises a pyrolyzer that can be operated at low pressure (for example, less than 172.3 or 344.7 kPa man., Or in the range of 172.3 to 344.7 kPa man .) and at least one component comprises low pressure flue gas (LP) (for example, having a pressure less than 172.3 or 689.4 kPa man., or in the range of 172.3 to 689.4 kPa man .).
[00018] [00018] In embodiments, the method further comprises using at least a portion of the gasifier product gas to produce energy, using at least a portion of the gasifier product gas in a catalytic operation downstream of the gasification apparatus, or both.
[00019] [00019] In embodiments, the method further comprises obtaining a desired molar ratio of hydrogen to carbon monoxide in the gas of the gasifier product by adjusting the amount, composition, or both the amount and composition of at least one component of the non-fluidizing gas steam.
[00021] [00021] In modalities, the method also comprises performing vacuum oscillation adsorption (VSA), pressure oscillation adsorption (PSA), or both, downstream of the gasification apparatus, thus producing at least one exhaust gas selected from the group which consists of exhaust gas VSA and exhaust gas PSA and use at least a portion of at least one exhaust gas as at least one component of the non-vapor fluidization gas.
[00022] [00022] In modalities, the method also comprises producing, downstream of the gasifier, at least one product selected from the group consisting of Fischer-Tropsch hydrocarbons, energy and non-Fischer-Tropsch chemicals from at least a portion of the product gas of the aerator. Such a method may further comprise using at least a portion of a hydrocarbon-containing fluid produced downstream of the gasifier as at least one component of the non-vapor fluidizing gas.
[00023] [00023] In embodiments, at least one fluidized component is selected from the group consisting of fluidized bed pyrolyzers, fluidized bed combustors, gasifier sealing pots and combustor sealing pots. In embodiments, at least one fluidized component is selected from the group consisting of pyrolysers and sealing jars. The method may comprise using at least a portion of the aerator product gas as the fluidizing gas.
[00024] [00024] Also described here is a system for the production of synthesis gas, the system comprising: a gasification apparatus configured to convert at least a portion of a gasifier feed material introduced therein into a gas from gasification products comprising synthesis gas having a molar ratio of hydrogen to carbon monoxide, wherein the gasification apparatus comprises at least one vessel configured to fluidize its contents by introducing into it a fluidizing gas comprising at least one non-vapor component; at least one additional apparatus selected from the group consisting of a feed preparation apparatus located upstream of the gasification apparatus and configured to prepare a carbonaceous material for introduction into the gasification apparatus; synthesis gas conditioning apparatus configured to produce a conditioned synthesis gas having a molar ratio of hydrogen to carbon monoxide that is different from the molar ratio of hydrogen to carbon monoxide in the gasification product gases, to provide a synthesis gas conditioned having a reduced amount of at least one component with respect to the amount of the component in the gaseous product gases, or both; and synthesis gas utilization apparatus configured to convert at least a portion of the synthesis gas into a desired product; and at least one current that fluidly connects to at least one additional apparatus or a gasifier outlet with at least one vessel from the gasifier, whereas a gas from at least one additional apparatus or outlet of the gasifier may provide at least one component of the non-vapor fluidization gas. At least one vessel can be configured for fluidization with a fluidizing gas comprising less than about 100, 90, 80, 70, 60, 50, 40, 30,
[00025] [00025] In modalities, the system comprises synthesis gas conditioning apparatus downstream of the gasification apparatus and a recycling stream that fluidly connects to the synthesis gas conditioning apparatus with the gasification apparatus, whereas at least one A portion of a gas exiting the synthesis gas conditioning apparatus can be used as a fluidizing gas. The synthesis gas conditioning apparatus may comprise a partial oxidation reactor. The partial oxidation reactor can be configured for operation at a temperature in the range of about 900ºC to about 1500ºC, from about 1000ºC to about 1300ºC, or from about 1150ºC to about 1250ºC. The system may further comprise air enrichment apparatus configured to supply air enriched with oxygen or substantially pure oxygen for introduction into a partial oxidation reactor, thereby producing a reduced oxygen product gas and a recycling stream that fluidly connects to the apparatus. air enrichment with at least one vessel, while at least a portion of the reduced oxygen product gas can be used as the fluidizing gas. The air enrichment device can be selected from the group consisting of vacuum oscillating adsorbents (VSA's) and pressure oscillating adsorbents (PSA's).
[00026] [00026] In embodiments, the system comprises synthesis gas conditioning apparatus comprising a carbon dioxide removal apparatus configured to remove a carbon dioxide-rich flue gas from at least a portion of the gasification product gases and a recycling stream that fluidly connects to the carbon dioxide removal apparatus with at least one vessel, while at least a portion of the carbon dioxide-rich flue gas can be used as the fluidizing gas. The carbon dioxide removal apparatus may comprise a pressure swing adsorption unit (PSA).
[00027] [00027] In embodiments, the system comprises a feed preparation apparatus and a current that fluidly connects to a vent gas outlet of the feeding preparation apparatus with the gasification apparatus, while at least a portion of a gas The ventilation fan exiting the feed preparation device can be used as a fluidizing gas. The feed preparation apparatus may comprise a dryer configured to reduce the moisture content of a relatively wet feed material of the gasifier to provide a lower moisture feed material to introduce into the gasifier by placing the relatively wet feed material of the gasifier in contact with a drying medium to supply the gasifier feed material with reduced humidity and a dry wind gas comprising volatile organic compounds (VOC's). The drying medium may comprise superheated steam.
[00028] [00028] In modalities, the desired product is selected from the group consisting of energy, Fischer-Tropsch hydrocarbons and non-Fischer-Tropsch chemicals. In embodiments, the synthesis gas utilization apparatus comprises Fischer-Tropsch synthesis apparatus configured to convert at least a portion of the gaseous product gases into Fischer-Tropsch hydrocarbons, thereby producing a Fischer-Tropsch exhaust gas and at least one recycle stream that fluidly connects to the Fischer-Tropsch synthesis apparatus in the gasification apparatus, while at least a portion of the Fischer-Tropsch exhaust gas can be used as the fluidization gas. In embodiments, a Fischer-Tropsch waste water comprising oxygenated components is also produced using the Fischer-Tropsch synthesis apparatus and the system further comprises a remover configured to contact at least a portion of the Fischer-Tropsch waste water. Tropsch with at least a portion of the Fischer-Tropsch exhaust gas, while oxygenates are removed from the Fischer-Tropsch waste water by the Fischer-Tropsch exhaust gas, thus producing a reduced oxygenated Fischer-Tropsch waste water and a oxygenated enriched Fischer-Tropsch exhaust gas and at least one recycle stream that fluidly connects to the remover with the gasifier, while at least a portion of the oxygenated enriched Fischer-ITropsch exhaust gas can be used as gas fluidization.
[00029] [00029] In modalities, the synthesis gas utilization apparatus comprises Fischer-Tropsch synthesis apparatus configured to convert at least a portion of the gasification product gases into Fischer-Tropsch hydrocarbons, thus producing a Fischer exhaust gas -Tropsch and at least one recycling stream that fluidly connects to the Fischer-Tropsch synthesis apparatus with the gasification apparatus, while at least a portion of the Fischer-Tropsch exhaust gas can be used as a fluidizing gas and water Fischer-Tropsch wastewater comprising oxygenated components is also produced using the Fischer-Tropsch synthesis apparatus and the system further comprises a steam remover configured to contact at least a portion of the Fischer-Tropsch wastewater with steam, while that oxygenates are removed from the waste water of
[00030] [00030] In modalities, the synthesis gas utilization apparatus comprises Fischer-Tropsch synthesis apparatus configured to convert at least a portion of the gasification product gases into Fischer-Tropsch hydrocarbons, thereby producing a Fischer exhaust gas -Tropsch and at least one recycling stream that fluidly connects to the Fischer-Tropsch synthesis apparatus with the gasification apparatus whereas at least a portion of the Fischer-Tropsch exhaust gas can be used as a fluidizing gas and the system still comprises a carbon dioxide removal apparatus configured to separate a carbon dioxide-rich gas from the Fischer-Tropsch exhaust gas, thereby providing a carbon dioxide-reduced Fischer-Tropsch exhaust gas and at least one current bottle that fluidly connects to the carbon dioxide removal device with the gasifier, while at least a portion of the gas r carbon dioxide can be used as a fluidizing gas. The system can comprise a recycling stream while the exhaust gas from Fischer-Tropsch reduced in carbon dioxide can be introduced into a synthesis gas conditioning apparatus upstream of the Fischer-Tropsch apparatus, a recycling stream whereas the Fischer-Tropsch exhaust gas reduced in carbon dioxide can be introduced into the Fischer-Tropsch synthesis apparatus, or both. The carbon dioxide removal apparatus may comprise a membrane designed for hydrogen recovery, configured to provide a flue gas enriched with low BTU carbon dioxide.
[00031] [00031] In embodiments, the synthesis gas utilization apparatus comprises Fischer-Tropsch synthesis apparatus configured to convert at least a portion of the gasification product gases into 'Fischer-Tropsch hydrocarbons, thereby producing an exhaust gas of . Fischer-Tropsch and at least one recycling stream that fluidly connects to the Fischer-Tropsch synthesis apparatus with the gasification apparatus, while at least a portion of the Fischer-Tropsch exhaust gas can be used as the fluidizing gas and the The system further comprises the product's heavy oil processing apparatus configured to convert at least a portion of the Fischer-Tropsch hydrocarbons to more desirable hydrocarbons, where the product's heavy oil processing apparatus is configured to produce a process exhaust gas. heavy product oil and at least one recycle stream that fluidly connects the product's heavy oil processing apparatus to the gasifier, while at least a portion of the product's heavy oil processing exhaust gas can be used as fluidizing gas. Such a system may further comprise synthesis gas conditioning apparatus downstream of the gasification apparatus and may further comprise hydrogen recovery apparatus configured to separate hydrogen from a portion of the conditioned synthesis gas and a current that fluidly connects to the apparatus of hydrogen separation with the product's heavy oil processing apparatus, while separate hydrogen can be used in it.
[00032] [00032] In modalities, the synthesis gas utilization apparatus comprises Fischer-Tropsch synthesis apparatus configured to convert at least a portion of the gasification product gases into Fischer-Tropsch hydrocarbons, thus producing an exhaust gas of
[00033] [00033] In system modalities, at least one additional device comprises at least one unit selected from the group consisting of pressure oscillating adsorbents (PSA's), vacuum oscillating adsorbents (VSA's) and heavy oil product processor (PU's) ) and in which at least one recycling stream that fluidly connects at least one unit with the gasification apparatus, while an exhaust gas produced in at least one unit can be used as a fluidizing gas.
[00034] [00034] In system embodiments, the gasification apparatus is a double fluidized bed gasifier comprising a fluidized bed pyrolyzer fluidly connected with a fluidized bed combustion, in such a way that a circulating stream comprising a heat transfer material be continuously circulated between the fluidized bed pyrolyzer, where the temperature of the circulating stream is reduced by means of endothermic pyrolysis and the fluidized bed combustor, where the circulating stream temperature is increased and the fluidized bed combustor can be operated to increase the temperature of the circulating stream by combustion of at least coal introduced into it with the circulating stream and the gasification apparatus optionally further comprises a gasifier sealing pot, a combustor sealing pot, or both and at least least one vessel is selected from the pyrolyzer, the combustion, the combustion sealing pot and the gasifier sealing pot. In embodiments, the combustion is configured to produce a combustion flue gas and at least one recycle stream that 7 fluidly connects to the combustion with at least one vessel while at least a portion of the combustion flue gas can be used as fluidizing gas. In embodiments, the feed preparation apparatus comprises a feed box configured for storing gasifier feed material and the system further comprises a recycling stream configured to introduce at least a portion of the combustion flue gas into the feed box, whereas direct contact of at least a portion of the combustion flue gas with the gasifier feed material provides a dry gasifier feed material for introducing into the aerator and a gas for opening the feed box and in which at least one current recycling fluid that fluidly connects to a dry wind gas outlet stream with the gasifier while at least a portion of a dry wind gas can be used as a fluidizing gas.
[00035] [00035] In system embodiments, the gasification apparatus is a double fluidized bed gasifier comprising a fluidized bed pyrolyzer fluidly connected with a fluidized bed combustor, in such a way that a circulating stream comprising a heat transfer material be continuously circulated between the fluidized bed pyrolyzer, where the temperature of the circulating stream is reduced by means of endothermic pyrolysis and the fluidized bed combustor, where the circulating stream temperature is increased and the fluidized bed combustor can be operated to increase the temperature of the circulating stream by combustion of at least coal introduced into it with the circulating stream and the gasification apparatus optionally further comprises a gasifier sealing pot, a combustor sealing pot, or both; at least one vessel is selected from the group i consisting of the pyrolyzer, the gasifier sealing pot and the combustor sealing pot; and the combustion is configured to increase the. temperature of the circulation stream by combustion of at least coal in the circulation stream by contact with hot combustion air; and at least one recycle stream that fluidly connects to a combustion air inlet stream with at least one vessel, while at least a portion of the hot combustion air can be used as the fluidizing gas.
[00036] [00036] The foregoing has largely emphasized the technical characteristics and advantages of the invention in such a way that the following detailed description of the invention can be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. Experienced in theology should realize that the concept and the specific modalities described can be readily used as a basis for modifying or designing other structures to accomplish the same purposes as the invention. Experienced in technology they must also realize that such equivalent constructions do not escape the spirit and scope of the invention as presented in the attached claims. BRIEF DESCRIPTION OF THE DRAWINGS
[00037] [00037] For a detailed description of the modalities of the invention, reference will now be made to the accompanying drawings, in which similar numbers indicate similar parts unless otherwise evident and in which: FIGURE 1 is schematic of a gasification system according to a modality of this description; FIGURE 2 is a schematic of a gasification system of
[00038] [00038] Certain terms are used throughout the following description and claims to refer to particular system components. This document is not intended to distinguish between components that differ in name, but not in function.
[00039] [00039] The terms "pyrolyzer and" gasifier are used interchangeably here to refer to a reactor configured for endothermic pyrolysis.
[00040] [00040] Use of the terms "fluidized" and "fluidizable * with reference to a component of the system should indicate that the component is configured for operation by introducing a fluidizing gas into it, for example, configured for operation as a fluidized bed. . DETAILED DESCRIPTION
[00041] [00041] Overview. Described here are a gasification system and method. The gasification system and method described incorporate the application of an alternative gas to fluidize the contents of at least one fluidizable unit of a gasification apparatus. Alternative fluidizing gas is used to partially or completely replace conventional vapor fluidization. A reduction in the amount of steam used for fluidization can desirably reduce the expense associated with steam production (eg, boiler wastewater treatment) and / or it can reduce the amount (eg, the mass of steam replaced by alternative gas fluidization) of the condensate that can form and thus reduce the expense associated with treating said condensate, if the product's synthesis gas is subsequently cooled and the moisture condensed from it.
[00043] [00043] As non-limiting examples, the alternative fluidizing gas can comprise flue gas (low pressure or high pressure flue gas (eg natural gas / methane), synthesis gas (eg product gas) gasifier or reduced hydrogen synthesis gas), exhaust gas (for example, PSA exhaust gas, VSA exhaust gas, heavy oil processor product exhaust gas, FT exhaust gas), combustion air, gas combustion combustion, dry wind gas, remover exhaust gas, CO2-rich gas, exhaust gas (for example, boiler exhaust gas, combustion turbine exhaust gas, exhaust from an HRSG), or some combination of these.
[00045] [00045] As discussed in detail below, the gasifier feed preparation apparatus is configured to prepare a carbonaceous raw material for gasification in the gasification apparatus. For example, the raw material preparation apparatus can be configured to shrink, dry and / or store a gasifier raw material. Synthesis gas conditioning apparatus is configured to change the gas composition of the gasifier product. For example, a synthesis gas conditioning apparatus can be configured to convert the synthesis gas introduced into it into a more desirable synthesis gas, for example, by changing the molar ratio of hydrogen to carbon monoxide in it. Alternatively or additionally, synthesis gas conditioning apparatus can be configured to remove a product gas component from the undesirable gasifier introduced into it (for example, to remove aerosols, sulfur constituents, inorganic nitrogen constituents, hydrochloric acid, carbon dioxide , excess of hydrogen, excess of carbon monoxide, coals, residual solids, water, etc., from this). Apparatus 7 for using synthesis gas is configured for the production of a product. synthesis gas produced in the gasification apparatus. For example, synthesis gas utilization apparatus may comprise energy generation apparatus, Fischer-Tropsch synthesis apparatus, apparatus configured for the production of non-Fischer-Tropsch fuels or synthesis gas chemicals, etc. Each of these components will be described in more detail below.
[00046] [00046] The Figure | it is a scheme of a gasification system I according to an embodiment of this description. Gasification system | comprises apparatus for preparing the gasifier 100, gasifier 200, synthesis gas conditioning apparatus 300 and synthesis gas utilization apparatus 400. Gross feed inlet current 105 is configured to introduce a feed raw material in the feed preparation apparatus 100. Gasification apparatus 200 is fluidly connected with feed preparation apparatus 100 by means of the prepared gasifier supply chain 110. Gasification apparatus 200 is fluidly connected with synthesis gas conditioning apparatus 300 per product gas medium of the gasifier outlet stream 210. Synthesis gas utilization apparatus 400 is fluidly connected with synthesis gas conditioning apparatus 300 by means of conditioner from the synthesis gas outlet stream 310. Product stream 410 loads the product out of the 400 syngas utilization apparatus. previously mentioned, synthesis gas can be used to produce energy, non-Fischer-Tropsch chemicals, Fischer-Tropsch hydrocarbons,
[00047] [00047] As shown in figure 1, at least one current that fluidly connects to the gasifier 200 with one another 7, 100, 300 and / or 400, or connects an outlet of the gasifier '200 with one input, while a gas from the additional apparatus or the gasifier itself can be used to fluidize (alone or in combination with at least one other fluidization gas) at least one unit of the gasifier 200. The fluidization gas described it can also be referred to here as an “alternative gas, an“ alternative gas, or an “alternative fluidizing gas,” indicates that the fluidizing gas is not completely vapor, although steam can be a component, even a major component, of some of the possible alternative fluidization gases provided here, as seen below. In embodiments, at least one unit fluidized by means of the alternative fluidizing gas described is a pyrolyzer. In embodiments, at least one unit is a combustion sealing pot. In embodiments, at least one component is an aerator sealing pot. In embodiments, at least one unit fluidized by means of the alternative fluidizing gas described is a combustor.
[00048] [00048] The alternative fluidizing gas may comprise a low pressure and / or low oxygen stream. In embodiments, the alternative fluidizing gas comprises ventilation gas process, boiler exhaust gas, combustion turbine, heat recovery steam generator (HRSG), process gas, or any combination of these.
[00049] [00049] In the embodiment of figure 1, apparatus for preparing the feed gas outlet stream 150 that fluidly connects to the feed preparation apparatus 100 with a gasification apparatus 200 while a gas produced or used in the feeding preparation apparatus 100 can be used to fluidize at least one component of the gasification apparatus 200. In the embodiment of figure 1, apparatus of the gasification outlet stream i 250 that fluidly connects to an outlet of at least one component of the apparatus 200 with an entry of. at least one component thereof, while a gas produced or used in the gasifier 200 may be used to fluidize at least one component thereof. For example, as discussed below, a portion of the gasifier product gas exiting the gasifier 200 via product gas from the gasifier outlet stream 210 may be introduced via the stream 250 into a fluidized unit of the apparatus gasification 200, and / or at least a portion of a combustion flue gas produced in an indirect double fluidized bed (DFB) gasifier (described in detail below) can be introduced by means of the gas outlet stream apparatus gasification 250 in a fluidized component of the gasification apparatus
[00050] [00050] Although gas outlet streams 150, 250, 350, 450 are shown combining with fluidization gas inlet stream 205 in the embodiment of figure 1, it should be understood that (a) any number of streams 150, 250, 350, 450 can be introduced directly into the gasification apparatus 200 (that is, in different fluidized units therefrom or by means of multiple fluidization inlets in a single fluidized device); (B) . there may be one or more gas streams from each additional apparatus or from the gasification apparatus itself (for example, two gas streams 150 from the feed preparation apparatus 100, three gas streams 450 from the synthesis gas utilization apparatus 400 and the like); and (c) one or more of the alternative fluidizing gases can be used to completely fluidize a gasifier unit 200 (i.e., stream 205 may essentially be absent, with substantially all fluidization gas to a fluidisable unit of the gasifier 200 being supplied by means of one or more of the chains 150, 250, 350, and / or 450). In addition, for ease of illustration, gas streams can be displayed exiting the base of the device to which they emanate. In practice, as those skilled in the art know, such gas streams can extract gas from a portion of the top or side of the respective apparatus from which the gas is obtained.
[00051] [00051] As mentioned earlier, syngas utilization apparatus 400 may comprise any apparatus known to a person skilled in the art that can be operated to provide a valuable syngas product. For example, by way of non-limiting example, synthesis gas utilization apparatus 400 may comprise a power generation apparatus, Fischer-Tropsch synthesis and other associated apparatus (some of which are described in more detail below with reference to Figure 2), chemical production apparatus configured for the production of non-Fischer-Tropsch synthesis gas chemicals, or any combination thereof.
[00052] [00052] Figure 2 is a schematic of a system II according to another embodiment of this description. System Il comprises feed preparation apparatus 100, gasification apparatus 200 and synthesis gas conditioning apparatus 300. In the embodiment of figure 2, apparatus 7 for using synthesis gas 400 comprises synthesis apparatus. Fischer-Tropsch (FT) 420, Fischer-Tropsch 430 exhaust gas remover, vapor remover 440, carbon dioxide removal apparatus 460, hydrogen recovery apparatus 470 and heavy oil processing apparatus of the Fischer product Tropsch 480. A system according to this description may comprise FT 420 synthesis apparatus and one or more selected Fischer-Tropsch 430 exhaust gas remover, vapor remover 440, carbon dioxide removal apparatus 460, recovery hydrogen apparatus 470 and heavy oil processing apparatus of Fischer-Tropsch 480 product.
[00053] [00053] As discussed earlier, at least a portion of a fluidizing gas for at least one gasifier unit 200 may be supplied by the feed preparation apparatus 100. A feed preparation apparatus may comprise any suitable apparatus for preparing a feed raw material, such as but without limitation biomass, for gasification in the gasification apparatus 200. In embodiments, the feed preparation apparatus 100 comprises a reduction or grinding apparatus, a dryer, a feed storage box, or a combination of this. For example, in the embodiment of figure 2, the feed preparation apparatus 100 comprises a dryer. A relatively hot drying medium 106 passes through the dryer, into which the feed material is introduced via the feed inlet stream 105. Indirect or direct contact of the drying medium with the feed material in the dryer serves to reduce the moisture in the feed material,
[00054] [00054] Referring again to figure 2, gasification apparatus 200 comprises a gasifier (also referred to here as a "producer" or "pyrolyzer"), configured to gasify a feed material introduced into it, thereby producing a product gas from the gasifier comprising hydrogen and carbon monoxide (ie, comprising synthesis gas or "synthesis gas"). Gasification apparatus 200 may comprise - any gasifier known in the art. In embodiments, gasification apparatus 200 comprises an indirect double fluidized bed gasifier (or "DFB '). A suitable DFB indirect gasifier is described in more detail below with reference to Figure 3 and in U.S. patent number 8,241,523 and U.S. patent application serial number
[00055] [00055] A DFB indirect gasifier can be configured for operation by introducing inlet gas at a low gas speed to fluidize a medium high density bed in a gasifier / pyrolysis vessel. The high medium density bed may comprise a relatively dense fluidized bed in a lower region thereof, the relatively dense fluidized bed containing a relatively heated circulating and inert particulate fine heat transfer material. Carbonaceous material can be introduced in the lower region at a relatively high rate and endothermic pyrolysis of the carbonaceous material carried out by means of a circulating heated inert material, producing a gas product product comprising synthesis gas (ie, comprising hydrogen and carbon monoxide) ). In modalities, in an upper region of the pyrolyzer is a low medium density entrained space region containing a entrained mixture comprising inert solid, particulate heat transfer material, coal, unreacted carbonaceous material and product gas. The entrained mixture is removed from the gasifier for one or more separators, such as a cyclone, in which solids (heat transfer particles, coal and / or unreacted carbonaceous material) are separated from the gasification product gases. At least a portion of the removed solids is returned to the pyrolyzer after reheating to a desired temperature by passing through a reaction zone. exotherm of an external combustor. Combustion of coal and optionally any supplementary combustion fuel, together with combustion air in the combustion produces a combustion combustion gas, as discussed below with reference to Figure 3.
[00056] [00056] As shown in figure 2, in modalities, a recycling stream 250 'that fluidly connects to a product gas from the gasifier outlet of the gasification system 200 (for example, a current outlet 21 of a pyrolyzer / gasifier 20 or an outlet 22/210 of a primary separator or a secondary 40/50 associated with it) with a gasifier inlet 200, while a portion of the gas from the gasifier product can be used to fluidize a fluidized component of the system gasification 200. In such embodiments, a compressor can be used to increase the gas pressure of the gasifier product before recycling to the system 200. In applications where the gasifier 200 comprises a double fluidized bed gasifier, such as indirect gasifier DFB 200 'shown in figure 3 and described in detail below, a recycling stream 250' can fluidly connect to a gas stream of the gasification product 210, with a fluidized unit of the DFB indirect gasifier. For example, a recycling stream 250 'can fluidly connect to a stream of product gas from aerator 210 with inlet gas from fluidizing gas from aerator 205, as shown in the embodiment of figure 3. In embodiments, the steam source 250 is external to gasification (i.e., except gasifier / pyrolyzer 20, such as combustor 30). Alternatively or in addition, one or more recycling streams 250 'can fluidly connect the gas stream of product from the aerator 210 with a sealing pot of the combustor 70, a sealing pot of the aerator 80, i a combustor 30, or some combination of these, while a portion "of the gaseous product gases (ie synthesis gas) can be used" to fluidize it.
[00057] [00057] Alternatively or additionally, in the manner indicated in figure 2, the gasification device 200 can produce or use a gas that can be recycled through the current 250 to a fluidized unit of the gasification system 200 for use as a fluidizing gas this. As shown in figure 2, at least a portion 202 of a gas from product 201 of the gasifier 200 can be recycled upstream of the gasifier 200. For example, a portion of the gas can be introduced into a fluidized unit of the system gasification 200 by means of a stream 250, and / or a portion of a gas other than product gasification gas can be introduced into the gasification apparatus 200 by means of streams 203 and / or 106, feed preparation apparatus 100 and stream recycling rate 150. As a non-limiting example, the non-synthesis gas may comprise combustion gas from the combustion produced in a combustion (for example, a combustion from a double fluidized bed gasifier as shown in figure 3), a portion of the air supplied for use as combustion air in a combustion, or both.
[00058] [00058] In applications where gasification apparatus 200 comprises a double fluidized bed gasifier, such as the indirect gasifier DFB 200 'shown in figure 3 and described in detail below, at least a portion of a combustion flue gas produced in a fluidized bed combustion 30 and leaving it via the combustion outlet stream 31 and / or combustion separator outlet stream 201A can be recycled in a fluidized bed unit of the DFB 200 'indirect gasifier. As indicated in the modality of figure 3, a recycling current 250A can fluidly connect to combustion i 30 (optionally via one or more separators of combustion 60 and / or 7 one or more heat exchangers, as described in more detail next): with pyrolyzer 20, while a portion of the combustion flue gas can be used to fluidize the pyrolyzer. Alternatively or in addition, a recycling stream 250B can fluidly connect to combustion 30 (optionally via one or more separators of combustion 60 and / or one or more heat exchangers, as described in more detail below) with a pot of gasifier sealing 80, while a portion of the combustion flue gas can be used to fluidize the gasifier sealing pot. Alternatively or in addition, a 250C recycling stream can fluidly connect to the combustion (optionally via one or more separators of the combustion 60 and / or one or more heat exchangers, as described in more detail below) with a sealing pot of the combustion 70, while a portion of the combustion flue gas can be used to fluidize the combustion sealing pot. Alternatively or additionally, a recycling stream can fluidly connect to combustion 30 (optionally via one or more separators of combustion 60 and / or one or more heat exchangers, as described in more detail below) with a combustion inlet , while a portion of the combustion flue gas can be used to fluidize the combustion. In embodiments, a compressor is used to increase the combustion flue gas pressure before subsequent use.
[00059] [00059] Alternatively or additionally, a stream 203 is configured to introduce a portion of a combustion flue gas by means of stream 202 as a drying medium for apparatus for preparing raw material 100. In such embodiments, the drying process, introduce into the feed preparation apparatus 100/100 'by means of stream 106 and used to dry the feed material in the dryer comprises at least a portion of the recycled gas by means of stream (s) 202/203 of the feeder gasification 200. The drying medium. can comprise another drying medium (e.g. steam) in addition to the gas recycled from the gasifier 200. In this way, gas produced or used in the gasifier can be recycled as fluidizing gas to a gasifier unit 200 by means of through feed preparation apparatus 100 and feed preparation gas outlet stream 150.
[00060] [00060] In applications where gasifier 200 comprises a double fluidized bed gasifier, such as DFB 200 'indirect gasifier shown in figure 3 and described in detail below, a stream 203 can be configured to recycle at least a portion of a combustion flue gas leaving the combustion 30 via the stream 31 in the raw material preparation apparatus 100 ', while (for example, direct) contact of the combustion flue gas (and optionally additional drying medium introduced by means of chain 106) with a feed material from the gasifier introduced by means of chain 105 can be used to reduce the moisture content of the feed material. Depending on its temperature, contact of the combustion flue gas (and optional additional drying medium) can produce a dry wind gas that can comprise volatile organic compounds (or VOC's) and / or other contaminants. As indicated in the modality of figure 3, recycling current 150 can be configured to introduce dry wind gas into indirect gasifier DFB 200 '. For example, current 150 can fluidly connect to dryer 101 with aerator 20, in such a way that dry wind gas can be introduced
[00061] [00061] In applications where gasification apparatus 200 comprises a double fluidized indirect gasifier, such as the DFB 200 'indirect gasifier shown in figure 3 and described in detail below, a portion of the combustion air produced for use in combustion can be rotated for use in fluidizing a fluidized component of the gasifier 200 '. For example, as indicated in the embodiment of figure 3, a current 250D can fluidly connect to a current combustion air 201B with pyrolyzer 20, while a portion of the combustion air can be used to fluidize pyrolyzer 20; a current 250E can fluidly connect to a current combustion air 201B with gasifier sealing pot 80, while a portion of the combustion air can be used to fluidize gasifier sealing pot 80; and / or a 250F chain can fluidly connect to a current combustion air 201B with combustion sealing pot 70, while a portion of the combustion air can be used to fluidize the combustion sealing pot 70. In embodiments, combustion is used as an alternative fluidizing gas for gasifier 20 and / or a sealing pot for gasifier 80. As with the other alternative gases mentioned here, the combustion air can be used either alone or in conjunction with other fluidizing gas components , for example, in combination with fluidizing steam. The use of combustion air as an alternative fluidizing gas will alter the composition gas of the gasifier product in such a way that it contains nitrogen. The additional nitrogen in the gasification product gases can serve as a non-water diluent, thus lowering the thermal content (BTU / SCF) of the gas in the gasification product. Use of combustion air as a gas | alternative fluidisation can increase the operating temperature of the gasifier, increasing the temperature of the product's synthesis gas and perhaps reducing the amount of tar in it. Since air has a lower: thermal capacity than steam, unit efficiency can be increased and / or the dew point of the product's synthesis gas lowered by a reduction in the amount of steam used as the fluidizing gas.
[00062] [00062] As indicated in the modalities of figures 1 and 2, gas gas from the gasifier (ie, comprising synthesis gas) produced in the gasifier 200 and which leaves it by means of the output stream of the gasifier product 210 may a synthesis gas conditioning apparatus 300 for conversion / conditioning prior to its production of a desired product by means of a synthesis gas utilization apparatus 400. As previously mentioned, in embodiments, a portion of the product gas of the The gasifier is recycled in the gasifier 200 by means of the stream 250 'for use as a fluidizing gas for at least one component of the gasifier 200.
[00063] [00063] A system according to one embodiment of this description comprises synthesis gas conditioning apparatus 300. Synthesis gas conditioning apparatus is configured to change the composition of the product gas from the aerator introduced into it by means of product gas from the gasifier outlet stream 210, to provide a conditioned synthesis gas for a desired downstream application. As shown in figure 2, one or more gas used or produced in the synthesis gas conditioning apparatus 300 can be recycled by means of the current 350 for use as fluidizing gas in the gasification apparatus
[00064] [00064] Conditioning apparatus 300 may comprise any apparatus known in the art to be used to alter the composition of the product's syngas gasifier. For example, a conditioning synthesis gas apparatus 300 can be configured to remove an unwanted component of the product gas from the aerator. A component. undesirable as this can be a sulfur compound (eg hydrogen sulfite), carbon dioxide, excess hydrogen, excess carbon monoxide, methane, etc.) A synthesis gas conditioning device can operate by removing a portion of a contaminant introduced into it by means of stream 210, and / or can reduce the amount or remove an unwanted component by converting it into another component. Synthesis gas conditioning apparatus 300 may comprise carbon dioxide removal apparatus configured to separate carbon dioxide from the product gas of the aerator introduced therein. Alternatively or additionally, synthesis gas conditioning apparatus 300 may comprise sulfur removal apparatus configured to separate sulfur or sulfur compounds (e.g., hydrogen sulfite) from the product gas of the gasifier introduced therein. Alternatively or additionally, synthesis gas conditioning apparatus 300 may comprise a water gas displacement reactor configured to reduce the amount of carbon monoxide in the gas of the gasifier product by reacting a portion of the carbon monoxide with water to produce carbon dioxide and additional hydrogen through the water gas displacement reaction (WGSR). Synthesis gas conditioning apparatus 300 may comprise a partial oxidation reactor or reformer (e.g., an autothermal reformer), as known in the art, configured to convert methane into the product gas of the additional synthesis gas gasifier.
[00065] [00065] Figure 4 is a schematic of a suitable synthesis gas conditioning apparatus 300 'according to an embodiment of this description. Synthesis gas conditioning device 300 'comprises air separation unit (eg vacuum oscillating adsorbent (VSA)) i 320, synthesis gas conditioner 330, finalizing device 340, 7 heat recovery device / washing with water 360, gas and synthesis compressor 370, sulfur removal apparatus 380 and carbon dioxide removal apparatus 390. A synthesis gas conditioning apparatus according to this description can comprise any combination of the units shown in figure 4, it may comprise other units in place in addition to those indicated in figure 4, the arrangement of the units may be other than the arrangement indicated in figure 4, and / or a single unit may effect the reduction / removal of multiple components of the gas undesirable synthesis. For example, carbon dioxide removal apparatus 390 may be positioned before the synthesis gas conversion apparatus 330 and / or a single acid gas removal unit (AGR) may be operated as an exhaust removal apparatus. sulfur 380 and carbon dioxide removal apparatus 390.
[00066] [00066] At least a portion 210 'of the gasifier product gas produced in the gasification apparatus 200 may be introduced into the 300/300' synthesis gas conditioning apparatus. In the embodiment of figure 4, at least a portion of the gas product gas from the gasifier is introduced by means of product gas from the gasifier outlet stream 210 'into a synthesis gas conversion unit or conditioner 330. Conversion gas unit synthesis 330 can be any synthesis gas conditioning apparatus known in the art For example, synthesis gas conditioning apparatus 330 can be selected from tar wash systems (eg, OLGA units), reformers and oxidation reactors partial. In modalities, synthesis gas conversion apparatus 330 comprises a partial oxidation reactor
[00067] [00067] Synthesis gas conditioning apparatus 300 'may further comprise completion apparatus 340 configured to cool or partially cool the conditioned synthesis gas and fluidly connected with synthesis gas conversion apparatus 330 by means of stream 303.
[00068] [00068] In modalities, conditioning comprises changing the composition of at least a portion of the gasification product gases with enriched air to produce altered gasification product gases; finalizing the altered gasification product gases; recovering heat 7 from the finished gasification product gases, altered to provide lower temperature gasification product gases; compressing the gases of lower temperature gasification product; and / or removing sulfur and / or carbon dioxide from the gases of the lower temperature compressed gasification product to provide conditioned synthesis gas for use downstream in the 400 synthesis gas utilization apparatus. As mentioned earlier, as known in the art, heat recovery during conditioning can provide a vapor (for example, a low or high pressure vapor), providing oxygen or oxygen-enriched air can produce a reduced oxygen exhaust gas and removal of carbon dioxide and / or sulfur can provide a flue gas rich in carbon dioxide. In such embodiments, one or more recycling streams 350 (350A, 350B, and / or 350C in figure 4) of synthesis gas conditioning apparatus 300 'can be incorporated into the system to recycle at least a portion of a high vapor pressure, an exhaust gas air separation unit, and / or a flue gas rich in carbon dioxide as the fluidization gas in the gasification apparatus
[00069] [00069] Referring again to figure 1, at least a portion of conditioned synthesis gas 310 is introduced into the synthesis gas utilization apparatus 400. Synthesis gas utilization apparatus 400 can be any apparatus known in the technology suitable for the production of a valuable synthesis gas product. For example, synthesis gas utilization apparatus 400 may comprise Fischer-Tropsch synthesis apparatus, hydrogen recovery apparatus, energy production apparatus, boilers
[00070] [00070] In the embodiment of figure 2, the synthesis gas utilization apparatus comprises Fischer-Tropsch 420 synthesis apparatus, heavy oil processing apparatus for the Fischer-Tropsch 480 product, separator 460, exhaust gas remover Fischer-Tropsch 430, vapor remover 440 and hydrogen recovery apparatus 470. A system according to this description may comprise none, one or a combination of any of two or more of the synthesis gas utilization apparatus shown in figure 2.
[00071] [00071] Fischer-Tropsch 420 synthesis apparatus is configured to produce Fischer-Tropsch hydrocarbons by means of catalytic conversion of synthesis gas. The Fischer-Tropsch 420 synthesis apparatus comprises at least one Fischer-Tropsch synthesis reactor. The Fischer-Tropsch synthesis reactor can be any suitable Fischer-Tropsch reactor known in the art. In modalities, the Fischer-Tropsch synthesis reactor can be operated with an iron-based catalyst. In modalities, the Fischer-Tropsch synthesis reactor can be operated with a cobalt-based catalyst. In embodiments, the catalyst is a precipitated iron catalyst. In embodiments, the precipitated Fischer-Tropsch catalyst is an iron-based catalyst formed as described or having the Fischer-Tropsch catalyst composition described in the patent
[00073] [00073] In embodiments, at least a portion of the FT exhaust gas extracted from the FT 420 synthesis apparatus via the FT exhaust gas stream 401 is recycled via the 450A stream in the gasification apparatus 200 for use as fluidizing gas for such a fluidized unit. In embodiments, one or more components are removed from at least a portion of the FT exhaust gas before use as a fluidizing gas. For example, in the embodiment of figure 2, at least a portion of the exhaust gas FT in the current 401 is introduced via the current 402 in a separation unit 460 configured to remove at least one component of the exhaust gas FT introduced into it. For example, separation unit 460 can be a carbon dioxide separation unit, such as a carbon dioxide removal membrane, as known in the art. In such embodiments, a gas rich in carbon dioxide (which is generally a low BTU gas) can be introduced, via stream 450B, into the gasifier 200 for use therein as a fluidizing gas. An exhaust gas FT reduced in CO 2 can leave the separator 460 via stream 413. The exhaust gas reduced FT of carbon dioxide, which can comprise hydrogen and carbon monoxide, can be used anywhere in system II . For example, in embodiments, exhaust gas FT 413 reduced by carbon dioxide, or a portion thereof, is reintroduced into the FT 420 synthesis apparatus for the production of additional FT synthesis products thereof. Recycling the exhaust gas FT in the gasification apparatus 200 (for example, as its fluidizing gas; in the fluidised bed or a free edge of the gasifier) may result in increased production of hydrogen and carbon monoxide and / or maintenance of a composition of product gas of the desired gasifier (ie synthesis gas). In applications where the gasifier 200 comprises a entrained flow type gasifier, FT exhaust gas recycling can help provide the gas velocity required to trap solids circulating above the gasifier. Use of FT exhaust gas recycling in a pyrolyzer can thus increase synthesis gas production and / or reduce the steam consumption of a pyrolyzer.
[00074] [00074] Production of Fischer-Tropsch synthesis products in the Fischer-Tropsch 420 synthesis apparatus can concurrently produce a Fischer-Tropsch 405 wastewater that must be disposed of properly. FT wastewater may contain a significant amount of oxygenates and / or other chemical compounds (which may be referred to here simply as "oxygenates") that mandate wastewater treatment to prepare the appropriate wastewater for disposal. In embodiments, at least a portion of the FT exhaust gas exiting the FT 420 synthesis apparatus via FT exhaust gas stream 401 is used to remove oxygenates from at least a portion of the residual Fischer-Tropsch water exiting the FT 420 synthesis device by means of FT 405 residual water outlet stream. This removal of oxygenate can be performed before the introduction of the FT gas as a fluidizing gas: in the gasification device 200. As indicated in the figure 2, a portion of the exhaust gas FT can be introduced by means of a stream 403, together with at least a portion of the waste water FT: by means of a stream 406, in exhaust gas remover FT or separator column 430 Residual water FT can be used as makeup steam for remover 430. Remover 430 is configured to come into contact with the exhaust gas FT introduced into it with the residual water FT introduced into it, while oxygenated s and optionally other contaminants in the FT wastewater are removed by the FT exhaust gas.
[00076] [00076] It is also noted here that, in modalities, at least a portion of the FT exhaust gas can be recycled in the raw material preparation apparatus for use as a carrier to pneumatically transport the solid raw material to the gasification, can be recycled to the raw material preparation apparatus or the gasification apparatus to be used to supply purge gas to the tap instrument and / or other process connections in the gasification apparatus, can be recycled to the conversion apparatus synthesis gas 330 from a synthesis gas conditioning apparatus 300/300 'in order to reform the gaseous components thereof, thereby increasing the amount of hydrogen and carbon monoxide in the conditioned synthesis gas and / or maintaining a desired composition thereof. , and / or can be recycled in a finishing device 340 of a synthesis gas conditioning device, such as 300 'in order to cool the hot gas coming out of a synthesis gas conversion apparatus 330 (for example, at a temperature below which ash particles and / or aerosols present therein will not adhere to the heat transfer and / or other downstream apparatus).
[00077] [00077] In modalities, a device for using synthesis gas 400 comprises a hydrogen recovery device. For example, the system can be used to supply hydrogen to a downstream synthesis gas utilization apparatus comprising a fuel cell, or to supply hydrogen for use in the heavy oil processing of the product comprising - hydrotreating - (for example, “hydroisomerization,
[00078] [00078] In embodiments, synthesis gas utilization apparatus 400 comprises Fischer-Tropsch product heavy oil processing apparatus 480. Fischer-Tropsch product heavy oil processing apparatus may be any suitable apparatus known in the art for convert Fischer-Tropsch synthesis products into other (for example, more desirable) products. For example, product 480 heavy oil processing apparatus may comprise one or: more “selected hydrocracker units, hydroisomerization units, hydrodesulfurization, hydrodesnitrogenation, fractionators, 7 such as distillation columns and the like. In modalities, product 480 heavy oil processing apparatus operates by contacting at least a portion of the Fischer-Tropsch synthesis products produced in the FT 420 synthesis apparatus with hydrogen, which can be introduced into it by means of a current 412. The heavy oil processing of the product can be catalytic in nature. In embodiments, a hydrogen recovery apparatus 470 is fluidly connected with a heavy oil product processor 480 via chain 411, while at least a separate portion of the hydrogen in the hydrogen recovery apparatus 470 is used in the hydrogen product processor. heavy oil 480. Chains 411 and 412 can be the same chain, in modalities. A current 410 is configured to extract updated Fischer-Tropsch product from the heavy oil product processor 480. The updated product may comprise mainly jet fuel, mainly diesel fuel, mainly gasoline, mainly naphtay, or some combination of one or more FT products selected from jet fuel, diesel fuel, gasoline and naphtha.
[00079] [00079] Heavy oil processing can create a heavy oil processor exhaust gas, removable from the product 480 heavy oil processing apparatus via chain 414. A 450F recycle chain can fluidly connect to the product processor of heavy oil 480 with gasifier 200, while at least a portion of the exhaust gas from the heavy oil processor product can be used as a fluidizing gas for a fluidized component thereof (for example, a CSP, a GSP, a combustor , and / or a pyrolyzer thereof). In embodiments, at least a portion of the exhaust gas from the heavy oil processor product is used as fuel for a combustor in a DFB indirect gasifier, such as DFB 200 'indirect gasifier in figure 3.
[00081] [00081] A suitable DFB indirect gascifier 200 'can be operated by introducing inlet gas at a low gas speed to fluidize a medium high density bed in a pyrolysis gasifier / vessel. The high medium density bed may comprise a relatively dense fluidized bed in a lower region thereof, the relatively dense fluidized bed containing a relatively heated circulating and inert particulate fine heat transfer material. Carbonaceous material can be introduced in the lower region at a relatively high rate and endothermic pyrolysis of the carbonaceous material carried out by means of a circulating heated inert material, producing a gas product product comprising synthesis gas (ie, comprising hydrogen and carbon monoxide) ). In modalities, in an upper region of the pyrolyzer is a low medium density entrained space region containing a entrained mixture comprising inert solid, particulate heat transfer material, coal, unreacted carbonaceous material and product gas. The entrained mixture 7 is removed from the gasifier for one or more separators, such as & cyclone, in which solids (heat transfer particles, coal and / or unreacted carbonaceous material) are separated from the gasification product gases. At least a portion of the removed solids is returned to the pyrolyzer by means of a heat transfer return current after reheating to a desired temperature by passing through an exothermic reaction zone of an external combustor.
[00082] [00082] DFB 200 'indirect gasification apparatus comprises gasifier 20 (also referred to here as “pyrolyzer 20º) which is fluidly connected with a combustor 30, while heat loss during endothermic gasification in the gasifier / pyrolyzer 20 can be supplied by means of exothermic combustion in combustion 30, as discussed below. Indirect gasifier DFB 200 'can further comprise at least one sealing pot for the combustor 70 and at least one sealing pot for the gasifier 80 or other sealing devices, such as one or more "J" or "L" valves. Pyrolyzer 20 can be operated to remove it from a circulating particulate phase and coal by trapping the gas in the gasifier product. Separation of solid, entrained particulates comprising particulate heat transfer material and coal from gasification product gases can be accomplished by gas / solid separators, such as conventional cyclone (s). In embodiments, substantially all solid systems are elutriated in spite of the use of which are generally considered to be low velocities of the gasifier fluidization inlet gas. The DFB indirect gasifier thus can still comprise one or more separator of the aerator particulate (for example, one or more cyclones of the aerator) and one or more separators of the combustor particulate (for example, one or more cyclones of the combustor). In the embodiment of figure 3, DFB 200 'indirect gasifier comprises cyclone (s) of primary gasifier 40 and cyclone (s) of secondary gasifier 7 50 and cyclone (s) of combustor 60. Each of these components will be discussed in more detail. follow.
[00083] [00083] Circulation between the gasifier and the combustion by means of heat transfer currents 25 and 35 is a heat transfer material (HTM). The heat transfer material is a substantially inert material (that is, substantially inert with respect to the carbonaceous feed material being aerated) which may have some catalytic tar reducing properties, depending on the material selected. In modalities, the heat transfer material is selected from the group consisting of sand, limestone and other calcites or oxides, such as iron oxide, olivine, magnesia (MgO), friction-resistant alumina, carbides, silica aluminas, resistant zeolites friction and combinations of these. The heat transfer material is heated by passing through an exothermic reaction zone of an extinguished combustion. In embodiments, the heat transfer material can participate as a reagent or catalytic agent, so 'relatively inert' as used herein with reference to the heat transfer material is like a comparison to carbonaceous materials and is not used here in a sense restricted. For example, in coal gasification, limestone can serve as a means of capturing sulfur to reduce sulfate emissions. Similarly, limestone can catalytically crack tar in the gasifier. In embodiments, the gasifier can be considered a catalytic gasifier and a catalyst can be introduced with or as a component of the particulate heat transfer material.
[00084] [00084] The heat transfer material can have an average particle size in the range of about 1 µm to about 10 mm, from about 1 µm to about | mm, from about 5 µm to about 700 µm, or about 5 µm; about 300 um. The heat transfer material can have an average density in the range of about 50 Ib / ftº (0.8 g / em ) To about 500 Ib / ftº (8 g / em ”), 7 of about 50 Ib / ft * (0.8 s / in ”) at about 300 Ib / ft * (4.8 sem”), or about 100 Ib / ft (1.6 g / in ) At about 300 Ib / ft * (4.8 g / in ").
[00085] [00085] As previously noted, gasification apparatus 200 'comprises a combustor configured to heat the separated heat transfer material by means of one or more separators (for example, cyclones) of the gasification product comprising entrained materials extracted from the pyrolyzer. The combustor can be any type of combustor known in the art, such as, but not limited to, fluidized, entrained and non-fluidized combustors. Combustor 30 can be associated with a combustor sealing pot (CSP) 70, or other sealing devices, such as "J 'or" L' valves, configured to prevent material backflow in the configured cyclone (s) 40, 50 gasifier to remove particulate gas from the gasifier product; and / or gasifier can be associated with a gasifier sealing pot (GSP) 80, or other sealing devices, such as "J 'or" L "valves, configured to prevent material reflux in the combustor cyclone (s) 60 configured to remove particulates from the combustion flue gas.
[00086] [00086] Combustor 30 can be configured for operation with supplementary fuel (in addition to the coal transferred from gasifier 20) being introduced into it, as indicated by chain 8 in figure 3. Supplementary fuel can be introduced into combustor 30 anywhere including, but not limited to, the HTM 35 inlet stream or 201B combustion air stream (s). For example, when the supplementary fuel is a gas (for example, combustion air comprising light coals), the supplementary fuel can be introduced into the combustion 30 together with combustion air (for example, by means of stream 201B in figure 3). In modalities, the fuel. supplementary fuel is introduced indirectly into the combustion 30, for example, by means of introduction into an air preheater (for example, a direct driven air preheater) upstream of the combustor 30. In 'embodiments, the supplementary fuel may comprise mainly liquids or gas. In embodiments, the supplementary fuel comprises or is mainly a solid. In such embodiments, the supplementary fuel can be introduced in combination with heat transfer material. For example, supplementary fuel, optionally combined with makeup sand in streams 9, 9a and / or 9b, can be introduced into combustor 30 directly or by means of separator combustion (s) 60 or gasifier sealing pot 80. In modalities , the supplementary fuel is introduced into the combustor 30 by means of the makeup sand inlet stream 9a. In modalities, the DFB indirect gasifier comprises a pump / compressor (for example, a positive displacement pump) and fuel injection nozzles configured for the introduction of supplementary fuels in the combustor 30. Chain 8 can be assigned to the injection liquid, fuel sources gaseous and / or solid directly in combustor 30,
[00087] [00087] Supplementary fuel provides additional energy to heat the circulating heat transfer medium. Supplementary fuels may be carbonaceous or non-carbonaceous residue vapors and may comprise or be mainly gaseous, liquid, and / or solid. Any “waste” steam containing hydrocarbons (for example, any steam having BTU value) can be used as a supplementary fuel to the combustor (and / or, in modalities, can be used for the production of additional synthesis gas / increased conversion of supply to the product synthesis gas by means of introduction into the pyrolyzer 20 of the indirect gasifier DFB 200). For example, it is contemplated that, in modalities, waste materials, such as, but not limited to, used car oil, animal fat (for example, gasoline), kitchen cedar, etc., can be used to supply fuel supplement to the combustor.
[00089] [00089] At least a portion of a supplementary fuel introduced into the combustor 30 by means of current supplementary fuel 8 may be a hydrocarbon-containing material produced by means of an upstream unit (s). In such embodiments, the upstream unit (s) can be fluidly connected with combustor 30, by means of chain 8, for example, in such a way that the hydrocarbon-containing material exiting the upstream process unit (s) can be used as supplementary fuel for combustor 30. For example, a 100/100 'feed preparation apparatus may comprise a dryer configured to dry. a gasifier feed material (as discussed earlier). Such drying may produce a wind current from the dryer 7 comprising, for example, substantial VOC's. A portion or all of the dry wind gas comprising hydrocarbons can be used as a supplementary fuel for combustion 30.
[00090] [00090] In modalities, the gasifier feed comprises a substantial moisture content, as discussed below. For example, the biomass feed may comprise "wet" biomass. The synthesis gas can be used for downstream processing in a synthesis gas utilization apparatus comprising Fischer-Tropsch synthesis. Synthesis gas conditioning can be used to provide a synthesis gas suitable for use downstream in the production of Fischer-Tropsch hydrocarbons. It may be desirable, in such modalities, to supply a low humidity synthesis gas to such conditioning processes / apparatus. In such modalities, drying of the gasifier raw material (for example, from a biomass feed) may be desirable in order to control the moisture content of the synthesis gas of the resulting product. The raw material dryer can be operated to provide an ultra-low level of HO (eg, O weight by weight at 30% by weight, 10% by weight at 30% by weight, 15% by weight at 30% by weight) weight, or even substantially 0 by weight, for example, with roasting) in the synthesis gas, suitable for subsequent downstream conditioning. As previously mentioned, in modalities, the 100/100 'feed preparation apparatus comprises a dryer that produces a waste gas product suitable for use as supplementary fuel in the combustor 30. The waste gas from the dryer may contain volatile organic compounds (VOC's) . In embodiments, the waste gas comprises about 0.01 to about 10 percent by volume of
[00091] [00091] In embodiments, at least a portion of the supplementary fuel for combustor 30 is produced by means of one or more unit (s) downstream 300/400. In such embodiments, the downstream unit (s) can be fluidly connected with combustor 30 directly, or via stream 8, for example, in such a way that a hydrocarbon-containing material exiting the downstream process unit (s) can be used as a supplementary fuel for combustion 30. In modalities, a vapor that remains in the hydrocarbon produced downstream of the DFB indirect gasifier (for example, tar which is recovered from a downstream tar removal system) is introduced into the combustor for heating value of this. Tar can be obtained from any tar removal apparatus known in the art, for example, from a liquid absorbent, such as, but not limited to, an OLGA unit (for example, a DAHLMAN OLGA). Such removed coals comprise heavy hydrocarbons which can be reused as a fuel / fuel component 30. In embodiments, exhaust gas (eg Fischer-Tropsch exhaust gas, PSA exhaust gas, VSA exhaust gas and / or heavy oil processor, exhaust gas) is used as a combustible fuel. The supplementary fuel can be a low pressure waste gas, such as PSA exhaust gas. As mentioned earlier, the recycled fluid as a supplementary fuel in the combustor of the DFB indirect gasifier can comprise or be mainly liquid, gaseous, or solid. For example, the supplementary fuel may comprise a vapor containing liquid tar, and / or combustion air improved with fuel (for example, light coals removed with combustion air).
[00093] [00093] A spent catalyst / wax vapor comprising spent catalyst and Fischer-Tropsch hydrocarbons can be separated from the liquid products of the downstream Fischer-Tropsch synthesis apparatus
[00094] [00094] In modalities, mainly air is fed at the base of the combustion 30 and steam is fed in CSP 70. In modalities, combustion air introduced in the combustion 30 (for example, through the current 201B) comprises air enriched with oxygen. The steam feed rate for CSP 70 can be around 4000lb / h (for a plant that operates at about 500 dry tones / day, for example). The vapor passes through and leaves the cyclone of the combustion 60. The efficiency of the cyclone is drastically affected by the surface velocity. The higher the surface speed, the better the cyclone's efficiency. If the ACFM (actual cubic foot per minute) can be reduced, the size of the cyclone can be reduced and the efficiency of capturing solids can be improved (based on a higher load of solids and the typical, higher efficiency of smaller cyclones) . Thus, in modalities, air can be fed in CSP 70, instead of steam. In modalities, 20-25% of the combustion fluidization gas (for example, air and / or alternative fluidization gas described here) required for combustion 30 is introduced directly into CSP 70 before entering combustion 30. In modalities, combustion air combustion and / or alternative fluidizing gas described here, instead of completely steam, is fed into CSP 70, in such a way that heat is not removed from combustion 30 due to the flow of steam through it and the separator (s) / cyclone combustion (s) downstream 60 may be incrementally smaller in size. That is, the introduction of air and / or alternative fluidizing gas described here (for example, air at about 537.7 ºC), instead of the introduction of (for example, 287.7 ºC) steam alone in CSP 70 ( which is heated in it, for example, to about 1426.6 ºC) can serve to reduce the amount of steam: in the gasification system.
[00095] [00095] In embodiments, the fluidizing gas for one or more of the gasifier 20, the gasifier sealing pot 80, the fuel sealing pot 70 and the fuel 30 comprise LP flue gas. The LP flue gas can have a pressure of less than 175.8 or 689.4 kPa man., And / or a pressure in the range of about 172.3 to about 689.4 kPa man. The fluidizing gas in the combustion 30 may comprise mainly air. The rate of supply of gas to the combustion can be greater, less or equal to about 0.9, 1.3, 1.8, 2.3, 2.7 or 3.2 meters / s in certain modalities.
[00096] [00096] The deviation of the sealing pot from the combustion 70 in the combustion can provide an angle a, such that the heat transfer medium (e.g., sand), air and combustion gas will flow up and back in the combustion. The flow rate of fluidization gas in the combustion can be determined by the heat transfer material. The inlet fluidization rate is at least the amount sufficient to fluidize the heat transfer medium in the combustion 30. In embodiments, the inlet combustion speed is greater than or about 0.9, 1.3, 1.8 , 2.3, or 2.7 m / s. In embodiments, the rate of entry of the fluidizing gas into the base of the combustion is in the range of about 1.3 to about 3.2 m / s, from about 1.8 to about 3.2 m / s, or from about 1.8 to about 2.7 m / s. At higher elevations in the combustion, flue gas is created. This limits the appropriate rate for introducing fluidization gas into the combustion.
[00097] [00097] In modalities, the combustor is operated in dragged flow mode. In modalities, the combustor is operated in a transport bed mode. In modalities, the combustion is operated in a choking flow mode. The combustion base (for example, at the entrance or close to the circulating heat transfer medium of the gasifier) can be operated at approximately 593.3 ºC, 648.8 ºC, 704.4 ºC, 760 ºC, 815.5 ºC, or 871.1 ºC 7 and the exit of the combustion (at or near the top; for example, at or near the material outlet the cyclone (s)) can be operated at approximately 760 ºC, 815.5 * C, 871.1 * C, 926.6 ºC, 982.2 ºC, 1037.7 “ ºC, or 1093.3 ºC. Thus, the actual cubic foot of gas present increases with elevation in the combustor (due to the combustion of coal and / or supplementary fuel). In modalities, excess air flow returns to the combustor.
[00098] [00098] The fluidizing gas for the combustion may be or may comprise oxygen in air (for example, 20 percent by volume), oxygen-enriched air (for example, 90 percent by volume), or substantially pure oxygen (for example, greater than 99, 99.5, 99.9, 99.99, or 99.99 percent by volume of oxygen), for example, from a vacuum swing adsorption unit (VSA) or a swing swing adsorption unit pressure (PSA), oxygen from a cryogenic distillation unit, oxygen from a pipe, or a combination thereof. As previously mentioned, reduced oxygen exhaust gas from an air separation unit like this can be used as an alternative fluidizing gas for pyrolyzer 20, CSP 70, GSP 80 or a combination thereof. The use of oxygen or oxygen enriched air as the combustion fluidization gas can allow a reduction in the vessel size, however, the melting temperature of the ash must be considered. The higher the O concentration in the fuel supply, the higher the combustion temperature. The oxygen concentration must be maintained at a value that guarantees a combustion temperature lower than the melting temperature of the feed ash. Thus, the maximum oxygen concentration fed into the combustion can be selected by determining the ash melting temperature of the specific feed used. In embodiments, the fluidization gas fed at the base of the combustion comprises about 20 to about 100 mole percent oxygen. In embodiments, the fluidizing gas comprises about 20 7 mole percent oxygen (for example, air). In embodiments, the combustion fluidization gas comprises substantially pure oxygen (limited by the coal-melting properties of coal, supplemental fuel and heat transfer material fed into it). In embodiments, the combustion fluidization gas comprises PSA exhaust gas.
[00099] [00099] The combustion can be designed for operation with about a volume percent of excess oxygen in the flue exhaust gas. In modalities, the combustor can be operated with excess oxygen in the range of about 0 to about 20 percent by volume, from about | to about 14 percent by volume, or from about 2 to about 10 percent by volume of excess O '. In modalities, the amount of excess O, fed into the combustion is greater than | volume percent and / or less than 14 percent volume. Desirably, sufficient excess air is supplied, in such a way that complete combustion is guaranteed and partial oxidation mode is avoided. In modalities, the DFB indirect gasification system can be operated with excess of O, in the combustor in the range of greater than 1 to less than 10 and the flue gas comprises less than 15, 10 or 7 ppm CO. In modalities, oxygen is used to produce more steam. In embodiments, for example, when the hot combustion gas will be introduced into a second combustion (for example, without limitation, in the second double fluidized bed (DFB) combustor as described, for example, in US patent application No. 12 /691,297 deposited on January 21, 2010 (and now US patent number 8,241,523), the description of which is incorporated herein for all purposes not contrary to this description), the amount of excess oxygen may be in the range of about 5 at about percent, or can be greater than about 5, 10, 15, 20, or 25%,: supplying oxygen to a downstream combustor. In modalities where steam can be sold in value, more excess O, can be used to produce more steam for sale / use. In embodiments, a flue gas' rich in CO, rich in nitrogen is produced by operating the combustion 30 of the DFB indirect gasification system described here in excess of oxygen greater than 7, 10 or 15%.
[000100] [000100] In modalities, the combustor is pressurized. The combustion can be operated at a pressure greater than 0 kPa man. at a pressure that is at least 13.7 kPa man. less than the gasifier operating pressure. That is, in order to maintain a continuous flow of combustion materials back into the gasifier, the combustion pressure, Pc, at the combustion inlet which can be measured by a gauge pressure located near the flue gas outlet, is less than the gasifier / pyrolyzer pressure, Pc. The pressure at the combustion outlet HTM, Pc.rase (which must be greater than Pç), is equal to the sum of the pressure, Pc, at the top of the combustion and the pressure head supplied by the material in the combustion. The pressure head supplied by the heat transfer material / gas mixture in the combustion is equal to pcgh, where pc is the average density of the material (for example, the fluidized bed of heat transfer material) in the combustion, g is the gravitational acceleration and there is the height of the “bed” of the material in the combustor. The height of the material (for example, heat transfer material, such as sand and other components, such as coal and etc.) in the combustor is adjusted to ensure the flow of materials back into the gasifier.
[000101] [000101] Thus, Pc, Base which is equal to Pc + pcgÃh must be greater than the pressure of the gasifier, Pcs. The heights and ratios between the combustor and aerator are selected, in such a way that adequate pressure is provided to maintain continuous flow of the combustor in the aerator.
[000102] [000102] In modalities, the operating pressure of the combustor, Pc, is up to or about 275.7, 310.2, 344.7 or 413.6 kPa man. In modalities, based on: based on design criteria of 1.8-3.7 meters / s for gas speed in the combustion, the maximum combustion operating pressure is about 310.2 kPa 7 man. In modalities, if the operating pressure of the combustion is higher, then pressure energy can be recovered by using an expander. Thus, in modalities, one or more expanders are positioned downstream of the combustion gas outlet and upstream of the heat recovery device (discussed further below). For example, when operated with pure oxygen, the diameter of the combustion may be smaller at the base than at the top. In modalities, an expander is incorporated after the cyclones (due to the cyclone's efficiency increasing with higher pressures). In embodiments, one or more expanders are positioned upstream of one or more vacuum cleaner filters, which can be desirably operated at lower pressures. In embodiments, the system comprises an expander downstream of one or more cyclones of the combustion. The expander can be operated at a pressure greater than 103.4, 137.8 or 206.8 kPa man. One or more expanders can be operated to recover PV energy.
[000103] [000103] The selected surface speed for gas / solid separators (which can be cyclones) can be selected to maximize efficiency and / or reduce erosion. Cyclones can be operated at a surface speed in the range of about 65 to about 11.1 m / s, from about 6 to about 9.2 m / s, from about 6.5 to about 7, 8 m / s, or about 6, 6.5,
[000104] [000104] As shown in figure 3, the combustion outlet can be fluidly connected via current 31 with one or more cyclones HTM 60. One or more cyclones can be configured in any arrangement, with any number of cyclones in series and / or in parallel. For example, a first cyclone bank (for example, 1 to four or more cyclones)
[000106] [000106] In alternative modalities, a heat recovery device is positioned between the HTM (s) cyclone and the ash removal cyclone. In such embodiments, combustion flue gas is introduced into one or more HTM cyclone combustors. The gas coming out of one or more HTM cyclones is introduced into one or more heat recovery devices. The gas coming out of one or more heat recovery devices is then introduced into one or more ash cyclones to remove ash from it. The heat recovery apparatus may comprise one or more selected from the group consisting of air preheaters (for example, a combustion air preheater), steam superheaters, heat recovery units: from waste (for example, boilers) and economizers. In modalities, heat recovery generates steam. In such embodiments comprising heat recovery upstream of ash removal, one or more ash removal cyclones may not be refractory lining, that is, one or more ash removal cyclones may be hard, but smaller cyclones temperature with respect to systems comprising ash removal upstream of heat recovery. In modalities, the ash removal cyclones are operated at temperatures below 204.4 ºC, below 176.6 ºC, or below 148.8 ºC. In modalities, the cyclones with the lowest ash removal temperature are made of silicon carbide.
[000107] [000107] In modalities, heat recovery is used to produce superheated steam. In modalities, superheated steam is produced at a temperature in the range of about 121.1 ° C to about 482.2 ° C, or from about 121.1 ° C to about 204.4 ° C and a pressure in the range of about of 689.4 kPa man. at about 4481.5 kPa man., or from about 689.4 kPa man to about 2068.4 kPa man.
[000108] [000108] In embodiments comprising heat recovery upstream of the ash recovery, the face of the tubes can be constituted and / or reduced speed in downward flow in order to minimize erosion of the heat recovery apparatus (for example, tubes of heat recovery). heat transfer). The speed for cyclones in such modalities can be less than
[000109] [000109] In modalities, combustion flue gas is introduced directly or indirectly into a boiler economizer for heat recovery and, for example, energy production.
[000110] [000110] In modalities, balance is pushed towards the formation of. hydrogen and carbon monoxide during pyrolysis by, for example, incorporating a material that effectively removes carbon dioxide. 7 For example, NaOH can be introduced into the 200 '' gasifier (for example, with or with the heat transfer material, in the aerator 20, in the combustor 30 or anywhere) to produce Na; CO; injection; and / or CaO can be used to absorb CO ,, forming CaCO ;, which can ultimately be separated into CO, and CaO which can be recycled in the system. NaOH and / or CaO can be injected into the gasifier or pyrolyzer 20. Addition of such material that reduces carbon dioxide can serve to increase the amount of synthesis gas produced (and thus available for downstream processes, such as, without limitation, Fischer-Tropsch synthesis and chemical production and / or non-Fischer-Tropsch fuel), and / or can serve to increase the Wobbe number of the gas from the gasifier product for downstream energy production. Such additional materials can also be used to adjust the ash melting temperature of the carbonaceous feed materials in the gasifier. As with optional carbon dioxide reducing materials, such as melt adjustment material, it can be incorporated by adding with or in the feed, with or in the heat transfer medium, to the gasifier 20, the combustor 30 and / or anywhere. In modalities, the additional material is added with or in the feed in the aerator. In embodiments, additional materials are added with or in the heat transfer medium.
[000111] [000111] Pyrolyzer 20 is a reactor comprising a fluid bed of heat transfer material at the base of the reactor and is operated at feed rates high enough to generate sufficient gas from the gasifier product to promote circulation of heat transfer material and coal carbonated, for example, by drag. The aerator may be a hybrid with a drag zone above a fluidized bed aerator, as described in U.S. Patent 4,828,581, which is incorporated herein by: reference in its entirety for all purposes not contrary to this description.
[000112] [000112] In embodiments, aerator / pyrolyzer 20 is an annular 7-shaped vessel comprising a conventional gas distribution plate 'near the base and comprising inlets for feed material (s), heat transfer material (s) and gas fluidization. The aerator vessel comprises an outlet at or near the top and is fluidly connected in this way to one or more separators from which gases from the aerator product are discharged and solids are recycled at the aerator base via an external, exothermic combustor that operated to reheat the separate heat transfer material. The gasifier operates with a circulating particulate phase (heat transfer material) and at inlet gas speeds in the range sufficient to fluidize the heat transfer material, as further discussed below.
[000113] [000113] Referring now to figure 3, the angle between the sealing pot and the vessel (that is, the angle a between the sealing pot of combustor 70 and combustor 30 and / or the angle y between the sealing pot sealing of aerator 80 and aerator 20) can be in the range of about 5 to about 90 °, from about to about 80 °, or from about 5 to about 60 °. In modalities, a and / or y is less than 45º. Using a greater angle usually results in a higher sealing pot. Smaller angles can be operated using fluidization / aeration to maintain fluidization. Generally, for angles between 5 and about 45 degrees, fluidization / aeration can also be used. In modalities, a smaller angle, such as an angle of about 5 degrees, is used in the design in such a way that the sealing pot (CSP and / or GSP) is relatively short and the overall height of the unit (ie, the chimney) can be reduced. [0001 14] As indicated in the modality of figure 3, the inlets for feed and recirculating heat transfer material can be located at or near the gasifier 20 base and / or can be. near the pyrolyzer gas distributor. The feed can be selected from any carbonaceous sources, including, without limitation, the group consisting of biomass, RDF, MSW, sewage sludge and combinations thereof. In modalities, the food comprises biomass. It is contemplated that coal can be added to the gasifier if it is suitable coal and this depends on the melting temperature of the ash. Refinery tank bases, heavy fuel oil, etc., which can, in modalities, be contaminated with small solids, can be introduced into the gasifier and / or non-combustor, as long as the melting temperature of the ash in it is not adversely affected. In modalities, petroleum coke is crushed to a size in the appropriate range to ensure volatilization in the pyrolyzer. In modalities, petroleum coke is introduced into the pyrolyzer as a component of the carbonaceous raw material. In embodiments, the gasifier feed still comprises Fischer-Tropsch synthesis products (for example, Fischer-Tropsch wax) and / or spent catalyst (for example, spent catalyst recycled into product wax). In modalities, Fischer-Tropsch synthesis products are produced downstream and a portion of Fischer-Tropsch products (for example, spent Fischer-Tropsch wax) that will be cracked under operating conditions is recycled as feed / fuel in the gasifier .
[000115] [000115] The gasifier feed material can be introduced into it by any suitable means known to those skilled in the art. The feed can be fed into the aerator using a water-cooled rotary screw. The feed can be substantially solid and can be fed using a screw feeder or a ram system. In modalities, the feed is introduced into the gasifier as mainly a solid. In modalities, double feed screws are used and the operation is alternated between them, thus ensuring continuous feeding. In the modality of figure 3, the apparatus: preparation / introduction of feed 100 'comprises feed box 101 (which can also serve as a dryer in some modalities), 7 feed handling screw 102, feed collection screw 103, valve (for example, a knife and / or rotary valve) 104 and gasifier feed screw 107. Operation of such components is known in the art.
[000116] [000116] In embodiments, a supply box 101 is configured for drying, as well as storage, by using residual heat from a low level heat source to partially dry a supply material for gasifier 200. In this way traditional, dedicated feed drying methods and equipment can be replaced or reduced in length or size. Suitable sources of low-level heat include, but are not limited to, hot water, flue gas from a process source, such as a combustor, low-level steam and hot air, for example, from an air cooler. The source of the drying gas can be a combination of flue gas from a process source, such as the combustor section of a gasifier, atmospheric air that is heated with low-level heat and steam sources, such as exhaust from a process heat exchanger (for example, a fin fan) or hot oil / water cooling system. Such low-level heat can also be used, in embodiments, to dry feed material in a day box storage silo upstream of a gasifier 101 feed box. Thus, feed box 101 can provide storage capacity for the raw material of the gasifier and be operated to at least partially4 dry the raw material. A drying feed box like this 101 can be operated to reduce the moisture content of a gasifier feed material, for example, from about 55 weight percent to about mild to below 30 weight percent moisture range . More drying can be achieved: using a hotter heat source and / or increasing the residence time of the feed material when drying the feed box 101. Wet raw material (eg wet biomass) can be introduced at the top from the drying feed box 101 via the feed inlet stream 105. A dust / particulate removal system can be used at the feed point in the box. A dust / particulate removal system can be used to remove particulates from the steam in the drying gas coming out of the supply box. In modalities, a domestic bag with cleaning supplies is used as a dust / particulate removal system. An induced fan (ID) can be located at the entrance or exit of the bag to assist in meeting the gas vapor flow requirements. Dry wind gas can be sent to a stack or, as discussed here, used as an alternative fluidizing gas, or separated therein. Feed material can pass through the feed box 101 against currently drying gas and "dry" feed material can come out of the feed box 101 via an outlet at its base. Drying of the gas, for example, combustion flue gas, can be introduced into a supply box by means of chains 203 and / or 106 nozzles on the sides and / or floor of the box.
[000117] [000117] As shown in figure 3, an inlet stream of gasifier 110 can be configured to provide an angle B between the inlet stream 110 and gasifier vessel
[000118] [000118] In modalities, the gasifier supply is pressurized. The carbonaceous feed material can be fed into the gasifier at a pressure in the range of about 0 to about 275.7 kPa man. A dryer can be used to dry the feed and / or it can be operated at a pressure, thus providing the feed material in the gasifier at a desired pressure and / or moisture content. The feed may be dried prior to introduction into the gasifier, and / or may be introduced hot (for example, at a temperature greater than room temperature). In modalities, the food is cold (for example, at a temperature equal to or less than room temperature). The feed can be introduced into the gasifier at a temperature in the range of about -40 to about 126.6 ºC. In modalities, the feeding is at a temperature in the range of -40 to about 121.1 ºC. In modalities, the food is at room temperature. In modalities, the food is at room temperature. In embodiments, a feed material is reduced prior to introduction into the aerator. In embodiments, a feed material is preheated and / or reduced (for example, cut into strips) prior to introduction into the aerator.
[000119] [000119] In modalities, 100/100 'feed preparation apparatus can be operated to provide a moisture content of the feed: which is in the range of about 5 weight percent to about 60 weight percent. In embodiments, the 100/100 '7 feed preparation apparatus provides a feed having a moisture content of greater than about 10, 20, 30 or 40 by weight. In embodiments, the 100/100 'feed preparation apparatus provides a feed having a moisture content of less than about 10, 20, 30 or 40 by weight. In embodiments, the 100/100 'feed preparation apparatus provides a feed having a moisture content that is in the range of about 20 to about 30 by weight. In embodiments, the 100/100 'feed preparation apparatus provides a prepared feed having a moisture content that is in the range of about 25 to about 25% by weight.
[000120] [000120] In embodiments, further drying of the feed material may be desired / used to supply synthesis gas (by means of, for example, drying of the feed, gasification and / or partial oxidation) at an appropriate Hy / CO molar ratio for a desired use downstream in the synthesis gas utilization apparatus 400. For example, in embodiments, the synthesis gas utilization apparatus 400 comprises Fischer-Tropsch 420 synthesis apparatus (as shown in the embodiment of figure 2). If FT synthesis is performed in the presence of an iron catalyst (i.e., where a molar ratio of hydrogen to carbon monoxide of about 1: 1 is generally desirable), further drying may be desired. In embodiments, less drying may be desired / used, for example, to provide a synthesis gas having a molar ratio of H / CO suitable for Fischer-Tropsch synthesis downstream in the presence of a cobalt catalyst (ie, where a molar ratio of hydrogen to carbon monoxide of about 2 is generally desirable). As previously mentioned, in modalities, the 100/100 'feed preparation apparatus comprises a dryer configured to dry a “wet” feed material (introduced into it by means of the chain 105). prior to introduction into the gasifier 200. Any suitable dryer known in the art can be used to dry the feed material. Dry feed material can be introduced into a feed box for introduction into the gasifier 200. As indicated in the embodiment of figure 2 and discussed earlier, a feed box 101 can also serve as a dryer.
[000121] [000121] In modalities, the feed rate (flow) of carbonaceous material to the pyrolyzer is greater than or equal to about 2000, 2500, 3000, 3400, 3500, Ib / h / ft ”, 4000 or 4200 Ib / Wft. The design can allow a superficial speed at the exit (top) of the pyrolyzer in the range of 1.3-4.1 m / s (assuming a certain carbon conversion / volatilization / expansion). In modalities, the carbon conversion is in the range of about 0 to about 100%. In modalities, the carbon conversion is in the range of about 30 to about 80%. The size of the pyrolyzer vessel, that is, its diameter, can be selected based on a desired outlet speed.
[000122] [000122] Gasifier fluidizing gas can be fed into the base of the pyrolyzer 20 (for example, through a distributor) at a surface speed in the range of about 0.04 m / s to about 0.9 m / s, of about 0.07 m / s about 0.7 m / s, or about 0.07 m / s about 0.6 m / s. In embodiments, the pyrolyzer's fluidizing gas (for example, steam and / or alternative fluidizing gas) inlet speed is greater than, less than or equal to about 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 or 0.7 m / s. In embodiments, a surface speed gasifier fluidizing gas of at least or about 0.4, 0.5, 0.6, or 0.7 m / s is used during the start of the operation.
[000123] [000123] As discussed in more detail earlier, the fluidizing gas in the gasifier can be, without limitation, selected from the group consisting of steam, flue gas, synthesis gas, low pressure gas fuel ('LP *), exhaust gas (eg. Fischer-Tropsch exhaust gas, heavy oil processor exhaust gas, VSA exhaust gas, and / or PSA exhaust gas) and combinations thereof. In] embodiments, the gasifier fluidizing gas comprises Fischer-Tropsch exhaust gas. In embodiments, the gasifier fluidizing gas comprises heavy oil processor exhaust gas. Using exhaust gas heavy oil processor, additional sulfur removal can be done by the system, as the exhaust gas heavy oil processor can comprise sulfur.
[000124] [000124] In modalities, the pyrolyzer fluidization gas comprises PSA exhaust gas. Such modalities can provide substantial hydrogen in the gas product of the gasifier and may be more suitable for subsequent use of the product gas in downstream processes for which higher molar ratios of hydrogen to carbon monoxide are desirable. For example, a higher molar ratio of hydrogen to carbon monoxide may be desirable for downstream processes, such as a dual fluidized nickel bed gasification (for example, for which HyCO ratio of about 1.8: 1 to about 2: 1 may be desired). A double fluidized bed gasifier (DFB) like this is described, for example, in US patent application No. 12 / 691,297 filed January 21, 2010 (and now US patent number 8,241,523), the description of which is incorporated herein for all purposes not contrary to this description. Use of exhaust gas PSA for gasifier fluidization gas may be less desirable for subsequent use of gas for POx (for which closer Hy / CO ratios or about 1: 1 may be more suitable), since the hydrogen can be undesirably high. In embodiments, the gasification product gases are controlled (for example, in a burner) to a dry moisture content of less than a desired amount (for example, less than about 10. 11, 12, 13, 14, or percent by weight) in order to provide a suitable composition (for example, molar ratio of H / CO) for downstream processing (for example, for downstream POx). In modalities, a combination of drying of Ú feeding (at 100), indirect gasification of DFB (at 200) and POx (at 300) is used to supply a synthesis gas suitable for synthesis of Fischer-Tropsch downstream (at 400) using an iron or cobalt catalyst.
[000125] [000125] The temperature near or at the top of the pyrolyzer (for example, near the removal of the pushed product from it) can be in the range of about 537.7 ºC to about 926.6 ºC, from about 593.3 ºC to about 871.1 ° C, from about 648.8 ° C to about 871.1 ° C, from about 537.7 Ca about 815.5 ° C, from about 593.3 ° C to about 815.5 ° C , from about 648.8 ° C to about 815.5 ° C, from about 537.7 ° C to about 760 ° C, from about 593.3 ° C to about 760 ° C, from about 648.8 ° C to about 760 ° C, from about 648.8 ° C to about 787.7 ° C, from about 648.8 ° C to about 732.2 ° C, from about 676.6 ° C to about 732.2 ° C, from about 704.4 ºC to about 732.2 ºC, or about 732.2 ºC.
[000126] [000126] In modalities, the pressure of the gasifier is greater than about 13.7 kPa man. In modalities, the pressure of the gasifier is less than or equal to about 310.2 kPa man. In modalities, the gasifier pressure is in the range of about 13.7 kPa man. at about 310.2 kPa man. In modalities, the gasifier / pyrolyzer can be operated at low pressure, for example, less than 13.7 or 344.7 kPa man., Or in the range of about 172.3-344.7 kPa man.)
[000127] [000127] Circulating heat transfer material can be introduced by means of heat transfer current 25 in a lower region of the pyrolyzer 20. The heat transfer material can be introduced approximately opposite to the introduction of the gasifier feed material. To maintain adequate flow, the HTM inlet can be at an angle y in the range of about 20 degrees to about 90 degrees, or at an angle y greater than or about 20, 30, 40, 50 or 60 degrees. The heat transfer material can be introduced at a temperature in the range of about 760 ºC to about 1093.3 ºC, from about 787.7 ºC to about 871.1: ºC, of about 829.4 ºC at about 857.2 ºC, or about 843.3 ºC.
[000128] [000128] In embodiments, a gas distributor 95 is configured to introduce gas from fluidizing gas in the pyrolyzer 20. In embodiments, the circulating heat transfer material is introduced into the pyrolyzer 20 at a location of at least 25.8, 32.2, 38.7 , 45.1, 51.6, 58 or 64.5 centimeters above the pyrolyzer 95 gas distributor. The heat transfer material can be introduced in a position in the range of about 25.8 to about 64.5 centimeters, or about 25.8 to 38.7 centimeters above the dispenser 95. In embodiments, the dispenser can be operated to provide a gas flow of at least or about 0.3,
[000129] [000129] In modalities, the temperature differential between the gasifier and the combustor (ie, Tc-Tg) is maintained at less than about 93.3 ºC, 98.8 ºC, 104.4 ºC, 110 * C, 115.5 ° C, 121.1 * C, 126.6 ° C, 132.2 * C,
[000131] [000131] The product's synthesis gas leaving the gasifier separators can be used for heat recovery in certain modalities. In modalities, the synthesis gas is not used for heat recovery. In modalities, heat recovery is incorporated into the synthesis gas and the system also comprises a POx unit (for example, conditioner 330), a double fluidized bed gasifier of: nickel and / or a boiler downstream of the separator gasifier (s ). It is contemplated that the heat recovery device can be positioned between and / or downstream of the primary and / or secondary separators. When used for heat recovery, the temperature of the synthesis gas can be maintained at a temperature of at least 315.5 ºC, at least 343.3 ºC, at least 371.1 ºC, at least 398.8 ºC or at least 426.6 ºC after heat recovery. For example, maintaining a temperature of more than 343.3 ºC, 371.1 ºC, 398.8 ºC, 426.6 ºC, 454.4 ºC, or 484.2 ºC may be desirable when heat recovery is upstream tar removal (for example, to prevent coal condensation). In modalities, the synthesis gas is maintained at a temperature in the range of about 343.3 ºC to approximately 426.6 ºC during heat recovery. In modalities, the system comprises a steam superheater and optionally following a heat boiler of residue or waste heat superheater downstream of the gasifier separators for heat recovery from the hot gasification gas comprising synthesis gas and for the production of steam. In embodiments, the system comprises an air preheater for heat recovery from the hot synthesis gas. In modalities, the system comprises a boiler water supply preheater (BF W) for heat recovery from the hot synthesis gas. The system may comprise an air preheater, (for example, to preheat air to introduce into the combustion, since the introduction of the warmer air into the combustion may be desirable). The system can comprise any other suitable apparatus known to one skilled in heat recovery technology.
[000132] [000132] As mentioned earlier, in addition to or in place of steam, the fluidizing gas sealing pot can comprise any of the alternative fluidizing gases described above. For example,
[000133] [000133] Sulfur can leave the DFB 200 'indirect gasification apparatus described with the process gas, the combustion gas of the combustion, and / or with the ash. Removal of sulfur as a solid may be desired. In embodiments, ash (eg wood ash) from the ash removal cyclones is used to remove sulfur mercaptan and / or H, S from synthesis gas. In modalities, removal of mercaptan sulfur and / or HS is carried out at a pH greater than or about 7.5, 7.7, or 8. In modalities, the ash (for example, wood ash) comprises, for example, NaOH and / or Ca (OH) ,. In embodiments, a 'sulfur trap' or sulfur extraction material is added with the heat transfer material, in such a way that sulfur can be removed with ash. The sulfur trap can comprise a calcium material, such as calcium oxide (CaO), which can be converted to calcium sulfite and are system-like as a solid. In modalities, ash water (comprising NaOH and / or Ca (OH),) is used to brush sulfur from the exhaust gases. For example, the system may comprise a scrubbing tower to clean the process gas. Depending on the basicity of the gray water, it can be used, in modalities, as scrubbing water. Such brushing can be performed upstream of an ESP or other particulate separator configured to: remove particulates.
[000134] [000134] The different fluidization gases mentioned for CSP Ú can also be used for GSP. (In modalities, a percentage of air (for example, less than 4 percent by volume) can be used in the GSP to provide a higher temperature in the aerator). In modalities, the fluidization gas in the GSP is selected from the group consisting of flue gas, steam, recycled synthesis gas and combinations of these.
[000135] [000135] For the GSP, the minimum fluidization speed for the heat transfer material is adjusted to any point in time. That is, the initial minimum fluidization rate can be determined by the initial average particle size (for example, 100 µm). After a period of steaming (for example, 120 days), the heat transfer material may have a reduced average particle size (for example, about 25 µm); thus to minimal fluidization speed changes (decreasing with time in reduction in steam / size of HTM). The CSP and GSP can be selected, in such a way that they have an adequate size to handle the highest anticipated fluidization speed, that is, generally the start-up value. In modalities, the minimum fluidization speed of the GSP is initially high and decreases with time. However, it is possible that, if agglomeration occurs, the minimum fluidization speed may increase. The minimum fluidization speed is determined by the heat transfer material, in particular the average particle size, the density, and / or the empty fraction thereof. In modalities, the minimum fluidization speed is greater than about 0.01 m / s. In modalities, the minimum fluidization speed is greater than about 0.13 m / s. As the PSD decreases, fluidization sealing pot speed decreases.
[000136] [000136] The diameter of the sealing pots can be adjusted by the number of immersion leg penetrations, that is, how many cyclones one has: and / or by the angles at which the immersion legs enter the sealing pot. Immersion legs can be angled to allow for smaller 'immersion leg size. In modalities, the immersion leg (s) of the combustor cyclone 61 enters the top of the gasifier sealing jars, as with the CSP (where the immersion leg of the 41/51 gasifier cyclone enters the CSP). The CSP and / or the GSP may contain a distributor configured to distribute gas evenly across its cross section (for example, diameter). In modalities, the distributor is positioned at or near the base of the CSP and / or the GSP. In modalities, to minimize / avoid erosion of the sealing leg, the minimum distance between the dispenser (that is, the fluidization nozzles) at the base of the sealing pot (GSP and / or CSP) and the base of the immersion leg (s ) that projects on it is 64.5, 70.9, 77.4, 83.8, 90.3, 96.7, 103.2, 109.6 or 116.1 centimeters. In modalities, there is a greater distance 96.7, 103.2,
[000137] [000137] A GSP can be designed with a suitable head of the heat transfer material to minimize reflux. The height of the GSP can be based on a design margin. In modalities, the project margin is in the range of about 6.8 kPa man. at about 34.4 kPa man ,, or is greater than or equal to about 6.8, 13.7, 20.6, 27.5, or 34.4 kPa man. At the head of: heat transfer material (eg, sand) will provide the AP (pressure drop) at least sufficient to prevent gas backflow / prevent backflow in the gasifier in the cyclone (s) of the combustor 60. The distribution of nozzles in both CSP and GSP it can be in the range of about one to about four nozzles per square foot. In modalities, the dispensers in any or all vessels (gasifier, combustor, CSP and GSP) comprise from about one to about four nozzles per ft ”.
[000138] [000138] In embodiments, one or more of the sealing pots (either or both a combustor sealing pot, CSP, and / or an aerator sealing pot, GSP) is replaced with an L valve or a J valve. In embodiments, the DFB indirect gasification system described comprises one or more J valves in place of a CSP. In modalities, the DFB indirect gasification system comprises one or more J valves in place of a GSP. In modalities, the DFB indirect gasification system comprises multiple CSPs. In modalities, the multiple CSPs are substantially identical. In modalities, the DFB indirect gasification system comprises multiple GSPs. In modalities, the multiple GSPs are substantially identical. In embodiments, the described gasification system comprises at least one or a CSP and at least one or a GSP. The sealing of the CSP can be in the CSP (whereas the sealing in the GSP can simply be an immersion leg). In embodiments, a J valve is used in the aerator instead of a GSP.
[000139] [000139] The height of the CSP can be determined by the pressure required for sealing, which is the differential pressure between the gasifier cyclone (s) (40 and / or 50) and the combustion 30. The combustion pressure plus a margin of the design can be used to determine the desired height of the CSP (that is, the desired height of the heat transfer material in it). In modalities, the pressure is close to atmospheric. In modalities, the AP is greater than 13.7 kpa man. In modalities, the AP is in the range of about 13.7 kpa man. about . 172.3 kpa man., about 13.7 kpa man. at about 137.8 kpa man., or about 13.7 kpa man. at about 103.4 kpa man. In modalities, the 'differential pressure is about 68.9, 82.7, 103.4, or 137.8 kpa man. Desirably, the AP is no less than about 13.7 kpa man, since pressure equalization is undesirable. In modalities, a smaller AP is used, thus allowing the use of a smaller CSP 70.
[000140] [000140] Although preferred embodiments of the invention have been shown and described, modifications of it can be made by one skilled in the art without departing from the spirit and teachings of the invention. The modalities described here are exemplary only and should not be considered limiting. Many variations and modifications of the invention described herein are possible and are within the scope of the invention. Where numerical ranges or limitations are expressly established, such expressed ranges or limitations must be understood to include iterative ranges or limitations of magnitude that fall within the expressly established ranges or limitations (for example, from about | to about 10 includes, 2, 3 , 4, etc .; greater than 0.10 includes 0.11, 0.12, 0.13 and so on). Use of the term “optionally” in relation to any element must mean that the element in question is required, or alternatively, is not required. Both alternatives must be within the scope of the claim. Use of broader terms, such as understand, include, having, etc. is to be understood to provide support for more rigid terms, such as consisting of, consisting essentially of, composed substantially of and the like.
[000141] [000141] In this way, the scope of protection is not limited by the description presented above, but is only limited by the following claims, the scope including all equivalents of the subject in question of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention.
Thus, the claims are an additional description and are in addition to: preferred embodiments of the present invention.
The descriptions of all patents, patent applications and publications cited herein are incorporated by reference, to the extent that they provide exemplary, procedural or other details in addition to those presented here.

权利要求:
Claims (34)
[1]
1. Method for the production of synthesis gas, characterized by the fact that the method comprises: introducing a feed material to be gasified in a gasification apparatus comprising at least one fluidized component that can be operated as a fluidized bed, in which the apparatus gasification is configured to convert at least a portion of the feed material into an aerator product gas comprising synthesis gas; and maintaining fluidization of at least one fluidized component by introducing a fluidizing gas therein, wherein the fluidizing gas comprises at least one component other than steam.
[2]
2. Method according to claim 1, characterized in that the fluidizing gas comprises less than about 100, 90, 80, 70, 60, 50, 40, 30, 20, or 10 percent by volume of steam , or substantially comprises the volume percent of steam.
[3]
3. Method according to claim 1, characterized by the fact that at least one component is selected from the group consisting of natural gas, flue gas, synthesis gas, LP flue gas, Fischer-Tropsch exhaust gas , exhaust gas from the heavy oil processor product, VSA exhaust gas, PSA exhaust gas, exhaust gas, CO2-rich gas, dry wind gas, combustion air, oxygenates and combinations thereof and in which at least one fluidized component is selected from the group consisting of fluidized bed pyrolyzers, fluidized bed combustors, gasifier sealing pots and combustor sealing pots, preferably wherein at least one fluidized component is selected from the group consisting of pyrolyzers and pots of sealing. sealing.
[4]
4. Method according to claim 1, characterized by the fact that it still comprises producing at least one component downstream or upstream of the gasification apparatus, in which at least one component comprises natural gas, in which the gasification apparatus comprises a double fluidized bed gasifier comprising a fluidized bed low pressure pyrolyzer fluidly connected with a fluidized bed combustor, such that a circulating stream comprising a heat transfer material can be continuously circulated between the pyrolyzer, wherein the circulating stream temperature is reduced by means of endothermic pyrolysis and the fluidized bed combustion, wherein the circulating stream temperature is increased, where the fluidized bed combustion can be operated to increase the circulating stream temperature by combustion medium of at least coal introduced into it with the circulating current, and in q that combustion in the combustion is carried out by introducing hot combustion air into it and wherein the method further comprises using a portion of the hot combustion air as the fluidizing gas for at least one other component of the double fluidized bed gasifier in addition to the combustion fluidized bed, and where combustion in the combustion produces a combustion flue gas and the method further comprises using at least a portion of the combustion flue gas as the fluidizing gas.
[5]
5. Method according to claim 4, characterized by the fact that it further comprises conditioning the product gas from the aerator to provide a conditioned synthesis gas having a molar ratio of hydrogen to carbon monoxide that is different from the molar ratio of hydrogen for carbon monoxide in the gasifier product gas, a reduced amount of at least one component with respect to the amount of the component in the gasifier product gas, or both and wherein it comprises using at least a portion of the gasifier product gas as fluidizing gas.
[6]
6. Method according to claim 5, characterized in that it further comprises separating hydrogen from at least a portion of the conditioned synthesis gas to provide a separate hydrogen stream and a reduced hydrogen gas, and using at least a portion of reduced hydrogen gas as a fluidizing gas and where the method further comprises converting at least a portion of the conditioned synthesis gas into Fischer-Tropsch hydrocarbons by means of Fischer-Tropsch synthesis and processing heavy oil at least a portion of the hydrocarbons Fischer-Tropsch by reaction with at least a portion of the separated hydrogen stream.
[7]
7. Method according to claim 5, characterized in that conditioning of the gasifier product gas comprises introducing at least a portion of the gasifier product gas into a synthesis gas conditioner configured to change the molar ratio of hydrogen for carbon monoxide in the gas from the gasifier product, where the synthesis gas conditioner comprises a partial oxidation reactor and where the partial oxidation reactor is configured for operation at a temperature in the range of 900ºC to 1500ºC, 1000ºC 1300ºC, or 1150ºC to 1250ºC.
[8]
8. Method, according to claim 7, characterized by the fact that it still comprises producing oxygen-enriched air to introduce into the partial oxidation reactor, while producing oxygen-enriched air produces a product rich in nitrogen and using at least a portion of the product rich in nitrogen as a gasifier fluidization gas, and in which producing oxygen-enriched air comprises adsorption by vacuum oscillation.
[9]
9. Method according to claim 5, characterized by the fact that conditioning synthesis gas comprises reforming at least a portion of the synthesis gas, thereby producing a conditioned synthesis gas having an molar ratio of hydrogen to carbon monoxide with with respect to the molar ratio of hydrogen to carbon monoxide in the gas product of the gasifier, and where the conditioning synthesis gas comprises extracting a flue gas rich in carbon dioxide from at least a portion of the product gas of the gasifier and in which the method further comprises using at least a portion of the flue gas rich in carbon dioxide as the fluidizing gas.
[10]
Method according to claim 9, characterized in that extracting a flue gas rich in carbon dioxide from at least a portion of the gasifier product gas comprises introducing at least a portion of the gas gas from the aerator in a carbon dioxide removal unit, where the carbon dioxide removal unit operates through pressure differentiation and where the carbon dioxide removal unit is a pressure swing adsorption unit (PSA) .
[11]
11. Method according to claim 4, characterized by the fact that it still comprises converting at least a portion of the synthesis gas into Fischer-Tropsch hydrocarbons by means of Fischer-Tropsch synthesis and in which the Fischer-Tropsch conversion at least a portion of the synthesis gas produces a Fischer-Tropsch exhaust gas and in which at least a portion of the Fischer-Tropsch exhaust gas is used as the fluidizing gas.
[12]
12. Method according to claim 11, characterized by the fact that it still comprises subjecting at least a portion of the Fischer-Tropsch hydrocarbons to heavy product oil processing, in which heavy product oil processing produces an exhaust gas heavy product processing oil and use at least a portion of the product's heavy oil processing exhaust gas as a fluidizing gas and wherein at least one fluidized component comprises a fluidized bed gasifier and in which at least a portion of the Exhaust gas from heavy oil processing of the product is introduced as gasifier fluidizing gas.
[13]
13. Method according to claim 11, characterized in that it further comprises extracting a gas enriched with carbon dioxide from at least a portion of the exhaust gas from Fischer-Tropsch and using at least a portion of the gas enriched with dioxide carbon as a fluidizing gas, in which the extraction of a gas enriched with carbon dioxide from at least a portion of the Fischer-Tropsch exhaust gas comprises bringing at least a portion of the Fischer-Tropsch exhaust gas into contact with a membrane designed for hydrogen recovery, thus providing a flue gas enriched with low BTU carbon dioxide and using at least a portion of the gas enriched with carbon dioxide as the fluidizing gas.
[14]
14. Method according to claim 11, characterized by the fact that Fischer-Tropsch synthesis is associated with the production of a Fischer-Tropsch waste water comprising oxygenates and in which the method further comprises removing oxygenates from at least a portion of Fischer-Tropsch waste water by contacting it with at least a portion of the Fischer-Tropsch exhaust gas, to produce an oxygenated Fischer-Tropsch exhaust gas and a reduced oxygenated and Fischer-Tropsch waste water using at least a portion of the Fischer-Tropsch exhaust gas containing oxygen as the fluidizing gas.
[15]
15. Method according to claim 11, characterized by the fact that Fischer-Tropsch synthesis is associated with the production of a Fischer-Tropsch residual water comprising oxygenates and in which the method further comprises removing oxygenates from at least one portion of the residual Fischer-Tropsch water by contacting it with steam, to produce a vapor containing oxygenate and a residual water of Fischer-Tropsch reduced in oxygenate and using at least a portion of the vapor containing oxygenate as the fluidizing gas a hydrocarbon-containing purge gas is extracted during Fischer-Tropsch synthesis and in which at least a portion of the hydrocarbon-containing purge gas is used as the fluidizing gas.
[16]
16. Method according to claim 4, characterized by the fact that it still comprises drying at least a portion of the feed material to reduce its moisture content before introduction into the gasification apparatus, in which drying at least a portion of the The feed material further comprises placing at least a portion of the feed material in contact with a drying medium to provide a gasifier feed material with reduced humidity and a dry wind gas comprising volatile organic compounds (VOC's), in which the method it further comprises using at least a portion of the dry wind gas as the fluidizing gas, and wherein the drying medium comprises superheated steam.
[17]
17. Method according to claim 5, characterized by the fact that the gasifier feed material is introduced into the pyrolyzer of a feed box configured for storing gasifier feed material and in which the method further comprises introducing at least a portion of the combustion flue gas in the supply box, while direct contact of the combustion flue gas with the gasifier feed material provides a dry gasifier feed material to introduce into the pyrolyzer and an opening gas from the fuel box where the method still comprises using at least a portion of the opening gas in the supply box as fluidizing gas, and where it further comprises using at least a portion of the gas from the gasifier product to produce energy, using at least one gas portion of the gasifier product in a catalytic operation downstream of the gasifier, or am bos.
[18]
18. Method according to claim 1, characterized by the fact that it still comprises obtaining a desired molar ratio of hydrogen to carbon monoxide in the gas of the gasifier product by adjusting the amount, composition, or both the amount and the composition of hair one component of the non-vapor fluidizing gas and the method further comprises adjusting the amount, composition, or both the amount and composition of at least one component of the non-vapor fluidizing gas, in such a way that the moisture content of the gas of the gasifier product is below a desired level.
[19]
19. Method, according to claim 1, characterized by the fact that it still comprises performing vacuum oscillation adsorption (VSA), pressure oscillation adsorption (PSA), or both, downstream of the gasification apparatus, thus producing at least least one exhaust gas selected from the group consisting of exhaust gas VSA and exhaust gas PSA and use at least a portion of at least one exhaust gas as at least one component of the non-vapor fluidization gas.
[20]
20. Method according to claim 1, characterized by the fact that it still comprises production, downstream of the gasifier, of at least one product selected from the group consisting of Fischer-Tropsch hydrocarbons, energy and non-Fischer-Tropsch chemicals of at least a portion of the product gas from the gasifier, and wherein the method further comprises using at least a portion of a hydrocarbon-containing fluid produced downstream of the gasifier and at least one component of the non-vapor fluidizing gas.
[21]
21. System for the production of synthesis gas, characterized by the fact that the system comprises:
a gasification apparatus configured to convert at least a portion of a gasifier feed material introduced therein into a gasification product gas comprising synthesis gas having a molar ratio of hydrogen to carbon monoxide, wherein the gasification apparatus comprises at least at least one vessel configured to fluidize its contents by introducing a fluidizing gas into it comprising at least one non-vapor component; at least one additional apparatus selected from the group consisting of the feed preparation apparatus located upstream of the gasification apparatus and configured to prepare a carbonaceous material for introduction into the gasification apparatus; synthesis gas conditioning apparatus configured to produce a conditioned synthesis gas having a molar ratio of hydrogen to carbon monoxide that is different from the molar ratio of hydrogen to carbon monoxide in the gasification product gases, to provide a synthesis gas conditioned having a reduced amount of at least one component with respect to the amount of the component in the gaseous product gases, or both; and synthesis gas utilization apparatus configured to convert at least a portion of the synthesis gas into a desired product; and at least one current that fluidly connects to at least one additional apparatus or an outlet of the gasifier with at least one vessel from the gasifier, whereas a gas from at least one additional apparatus or which leaves the gasifier may supply at least one component of the non-vapor fluidization gas.
[22]
22. System according to claim 21, characterized in that at least one vessel is configured for fluidization with a fluidizing gas comprising less than about 100. 90. 80. 70. 60. 50.
40. 30. 20. or 10 percent by volume of steam, or substantially comprising 0 percent by volume of steam.
[23]
23. System according to claim 21, characterized by the fact that at least one non-vapor component is selected from the group consisting of flue gas, synthesis gas, LP flue gas, Fischer-Tropsch exhaust gas, exhaust gas from the heavy oil processor product, VSA exhaust gas, PSA exhaust gas, exhaust gas, CO2-rich gas, dry wind gas, combustion air, oxygenates, VOC's and combinations of these and in which the product is selected from the group consisting of energy, Fischer-Tropsch hydrocarbons and non-Fischer-Tropsch chemicals.
[24]
24. System according to claim 21, characterized by the fact that it comprises synthesis gas conditioning apparatus downstream of the gasification apparatus and a recycling stream that fluidly connects to the synthesis gas conditioning apparatus with the apparatus gasification, while at least a portion of a gas leaving the synthesis gas conditioning apparatus can be used as a fluidizing gas, wherein the synthesis gas conditioning apparatus comprises a partial oxidation reactor, in which the partial oxidation reactor is configured for operation at a temperature in the range of 900ºC to 1500ºC, 1000ºC to 1300ºC, or 1150ºC to 1250ºC, in which the synthesis gas conditioning apparatus comprises a carbon dioxide removal apparatus configured to remove a carbon dioxide-rich flue gas from at least a portion of the gasification product gases and a recycling stream that fluidly connects to the carbon dioxide removal apparatus with at least one vessel, while at least a portion of the carbon dioxide-rich flue gas can be used as a fluidizing gas and the carbon dioxide removal apparatus comprises a unit adsorption by pressure oscillation (PSA).
[25]
25. System according to claim 24, characterized by the fact that it still comprises an air enrichment apparatus configured to supply air enriched with oxygen or substantially pure oxygen to introduce into the partial oxidation reactor, thus producing a reduced product gas of oxygen and a recycling stream that fluidly connects to the air enrichment apparatus with at least one vessel, while at least a portion of the reduced oxygen product gas can be used as the fluidizing gas and the oxygen enrichment apparatus air is selected from the group consisting of vacuum swing adsorbents and pressure swing adsorbents.
[26]
26. System according to claim 21, characterized by the fact that it comprises a feed preparation apparatus and a current that fluidly connects to a vent gas outlet of the feed preparation apparatus with the gasification apparatus, whereas at least a portion of a vent gas which is from the feed preparation apparatus can be used as a fluidizing gas, wherein the feed preparation apparatus comprises a dryer configured to reduce the moisture content of a relatively wet feed material of the gasifier to provide a lower moisture feed material to introduce into the gasifier by contacting the relatively wet feed material of the gasifier with a drying medium to provide the gasifier feed material with reduced humidity and a wind gas dry matter comprising volatile organic compounds (VOC's) and in which the drying medium comprises overheated steam.
[27]
27. System according to claim 23, characterized by the fact that the synthesis gas utilization apparatus comprises Fischer-Tropsch synthesis apparatus configured to convert at least a portion of the gasification product gases into Fischer-hydrocarbons Tropsch, thus producing a Fischer exhaust gas
Tropsch, in which at least one recycling stream that fluidly connects to the Fischer-Tropsch synthesis apparatus with the gasification apparatus, while at least a portion of the Fischer-Tropsch exhaust gas can be used as a fluidizing gas and in that the syngas utilization apparatus produces a hydrocarbon-containing purge gas and wherein the syngas utilization apparatus is fluidly connected with the gasification apparatus whereas at least a portion of the hydrocarbon-containing purge gas may be used as fluidizing gas.
[28]
28. System according to claim 27, characterized by the fact that a residual Fischer-Tropsch water comprising oxygenated components is also produced by means of the Fischer-Tropsch synthesis apparatus and in which the system still comprises a remover configured for contact at least a portion of the Fischer-Tropsch waste water with at least a portion of the Fischer-Tropsch exhaust gas, while oxygenates are removed from the Fischer-Tropsch waste water by the Fischer-Tropsch exhaust gas, thus producing a waste water of Fischer-Tropsch reduced in oxygenate and an exhaust gas of Fischer-Tropsch enriched with oxygenate and in which at least one recycling stream that fluidly connects to the remover with the gasifier, while at least a portion of the exhaust gas of Fischer-Tropsch enriched with oxygenate can be used as a fluidizing gas.
[29]
29. System according to claim 27, characterized by the fact that a Fischer-Tropsch waste water comprising oxygenated components is also produced by means of the Fischer-Tropsch synthesis apparatus and in which the system further comprises a vapor remover configured to contact at least a portion of the Fischer-Tropsch waste water with steam while oxygenates are removed from the Fischer-Tropsch waste water by steam, thus producing a reduced oxygenated Fischer-Tropsch waste water and an enriched steam with oxygenate and in which at least one recycling stream that fluidly connects to the vapor remover with the gasification apparatus, while at least a portion of the oxygen-enriched steam can be used as a fluidizing gas.
[30]
30. System according to claim 27, characterized by the fact that the system still comprises a carbon dioxide removal apparatus configured to separate a carbon dioxide-rich gas from the Fischer-Tropsch exhaust gas, thus providing a Fischer-Tropsch exhaust gas reduced in carbon dioxide and where at least one recycle stream that fluidly connects to the carbon dioxide removal apparatus with the gasifier, while at least a portion of the gas rich in carbon dioxide carbon can be used as a fluidizing gas, where the system still comprises a recycling stream whereas the exhaust gas of Fischer-Tropsch reduced in carbon dioxide can be introduced in a synthesis gas conditioning device upstream of the device of Fischer-Tropsch synthesis, a recycling stream while the exhaust gas of Fischer-Tropsch reduced in carbon dioxide can be introduced into the apparatus Fischer-Tropsch synthesis loop, or both, and in which the carbon dioxide removal apparatus comprises a membrane designed for hydrogen recovery, configured to provide a flue gas enriched with low BTU carbon dioxide.
[31]
31. System according to claim 27, characterized by the fact that it still comprises heavy oil processing apparatus of the product configured to convert at least a portion of the Fischer-Tropsch hydrocarbons to more desirable hydrocarbons, in which the processing apparatus heavy product oil is configured to produce a product heavy oil processing exhaust gas and in which at least one recycle stream that fluidly connects to the product's heavy oil processing apparatus with the gasifier while at least A portion of the product's heavy oil processing exhaust gas can be used as a fluidizing gas and in which it comprises synthesis gas conditioning apparatus downstream of the gasification apparatus and further comprises hydrogen recovery apparatus configured to separate hydrogen from a portion of the conditioned synthesis gas and a stream that fluidly connects a to the hydrogen separation apparatus with the product's heavy oil processing apparatus, while separate hydrogen may be used in it.
[32]
32. System according to claim 21, characterized in that at least one additional device comprises at least one unit selected from the group consisting of pressure swing adsorbents, vacuum swing adsorbents and heavy oil product processor and in which at least one recycling stream that fluidly connects at least one unit with the gasification apparatus, while an exhaust gas produced in at least one unit can be used as a fluidizing gas.
[33]
33. System according to claim 21, characterized by the fact that the gasification apparatus is a double fluidized bed gasifier comprising a fluidized bed pyrolyzer fluidly connected with a fluidized bed combustor, such that a circulating current comprising a heat transfer material can be continuously circulated between the fluidized bed pyrolyzer, where the temperature of the circulating stream is reduced by means of endothermic pyrolysis and the fluidized bed combustion, where the circulating stream temperature is increased , in which the fluidized bed combustion can be operated to increase the temperature of the circulating stream by combustion of at least coal introduced into it with the circulating stream and in which the gasifier optionally still comprises a gasifier sealing pot , a combustion sealing pot, or both and in which at least one vessel is selected that of the pyrolyzer, the combustor, the sealing pot of the combustion and the sealing pot of the gasifier, in which the combustion is configured to produce a combustion combustion gas and in which at least one recycling stream that fluidly connects to the combustion at least one vessel while at least a portion of the combustion flue gas can be used as a fluidizing gas and in which the feed preparation apparatus comprises a feed box configured for storing gasifier feed material and in which the The system further comprises a recycling stream configured to introduce at least a portion of the combustion flue gas into the supply box, while direct contact of at least a portion of the combustion flue gas with the gasifier feed material provides a material of the dry gasifier to introduce into the aerator and a gas to open the feed box and in which at least one recycle stream that fluidly connects to a dry wind gas outlet stream with the gasifier while at least a portion of a dry wind gas can be used as the fluidization gas.
[34]
34. System according to claim 33, characterized by the fact that at least one vessel is selected from the group consisting of the fluidized bed pyrolyzer, the gasifier sealing pot and the fuel sealing pot and in which the combustor is configured to increase the temperature of the circulation stream by combustion of at least coal in the circulation stream by contact with hot combustion air and in which at least one recycle stream that fluidly connects to an air inlet stream of combustion with at least one vessel, while at least a portion of the hot combustion air can be used as a fluidizing gas.

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同族专利:

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公开号 | 公开日

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CA2852761C|2017-05-16|

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EP2771435A1|2014-09-03|

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US9168500B2|2015-10-27|

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US20130109765A1|2013-05-02|

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EP2771435A4|2015-11-11|

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WO2013062800A1|2013-05-02|

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US10125330B2|2018-11-13|

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CA2852761A1|2013-05-02|

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US20160002547A1|2016-01-07|

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法律状态:
2020-12-15| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE AS 7A E 8A ANUIDADES. |

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2020-12-15| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2021-01-12| B08G| Application fees: restoration [chapter 8.7 patent gazette]|

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2021-04-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-06-01| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-08-10| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 9A ANUIDADE. |

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2021-10-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-11-09| B08G| Application fees: restoration [chapter 8.7 patent gazette]|

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2021-11-16| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: PAGAR RESTAURACAO. |

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2021-12-07| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2022-03-08| B08K| Patent lapsed as no evidence of payment of the annual fee has been furnished to inpi [chapter 8.11 patent gazette]|Free format text: EM VIRTUDE DO ARQUIVAMENTO PUBLICADO NA RPI 2654 DE 16-11-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDO O ARQUIVAMENTO DO PEDIDO DE PATENTE, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161551582P| true| 2011-10-26|2011-10-26|

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US61/551582|2011-10-26|

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PCT/US2012/060231|WO2013062800A1|2011-10-26|2012-10-15|Gasifier fluidization|

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