Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/72—Other features
  • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
  • B01J23/04—Alkali metals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/46—Gasification of granular or pulverulent flues in suspension
  • C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/46—Gasification of granular or pulverulent flues in suspension
  • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/02—Dust removal
  • C10K1/024—Dust removal by filtration
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/02—Dust removal
  • C10K1/026—Dust removal by centrifugal forces
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0903—Feed preparation
  • C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/094—Char
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0943—Coke
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0959—Oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0969—Carbon dioxide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0973—Water
  • C10J2300/0976—Water as steam
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0983—Additives
  • C10J2300/0986—Catalysts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0983—Additives
  • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/12—Heating the gasifier
  • C10J2300/1253—Heating the gasifier by injecting hot gas
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
  • C10J2300/1656—Conversion of synthesis gas to chemicals
  • C10J2300/1662—Conversion of synthesis gas to chemicals to methane (SNG)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1838—Autothermal gasification by injection of oxygen or steam
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1853—Steam reforming, i.e. injection of steam only
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present invention relates to the gasification of petroleum coke-based feed materials. More particularly, the invention relates to an improved process to convert petroleum coke- based feed materials and steam to a hydrogen rich gaseous mixture, wherein material costs are reduced, and energy efficiency is increased.
• Petroleum coke is produced in large amounts in refinery cooker units as byproduct.
• Several options are known to utilize this byproduct. The simplest way is to use it as fuel, providing heat energy or electricity for various refinery processes. More attractive ways are to convert petroleum coke to value added products, such as by converting it to activated carbon.
• Such activated carbons can be used in water or gas treatment or for the production of electrical components, such as capacitors or electrodes. Synthesis gas is in this case a byproduct.
• Gasification of carbonaceous materials including petroleum coke is a well-known technology.
• the gasification reaction is performed either thermally or catalytically. In thermal processes, very high temperatures (1300-1600°C) are required to achieve nearly complete (95-98%) carbon conversion (WO 1995013339, US 3544291 , US 4332641).
• Catalytic gasification can be performed at significantly lower temperatures (650-800°C) (US 8114176, US 20090090055, US 20090090056, US 3600130, EP 0019487, EP 0024792).
• Catalysts used contain alkali metal hydroxides or carbonates or their mixture, at a relatively high ratio of 5-20%.
• Such catalysts are applied by wet impregnation on the surfaces of the particulate feed, can be separated after the completion of the reaction with the char, and are expediently recovered and reused by leaching (US 8114176).
• Gasification reactions are performed in most cases in continuous fluid bed reactors, the carbonaceous feed must be particulated before impregnation to well fluidizable particulate sizes, which is 0.5-5 mm. (US 20090090055, US 20090090056, US 20100024300). Impregnation is the point, where the applicability of petroleum coke sharply differs from that of other carbonaceous materials, including coal: while e.g.
• coal can be readily impregnated with the aqueous solutions of the large amounts of catalyst mentioned above, petroleum coke, due to its inherently low specific surface, low water content and low water soaking ability, is difficult to impregnate, it may not take up all catalysts from the solution, and uniform coverage may not be reached.
• entrained flow reactors are also applied, where the feed must be milled to below 100m particulate size. The energy consumption of the milling work to produce such particulates, together with the high oxygen consumption and high reaction temperatures increase the energy requirement of entrained flow technologies considerably (WO 1995013339, US 4475925).
• reaction temperature is extremely high (non-catalytic processes), or the amount of catalyst to be used is high (5-20% in catalytic processes),
• the energy consumption of the preparatory work, particularly for the catalytic processes, is high (milling; mixing),
• the energy consumption of catalyst recovery is also high and produces losses (leaching of the char can be performed with losses).
• the feed is gasified with steam and oxygen thermally below 1000°C, preferably between 900°C and 980°C, more preferably between 920°C and 950°C and at pressure of 1-20 Bar, preferably at 10-20 Bar. At that temperature range 75-85% carbon conversion to hydrogen rich synthesis gas can be achieved.
• Entrained fines are separated by a suitable separating device and are united with the char withdrawn at the bottom of the reactor.
• the carbon content in such fines and bottom char is already partially gasified, enlarged surface area and a porous structure and can be more effectively impregnated with the aqueous solution of an alkali metal compound or alkaline earth metal compound or their mixture suitable to catalyze gasification reaction.
• Impregnated particles are then gasified in the second, catalytic gasifier reactor of said reactor system between 700°C and 800°C, preferably between 730°C and 770°C and between 2-10 Bar, preferably between 3-5 Bar.
• Carbon yield in the combined gaseous products of the first and second gasifiers is 95-98%
• the hydrogen content is 61-66 v/v%
• combined hydrogen yield in the two reactors is 0,15-0,25 kg/kg coke/s.
• Figure 1 is the schematic bloc diagram of the preferred embodiment of the invention.
• petroleum coke-based feedstock refers to a feedstock, which is a mixture of 70-100% petroleum coke and 0-30% of other carbonaceous material(s), where other carbonaceous material is one or more of biomass, coal, municipal solid waste or petroleum heavy residue.
• hydrogen rich gaseous products or“hydrogen rich gaseous mixture” refer to a mixture of gases obtained by the steam gasification of petroleum coke-based feedstocks, that contain at least 60 v/v% hydrogen, 0-30 v/v% carbon monoxide, 0-30 v/v% carbon dioxide and 0-2% methane.
• the petroleum coke-based feedstock is particulated over 90% to particulate sizes of 0.5-5 mm, preferably to 0.5-2 mm and is fed into the bottom part of a continuously operated gasification reactor.
• the reactor can be a circulating fluidized bed or a bubbling fluidized bed reactor and is reacted with a stream of steam and oxygen, optionally in the presence of a fluidizing gas, which can be any inert gas known in the art, for example nitrogen or carbon dioxide.
• Reaction temperature is below 1000°C, preferably between 900°C and 980°C, more preferably between 920°C and 950°C
• reaction pressure is between 1-20 bar, preferably 3-10 bar.
• Limestone or dolomite may be added into the gasification reactor to facilitate gasification and the decomposition of tar, as well as for sulfur capture.
• the gasification system may include a first, recycling cyclone, which increases the residence time of the smaller particles.
• the product of the first reactor is a hydrogen-rich gaseous mixture, it is composed of 60-65 v/v% hydrogen, 12-25 v/v% carbon monoxide, 18-23 v/v% carbon dioxide and 1-1 ,5 v/v% methane. The latter three components contain 75-85% of the feed carbon.
• Fines escaping the first recycling cyclone, rich in carbon and containing some calcium, are led through a gas cooler for the recovery of the sensible heat and separated by any suitable separating device known in the art, for example a cyclone, a filter or a wet scrubber.
• the fines- char mixture can be considered as intermediate product, still contains 15-25% of the feed carbon, and is practically activated carbon, as it was activated by steam in the first reactor, and thus it has enlarged specific surface (150-250 m 2 /g) and pore volume (0,10-0,3 cm 3 /g). Consequently, its water soaking capability is considerably higher, than that of the original petroleum coke feed, and thus it can be more effectively impregnated with the aqueous solution of a catalyst composition.
• Suitable catalysts known in the art, are alkali metal compounds or alkaline earth metal compounds or their mixtures.
• the fines-char mixture is homogenized in a suitable mixer-drier unit with simultaneous spraying of the aqueous solution of the catalytic compounds, optionally followed by a drying process or section. It is within the scope of this invention, that impregnation may optionally aided by a small amount of wetting agents, for example by ethanol, ligno-sulfonic acid or black liquor. Drying is preferably performed at low temperatures, such as at ambient temperature in vacuum. Our experiments have shown, that 2-5% catalyst loading will provide, above 700°C reaction temperature, the same reactivity in the second catalytic reactor, as was achieved above 900°C in the first non-catalytic reactor.
• the energy consumption and material costs of the impregnation process have been significantly reduced as compared to conventional methods.
• the activated carbon intermediate product can be impregnated under milder conditions: lower temperature, shorter mixing time, lower drying temperature.
• the impregnated carbon intermediate may be optionally granulated to fluidizable particles, and then fed into the bottom of the second reactor.
• This second gasifier can be also a fluidized bed reactor, which can be operated as an adiabatic reactor with high steam-to- oxygen ratio, or it can be designed as an externally heated fluidized bed.
• the second reactor has a very efficient recycling system, comprising a recycling cyclone and a filter.
• the second, catalytic gasifier is operated at 680 - 800°C, preferably at 700-780°C, more preferably at 730-750°C, where the reactivity is reasonably high, and the catalyst is not yet sintering or vaporized.
• the selected pressure level for the second reactor is 2-10 bar, preferably 3-5 bar.
• the secondary gasifier is operated at higher steam-to oxygen ratio and can be operated as an adiabatic reactor.
• Carbon conversion in the second reactor is 80-90%, the overall carbon conversion is 95-98%.
• 65-85% of the hydrogen rich gaseous product is produced in the first, thermal reactor, and 15-35% in the second, catalytic reactor. After initial cooling and cleaning the two product streams can be mixed.
• the composition of the second reactor product is: hydrogen 68-70 v/v%; carbon monoxide 2-5 v/v%; carbon dioxide 26-30 v/v%; methane 0,3-0, 7 v/v%.
• Composition of the united feed is: hydrogen 61-66 v/v%, carbon monoxide 10-15 v/v%; carbon dioxide 20-25 v/v%, methane 1-1 ,5 v/v%.
• Total hydrogen yield is 0,15-0,25 kg/kg coke/s.
• the invention relates to a process for the gasification of carbonaceous materials by providing a petroleum coke-based feed material, comminution of said petroleum coke-based feed material to 0,5-5 mm particle size, gasification of said petroleum coke-based feed material with steam and/or carbon-dioxide in the presence of oxygen and optionally a fluidizing gas, characterized by:
• the temperature of the first reactor is set between 900°C and 980°C, more preferably between 920°C and 950°C; that of the second reactor between 700-780°C, more preferably between 730-750°C.
• the pressure of the first reactor is preferably set between 10-20 bar, that of the second reactor between 3-5 bar.
• feed material 70-100% petroleum coke and 0-30% one or more carbonaceous material such as biomass, coal, municipal solid waste, heavy petroleum residue as balance containing petroleum coke-based feed material is used.
• a circulating- or bubbling fluidized bed thermal gasifier can be used as a first reactor.
• the petroleum coke may be fed to the bottom of the reactor and the different carbonaceous materials (such as solid recovered fuel or biomass) to the riser section of the reactor;
• a cyclone As separating device, a cyclone, a filter or a wet scrubber may be used.
• the impregnation may be performed with continuous spraying in an agitated homogenizer, followed by drying under vacuum at mild temperatures in the same device under mild agitation and optionally granulated.
• alkali metal and alkaline earth metal one or more of sodium, potassium, calcium and magnesium, and as anion one or more of hydroxide, carbonate, sulphate, nitrate and chloride can be used.
• a circulating or bubbling catalytic gasifier may be used, smaller than the first reactor.
• the catalytic stage processes only 15-25% of the original feed, consequently the required amount of the catalyst is drastically reduced to 10-20% of that of conventional catalytic gasification’s.
• the intermediate product of the first gasification stage to be impregnated is activated carbon, which has an increased specific surface with increased pore volume compared to the original feed, therefore it requires lower energy input during the preparation labor and provides uniform catalyst coverage at the lowest catalyst concentration of the conventional range (2-5%).
• the first gasifier is a circulating fluid bed reactor, bed id is 2,5m. Petroleum coke 8,68 kg/s (dry basis) is fed into this first gasifier and is fluidized with 13,4 kg/s steam and 5,60 kg/s oxygen. Reactor temperature is 930°C, the pressure is 10 bar, fluidization velocity is 1 ,9 m/s.
• the reactor is equipped with a recycling cyclone. The gaseous product containing 1 ,5 kg/s hydrogen is led through a second cyclone, where fines escaping the first reactor and the first, recycling cyclone are separated. The fines collected from the second, separating cyclone are united with the bottom char withdrawn from the reactor.
• This mixture is practically activated carbon (specific surface 182 m 2 /g, pore volume 0,155 cm 3 /g) and is homogenized during spraying with the aqueous solution 2-5% potassium carbonate, and dried at ambient temperature in vacuum during mild continuous agitation.
• This catalyzed activated carbon is fed into the second gasifier (1 ,86 kg/s).
• the second gasifier is a similar circulating fluidized bed reactor, bed id 2,2 m, is operated at 740°C temperature and 3 bar pressure.
• the feed is fluidized with 5,48 kg/s steam and 1 ,30 kg/s oxygen.
• Synthesis gas product contains 0,3 kg/s hydrogen and is combined with the product of the first gasifier.
• the synthesis gas product may be optionally separated by pressure swing adsorption.
• Carbon conversion to hydrogen rich gaseous mixture is 78 and 85% in the first and second gasifiers, respectively. Total carbon conversion is 97%.
• Combined hydrogen production is 1 ,8 kg/s, hydrogen yield is 0,21 kg/kg coke/s.
• the catalyst used in the second gasifier is recovered and reused. Filter fines and withdrawn bottom char are united and homogenized. 100 g of the homogenized mixture is placed in a Soxhlet extractor and extracted for 2 hours. The resulting aqueous solution contains 3,0 g potassium carbonate (86% catalyst recovery) Example 3
• aqueous solution obtained according to Example 2 0,5g potassium carbonate is dissolved as catalyst make-up.
• the petroleum coke impregnation with the potassium enriched aqueous solution is made via modelling a Lodige similar industrial mixing device.
• 100 g homogenized filter fines and bottom char from the first gasifier are filled into a mixing device (e.g. Kitchen Aid 5KSM150PS) for 5-15 minutes with the aqueous solution spraying.
• the impregnated solids then dried in vacuum at ambient temperature for 1 hours in a rotadest device (e.g. Heidolph or Buchi type with Teflon flasks to avoid alkali deposit on glass wall)
• a rotadest device e.g. Heidolph or Buchi type with Teflon flasks to avoid alkali deposit on glass wall

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