WO2009045112A1 - Material and method for partial oxidation of natural gas - Google Patents

Material and method for partial oxidation of natural gas Download PDF

Info

Publication number
WO2009045112A1
WO2009045112A1 PCT/NO2008/000352 NO2008000352W WO2009045112A1 WO 2009045112 A1 WO2009045112 A1 WO 2009045112A1 NO 2008000352 W NO2008000352 W NO 2008000352W WO 2009045112 A1 WO2009045112 A1 WO 2009045112A1
Authority
WO
WIPO (PCT)
Prior art keywords
temperature
activated
oxide component
material according
oxygen
Prior art date
Application number
PCT/NO2008/000352
Other languages
French (fr)
Inventor
Bjørnar AARSTAD
Unni Olsbye
Helmer FJELLVÅG
Original Assignee
Sinvent As
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinvent As filed Critical Sinvent As
Publication of WO2009045112A1 publication Critical patent/WO2009045112A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • 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
    • 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
    • C01B2203/1082—Composition of support materials
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention comprises a material for partial oxidation of natural gas into synthesis gas in a one step process and a process for producing said material.
  • WO 03/072490 describes a process for producing synthesis gas by a net catalytic partial oxidation reaction using a catalyst comprising lattice oxygen of a reducible metal oxide as an oxygen source.
  • the objective of the present invention is to provide a material and process for converting natural gas into synthesis gas. High selectivity to CO and H 2 are obtained according to the present invention.
  • the present invention comprises a material for partial oxidation of natural gas into synthesis gas in a one step process, said material comprising at least one oxide component with lattice oxygen, said material also comprising particles of at least one metal component deposited on said oxide component, said material having been calcined in at least one temperature interval and activated in a process of at least one step.
  • the oxide component possesses reversible liberation and uptake of oxygen and contains at least one cation. Further, said oxide component possess a crystal structure type chosen from one of the following types: fluorite, perovskite, Ruddelsden Popper or YBaCo 4 O 7 .
  • the particles of the present invention comprise one or several transition metals, alloys of transition metals or metal composites.
  • said transition metals are chosen from the group 3-12 of the periodic system, more preferably chosen from the group 9-11 of the periodic system, and most preferably is Au.
  • the largest dimension of said particle according to the present invention is in the range of 2-200 nm, 5-200 nm, 70-200 nm or 50-1 OOnm. The largest dimension of said particle can also be defined as ⁇ 70 nm or ⁇ 2 nm.
  • the material according to the present invention has been calcined in a temperature interval of 700-1100 ° C, preferably 800 - 1000°C, most preferably 850 - 900 0 C.
  • said material After being calcined, said material has been activated in at least a one step process in a temperature interval of 780-950°C, or in at least a two step process in the temperature intervals of 780-950 0 C and 680-750 °C or in at least a three step process in the temperature intervals of 780-950°C, 680-750 0 C and 500-650 0 C.
  • the temperature for partial oxidation of natural gas according to the present invention is below 800 0 C, preferably below 700 0 C, most preferably 550-650 0 C.
  • the present invention also comprises a process for conditioning a material for partial oxidation of natural gas, said material comprising at least one oxide component with lattice oxygen, said material also comprising particles of at least one metal component deposited on said oxide component, said process comprising the following steps:
  • the oxide component possesses reversible liberation and uptake of oxygen and contains at least one cation. Further, said oxide component possess a crystal structure type chosen from one of the following types: fluorite, perovskite, Ruddelsden Popper or YBaCo 4 O 7 .
  • the particles according to the present invention comprise one or several transition metals, alloys of transition metals or metal composites. Said transition metals are chosen from the group 3-12 of the periodic system, more preferably are chosen from the group 9-11 of the periodic system, and most preferably are Au.
  • the sizes of the particles are in the range of 2-200 nm, 5-200nm, 70-200 nm or 50-1 OOnm. Further, said particles are ⁇ 70 nm or ⁇ 2 nm.
  • said material is calcined in a temperature interval of from 700-1100 0 C, preferably 800-1000°C, most preferably 850-900 0 C. Further said material has been activated in at least a one step process in a temperature interval of 780-950 0 C. In said process said material is activated in at least a two step process in the temperature intervals of 780-950°C and 680-750 ° C or in at least a three step process in the temperature intervals of 780-950 0 C, 680- 750 ° C and 500-650 0 C.
  • the temperature for partial oxidation of natural gas according to the present invention is below 800 0 C, preferably below 700 0 C and most preferably 550 - 650 0 C.
  • Figure 1 shows CO selectivity as a function of CH 4 conversion during methane pulses over the 0.5 wt% Au / 35 wt% CeO 2 / AI 2 O 3 material, all at 600 0 C.
  • Figure 2 shows CH 4 conversion versus pulse number during methane pulses over the 0.5 wt% Au / 35 wt% CeO 2 / AI 2 O 3 material at 600-800 0 C.
  • Figure 3 shows CO selectivity as a function of CH 4 conversion during methane pulses over the 0.5 wt% Au / 35 wt% CeO 2 / AI 2 O 3 material at 600-800 0 C.
  • the material according to the present invention comprises material which gives high selectivity to CO and H 2 in the preferred operating temperature intervals for the syngas production.
  • the present material has been calcined and further activated at specified temperature intervals according to the present invention in order to obtain a material with full selectivity to CO and H2 at short contact times during conversion of natural gas.
  • the partial oxidation of natural gas according to the present invention is performed at temperatures below 800°C, and most preferably in the range of 550 - 650 0 C in order to obtain synthesis gas in a one step process.
  • the oxide component holds a crystal structure of e.g. perovskite- or fluorite-type (or distorted/related variants of these structures). These crystal structures offer opportunity for oxygen ion transport. High oxygen mobility at the temperatures of concern is a requirement. This is offered by the fluorite type atomic arrangement owing to either interstitial oxygen atoms in octahedral sites of the ccp lattice of cations and/or by vacancies on the tetrahedral oxygen sub lattice. For the perovskite related oxides this is offered either by vacancies on the oxygen sub lattice or by oxygen atoms in interstitial positions on layer-like structural units being combined with perovskite type buildings units.
  • the oxide component holds furthermore capacity for reversible uptake and release of oxygen. This facilitates a continuous supply of reactive oxygen to the surface during process sequences of CPO and facilitates refilling of the oxygen reservoir capacity during process sequences of material regeneration.
  • the oxygen mobility, reactivity, and the oxygen capacity of the oxide in question is tuned through chemical substitution on one or more sub lattices of the involved crystal structures.
  • the metal component according to the present invention comprises one or several transition metals, alloys of transition metals or metal composites.
  • the metal component represents preferably a noble metal or a noble metal based alloy or metal composite, and is during material preparation dispersed on the oxygen carrier material, either in oxidized form or in metallic form.
  • the preferred metal component has as such no or just a minor ability to promote reforming reactions (i.e. reactions between CH 4 and either H 3 O or CO 3 leading to CO and H 3 formation).
  • the preferred metal component will be deposited as or will be converted to particles with the largest dimension of said particle in the range of 2- 200nm, 5-200nm, 70-200nm, 50-1 OOnm, ⁇ 70nm or ⁇ 2nm, under conditions that facilitate a certain distribution of particle sizes.
  • this includes all materials with crystal structures that provide certain specific abilities as follow: 1) contain one or more cations capable of undergoing redox reactions upon release/uptake of oxygen. These cations take certain positions in the crystal structure and are normally bonded to oxygen atoms. 2) exhibit a small or large oxygen non-stoichiometry, that can be induced upon
  • the surrounding atmosphere i.e. the oxygen partial pressure or the reductive or oxidative nature of the surrounding atmosphere, including flowing gases
  • One or both of these distinct chemical compounds may show oxygen non- stoichiometry as outlined in (2) 4) offer opportunity for oxygen transport (diffusion) from the bulk of a crystallite to its surface.
  • These pathways may include vacancy formation (through heterovalent substitution or Schottky defects; as e.g. for rocksalt and perovskite type oxides; internal reduction as for ceria or reducible perovskites), or interstitial positions (as e.g. for fluorite and anti-fluorite type oxides or Ruddlesden Popper related oxide types), or may represent topochemical pathways connecting distinct phases (as e.g. for YBaCo 4 O 7 type oxides).
  • compositions for perovskite type oxides are:
  • the ideal perovskite type structure is cubic. With perovskite related one understands all solid solution derivatives, and all structures with more complex symmetry (lower symmetry, larger unit cells) however with the perovskite type arrangement as a common backbone.
  • Oxides with reducible cations offer intrinsically a possibility for non-stoichiometry as function of oxygen partial pressure and temperature.
  • iron can be reduced from (IV) to (III) forming Sr 2 Fe 2 O 5 or SrFeO 2 . 5 (vacancies) 0 . 5 .
  • all intermediate compositions may be foreseen.
  • perovskite such processes are accompanied by formation of vacancies.
  • LaMnOs where oxidation of Mn(III) into Mn(IV) gives LaMnO 3+X , where the structural adaption to this O-enrichment is formation of La and Mn vacancies rather than O interstitials.
  • Non-stocihiometry can be created by heterovalent substitution. If e.g. La(III) is exchanged partly by Sr(II), this can be compensated by oxidation of the actual cation, e.g. La(i -X )Sr (X) FeO 3 without O-vacancy formation, however, substantial O- non-stoichiometry is likely at reducing conditions since all oxidized Fe(IV) will then be reduced to Fe(III); i.e. La (1-X) Sr( X) FeO (3-x/2) .
  • Material for selective catalytic oxidation of methane to synthesis gas in one step process, in which said material comprises at least one oxide component with lattice oxygen and nanoparticles (the largest dimension is in the range of 2- 200nm, 5-200nm, 70- 200nm, 50-1 OOnm, ⁇ 70nm or ⁇ 2nm) of at least one metal component in which said material is calcined in a three step process and is non active of reforming methane.
  • a 35 wt.%CeO 2 /AI 2 O 3 was synthesised by conventional impregnation techniques of CeO 2 on ⁇ -alumina using Ce(NO 3 ) x -salt.
  • Au was added by the incipient wetness impregnation technique and the material was subsequently dried and calcined at 800°C. Calcination at 600 and 700 0 C did give materials significant less active than those calcined at 800 0 C.
  • the nominal Au content on the final material was 0.5 wt%.
  • Powder X-ray diffraction showed the correct structure and phase purity of the material after the impregnation and subsequent calcination.
  • a Au/CeO 2 /AI 2 O 3 material was prepared as described in Example 1 ; however, the nominal Au content of the resulting material was 1 wt.%.
  • the CeO 2 /AI 2 O 3 material was prepared as described in Example 1.
  • Au was deposited on the carrier material (CeO 2 /AI 2 O 3 ) by the standard deposition- precipitation method using urea to increase the pH of the solution.
  • Au is deposited on the oxide when the pH increases.
  • 1 g CeO 2 /AI 2 O 3 was immersed in 100 mL distilled water having a urea concentration of 0.42 M.
  • HAuCI 4 was added such that the nominal loading would be 0.5 wt.%. The mixture was then stirred at 80 0 C for 4 hours. After thorough washing, the material was calcined at 800 0 C as above.
  • a material prepared as described in Example 1 was subjected to catalytic testing for the catalytic partial oxidation at 600°C by the following procedure:
  • the material (0.1 g material diluted with 0.4 g quartz) was placed in a tubular quartz reactor and heated to 600 0 C under a continuous stream of 5 % O 2 balanced with He. When reaching 600 0 C, the continuous gas stream was switched to He and a 6-way valve with a sample loop was used to send 10 pulses with 3 micromoles CH 4 (10 % CH 4 balanced with He) over the material with 30 minutes interval. After this series of 10 pulses, another 10 pulses, each with 1.5 micromoles O 2 (10 % O 2 balanced with He) was sent through the reactor.
  • MS Mass Spectrometer
  • the CO selectivity obtained during the 10 pulses is shown as a function of CH 4 conversion in Figure 1.
  • the CO selectivity was less than 10% during the full pulse . Kjuence.
  • a 'material prepared as described in Example 1 was subjected to catalytic testing for the catalytic partial oxidation at 600-800°C by the following procedure:
  • the material (0.1 g material diluted with 0.4 g quartz) was placed in a tubular quartz reactor and heated to 800 0 C under a continuous stream of 5 % O 2 balanced with He. When reaching 800 0 C, the continuous gas stream was switched to He and a 6-way valve with a sample loop was used to send 10 pulses with 3 micromoles CH 4 (10 % CH 4 balanced with He) over the material with 30 minutes interval. After this series of 10 pulses, another 10 pulses, each with 1.5 micromoles O2 (10 % O2 balanced with He) was sent through the reactor.
  • the sample was kept in a 5 % oxygen/He gas stream while the temperature was lowered to 700 0 C.
  • the same pulse sequence as above was repeated before lowering the temperature to 62O 0 C in 5% O 2 /He where the same pulse sequence was repeated once more.
  • the temperature was lowered to 600 0 C under a continuous stream of 5 % O 2 balanced with He, after which the pulse sequence was again repeated.
  • MS Mass Spectrometer
  • the methane conversion obtained during methane pulses at 800, 700, 620 and 600 0 C, respectively, are shown as functions of the pulse number in Figure 2.
  • the methane conversion decreased with a decrease in reaction temperature, and with an increasing pulse number at each temperature.
  • the CO selectivity versus methane conversion obtained during methane pulses at each temperature is shown in Figure 3.
  • the CO selectivity is most often inferior to that obtained during subsequent pulses, at a given temperature.
  • the CO selectivity is highest for temperatures below 700 0 C. This result is opposite to the expected temperature- selectivity relationship from thermodynamic considerations, and may suggest that the selectivity is governed by kinetics.
  • Example 1 A material prepared as described in Example 1 was subjected to catalytic testing for the catalytic partial oxidation at 600-800°C by using the procedure described in Example 5. During testing at 600 0 C, the methane pulses were contaminated by small amounts of molecular oxygen.
  • the CO selectivity obtained during the methane pulses for each test is shown as a function of CH 4 conversion in Figure 1.
  • the CO selectivity decreased with an increased oxygen content in the gas phase.
  • a material prepared as described in Example 1 was subjected to catalytic testing for the catalytic partial oxidation at 250-800°C by co-feeding a continuous flow of methane and molecular oxygen over the material, and using the following procedure:
  • reaction temperature and effluent concentration for each reactant and product are shown as functions of test duration in Figure 4.
  • CH 4 conversion into CO 2 starts already at 500 0 C.
  • CO and H 2 production do not start until appx. 700 0 C.
  • the CO and H 2 production decrease with time on stream, suggesting that material deactivation takes place.
  • CO and H 2 production stops at approximately 700 and 600 0 C, respectively, while CO 2 production continues until the temperature has reached 35O 0 C.
  • Example 8 Material testing A material prepared as described in Example 1 was subjected to catalytic testing for the dry reforming of methane to synthesis gas at 250-800°C by co-feeding a continuous flow of methane and CO 2 over the material, and using the following procedure:
  • reaction temperature and effluent concentration for each reactant and product are shown as functions of test duration in Figure 5.
  • CH4 and CO 2 conversion into CO and H 2 does not start until approximately 700 0 C. Full conversion is not obtained even at the highest temperature (800 0 C).
  • the CO and H 2 production decrease with time on stream, suggesting that material deactivation takes place.
  • the results obtained may indicate that this material is not reforming active at the temperatures where the maximum selectivities to CO and H 2 have been observed during pulse experiments in Example 5. They further suggest that the production of CO and H 2 observed at T > 700 0 C in the cofeed experiment in Example 7 were obtained by methane reforming with CO 2 and/or H 2 O.
  • a material prepared as described in Example 1 was subjected to catalytic testing for the water gas shift reaction at 250-800°C by co-feeding a continuous flow of H 2 and CO 2 over the material, and using the following procedure:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

The present invention comprises a material and a process for producing a material for partial oxidation of natural gas into synthesis gas in a one step process comprising at least one oxide component with lattice oxygen, wherein said material also comprises particles of at least one metal component deposited on said oxide component, said material having been calcined in at least one temperature interval and activated in a process of at least one step.

Description

Material and method for partial oxidation of natural gas
Introduction
The present invention comprises a material for partial oxidation of natural gas into synthesis gas in a one step process and a process for producing said material.
Background
WO 03/072490 describes a process for producing synthesis gas by a net catalytic partial oxidation reaction using a catalyst comprising lattice oxygen of a reducible metal oxide as an oxygen source.
Summary of the invention
The objective of the present invention is to provide a material and process for converting natural gas into synthesis gas. High selectivity to CO and H2 are obtained according to the present invention.
The present invention comprises a material for partial oxidation of natural gas into synthesis gas in a one step process, said material comprising at least one oxide component with lattice oxygen, said material also comprising particles of at least one metal component deposited on said oxide component, said material having been calcined in at least one temperature interval and activated in a process of at least one step. The oxide component possesses reversible liberation and uptake of oxygen and contains at least one cation. Further, said oxide component possess a crystal structure type chosen from one of the following types: fluorite, perovskite, Ruddelsden Popper or YBaCo4O7. The particles of the present invention comprise one or several transition metals, alloys of transition metals or metal composites. Further, said transition metals are chosen from the group 3-12 of the periodic system, more preferably chosen from the group 9-11 of the periodic system, and most preferably is Au. The largest dimension of said particle according to the present invention is in the range of 2-200 nm, 5-200 nm, 70-200 nm or 50-1 OOnm. The largest dimension of said particle can also be defined as <70 nm or < 2 nm. The material according to the present invention has been calcined in a temperature interval of 700-1100°C, preferably 800 - 1000°C, most preferably 850 - 900 0C. After being calcined, said material has been activated in at least a one step process in a temperature interval of 780-950°C, or in at least a two step process in the temperature intervals of 780-950 0C and 680-750 °C or in at least a three step process in the temperature intervals of 780-950°C, 680-7500C and 500-6500C. The temperature for partial oxidation of natural gas according to the present invention is below 8000C, preferably below 7000C, most preferably 550-6500C.
The present invention also comprises a process for conditioning a material for partial oxidation of natural gas, said material comprising at least one oxide component with lattice oxygen, said material also comprising particles of at least one metal component deposited on said oxide component, said process comprising the following steps:
- calcination of said material in at least one temperature interval, - activation of said calcined material in at least one step.
The oxide component possesses reversible liberation and uptake of oxygen and contains at least one cation. Further, said oxide component possess a crystal structure type chosen from one of the following types: fluorite, perovskite, Ruddelsden Popper or YBaCo4O7. The particles according to the present invention comprise one or several transition metals, alloys of transition metals or metal composites. Said transition metals are chosen from the group 3-12 of the periodic system, more preferably are chosen from the group 9-11 of the periodic system, and most preferably are Au. The sizes of the particles are in the range of 2-200 nm, 5-200nm, 70-200 nm or 50-1 OOnm. Further, said particles are <70 nm or < 2 nm. According to the present invention said material is calcined in a temperature interval of from 700-1100 0C, preferably 800-1000°C, most preferably 850-9000C. Further said material has been activated in at least a one step process in a temperature interval of 780-950 0C. In said process said material is activated in at least a two step process in the temperature intervals of 780-950°C and 680-750 °C or in at least a three step process in the temperature intervals of 780-9500C, 680- 750 °C and 500-650 0C. The temperature for partial oxidation of natural gas according to the present invention is below 800 0C, preferably below 7000C and most preferably 550 - 6500C.
Brief description of drawings Embodiments of the invention will now be described with reference to the followings drawings, where:
Figure 1 shows CO selectivity as a function of CH4 conversion during methane pulses over the 0.5 wt% Au / 35 wt% CeO2 / AI2O3 material, all at 6000C. Figure 2 shows CH4 conversion versus pulse number during methane pulses over the 0.5 wt% Au / 35 wt% CeO2 / AI2O3 material at 600-8000C.
Figure 3 shows CO selectivity as a function of CH4 conversion during methane pulses over the 0.5 wt% Au / 35 wt% CeO2 / AI2O3 material at 600-8000C. Figure 4 shows the reaction temperature and effluent concentration of reactants and products versus test duration during a temperature-programmed experiment, feeding a continuous CH4 : O2 : N2 : He = 2 : 1 : 2 : 20 flow over the 0.5 wt.% Au/ 35 wt% CeO2 / AI2O3 material at 250-8000C.
Figure 5 shows the reaction temperature and effluent concentration of reactants and products versus test duration during a temperature-programmed experiment, feeding a continuous CH4 : CO2 : N2 : He = 2 : 2 : 2 : 20 flow over the 0.5 wt.% Au/ 35 wt% CeO2 / AI2O3 material at 250-8000C.
Figure 6 shows the reaction temperature and effluent concentration of reactants and products versus test duration during a temperature-programmed experiment, feeding a continuous H2 : CO2 : N2 : He = 2 : 2 : 2 : 20 flow over the 0.5 wt.% Au/ 35 wt% CeO2 / AI2O3 material at 250-8000C.
Detailed description
The objective of the present invention may be obtained by the features as set forth in the following description of the invention.
The material according to the present invention comprises material which gives high selectivity to CO and H2 in the preferred operating temperature intervals for the syngas production. The present material has been calcined and further activated at specified temperature intervals according to the present invention in order to obtain a material with full selectivity to CO and H2 at short contact times during conversion of natural gas. Further, the partial oxidation of natural gas according to the present invention is performed at temperatures below 800°C, and most preferably in the range of 550 - 6500C in order to obtain synthesis gas in a one step process.
The oxide component holds a crystal structure of e.g. perovskite- or fluorite-type (or distorted/related variants of these structures). These crystal structures offer opportunity for oxygen ion transport. High oxygen mobility at the temperatures of concern is a requirement. This is offered by the fluorite type atomic arrangement owing to either interstitial oxygen atoms in octahedral sites of the ccp lattice of cations and/or by vacancies on the tetrahedral oxygen sub lattice. For the perovskite related oxides this is offered either by vacancies on the oxygen sub lattice or by oxygen atoms in interstitial positions on layer-like structural units being combined with perovskite type buildings units.
The oxide component holds furthermore capacity for reversible uptake and release of oxygen. This facilitates a continuous supply of reactive oxygen to the surface during process sequences of CPO and facilitates refilling of the oxygen reservoir capacity during process sequences of material regeneration.
The oxygen mobility, reactivity, and the oxygen capacity of the oxide in question is tuned through chemical substitution on one or more sub lattices of the involved crystal structures.
The metal component according to the present invention comprises one or several transition metals, alloys of transition metals or metal composites. The metal component represents preferably a noble metal or a noble metal based alloy or metal composite, and is during material preparation dispersed on the oxygen carrier material, either in oxidized form or in metallic form. The preferred metal component has as such no or just a minor ability to promote reforming reactions (i.e. reactions between CH4 and either H3O or CO3 leading to CO and H3 formation). The preferred metal component will be deposited as or will be converted to particles with the largest dimension of said particle in the range of 2- 200nm, 5-200nm, 70-200nm, 50-1 OOnm, <70nm or <2nm, under conditions that facilitate a certain distribution of particle sizes.
Concerning the oxide component it should also be mentioned that this includes all materials with crystal structures that provide certain specific abilities as follow: 1) contain one or more cations capable of undergoing redox reactions upon release/uptake of oxygen. These cations take certain positions in the crystal structure and are normally bonded to oxygen atoms. 2) exhibit a small or large oxygen non-stoichiometry, that can be induced upon
- chemical modification; i.e. introduction of heterovalent cations into normal cation sites; or by
- the surrounding atmosphere; i.e. the oxygen partial pressure or the reductive or oxidative nature of the surrounding atmosphere, including flowing gases
3) or alternatively to (2); exhibits related, yet distinct chemical compounds where phase reactions between these involve oxidation or reduction. One or both of these distinct chemical compounds may show oxygen non- stoichiometry as outlined in (2) 4) offer opportunity for oxygen transport (diffusion) from the bulk of a crystallite to its surface. These pathways may include vacancy formation (through heterovalent substitution or Schottky defects; as e.g. for rocksalt and perovskite type oxides; internal reduction as for ceria or reducible perovskites), or interstitial positions (as e.g. for fluorite and anti-fluorite type oxides or Ruddlesden Popper related oxide types), or may represent topochemical pathways connecting distinct phases (as e.g. for YBaCo4O7 type oxides).
As outlined below the material according to item 1) mentioned above may contain a larger number of reducible cations:
Relevant compositions for fluorite type oxides are: - CeO2 - Heterovalent substituted ceria; (Ce1M)O2.* with M = RE (trivalent rare earth; di- or trivalent transition metal or main group 2 or 13 element); Ce(i.y)REzMvθ2-x. These correspond to substitution well known for so called stabilized zirconia (same structure type) - Substitutions affecting just chemical properties (without creating vacancies): Ce^- x)Zr(X)O2.
Relevant compositions for perovskite type oxides are:
(La1Sr)(Co, Fe)O3-x; e.g. Lao.8Sro.2Cθo.8Feo.2θ3-x: however all mixing ratios for the A- cations (larger cations, twelve coordinated ideally, here La and Sr) and the B- cations (in octahedral sites; smaller; here Co and Fe) are in principle feasible. This implies that the possibilities for tuning the chemistry of these oxides are huge. Typically they show large flexibility with respect to solid solubility. More than two elements can be included at the same site. E.g. at the B-site one may foresee a complex mix of e.g. Mn, Co, Fe, Ni and even 4d-elements - which actually may enhance certain properties.
The ideal perovskite type structure is cubic. With perovskite related one understands all solid solution derivatives, and all structures with more complex symmetry (lower symmetry, larger unit cells) however with the perovskite type arrangement as a common backbone.
For Ruddelsden Popper related oxides compounds like La2NiO4, La4Co3O10, Sr3Fe2O7 etc are included. They have the general formula A(n+i)BnO(3n+i); n = 1 , 2, 3,....In these compounds there exists blocks of perovskite type arrangement separated by blocks of rock salt arrangement. One may foresee oxygen vacancies in the perovskite blocks, and interstitial oxygen sites in the rock salt block. With related compounds one understands compounds that have a related stacked structure where the essential blocks have the perovskite type arrangement; however, the second block could take the rock salt, fluorite or a different atomic arrangement.
For the YBaCo4O7 material one may oxidize this into YBaCo4O85. However, in-situ experiments show that the Oγ and O8.5 compositions are not the same compound, they are distinct compounds, and there is no smooth compositional intermediate. Hence, the text states that one may have O-release/uptake in systems between structurally closely related phases. When this is imagined being done without major structural reconstruction, the reaction is said to be topochemical. This is the case here. However, in related system like LuBaCo4O7 this reaction proceeds within the same phase. This is already included in the other points mentioned under (4)
Concerning item 2) it should also be stressed that the non-stoichiometry is normally required in order to facilitate diffusion. I.e. the O-atoms need to have positions where they may jump into during their migration through the structure from the bulk to the surface. In addition, the O-release will imply a change in oxidation state of one of the relevant cations. This correlates closely with the non- stoichiometry.
Oxides with reducible cations offer intrinsically a possibility for non-stoichiometry as function of oxygen partial pressure and temperature. For instance; for SrFeO3, iron can be reduced from (IV) to (III) forming Sr2Fe2O5 or SrFeO2.5(vacancies)0.5. Indeed, also all intermediate compositions may be foreseen. In almost all perovskite such processes are accompanied by formation of vacancies. There is at least one important exception; LaMnOs, where oxidation of Mn(III) into Mn(IV) gives LaMnO3+X, where the structural adaption to this O-enrichment is formation of La and Mn vacancies rather than O interstitials.
Non-stocihiometry can be created by heterovalent substitution. If e.g. La(III) is exchanged partly by Sr(II), this can be compensated by oxidation of the actual cation, e.g. La(i-X)Sr(X)FeO3 without O-vacancy formation, however, substantial O- non-stoichiometry is likely at reducing conditions since all oxidized Fe(IV) will then be reduced to Fe(III); i.e. La(1-X)Sr(X)FeO(3-x/2). Material for selective catalytic oxidation of methane to synthesis gas (in one step process) in which said material comprises at least one oxide component with lattice oxygen and nanoparticles (the largest dimension is in the range of 2- 200nm, 5-200nm, 70- 200nm, 50-1 OOnm, <70nm or <2nm) of at least one metal component in which said material is calcined in a three step process and is non active of reforming methane.
Example 1. Material preparation
A 35 wt.%CeO2/AI2O3 was synthesised by conventional impregnation techniques of CeO2 on γ-alumina using Ce(NO3)x-salt.
The thus obtained Ce(NO3)x/AI2O3 material was dried and calcined at 800°C?
Au was added by the incipient wetness impregnation technique and the material was subsequently dried and calcined at 800°C. Calcination at 600 and 700 0C did give materials significant less active than those calcined at 800 0C.
The nominal Au content on the final material was 0.5 wt%.
Powder X-ray diffraction showed the correct structure and phase purity of the material after the impregnation and subsequent calcination.
High Resolution Transmission Electron Microscopy (HRTEM) analysis of the final material showed that both Ce and Al species were visible on the material surface. Ce was distributed quite evenly over the surface. Au was present as distinct, smaller (< 5 nm) and larger (50- 200 nm) nanoparticles. The larger Au nanoparticles appeared to be agglomerates composed of particles less than approximately 10 nm in size.
Example 2. Material preparation
A Au/CeO2/AI2O3 material was prepared as described in Example 1 ; however, the nominal Au content of the resulting material was 1 wt.%.
Example 3. Material preparation
The CeO2/AI2O3 material was prepared as described in Example 1. Au was deposited on the carrier material (CeO2/AI2O3) by the standard deposition- precipitation method using urea to increase the pH of the solution. Au is deposited on the oxide when the pH increases. 1 g CeO2/AI2O3was immersed in 100 mL distilled water having a urea concentration of 0.42 M. HAuCI4 was added such that the nominal loading would be 0.5 wt.%. The mixture was then stirred at 80 0C for 4 hours. After thorough washing, the material was calcined at 800 0C as above.
Example 4. Material testing
A material prepared as described in Example 1 was subjected to catalytic testing for the catalytic partial oxidation at 600°C by the following procedure:
The material (0.1 g material diluted with 0.4 g quartz) was placed in a tubular quartz reactor and heated to 600 0C under a continuous stream of 5 % O2 balanced with He. When reaching 6000C, the continuous gas stream was switched to He and a 6-way valve with a sample loop was used to send 10 pulses with 3 micromoles CH4 (10 % CH4 balanced with He) over the material with 30 minutes interval. After this series of 10 pulses, another 10 pulses, each with 1.5 micromoles O2 (10 % O2 balanced with He) was sent through the reactor.
The reactor effluent was monitored by an on-line Mass Spectrometer (MS), following masses (m/e) = 2, 4, 15, 17, 18, 28 and 44. The CH4 conversion and CO selectivity were calculated by integrating the intensities of the (m/e) = 15 and (m/e) = 28 peaks during each pulse.
The CO selectivity obtained during the 10 pulses is shown as a function of CH4 conversion in Figure 1. The CO selectivity was less than 10% during the full pulse . Kjuence.
Example 5. Material testing
A 'material prepared as described in Example 1 was subjected to catalytic testing for the catalytic partial oxidation at 600-800°C by the following procedure:
The material (0.1 g material diluted with 0.4 g quartz) was placed in a tubular quartz reactor and heated to 800 0C under a continuous stream of 5 % O2 balanced with He. When reaching 8000C, the continuous gas stream was switched to He and a 6-way valve with a sample loop was used to send 10 pulses with 3 micromoles CH4 (10 % CH4 balanced with He) over the material with 30 minutes interval. After this series of 10 pulses, another 10 pulses, each with 1.5 micromoles O2 (10 % O2 balanced with He) was sent through the reactor.
Subsequently, the sample was kept in a 5 % oxygen/He gas stream while the temperature was lowered to 700 0C. At this new temperature the same pulse sequence as above was repeated before lowering the temperature to 62O0C in 5% O2/He where the same pulse sequence was repeated once more. Finally, the temperature was lowered to 6000C under a continuous stream of 5 % O2 balanced with He, after which the pulse sequence was again repeated.
The reactor effluent was monitored by an on-line Mass Spectrometer (MS), following masses (m/e) = 2, 4, 15, 17, 18, 28 and 44. The CH4 conversion and CO selectivity were calculated by integrating the intensities of the (m/e) = 15 and (m/e) = 28 peaks during each pulse.
The methane conversion obtained during methane pulses at 800, 700, 620 and 6000C, respectively, are shown as functions of the pulse number in Figure 2. The methane conversion decreased with a decrease in reaction temperature, and with an increasing pulse number at each temperature.
The CO selectivity versus methane conversion obtained during methane pulses at each temperature is shown in Figure 3. During the initial pulses, the CO selectivity is most often inferior to that obtained during subsequent pulses, at a given temperature. For a given methane conversion, the CO selectivity is highest for temperatures below 7000C. This result is opposite to the expected temperature- selectivity relationship from thermodynamic considerations, and may suggest that the selectivity is governed by kinetics.
HRTEM images of the used material were similar to those obtained before testing, but may suggest that the larger Au particles had been smoothened during testing. Example 6. Material testing
A material prepared as described in Example 1 was subjected to catalytic testing for the catalytic partial oxidation at 600-800°C by using the procedure described in Example 5. During testing at 6000C, the methane pulses were contaminated by small amounts of molecular oxygen.
The CO selectivity obtained during the methane pulses for each test is shown as a function of CH4 conversion in Figure 1. The CO selectivity decreased with an increased oxygen content in the gas phase.
Example 7. Material testing
A material prepared as described in Example 1 was subjected to catalytic testing for the catalytic partial oxidation at 250-800°C by co-feeding a continuous flow of methane and molecular oxygen over the material, and using the following procedure:
The material (0.1 g material diluted by 0.4 g quartz) was inserted into a tubular quartz reactor and heated to 25O0C under a He flow. The gas flow was then switched to a CH4 : O2 : N2 : He = 2 : 1 : 2 : 20 flow. Under this atmosphere, the reactor was further heated to 8000C (10°C/min), then kept at 8000C for 2 hours and subsequently cooled to 25O0C (10°C/min). The reactor effluent was monitored by an on-line micro-Gas Chromatograph, following the quantities of CH4, He, N2, H2, CO, CO2 and higher hydrocarbons.
The reaction temperature and effluent concentration for each reactant and product are shown as functions of test duration in Figure 4. During heating, CH4 conversion into CO2 starts already at 5000C. CO and H2 production do not start until appx. 7000C. At 8000C, the CO and H2 production decrease with time on stream, suggesting that material deactivation takes place. During cooling, CO and H2 production stops at approximately 700 and 6000C, respectively, while CO2 production continues until the temperature has reached 35O0C. This test confirms that the presence of molecular oxygen in the gas phase is detrimental for reaction selectivity of catalytic partial oxidation over the 0.5 wt% Au / 35 wt% CeO2 / AI2O3 material at 6000C, as was already indicated during the pulse experiments in Example 6.
Example 8. Material testing A material prepared as described in Example 1 was subjected to catalytic testing for the dry reforming of methane to synthesis gas at 250-800°C by co-feeding a continuous flow of methane and CO2 over the material, and using the following procedure:
The material (0.1 g material diluted by 0.4 g quartz) was inserted into a tubular quartz reactor and heated to 25O0C under a He flow. The gas flow was then switched to a CH4 : CO2 : N2 : He = 2 : 2 : 2 : 20 flow. Under this atmosphere, the reactor was further heated to 8000C (10°C/min), then kept at 8000C for 2 hours and subsequently cooled to 25O0C (10°C/min). The reactor effluent was monitored by an on-line micro-Gas Chromatograph, following the quantities of CH4, He, N2, H2, CO, CO2 and higher hydrocarbons.
The reaction temperature and effluent concentration for each reactant and product are shown as functions of test duration in Figure 5. During heating, CH4 and CO2 conversion into CO and H2 does not start until approximately 7000C. Full conversion is not obtained even at the highest temperature (8000C). At 8000C, the CO and H2 production decrease with time on stream, suggesting that material deactivation takes place. During cooling, CO and H2 production stops at appx. 6500C. The results obtained may indicate that this material is not reforming active at the temperatures where the maximum selectivities to CO and H2 have been observed during pulse experiments in Example 5. They further suggest that the production of CO and H2 observed at T > 7000C in the cofeed experiment in Example 7 were obtained by methane reforming with CO2 and/or H2O.
Example 9. Material testing
A material prepared as described in Example 1 was subjected to catalytic testing for the water gas shift reaction at 250-800°C by co-feeding a continuous flow of H2 and CO2 over the material, and using the following procedure: The material (0.1 g material diluted by 0.4 g quartz) was inserted into a tubular quartz reactor and heated to 25O0C under a He flow. The gas flow was then switched to a H2 : CO2 : N2 : He = 2 : 2 : 2 : 20 flow. Under this atmosphere, the s reactor was further heated to 8000C (10°C/min), then kept at 8000C for 2 hours and subsequently cooled to 25O0C (10°C/min). The reactor effluent was monitored by an on-line micro-Gas Chromatograph, following the quantities of CH4, He, N2, H2, CO, CO2 and higher hydrocarbons.
I0 The reaction temperature and effluent concentration for each reactant and product are shown as functions of test duration in Figure 6. During heating, H2 and CO2 conversion into CO (and H2O, which was not monitored) starts at appx. 4000C. However, the conversion is still low at 6000C and not at equilibrium even at 8000C. The heating and cooling profile are similar. The results obtained in this test shows is that the 0.5 wt% Au / 35 wt% CeO2 / AI2O3 material is active for inter-conversion of gas phase products containing oxygen at the temperatures where the highest CO selectivity have been obtained during methane pulse experiments (Example 5). However, the reaction is quite slow.
20 Having described preferred embodiments of the invention it will be apparent to those skilled in the art that other embodiments incorporating the concepts may be used. These and other examples of the invention illustrated above are intended by way of example only and the actual scope of the invention is to be determined from the following claims.
2S

Claims

Claims
1. Material for partial oxidation of natural gas into synthesis gas in a one step 5 process, said material comprising at least one oxide component with lattice oxygen, wherein said material also comprises particles of at least one metal component deposited on said oxide component, said material having been calcined in at least one temperature interval and activated in a process of at least one step. 0
2. Material according to claim 1, wherein said oxide component contains at least one cation.
3. Material according to claim 1 , wherein said oxide component possess as crystal structure type chosen from one of the following types: fluorite, perovskite, Ruddelsden Popper or YBaCo4O7, said oxide component thereby possess reversible liberation and uptake of oxygen.
4. Material according to claim 1, wherein said particles comprise one oro several transition metals, alloys of transition metals or metal composites.
5. Material according to claim 4, wherein said transition metals are selected from the group 3-12 of the periodic system. 5
6. Material according to claim 5, wherein said transition metals more preferably are selected from the group 9-11 of the periodic system.
7. Material according to claim 6, wherein said transition metals most preferably are Au. 0
8. Material according to claim 1 , wherein the largest dimension of said particle is in the range of 2-200 nrti, 5-200 nm, 70-200 nm or 50-1 OOnm.
9. Material according to claim 1 , wherein the largest dimension of said particle is <70 nm.
10. Material according to claim 1 , wherein the largest dimension of said particle is < 2 nm.
11. Material according to claim 1 , wherein said material has been calcined in a temperature interval of 700-1100°C, preferably 800-1000°C, most preferably 850-9000C
12. Material according to claim 1, wherein said material has been activated in at least a one step process in a temperature interval of 780-950 0C.
13. Material according to claim 1 , wherein said material has been activated in at least a two step process in the temperature intervals of 780-950°C and 680-
750 0C.
14. Material according to claim 1 , wherein said material has been activated in at least a three step process in the temperature intervals of 780-950°C, 680-0 750 0C and 500-650 °C.
15. Process for conditioning a material for partial oxidation of natural gas, said material comprising at least one oxide component with lattice oxygen, said material also comprising particles of at least one metal component 5 deposited on said oxide component, said process comprising the following steps:
- calcination of said material in at least one temperature interval,
- activation of said calcined material in at least one step. o
16. Process according to claim 15, wherein said material is calcined in a temperature interval of from 700-11000C1 preferably 800-1000°C, most preferably 850-900°C.
17. Process according to claim 15, wherein said material is activated in at least a one step process in a temperature interval of 780-950 0C.
18. Process according to claim 15, wherein said material is activated in at least a two step process in the temperature intervals of 780-950 0C and 680-750
0C.
19. Process according to claim 15, wherein said material is activated in at least a three step process in the temperature intervals of 780-950 °C, 680-750 °C and 500-650 0C.
20. Process according to claim 15, wherein the temperature for partial oxidation of natural gas is below 800 °C, preferably below 7000C and most preferably 550 - 6500C.
PCT/NO2008/000352 2007-10-04 2008-10-03 Material and method for partial oxidation of natural gas WO2009045112A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20075030 2007-10-04
NO20075030A NO20075030L (en) 2007-10-04 2007-10-04 Material and process for partial oxidation of natural gas

Publications (1)

Publication Number Publication Date
WO2009045112A1 true WO2009045112A1 (en) 2009-04-09

Family

ID=40526414

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NO2008/000352 WO2009045112A1 (en) 2007-10-04 2008-10-03 Material and method for partial oxidation of natural gas

Country Status (2)

Country Link
NO (1) NO20075030L (en)
WO (1) WO2009045112A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104045057A (en) * 2014-06-20 2014-09-17 北京神雾环境能源科技集团股份有限公司 Process for directly producing sponge iron by catalytic partial oxidation of natural gas
EP2926904A1 (en) 2014-04-01 2015-10-07 Kemijski Institut Catalyst support, a methof for producing thereof, a catalyst comprising said support and the process for converting gas mixtures of methane and carbon dioxide into syngas using said catalyst

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001028678A1 (en) * 1999-10-18 2001-04-26 Conoco, Inc. Nickel-rhodium based catalysts and process for preparing synthesis gas
US20030096880A1 (en) * 2001-11-02 2003-05-22 Conoco Inc. Combustion deposited metal-metal oxide catalysts and process for producing synthesis gas
WO2003072490A1 (en) * 2002-02-22 2003-09-04 Conoco Inc. Oxidation catalyst and gaseous o2-free processes for production of synthesis gas
EP1419814A1 (en) * 2002-11-15 2004-05-19 L'AIR LIQUIDE, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Perovskite catalyst for the partial oxidation of natural gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001028678A1 (en) * 1999-10-18 2001-04-26 Conoco, Inc. Nickel-rhodium based catalysts and process for preparing synthesis gas
US20030096880A1 (en) * 2001-11-02 2003-05-22 Conoco Inc. Combustion deposited metal-metal oxide catalysts and process for producing synthesis gas
WO2003072490A1 (en) * 2002-02-22 2003-09-04 Conoco Inc. Oxidation catalyst and gaseous o2-free processes for production of synthesis gas
EP1419814A1 (en) * 2002-11-15 2004-05-19 L'AIR LIQUIDE, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Perovskite catalyst for the partial oxidation of natural gas

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BERRY D. A. ET AL.: "Role of lattice oxygen in the partial oxidation of methane over RH & PT/zirconium- doped ceria catalysts, mechanistic aspects", PREPRINTS/AMERICAN CHEMICAL SOCIETY DIVISION OF PETROLEUM CHEMISTRY, vol. 51, no. 2, 2006, pages 491 - 498, XP003024912 *
CENTENO M.A. ET AL.: "Catalytic combustion of volatile organic compounds on Au/Ce02/A1203 and Au/A1203 catalysts", APPLIED CATALYSIS A: GENERAL, vol. 234, 2002, pages 65 - 78, XP004370576 *
SADYKOV V. ET AL.: "Methane selective oxidation into syngas by the lattice oxygen in ceria-based solid electrolytes promoted by Pt", STUDIES IN SURFACE SCIENCE AND CATALYSIS, vol. 147, 2004, pages 241 - 246, XP003024913 *
SADYKOV V.A. ET AL.: "Cation/anion modified ceria- zirconia solid solutions promoted by Pt as catalyst of methane oxidaiton into syngas by water in reversible redox cycles", REACTION KINETICS AND CATALYSIS LETTERS, vol. 76, no. 1, 2002, pages 83 - 92, XP003024914 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2926904A1 (en) 2014-04-01 2015-10-07 Kemijski Institut Catalyst support, a methof for producing thereof, a catalyst comprising said support and the process for converting gas mixtures of methane and carbon dioxide into syngas using said catalyst
WO2015150503A1 (en) 2014-04-01 2015-10-08 Kemijski Institut Catalyst and the process for converting gas mixtures of methane and carbon dioxide into syngas
CN104045057A (en) * 2014-06-20 2014-09-17 北京神雾环境能源科技集团股份有限公司 Process for directly producing sponge iron by catalytic partial oxidation of natural gas

Also Published As

Publication number Publication date
NO20075030L (en) 2009-04-06

Similar Documents

Publication Publication Date Title
Dama et al. Active and durable alkaline earth metal substituted perovskite catalysts for dry reforming of methane
Sim et al. Catalytic behavior of ABO3 perovskites in the oxidative coupling of methane
Boukha et al. Behaviour of Rh supported on hydroxyapatite catalysts in partial oxidation and steam reforming of methane: on the role of the speciation of the Rh particles
Royer et al. Perovskites as substitutes of noble metals for heterogeneous catalysis: dream or reality
He et al. RE0. 6Zr0. 4− xYxO2 (RE= Ce, Pr; x= 0, 0.05) solid solutions: an investigation on defective structure, oxygen mobility, oxygen storage capacity, and redox properties
Ferri et al. Methane combustion on some perovskite-like mixed oxides
Ivanov et al. Effect of surface decoration with LaSrFeO4 on oxygen mobility and catalytic activity of La0. 4Sr0. 6FeO3− δ in high-temperature N2O decomposition, methane combustion and ammonia oxidation
Wang et al. Low temperature partial oxidation of methane via BaBi0. 05Co0. 8Nb0. 15O3− δ-Ni phyllosilicate catalytic hollow fiber membrane reactor
Touahra et al. Role of the nanoparticles of Cu-Co alloy derived from perovskite in dry reforming of methane
Wu et al. Stoichiometric and non-stoichiometric perovskite-based catalysts: Consequences on surface properties and on catalytic performances in the decomposition of N2O from nitric acid plants
Glisenti et al. Steam reforming and oxidative steam reforming of methanol and ethanol: The behaviour of LaCo0. 7Cu0. 3O3
Xiang et al. Catalytic combustion of methane on La1− xCexFeO3 oxides
Pantaleo et al. Synthesis and support composition effects on CH4 partial oxidation over Ni–CeLa oxides
JP2002509483A (en) Autothermal reactor including oxygen ion conductive dense ceramic membrane and method for producing synthesis gas using autothermal reactor
Wang et al. Study of carbon dioxide reforming of methane over Ni/yttria-doped ceria and effect of thermal treatments of support on the activity behaviors
Li et al. Investigations on the effect of Cu2+/Cu1+ redox couples and oxygen vacancies on photocatalytic activity of treated LaNi1− xCuxO3 (x= 0.1, 0.4, 0.5)
Hammami et al. Effects of thermal treatment on physico-chemical and catalytic properties of lanthanum manganite LaMnO3+ y
Rezlescu et al. Characterization and catalytic properties of some perovskites
Gómez et al. TAP study of toluene total oxidation over a Co 3 O 4/La-CeO 2 catalyst with an application as a washcoat of cordierite honeycomb monoliths
Weng et al. Hydrogen production from oxidative steam reforming of ethanol on nickel-substituted pyrochlore phase catalysts
Najjar et al. Effect of praseodymium and europium doping in La1− xLnxMnO3+ δ (Ln: Pr or Eu, 0≤ x≤ 1) perosvkite catalysts for total methane oxidation
RU2453366C1 (en) Catalyst and method of producing synthetic gas
Li et al. Synergistic effect for promoted benzene oxidation over monolithic CoMnAlO catalysts derived from in situ supported LDH film
WO2007148057A1 (en) Oxygen separation membrane
Kongzhai et al. Catalytic performance of cerium iron complex oxides for partial oxidation of methane to synthesis gas

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08835540

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08835540

Country of ref document: EP

Kind code of ref document: A1