WO2018170543A1 - System for the production of hydrogen and graphitic carbon - Google Patents
System for the production of hydrogen and graphitic carbon Download PDFInfo
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- WO2018170543A1 WO2018170543A1 PCT/AU2018/050254 AU2018050254W WO2018170543A1 WO 2018170543 A1 WO2018170543 A1 WO 2018170543A1 AU 2018050254 W AU2018050254 W AU 2018050254W WO 2018170543 A1 WO2018170543 A1 WO 2018170543A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/049—Composition of the impurity the impurity being carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
- C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
Definitions
- the present invention provides a system for the production of hydrogen and graphitic carbon. More particularly, the system of the present invention is adapted to catalytically convert a hydrocarbon feedstock to hydrogen gas and graphitic carbon.
- TCMD Thermo-Catalytic Methane Decomposition
- catalysts that have been researched for this reaction have been complex supported catalysts that are too expensive to be left as an impurity in the graphite product.
- the catalysts are synthesised by loading nano-sized catalytic species (such as Ni, Fe, Pb, Co, etc) onto inert catalyst supports (such as Al 2 0 3 , Si0 2 , zeolites, etc).
- nano-sized catalytic species such as Ni, Fe, Pb, Co, etc
- inert catalyst supports such as Al 2 0 3 , Si0 2 , zeolites, etc.
- the inert catalyst supports assist in keeping the catalytic elements from
- a system for the conversion of a hydrocarbon feedstock to hydrogen gas and graphitic carbon comprising: one or more reactors adapted to contact at a temperature between 600 °C and 1 000 °C an iron oxide catalyst with the hydrocarbon feedstock to produce one or more mixed phase streams containing hydrogen gas and graphitic carbon,; and one or more solid/gas separators adapted to separate at least a portion of the one or more mixed phase streams of the one or more reactors into one or more gas streams comprising hydrogen gas and one or more solid streams comprising graphitic carbon.
- the or each reactor comprises a catalyst inlet, a feedstock inlet and a mixed phase outlet.
- the or each solid/gas separators comprise an inlet, a gas outlet and a solid outlet.
- the inlet of at least one of the one or more solid/gas separators is in communication with at least one reactor mixed phase outlet.
- reactors may be arranged in series, parallel or a combination of each.
- the contact of the hydrocarbon feedstock with the iron oxide catalyst in the one or more reactors may not completely convert the hydrocarbon feedstock and iron oxide catalyst to hydrogen gas and graphitic carbon.
- the mixed phase stream may include unreacted hydrocarbon feedstock and unreacted iron oxide catalyst. It is envisaged that by directing either the mixed phase stream, the separated gas stream or the solid stream to downstream reactors may further complete the conversion to hydrogen gas and graphic carbon.
- the gas stream and/or the solid stream may be fed into a downstream reactor to produce a further mixed phase stream.
- iron oxide catalyst may be added to one or more of the downstream reactors.
- hydrocarbon feedstock may be added to one or more of the downstream reactors.
- each reactor produces a mixed phase stream.
- the multiple mixed phase streams may be combined and at least a portion of the combined mixed phase stream may be fed into a single solid/gas separator, or at least a portion of each mixed phase stream may be fed into a dedicated solid/gas separator.
- At least a portion of a first mixed phase stream may be fed from a first reactor to a first solid/gas separator to produce a first gaseous stream and a first solid stream, wherein at least a portion of the first gaseous stream may be fed into a second reactor with additional iron oxide catalyst to produce a second mixed phase stream.
- at least a portion of the second mixed phase stream may be fed from the second reactor to a second solid/gas separator to produce a second gaseous stream and a second solid stream.
- At least a portion of the second gaseous stream may be fed into a third reactor with additional iron oxide catalyst to produce a third mixed phase stream.
- at least a portion of a third mixed phase stream may be fed from the third reactor to a third solid/gas separator to produce a third gaseous stream and a third solid stream.
- the term "residence time” will be understood to refer to the time in which the reactants are subjected to the selected temperature and pressure in a reactor. Residence time for example, does not include any time the reactants and/or products are in the reactors when the reactors are not operated at required temperature and pressure, nor does it include any time in which the reactants and/or products are outside of the reactor.
- Residence time for example, does not include any time the reactants and/or products are in the reactors when the reactors are not operated at required temperature and pressure, nor does it include any time in which the reactants and/or products are outside of the reactor.
- more than three reactors may be arranged in a similar fashion such that the residence time of the gaseous feedstock and subsequent gaseous streams is increased over the one or more reactors. This embodiment is particularly advantageous in fluidised bed reactors where the residence time of the gas needs to be increased and/or the reactant particles in the fluidised bed are difficult to fluidise.
- At least a portion of a first mixed phase stream may be fed from the first reactor to a first solid/gas separator to produce a first gaseous stream and a first solid stream, wherein the first solid stream may be fed into a second reactor with additional gaseous feedstock to produce a second mixed phase stream.
- at least a portion of the second mixed phase stream may be fed from the second reactor to a second solid/gas separator to produce a second gaseous stream and a second solid stream.
- At least a portion of the second solid stream may be fed into a third reactor together with additional gaseous feedstock to produce a third mixed phase stream.
- at least a portion of the third mixed phase stream may be fed from the third reactor to a third solid/gas separator to produce a third gaseous stream and a third solid stream.
- reactors may be arranged in a series such that the residence time of the catalyst and subsequent solid streams is increased over the one or more reactors.
- This embodiment is particularly advantageous in fluidised bed reactors where the residence time of the catalyst and subsequent solid streams needs to be increased and/or where the reactant particles in the fluidised bed fluidise readily. It is envisaged that the residence time may also be increased by decreasing the angle of repose of a rotating drum or continuous stirred tank reactor or by increasing the time reactants are maintained in the reactor.
- At least a portion of a first mixed phase stream may be fed from the first reactor to a first solid/gas separator to produce a first gaseous stream and a first solid stream, wherein the first gaseous stream and the first solid stream are fed into a second reactor to produce a second mixed phase stream.
- at least a portion of the second mixed phase stream may be fed from the second reactor to a second solid/gas separator to produce a second gaseous stream and a second solid stream.
- At least a portion of the second gaseous stream and the second solid stream may be fed into a third reactor to produce a third mixed phase stream.
- at least a portion of the third mixed phase stream may be fed from the third reactor to a third solid/gas separator to produce a third gaseous stream and a third solid stream.
- At least a portion of a first mixed phase stream may be fed from the first reactor to a next reactor without separation of the gas/solids.
- the inventors have discovered that the use of a solid/gas separator between two reactors in series in order to separate at least a portion of the mixed stream into its separate components and then injecting them into a subsequent reactor avoids the difficulty in injecting a mixed phase stream into a reactor.
- This is particularly useful where the reactants must bypass a distributer plate, such as in a fluidised bed reactor.
- This embodiment is particularly advantageous in fluidised bed reactors where the residence time of the catalyst and subsequent solid streams, and gas streams needs to be increased.
- each of the two or more reactors operates at the same pressure and temperature as each other.
- the system comprises two or more reactors
- at least one of the two or more reactors operates at a different pressure to the other reactors.
- the system comprises two or more reactors
- at least one of the two or more reactors operates at a different temperature to the other reactors.
- each downstream reactor in the series operates at a lower pressure than the preceding reactor, allowing the gaseous stream to travel to reactors of lower pressure and the solid stream to travel to reactors of higher pressure.
- any unreacted hydrocarbon feedstock passes to a downstream reactor of lower pressure.
- the lower pressure will drive the reaction at a higher conversion rate towards thermodynamic completion, without being limited to the lower thermodynamic limit at higher pressures.
- any unreacted catalyst may be fed to an upstream reactor of higher pressure to contact additional hydrocarbon feedstock.
- the higher pressure increases the hydrocarbon penetration through the graphitic layers, which increases the utility of the catalyst and accesses higher graphitic purity.
- reactors may be operated independently of each other reactor.
- a system for the conversion of a hydrocarbon feedstock to hydrogen gas and graphitic carbon comprising: two or more reactors adapted to contact at a temperature between 600 °C and 1 000 °C an iron oxide catalyst with the hydrocarbon feedstock to produce one or more mixed phase streams containing hydrogen gas and graphitic carbon, wherein the two or more reactors are arranged in parallel, such that one or more or the two or more reactors may be operated independently of each other reactor; and one or more solid/gas separators adapted to separate at least a portion of the one or more mixed phase streams of the two or more reactors into a gas stream comprising hydrogen gas and a solid stream comprising graphitic carbon,.
- each reactor comprises a catalyst inlet, a feedstock inlet and a mixed phase outlet.
- the or each solid/gas separators comprise an inlet, a gas outlet and a solid outlet.
- the inlet of at least one of the one or more solid/gas separators is in communication with the reactor mixed phase outlets.
- the independent operation of the reactors allows for the continuous processing of the hydrocarbon feedstock. More specifically, one reactor may be operated for a set period and then the operation of the reactor may be ceased, whilst the hydrocarbon feedstock may be diverted to one or more additional reactors. Once operation of a reactor has ceased, the contents may be allowed to settle for a period of time. In this manner, at least a portion of the solid particles suspended in the mixed phase may settle. The resulting mixed phase removed from the reactor then has a reduced solid content. Operation of the present invention in this manner may be particularly useful in applications where the production of hydrogen is favored over the graphite production or in applications where particular amounts or morphologies of graphite are required.
- the reactor can be de-pressurised and additional iron ore catalyst can be injected into the reactor.
- the reactor can then be repressurised and heated to recommence the thermocatalytic decomposition reaction.
- the or each of the two or more reactors are configured to produce the same form or a different form of graphitic carbon.
- the iron oxide catalyst is low grade iron oxide catalyst.
- the iron oxide catalyst is a high grade iron oxide catalyst.
- the iron oxide catalyst is a high grade iron oxide catalyst. More preferably, the high grade iron oxide catalyst is at least 95% pure, 96%, 97%, 98%, 99%, 99.5%, 99.99% or at least 99.995% pure.
- low grade will be understood to imply that the material is not synthesised. As would be understood by a person skilled in the art, synthesised materials are produced by the chemical reaction of precursor materials. Standard synthesis techniques for catalysts which are excluded from the present invention are, for example, impregnating nano- sized catalytic elements onto inert supports. Whilst the term “low grade” does include naturally occurring materials, it should not be understood to exclude materials that have gone through physical beneficiation such as crushing and screening or classification.
- the process of contacting the iron oxide catalyst with the hydrocarbon feedstock more specifically comprises the steps of: reducing at least a portion of the iron oxide to iron; decomposing the hydrocarbon gas to produce hydrogen gas and an iron carbide intermediate; precipitating graphitic carbon on the surface of the iron; and fragmentation of the catalyst.
- the inventors understand that the gaseous feedstock adsorbs and disassociates on the surface of the iron oxide catalyst and the resulting carbon diffusing on the surface of the catalyst. Once the outer layer is saturated with carbon, it forms metal carbide and then precipitates from the metal grain boundaries as graphitic carbon. Over time this causes inter-granular pressure that separates the metal carbide particles from the catalyst, which causes the metal structure to disintegrate by "dusting". As such, the process is able to have high catalytic activity without requiring catalyst recovery, significantly increasing the economics of the process.
- the inventors understand that the above process enables the preferential physical separation of the dusted graphitic carbon coated iron particles from the parent iron oxide particles or gangue impurity.
- the graphitic carbon coated iron particles have a small particle size, allowing suspension of the graphitic carbon coated iron particles in the mixture of the gases in the reactor thereby forming the mixed phase stream.
- At least one of the one or more reactors is operated at a pressure above atmospheric.
- at least one of the one or more reactors is operated at a pressure between 0 and 1 00 bar/g.
- the mixed phase outlet may be in communication with the gas inlet. This communication allows for the mixed phase stream to be recycled through the one or more reactors for further catalytic conversion.
- the system comprises a pre-reactor conditioner.
- the pre-reactor conditioner is adapted to condition the hydrocarbon feedstock prior to introduction to the one or more or each of the reactors. It is envisaged that the conditioning may comprise any one or more of heating, pressurising, plasma treatment, cooling, desulfurisation, drying, purification and expansion of the hydrocarbon feedstock.
- the plasma treatment produces free radicals.
- the free radicals include one of more of CH 4 + ; CH 3 + ; CH 2 + ; CH + ; C + ; C2 + ; C2H6 + ; C2H6 + ; C2H6 ; C2H5 + ; C2H 4 + ; C2H3 + ; C2H2 + ; C2H + ; C3H8 + ; C3H8 ; C3H6 + ; C3H6 ; O2 + ; O2 ; 0 + ; O ; H2 + ; H + ; H ; H 2 0 + ; CO2 + ; CO + ; and/or OH " .
- the hydrocarbon feedstock is heated to a temperature to within 50% below the reactor's operational temperature. . More preferably, the hydrocarbon feedstock is heated to a temperature to within 45% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 40% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 35% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 30% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 25% below the reactor's operational temperature.
- the hydrocarbon feedstock is heated to a temperature to within 20% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 15% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 10% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 5% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 4% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 3% below the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 2% below the reactor's operational temperature.
- the hydrocarbon feedstock is heated to a temperature to within 1 % below the reactor's operational temperature. It is understood by the inventors that elevating the hydrocarbon feedstock to a temperature near that of the operational temperature of the reactor provides reactor consistency in temperature, reduces the chance for side reactions, such as Fischer-Tropsch like reactions, to start, and lowers the thermal load required to heat the reactor(s)..
- the hydrocarbon feedstock is heated to a temperature to within 1 % above the reactor's operational temperature.
- the hydrocarbon feedstock is heated to a temperature to within 2% above the reactor's operational temperature. More preferably, the hydrocarbon feedstock is heated to a temperature to within 3% above the reactor's operational temperature.
- the hydrocarbon feedstock is heated to a temperature to within 4% above the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 5% above the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 6% above the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 7% above the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 8% above the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 9% above the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 10% above the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 15% above the reactor's operational temperature. Still preferably, the hydrocarbon feedstock is heated to a temperature to within 20% above the reactor's operational temperature.
- the inventors understand that the plasma conditioning of the hydrocarbon feedstock prior to introduction into the one or more reactors will produce predominantly one radical form that will favour one morphology of graphite, preferably CNO, CNT, graphene, or CMS form.
- the system comprises a catalyst conditioner adapted to condition the catalyst.
- the catalyst conditioner may include one or more of beneficiation, washing, drying, crushing, milling, sieving, purification, heating, and chemical treatment of the catalyst.
- beneficiation is a process of increasing the percentage of iron in the catalyst.
- Methods of beneficiation may include density media separation, magnetic separation, hydroclassification.
- Beneficiation not only increases the percentage of iron in the catalyst, it also leads to reduced impurity in the resultant graphitic product(s). It is understood by the applicant that beneficiation improves the efficiency of the process as there is less energy wasted on heating elements in the catalyst that do not take part in the catalytic reaction.
- washing the catalyst will remove the smallest fractions of the catalyst material, resulting in a narrower particle size distribution.
- the narrow particle size distribution will assist in maintaining a fluidised state.
- washing the catalyst will wash off any water soluble impurities.
- drying the catalyst will remove any excess moisture from the catalyst to thereby improve the efficiency of the process. Any water is vaporised from the catalyst before it is inserted into the reactor, which decreases the thermal energy required to bring the catalyst up to the temperature required for the reactor.
- crushing/milling/sieving steps may be used to obtain preferred average particle size distribution of the catalyst (assist with fluidisation). Narrower particle size distribution assists in fluidising the catalytic particles.
- the system further comprises a post- reactor conditioner adapted to remove heat from the mixed phase stream.
- the system further comprises a post- reactor conditioner adapted to condition the mixed phase stream.
- the conditioning may comprise any one or more of pressurising, cooling, drying, and expansion of the mixed phase stream.
- the gas stream produced at the gas outlet of the one or more solid/gas separators comprise one or more of H 2 , C0 2 , CO, H 2 O and CH 4 , as well as impurities.
- H 2 and CH 4 form the majority of the gas stream with CO 2 , H 2 O and CO being present in trace amounts.
- the gas outlet of the one or more solid/gas separators is in communication with a pre-gas separation conditioner adapted to condition the gas stream. It is envisaged that the conditioning may comprise any one or more of pressurising, cooling, drying, and expansion of the gas stream.
- At least a portion of the gas stream is recycled to other parts of the system.
- at least a portion of the gas stream is used as a fuel source for heating the pre-reactor conditioner and/or as a fuel source for a reactor heater for heating the one or more reactors.
- the reactor heater may electrical and may be heated using electrical means or may comprise a burner and may be heated by burning a combustible gas to produce combustion gases.
- Suitable combustible gases include methane, hydrogen or a portion of the gas stream from the one or more reactors or solid/gas separators.
- At least a portion of the gas stream may be fed into an electricity generator to be used as a fuel source for producing electricity, which optionally may be used to at least partially provide electricity to the system, such as, the reactor heater.
- at least a portion of the gas stream is fed into the pre-reactor conditioner for supply to the one or more reactors as the hydrocarbon feedstock.
- the reactor heater directly heats the one or more reactors.
- the reactor heater directly heats the one or more reactors by injecting the combustion gases into the one or more reactors.
- the combustion gases can be used as, or to supplement the hydrocarbon feedstock.
- the reactor heater indirectly heats the one or more reactors.
- the reactor heater indirectly heats the one or more reactors by injecting the combustion gases into one or more heating jackets that at least partially surrounds each of the one or more reactors.
- the gas outlet of pre-gas separation conditioner is in communication with a gas separator adapted to separate at least a portion of the gas stream into one or more purified gaseous product streams.
- the gas separator separates at least a portion of the gas stream into one or more purified gaseous product streams each exiting the gas separator at one or more purified gaseous product outlets. More preferably, the gas separator separates at least a portion of the gas stream into one or more purified gaseous product streams selected from the group comprising a purified H 2 stream, a purified CO stream, a purified C0 2 stream, and a purified CH 4 stream or the gas separator separates at least a portion of the gas stream into a purified H 2 stream and a mixed gaseous stream of one or more of CO, C0 2 , and CH 4 .
- At least a portion of the mixed gaseous stream is used as a fuel source for heating the pre-reactor conditioner and/or as a fuel source for the reactor heater for heating the one or more reactors.
- at least a portion of the mixed gaseous stream may be fed into a electricity generator to be used as a fuel source for producing electricity.
- at least a portion of the mixed gaseous stream may be fed into the pre- reactor conditioner for supply to the one or more reactors as the hydrocarbon feedstock.
- one or more of the one or more purified gaseous product outlets are in communication with a post-gas separation conditioner adapted to condition one or more of the purified H 2 stream, the purified CO stream, the purified C0 2 stream, and/or the purified CH 4 stream. It is envisaged that the
- conditioning may comprise any one or more of pressurising or cooling of the purified gaseous product streams.
- the purified H 2 stream is passed to one or more gas storage tanks, piped to an end user, used as an energy source for one or each of the one or more of or all of the conditioners or the reactor heater, or optionally fed into the electricity generator for electricity generation.
- the electricity generation may be achieved using one or more of a fuel cell or direct combustion to drive a gas turbine or a gas engine.
- one or more of the purified gaseous product streams are recycled into other parts of the system.
- the purified gaseous stream is mixed with the hydrocarbon feedstock in the pre-reactor conditioner for use in the one or more reactors.
- the purified gaseous stream is used as a fuel source for heating the one or more of or all of the conditioners or is used as a fuel source for the reactor heater to heat the one or more reactors.
- the mixed gaseous stream is mixed with the hydrocarbon feedstock in the pre-reactor conditioner for use in the one or more reactors.
- the mixed stream is used as a fuel source for heating the one or more of or all of the conditioners or is used as a fuel source for the reactor heater to heat the one or more reactors.
- the solid stream comprises carbon in a variety of graphitic forms.
- the solid outlet of the one or more solid/gas separators are in communication with a solids conditioner adapted to condition the solid stream.
- the solids conditioner conditions at least a portion of the solid stream into a conditioned solid product stream. Conditioning may include packaging (pellitising, compressing), functionalising, and/or purifying.
- the first reactor is at a pressure between 15 and 25 bar(g); and the second reactor is at a pressure between 0 and 1 bar(g).
- the first reactor is at a pressure between 15 and 25 bar(g); the second reactor is at a pressure between 5 and 10 bar(g); and the third the first reactor is at a pressure between 0 and 1 bar(g).
- the first reactor is at a pressure between 20 and 30 bar(g); the second reactor is at a pressure between 5 and 15 bar(g); the third reactor is at a pressure between 4 and 6 bar(g); and the fourth reactor is at a pressure between 0 and 1 bar(g).
- the first reactor is at a pressure between 25 and 35 bar(g); the second reactor is at a pressure between 10 and 20 bar(g); the third reactor is at a pressure between 5 and 1 0 bar(g); the fourth reactor is at a pressure between 4 and 6 bar(g); and the fifth reactor is at a pressure between 0 and 1 bar(g).
- the first reactor is at a pressure between 0 and 1 bar(g); and the second reactor is at a pressure between 15 and 25 bar(g).
- the first reactor is at a pressure between 0 and 1 bar(g); the second reactor is at a pressure between 5 and 10 bar(g); and the third the first reactor is at a pressure between 1 5 and 25 bar(g).
- the first reactor is at a pressure between 0 and 1 bar(g); the second reactor is at a pressure between 4 and 6 bar(g); the third reactor is at a pressure between 5 and 1 5 bar(g); and the fourth reactor is at a pressure between 20 and 30 bar(g).
- five pressurised reactors are used in series. Where five pressurised reactors are used in series, the first reactor is at a pressure between 0 and 1 bar(g); the second reactor is at a pressure between 4 and 6 bar(g); the third reactor is at a pressure between 5 and 1 0 bar(g); the fourth reactor is at a pressure between 10 and 20 bar(g); and the fifth reactor is at a pressure between 25 and 35 bar(g).
- five pressurised reactors are used in series. Where five pressurised reactors are used in series, the pressure in each reactor is between 0 and 10 bar(g).
- two pressurised reactors are used in series. Where two pressurised reactors are used in series, the pressure in each reactor is between 0 and 10 bar(g).
- each reactor is adapted to selectively synthesise graphitic material with a desired morphology.
- each of the two or more reactors may be in series with one or more secondary reactors.
- each of the two or more reactors operate at the same pressure and temperature.
- each of the two or more reactors operate at a different pressure and the same temperature.
- each of the two or more reactors operate at a different temperature and the same pressure.
- each of the two or more reactors operate at a different pressure and a different temperature.
- graphitic material can exist in many forms, such as: graphitic fibres, which are fibrous carbon structures typically ranging from 100 nm to 100 microns in length, carbon nano-tubes (CNTs), which are cylindrical nano- structures comprising single or multiple graphitic sheets aligned concentrically or perpendicular to a central axis also fall within the scope of graphitic fibres; carbon nano-onions (CNOs), which are structures that consist of multiple spherical graphitic sheets that are concentrically layered from a central core, which is typically a catalyst particle or a void.
- CNOs carbon nano-onions
- each of the one or more reactors may be adapted to selectively synthesise graphitic material with any one of carbon micro-spheres (CMSs), graphitic fibres, carbon nano-tubes (CNTs), carbon nano-onions (CNOs), or graphene
- CNOs are selectively synthesised where the reactor is adapted to contact at a temperature between 700 °C and 900 °C and a pressure between 0 bar(g) to 8 bar(g) the iron oxide catalyst with the hydrocarbon feedstock.
- the temperature is 800 °C to 900 °C and the pressure is 2 bar(g) to 4 bar(g). In an alternative form of the present invention, the temperature is 800 °C and the pressure is 2 bar(g). In an alternative form of the present invention, the temperature is 850 °C and the pressure is 2 bar(g). In an alternative form of the present invention, the temperature is 900 °C and the pressure is 2 bar(g). In an alternative form of the present invention, the temperature is 750 °C and the pressure is 8 bar(g). In an alternative form of the present invention, the temperature is 800 °C and the pressure is 8 bar(g).
- graphitic fibres are selectively synthesised where the reactor is adapted to contact at a temperature between 700 °C to 900 °C and a pressure between 0 bar(g) to 8 bar(g) the iron oxide catalyst with the hydrocarbon feedstock and the iron oxide catalyst is goethite iron oxide.
- the temperature is 750 °C to 850 °C and the pressure is 0 bar(g) to 4 bar(g). More preferably, the temperature is 800 °C and the pressure is 0 bar(g).
- the iron oxide catalyst is a purified or naturally occurring iron ore.
- the iron oxide catalyst is an iron ore.
- the iron ore is goethite ore.
- the iron ore is low grade iron ore.
- CMSs are selectively synthesised where the reactor is adapted to contact at a temperature between 800 °C to 900 °C and a pressure between 4 bar(g) to 9 bar(g) the iron oxide catalyst with the hydrocarbon feedstock.
- the temperature is 850 °C to 900 °C and the pressure is 6 bar(g) to 8 bar(g).
- the temperature is 900 °C and the pressure is 8 bar(g).
- the temperature is 850 °C and the pressure is 6 bar(g). More preferably, the temperature is 900 °C and the pressure is 6 bar(g).
- the temperature is 850 °C and the pressure is 7 bar(g).
- the temperature is 900 °C and the pressure is 7 bar(g).
- the temperature is 850 °C and the pressure is 8 bar(g).
- the present invention the
- the temperature is 900 °C and the pressure is 4 bar(g). In a further alternative form of the present invention, the temperature is 900 °C and the pressure is 8 bar(g).
- graphene is selectively synthesised where the reactor is adapted to contact at a temperature between 600 °C to 750 °C and pressure is 0 bar(g) to 1 bar(g) the iron oxide catalyst with the hydrocarbon feedstock.
- the temperature is 600 °C to 700 °C and the pressure is 0 bar(g). More preferably, the temperature is 650 °C and the pressure is 0 bar(g).
- the one or more reactors may be selected from the group comprising static bed, continuous stirred tank reactor (CSTR), moving bed, agitated bed, fluidised bed, assisted fluidised bed, rotary bed, vibrating bed, plug flow or continuous flow stirred- tank reactors.
- CSTR continuous stirred tank reactor
- the one or more reactors are static bed, moving bed, CSTR or fluidised bed reactors. More preferably, when the one or more reactors are in series, the one or more reactors are fluidised bed reactors, rotary bed reactors, or CSTRs.
- the catalyst is disposed on a
- the catalyst is suspended in a fluidised bed reactor and the hydrocarbon feedstock is flowed through the fluidised bed.
- the hydrocarbon feedstock should preferably be at a higher pressure than the pressure of the one or more reactors to enable mass transport of the hydrocarbon feedstock into the one or more reactors.
- the pressure of the hydrocarbon feedstock entering the one or more reactors is less than about 100 bar(g).
- the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 90 bar(g).
- the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 80 bar(g).
- the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 70 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 60 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 50 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 40 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 30 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 20 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 15 bar(g).
- the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 14 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 13 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 12 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 1 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 10 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 9 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 8 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 7 bar(g).
- the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 6 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 5 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 4 bar(g).
- the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 3 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 2 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is less than 1 bar(g).
- the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 1 00 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 90 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 80 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 70 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 60 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 50 to 1 bar(g).
- the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 40 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 30 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 20 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 1 5 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 10 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 9 to 1 bar(g).
- the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 8 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 7 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 6 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 5 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 4 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 3 to 1 bar(g). Alternatively, the pressure of the hydrocarbon feedstock entering the one or more reactors is between about 2 to 1 bar(g).
- the temperature of the hydrocarbon feedstock entering the one or more reactors is between about 600-1000 °C
- the temperature of the hydrocarbon feedstock entering the one or more reactors is between about 650-1000 °C. Alternatively, the temperature of the hydrocarbon feedstock entering the one or more reactors is between about 700-1 000 °C. Alternatively, the temperature of the hydrocarbon feedstock entering the one or more reactors is between about 750-1000 °C. Alternatively, the temperature of the hydrocarbon feedstock entering the one or more reactors is between about 800-1 000°C. Alternatively, the temperature of the hydrocarbon feedstock entering the one or more reactors is between about 850-1000 °C. Alternatively, the temperature of the
- hydrocarbon feedstock entering the one or more reactors is between about 900-1 000 or 950-1000 °C.
- the hydrocarbon feedstock is selected from any one of methane, LPG (liquid petroleum gas) biogas or natural gas/LNG (liquid natural gas).
- the hydrocarbon feedstock is selected from a gaseous hydrocarbon, such as methane, ethane, propane, pentane or any mixture thereof. It is envisaged that a biomass feedstock may be processed to produce a biogas feedstock to be used as the hydrocarbon feedstock.
- the iron oxide catalyst may be iron ore.
- the iron oxide is used without any form of beneficiation. It is envisaged that iron ore may be removed directly from the quarry or mining site and used in the system of the present invention.
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 20 mm.
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 1 5 mm.
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 10 mm.
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 5 mm.
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 1 mm. Alternatively, the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 0.5 mm. Alternatively, the mean particle size of the iron oxide catalyst entering the one or more reactors of less than 0.1 mm. Alternatively, the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 900 ⁇ . Alternatively, the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 800 ⁇ . Alternatively, the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 700 ⁇ . Alternatively, the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 600 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 500 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 400 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 300 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 200 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 100 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 90 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 80 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 70 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 60 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 50 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 40 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 30 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 20 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 10 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is less than 1 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 1 0 ⁇ and 1000 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 20 ⁇ and 800 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 30 ⁇ and 600 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 40 ⁇ and 500 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 50 ⁇ and 400 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 60 ⁇ and 300 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 80 ⁇ and 250 ⁇ . Alternatively, the mean particle size of the iron oxide catalyst entering the one or more reactors is between 80 ⁇ and 225 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 80 ⁇ and 220 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 85 ⁇ and 215 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 90 ⁇ and 210 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 95 ⁇ and 205 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is between 100 ⁇ and 200 ⁇ .
- the mean particle size of the iron oxide catalyst entering the one or more reactors is about 90 ⁇ - ⁇ , 95, 100, 105, 1 10, 1 1 5, 1 20, 130, 140, 145, 155, 160, 165, 1 70, 175, 1 80, 195, 200, 205 or 21 0 ⁇ .
- mean particle size will be understood as the average particle size of the particulate material when obtained by wet or dry sieving or alternative means through a mesh of predetermined size. As would be understood by a person skilled in the art, the mean particle size can be determined by sieving the particulate material through various sized screens to obtain the desired particle size using wet or dry sieving techniques.
- Such screening methods are, for example, set out in several international standards for obtaining various characteristic particle sizes, ISO 9276 (representation of results of particle size analysis), which provide means for calculating and measuring mean particle sizes; ISO 565 and ISO 3310-1 provides details of mesh/screen sizing; and ISO 1441 .1 1 provides for sampling and testing aggregates for particle size distribution .
- Alternative methods for obtaining fractions of known mean particle size are known to those of skill in the art and include using cyclonic means (water, air, pneumatic), density separation/floatation.
- At least 1 0 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 15 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 20 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 25 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 30 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 35 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- At least 40 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 45 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 50 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 55 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 60 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 65 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- At least 70 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 75 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 80 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- at least 85 % of the hydrocarbon feedstock is catalytically converted in the one or more reactors.
- hydrocarbon feedstock is catalytically converted in the one or more reactors.
- hydrocarbon feedstock is catalytically converted in the one or more reactors.
- hydrocarbon feedstock is catalytically converted in the one or more reactors.
- hydrocarbon feedstock is catalytically converted in the one or more reactors.
- the purity of the graphitic carbon in the solid stream is at least 50%.
- the pu rity of the graphitic carbon in the solid stream is at least 55%.
- the purity of the graphitic carbon in the solid stream is at least 60%.
- the purity of the graphitic carbon in the solid stream is at least 65%.
- the purity of the graphitic carbon in the solid stream is at least 70%.
- the purity of the graphitic carbon in the solid stream is at least 75%.
- the purity of the graphitic carbon in the solid stream is at least 80%.
- the purity of the graphitic carbon in the solid stream is at least 85%.
- the purity of the graphitic carbon in the solid stream is at least 90%. Alternatively, the purity of the graphitic carbon in the solid stream is at least 95%. Alternatively, the purity of the graphitic carbon in the solid stream is at least 96%. Alternatively, the purity of the graphitic carbon in the solid stream is at least 97%. Alternatively, the purity of the graphitic carbon in the solid stream is at least 98%. Alternatively, the purity of the graphitic carbon in the solid stream is at least 99%.
- the iron oxide catalyst is unsupported.
- unsupported catalysts are catalysts which are not attached or bonded to a catalyst support, which is the material to which the catalyst is affixed.
- Catalyst supports are typically a solid material with a high surface area and are used to increase the available surface area of a catalyst to maximise the yield of a desired material. Extremely small catalyst particles with very high surface area tend to agglomerate when unsupported. Catalyst supports effectively allow such catalyst particles to be used without
- Catalysts may also be supported in their natural state, that is, the surface of the iron oxide catalyst is coated/bonded with the active species and is supported by the core which may be different material to the iron oxide catalyst coating or the same material as the iron oxide catalyst coating.
- the iron oxide catalyst is a supported catalyst.
- the supported catalyst comprises the catalyst and a support.
- the support is of a different chemical composition to the iron oxide catalyst.
- the support is of the same chemical composition as the iron oxide catalyst.
- the solid/gas separator is selected from the group comprising, a baghouse filter, a sintered metal filter and electrostatic precipitator.
- the one or more reactors are selected from the group of static, moving or fluidized bed reactors.
- the gas conditioner is preferably selected from the group comprising a heat exchanger and a burner. Where the gas stream requires cooling, the gas conditioner is preferably a heat exchanger. Where the gas stream requires purification, the gas conditioner is preferably selected from the group comprising a water scrubber and a pressure swing adsorption concentrator. Where the gas stream requires pressurising, the gas conditioner is preferably a compressor. Where the gas stream requires despressuring, the gas conditioner is preferably an expander.
- the selections of the various solids conditioners used in the present invention will depended on the particular conditioning requirements. Where the solid stream requires heating, the solids conditioner is preferably selected from the group comprising a heat exchanger and a burner. Where the solid stream requires cooling, the solids conditioner is preferably a heat exchanger.
- the gas separator is preferably selected from separators that utilise pressure swing adsorption or membrane filtrations to separate one or more gas species.
- Figure 1 is a schematic representation of the system in accordance with a first aspect of the present invention.
- Figure 2 is a schematic representation of the system of Figure 1 in which two or more reactors are arranged in series.
- Figure 3 is a schematic representation of the system of Figure 1 in which two or more reactors are arranged in series.
- Figure 4 is a schematic representation of the system of Figure 1 in which two or more reactors are arranged in series.
- Figure 5 is a schematic representation of Figure 1 in which two or more reactors are arranged in series.
- Figure 6 is a schematic representation of the system in accordance with the second aspect of the present invention.
- the invention described herein may include one or more range of values (e.g. size, concentration etc).
- a range of values will be understood to include all values within the range, including the values defining the range, and values adjacent to the range which lead to the same or substantially the same outcome as the values immediately adjacent to that value which defines the boundary to the range.
- the invention in a general form, relates to a system for producing hydrogen and graphitic carbon from a hydrocarbon feedstock.
- the present invention provides a process for catalytically converting a hydrocarbon feedstock to hydrogen and graphitic carbon using an iron oxide catalyst.
- FIG. 1 a system 10 for the conversion of a hydrocarbon feedstock 1 2 to hydrogen gas 14 and graphitic carbon 16 is shown.
- the hydrocarbon feedstock 1 2 is introduced into a pre-reactor conditioner 1 8 adapted to condition the hydrocarbon feedstock 12 to produce a conditioned hydrocarbon feedstock 20.
- the pre-reactor conditioner 18 is adapted to perform one or more of heating, pressurising, plasma treatment, cooling, desulfurisation, drying, purification and expansion of the hydrocarbon feedstock 12 producing a conditioned hydrocarbon feedstock 20.
- the pre-reactor conditioner is in communication with one or more reactors 26.
- the one or more reactors 26 are adapted to contact at a temperature between 600 °C and 1 000 °C a conditioned iron oxide catalyst 29 with the conditioned hydrocarbon feedstock 20 to produce a mixed phase stream 30 containing hydrogen gas, graphitic carbon, and unreacted hydrocarbon.
- Each reactor 26 comprises a catalyst inlet 32, a gas inlet 34 and a mixed phase outlet 36.
- the pre-reactor conditioner will typically increase the temperature and pressure of the hydrocarbon feedstock prior to injection into the one or more reactors 26.
- the catalyst conditioner 37 is adapted to condition the iron oxide catalyst 28 prior to entry to the one or more reactors 26 to produce a conditioned iron oxide catalyst 29. It is envisaged the conditioning may include one or more of beneficiation, washing, drying, crushing, milling, sieving, purification, and heating of the catalyst.
- the mixed phase outlet 36 is in communication with a post-reactor conditioner 42.
- the post-reactor conditioner 42 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the post-reactor conditioner 42 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30, preferably post-reactor conditioner 42 cools and/or dewaters mixed phase stream 30.
- the post-reactor conditioner 42 is in communication with one or more solid/gas separators 46.
- One or more solid/gas separator 46 comprise an inlet 52, a gas outlet 54, a second gas outlet 63, and a solid outlet 56.
- the one or more solid/gas separators 46 are adapted to separate at least a portion of the conditioned mixed phase stream 44 into a gas stream 48 comprising hydrogen gas and a solid stream 50 comprising graphitic carbon.
- the second gas outlet 63 may optionally be in communication with one or more of the pre-reactor conditioner 18, reactor heater 65, and/or electricity generator 69 such that at least a portion of gas stream 48 may be recycled. Electricity generator 69 may optionally be used to provide electricity 80 to reactor heater 65 or to other parts of the system, as required.
- the solid outlet 56 is in communication with a solids conditioner 58.
- the solids conditioner 58 is adapted to condition the solid stream 50 to produce a graphitic carbon stream 1 6.
- the solids conditioner 58 may perform one or more of the conditioning functions of packaging (pellitising, compressing), functionalising, and/or purifying the solid stream 50.
- the gas outlet 54 is in communication with a pre-gas separation conditioner 60, which comprises a conditioned gas outlet 61 , such that at least a portion of the gas stream 48 is conditioned to produce a conditioned gas stream 62.
- the pre-gas separation conditioner 60 may do any one or more of pressurising, cooling,
- pre- gas separation conditioner 60 pressurises and/or scrubs gas stream 48.
- the pre-gas separation conditioner 60 is in fluid connection with a gas separator 64 which is adapted to separate and purify at least a portion of the
- At least one of the purified gaseous product streams 66 comprises hydrogen gas.
- the gas separator 64 is in communication with a post-gas separation conditioner 68 adapted to condition the purified gaseous product streams 66 to provide hydrogen gas 14 in purified form and one or more conditioned gaseous streams 70 that may comprise one or more of CH 4 , C0 2 , CO or the mixed gaseous stream.
- Purified hydrogen stream 14 may be connected to one or more gas storage tanks, piped to an end user, or optionally used as an energy means for one or each of the one or more of or all of the conditioners 18, 42, 58, 60, 68 or reactor heater 65, or optionally fed into electricity generator 69 for electricity generation.
- Reactor heater 65 may directly or indirectly heat reactor 26.
- direct heating will involve heating the reactor 26 by injection of combustion products from reactor heater 65 into reactor 26 in addition to the hydrocarbon feedstock 20.
- Indirect heating heats by indirect heat transfer of the heat from combustion into reactor 26 or by heating the hydrocarbon gas prior to or on injection into reactor 26.
- indirect heating can include the use of heating jackets, heating coils, or heat exchangers and the like. The skilled person is aware of the different means of indirect heating that are known in the art and would be able to choose the appropriate means.
- conditioned gaseous product stream 70 comprises a mixed gaseous stream of one or more of CO, C0 2 , and CH 4
- the mixed gaseous stream may also be optionally connected to pre-reactor conditioner 18 for supply to the one or more reactors as the hydrocarbon feedstock or optionally fed into electricity generator 69 for electricity generation.
- Electricity generator 69 may optionally be used to provide electricity 80 to reactor heater 65 or to other parts of the system, as required.
- FIG. 2 there is shown a system 1 00 for the conversion of a hydrocarbon feedstock 12 to hydrogen gas 14 and graphitic carbon 16.
- the hydrocarbon feedstock 12 is introduced into a pre-reactor conditioner 18 adapted to condition the hydrocarbon feedstock 18 to produce a conditioned hydrocarbon feedstock 20.
- the pre-reactor conditioner 18 is adapted to perform one or more of heating, pressurising, plasma treatment, cooling, desulfurisation, drying, purification and expansion of the hydrocarbon feedstock 12 producing a conditioned hydrocarbon feedstock 20.
- the pre-reactor conditioner is in communication with a first reactor 124.
- First reactor 1 24 is adapted to contact at a temperature between 600 °C and 1 000 °C a conditioned iron oxide catalyst 29 with the conditioned hydrocarbon feedstock 20 to produce a mixed phase stream 30 containing hydrogen gas, graphitic carbon and unreacted hydrocarbon.
- the first reactor 124 comprises a catalyst inlet 32, a gas inlet 34, a mixed phase outlet 36.
- the mixed phase outlet 36 is in communication with a first post-reactor conditioner 142.
- the post-reactor conditioner 142 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the first post-reactor conditioner 142 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30, preferably the first post-reactor conditioner 142 cools and/or dewaters the mixed phase stream 30.
- the first post-reactor conditioner 142 is in communication with a first solid/gas separator 146.
- the first solid/gas separator 146 comprises an inlet 52, a gas outlet 54 and a solid outlet 56.
- the first solid/gas separator 146 is adapted to separate at least a portion of the conditioned mixed phase stream 44 into a gas stream 48 comprising hydrogen gas and a solid stream 50 comprising graphitic carbon.
- the solid outlet 56 is in communication with a solids conditioner 58.
- the solids conditioner 58 is adapted to condition the solid stream 50 to produce a graphitic carbon stream 1 6.
- the solids conditioner may perform one or more of the conditioning functions of packaging (pelletising, compressing), functionalising, and/or purifying the solid stream 50.
- the gas outlet 54 is in communication with a second pre-reactor conditioner 150 to condition gas stream 48.
- the second pre-reactor conditioner 150 is in
- Second conditioned hydrocarbon feedstock 1 52 comprises a mixture of hydrocarbons, hydrogen, and trace amounts of carbon monoxide and carbon dioxide.
- the second reactor 126 is adapted to contact at a temperature between 600 °C and 1000 °C a conditioned iron oxide catalyst 29 with the second conditioned hydrocarbon feedstock 1 52 to produce a mixed phase stream 30 containing hydrogen gas, graphitic carbon, and unreacted hydrocarbon.
- the second reactor 126 comprises a catalyst inlet 32, a second conditioned hydrocarbon feedstock inlet 134 and a mixed phase outlet 36.
- the second pre-reactor conditioner 150 will typically increase the temperature and pressure of the second conditioned hydrocarbon feedstock to that of the second reactor 126.
- a catalyst conditioner 37 In communication with the catalyst inlet 32 in the second reactor 1 26 is a catalyst conditioner 37.
- the catalyst conditioner 37 is adapted to condition the iron oxide catalyst 28 prior to entry to the second reactor 126 to produce a conditioned iron oxide catalyst 29. It is envisaged the conditioning may include one or more of beneficiation, washing, drying, crushing, milling, sieving, purification, and heating of the catalyst.
- the mixed phase outlet 36 is in communication with a second post-reactor conditioner 144.
- the second post-reactor conditioner 144 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the second post-reactor conditioner 144 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30.
- the post-reactor conditioner 144 is in communication with a second solid/gas separator 148.
- the solid/gas separator 148 comprise an inlet 52, a gas outlet 54, a second gas outlet 63, and a solid outlet 56.
- the second solid/gas separator 148 is adapted to separate at least a portion of the conditioned mixed phase stream 44 into a gas stream 48 comprising hydrogen gas and a solid stream 50 comprising graphitic carbon. It is envisaged that the second gas outlet 63 may optionally be in
- Reactor heater 65 may directly or indirectly heat first reactor 1 24 and/or second reactor 126.
- Electricity generator 69 may optionally be used to provide electricity 80 to reactor heater 65 or to other parts of the system, as required.
- the solid outlets 56 of the first and second solid/gas conditioners are in communication with a solids conditioner 58.
- the solids conditioner 58 is adapted to condition the solid stream 50 to produce a graphitic carbon stream 16.
- the solids conditioner may perform one or more of the conditioning functions of packaging
- the gas outlet 54 is in communication with a pre-gas separation conditioner 60, which comprise a conditioned gas outlet 61 , to produce a conditioned gas stream 62.
- the pre-gas separation conditioner 60 may do any one or more of pressurising, cooling, scrubbing/purification to remove impurities of the gas outlet product 48.
- the pre-gas separation conditioner 60 is in fluid connection with a gas separator 64 which is adapted to separate and purify at least a portion of the
- At least one of the purified gaseous product streams 66 comprises hydrogen gas.
- the gas separator 64 is in communication with a post-gas separation conditioner 68 adapted to condition the purified gaseous product streams 66 to provide hydrogen gas 14 in purified form and one or more conditioned gaseous streams 70 that may comprise one or more of CH 4 , C0 2 , CO or the mixed gaseous stream.
- Purified hydrogen stream 14 may be connected to one or more gas storage tanks, piped to an end user, or optionally used as an energy source for one or each of the one or more of or all of the conditioners 18, 142, 144, 1 50, 58, 60, 68 or reactor heater 65, or optionally fed into electricity generator 69 for electricity generation.
- conditioned gaseous product stream 70 comprises a mixed gaseous stream of one or more of CO, C0 2 , and CH 4
- the mixed gaseous stream may also optionally be connected to pre-reactor conditioner 18 for supply to the one or more reactors as the hydrocarbon feedstock, fed into electricity generator 69 for electricity generation, or optionally fed into reactor heater 65 for use as a combustible fuel.
- Reactor heater 65 may directly or indirectly heat first reactor 124 and/or second reactor 126.
- Electricity generator 69 may optionally be used to provide electricity 80 to reactor heater 65 or to other parts of the system, as required.
- FIG. 3 there is shown a system 200 for the conversion of a hydrocarbon feedstock 12 to hydrogen gas 14 and graphitic carbon 16.
- the hydrocarbon feedstock 12 is introduced into a pre-reactor conditioner 18 adapted to condition the hydrocarbon feedstock 18 to produce a conditioned hydrocarbon feedstock 20.
- the pre-reactor conditioner 18 is adapted to perform one or more of heating, pressurising, plasma treatment, cooling, desulfurisation, drying, purification and expansion of the hydrocarbon feedstock 12 producing a conditioned hydrocarbon feedstock 20.
- the pre-reactor conditioner is in communication with a first reactor 124.
- First reactor 1 24 is adapted to contact at a temperature between 600 °C and 1 000 °C a conditioned iron oxide catalyst 29 with the conditioned hydrocarbon feedstock 20 to produce a mixed phase stream 30 containing hydrogen gas, graphitic carbon and unreacted hydrocarbon.
- the first reactor 124 comprises a catalyst inlet 32, a gas inlet 34, a mixed phase outlet 36.
- the mixed phase outlet 36 is in communication with a first post-reactor conditioner 142.
- the first post-reactor conditioner 142 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the first post-reactor conditioner 142 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30.
- the first post-reactor conditioner 142 is in communication with a first solid/gas separator 146.
- the first solid/gas separator 146 comprises an inlet 52, a gas outlet 54 and a solid outlet 56.
- the first solid/gas separator 146 is adapted to separate at least a portion of the conditioned mixed phase stream 44 into a gas stream 48 comprising hydrogen gas and a solid stream 50 comprising graphitic carbon.
- the solid outlet 56 is in communication with a second pre-reactor conditioner 150 to condition solid stream 50.
- the second pre-reactor conditioner 150 is in communication with the second reactor 126 to provide a second conditioned solid stream 250.
- the second reactor 126 is adapted to contact at a temperature between 600 °C and 1000 °C a conditioned solid stream 250 with the conditioned hydrocarbon feedstock 20 to produce a mixed phase stream 30 containing hydrogen gas, graphitic carbon, and unreacted hydrocarbon.
- the second reactor 126 comprises a solid injection inlet 252, a gas inlet 34 and a mixed phase outlet 36.
- the pre-reactor conditioner will typically increase the temperature and pressure of the conditioned solid stream to that of the second reactor 126.
- the mixed phase outlet 36 of the second reactor 126 is in communication with a second post-reactor conditioner 144.
- the second post-reactor conditioner 144 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the second post-reactor conditioner 144 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30.
- the post-reactor conditioner 144 is in communication with a second solid/gas separator 148.
- the solid/gas separator 148 comprise an inlet 52, a gas outlet 54, a second gas outlet 63, and a solid outlet 56.
- the second solid/gas separator 148 is adapted to separate at least a portion of the conditioned mixed phase stream 44 into a gas stream 48 comprising hydrogen gas and a solid stream 50 comprising graphitic carbon.
- the second gas outlet 63 may be in communication with one or more of the pre-reactor conditioner 18 and/or reactor heater 65 such that at least a portion of gas stream 48 may be recycled.
- Reactor heater 65 may directly or indirectly heat first reactor 124 and/or second reactor 126.
- the solid outlet 56 of second solid/gas conditioner is in communication with a solids conditioner 58.
- the solids conditioner 58 is adapted to condition the solid stream 50 to produce a graphitic carbon stream 16.
- the solids conditioner may perform one or more of the conditioning functions of packaging (pellitising, compressing),
- the gas outlets 54 of the first and second solid/gas conditioners are in communication with a pre-gas separation conditioner 60, which comprises a conditioned gas outlet 61 , to produce a conditioned gas stream 62.
- the pre-gas separation conditioner 60 may do any one or more of pressurising, cooling, scrubbing/purification to remove impurities of the gas outlet product 48.
- the pre-gas separation conditioner 60 is in fluid connection with a gas separator 64 which is adapted to separate and purify at least a portion of the
- At least one of the purified gaseous product streams 66 comprises hydrogen gas.
- the gas separator 64 is in communication with a post-gas separation conditioner 68 adapted to condition the purified gaseous product streams 66 to provide hydrogen gas 14 in purified form and one or more conditioned gaseous streams 70 that may comprise one or more of CH 4 , C0 2 , CO or the mixed gaseous stream.
- Purified hydrogen stream 14 may be connected to one or more gas storage tanks, piped to an end user, used as an energy source for one or each of the one or more of or all of the conditioners 18, 142, 144, 1 50, 58, 60, 68 or reactor heater 65, or optionally fed into electricity generator 69 for electricity generation.
- conditioned gaseous product stream 70 comprises a mixed gaseous stream of one or more of CO, CO 2 , and CH 4
- the mixed gaseous stream may also optionally be connected to pre-reactor conditioner 18 for supply to the one or more reactors as the hydrocarbon feedstock, used in reactor heater 65 as a fuel source, or optionally fed into electricity generator 69 for electricity generation.
- Reactor heater 65 may directly or indirectly heat first reactor 124 and/or second reactor 126.
- Electricity generator 69 may optionally be used to provide electricity 80 to reactor heater 65 or to other parts of the system, as required.
- FIG. 4 there is shown a system 300 for the conversion of a hydrocarbon feedstock 12 to hydrogen gas 14 and graphitic carbon 16.
- the hydrocarbon feedstock 12 is introduced into a pre-reactor conditioner 18 adapted to condition the hydrocarbon feedstock 18 to produce a conditioned
- the pre-reactor conditioner 18 is adapted to perform one or more of heating, pressurising, plasma treatment, cooling, desulfurisation, drying, purification and expansion of the hydrocarbon feedstock 12 producing a conditioned hydrocarbon feedstock 20.
- the pre-reactor conditioner is in communication with a first reactor 124.
- First reactor 1 24 is adapted to contact at a temperature between 600 °C and 1 000 °C a conditioned iron oxide catalyst 29 with the conditioned hydrocarbon feedstock 20 to produce a mixed phase stream 30 containing hydrogen gas, graphitic carbon and unreacted hydrocarbon.
- the first reactor 124 comprises a catalyst inlet 32, a gas inlet 34, a mixed phase outlet 36.
- the mixed phase outlet 36 is in communication with a first post-reactor conditioner 142.
- the first post-reactor conditioner 142 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the first post-reactor conditioner 142 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30.
- the first post-reactor conditioner 142 is in communication with a first solid/gas separator 146.
- the first solid/gas separator 146 comprises an inlet 52, a gas outlet 54 and a solid outlet 56.
- the first solid/gas separator 146 is adapted to separate at least a portion of the conditioned mixed phase stream 44 into a gas stream 48 comprising hydrogen gas and a solid stream 50 comprising graphitic carbon.
- the gas outlet 54 and the solid outlet 56 are in communication with a second pre-reactor conditioner 150 to condition solid stream 50 and gas stream 48.
- the second pre-reactor conditioner 150 is in communication with the second reactor 126 to provide a second conditioned solid stream 250 and a second conditioned hydrocarbon feedstock 1 52.
- the second conditioned hydrocarbon feedstock 152 comprises a mixture of hydrocarbons, hydrogen, and trace amounts of carbon monoxide and carbon dioxide.
- the second reactor 126 is adapted to contact at a temperature between 600 °C and 1 000 °C a conditioned solid stream 250 with the second conditioned
- the second reactor 1 26 comprises a solid injection inlet 252, a second conditioned hydrocarbon feedstock inlet 134 and a mixed phase outlet 36.
- the second pre-reactor conditioner will typically increase the temperature and pressure of the conditioned solid stream 250 and the second conditioned hydrocarbon feedstock 1 52 to that of the second reactor 126.
- the mixed phase outlet 36 of the second reactor 126 is in communication with a second post-reactor conditioner 144.
- the second post-reactor conditioner 144 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the second post-reactor conditioner 144 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30.
- the post-reactor conditioner 144 is in communication with a second solid/gas separator 148.
- the solid/gas separator 148 comprise an inlet 52, a gas outlet 54, a second gas outlet 63, and a solid outlet 56.
- the second solid/gas separator 148 is adapted to separate at least a portion of the conditioned mixed phase stream 44 into a gas stream 48 comprising hydrogen gas and a solid stream 50 comprising graphitic carbon. It is envisaged that the second gas outlet 63 may be in communication with one or more of the pre-reactor conditioner 18, electricity generator 69, and/or reactor heater 65 such that at least a portion of gas stream 48 may be recycled.
- the solid outlet 56 of second solid/gas conditioner 148 is in communication with a solids conditioner 58.
- the solids conditioner 58 is adapted to condition the solid stream 50 to produce a graphitic carbon stream 16.
- the solids conditioner may perform one or more of the conditioning functions of packaging (pellitising, compressing), functionalising, and/or purifying the solid stream 50.
- the gas outlet 54 of the second solid/gas conditioner is in communication with a pre-gas separation conditioner 60, which comprise a conditioned gas outlet 61 , to produce a conditioned gas stream 62.
- the pre-gas separation conditioner 60 may do any one or more of pressurising, cooling, scrubbing/purification to remove impurities of the gas outlet product 48.
- the pre-gas separation conditioner 60 is in fluid connection with a gas separator 64 which is adapted to separate and purify at least a portion of the
- At least one of the purified gaseous product streams 66 comprises hydrogen gas.
- the gas separator 64 is in communication with a post-gas separation conditioner 68 adapted to condition the purified gaseous product streams 66 to provide hydrogen gas 14 in purified form and one or more conditioned gaseous streams 70 that may comprise one or more of CH 4 , C0 2 , CO or the mixed gaseous stream.
- Purified hydrogen stream 14 may be connected to one or more gas storage tanks, piped to an end user, or optionally used as an energy source for one or each of the one or more of or all of the conditioners 18, 142, 144, 1 50, 58, 60, 68 or reactor heater 65, or optionally fed into electricity generator 69 for electricity generation.
- conditioned gaseous product stream 70 comprises a mixed gaseous stream of one or more of CO, C0 2 , and CH 4
- the mixed gaseous stream may also be connected to pre-reactor conditioner 18 for supply to the one or more reactors as the hydrocarbon feedstock or optionally fed into electricity generator 69 for electricity generation.
- Electricity generator 69 may optionally be used to provide electricity 80 to reactor heater 65 or to other parts of the system, as required.
- FIG. 5 there is shown a system 400 for the conversion of a hydrocarbon feedstock 12 to hydrogen gas 14 and graphitic carbon 16.
- system 400 shares feature with system 10, 100, 200, and 300, like numerals denote like parts.
- the hydrocarbon feedstock 12 is introduced into a pre-reactor conditioner 18 adapted to condition the hydrocarbon feedstock 18 to produce a conditioned
- the pre-reactor conditioner 18 is adapted to perform one or more of heating, pressurising, plasma treatment, cooling, desulfurisation, drying, purification and expansion of the hydrocarbon feedstock 12 producing a conditioned hydrocarbon feedstock 20.
- the pre-reactor conditioner is in communication with a first reactor 124.
- First reactor 1 24 is adapted to contact at a temperature between 600 °C and 1000 °C a second conditioned solid stream 415 with the conditioned hydrocarbon feedstock 20 to produce a mixed phase stream 30 containing hydrogen gas, graphitic carbon and unreacted hydrocarbon.
- the first reactor 124 comprises a solids inlet 410, a gas inlet 34, a mixed phase outlet 36.
- the mixed phase outlet 36 is in communication with a first post-reactor conditioner 142.
- the first post-reactor conditioner 142 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the first post-reactor conditioner 142 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30.
- the first post-reactor conditioner 142 is in communication with a first solid/gas separator 146.
- the first solid/gas separator 146 comprises an inlet 52, a gas circulation outlet 416 and a solid outlet 56.
- the first solid/gas separator 146 is adapted to separate at least a portion of the conditioned mixed phase stream 44 into a circulating gas stream 420 comprising hydrogen gas and a solid stream 50 comprising graphitic carbon.
- the solids conditioner 58 is adapted to condition the solid stream 50 to produce a graphitic carbon stream 16.
- the solids conditioner may perform one or more of the conditioning functions of packaging
- the circulating gas outlet 416 is in communication with a second pre-reactor conditioner 150 to condition circulation gas stream 420.
- the second pre-reactor conditioner 150 is in communication with the second reactor 126 to provide a second conditioned hydrocarbon feedstock 1 52.
- Second conditioned hydrocarbon feedstock 152 comprises a mixture of hydrocarbons, hydrogen, and trace amounts of carbon monoxide and carbon dioxide.
- the second reactor 126 is adapted to contact at a temperature between 600 °C and 1 000 °C a conditioned iron oxide catalyst 29 with the second conditioned hydrocarbon feedstock 152 to produce a mixed phase stream 30 containing hydrogen gas, graphitic carbon, and unreacted hydrocarbon.
- the second reactor 1 26 comprises a catalyst inlet 32, a second conditioned hydrocarbon feedstock inlet 134 and a mixed phase outlet 36.
- the second pre-reactor conditioner 1 50 will typically increase the temperature and pressure of the second conditioned hydrocarbon feedstock 1 52 to that of the second reactor 126.
- the mixed phase outlet 36 of the second reactor 126 is in communication with a second post-reactor conditioner 144.
- the second post-reactor conditioner 144 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the second post-reactor conditioner 144 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30.
- the second post-reactor conditioner 144 is in communication with a second solid/gas separator 148.
- the solid/gas separator 148 comprise an inlet 52, a gas outlet 54, a second gas outlet 63, and a circulating solid outlet 41 2.
- the second solid/gas separator 148 is adapted to separate at least a portion of the conditioned mixed phase stream 44 into a gas stream 48 comprising hydrogen gas and a circulating solid stream 414 comprising uncreacted catalyst and graphitic carbon. It is envisaged that the second gas outlet 63 may be in communication with one or more of the pre-reactor conditioner 18, electricity generator 69, and/or reactor heater 65 such that at least a portion of gas stream 48 may be recycled. Reactor heater 65 may directly or indirectly heat first reactor 124 and/or second reactor 126.
- the second solid/gas separation unit is in communication with a third pre- reactor conditioner 422, which is adapted to condition circulating solid stream 414 to provide a second conditioned solid stream 415.
- Third pre-reactor conditioner 422 is in communication with first reactor 124 to provide delivery of the second conditioned solid stream 415 to the solids inlet 410 in the first reactor 124.
- the gas outlet 54 of the second solid/gas conditioner is in communication with a pre-gas separation conditioner 60, which comprise a conditioned gas outlet 61 , to produce a conditioned gas stream 62.
- the pre-gas separation conditioner 60 may do any one or more of pressurising, cooling, scrubbing/purification to remove impurities of the gas outlet product 48.
- the pre-gas separation conditioner 60 is in fluid connection with a gas separator 64 which is adapted to separate and purify at least a portion of the
- At least one of the purified gaseous product streams 66 comprises hydrogen gas.
- the gas separator 64 is in communication with a post-gas separation conditioner 68 adapted to condition the purified gaseous product streams 66 to provide hydrogen gas 14 in purified form and one or more conditioned gaseous streams 70 that may comprise one or more of CH 4 , C0 2 , CO or the mixed gaseous stream.
- Purified hydrogen stream 14 may be connected to one or more gas storage tanks, piped to an end user, or optionally used as an energy source for one or each of the one or more of or all of the conditioners 18, 142, 144, 1 50, 422 58, 60, 68 or reactor heater 65, or optionally fed into electricity generator 69 for electricity generation.
- conditioned gaseous product stream 70 comprises a mixed gaseous stream of one or more of CO, C0 2 , and CH 4
- the mixed gaseous stream may also optionally be connected to pre-reactor conditioner 18 for supply to the one or more reactors as the hydrocarbon feedstock or optionally fed into electricity generator 69 for electricity generation.
- Electricity generator 69 may optionally be used to provide electricity 80 to reactor heater 65 or to other parts of the system, as required.
- FIG. 6 there is shown a system 500 for the conversion of a hydrocarbon feedstock 12 to hydrogen gas 14 and graphitic carbon 16 in accordance with a second aspect of the present invention.
- system 500 shares features with system 10, 100, 200, 300, and 400, like numerals denote like parts.
- the hydrocarbon feedstock 12 is introduced into a pre-reactor conditioner 18 adapted to condition the hydrocarbon feedstock 18 to produce a conditioned hydrocarbon feedstock 20.
- the pre-reactor conditioner is in communication with two or more reactors 650. Each reactor is adapted to contact at a temperature between 600 °C and 1 000 °C an iron oxide catalyst 28 with the heated hydrocarbon feedstock 24 to produce a mixed phase stream 30 containing hydrogen gas, graphitic carbon and unreacted
- Each of the two or more reactor 650 comprises a catalyst inlet 32, a gas inlet 34, a mixed phase outlet 36, and an optional solid outlet 660.
- the pre-reactor conditioner will typically increase the temperature and pressure of the second conditioned hydrocarbon feedstock to that of the two or more reactors 650.
- Each of the solids outlets 660 in the two or more reactors is in communication with solids conditioners 58 via solid inlets 658.
- the two or more reactors 650 are arranged in parallel. In the parallel arrangement, both the hydrocarbon feedstock 24 and iron oxide catalyst 28 streams may be directed to each of the two or more reactors 650 independently. This arrangement allows for independent operation of each of the two or more reactors 650.
- the independent operation of the two or more reactors 650 has been found to be particularly advantageous as operation of individual reactors may be ceased while maintaining the processing of the hydrocarbon feedstock 12 in other reactors. By ceasing operation of a reactor for a period of time following the operation of the reactor, at least of portion of the solid graphite reactor will settle and may be moved via sold outlet 662 to solids conditioners 58.
- the mixed phase outlet 36 is in communication with a post-reactor conditioner 42.
- the post-reactor conditioner 42 is adapted to condition the mixed phase stream 30 to produce a conditioned mixed phase stream 44.
- the post-reactor conditioner 42 may do any one or more of dewatering, cooling, and/or extraction of volatiles of the mixed phase stream 30, preferably post-reactor conditioner 42 cools and/or dewaters mixed phase stream 30.
- the post-reactor conditioner 42 is in communication with one or more solid/gas separators 46.
- One or more solid/gas separator 46 comprise an inlet 52, a gas outlet 54, a second gas outlet 63, and a solid outlet 56.
- the one or more solid/gas separators 46 are adapted to separate at least a portion of the conditioned mixed phase stream 44 into a gas stream 48 comprising hydrogen gas and a solid stream 50 comprising graphitic carbon.
- the second gas outlet 63 may be in communication with one or more of the pre-reactor conditioner 18 and/or reactor heater 65 such that at least a portion of gas stream 48 may be recycled.
- Reactor heater 65 may directly or indirectly two or more reactors 650.
- the solid outlet 56 is in communication with a solids conditioner 58.
- the solids conditioner 58 is adapted to condition the solid stream 50 to produce a graphitic carbon stream 1 6.
- the solids conditioner may perform one or more of the conditioning functions of packaging (pellitising, compressing), functionalising, and/or purifying the solid stream 50.
- the gas outlet 54 is in communication with a pre-gas separation conditioner 60, which comprise a conditioned gas outlet 61 , such that at least a portion of the gas stream 48 is conditioned to produce a conditioned gas stream 62.
- the pre-gas separation conditioner 60 may do any one or more of pressurising, cooling,
- the pre-gas separation conditioner 60 is in fluid connection with a gas separator 64 which is adapted to separate and purify at least a portion of the
- At least one of the purified gaseous product streams 66 comprises hydrogen gas.
- the gas separator 64 is in communication with a post-gas separation conditioner 68 adapted to condition the purified gaseous product streams 66 to provide hydrogen gas 14 in purified form and one or more conditioned gaseous streams 70 that may comprise one or more of CH 4 , C0 2 , CO or the mixed gaseous stream.
- Purified hydrogen stream 14 may be connected to one or more gas storage tanks, piped to an end user, or optionally used as an energy source for one or each of the one or more of or all of the conditioners 18, 42, 58, 60, 68 or reactor heater 65, or optionally fed into electricity generator 69 for electricity generation.
- conditioned gaseous product stream 70 comprises a mixed gaseous stream of one or more of CO, C0 2 , and CH 4
- the mixed gaseous stream may also optionally be connected to pre-reactor conditioner 18 for supply to the one or more reactors as the hydrocarbon feedstock or optionally fed into electricity generator 69 for electricity generation.
- Electricity generator 69 may optionally be used to provide electricity 80 to reactor heater 65 or to other parts of the system, as required.
- each of the two or more reactors may be comprised of two or more secondary reactors used in series in any one of the arrangements described herein.
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Abstract
Description
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AU2017900982A AU2017900982A0 (en) | 2017-03-20 | System for the Production of Hydrogen and Graphitic Carbon | |
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IT201800011082A1 (en) | 2018-12-13 | 2020-06-13 | Graf S P A | HYDROGEN FILLING STATION |
WO2020193254A1 (en) * | 2019-03-28 | 2020-10-01 | Primetals Technologies Austria GmbH | Method for producing hydrogen and carbon from a hydrocarbon-containing gas |
WO2024077371A1 (en) * | 2022-10-12 | 2024-04-18 | Innova Hydrogen Corp. | Apparatus and method for catalytic pyrolysis of light hydrocarbons |
WO2024119237A1 (en) * | 2022-12-09 | 2024-06-13 | Hazer Group Limited | System and methods configured to enable improved/optimised control of a hydrocarbon pyrolysis process |
WO2024138017A3 (en) * | 2022-12-22 | 2024-08-02 | Czero, Inc. | Processes and methods for producing hydrogen and carbon from hydrocarbons using heat carrier particles |
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WO2024138017A3 (en) * | 2022-12-22 | 2024-08-02 | Czero, Inc. | Processes and methods for producing hydrogen and carbon from hydrocarbons using heat carrier particles |
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