method for the production of synthesis gas

专利摘要:
METHOD FOR THE PRODUCTION OF SYNTHESIS GAS A system configured for the production of at least one product selected from the group consisting of syngas, Fischer-Tropsch synthesis products, energy, and chemicals is described, the system comprising a bed gasification apparatus double fluidized and at least one device selected from an energy production device configured to produce energy from gas from the gasification, partial oxidation reactors configured to oxidize at least a portion of the product gas, tar removal device configured to reduce the amount of tar in the product gas, Fischer-Tropsch synthesis device configured to produce Fischer-Tropsch synthesis products from at least a portion of the product gas, chemical production apparatus configured to produce at least one non-product Fischer-Tropsch of at least a portion of the product gas, and fluidized bed gasification units d configured to change the composition of the product gas. Methods of operating the system are also provided.
公开号:BR112014001851B1
申请号:R112014001851-0
申请日:2012-07-27
公开日:2021-03-09
发明作者:Weibin Jiang；Bruce Mccomish；Bryan C. Borum；Benjamin Carryer；Mark Ibsen；Mark Robertson；Eric Elrod；Sim Weeks；Harold A. Wright
申请人:Rentech, Inc；
IPC主号:

专利说明:

Field of invention
[0001] This disclosure refers in general to the gasification field. More specifically, the disclosure relates to a system and method for the production of syngas by means of gasification of carbonaceous materials. Even more specifically, the disclosed system and method are suitable for the production of synthesis gas for use in Fischer-Tropsch hydrocarbon synthesis, in energy production, in the production of non-Fischer-Tropsch chemicals / fuels, or a combination thereof. Fundamentals of the Invention
[0002] 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 serve as carbonaceous sources for gasification, including, for example, chopped tree bark, wood chips, sawdust, sludge (for example, sewage sludge), municipal solid waste, RDF, and a variety of other carbonaceous materials .
[0003] 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 "syngas". The liquid product of the reaction is typically refined to produce a range of synthetic fuels, lubricants and waxes. The primary metals used as catalysts are cobalt and iron. Providing synthesis gas with a desired molar ratio of hydrogen to carbon monoxide is necessary for economical production of Fischer-Tropsch synthesis products.
[0004] There is a need in the art for improved gasification systems and methods, whereby materials (which can generally be considered waste) can be converted into gas suitable for the production of energy and / or for the production of various products chemicals and / or fuels (including, without limitation, Fischer-Tropsch synthesis products). SUMMARY OF THE INVENTION
[0005] Here is revealed a system configured for the production of at least one product selected from the group consisting of synthesis gas, Fischer-Tropsch synthesis products, energy, and chemicals, the system comprising: a fluidized bed gasification apparatus double including a gasifier and a combustion, in which the combustion is configured to heat a particulate heat transfer material, thus producing a combustion waste gas; and where the gasifier is configured to receive the heated particulate heat transfer material and a carbonaceous feed charge, whereby the heated particulate heat transfer material provides heat for endothermic gasification of the carbonaceous feed charge, thereby producing a gas gasification product comprising hydrogen and carbon monoxide; and at least one apparatus selected from the group consisting of an energy generating apparatus configured to produce energy from at least a portion of the gas resulting from gasification, partial oxidation reactors configured to oxidize at least a portion of the gas resulting from gasification, tar removal apparatus configured to reduce the amount of tar in the gas from gasification, Fischer-Tropsch synthesis apparatus configured to produce Fischer-Tropsch synthesis products from at least a portion of the gas from gasification, gas production apparatus chemicals configured to produce at least one non-Fischer-Tropsch product from at least a portion of the gasification product gas, and double fluidized bed gasification units configured to change the composition of at least a portion of the product gas from gasification.
[0006] In modalities, the system comprises Fischer-Tropsch synthesis apparatus. The Fischer-Tropsch synthesis device can be operated with an iron-based Fischer-Tropsch catalyst; and (a) the double fluidized bed gasification apparatus is operable to provide a gas product of the gasification with a molar ratio of hydrogen to carbon monoxide which is in the range of about 0.5: 1 to about 1.5: 1, (b) the system additionally comprises apparatus configured to adjust the molar ratio of hydrogen to carbon monoxide in at least a portion of the gas product of the gasification to a value in the range of about 0.5: 1 to about 1, 5: 1, or both (a) and (b). In modalities, the Fischer-Tropsch synthesis device is operable with a cobalt-based Fischer-Tropsch catalyst; and (a) the double fluidized bed gasification apparatus is operable to provide a gas product of the gasification with a molar ratio of hydrogen to carbon monoxide in the range of about 1.5: 1 to about 2.5: 1, (b) the system additionally comprises apparatus configured to adjust the molar ratio of hydrogen to carbon monoxide in at least a portion of the gas product of the gasification in a value in the range of about 1.5: 1 to about 2.5: 1, or both (a) and (b). The Fischer-Tropsch synthesis apparatus may comprise at least one Fischer-Tropsch synthesis reactor configured to produce non-gaseous Fischer-Tropsch synthesis products from at least a portion of the gasification product. The Fischer-Tropsch synthesis reactor can be additionally operable to provide a residual process gas with a Fischer-Tropsch. In such embodiments, the system may additionally comprise a recycling line through which at least a portion of the residual Fischer-Tropsch process gas can be introduced into the double fluidized bed gasification apparatus. In embodiments, at least a portion of the residual Fischer-Tropsch process gas is introduced into a component of the system selected from the group consisting of the combustor, the aerator, and sealing pots configured to prevent reflux of material from the combustor or aerator.
[0007] The system may comprise an energy production apparatus. The energy producing apparatus may comprise a gas turbine.
[0008] In embodiments, the system comprises a Fischer-Tropsch synthesis apparatus comprising a solid / liquid separator configured to separate a used catalyst product comprising Fischer-Tropsch catalyst and Fischer-Tropsch synthesis product from non-gaseous Fischer-Tropsch synthesis products . Such a system may additionally comprise one or more recycling lines configured to introduce at least a portion of the catalyst product used in the double fluidized bed gasification apparatus. The system may comprise at least one recycling line selected from the group consisting of recycling lines fluidly connecting the solid / liquid separator with the combustor, whereby the used catalyst product can be introduced into the combustor for use as a fuel; and recycling lines fluidly connecting the solid / liquid separator with the gasifier, whereby additional product gas can be produced via the gasification of at least a portion of the used catalyst product.
[0009] In modalities, the gasifier is configured to convert at least a portion of the carbonaceous feed load into animal coal and the system is configured to transfer the animal coal out of the gasifier. In embodiments, the system is configured to transfer at least a portion of the animal coal to the combustor, and the combustor is configured to burn the animal coal to provide at least a portion of the heat to heat the particulate heat transfer material. In embodiments, the combustion is configured to operate substantially without fuel in addition to animal coal. In modalities, the combustion is configured for operation with a supplementary fuel selected from the group consisting of tar, Fischer-Tropsch wax, Fischer-Tropsch residual process gas, quality improving process residual gas, refinery tank waste, heavy fuel oil , liquid fuel oil, and combinations thereof.
[00010] In embodiments, the system comprises a tar removal apparatus, and the supplementary fuel for the combustion comprises tar removed by means of the tar removal apparatus. In embodiments, the system comprises a tar removal apparatus, and the system additionally comprises at least one recycling line selected from the group consisting of recycling lines fluidly connecting the tar removal apparatus with the combustor, whereby at least a portion of the tar removed by means of the tar removal apparatus can be burned to heat the particulate heat transfer material; and recycling lines fluidly connecting the tar removal apparatus with the aerator, whereby at least a portion of the tar removed by means of the tar removal apparatus can be aerated to provide additional gasification gas.
[00011] In modalities, the system comprises Fischer-Tropsch synthesis apparatus and the supplementary fuel for the combustor comprises Fischer-Tropsch residual process gas, Fischer-Tropsch wax (for example, liquid FT products), or both produced in the Fischer-Tropsch synthesis.
[00012] In modalities, the system comprises Fischer-Tropsch synthesis apparatus and quality improvement apparatus located downstream of the Fischer-Tropsch synthesis apparatus, and the supplementary fuel for the combustion comprises quality improving process waste gases produced in the apparatus quality improvement.
[00013] In modalities, the gasifier is configured for operation in a pressure gasifier and the combustor is configured for operation at a combustion pressure in the range of about 0 kPaman. up to a pressure that is at least 13.78951 kPaman less than the gasifier pressure.
[00014] In embodiments, the aerator is configured to provide an entrapped product comprising particulate heat transfer material trapped in the gas product of the aeration, and the system comprises at least one particulate separator selected from the group consisting of configured aerator particulate separators. to separate gas product from gasification from the trapped product; and combustor particulate separators configured to separate heated particulate heat transfer material from the combustor waste gas. Such a system can additionally comprise at least one expander downstream of at least one particulate separator from the combustor. The system may additionally comprise heat recovery apparatus downstream of at least one expander. The system can comprise at least one combustor particulate separator which is a cyclone, and the at least one combustor cyclone can be operable at a surface speed in the range of about 21.34 to about 25.91 m / s.
[00015] In embodiments, the system comprises (a) at least one particulate separator from the primary gasifier configured to separate particulate heat transfer material from the trapped product, thus providing a low particulate product comprising ash, and at least one particulate separator of the secondary gasifier configured to separate particulate heat transfer material from the low particulate product, (b) at least one particulate separator from the primary combustor configured to separate particulate heat transfer material from the waste gas, thereby providing a low waste gas particulate comprising ash, and at least one particulate separator from the secondary combustion configured to separate particulate heat transfer material from the particulate low disposal gas; or both (a) and (b). Such a system can be configured to introduce particulate materials separate from the particulate separator of the primary gasifier, the particulate separator of the secondary gasifier, or both, into the combustor for heating in it and / or can additionally comprise a downstream washing system the particulate separator of the secondary gasifier, a washing system downstream of the particulate separator of the secondary combustion, or both, in which the washing system is configured to wash sulfur from a gas introduced into it, through its contact with a liquid comprising at least a portion of the ash. In embodiments, the at least one particulate separator from the primary gasifier, the at least one particulate separator from the primary combustor, or both, is configured to remove more than 99, 99.9 or 99.98 percent by weight of the material of particulate heat transfer from a gas introduced into it. In embodiments, the at least one particulate separator from the secondary gasifier, the at least one particulate separator from the secondary combustor, or both, is configured to remove more than about 60, 70, 80, 85 or 90 percent by weight of the ash of a gas introduced into it.
[00016] Various embodiments of the system comprise one or more heat recovery devices configured for heat recovery from gas from the gasification, the combustion gas, or both, from the gasification gas and the combustion gas. . In embodiments, the system comprises a tar removal apparatus and a heat recovery apparatus configured to use the heat from the gas from the gasification, in which the heat recovery apparatus is configured to reduce the temperature of the gas from the gasification to no. less than about 427 ° C, 371 ° C or 316 ° C upstream of the tar removal apparatus. The at least one heat recovery apparatus may comprise at least one component selected from the group consisting of air preheaters, boiler feed water preheaters, steam superheaters, residual heat boilers, residual heat superheaters and economizers. In modalities, the system comprises an air preheater air configured to recover heat from the gas from the gasification and introduce heated air into the combustion. In embodiments, the system comprises (a) at least one heat recovery device located downstream of at least one particulate separator from the primary gasifier, (b) at least one heat recovery device located downstream of at least one separator. of particulate from the primary combustor, or both (a) and (b). In embodiments, the system comprises (a) at least one heat recovery device located upstream of at least one particulate separator from the secondary gasifier, (b) at least one heat recovery device located upstream of at least one separator of particulate from the secondary combustion, either (a) or (b). In embodiments, the system comprises at least one secondary particulate separator located downstream of at least one heat recovery apparatus and operable at a temperature below about 204 ° C.
[00017] In modalities, the system comprises heat recovery apparatus downstream of at least one particulate separator. In embodiments, the system comprises at least one sealing device selected from sealing pots and valves configured to prevent reflux of material from the combustor to the at least one particulate separator from the aerator or aerator to the at least one particulate separator from the combustor. . The valve can be selected from J valves and L valves. In embodiments, the system comprises a J valve configured to prevent backflow of material from the gasifier to at least one particulate separator from the combustor. In embodiments, the system comprises at least one sealing pot selected from combustor sealing pots configured to prevent reflux of material from the combustor to the at least one particulate separator from the aerator and sealing pots of the aerator configured to prevent reflux of material from the combustor. aerator in at least one particulate separator of the combustor. The at least one sealing pot can be configured for operation at a minimum fluidization speed greater than about 0.06 m / s. The at least one sealing pot can be configured for operation at a minimum fluidization speed greater than about 0.46 m / s. The pressure drop across at least one sealing pot can be at least 13.78951 kPaman, and / or less than about 137.8951 kPaman. In embodiments, the at least one particulate separator comprises an extending leg from or near its base, and the leg extends a distance into the at least one sealing pot from or near its top. The at least one sealing pot may comprise a dispenser and the leg of the at least one particulate separator may extend a distance of not less than about 25.4, 27.94, 30.48, 33.02, 35 , 56, 38.1, 40.64, 43.18 or 45.72 cm (from the sealing pot dispenser). In modalities, the minimum distance from the leg to a side or base of the sealing pot is at least 25.4 centimeters.
[00018] In modalities, the system comprises at least two particulate separators of the aerator, each comprising a leg extending a distance inside a combustion sealing pot; at least two particulate separators of the combustor, each comprising a leg extending a distance into a gasifier sealing pot; or both, where the minimum leg-to-leg separation within a sealing pot is at least 25.4 centimeters. In embodiments, an angle selected from the group consisting of an angle formed between at least one sealing pot of the combustor and the combustor and an angle formed between at least one sealing pot of the aerator and the aerator is in the range of about 5 ° to about 90 °. In modalities, the angle is less than about 45 °. In embodiments, the system comprises at least one combustor sealing pot, and the at least one combustor sealing pot is fluidized by a fluidizing gas from the combustor sealing pot. The combustion can be configured for fluidization with a combustion fluidization gas (which can be introduced via line 121) comprising basically air or oxygen. In modalities, the combustion is configured for operation with excess oxygen in the range of about 0 to about 20 percent by volume. In embodiments, at least or about 20% of the combustor fluidization gas required in the combustor is introduced through at least one combustion sealing pot. The at least one sealing pot may be substantially round or substantially rectangular. In embodiments, the at least one sealing pot is substantially rectangular and the operating pressure of at least one rectangular sealing pot is less than about 103.4214 kPaman.
[00019] In system modalities, particulate heat transfer material is selected from the group consisting of sand, limestone, and other calcites or oxides including iron oxide, olivine, and magnesia, alumina, carbides, silica alumina, zeolites, and combinations of these. The particulate heat transfer material may comprise a catalyst.
[00020] In modalities, the system comprises a feed input of carbonaceous material fluidly connected with the aerator and configured to introduce the load of carbonaceous feed into the aerator. In embodiments, an angle formed between the carbonaceous material inlet and the gasifier is in the range of about 5 ° to about 20 °. The carbonaceous feed load may comprise at least one material selected from the group consisting of biomass, RDF, MSW, sewage sludge, coal, Fischer-Tropsch synthetic wax, and combinations thereof. In modalities, the gasifier is operable with carbonaceous feed stocks at any temperature in the range of about -40 ° C to about 127 ° C. The system can be configured to introduce a purge gas with the carbonaceous feed charge. The purge gas can be selected from the group consisting of carbon dioxide, steam, waste gas, nitrogen, synthesis gas, combustor waste gas, and combinations thereof. The system may comprise apparatus (for example, apparatus downstream 100) for the removal of carbon dioxide from the combustor waste gas, gas from the gasification, or both; and one or more recycling lines fluidly connecting the carbon dioxide removal apparatus (for example, via line 115) with a carbonaceous material feed inlet from the gasifier, whereby at least a portion of the carbon dioxide removed can be introduced into the aerator as a purge gas.
[00021] In modalities, the combustion is operable in such a way that an operating temperature at or near its inlet for heat transfer material is in the range of about 538 ° C to about 760 ° C, and a temperature operational at or near its outlet for a combustor particulate separator in the range of about 760 ° C to about 982 ° C. The system may comprise a dryer upstream of the aerator, in which the dryer is configured to remove moisture from the carbonaceous feed load before being introduced into the aerator. The system may comprise a line configured to introduce at least a portion of the combustion waste gas into the dryer, whereby hot combustion waste gas can be used to dry the carbonaceous feed charge. In embodiments, the gasifier is operable with a carbonaceous feed load with a moisture content in the range of about 10 to about 40 weight percent.
[00022] The system can be operable to convert at least about 30, 40, 50, 60, 70 or 80% of the carbon in the carbonaceous feed load into gas from gasification. In embodiments, the gasifier is operable at a carbonaceous feed charge rate of at least 10,000 kg / h.m2, 12,000 kg / h.m2, 12,500 kg / h.m2, 15,000 kg / h.m2, 17,000 kg / h .m2 or 20,000 kg / h.m2. In embodiments, the aerator is configured to fluidize with an aerator fluidizing gas with a surface velocity of the inlet aerator fluidizing gas in the range of about 15.24 cm / s to about 304.8 cm / s. In embodiments, the gasifier is operable at a shallow gas outlet velocity product of the gasification comprising particulate heat transfer material trapped in the range of about 1,067 to about 1,524 cm / s. In embodiments, the gasifier is operable at an operating temperature in the range of about 538 ° C to about 871 ° C. In modalities, the gasifier is operable at an operating pressure greater than about 13.78951 kPaman. In embodiments, the gasifier is operable at an operating pressure of less than about 310.2641 kPaman. In embodiments, the combustor is configured to fluidize with a combustor fluidizing gas with a surface velocity of the incoming combustor fluidizing gas. in the range of about 457 to about 762 cm / s. In embodiments, the combustion is operable with a surface velocity of the exhaust gas in the range of about 762 to about 1,219 cm / s. In embodiments, the aerator comprises an aerator distributor configured to introduce gasification fluidization gas substantially uniformly across the diameter of the aerator, the combustion comprises a combustor distributor configured to introduce fluidization gas from the combustor substantially uniformly across the diameter of the combustion, or both. In embodiments, the combustion is configured to receive particulate heat transfer material at a location at least about 122, 152 or 183 centimeters above the combustion distributor; the gasifier is configured to receive fluidized particulate heat transfer material heated in a location at least about 122, 152 or 183 centimeters above the gasifier distributor; or both.
[00023] In modalities, the system is operable to provide, from the combustor to the gasifier, fluidized particulate heat transfer material heated with a temperature in the range of about 760 ° C to about 871 ° C. In modalities, the operating temperature differential between the gasifier and the combustion is less than about 167 ° C. In embodiments, the system optionally comprises at least one sealing pot selected from combustor sealing pots configured to prevent reflux of combustor material to the at least one particulate separator from the aerator, and gasifier sealing pots configured to prevent reflux from gasifier material for at least one particulate separator of the combustor; and at least one component selected from the group consisting of the gasifier, the combustor, at least one sealing pot of the combustor and at least one sealing pot of the gasifier is configured with a dead zone between a distributor and a base thereof, in accordance with in such a way that elimination of occasional services can be done during operation.
[00024] Also disclosed here is a method comprising: introducing a carbonaceous feed charge and a heated particulate heat transfer material into a gasifier comprising a fluidized bed, whereby at least a portion of the carbonaceous material is pyrolyzed to produce a gasification product gas comprising hydrogen and carbon monoxide, and wherein the fluidized bed comprises fluidized particulate heat transfer material by introducing a fluidizing gas from the gasifier into the gasifier; removing, from a region of the trapped space of lower average density of the gasifier, a gas product of the gasification comprising, trapped therein, animal charcoal, particulate heat transfer material, and optionally unreacted carbonaceous feed charge; separating at least one solid product comprising animal charcoal, particulate heat transfer material, and optionally unreacted carbonaceous material from the gas product of the gasification, providing a low particulate product gas; heating at least a portion of the at least one solids product by passing it through a combustion, thereby producing a heated portion of the at least one solids product and a combustion waste gas, wherein at least a portion of the heat for heating it is obtained by combustion of the animal charcoal in at least a portion of the at least one solids product; and introducing at least a portion of the heated portion of the at least one solids product into the gasifier, providing heat for pyrolysis. In embodiments, the product comprises Fischer-Tropsch synthesis products, and the method additionally comprises subjecting at least a portion of the gasification product to Fischer-Tropsch synthesis. Subjecting at least a portion of the gasification product to Fischer-Tropsch synthesis may comprise putting at least a portion of the gasification product in contact with an iron-based Fischer-Tropsch catalyst. The method may further comprise adjusting the molar ratio of hydrogen to carbon monoxide in the gas product of the gasification to provide a molar ratio in the range of about 0.5: 1 to about 1.5: 1 before subjecting to at least one portion of the gas product of the gasification the Fischer-Tropsch synthesis. Adjustment may comprise subjecting the gas from the gasification to partial oxidation. Subjecting at least a portion of the gasification product to Fischer-Tropsch synthesis may comprise putting at least a portion of the gasification product in contact with a cobalt-based Fischer-Tropsch catalyst. Such methods may further comprise adjusting the molar ratio of hydrogen to carbon monoxide in the gas product of the gasification to provide a molar ratio in the range of about 1.5: 1 to about 2.5: 1 before subjecting to at least one portion of the gas product of the gasification the Fischer-Tropsch synthesis. Subjecting at least a portion of the gasification product to Fischer-Tropsch synthesis can produce non-gaseous Fischer-Tropsch synthesis products, a residual Fischer-Tropsch process gas, and a used catalyst product comprising used Fischer-Tropsch catalyst and liquid hydrocarbons. The method may comprise introducing at least a portion of a residual Fischer-Tropsch process gas into a component selected from the group consisting of the combustor, aerator, and sealing pots configured to prevent reflux of material from the combustor or aerator. The method may comprise introducing at least a portion of the catalyst product used in the gasifier, the combustor, or both.
[00025] In modalities, the method additionally comprises producing energy through at least a portion of the gas resulting from gasification. The method can comprise producing energy from at least about 10, 20, or 30 percent by volume of the gasification gas, and subjecting at least a portion of the remaining gasification gas to Fischer-Tropsch synthesis.
[00026] In modalities, the method comprises introducing an additional fuel into the combustor. Supplementary fuel can be selected from the group consisting of tar, Fischer-Tropsch wax, Fischer-Tropsch residual process gas, quality improving process residual gas, refinery tank waste, heavy fuel oil, liquid fuel oil, and combinations of these . In embodiments, the method further comprises removing tar from the gas resulting from gasification and using at least a portion of the removed tar as supplementary fuel for the combustor, as a carbonaceous feed charge for the aerator, or both. The method may comprise subjecting at least a portion of the gasification product to Fischer-Tropsch synthesis, thereby producing non-gaseous Fischer-Tropsch synthesis products, a residual Fischer-Tropsch process gas, and a used catalyst product comprising Fischer-Tropsch catalyst used and liquid hydrocarbons, and use at least a portion of the residual Fischer-Tropsch process gas, at least a portion of the used catalyst product, or both, as supplementary fuel for the combustion. The method may comprise subjecting at least a portion of the gaseous product gas to Fischer-Tropsch synthesis, thereby producing non-gaseous Fischer-Tropsch synthesis products, and subjecting at least a portion of the non-gaseous Fischer-Tropsch synthesis products to quality improvement , thus producing a residual gas for quality improvement process. In embodiments, the method comprises using at least a portion of a waste gas from the quality improvement process as supplementary fuel for the combustion.
[00027] In modalities, the method comprises operating the gasifier at a pressure of the gasifier and operating the combustor at a pressure of the combustor which is in the range of about 0 kPaman. up to a pressure that is at least 13.78951 kPaman less than the gasifier pressure. In embodiments, the method comprises separating heated particulate heat transfer material from the combustion waste gas. Separating heated particulate heat transfer material from the combustor waste gas may comprise introducing the combustor waste gas into at least one gas / solid separator of the combustor. In embodiments, the at least one gas / solid separator of the combustor is operated at a surface speed in the range of about 21.34 to about 25.91 m / s. In embodiments, (a) separating at least one solid product comprising animal charcoal, particulate heat transfer material and optionally unreacted carbonaceous material from the gasification gas comprises introducing at least a portion of the gasification gas into at least one gas separator. primary gasifier particulate configured to separate particulate heat transfer material from the gasification product gas, thereby providing a low particulate product gas comprising ash, and introducing the low particulate product gas comprising ash trapped therein in at least one particulate separator of the secondary gasifier configured to separate ash from the low particulate product gas, (b) separating heated particulate heat transfer material from the combustor waste gas comprises introducing at least a portion of the combustor waste gas into at least one configured primary combustor particulate separator for separating particulate heat transfer material from the combustor waste gas, thereby providing a low particulate waste gas comprising ash, and introducing the low particulate waste gas into at least one secondary combustor particulate separator configured to separate ash from the waste gas. low particulate disposal; or both (a) and (b). Such methods may further comprise introducing at least a portion of the particulate materials separated from the particulate separator of the primary gasifier, the particulate separator of the secondary gasifier, or both, into the combustor for heating therein. The method may further comprise washing sulfur from a gas, bringing the gas into contact with a liquid comprising at least a portion of the separated ash. The washed gas may comprise at least a portion of the gas produced by the gasification.
[00028] In embodiments, the method comprises removing more than 99, 99.9 or 99.98 percent by weight of the particulate heat transfer material from the gas product of the gasification, the combustion waste gas, or both. In modalities, the method comprises recovering heat from gas from the gasification, from the combustion waste gas, or both. Ash can be removed from the gas product from the gasification, from the combustion waste gas, or from both, subsequent to the heat recovery from it. Tar can be removed from the gas from the gasification after recovery. Recovering heat from the gasification gas can reduce the temperature of the gasification gas to no less than about 482 ° C, 454 ° C, 427 ° C, 399 ° C, 371 ° C, 343 ° C or 316 ° C, before removing the tar from it. Recovering heat may comprise heating air by means of heat transfer with the gas from the gasification, the combustion waste gas, or both, and the method may comprise introducing at least a portion of the heated air into the combustion.
[00029] In modalities, the method comprises fluidizing the combustion by means of a combustion fluidizing gas. The combustor can be fluidized with a combustor fluidizing gas with a surface velocity of the inlet combustor fluidizing gas in the range of about 457 to about 762 cm / s. The combustion can be operated with a surface velocity of the exhaust gas in the range of about 762 to about 1,219 cm / s. At least a portion of the combustion fluidization gas can be introduced through at least one combustion sealing pot configured to prevent reflux of material from the combustion. In embodiments, at least or about 20% of the combustion fluidization gas required to fluidize a bed in the combustion is introduced through at least one combustion sealing pot.
[00030] In embodiments, the method comprises preventing backflow of gasifier material through at least one gasifier sealing pot, preventing backflow of combustor material through at least one combustor sealing pot, or both. In embodiments, the particulate heat transfer material is selected from the group consisting of sand, limestone, and other calcites or oxides including iron oxide, olivine, and magnesia, alumina, carbides, silica alumina, zeolites, and combinations thereof. The method may comprise introducing a catalyst into the aerator. A catalyst like this can promote tar reform, thus generating a cleaner gas product than that formed in the absence of the catalyst. In embodiments, the catalyst comprises nickel.
[00031] In modalities, the method comprises introducing a sulfur extraction component, in which the sulfur extraction component promotes recovery of sulfur in solid form from gasification. The sulfur extraction component may comprise calcium oxide. The sulfur extraction component can be introduced with the heat transfer material.
[00032] In embodiments, the method comprises introducing a carbon dioxide removal component, the carbon dioxide removal component suitable for converting carbon dioxide into a solid product that is at least partially separated from the gas product of the gasification with the at least one solids product. The method may comprise operating the combustion with excess oxygen in the range of about 0 to about 20 percent by volume. The method may comprise introducing the carbonaceous feed charge at a temperature in the range of about -40 ° C to about 127 ° C. In modalities, the carbonaceous feed load comprises at least one material selected from the group consisting of biomass, RDF, MSW, sewage sludge, coal, Fischer-Tropsch synthesis wax, and combinations thereof. The method may comprise introducing a purge gas with or as a part of the carbonaceous feed charge. The purge gas can comprise at least one gas selected from the group consisting of carbon dioxide, steam, waste gas, nitrogen, synthesis gas, and combustor waste gas. In embodiments, the method comprises removing carbon dioxide from the combustor's disposal gas, the gas product from gasification, or both; and use at least a portion of the removed carbon dioxide as a purge gas. In embodiments, the method comprises operating the combustor at an operating temperature at or near its inlet for heat transfer material in the range of about 538 ° C to about 760 ° C and an operating temperature at its outlet, or close to it, for a combustor particulate separator in the range of about 760 ° C to about 982 ° C.
[00033] The method may comprise removing moisture from a relatively wet carbonaceous material to provide a carbonaceous feed load. At least a portion of the heat from the combustion waste gas can be used to dry the carbonaceous material. The method may comprise drying a carbonaceous material to a moisture content in the range of about 10 to about 40 weight percent to provide the carbonaceous feed load. The method may comprise converting at least about 30, 40, 50, 60, 70 or 80% of the carbon in the carbonaceous feed charge into gas resulting from gasification. The method may comprise introducing the carbonaceous feed charge into the gasifier at a flow of at least or about 10,000 kg / h.m2, 12,000 kg / h.m2, 12,500 kg / h.m2, 15,000 kg / h.m2, 17,000 kg / h.m2 or 20,000 kg / h.m2 .. The gasifier fluidization gas can be introduced into the gasifier at a surface speed in the range of about 15.24 cm / s to about 304.8 cm / s. In embodiments, the method comprises removing the gas product from the gasification of the gasifier at a surface speed in the range of about 35 to about 1,067 to 1,524 cm / s. The gasifier fluidization gas can be selected from the group consisting of steam, waste gas, synthesis gas, LP waste gas, waste process gas (eg Fischer-Tropsch waste process gas, waste gas improving process gas) quality, residual process gas VSA, and / or residual process gas PSA), gas product of the gasification, and combinations thereof. The aerator can be operated at an operating temperature in the range of about 538 ° C to about 871 ° C. The gasifier can be operated at an operating pressure greater than about 13.78951 kPaman and / or less than about 310.2641 kPaman.
[00034] In embodiments, the aerator comprises an aerator distributor configured to introduce gasification fluidizer gas substantially uniformly across the diameter of the aerator, the combustor comprises a combustor distributor configured to introduce fluidization gas combustor substantially uniformly through the diameter of the combustion, or both. The method may comprise introducing particulate heat transfer material into the combustor at a location at least about 122, 152 or 183 centimeters above a combustor distributor; introducing heated fluidized particulate heat transfer material from the combustor into the gasifier at a location at least about 122, 152 or 183 centimeters above a gasifier distributor; or both. At least a portion of the heated portion of the at least one solids product can be introduced into the gasifier at a temperature in the range of about 760 ° C to about 871 ° C. An operating temperature differential of less than about 194 ° C, 183 ° C, 167 ° C, 150 ° C, or 139 ° C can be maintained between the gasifier and the combustion.
[00035] The above presented in a very general way the resources and technical advantages of the invention in order that the detailed description of the following invention can be better understood. Additional features and advantages of the invention will be described below, which form the subject of the claims of the invention. Those skilled in the art should realize that the concept and the specific modalities revealed can be easily used as a basis for modifying and designing other structures to accomplish the same purposes as the invention. Those skilled in the art should also realize that such equivalent constructions are not outside the spirit and scope of the invention presented in the following claims. BRIEF DESCRIPTION OF THE DRAWINGS
[00036] For a detailed description of the preferred embodiments of the invention, reference will now be made to the accompanying drawings, in which:
[00037] Figure 1 is a schematic of a gasification system according to this disclosure; and
[00038] Figure 2 is a schematic of an integrated system comprising a gasification system according to this revelation integrated with Fischer-Tropsch synthesis and energy production. NOTATION AND NOMENCLATURE
[00039] Certain terms are used in the following description and claims to refer to particular system components. This document is not intended to differentiate components that differ in name, but not in function.
[00040] The terms "pyrolyzer" and "gasifier" are used interchangeably here to refer to a reactor configured for endothermic pyrolysis. DETAILED DESCRIPTION OF THE INVENTION
[00041] General Double Fluidized Bed System (DFB). Here, a dual fluidized bed gasification system, its unpublished components, and gasification methods using the same are disclosed. A combustor, a pyrolyser, a fuel sealing pot, a gasifier sealing pot, a primary gasifier separator (for example, heat transfer material, HTM, cyclone), a secondary gasifier separator (for example, cyclone) are disclosed here. gray), combustion separators (for example, primary and / or secondary cyclones), and a system comprising a combination of one or more of these components and optionally comprising downstream apparatus configured for the production of chemicals, fuels and / or energy from from the gas produced in the gasifier.
[00042] The disclosed method comprises introducing inlet gas at a low gas velocity to fluidize a medium high density bed in an aerator / pyrolysis vessel. The medium high density bed may comprise a relatively dense fluidized bed in a lower region thereof, the relatively dense fluidized bed containing a circulating inert and relatively fine particulate heat transfer material. Carbonaceous material is introduced into the lower region at a relatively high rate, and endothermic pyrolysis of the carbonaceous material is carried out by means of a circulating heated inert material, producing a gas product from the aerator comprising synthesis gas (ie, comprising hydrogen and carbon monoxide) ). In modalities, in an upper region of the pyrolyzer there is a region of the trapped space of lower average density containing a trapped mixture comprising inert solid particulate heat transfer material, animal coal, unreacted carbonaceous material and product gas. The trapped mixture is removed from the gasifier for one or more separators, such as a cyclone, in which solids (heat transfer particles, animal coal and / or unreacted carbonaceous material) are separated from the gas product of the gasification. At least a portion of the removed solids is returned to the pyrolyzer after reheating to a desired temperature by passing through an exothermic reaction zone of an external combustor.
[00043] Figure 1 is a schematic of a double fluidized (or “DFB”) gasification system 10 according to this disclosure. The DFB 10 gasification system comprises a gasifier 20 (also referred to here as a “pyrolyzer”) which is fluidly connected with a combustor 30, whereby heat lost during endothermic gasification in a gasifier / pyrolyzer 20 can be supplied by means of combustion exotherm in combustor 30, as further discussed below. The DFB 10 gasification system additionally comprises at least one sealing pot for the combustor 70 and at least one sealing pot for the gasifier 80. The pyrolyzer 20 is operable to remove it from a phase of circulating particulate and animal coal by trapping in the product gas of the aerator. Separation of solid trapped particulates comprising particulate heat transfer material and animal coal from the gas product of gasification, can be carried out by gas / solid separators, such as conventional cyclone (s). In embodiments, substantially all of the solids in the system are decanted by the method disclosed herein in spite of the use of what are generally considered to be low velocities of the gasifying fluidization inlet gas. The DFB gasification system thus further comprises one or more particulate separators of the gasifier (for example, one or more cyclones of the gasifier) and one or more particle separators of the combustor (for example, one or more cyclones of the combustor). In the embodiment of figure 1, the DFB 10 gasification system comprises cyclones of the primary gasifier 40 and cyclones of the secondary gasifier 50 and cyclones of the combustor 60. Each of these components will be discussed in more detail below.
[00044] Circulating between the gasifier and the combustor is a heat transfer material (HTM). The heat transfer material is relatively inert, compared to the carbonaceous feed material being gasified. 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, zeolites resistant to friction wear, and combinations thereof. The heat transfer material is heated by passing through an exothermic reaction zone of an external combustor. In embodiments, the heat transfer material can participate as a reagent or catalytic agent, so "relatively inert" in the form used here with reference to the heat transfer material is like a comparison with carbonaceous materials and is not used here in a strict sense. For example, in coal gasification, limestone can serve as a means to capture 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. For example, in embodiments, a nickel catalyst is introduced together with another heat transfer material (for example, olivine or other heat transfer material) to promote tar reform, thus generating a “clean” synthesis gas that comes out of the aerator. The clean synthesis gas can be a synthesis gas essentially without tar. In embodiments, an amount of nickel catalyst (for example, about 5, 10, 15 or 20 weight percent nickel) is circulated along with other heat transfer materials.
[00045] The heat transfer material can have an average particle size in the range of about 1 μm to about 100 mm, from about 1 μm to about 1 mm, or from about 5 μm to about 300 μm. The heat transfer material can have an average density in the range of about 0.8 g / cm3 to about 8 g / cm3, from about 0.8 g / cm3 to about 4.8 g / cm3, or from about 1.6 g / cm3 to about 4.8 g / cm3.
[00046] In modalities, balance is shifted to the formation of hydrogen and carbon monoxide during pyrolysis, for example, through the incorporation of a material that effectively removes carbon dioxide. For example, NaOH can be introduced into the system (for example, in heat transfer material, or together with it, in the gasifier 20, combustor 30, or anywhere in the system) to produce Na2CO3, and / or CaO injection it can be used to absorb CO2, forming CaCO3 which can later be separated into CO2 and CaO which can be recycled to the system. NaOH and / or CaO can be injected into the gasifier or pyrolyzer 20. The addition of such carbon dioxide reducing material can serve to increase the amount of synthesis gas produced (and thus for downstream processes, such as, without limitation, Fischer-Tropsch synthesis and production of chemicals and / or non-Fischer-Tropsch fuel), and / or can serve to increase the Wobbe number of the gas product of the gasifier for the production of downstream energy. Such materials, or additional materials, can also be used to adjust the ash melting temperature of the carbonaceous feed materials within the gasifier. As with optional carbon dioxide reducing materials, such ash melt adjustment material (s) can be incorporated by addition to or in the feed, or in the heat transfer medium. , or with it, in the aerator 20, the combustor 30 and / or anywhere. In modalities, the additional material (s) is (are) added with the feed, or in it, in the gasifier. In embodiments, the additional material (s) is (are) added with or in the heat transfer medium.
[00047] Reactor / Aerator / Pyrolyzer 20. The 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 gas product of the aerator enough to promote circulation of heat transfer material and carbonated animal charcoal, for example, by imprisonment. The gasifier may be a hybrid, with a trapped zone above a fluidized bed gasifier, described in U.S. Patent 4,828,581, which is hereby incorporated by reference in its entirety for all purposes not contrary to this disclosure.
[00048] In embodiments, the gasifier / pyrolyzer 20 is an annular shaped vessel comprising a conventional gas distribution plate near the base and comprising inlets for feed material, heat transfer material (s), and fluidizing gas. The gasifier vessel comprises an outlet at or near its top and is fluidly connected therewith (for example, via the gasifier outlet line 114) in one or more separators from which gasification gas is discharged and solids are discharged. recycled to the gasifier base via an external exothermic combustor operable to reheat the separate heat transfer material. The gasifier operates with a recirculating particulate phase (heat transfer material) and at inlet gas speeds in the range sufficient to fluidize the heat transfer material, as further discussed below.
[00049] Gasifier supply. As indicated in the modality of figure 1, the inlets for feeding (for example, through line 90) and recirculating heat transfer material (for example, via the “hot” circulation line 35) are located on the gasifier base 20, or close to it, and can be close to the pyrolyzer 95 gas distributor. The feed can be selected from the group consisting of biomass, RDF, MSW, sewage sludge, and combinations of these. In modalities, the food comprises biomass. It is considered 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 residues, heavy fuel oil, etc., which can, in modalities, without being contaminated with small solids, can be introduced into the gasifier and / or the combustor, as long as the melting temperature of the ash in them is not adversely affected. In modalities, petroleum coke is ground to a size in the appropriate range to ensure volatilization within the pyrolyzer. In modalities, petroleum coke is introduced into the pyrolyzer as a component of the carbonaceous feed load. In embodiments, the gasifier feed additionally comprises Fischer-Tropsch synthesis products (for example, Fischer-Tropsch wax) and / or used catalyst (for example, used catalyst recycled into product wax). In modalities, Fischer-Tropsch synthesis products are produced downstream and a portion of the Fischer-Tropsch product (s) (for example, used Fischer-Tropsch wax) that will crack under the operating conditions is (are) recycled (s) ) as feed / fuel for the aerator.
[00050] The supply of the gasifier can be introduced into it by any suitable device known to those skilled in the art. The feed can be fed to the aerator using a water-cooled rotary auger. The feed can be substantially solid and can be fed using an auger feeder or a discharge system. In embodiments, the feed is introduced into the gasifier as a solid extrudate. In modalities, double feeding augers are used and the operation is alternated between them, thus guaranteeing continuous feeding.
[00051] As shown in figure 1, an inlet line for the gasifier 90 can be configured to provide an angle β between the inlet line 90 and the gasifier vessel 20. The angle β of the inlet can be in the range of about 5 to about 20 degrees or about 10 to about 15 degrees in such a way that the feed flows substantially uniformly (that is, through its cross section) from the pyrolyzer 20. In this way, feed it is not limited to one side of the pyrolyzer, for example. A purge gas can also be introduced (for example, via line 91) with the feed (for example, from a holding hopper) via the feed inlet to maintain a desired pressure and / or help supply the feed to the pyrolyzer . In modalities, the purge gas is selected from the group consisting of carbon dioxide, steam, waste gas, nitrogen, synthesis gas, combustor waste gas and combinations of these. In modalities, the purge gas comprises nitrogen. In modalities, the food is not purged. If CO2 recovery is present, for example, downstream in the system, it may be desirable for the supply purge gas to be carbon dioxide, or comprise the same.
[00052] 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 275.7903 kPaman .. A dryer can be used to dry the feed and / or 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 may be introduced hot (for example, at a temperature above room temperature). In modalities, the food is cold (for example, at a temperature lower than the room temperature). The feed can be introduced into the gasifier at a temperature in the range of about -40 to about 127 ° C. In modalities, the feeding is at a temperature in the range of -40 to about 139 ° C. In modalities, the food is at room temperature. In modalities, the food is at room temperature. In embodiments, a feed material is crushed prior to introduction into the gasifier. In embodiments, a feed material is preheated and / or crushed (for example, chopped) prior to introduction into the aerator.
[00053] Optimization of the Gasifier Feed Drying to Control the H2: CO Ratio in Synthesis Gas Product. In modalities, the moisture content of the food is in the range of about 5% to about 60%. In modalities, the feed has a moisture content of more than about 10, 20, 30 or 40% by weight. In modalities, the feed has a moisture content of less than about 10, 20, 30, or 40% by weight. In modalities, the moisture content of the feed is in the range of about 20 to about 30% by weight. In modalities, the moisture content of the feed is in the range of about 20 to about 25% by weight.
[00054] In modalities, further drying of the feed material may be desired / used to provide synthesis gas (via, for example, drying of the feed, gasification and / or partial oxidation) at a molar ratio of H2 / CO suitable for synthesis Fischer-Tropsch downstream in the presence of an iron catalyst (ie, about 1: 1). In modalities, less drying may be desired / used, for example, to provide a synthesis gas with a molar ratio of H2 / CO suitable for Fischer-Tropsch synthesis downstream in the presence of a cobalt catalyst (ie, about 2 ).
[00055] Energy Integration for the Dryer. A dryer 155 can be configured to reduce the moisture content of a "wet" carbonaceous feed material (for example, biomass, BM). Carbonaceous feed material (eg biomass) can be introduced into the dryer 155 via the carbonaceous feed material inlet line BM, drying fluid (eg “hot” combustion waste gas) can be introduced into the dryer 155 via the drying agent inlet line 156, and / or dryer exhaust can be extracted from the dryer 155 via the dryer exhaust line 157. In embodiments, at least a portion of the hot combustion gas ( described further below) is used to dry a gasifier supply prior to introduction into the gasifier 20. In such embodiments, the combustion discharging gas outlet line 112 can be fluidly connected with the dryer 155, for example, by means of drying agent inlet line 156.
[00056] In modalities, the feed rate (flow) of carbonaceous material to the gasifier is greater than or equal to about 10,000, 12,500, 15,000, 17,000, 20,000 or 21,000 kg.h.m2. The design can allow a superficial velocity at the outlet (top) of the gasifier in the range of 12.19 - 13.72 m / s (assuming a certain conversion / volatilization / expansion of carbon). 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 aerator vessel, that is, its diameter, can be selected based on a desired outlet speed.
[00057] Aerator fluidizing gas can be fed to a bottom of the aerator 20 (for example, via a distributor 95) at a surface speed in the range of about 15.24 cm / s to about 304.8 cm / s, from about 24.38 cm / s to about 243.8 cm / s, or from about 24.38 cm / s to about 213.36 cm / s. In embodiments, the rate of entry of the pyrolyzer fluidization gas (for example, steam) is greater, less, or equal to about 30.48, 60.96, 91.44, 152.4, 182.88, 213 , 36 or 243.8 cm / s. In embodiments, a surface velocity of the gasifier fluidizing gas of at least or about 152.4, 182.88, 213.36 or 243.8 cm / s is used during startup.
[00058] The fluidizing gas introduced into the gasifier via line 141 and 141a (and optionally introduced into circulation line 35 via line 141d) can be selected from the group consisting of steam, waste gas, synthesis gas, gas LP waste gas, waste process gas (eg Fischer-Tropsch waste process gas, quality-improving waste gas, VSA waste gas, and / or PSA waste gas) and combinations thereof. In embodiments, the gasifier fluidization gas comprises residual Fischer-Tropsch process gas. In embodiments, the gasifier fluidization gas comprises residual gas from a quality improvement process. Using waste gas from the quality improvement process, removal of additional sulfur can be achieved, since the waste gas from the quality improvement process can comprise sulfur.
[00059] In embodiments, the pyrolyzer fluidization gas comprises PSA process waste gas. Such modalities can provide substantial hydrogen and may be more suitable for the subsequent use of the product gas in downstream processes for which higher molar ratios of hydrogen to carbon monoxide are desirable. For example, higher molar ratios of hydrogen to carbon monoxide may be desirable for downstream processes such as a nickel double fluidized gasification system (for which the H2 / CO ratio of about 1.8: 1 to about 2: 1 may be desired). A double fluidized bed gasifier (DFB) like this is disclosed, for example, in US patent application No. 12 / 691,297 filed on January 21, 2010, the disclosure of which is hereby incorporated here for all purposes other than contrary to this revelation. The use of PSA process waste gas for gasifier fluidization gas may be less desirable for subsequent use of the gas for POx (for which H2 / CO ratios closer to or equal to about 1: 1 may be more suitable), since that hydrogen can be undesirably high. In embodiments, the gas from the gasification is dried (for example, in a burner) to a moisture content less than a desired value (for example, less than about 10, 11, 12, 13, 14 or 15 percent) in order to provide a suitable composition (for example, H2 / CO molar ratio) for downstream processing (for example, for downstream POx). In embodiments, a combination of feed drying, DFB and POx gasification is used to provide a synthesis gas suitable for Fischer-Tropsch synthesis downstream using a cobalt catalyst.
[00060] The temperature at or near the top of the gasifier (for example, near the removal of trapped product from it) can be in the range of about 538 ° C to about 871 ° C, from about 593 ° C to about 871 ° C, from about 649 ° C to about 871 ° C, from about 538 ° C to about 816 ° C, from about 593 ° C to about 816 ° C, from about 649 ° C to about 816 ° C, about 538 ° C to about 760 ° C, about 593 ° C to about 760 ° C, about 649 ° C to about 760 ° C, about 649 ° C to about 788 ° C, about 649 ° C to about 732 ° C, about 677 ° C to about 732 ° C, about 704 ° C to about 732 ° C or about 732 ° Ç.
[00061] In modalities, the pressure of the gasifier is greater than about 13.78951 kPaman. In modalities, the gasifier pressure is less than or equal to about 310.2641 kPaman .. In modalities, the gasifier pressure is in the range of about 13.78951 kPaman to about 310.2641 kPaman ..
[00062] Heat transfer material is introduced, via the “hot” circulation line 35, in a lower region of the gasifier. 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 equal to about 20, 30, 40, 50 or 60 degrees. The heat transfer material can be introduced at a temperature in the range of about 760 ° C to about 871 ° C, from about 788 ° C to about 871 ° C, from about 829 ° C to about 857 ° C, or about 843 ° C.
[00063] In embodiments, the pyrolyzer comprises a 95 gas distributor. In embodiments, the heat transfer material is introduced into the pyrolyzer 20 in a location at least 10.16, 12.7, 15.24, 17.78, 20.32, 22.86 or 25.4 centimeters above the pyrolyzer 95 gas distributor. The heat transfer material can be introduced in a position in the range of about 10.16 to about 25.4 centimeters, or from about 10.16 to about 15.24 centimeters above the distributor. In modalities, the distributor is operable to provide a gas flow of at least or about 121.92, 152.4, 182.9, 213.4, 243.8 274.3 or 304.8 cm / s, for example example, during the match. The aerator distributor (and / or a distributor in a sealing combustion pot, a sealing sealing pot and / or combustion) may comprise a ring distributor, a tube distributor, a Christmas tree distributor, or another suitable distributor design known in the art. In embodiments, the dispenser comprises a tube dispenser that can be loaded through one side of the vessel to facilitate the exchange of the nozzle in it (generally suitable in modalities in which the operating pressure is less than 82.73709 or 103.4214 kPaman . including). Distributors with a lower number of entries (for example, Christmas tree distributors and / or ring distributors) may be more desirable for higher pressure applications.
[00064] In modalities, the temperature differential between the gasifier and the combustion (ie TC-TG) is kept below about 139 ° C, 144 ° C, 150 ° C, 156 ° C, 161 ° C, 167 ° C, 172 ° C, 178 ° C, 183 ° C, 189 ° C or 194 ° C, or is maintained at a temperature in the range between these. If TC-TG is greater than about 167 ° C, sand or other heat transfer material at elevated temperature can be added to the system.
[00065] System for the Elimination of occasional services. The gasifier distributor 95 can be positioned 91 to 182 centimeters above the refractory bottom. In embodiments, the dispenser is positioned at least 91, 122, 152 or at least 183 centimeters above the refractory bottom. Below the dispenser, a dead space or “dead zone” 96 is created, indicated (out of scale) as shown in figure 1. Dead zone 96 is located between the dispenser and the bottom of the vessel. In embodiments, a dead zone like this can be designed to facilitate the removal of heat transfer material from below a dispenser. Any material that is too heavy to fluidize can settle below the distributor of a component in the system, thus creating a heat dissipating area. Because there may be little or no fluidization below the distributor, heat transfer material can become trapped below the distributor and cool (for example, below 843 ° C or below the temperature of another HTM inlet gasifier). The bottom of the aerator (or another component such as a sealing pot for the combustor 70, a sealing pot for the aerator 80, or combustor 30) can be designed with two valves and a pipe whereby the elimination of eventual services can be affected during operation. The design of a locking hopper such as this allowing removal of in-line heat transfer material from the dead zone can desirably eliminate the need for downtime during the elimination of occasional services. As indicated, a system for eliminating occasional services like this can also be used in the combustor, CSP, GSP or any combination of vessels, whereby materials can be removed from it without removing the system (s) of the line.
[00066] Aerator cyclones. The DFB system disclosed herein comprises one or more gas / solid separators (e.g., one or more cyclones) on the outlet line of the gasifier 114. The system may comprise particulate separator (s) from the primary gasifier (s) 40 and separator ( s) of particulate from the secondary gasifier (s) 50 (for example, cyclones of the primary and secondary gasifier). Low particulate gasification gas extracted from the particulate separator of primary gasifier 40 can be introduced into the particulate separator of secondary gasifier 50 via line 114a. Solids (eg, animal charcoal, unreacted carbonaceous material, and / or HTM) extracted from the gas product of the gasification by means of the particulate separator of the primary gasifier 40 can be introduced into the sealing pot of the combustor 70, for example, by means of of the leg 41. Low particulate gasification gas extracted from the particulate separator of the secondary gasifier 50 can be introduced into the apparatus downstream 100 by means of line 114b. Solids (eg, animal charcoal, unreacted carbonaceous material, and / or HTM) extracted from the gas product of the gasification by means of the particulate separator of the secondary gasifier 50 can be introduced into the sealing pot of the combustor 70, for example, by means of of the leg 51.
[00067] In modalities, the gasifier separators are operable / configured to provide an HTM removal efficiency of at least or about 98, 99, 99.9 or 99.99%. In embodiments, the primary gasifier separators 40 are operable to remove at least or about 99.99% of the heat transfer material from a gas introduced therein. Greater removal of heat transfer material is generally desirable, since the cost of constituted particulate heat transfer material and the cost of heating it to operating temperature are considerable. The particulate separator (s) of the secondary gasifier 50 (for example, cyclones) can be configured to remove at least about 80, 85, 90 or 95% of the charcoal (and / or gray) in the gas product of the gasifier introduced into it by means of line 114a. In embodiments, the separators of the secondary gasifier are operable to remove at least about 95% of the ash and / or animal charcoal introduced in them. There may be a certain amount (preferably, minimal) of recycling ash. As noted earlier, solids extracted by means of the separator (s) of the primary gasifier 40 and / or particulate separator (s) of the secondary gasifier 50 can be introduced into the sealing pot of the combustor 70 by means of the legs. 41 and 51, respectively. The aerator outlet for the aerator's primary cyclones may comprise a 90 degree flange.
[00068] Heat Recovery from Synthesis Gas. The synthesis gas product that comes out of the separators of the gasifier can be used for heat recovery in certain modalities. In modalities, the synthesis gas is not used for heat recovery. In embodiments, no heat recovery is incorporated into the synthesis gas and the DFB gasification system additionally comprises a POx unit, a nickel double fluidized bed gasifier and / or a boiler downstream of the gasifier separator (s) . It is considered that the heat recovery device can be positioned between the primary and secondary separators. When used for heat recovery, the synthesis gas can be kept at a temperature of at least 316 ° C, at least 343 ° C, at least 371 ° C, at least 399 ° C or at least 427 ° C after recovery of heat. For example, maintaining a temperature of more than 343 ° C, 371 ° C, 399 ° C, 427 ° C, 454 ° C or 482 ° C may be desirable when heat recovery is upstream of tar removal (eg example, to prevent condensation of tars). In embodiments, the synthesis gas is maintained at a temperature in the range of about 343 ° C to about 427 ° C during heat recovery. In embodiments, the system comprises a steam superheater and optionally following there a residual heat boiler or residual heat superheater downstream of the gasifier separators for heat recovery from the hot gasification gas comprising synthesis gas and steam production. In modalities, the system comprises an air preheater for heat recovery from the hot synthesis gas. In modalities, the system comprises a boiler feed water pre-heater (BFW) for heat recovery from the hot synthesis gas. The system may comprise preheating air, (for example, to preheat air for introduction into the combustion, as the introduction of warmer air into the combustion may be desirable). The system can comprise any other suitable apparatus known to those skilled in the art for heat recovery.
[00069] Combustor / CSP. The system 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 trapped materials extracted from the pyrolyzer. The combustor can be any type of combustor known in the art, such as, but not limited to, fluidized, trapped and / or non-fluidized combustors. The "cold" circulation line 25 is configured to introduce "cold" HTM into the combustor 30, while the "hot" circulation line 35 is configured to introduce "hot" HTM into the aerator 20.
[00070] Referring now to figure 1, the combustion 30 is associated with a combustion sealing pot 70 (CSP) configured to prevent backflow of materials into the gasifier cyclone (s) 40, 50; and one or more cyclones of the combustion 60 configured to remove particulates from the combustion waste gas.
[00071] In modalities, air is fed to the bottom of the combustion 30 (for example, via line 121) and steam is fed to the CSP 70. The steam feed rate can be about 1,493 kg / h (for a plant operating at around 500 dry tons / day, for example). The vapor passes through and exits the cyclone of the combustor 60. The efficiency of the cyclone is drastically affected by the surface velocity in it. The higher the surface velocity, the greater the efficiency of the cyclone. If the ACFM (actual cubic feet per minute) can be reduced, the cyclone's efficiency can be improved (based on more solids per cubic foot). Thus, in modalities, air is fed into the CSP 70, instead of steam. In modalities, 20-25% of the fluidizing gas (for example, air) for the combustion 30 is introduced in the CSP 70, or through it, for example, through the line 141b, and / or in the circulation line 25, for example, via line 141c. In modalities, combustion air, instead of steam, is fed into the CSP 70, in such a way that heat is not removed from the combustion 30 because of the flow of steam through it and the separator (s) / cyclone (s) ) of the downstream combustor 60 and / or the downstream gasifier 20 may be of incrementally smaller size (s). That is, the introduction of air (for example, at about 538 ° C), instead of the introduction (for example, 288 ° C) of steam into the CSP 70 (which is heated in it, for example, to about 982 ° C) can serve to reduce the amount of steam in the gasification system 10. This can allow the vessel (s) downstream to be smaller. When air is introduced into the CSP 70, partial combustion of animal charcoal may occur in the sealing pot with air (instead of steam) and the cyclone of combustor 60 and / or gasifier 20 downstream may be smaller. Thus, in modalities, the combustor is reduced in size by introducing a portion of the combustion fluidization gas into the CSP 70. For example, if the desired fluidization speed at the top (for example, close to the waste gas outlet) of the combustion is 9.14 - 10.67 meters / s, only about 75-80% (that is, about 6.1 m / s) may need to be introduced into the bottom of the combustion due to 20-25% of the fluidizing gas can be introduced into, or through, the CSP. Thus, the size of the combustion can be reduced. Another benefit of introducing combustion fluidization gas via the CSP is that the combustion cyclone (s) can be incrementally smaller, or can be operated more efficiently. Also, nitrogen in the air can be heated and the thermal efficiency achieved by eliminating or reducing the need for steam overheating (for example, at 1,493 kg / h of steam).
[00072] 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 combustor 30 comprises LP waste gas. The fluidizing gas in the combustion 30 can basically comprise air. The gas feed rate in the combustion can be higher, lower, or equal to about 3.05, 4.57, 6.1, 7.62, 9.14 or 10.67 meters / s) (in certain modalities ).
[00073] The inclination of the sealing pot of the combustion 70 with the combustion 30 provides the angle α, in such a way that the heat transfer medium (for example, sand), air and waste gas flow over the combustion and back from him. The inlet flow of fluidizing gas to the combustion can be determined by the heat transfer material. The inlet fluidization speed is at least an amount sufficient to fluidize the heat transfer medium within the combustion 30. In embodiments, the inlet combustion speed is greater than or equal to about 3.05, 4.57, 6 , 1, 7.62 or 9.14 meters / s. In modalities, the rate of entry of the fluidization gas into the bottom of the combustion is in the range of about 15 to about 35 ft / s, (4.57 to 10.67 meters / s) from about 20 to about 35 feet / s (6.1 to 10.67 meters / s), or from about 20 to about 30 feet / s (6.1 to 9.14 meters / s). At higher elevations in the combustion, waste gas is created. This limits the proper rate for introducing fluidizing gas into the combustion.
[00074] In modalities, the combustor is operated in the trapped flow mode. In modalities, the combustor is operated in the transport bed mode. In modalities, the combustion is operated in a choke flow mode. The bottom of the combustion (for example, at or near the inlet of the circulating heat transfer medium of the gasifier) can be operated at approximately 593 ° C, 649 ° C, 167 ° C or 760 ° C, and the outlet of the The combustor (at or near its top; for example, at the exit of materials to or near the cyclone (s)) can be operated at approximately 760 ° C, 816 ° C, or 871 ° C. Thus, the actual cubic feet of gas present increase with the rise in the combustion (due to the combustion of animal coal and / or supplementary fuel). In modalities, excess air flow is returned to the combustion.
[00075] The fluidizing gas for the combustion may be or may comprise oxygen in the air, oxygen-enriched air, substantially pure oxygen, for example, from a vacuum oscillating adsorption unit (VSA) or an oscillating adsorption unit pressure (PSA), oxygen from a cryogenic distillation unit, oxygen from a pipe, or a combination of these. The use of oxygen or oxygen-enriched air can allow a reduction in the size of the vessel, however, the melting temperature of the ash must be considered. The higher the O2 concentration in the fuel supply, the higher the combustion temperature. The oxygen concentration is maintained at a value that maintains a combustion temperature lower than the melting temperature of the feed ash. Thus, the maximum concentration of oxygen fed into the combustor can be selected by determining the melting temperature of the ash of the specific feed used. In embodiments, the fluidization gas fed to the bottom of the combustion comprises from about 20 to about 100 mol percent of oxygen. In embodiments, the fluidizing gas comprises about 20 mol percent oxygen (for example, air). In embodiments, the fluidizing gas comprises substantially pure oxygen (limited by the melting properties of the charcoal ash, supplemental fuel and heat transfer material fed into it). In embodiments, the combustion fluidization gas comprises PSA process waste gas.
[00076] The combustion can be designed for operation with about 10 percent by volume of excess oxygen in the combustion process gas. In embodiments, the combustion is operable with excess oxygen in the range of about 0 to about 20 percent by volume, from about 1 to about 14 percent by volume, or from about 2 to about 10 percent in excess volume of O2. In modalities, the amount of excess O2 fed into the combustor is greater than 1 percent by volume and / or less than 14 percent by volume. Desirably, sufficient excess air is provided so that the partial oxidation mode is avoided. In modalities, the DFB gasification system is operable with excess O2 in the combustor in the range of more than 1 to less than 10 and the waste 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 waste gas will be introduced into a second combustor (for example, without limitation, in the combustor of a second double fluidized bed gasifier (DFB) disclosed, for example, in US patent application No. 12 / 691,297, deposited on January 21, 2010, whose disclosure is hereby incorporated here for all purposes not contrary to this disclosure), the amount of excess oxygen may be in the range of about 5 to about 25 per percent, or it may be more than about 5, 10, 15, 20 or 25%, providing oxygen for a downstream combustor. In modalities in which steam can be sold in value, more excess O2 can be used to produce more steam for sale / use. In modalities, a CO-rich, nitrogen-rich waste gas is produced by the operation of combustion 30 of the DFB gasification system revealed here with excess oxygen of more than 7, 10 or 15%.
[00077] Supplementary Fuels for Combustor. In embodiments, supplementary fuels can be introduced into combustor 30, for example, through the supplementary fuel inlet line 122. Supplementary fuels can be residual carbonaceous or non-carbonaceous currents and can be gaseous, liquid and / or solid. For example, in embodiments, used Fischer-Tropsch wax (which can contain up to about 5, 10, 15, 20, 25 or 30 weight percent catalyst) can be introduced into the combustor (and / or gasifier, as discussed additionally below). In modalities, Fischer-Tropsch wax is produced downstream and used Fischer-Tropsch wax is recycled as fuel for the combustion. As further discussed below, such used wax may alternatively, or additionally, also be introduced into the aerator, provided that it crackes under operational conditions therein. In modalities, petroleum coke is fed into the combustion as a fuel source.
[00078] In modalities, a stream of suspended hydrocarbons (for example, tar, which may result from a tar removal system) is introduced into the combustor to recover its calorific value. Tar can be obtained from any tar removal apparatus known in the art, for example, from a liquid absorber such as, but not limited to, an OLGA unit (for example, a Dahlman OLGA). Such removed tars comprise heavy hydrocarbons that can be reused as a fuel / fuel component in the combustor 30. In embodiments, residual process gas (eg Fischer-Tropsch process gas, PSA process gas, waste process gas VSA and / or waste gas from a quality improvement process) is used as a fuel for the combustion.
[00079] In modalities, a liquid feed such as, but not limited to, refinery tank waste, heavy fuel oil, liquid fuel oil (LFO), Fischer-Tropsch tar and / or another material (for example, waste material) with a calorific value, it is introduced into the combustion. Nozzles can be positioned above the leg to introduce such liquid material (s) into the combustor. This can help the flow of liquid to the leg and prevent the production of cold spots in the refractory. In this way, circulating heat transfer material can be used to circulate the liquid and the liquid can be charged to the combustion by means of the combustion fluidization gas (for example, air).
[00080] The combustor 30 can be manufactured with a hard face refractory from 50.8 to 101.6 mm thick. In modalities, the combustion has at least 50.8 mm of hard face. In embodiments, the combustor 30 has at least 76.2 mm of hard face. In embodiments (for example, in inferior insulation modes), the combustor may comprise a hard-faced refractory with an insulating layer surrounding the hard face. The insulating layer can be thicker than 50.8 mm. In modalities, the insulating layer is thicker than the hard face layer. The hard face layer may have greater thermal conductivity and durability than the insulating layer.
[00081] In modalities, the combustor is substantially cylindrical. In embodiments, the combustion is non-cylindrical. In modalities, the combustion is tapered at the bottom and / or at the top. In embodiments, the combustion is tapered at the bottom, for example, when the fluidizing gas for the combustion comprises a high concentration of oxygen. In embodiments, the combustor comprises a conical disengagement section at the top (however, this modality may undesirably reduce the surface speed in the gas / solid separator of the downstream combustor (s)). In embodiments, the combustion outlet comprises channels configured for recycling heat transfer material to the fluidized bed of the combustion and reducing particulate loading in the primary separator (s). In modalities, the combustion outlet is corrugated to reduce the loading of particulates in the primary cyclone (s).
[00082] In modalities, the combustor is pressurized. The combustion can be operated at a pressure of more than 0 kPaman. up to a pressure that is at least 13.78951 kPaman less than the operational pressure of the gasifier. That is, in order to maintain a continuous flow of materials from the combustion back to the gasifier, the combustion pressure, PC, at the inlet of the combustion, which can be measured by a manometer located near the exhaust gas outlet, is less than the gasifier / pyrolyzer pressure, PG. The pressure at the HTM outlet of the combustion, PC, BACKGROUND (which must be greater than PG), is equal to the sum of the pressure, PC, at the top of the combustion and the pressure column provided by the material in the combustion. The pressure column provided by the mixture of heat transfer material / gas inside the combustion is equal to pCgh, where pC is the average density of the material (for example, the fluidized bed of heat transfer material) inside the combustion, g is the acceleration of gravity, and h is the height of the "bed" of material inside the combustion. The height of material (e.g., heat transfer material such as sand, and other components such as charcoal, etc.) within the combustor is adjusted to ensure the flow of materials back to the gasifier.
[00083] Thus, PC, FUND which is equal to PC + pCgAh must be greater than the pressure of the gasifier, PG. The heights and relationships between the combustor and aerator are selected in such a way that adequate pressure is provided to maintain continuous flow from the combustor to the aerator, and back.
[00084] In modalities, the operating pressure of the combustion, PC, is up to or about 275.7903, 310.2641 or 344.7379 kPaman .. In modalities, based on the design criteria for 30-40 feet / for speed of the gas in the combustion, the maximum operating pressure of the combustion is about 310.2641 kPaman .. In modalities, if the operating pressure of the combustion is increased, then the pressure energy can be recovered by using an expander. Thus, in modalities, one or more expanders are positioned downstream of the gas outlet of the combustion 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 bottom 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 bag 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 operable at a pressure greater than 103.4214, 137.8951, 206.8427 kPaman. One or more expanders can be operable to recover PV energy.
[00085] Combustion / Heat Recovery Separator (s): The selected surface speed for the gas / solid separators (which can be cyclones) will be selected in order to maximize their efficiency and / or reduce erosion. Cyclones can be operable at a surface speed in the range of about 19.8 to about 25.9 m / s, about 21.3 to about 25.9 m / s, or about 19.8 , 21.3, 22.9, 24.4 or 25.9 m / s.
[00086] As shown in figure 1, the combustion outlet can be fluidly connected, via the combustion outlet line 106, with one or more particulate separators of the combustion 60 (e.g., HTM cyclones). Disposal gas is extracted from the combustion separator (s) 60 via the low particulate waste gas line 112, while separate solids (eg HTM) are introduced into the GSP 80, for example, via leg 61. 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, one to four or more cyclones) operated in parallel may be in series with a second cyclone bank comprising one to four or more cyclones in parallel, and so on. The system can comprise any number of cyclone banks.
[00087] One or more HTM combustion cyclones can be connected with one or more ash cyclones, and the gray cyclones can be followed by heat recovery. In such modalities, cyclones are cyclones coated with refractory or exotic material of high temperature. In modalities, the DFB gasification system comprises two, three or four separators of the combustor in series. In modalities, one to two banks of combustion HTM cyclones are followed by one or more banks of ash cyclones. In modalities, two combustion HTM cyclones are followed by one or more than one combustion ash cyclone. One or more HTM cyclones can have a performance specification of more than 99, more than 99.9 or more than 99.98% heat transfer material removal (two or more combustion cyclones can be used to achieve the desired efficiency) . In embodiments, one or more ash cyclones can be operated to remove ash, for example, in order to reduce the size of a downstream filter bag. In embodiments, one or more ash cyclones are operable to provide more than about 60%, 70%, 80%, 85% or 90% removal of ash from a gas introduced into it.
[00088] In alternative modalities, the heat recovery device is positioned between the HTM cyclone (s) and the ash removal cyclone (s). In such embodiments, combustion waste gas is introduced into one or more HTM cyclones of the combustion. 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, residual heat recovery units (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 coated with refractory, i.e., one or more ash removal cyclones may be hardened on the face, but cyclone (s ) of lower temperature in relation to systems comprising ash removal upstream of the heat recovery. In modalities, ash removal cyclones are operable at temperatures below 204 ° C, below 194 ° C, or below 167 ° C. In modalities, the lower temperature ash removal cyclones are made of silicon carbide.
[00089] In modalities, heat recovery is used to produce superheated steam. In embodiments, superheated steam is produced at a temperature in the range of about 139 ° C to about 400 ° F (204 ° C) and a pressure in the range of about 689.4757 kPaman. at about 2068,427 kPaman.
[00090] 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, transfer tubes of heat). The speed for cyclones in such modalities can be less than 24.4, 22.9, 21.3 or 19.8 m / s. If the speed is reduced properly, the ash will not stick to the heat recovery device (for example, the tubes of the residual heat boiler and / or the tubes of the superheater), and will not run unacceptably.
[00091] In modalities, combustion waste gas is introduced directly or indirectly into a boiler economizer for heat recovery and, for example, energy production.
[00092] In modalities, the DFB system comprises one or more undocking boxes. A release box like this can be used as a replacement or in addition to the combustor cyclone (s) and / or the gasifier cyclone (s). Such a detachable box can comprise a plurality of channels. A release box like this may be more desirable on the process gas side (gasifier / pyrolyzer) to further ensure that HTM is effectively removed from the gasification process gas.
[00093] Gasifier Sealing Pot (GSP) and Combustor Sealing Pot (CSP). Referring now to figure 1, the angle α between the sealing pot and the vessel (that is, between the sealing pot of the combustor and the combustor and / or between the sealing pot of the aerator and the aerator) can be in the range from about 5 to about 90 °, from about 5 to about 80 °, or from about 5 to about 60 °. In modalities, α is less than 45 °. Use of a larger α in general dictates a smaller sealing pot. Smaller angles can be operable with the use of fluidization / aeration to maintain fluidization. In general, for angles α 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 so that the sealing pot (CSP and / or GSP) is relatively small and the overall height of the unit (ie the stacking ) can be reduced.
[00094] As mentioned earlier, the sealing pot fluidization gas can be or comprise another gas, in addition or without replacement to steam. For example, combustor waste gas and / or recycled synthesis gas can be used as a fluidizing gas for GSP. In embodiments, the fluidizing gas for CSP, GSP or both comprises steam. When recycled synthesis gas is used to fluidize the GSP, the synthesis gas is returned to the gasifier and can provide additional clean synthesis gas from the DFB system. By using non-steam as the fluidizing gas in the sealing pot (s), steam can be reduced or substantially eliminated from the product gas, thereby increasing its Wobbe number, which can be beneficial for downstream processes (such as , for example, downstream energy production, discussed further below). In embodiments, residual gas from a quality improvement process comprising sulfur is used as a fluidizing gas for the GSP.
[00095] Removal of Sulfur Compounds from the Synthesis Gasification Product by Using Wood Ash. Sulfur can come out of the revealed DFB gasification system with process gas, combustion waste gas, and / or ash. Removal of sulfur as a solid may be desired. In modalities, ash (for example, wood ash) from the ash removal cyclones is used to remove mercaptan sulfur and / or H2S from the synthesis gas. In modalities, removal of mercaptan sulfur and / or H2S is done at a pH greater than or equal to about 7.5, 7.7 or 8. In modalities, the ash (for example, wood ash) comprises, for example, NaOH and / or Ca (OH) 2. In embodiments, a sulfur extraction material is added with the heat transfer material, in such a way that sulfur can be removed with ash. The sulfur extraction material can comprise a calcium material, such as calcium oxide (CaO), which can be converted to calcium sulfate and the output of the system with a solid. In modalities, ash water (comprising NaOH and / or Ca (OH) 2) is used to wash sulfur from the exhaust gases. For example, the system may comprise a washing tower to clean the process gas. Depending on the basicity of the gray water, it can be used, in modalities, as washing water. Such washing can be done upstream of an ESP or other particulate separator configured to remove particulates.
[00096] Except for air, the different fluidization gases mentioned for the CSP can also be used for the 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). The fluidizing gas in the GSP can be selected from the group consisting of waste gas, steam, recycled synthesis gas, and combinations of these.
[00097] In modalities, the sealing pots are round. In modalities, the sealing pots are rectangular. In modalities, the sealing pots are square. In modalities, the operating pressure is less than about 103.4214 kPaman. and the sealing pots are not round. The use of square and / or rectangular sealing pot designs can allow for a narrower spacing between them.
[00098] For the GSP, the minimum fluidization speed for the heat transfer material is established at any point in time. That is, the minimum initial fluidization speed is determined by the average initial particle size (for example, 100 μm). After a time in the stream (for example, 120 days), the heat transfer material may have a reduced average particle size (for example, about 25 μm); thus, the minimum fluidization speed changes (decreasing with time in the current / reducing the HTM size). The CSP and GSP can be selected in such a way that they are of an adequate size to handle the anticipated maximum fluidization speed, that is, usually the starting 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, density and / or its void fraction. In modalities, the minimum fluidization speed is greater than about 0.06 m / s. In modalities, the minimum fluidization speed is greater than about 0.46 m / s. As the particle size distribution (PSD) decreases, the fluidization speed of the sealing pot decreases.
[00099] The diameter of the sealing pots can be established by the number of leg penetrations, that is, how many cyclones you have and / or by the angles at which the legs enter the sealing pot. Legs can be angled to allow for shorter leg length. In modalities, the legs of the combustion cyclone enter the top of the gasifier sealing jars, as with the CSP (where the legs of the gasifier cyclone enter the CSP). The CSP and / or the GSP may contain a distributor configured to distribute gas evenly across its cross section (for example, the diameter). In modalities, the distributor is positioned at or near the bottom of the CSP and / or the GSP. In modalities, to minimize / prevent erosion of the sealing leg, the minimum distance between the distributor (ie, the fluidization nozzles) at the bottom of the sealing pot (GSP and / or CSP) and at the bottom of the leg (s) ( s) projecting on it is 25.4, 27.94, 30.48, 33.02, 35.56, 38.1, 40.64, 43.18 or 45.72 centimeters. In modalities, there is a distance of more than 38.1, 40.6, 43.2 or 45.7 centimeters between the sealing pot distributor and the cyclone leg (s). Desirably, the leg-to-leg spacing and / or the leg ID spacing for the refractory is at least 25.4, 27.94 or 30.48 centimeters. In modalities, the leg-to-leg spacing and the leg-ID spacing for the refractory are at least about 30.48 centimeters. In modalities, the legs are supported. Such support can be provided to minimize / prevent vibration of the legs. For the GSP, the seal can actually be inside the leg of the combustion cyclone (s) and the GSP (since the aerator 20 is under greater pressure than the separator of the combustion 60).
[000100] The GSP is designed with a suitable head of heat transfer material to minimize reflux. The height of the GSP is based on a design margin. In modalities, the project margin is in the range of about 6,894757 kPaman. at about 34.47379 kPaman., or is greater than or equal to about 6.894757, 13.78951, 20.68427, 27.57903 or 34.47379 kPaman .. The head of heat transfer material (for example, sand) will provide at least ΔP (pressure drop) enough to prevent gas backflow / prevent gasifier from reflecting back into the combustion cyclone. The nozzle distribution in both the CSP and GSP 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 foot2.
[000101] In embodiments, one or more of the sealing pots (either or both of 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 disclosed DFB gasification system comprises one or more J valves in place of a CSP. In embodiments, the DFB gasification system comprises one or more J valves in place of a GSP. In modalities, the DFB gasification system comprises multiple CSPs. In modalities, the multiple CSPs are substantially identical. In modalities, the DFB gasification system comprises multiple GSPs. In modalities, the multiple GSPs are substantially identical. In embodiments, the disclosed gasification system comprises at least one or more CSP and at least one or more GSP. The CSP seal can be inside the CSP (while the GSP seal can simply be inside one leg). In modalities, a J valve is used in the aerator, instead of a GSP.
[000102] The height of the CSP is determined by the pressure required for the seal, which is the pressure differential between the gasifier cyclone and the combustor. The combustion pressure plus a design margin 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, ΔP is greater than 13.78951 kPaman .. In modalities, ΔP is in the range of about 13.78951 kPaman. at about 172.3689 kPaman., from about 13.78951 kPaman. at about 137.8951 kPaman., or about 13.78951 kPaman. at about 103.4214 kPaman .. In modalities, the pressure differential is around 68.94757, 82.73709, 103.4214, 137.8951 kPaman .. Desirably, ΔP is not less than about 13.78951 kPaman., since pressure equalization is undesirable. In modalities, a smaller ΔP is used, thus allowing the use of a smaller CSP 70.
[000103] Downstream systems. The DFB gasification system can additionally comprise the apparatus 100 downstream of the double fluidized bed gasifier. For example, the downstream apparatus 100 may include one or more selected from the Fischer-Tropsch synthesis apparatus, the energy producing apparatus, the non-Fischer-Tropsch chemical production apparatus, the tar removal apparatus, the apparatus heat recovery, carbon dioxide removal apparatus, washing systems, expanders, and combinations thereof. In figure 1, line 117 generally indicates the removal of product and / or by-product (for example, tar, low tar gas, FT synthesis products, residual FT process gas, residual PU process gas, washed gas, energy, product with improved quality, chemicals, fuels, carbon dioxide, low carbon dioxide gas, etc.) from the device downstream 100.
[000104] In modalities, the DFB gasification system is integrated into a system of biomass in fuels and / or biomass in energy. In modalities, both energy and Fischer-Tropsch fuels are produced from the gaseous products of the revealed DFB gasifier. In modalities, the DFB gasification system is integrated with an energy production apparatus, whereby the system is used (for example, basically) for the production of energy. In modalities, the system is integrated with Fischer-Tropsch synthesis apparatus and used used basically for the production of liquid fuels (for example, Fischer-Tropsch fuels).
[000105] In modalities, about 10 to about 30% of the synthesis gas product of a DFB disclosed here is diverted to power generation and at least a portion of the remaining product gas is used for the production of Fischer-Tropsch fuels. In such embodiments, at least a portion of the residual Fischer-Tropsch process gas from the production of Fischer-Tropsch fuels can be mixed with the synthesis gas diverted to provide a gas with a Wobbe number suitable for energy production. Figure 2 is a schematic of an integrated system 10A comprising a fluidized bed gasification system / double "gasifier" 110 according to this disclosure, and the apparatus downstream 100A configured for Fischer-Tropsch synthesis and energy production. The gasification system 110 is as described with respect to the gasification system 10 in figure 1. The integrated system 10A comprises a DFB 110 gasifier, an energy production apparatus 140, and a Fischer-Tropsch 130 synthesis apparatus. The carbonaceous feed is aerated in the DFB 110 gasifier, as previously described, producing “dirty” synthesis gas. The integrated system 10A may comprise apparatus 120 configured to clean the “dirty” synthesis gas to provide a synthesis gas with fewer undesirable components (that is, with reduced amounts of hydrogen, carbon monoxide, carbon dioxide, water vapor) , hydrogen sulfide, and / or etc.) and / or a desired molar ratio of hydrogen to carbon monoxide. For example, apparatus 120 may comprise a partial oxidation apparatus fluidly connected via line 115 with the DFB 110 gasifier, and configured to subject the "dirty" synthesis gas to oxidation, producing a "clean" synthesis gas. A POx reactor can be operable at a temperature greater than or equal to about 1,093 ° C, 1,149 ° C or 1,204 ° C. Oxygen can be introduced into device 120 (for example, a POx reactor) via line 116. A line 125 can be configured to introduce at least a portion of the “clean” synthesis gas from cleaning device 120, for example, in a Fischer-Tropsch production reactor of the FT 130 synthesis apparatus. A line 126 can be configured to introduce at least a portion of the synthesis gas into the energy generating apparatus 140, configured for energy production.
[000106] The Fischer-Tropsch 130 synthesis reactor can be any suitable Fischer-Tropsch reactor known in the art. In embodiments, the Fischer-Tropsch synthesis reactor comprises an iron-based catalyst. In embodiments, the Fischer-Tropsch synthesis reactor comprises 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 US patent No. 5,508,118 and / or US patent applications No. 12 / 189,424, 12 / 198.459, 12 / 207.859, 12 / 474.552 and / or 12 / 790.101, whose disclosure of each is hereby incorporated in its entirety here with all purposes not contrary to this disclosure.
[000107] The Fischer-Tropsch 130 production reactor produces residual Fischer-Tropsch process gas and a variety of products that are generally liquid at the operating temperature of the Fischer-Tropsch reactor. Fischer-Tropsch liquid products can basically comprise hydrocarbons. Liquid Fischer-Tropsch products can basically comprise long-chain aliphatic hydrocarbons. Residual process gas can be removed from the Fischer-Tropsch reactor 130 via a residual process gas line 136 and Fischer-Tropsch synthesis products can be removed via line 137 and / or 135.
[000108] The integrated system 10A may additionally comprise a product quality improvement device 130B configured to improve the quality of liquid products of the Fischer-Tropsch synthesis and fluidly connected with a Fischer-Tropsch 130 synthesis device via line 135, by means of than at least a portion of the liquid products of the Fischer-Tropsch 130 reactor can have improved quality in more desired products. The product quality improvement apparatus 130B may comprise hydrotreating apparatus, hydrocracking apparatus, hydroisomerization apparatus and / or any other product quality improvement apparatus known to those skilled in the art. The products of the Fischer-Tropsch 130 reactor and / or the product quality improvement device 130B removed via lines 137 and 138, respectively, can basically comprise jet fuel, basically diesel fuel, basically gasoline, basically naphtha, or some combination of one or more selected jet fuel, diesel fuel, gasoline, and naphtha.
[000109] Quality improvement can create a waste gas for quality improvement process, removed from the integrated system 10A via line 139. As previously discussed, a waste gas for quality improvement process like this can be used as fuel for the combustor of the DFB gasification system 110, and / or as a fluidizing gas in a CSP, a GSP, and / or its gasifier. In such embodiments, the quality improvement process residual gas outlet line 139 can fluidly connect the product quality enhancer 130B with combustor 30, CSP 70, GSP 80 and / or gasifier 20.
[000110] The energy production apparatus 140 can be any apparatus known in the art for the production of energy, indicated in figure 2 by means of line 145. In embodiments, the energy production apparatus 140 comprises a gas turbine. In embodiments, at least a portion of the residual process gas removed from the Fischer-Tropsch 130 synthesis reactor via line 136 is introduced into the energy generating apparatus 140. In embodiments, a portion of the residual Fischer-Tropsch process gas is used for energy production and a portion is used in the DFB gasifier 110 gasification system, as discussed in detail earlier. For example, a portion of the residual Fischer-Tropsch process gas can be used as fuel for the combustor of the DFB 10/110 gasification system, and / or as a fluidizing gas in a CSP, a GSP and / or its gasifier. In such embodiments, the process residual gas outlet line FT 136 can be fluidly connected with the combustor 30, the CSP 70, the GSP 80 and / or the gasifier 20.
[000111] In modalities, a DFB gasification system of this disclosure additionally comprises a system of tar removal downstream of the gasifier cyclones and configured to remove tar from the synthesis gas product. In modalities, the tar removal system is a downstream heat recovery device. The tar removal system may comprise a Dahlman unit, which comprises a multistage solvent wash (i.e., oil). The Dahlman unit can be operated with synthesis gas at a temperature of at least or about 343 ° C, 371 ° C, 399 ° C, 427 ° C, 454 ° C or 482 ° C. As previously discussed, a portion of the removed tar can be recycled to the DFB gasification system combustor for use as a fuel.
[000112] In modalities, the DFB gasification system additionally comprises a POx unit, a boiler or a NiDFB (previously mentioned) downstream of the gasifier. In modalities, the synthesis gas is provided for the production downstream of chemicals and the DFB gasification system additionally comprises apparatus for the production downstream of chemicals and / or fuels other than fuels and / or Fischer-Tropsch chemicals. The downstream apparatus can be any apparatus known in the art configured for the production of methanol, ethanol, ammonia, fertilizer, etc., from gasification gas comprising hydrogen and carbon monoxide.
[000113] In modalities, a system for the production of jet fuel is provided, the system comprising a DFB gasifier disclosed here, tar reforming apparatus, one or more Fischer-Tropsch mud reactors, hydrocracking apparatus and / or apparatus hydrotreatment.
[000114] Features / Advantages: The revealed system and method allow the production of gas by the use of a high production pyrolyzer and an external combustor, incorporating circulation of a heat transfer material to provide heat for the endothermic gasification reactions. By means of the revealed system and method, exothermic combustion reactions are separated from endothermic gasification reactions. Exothermic combustion reactions take place in or near a combustor, while endothermic gasification reactions take place in the gasifier / pyrolyzer. This separation of endothermic and exothermic processes can provide a high energy density product gas without the dilution of nitrogen present in conventional air blowing gasification systems.
[000115] Although preferred embodiments of the invention have been shown and described, their modifications can be made by those skilled in the art without departing from the spirit and precepts of the invention. The modalities described here are only exemplary, and are not intended to be limiting. Many variations and modifications of the invention disclosed here are possible and are within the scope of the invention. Where ranges or numerical limitations are expressly stated, it should be understood that such ranges or expressed limitations include bands or interactive limitations of the same magnitude that fall within the ranges or limitations expressly stated (for example, from about 1 to about 10 includes, 2 , 3, 4, etc .; more than 0.10 includes 0.11, 0.12, 0.13, and so on). The use of the term "optionally" in relation to any element of a claim must mean that the element in question is required, or, alternatively, is not required. Both alternatives must be within the scope of the claim. The use of broader terms such as understand, include, with, etc. it is to be understood in order to provide support for more restricted terms such as consisting, essentially consisting, substantially understood, and the like.
[000116] Thus, the scope of protection is not limited by the description presented here, but is limited only by the following claims, this scope including all equivalents of the subject in question of the claims. Any and all claims are incorporated into the specification as an embodiment of the present invention. Thus, the claims are an additional description and are an addition to the preferred embodiments of the present invention. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those presented here.

权利要求:
Claims (23)
[0001]
1. Method for the production of synthesis gas, characterized by the fact that it comprises: introducing (90) a carbonaceous feed load and a particulate heat transfer material heated in a gasifier (20) comprising a fluidized bed, through the that at least a portion of the carbonaceous material is pyrolysed to produce a gasification gas product comprising hydrogen and carbon monoxide, and in which the fluidized bed comprises fluidized particulate heat transfer material by introducing (141, 141a) a fluidizing gas from the gasifier in the aerator; removing (114), from a region of the trapped space of lower average density of the gasifier, a gas product of the gasification comprising, trapped therein, animal charcoal, particulate heat transfer material, and optionally unreacted carbonaceous feed charge; separating (40, 50) at least one solid product comprising animal charcoal, particulate heat transfer material and optionally unreacted carbonaceous material from the gas product of the gasification, providing a low particulate product gas; heating at least a portion of the at least one solids product by passing it through a combustion (30), thereby producing a heated portion of the at least one solids product and a combustion waste gas, wherein at least a portion of the heat for heating is obtained by combustion of the animal charcoal in at least a portion of the at least one solids product; introducing (35) at least a portion of the heated portion of the at least one solids product into the gasifier, providing heat for pyrolysis; and subjecting (114b) at least a portion of the gas from the gasification to Fischer-Tropsch synthesis, producing energy from at least a portion of the gas from the gasification, or both.
[0002]
2. Method according to claim 1, characterized by the fact that subjecting at least a portion of the gas product of the gasification to the Fischer-Tropsch synthesis comprising putting at least a portion of the gas product of the gasification in contact with a Fischer-Tropsch catalyst iron based, and wherein the method further comprises subjecting the gasification product gas to partial oxidation to adjust the molar ratio of hydrogen to carbon monoxide in the gasification product gas to provide a molar ratio in the range of 0.5: 1 to 1.5: 1 before subjecting at least a portion of the gas from the gasification to Fischer-Tropsch synthesis; or a cobalt based Fischer-Tropsch catalyst, and wherein the method further comprises subjecting the gasification product gas to partial oxidation to adjust the molar ratio of hydrogen to carbon monoxide in the gas product of the gasification to provide a molar ratio in the range 1.5: 1 to 2.5: 1 before subjecting at least a portion of the gas from the gasification to the Fischer-Tropsch synthesis, in which submitting at least a portion of the gas from the gasification to the Fischer-Tropsch synthesis produces products of non-gaseous Fischer-Tropsch synthesis, a residual Fischer-Tropsch process gas, and a used catalyst product comprising used Fischer-Tropsch catalyst and liquid hydrocarbons.
[0003]
3. Method according to claim 2, characterized by the fact that it additionally comprises introducing at least a portion of the residual Fischer-Tropsch process gas into a component selected from the group consisting of the combustor (30), the gasifier (20) and in sealing pots (70, 80) configured to prevent reflux of material from the combustor or aerator.
[0004]
Method according to claim 2, characterized in that it additionally comprises introducing at least a portion of the catalyst product used in the gasifier, the combustion, or both.
[0005]
5. Method according to claim 1, characterized in that it comprises producing energy (126) through at least 10, 20, or 30 percent by volume of the gas product of the gasification and submitting (125) at least a portion of the gas resulting from the remaining gasification the Fischer-Tropsch synthesis.
[0006]
6. Method according to claim 1, characterized by the fact that it further comprises operating the gasifier at a pressure of the gasifier, and operating the combustor at a pressure of the combustor which is in the range of 0 kPaman at a pressure which is at least 13.78951 kPaman less than the gasifier pressure.
[0007]
Method according to claim 1, characterized in that it further comprises fluidizing the combustion with a combustion fluidizing gas at a surface speed of the incoming combustor fluidizing gas in the range of 457 to 762 cm / s, a surface velocity of the outgoing gas in the range of 762 to 1,219 cm / s, or both.
[0008]
Method according to claim 7, characterized in that it additionally comprises introducing at least 20% of the combustion fluidization gas through at least one combustion sealing pot (70) configured to prevent reflux of combustor material .
[0009]
Method according to claim 1, characterized in that it further comprises preventing backflow of gasifier material through at least one sealing pot (80) of the gasifier, preventing backflow of combustor material through at least one pot seals (70) of the combustion, or both.
[0010]
10. Method according to claim 1, characterized by the fact that the particulate heat transfer material is selected from the group consisting of sand, limestone, and other calcites or oxides including iron oxide, olivine, and magnesia, alumina, carbides, silica alumina, zeolites, and combinations thereof.
[0011]
11. Method, according to claim 1, characterized by the fact that it additionally comprises operating the combustor with excess oxygen in the range of 0 to 20 percent by volume.
[0012]
12. Method according to claim 1, characterized by the fact that it additionally comprises introducing the carbonaceous feed charge at a temperature in the range of -40 ° C to 127 ° C, wherein the carbonaceous feed load comprises at least one selected from the group consisting of biomass, RDF, MSW, sewage sludge, coal, Fischer-Tropsch synthetic wax, and combinations of these.
[0013]
13. Method according to claim 1, characterized by the fact that it additionally comprises operating the combustor at or near its inlet operating temperature for heat transfer material in the range of 538 ° C to 760 ° C, and an operating temperature at or near its outlet for a combustor particulate separator in the range of 760 ° C to 982 ° C.
[0014]
14. Method, according to claim 1, characterized by the fact that it additionally comprises removing moisture (155) from a carbonaceous material up to a moisture content in the range of 10 to 40 weight percent to provide a carbonaceous feed load, using at least a portion of the heat from the combustion waste gas to dry the carbonaceous material, or both.
[0015]
15. Method according to claim 1, characterized in that it additionally comprises converting at least 30, 40, 50, 60, 70 or 80% of the carbon in the carbonaceous feed charge into gas from the gasification.
[0016]
16. Method according to claim 1, characterized by the fact that it additionally comprises introducing the carbonaceous feed load into the gasifier at a flow of at least 10,000 kg / h.m2, 12,000 kg / h.m2, 12,500 kg / h .m2, 15,000 kg / h.m2, 17,000 kg / h.m2 or 20,000 kg / h.m2.
[0017]
17. Method, according to claim 1, characterized by the fact that it additionally comprises introducing the gasifier fluidization gas into the gasifier at a surface speed in the range of 15.24 cm / s to 304.8 cm / s, removing the gas aerator gasification product at a surface speed in the range of 1,067 to 1,524 cm / s, or both, where the gasifier fluidization gas is selected from the group consisting of steam, waste gas, synthesis gas, LP waste gas , residual process gas, gas from the gasification, and combinations thereof.
[0018]
18. Method according to claim 1, characterized by the fact that it additionally comprises operating the gasifier at an operating temperature in the range of 538 ° C to 871 ° C.
[0019]
19. Method, according to claim 1, characterized by the fact that it additionally comprises operating the gasifier at an operating pressure greater than 13.78951 kPaman and / or less than 310.2641 kPaman, or both.
[0020]
20. Method according to claim 1, characterized in that the gasifier comprises a gasifier distributor (95) configured to introduce gasification fluidization gas in a substantially uniform manner across the diameter of the gasifier, wherein the combustor comprises a combustion distributor configured to introduce combustion fluidizing gas substantially uniformly across the diameter of the combustion, or both.
[0021]
21. Method according to claim 1, characterized in that it further comprises introducing particulate heat transfer material into the combustor at a location at least 122, 152 or 183 centimeters above a combustor distributor; introducing heated fluidized particulate heat transfer material from the combustor into the gasifier at a location at least 122, 152 or 183 centimeters above a gasifier distributor; or both.
[0022]
22. Method according to claim 1, characterized in that the at least a portion of the heated portion of the at least one solids product is introduced into the gasifier at a temperature in the range of 760 ° C to 871 ° C.
[0023]
23. Method according to claim 1, characterized by the fact that it additionally comprises maintaining an operating temperature differential below 194 ° C, 183 ° C, 167 ° C, 150 ° C, or 139 ° C between the gasifier and the combustor.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112014001851B1|2021-03-09|method for the production of synthesis gas

---

US9188331B2|2015-11-17|Supplemental fuel to combustor of dual fluidized bed gasifier

---

BR112014009997A2|2020-12-01|method and system for the production of synthesis gas

---

US9163179B2|2015-10-20|System and method for production of Fischer-Tropsch synthesis products and power

---

US20160362622A1|2016-12-15|Seal pot design

同族专利:

---

公开号 | 公开日

---

EP2737035A2|2014-06-04|

---

US20130030062A1|2013-01-31|

---

EP2737033A2|2014-06-04|

---

ZA201309751B|2014-11-26|

---

CA2843038C|2017-10-10|

---

EP2737035A4|2015-03-04|

---

US20130028801A1|2013-01-31|

---

US9089827B2|2015-07-28|

---

EP2737035B1|2018-06-27|

---

CA2843040A1|2013-01-31|

---

EP2737034A2|2014-06-04|

---

US9050574B2|2015-06-09|

---

CA2842079C|2017-02-28|

---

WO2013016705A2|2013-01-31|

---

US20130030064A1|2013-01-31|

---

WO2013016703A2|2013-01-31|

---

BR112014001775A2|2017-02-21|

---

US20150232769A1|2015-08-20|

---

US20130025281A1|2013-01-31|

---

EP2737034A4|2015-03-11|

---

BR112014001765A2|2017-02-21|

---

WO2013016706A2|2013-01-31|

---

WO2013016704A2|2013-01-31|

---

ZA201309752B|2017-02-22|

---

BR112014001773A2|2017-02-21|

---

CA2842079A1|2013-01-31|

---

WO2013016704A3|2013-04-18|

---

WO2013016702A3|2013-05-02|

---

ZA201309750B|2014-09-25|

---

BR112014001851A2|2017-02-21|

---

CA2842102C|2017-08-08|

---

EP2737032A4|2015-03-04|

---

CA2843038A1|2013-01-31|

---

US9101900B2|2015-08-11|

---

US20130028802A1|2013-01-31|

---

BR112014001781A2|2017-02-21|

---

CA2842102A1|2013-01-31|

---

ZA201309753B|2017-11-29|

---

EP2737034B1|2018-06-27|

---

WO2013016702A2|2013-01-31|

---

CA2843040C|2017-10-10|

---

CA2842096C|2017-06-27|

---

BR112014001781B1|2021-03-09|

---

CA2842096A1|2013-01-31|

---

WO2013016706A3|2013-04-25|

---

WO2013016703A3|2013-04-18|

---

WO2013016705A3|2013-04-18|

---

EP2737032A2|2014-06-04|

---

EP2737033A4|2015-03-04|

---

US9255232B2|2016-02-09|

---

US9314763B2|2016-04-19|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2592377A|1946-08-08|1952-04-08|Standard Oil Dev Co|Manufacture of gas mixtures containing carbon monoxide and hydrogen|

---

US3853498A|1972-06-28|1974-12-10|R Bailie|Production of high energy fuel gas from municipal wastes|

---

US3941820A|1975-01-09|1976-03-02|Continental Oil Company|Predominantly aliphatic hydrocarbon materials from carbonaceous solids|

---

US3975168A|1975-04-02|1976-08-17|Exxon Research And Engineering Company|Process for gasifying carbonaceous solids and removing toxic constituents from aqueous effluents|

---

US4444007A|1982-03-12|1984-04-24|Chevron Research Company|Method for combined cycle electrical power generation|

---

ZA848473B|1983-11-14|1985-09-25|Krw Energy Systems Inc|Particulate solids conveyance seal and injection system|

---

NL8400609A|1984-02-28|1985-09-16|Shell Int Research|PROCESS FOR PREPARING HYDROCARBONS.|

---

US4828581A|1985-09-20|1989-05-09|Battelle Development Corporation|Low inlet gas velocity high throughput biomass gasifier|

---

US4761131A|1987-04-27|1988-08-02|Foster Wheeler Corporation|Fluidized bed flyash reinjection system|

---

US5242662A|1989-05-18|1993-09-07|Foster Wheeler Energy Corporation|Solids recycle seal system for a fluidized bed reactor|

---

US5022893A|1990-03-01|1991-06-11|Foster Wheeler Energy Corporation|Fluidized bed steam temperature enhancement system|

---

JP3277226B2|1992-07-03|2002-04-22|株式会社アライドマテリアル|Rotating anode for X-ray tube and method for producing the same|

---

US5666800A|1994-06-14|1997-09-16|Air Products And Chemicals, Inc.|Gasification combined cycle power generation process with heat-integrated chemical production|

---

US5645620A|1995-05-25|1997-07-08|Foster Wheeler Development Corp.|System for separating particulates and condensable species from a gas stream|

---

US5666801A|1995-09-01|1997-09-16|Rohrer; John W.|Combined cycle power plant with integrated CFB devolatilizer and CFB boiler|

---

US6025403A|1997-07-07|2000-02-15|Mobil Oil Corporation|Process for heat integration of an autothermal reformer and cogeneration power plant|

---

US20010051662A1|2000-02-15|2001-12-13|Arcuri Kym B.|System and method for preparing a synthesis gas stream and converting hydrocarbons|

---

WO2002050214A2|2000-12-21|2002-06-27|Future Energy Resources Corporation|Biomass gasification system and method|

---

US6494153B1|2001-07-31|2002-12-17|General Electric Co.|Unmixed combustion of coal with sulfur recycle|

---

US20030083390A1|2001-10-23|2003-05-01|Shah Lalit S.|Fischer-tropsch tail-gas utilization|

---

US6596780B2|2001-10-23|2003-07-22|Texaco Inc.|Making fischer-tropsch liquids and power|

---

JP2004060041A|2002-07-25|2004-02-26|Ebara Corp|Method and apparatus for producing high purity hydrogen|

---

US20050058507A1|2003-09-17|2005-03-17|Cedarapids, Inc.|Multi-use paving tractor with tool attachments|

---

MX2008005225A|2005-10-21|2008-09-11|Taylor Biomass Energy Llc|Process and system for gasification with in-situ tar removal.|

---

US7951350B1|2007-01-26|2011-05-31|West Biofuels, Llc|Fuel-gas reforming systems and methods|

---

US8292977B2|2007-03-02|2012-10-23|Ihi Corporation|System for controlling circulatory amount of particles in circulating fluidized bed furnace|

---

TWI398689B|2007-03-20|2013-06-11|Au Optronics Corp|Liquid crystal display panel|

---

EP2175989A4|2007-08-10|2012-02-01|Rentech Inc|Precipitated iron catalyst for hydrogenation of carbon monoxide|

---

AT505526B1|2007-08-14|2010-09-15|Univ Wien Tech|FLUID BED REACTOR SYSTEM|

---

US10086365B2|2007-08-30|2018-10-02|Res Usa, Llc|Strengthened iron catalyst for slurry reactors|

---

US9018128B2|2007-09-14|2015-04-28|Res Usa Llc|Promoted, attrition resistant, silica supported precipitated iron catalyst|

---

US8084656B2|2007-10-09|2011-12-27|Rentech, Inc.|Systems and methods for oxidation of synthesis gas tar|

---

AU2009256463B2|2008-06-02|2014-10-09|Res Usa, Llc|Strengthening iron Fischer-Tropsch catalyst by co-feeding iron nitrate and precipitating agent or separately precipitating from ferrous nitrate and ferric nitrate solutions|

---

US8110012B2|2008-07-31|2012-02-07|Alstom Technology Ltd|System for hot solids combustion and gasification|

---

PE20110403A1|2008-07-31|2011-07-04|Genentech Inc|PYRIMIDINE FUSED BICYCLE COMPOUNDS IN THE TREATMENT OF CANCER|

---

CN102186953A|2008-08-20|2011-09-14|株式会社Ihi|Fuel gasification equipment|

---

TWI447329B|2008-09-26|2014-08-01|Univ Ohio State|Conversion of carbonaceous fuels into carbon free energy carriers|

---

US20100162625A1|2008-12-31|2010-07-01|Innovative Energy Global Limited|Biomass fast pyrolysis system utilizing non-circulating riser reactor|

---

CA2881239C|2009-01-21|2017-02-28|Res Usa, Llc|System and method for dual fluidized bed gasification|

---

US8791041B2|2009-06-03|2014-07-29|Rentech, Inc.|Slurry bed fischer-tropsch catalysts with silica/alumina structural promoters|

---

PL2273192T3|2009-06-12|2013-09-30|General Electric Technology Gmbh|System for converting fuel material|

---

ES2656144T3|2009-09-08|2018-02-23|The Ohio State University Research Foundation|Production of synthetic fuels and chemical products with CO2 capture in situ|

---

US8580151B2|2009-12-18|2013-11-12|Lummus Technology Inc.|Flux addition as a filter conditioner|RU2663745C2|2013-02-05|2018-08-09|Релайанс Индастриз Лимитед|Method for catalytic gasification of carbonaceous feed|

---

GB2503065B|2013-02-20|2014-11-05|Recycling Technologies Ltd|Process and apparatus for treating waste comprising mixed plastic waste|

---

US10518238B2|2013-03-15|2019-12-31|Synthesis Energy Systems, Inc.|Apparatus using multiple jets for gas delivery and methods of fluidizing|

---

KR102263205B1|2013-07-04|2021-06-09|리껭테크노스 가부시키가이샤|Method for producing anti-blocking hard coat film|

---

US9266123B2|2013-12-05|2016-02-23|Exxonmobil Research And Engineering Company|Integrated cyclone assembly|

---

US9650574B2|2014-07-01|2017-05-16|Gas Technology Institute|Hydropyrolysis of biomass-containing feedstocks|

---

FI127201B|2015-04-17|2018-01-31|Valmet Technologies Oy|Catalytic refining of pyrolysis vapors|

---

JP2017071692A|2015-10-07|2017-04-13|Ｊｆｅスチール株式会社|Gasification method of carbonaceous fuel, operation method of iron mill and manufacturing method of gasified gas|

---

KR102184265B1|2016-03-04|2020-11-30|루머스 테크놀로지 엘엘씨|Gasification process with two-stage gasifier and feedstock flexibility|

---

US20180201851A1|2017-01-19|2018-07-19|General Electric Technology Gmbh|System and method for chemical looping|

---

CN108504394B|2017-02-23|2020-07-07|中国石油化工股份有限公司|Catalytic pyrolysis-gasification integrated reaction device and method|

---

US10745276B2|2018-06-29|2020-08-18|Praxair Technology, Inc.|Tail gas heating within PSA surge tank|

---

WO2020026068A1|2018-07-31|2020-02-06|Viraraghavan Shweta|A composition and method for the production of biofuel from edible oil refinery by-products and wastes|

---

CN112500892B|2019-09-16|2021-10-08|中国科学院工程热物理研究所|Integrated treatment device and method for gasification and fly ash melting of circulating fluidized bed|

---

CN111826207A|2020-07-03|2020-10-27|新奥科技发展有限公司|Gasification ash treatment device and method and coal catalytic gasification system|

法律状态:
2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-07-16| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

---

2020-06-16| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

---

2020-10-20| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 8A ANUIDADE. |

---

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

---

2021-02-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-03-09| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |

---

2021-06-01| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |

---

2021-09-21| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2630 DE 01-06-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201161512365P| true| 2011-07-27|2011-07-27|

---

US61/512,365|2011-07-27|

---

PCT/US2012/048718|WO2013016705A2|2011-07-27|2012-07-27|Gasification system and method|

---