Gas Technology Institute

Gti Energy

Jim Wangerow

Martin Brendan Linck

Terry L Marker

Pedro Ortiz-Toral

Dane Andrew Boysen

Naomi Klinghoffer

Terry Marker

Processes for converting methane and/or other hydrocarbons to synthesis gas (i.e., a gaseous mixture comprising Hand CO) are disclosed, in which at least a portion of the hydrocarbon(s) is reacted with CO. At least a second portion of the methane may be reacted with HO (steam), thereby improving overall thermodynamics of the process, in terms of reducing endothermicity (ΔH) and the required energy input, compared to 'pure' dry reforming in which no HO is present. Catalysts for such processes advantageously possess high activity and thereby can achieve significant levels of methane conversion at temperatures below those used conventionally under comparable conditions. These catalysts also exhibit high sulfur tolerance, in addition to reduced rates of carbon (coke) formation, even in the processing (reforming) of heavier (e.g., naphtha boiling-range or jet fuel boiling-range) hydrocarbons. The robustness of the catalyst translates to high operating stability. A representative catalyst comprises 1 wt-% Pt and 1 wt-% Rh as noble metals, on a cerium oxide support.

Noble metal catalysts and processes for reforming of methane and other hydrocarbons

Processes for converting methane and/or other hydrocarbons to synthesis gas (i.e., a gaseous mixture comprising Hand CO) are disclosed, in which at least a portion of the hydrocarbon(s) is reacted with CO. At least a second portion of the methane may be reacted with HO (steam), thereby improving overall thermodynamics of the process, in terms of reducing endothermicity (ΔH) and the required energy input, compared to 'pure' dry reforming in which no HO is present. Such dry reforming (reaction with COonly) or CO-steam reforming (reaction with both COand steam) processes are advantageously integrated with Fischer-Tropsch synthesis to yield liquid hydrocarbon fuels. Further integration may involve the use of a downstream finishing stage involving hydroisomerization to remove FT wax. Yet other integration options involve the use of combined CO-steam reforming and FT synthesis stages (optionally with finishing) for producing liquid fuels from gas streams generated in a number of possible processes, including the hydropyrolysis of biomass.

Processes and systems for reforming of methane and light hydrocarbons to liquid hydrocarbon fuels

Electrically heated reforming reactors and associated reforming processes are disclosed, which benefit from a number of advantages in terms of attaining and controlling the input of heat to catalytic conversion processes such as in the reforming of hydrocarbons (e.g., methane) using HO and/or COas an oxidant. The disclosed reactors provide the ability to target the input of heat to specific regions within a catalyst bed volume. This allows for the control of the temperature profile in one or more dimensions (e.g., axially and/or radially) and/or otherwise tailoring heat input for processing specific reformer feeds, achieving specific reformer products, effectively utilizing the catalyst, and/or compensating for a number of operating parameters (e.g., flow distribution). Dynamic control of the heat input may be used in response to changes in feed or product composition and/or catalyst activity.

Electrically heated reforming reactor for reforming of methane and other hydrocarbons

Processes and catalysts for producing hydrogen by reforming methane are disclosed, which afford considerable flexibility in terms of the quality of the reformer feed. This can be attributed to the robustness of the noble metal-containing catalysts described herein for use in reforming, such that a number of components commonly present in methane-containing process streams can advantageously be maintained without conventional upgrading (pretreating) steps, thereby improving process economics. This also allows for the reforming of impure reformer feeds, even in relatively small quantities, which may be characterized as complex gas mixtures due to significant quantities of non-methane components. A representative reforming catalyst comprises 1 wt-% Pt and 1 wt-% Rh as noble metals, on a cerium oxide support.

Processes and catalysts for reforming of impure methane-containing feeds

Process are disclosed for converting plastics, and especially thermoplastic oxygenated polymers, by hydrodeoxygenation (HDO) to hydrocarbons, such as aromatic hydrocarbons including benzene, toluene, ethylbenzene, and xylene isomers. These hydrocarbons may be recovered as chemicals and/or fuels, depending on the particular chemical structures of the starting materials, including the presence of oxygen in the polymer backbones. Advantageously, using a sufficiently active catalyst, only moderate conditions, such as in terms of hydrogen partial pressure, are required, in comparison to known hydrotreating processes. This leads to the formation, with fewer non-selective side reactions, of desired liquid hydrocarbons from substantially all carbon in the oxygenated polymer, as well as water from substantially all oxygen in the oxygenated polymer. In some cases, the liquid hydrocarbons obtained are platform chemicals that can be used for a number of specialized purposes. For example, they may be converted to monomers for regenerating the oxygenated polymer or otherwise for producing a different polymer.

Hydrodeoxygenation of oxygenated polymers to liquid hydrocarbons

Processes for converting methane and/or other hydrocarbons to synthesis gas (i.e., a gaseous mixture comprising Hand CO) are disclosed, in which at least a portion of the hydrocarbon(s) is reacted with CO. At least a second portion of the methane may be reacted with HO (steam), thereby improving overall thermodynamics of the process, in terms of reducing endothermicity (&#x394;H) and the required energy input, compared to 'pure' dry reforming in which no HO is present. Such dry reforming (reaction with COonly) or CO-steam reforming (reaction with both COand steam) processes are advantageously integrated with Fischer-Tropsch synthesis to yield liquid hydrocarbon fuels. Further integration may involve the use of a downstream finishing stage involving hydroisomerization to remove FT wax. Yet other integration options involve the use of combined CO-steam reforming and FT synthesis stages (optionally with finishing) for producing liquid fuels from gas streams generated in a number of possible processes, including the hydropyrolysis of biomass.

Processes and catalyst systems are disclosed for performing Fischer-Tropsch (FT) synthesis to produce Chydrocarbons, such as gasoline boiling-range hydrocarbons and/or diesel boiling-range hydrocarbons. Advantageously, catalyst systems described herein have additional activity (beyond FT activity) for in situ hydroisomerization and/or hydrocracking of wax that is generated according to the distribution of hydrocarbons obtained from the FT synthesis reaction. This not only improves the yield of hydrocarbons (e.g., Chydrocarbons) that are useful for transportation fuels, but also allows for alternative reactor types, such as a fluidized bed reactor.

Fluidized bed processes and catalyst systems for Fischer-Tropsch conversion

Processes for converting methane and/or other hydrocarbons to synthesis gas (i.e., a gaseous mixture comprising Hand CO) are disclosed, in which at least a portion of the hydrocarbon(s) is reacted with CO. At least a second portion of the methane may be reacted with HO (steam), thereby improving overall thermodynamics of the process, in terms of reducing endothermicity (&#x394;H) and the required energy input, compared to 'pure' dry reforming in which no HO is present. Catalysts for such processes advantageously possess high activity and thereby can achieve significant levels of methane conversion at temperatures below those used conventionally under comparable conditions. These catalysts also exhibit high sulfur tolerance, in addition to reduced rates of carbon (coke) formation, even in the processing (reforming) of heavier (e.g., naphtha boiling-range or jet fuel boiling-range) hydrocarbons. The robustness of the catalyst translates to high operating stability. A representative catalyst comprises 1 wt-% Pt and 1 wt-% Rh as noble metals, on a cerium oxide support.

Aspects of the invention are associated with the discovery of approaches for the conversion of sour natural gas streams, by conversion to liquid hydrocarbons. Particular processes and their associated apparatuses advantageously combine (i) dehydroaromatization (DHA) of methane in a gaseous feedstock, to produce aromatic hydrocarbons such as benzene, with (ii) the reaction of HS and methane in this feedstock, to produce organic sulfur compounds such as carbon disulfide (CS) and thiophene (CHS). A gaseous product having a reduced concentration of HS is thereby generated. The aromatic hydrocarbons and organic sulfur compounds may be recovered in a liquid product. Both the gaseous and liquid products may be easily amenable to further upgrading. Other advantages of the disclosed processes and apparatuses reside in their simplicity, whereby the associated streams, including a potential gaseous recycle, generally avoid high partial pressures of HS.

Production of liquids and reduced sulfur gaseous products from sour natural gas

Aspects of the invention are associated with the discovery of processes for converting methane (CH), present in a methane-containing feedstock that may be obtained from a variety of sources such as natural gas, to higher hydrocarbons (e.g., Chydrocarbons) such as gasoline, diesel fuel, or jet fuel boiling-range hydrocarbons, which may optionally be separated (e.g., by fractionation) for use as transportation fuels, or otherwise as blending components for such fuels. Particular aspects of the invention are associated with advantages arising from maintaining reaction conditions that improve the yield of Chydrocarbons. Further aspects relate to the advantages gained by integration of the appropriate reactions to carry out the methane conversion, with downstream separation to recover and recycle desirable components of the reaction effluent, thereby improving process economics to the extent needed for commercial viability.

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Oak Park, IL, United States of America

Jim Wangerow