WO2018234971A1 - Procédé amélioré de production de gaz de synthèse pour des applications pétrochimiques - Google Patents

Procédé amélioré de production de gaz de synthèse pour des applications pétrochimiques Download PDF

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Publication number
WO2018234971A1
WO2018234971A1 PCT/IB2018/054470 IB2018054470W WO2018234971A1 WO 2018234971 A1 WO2018234971 A1 WO 2018234971A1 IB 2018054470 W IB2018054470 W IB 2018054470W WO 2018234971 A1 WO2018234971 A1 WO 2018234971A1
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reactor
syngas
isothermal
ratio
reactant mixture
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PCT/IB2018/054470
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English (en)
Inventor
Sivadinarayana Chinta
Miasser AL-GHAMDI
Atul Pant
Rami EDREES
Marwan AL-AMAR
Saud AL-HAGBANI
Arwa RABIE
Aspi Kolah
Sulaiman BINKHAMIS
Sultan AL-TURKISTANI
Ravichander Narayanaswamy
Karam RAJAB
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Sabic Global Technologies, B.V.
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Publication of WO2018234971A1 publication Critical patent/WO2018234971A1/fr

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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
    • C01B3/32—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
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • 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
    • C01B2203/08—Methods of heating or cooling

Definitions

  • the present disclosure relates to methods of producing syngas, more specifically methods of producing syngas by catalytic partial oxidation of hydrocarbons, such as methane.
  • Synthesis gas is a mixture comprising carbon monoxide (CO) and hydrogen (H 2 ), as well as small amounts of carbon dioxide (C0 2 ), water (H 2 0), and unreacted methane (CH 4 ).
  • Syngas is generally used as an intermediate in the production of methanol and ammonia, as well as an intermediate in creating synthetic petroleum to use as a lubricant or fuel.
  • Syngas is produced conventionally by steam reforming of natural gas, although other hydrocarbon sources can be used for syngas production, such as refinery off-gases, naphtha feedstocks, heavy hydrocarbons, coal, biomass, etc.
  • the steam reforming is an endothermic process and requires a lot of energy input to drive the reaction forward. Further, the use of excess steam results in formation of excess hydrogen which is stoichiometrically more than what is required by a variety of processes that use syngas; such as methanol synthesis, or certain Fischer-Tropsch (FT) processes for the production of liquid hydrocarbons via a gas to liquid (GTL) process that does not employ C0 2 as a reactant.
  • syngas such as methanol synthesis, or certain Fischer-Tropsch (FT) processes for the production of liquid hydrocarbons via a gas to liquid (GTL) process that does not employ C0 2 as a reactant.
  • ATR autothermal reforming
  • a portion of the natural gas is burned as fuel to drive the conversion of natural gas to syngas with resulting in relatively low hydrogen and high C0 2 concentrations.
  • ATR could reduce the hydrogen content of the syngas, but the hydrogen content of the resulting syngas would still be more than what is required by a variety of processes that use syngas, such as methanol synthesis or certain FT processes.
  • the conventional 0 2 to C ratio used in autothermal reformers can lead to production of high amounts of C0 2 , significantly affecting the composition of the syngas.
  • Syngas can also be produced (non-commercially) by catalytic partial oxidation (CPO) of natural gas.
  • CPO process employ partial oxidation of hydrocarbon feeds to syngas comprising CO and H 2 .
  • the CPO process is exothermic, thus eliminating the need for external heat supply.
  • the composition of the produced syngas is not suitable for methanol synthesis, for example; and requires external hydrogen addition that generally involve further investments.
  • CPO reactors are operated in an adiabatic mode with no control of exit temperatures and hence no control of exit concentrations (e.g., no control of the composition of the produced syngas).
  • Syngas produced via conventional processes contains stoichiometrically excess hydrogen.
  • downstream operations that use syngas operate at elevated pressures. Higher energy is required to compress a hydrogen rich syngas stream.
  • Conventional syngas processes cannot produce a syngas having just stoichiometric amount of hydrogen required by the downstream processes, due to excess steam required to generate syngas in conventional processes. Consequently, hydrogen gas accumulates in recycle loops of downstream operation and/or is burned as fuel as part of the purge stream; resulting in lower energy efficiency and poor carbon efficiency of the conventional process.
  • syngas production processes that can control the composition of the produced syngas, as well as produce a syngas that could be suitable for downstream processes.
  • a process for producing syngas comprising reacting under non- adiabatic and near-isothermal conditions, via a catalytic partial oxidation (CPO) reaction, a reactant mixture in a reactor to produce syngas; wherein the reactant mixture comprises hydrocarbons and oxygen; wherein the reactor comprises a CPO catalyst; wherein the reactor is characterized by a contact time of from about 0.001 milliseconds (ms) to about 5 s; and wherein the syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons.
  • CPO catalytic partial oxidation
  • a process for producing syngas comprising reacting under non- adiabatic and near-isothermal conditions, via a catalytic partial oxidation (CPO) reaction, a reactant mixture in an isothermal reactor to produce syngas, wherein the reactant mixture comprises methane and oxygen, wherein the isothermal reactor comprises a CPO catalyst, wherein the reactor is characterized by a contact time of from about 0.001 milliseconds (ms) to about 1.2 ms, and wherein the syngas comprises hydrogen, carbon monoxide, water, carbon dioxide, and unreacted.
  • CPO catalytic partial oxidation
  • Figure 1 displays a graph of the variation of syngas composition with the reaction temperature under various process conditions; and [0012] Figure 2 displays a graph of heat exchange required for maintaining isothermal conditions at different temperatures under various process conditions.
  • a catalytic partial oxidation (CPO) reaction a reactant mixture in a reactor to produce syngas; wherein the reactant mixture comprises hydrocarbons and oxygen; wherein the reactor comprises a CPO catalyst; wherein the reactor is characterized by a contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s), or alternatively from about 0.001 ms to about 5 ms; and wherein the syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons.
  • the reactant mixture can further comprise a diluent, wherein the diluent contributes to the near-isothermal conditions via direct heat exchange. Indirect heat exchange can also be employed for providing the near-isothermal conditions.
  • the terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms include any measurable decrease or complete inhibition to achieve a desired result.
  • the term "effective,” means adequate to accomplish a desired, expected, or intended result.
  • the terms “comprising” (and any form of comprising, such as “comprise” and “comprises"), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “include” and “includes”) or “containing” (and any form of containing, such as “contain” and “contains”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • a process for producing syngas as disclosed herein can comprise reacting, under non-adiabatic and near-isothermal conditions, via a catalytic partial oxidation (CPO) reaction, a reactant mixture in a reactor to produce syngas, wherein the reactant mixture comprises hydrocarbons and oxygen.
  • CPO catalytic partial oxidation
  • CPO reaction is based on partial combustion of fuels, such as various hydrocarbons, and in the case of methane, CPO can be represented by equation (1):
  • the CPO reaction as depicted in equation (1) is an exothermic heterogeneous catalytic reaction (i.e., a mildly exothermic reaction) and it occurs in single reactor unit (as opposed to more than one reactor unit as is the case in conventional processes for syngas production, such as steam methane reforming (SMR) - autothermal reforming (ATR) combinations).
  • SMR steam methane reforming
  • ATR autothermal reforming
  • homogeneous partial oxidation of hydrocarbons process entails excessive temperatures, long residence times, as well as excessive coke formation, which strongly reduce the controllability of the partial oxidation reaction, and may not produce syngas of the desired quality in a single reactor unit.
  • the CPO reaction is fairly resistant to chemical poisoning, and as such it allows for the use of a wide variety of hydrocarbon feedstocks, including some sulfur containing hydrocarbon feedstocks; which, in some cases, can enhance catalyst life-time and productivity.
  • the hydrocarbons suitable for use in a CPO reaction as disclosed herein can include methane, natural gas, natural gas liquids, associated gas, well head gas, enriched gas, paraffins, shale gas, shale liquids, fluid catalytic cracking (FCC) off gas, refinery process gases, stack gases, and the like, or combinations thereof.
  • the hydrocarbons can include any suitable hydrocarbons source.
  • the reactant mixture can comprise CH 4 and 0 2 .
  • the oxygen used in the reactant mixture can comprise 100% oxygen (substantially pure 0 2 ), oxygen gas (which may be obtained via a membrane separation process), technical oxygen (which may contain some air), air, oxygen enriched air, oxygen-containing gaseous compounds (e.g., NO), oxygen-containing mixtures (e.g., 0 2 /C0 2 , 0 2 /H 2 0, O 2 /H 2 O 2 /H 2 O), oxy radical generators (e.g., CH 3 OH, CH 2 0), hydroxyl radical generators, and the like, or combinations thereof.
  • the reactant mixture can be characterized by a methane to oxygen (CH 4 /O 2 ) molar ratio of equal to or greater than about 1:1, alternatively equal to or greater than about 2:1, alternatively equal to or greater than about 3:1, alternatively from about 1 : 1 to about 3:1, alternatively from about 1.5:1 to about 2.5:1, or alternatively from about 1.6:1 to about 2.2:1.
  • CH 4 /O 2 methane to oxygen
  • the CH 4 /O 2 molar ratio can be adjusted along with other reactor process parameters (e.g., temperature, pressure, flow velocity, etc.) to provide for near-isothermal conditions, as well as a syngas with a desired composition (e.g., a syngas with a desired hydrogen to carbon monoxide (H 2 /CO) molar ratio).
  • a syngas with a desired composition e.g., a syngas with a desired hydrogen to carbon monoxide (H 2 /CO) molar ratio.
  • the CH4/O2 molar ratio can also vary with the addition of a diluent to the reactant mixture (e.g., water addition to the reactant mixture, C0 2 , addition to the reactant mixture, etc.).
  • the reactant mixture can further comprise a diluent, wherein the diluent contributes to the near-isothermal conditions via direct heat exchange, as disclosed herein.
  • the diluent can comprise water, steam, inert gases (e.g., argon), nitrogen, carbon dioxide, and the like, or combinations thereof.
  • the diluent is inert with respect to the CPO reaction, e.g., the diluent does not participate in the CPO reaction.
  • some diluents e.g., water, steam, carbon dioxide, etc.
  • some diluents might undergo chemical reactions other than the CPO reaction within the reactor, and can change the composition of the resulting syngas
  • other diluents e.g., nitrogen (N 2 ), argon (Ar)
  • the diluent can be used to vary the composition of the resulting syngas.
  • the diluent can be present in the reactant mixture in any suitable amount.
  • a diluent comprising water and/or steam can increase a hydrogen content of the resulting syngas.
  • the syngas can be characterized by a hydrogen to carbon monoxide molar ratio that is increased when compared to a hydrogen to carbon monoxide molar ratio of a syngas produced by an otherwise similar process conducted with a reactant mixture comprising hydrocarbons and oxygen without the water and/or steam diluent.
  • water and/or steam diluent can react with coke inside the reactor and generate additional CO and H 2 .
  • the steam that is introduced to the reactor for use as a diluent in a CPO reaction as disclosed herein is in significantly smaller amounts than the amounts of steam utilized in steam reforming processes, and as such, a process for producing syngas as disclosed herein can yield a syngas with lower amounts of hydrogen when compared to the amounts of hydrogen in a syngas produced by steam reforming.
  • a diluent comprising carbon dioxide can increase a carbon monoxide content of the resulting syngas.
  • the syngas can be characterized by a hydrogen to carbon monoxide molar ratio that is decreased when compared to a hydrogen to carbon monoxide molar ratio of a syngas produced by an otherwise similar process conducted with a reactant mixture comprising hydrocarbons and oxygen without the carbon dioxide diluent.
  • carbon dioxide can react with coke inside the reactor and generate additional CO.
  • carbon dioxide can participate in a dry reforming of methane reaction, thereby generating additional CO and H 2 . Dry reforming of methane is generally accompanied by a reaction between carbon dioxide and hydrogen which results in the formation of additional CO and water.
  • the CPO reaction is an exothermic reaction (e.g., heterogeneous catalytic reaction; exothermic heterogeneous catalytic reaction) that is generally conducted in the presence of a CPO catalyst comprising a catalytically active metal, i.e., a metal active for catalyzing the CPO reaction.
  • a CPO catalyst comprising a catalytically active metal, i.e., a metal active for catalyzing the CPO reaction.
  • the catalytically active metal can comprise a noble metal (e.g., Pt, Rh, Ir, Pd, Ru, Ag, and the like, or combinations thereof); a non-noble metal (e.g., Ni, Co, V, Mo, P, Fe, Cu, and the like, or combinations thereof); rare earth elements (e.g., La, Ce, Nd, Eu, and the like, or combinations thereof); oxides thereof; and the like; or combinations thereof.
  • a noble metal is a metal that resists corrosion and oxidation in a water-containing environment.
  • the components of the CPO catalyst e.g., metals such as noble metals, non-noble metals, etc., rare earth elements, can be either phase segregated or combined within the same phase.
  • the CPO catalysts suitable for use in the present disclosure can be supported catalysts and/or unsupported catalysts.
  • the supported catalysts can comprise a support, wherein the support can be catalytically active (e.g., the support can catalyze a CPO reaction).
  • the catalytically active support can comprise a metal gauze or wire mesh (e.g., Pt gauze or wire mesh); a catalytically active metal monolithic catalyst; etc.
  • the supported catalysts can comprise a support, wherein the support can be catalytically inactive (e.g., the support cannot catalyze a CPO reaction), such as Si0 2 ; alumina; a catalytically inactive monolithic support; etc.
  • the supported catalysts can comprise a catalytically active support and a catalytically inactive support.
  • a CPO catalyst can be wash coated onto a support, wherein the support can be catalytically active or inactive, and wherein the support can be a monolith, a foam, an irregular catalyst particle, etc.
  • the CPO catalyst can be a monolith, a foam, a powder, a particle, etc.
  • CPO catalyst particle shapes suitable for use in the present disclosure include cylindrical, discoidal, spherical, tabular, ellipsoidal, equant, irregular, cubic, acicular, and the like, or combinations thereof.
  • the support comprises an inorganic oxide, alpha, beta or theta alumina (AI 2 O 3 ), activated AI 2 O 3 , silicon dioxide (Si0 2 ), titanium dioxide (Ti0 2 ), magnesium oxide (MgO), zirconium oxide (Zr0 2 ), lanthanum (III) oxide (La 2 0 3 ), yttrium (III) oxide (Y 2 0 3 ), cerium (IV) oxide (Ce0 2 ), zeolites, ZSM-5, perovskite oxides, hydrotalcite oxides, and the like, or combinations thereof.
  • AI 2 O 3 inorganic oxide, alpha, beta or theta alumina
  • activated AI 2 O 3 silicon dioxide
  • Si0 2 silicon dioxide
  • Ti0 2 titanium dioxide
  • MgO magnesium oxide
  • Zr0 2 zirconium oxide
  • Zr0 2 zirconium oxide
  • lanthanum oxide III
  • La 2 0 3 yttrium oxide
  • Y 2 0 3
  • a process for producing syngas as disclosed herein can comprise conducting a CPO reaction under non-adiabatic and near-isothermal conditions to produce syngas.
  • non-adiabatic conditions refers to process conditions wherein a reactor is subjected to external heat exchange or transfer (e.g., the reactor is heated; or the reactor is cooled), which can be direct heat exchange and/or indirect heat exchange.
  • adiabatic conditions refers to process conditions wherein a reactor is not subjected to external heat exchange (e.g., the reactor is not heated; or the reactor is not cooled).
  • external heat exchange implies an external heat exchange system (e.g., a cooling system; a heating system) that requires energy input and/or output.
  • isothermal conditions generally refer to process conditions wherein the reactor has a substantially constant temperature that can be defined as a temperature that varies by less than about + 10 °C, alternatively less than about + 9 °C, alternatively less than about + 8 °C, alternatively less than about + 7 °C, alternatively less than about + 6 °C, alternatively less than about + 5 °C, alternatively less than about + 4 °C, alternatively less than about + 3 °C, alternatively less than about + 2 °C, or alternatively less than about + 1 °C.
  • the term "near-isothermal conditions" refers to process conditions that allow for a fairly constant temperature of the reactor, which can be defined as a temperature that varies by less than about + 100 °C, alternatively less than about + 90 °C, alternatively less than about + 80 °C, alternatively less than about + 70 °C, alternatively less than about + 60 °C, alternatively less than about + 50 °C, alternatively less than about + 40 °C, alternatively less than about + 30 °C, alternatively less than about + 20 °C, alternatively less than about + 10 °C, alternatively less than about + 9 °C, alternatively less than about + 8 °C, alternatively less than about + 7 °C, alternatively less than about + 6 °C, alternatively less than about + 5 °C, alternatively less than about + 4 °C, alternatively less than about + 3 °C, alternatively less than about + 2 °C, or alternatively less than about +
  • near-isothermal conditions is understood to include “isothermal” conditions.
  • near- isothermal conditions allow for a temperature variation (e.g., a temperature variation within the reactor; a temperature variation within a catalyst bed) of less than about + 50 °C, alternatively less than about + 25 °C, or alternatively less than about + 10 °C.
  • the term “near-isothermal conditions” refers to process conditions, such as a reactor temperature, effective for achieving a desired composition of the syngas (e.g., a desired hydrogen to carbon monoxide ratio; a desired M ratio, wherein the M ratio is a molar ratio defined as (H 2 -C0 2 )/(CO+C0 2 ); etc.), for a given set of operating conditions (e.g., pressure, CH 4 /O 2 molar ratio, etc.).
  • a desired composition of the syngas e.g., a desired hydrogen to carbon monoxide ratio; a desired M ratio, wherein the M ratio is a molar ratio defined as (H 2 -C0 2 )/(CO+C0 2 ); etc.
  • a desired composition of the syngas e.g., a desired hydrogen to carbon monoxide ratio; a desired M ratio, wherein the M ratio is a molar ratio defined as (H 2 -C0 2 )/(CO+
  • a near-isothermal temperature refers to the temperature effective for producing a syngas that is characterized by a hydrogen to carbon monoxide molar ratio that varies by less than about 20%, alternatively less than about 15%, alternatively less than about 10%, or alternatively less than about 5%.
  • a near-isothermal temperature refers to the temperature effective for producing a syngas that is characterized by an M ratio that varies by less than about 20%, alternatively less than about 15%, alternatively less than about 10%, or alternatively less than about 5%; wherein the M ratio is a molar ratio defined as (H 2 - C0 2 )/(CO+C0 2 ).
  • a near-isothermal temperature range effective for producing a syngas that is characterized by a hydrogen to carbon monoxide molar ratio that varies by less than about 20% is more narrow than at higher operating temperatures (e.g., from about 800 °C to about 1,600 °C).
  • a near-isothermal temperature range effective for producing a syngas that is characterized by a hydrogen to carbon monoxide molar ratio x that varies by less than about 20% can be an isothermal temperature that varies within about + 20 °C; while at higher operating temperatures a near-isothermal temperature range effective for producing a syngas that is characterized by the same hydrogen to carbon monoxide molar ratio x that varies by less than about 20% can be an isothermal temperature that varies within about + 100 °C.
  • a near-isothermal temperature range effective for producing a syngas that is characterized by an M ratio that varies by less than about 20% is more narrow than at higher operating temperatures (e.g., from about 800 °C to about 1,600 °C).
  • a near-isothermal temperature range effective for producing a syngas that is characterized by an M ratio y that varies by less than about 10% can be an isothermal temperature that varies within about + 25 °C; while at higher operating temperatures a near-isothermal temperature range effective for producing a syngas that is characterized by the same M ratio y that varies by less than about 10% can be an isothermal temperature that varies within about + 80 °C.
  • Near-isothermal conditions can be provided by a variety of process and catalyst variables, such as temperature (e.g., heat exchange), pressure, gas flow rates, reactor configuration, catalyst bed configuration, catalyst bed composition, reactor cross sectional area, feed gas staging, feed gas injection, feed gas composition, and the like, or combinations thereof.
  • a reactor suitable for use in the present disclosure can comprise a tubular reactor, a continuous flow reactor, an isothermal reactor, a fixed bed reactor, a fluidized bed reactor, a bubbling bed reactor, a circulating bed reactor, an ebullating bed reactor, a rotary kiln reactor, and the like, or combinations thereof.
  • the term "near-isothermal reaction temperature" can be defined as a temperature that varies by less than about + 100 °C, alternatively less than about + 90 °C, alternatively less than about + 80 °C, alternatively less than about + 70 °C, alternatively less than about + 60 °C, alternatively less than about + 50 °C, alternatively less than about + 40 °C, alternatively less than about + 30 °C, alternatively less than about + 20 °C, alternatively less than about + 10 °C, alternatively less than about + 9 °C, alternatively less than about + 8 °C, alternatively less than about + 7 °C, alternatively less than about + 6 °C, alternatively less than about + 5 °C, alternatively less than about + 4 °C, alternatively less than about + 3 °C, alternatively less than about + 2 °C, or alternatively less than about + 1 °C.
  • the near-isothermal reaction temperature can vary by less than about + 100 °C, alternative
  • the reactor can be characterized by a near-isothermal temperature of from about 300 °C to about 1,600 °C, alternatively from about 600 °C to about 1,200 °C, or alternatively from about 700 °C to about 1,100 °C.
  • the reactor can be characterized by a near-isothermal temperature of from about 300 °C to about 1,200 °C, alternatively from about 400 °C to about 1,100 °C, or alternatively from about 500 °C to about 1,000 °C; wherein the near-isothermal conditions can be provided by removal of process heat from the reactor.
  • a near-isothermal temperature of from about 300 °C to about 1,200 °C, alternatively from about 400 °C to about 1,100 °C, or alternatively from about 500 °C to about 1,000 °C; wherein the near-isothermal conditions can be provided by removal of process heat from the reactor.
  • near-isothermal conditions can be provided by removal of process heat from the reactor.
  • near-isothermal conditions e.g., near- isothermal temperature.
  • the reactor can be characterized by a near-isothermal temperature of from about 800 °C to about 1,600 °C, alternatively from about 850 °C to about 1,400 °C, or alternatively from about 900 °C to about 1,200 °C; wherein the near-isothermal conditions can be provided by supplying heat to the reactor.
  • a near-isothermal temperature of from about 800 °C to about 1,600 °C, alternatively from about 850 °C to about 1,400 °C, or alternatively from about 900 °C to about 1,200 °C; wherein the near-isothermal conditions can be provided by supplying heat to the reactor.
  • the process e.g., heat the reactor
  • the reactor can be characterized by a pressure of from about 0.1 barg to about 90 barg, alternatively from about 0.1 barg to about 40 barg, or alternatively from about 1 barg to about 25 barg.
  • the catalyst bed can comprise a bed inlet, a bed outlet, a first intermediate bed zone, a second intermediate bed zone, and optionally a third intermediate bed zone; wherein the first intermediate bed zone and the second intermediate bed zone are disposed between the bed inlet and the bed outlet; wherein the second intermediate bed zone is downflow of the first intermediate bed zone; wherein the third intermediate bed zone is disposed between the first intermediate bed zone and the second intermediate bed zone; wherein the third intermediate bed zone is downflow of the first intermediate bed zone; wherein the third intermediate bed zone is upflow of the second intermediate bed zone; wherein a reactor inner wall surface and an outer surface of the first intermediate bed zone define a first annular space; wherein a reactor inner wall surface and an outer surface of the second intermediate bed zone define a second annular space; wherein the bed inlet is characterized by a bed inlet surface area; wherein the bed outlet is characterized by a bed outlet surface area; wherein the first intermediate bed zone is characterized by a first intermediate bed cross sectional area;
  • the first annular space, the second annular space, or both can comprise a radiation shield; and/or one or more structural elements that are configured to provide for a catalyst bed configuration that is characterized by a non-uniform cross section along the catalyst bed.
  • the catalyst bed can comprise a structured catalyst that provides for a catalyst bed configuration that is characterized by a non-uniform cross section along the catalyst bed; and wherein the structured catalyst comprises a metallic monolithic catalyst, a non-metallic monolithic catalyst, or both.
  • catalyst bed shapes suitable for use in the present disclosure include a spherical shape; a prolate spheroidal shape; an oblate spheroidal shape; etc.
  • the syngas produced under non-adiabatic and near-isothermal conditions as disclosed herein can comprise hydrogen, carbon monoxide, water, carbon dioxide, and unreacted hydrocarbons.
  • the syngas can be used in a downstream process as recovered from the reactor (e.g., "as is;" without further processing).
  • the syngas can be further processed prior to being used in a downstream process.
  • unreacted hydrocarbons, diluent, water, etc. can be recovered from the syngas prior to using the syngas in a downstream process.
  • water can be condensed and separated from the syngas, for example in a cooling tower.
  • a process for producing syngas as disclosed herein can further comprise (i) recovering at least a portion of the unreacted hydrocarbons from the syngas to yield recovered hydrocarbons, and (ii) recycling at least a portion of the recovered hydrocarbons to the reactor.
  • the unconverted hydrocarbons could be recovered and recycled back to the reactor.
  • the syngas can be characterized by an M ratio that varies by less than about 20%, alternatively less than about 15%, alternatively less than about 10%, or alternatively less than about 5%, (as compared to a desired M ratio) under near-isothermal operating conditions for a set reactor operating conditions, such as pressure and CH 4 /0 2 molar ratio.
  • Syngas recovered from the reactor can be used for any suitable purpose, such as methanol production, olefins production, aromatics production, liquid hydrocarbons production, liquid hydrocarbons production via a gas to liquids (GTL) process, liquid hydrocarbons production via a Fischer-Tropsch (FT) process, dimethyl ether (DME) production, oxo-synthesis of aliphatic aldehydes and/or alcohols, petrochemicals, and the like, or combinations thereof.
  • GTL gas to liquids
  • FT Fischer-Tropsch
  • DME dimethyl ether
  • each process that uses syngas for the synthesis of a particular product may benefit from using a syngas with a specific composition (e.g., specific M ratio; specific H 2 /CO molar ratio; etc.).
  • a syngas with a specific composition
  • the syngas is characterized by an M ratio of from about 1.6 to about 2.2, alternatively from about 1.9 to about 2.2, or alternatively about 2.0
  • the syngas can be further used for methanol production.
  • at least a portion of the syngas recovered from the reactor can be contacted with a methanol production catalyst in a methanol production unit to produce methanol.
  • the methanol production unit can comprise any reactor suitable for a methanol synthesis reaction from CO and H 2 , such as for example an isothermal reactor, an adiabatic reactor, a trickle bed reactor, a fluidized bed reactor, a slurry reactor, a loop reactor, a cooled multi tubular reactor, and the like, or combinations thereof.
  • a reactor suitable for a methanol synthesis reaction from CO and H 2 such as for example an isothermal reactor, an adiabatic reactor, a trickle bed reactor, a fluidized bed reactor, a slurry reactor, a loop reactor, a cooled multi tubular reactor, and the like, or combinations thereof.
  • Methanol synthesis from CO, C0 2 and H 2 is a catalytic process, and is most often conducted in the presence of copper based catalysts.
  • the methanol production unit can comprise a methanol production catalyst, such as any suitable commercial catalyst used for methanol synthesis.
  • the syngas recovered from the reactor can be characterized by a H 2 /CO molar ratio of about 1 :1, wherein at least a portion of the syngas can be used for oxo-synthesis of aliphatic aldehydes and/or alcohols.
  • the alcohol can comprise 2-ethyl hexanol.
  • the syngas recovered from the reactor can be further converted to olefins.
  • the syngas can be converted to alkanes by using a Fisher-Tropsch process, and the alkanes can be further converted by dehydrogenation into olefins.
  • the syngas recovered from the reactor can be further converted to liquid hydrocarbons (e.g., alkanes) by a Fisher-Tropsch process.
  • the liquid hydrocarbons can be further converted by dehydrogenation into olefins.
  • a process for producing syngas as disclosed herein can comprise reacting under non-adiabatic and near-isothermal conditions, via a MSR-CPO reaction, a reactant mixture in an isothermal reactor to produce syngas; wherein the isothermal reactor comprises a fixed CPO catalyst bed; wherein the reactant mixture comprises methane and oxygen; wherein the reactant mixture is characterized by a methane to oxygen (CH 4 /O 2 ) molar ratio of from about 1.6:1 to about 2.2:1; wherein the reactor is characterized by a near-isothermal temperature of from about 600 °C to about 1,200 °C; wherein the reactor is characterized by a pressure of from about 0.1 barg to about 40 barg; wherein the reactor is characterized by a short contact time of from about 0.001 ms to about 1.2 ms; wherein the syngas comprises hydrogen, carbon monoxide, water, carbon dioxide, and unconverted hydrocarbons; and wherein the syngas is
  • a process for producing syngas as disclosed herein can comprise selecting a set of process conditions for producing syngas; wherein the syngas comprises hydrogen, carbon monoxide, water, carbon dioxide, and unconverted hydrocarbon; and wherein the syngas is characterized by an M ratio ((H 2 -C0 2 )/(CO+CC> 2 )) that varies by less than about 20% from a targeted or desired M ratio under the near-isothermal conditions for a given set of isothermal reactor operating conditions.
  • selecting the set of process conditions for producing syngas can comprise: (a) constructing a first two-coordinate graph containing a vertical axis for M ratio (syngas composition) and a horizontal axis for reactor temperature; (b) generating, via mathematical simulations and/or experimental data, one or more M ratio versus reactor temperature (M-T) data curves, wherein each M-T data curve of the one or more M-T data curves corresponds to a given set of pressure (reactor pressure) and CH 4 /O 2 molar ratio values; (c) representing the one or more M-T data curves upon the first two-coordinate graph; (d) identifying a desired M ratio value, based on a downstream process intending to utilize the produced syngas; and (e) for each M-T data curve, with the help of the first two-coordinate graph, determining one or more reactor temperatures corresponding to the desired M ratio value.
  • M-T M ratio versus reactor temperature
  • Selecting the set of process conditions for producing syngas can further comprise (i) constructing a second two-coordinate graph containing a vertical axis for heat transfer necessary for maintaining a particular reactor temperature (e.g., near-isothermal temperature), and a horizontal axis for reactor temperature; (ii) generating, via mathematical simulations and/or experimental data, one or more heat versus reactor temperature (Q-T) data curves, wherein each Q-T data curve of the one or more Q-T data curves corresponds to a given set of pressure (reactor pressure) and CH 4 /O 2 molar ratio values; (iii) representing the one or more Q-T data curves upon the second two-coordinate graph; and (iv) for each temperature or temperature range corresponding to the desired M ratio value determined by using the first two-coordinate graph, determining the heat transfer necessary for maintaining near-isothermal conditions within the reactor.
  • a particular reactor temperature e.g., near-isothermal temperature
  • Q-T heat versus reactor temperature
  • first two-coordinate graph e.g., Figure 1
  • second two-coordinate graph e.g., Figure 2
  • the near-isothermal temperatures and the heat transfer values necessary to maintain the near-isothermal temperatures are known (e.g., from the first two -coordinate graph, the second two-coordinate graph)
  • a variety of other considerations can be applied by one of skill in the art, and with the help of this disclosure, to select the set of process conditions for producing syngas, wherein an optimum operating window of process conditions can be established based on the feedstock quality and availability, the metallurgy of the reactor and associated piping and equipment, energy utilization, needs of downstream process utilizing the produced syngas, etc.
  • a process for producing syngas as disclosed herein can advantageously display improvements in one or more process characteristics when compared to an otherwise similar process that does not employ non-adiabatic and near-isothermal process conditions for producing syngas.
  • the process for producing syngas as disclosed herein can advantageously yield syngas of different desired qualities (e.g., syngas with specific H 2 /CO molar ratios, with specific M ratios, with or without C0 2 , etc.); by employing specific combinations of process and catalyst variables, such as temperature (e.g., near-isothermal temperature), pressure, CH 4 /O 2 molar ratio, gas flow, reactor configuration, catalyst bed configuration, and the like, or combinations thereof.
  • the process for producing syngas as disclosed herein can advantageously reduce operating costs by producing syngas having a stoichiometric amount of hydrogen to CO required by downstream processes.
  • syngas e.g., the syngas composition
  • the quality of syngas can have an important impact on the process gas flows, as well as product selectivity.
  • the syngas composition used for producing methanol can change a composition of the crude methanol recovered from a methanol production reactor (e.g., a loop reactor), wherein the crude methanol can be rich in methanol (as opposed to rich in water); thereby advantageously changing the process downstream of the methanol production reactor, owing to reduced recycle streams (due to having only the necessary amount of hydrogen in the syngas), as well as to a reduced amount water in the crude methanol product.
  • the methanol production process can advantageously be more energy efficient; owing to a lower energy consumption in a methanol purification section, for example by elimination of one or more distillation columns.
  • a process for producing syngas as disclosed herein can advantageously employ near-isothermal conditions.
  • water and/or steam diluent e.g., the steam can be wet, dry, saturated, superheated, etc.
  • the reactor can capture or augment process heat in order to target a near-isothermal temperature, which near-isothermal temperature enables the production of a syngas with a desired composition.
  • Conventional processes catalytic or thermal partial oxidation processes
  • the addition of steam of different qualities can enable temperature control.
  • superheated steam can enhance (e.g., augment) the heating, and hence it can be useful in a case where heat has to be added for achieving and/or maintaining near-isothermal conditions.
  • water or wet steam can allow heat removal, which can be useful in a case where heat has to be removed for achieving and/or maintaining near-isothermal conditions.
  • a process for producing syngas as disclosed herein can advantageously employ carbon dioxide diluent.
  • the use of carbon dioxide diluent can advantageously lead to a decreased amount of coke, thus decreasing catalyst deactivation (e.g., maintaining the catalyst in an active state).
  • the use of carbon dioxide diluent can advantageously allow for producing a syngas with an increased carbon monoxide amount, as required by a downstream process.
  • carbon dioxide emissions can advantageously be reduced.
  • a process for producing syngas as disclosed herein can advantageously employ short contact times, such as the millisecond regime (MSR), which increases selectivity to a syngas having a desired composition (e.g., syngas with specific H 2 /CO molar ratios, with specific M ratios, with or without C0 2 , etc.).
  • MSR millisecond regime
  • a syngas reactor can advantageously minimize side reactions, such as complete combustion, that could result in a decrease in selectivity to desired syngas components. Additional advantages of the processes for the production of syngas as disclosed herein can be apparent to one of skill in the art viewing this disclosure.
  • Syngas composition was investigated as a function of temperature for a catalytic partial oxidation (CPO) reaction under various process conditions.
  • the syngas composition was calculated by using a mathematical model of the CPO reactor, and the resulting data are displayed in Figure 1.
  • the mathematical model was developed in Aspen Plus software.
  • the reactor was represented by a Gibbs reactor which approaches equilibrium composition for a given set of process conditions.
  • the feed composition and reactor operating parameters were varied to obtain the change in exit stream composition.
  • the exit stream composition was used to calculate the M ratio value.
  • the y axis in Figure 1 plots M ratio values, wherein the M ratio is a molar ratio defined as (H 2 -C0 2 )/(CO+C0 2 ).
  • the heat (Q) transfer necessary for maintaining isothermal conditions was estimated by using the heat load predicted by the model described above, and the resulting data are displayed in Figure 2.
  • Negative Q values represent the amount of heat that has to be removed from the reactor (reacting system), for example by cooling the reactor, to maintain a particular temperature (near-isothermal temperature).
  • Positive Q values represent the amount of heat that has to be introduced to the reactor (reacting system), for example by heating the reactor, to maintain a particular temperature (near-isothermal temperature).
  • a value of 0 (zero) for Q signifies that no heat transfer is necessary for achieving the particular corresponding temperature (near-isothermal temperature) under the given process conditions.
  • FIG. 1 and 2 provide an example of how to select a temperature (e.g., near-isothermal temperature) for the production of a syngas with a desired composition (e.g., with a specific M ratio).
  • a temperature e.g., near-isothermal temperature
  • a desired composition e.g., with a specific M ratio.
  • the concepts herein can be carried out by using mathematical or computational simulations to generate graphs of syngas composition variation with reactor temperature, under given process conditions, such as pressure and CH 4 /O 2 molar ratio.
  • the graphs of syngas composition variation with reactor temperature could plot the M ratio versus the reactor temperature, in a similar fashion to Figure 1.
  • the graphs of syngas composition variation with reactor temperature could plot the H 2 /CO molar ratio versus the reactor temperature. Similar graphs can be generated for any feedstock of interest with any oxidant of interest. An optimum operating window of process conditions could be established based on the feedstock quality and availability, the metallurgy of the reactor and associated piping and equipment, energy utilization, needs of downstream process utilizing the produced syngas, etc.; and then graphs of syngas composition variation with reactor temperature could allow for selecting specific process operating conditions that would enable maintaining near-isothermal temperatures for the production of a syngas with a specific desired composition.
  • option (1) has a steeper curve (e.g., greater slope) going through the data point corresponding to an M ratio of 1.7 and 830 °C, indicating that a variation in temperature around the value of 830 °C will cause a larger deviation from a target M ratio value (e.g., M ratio of 1.7) of the resulting syngas when operating under near-isothermal conditions around the value of 830 °C; when compared to option (3) which has a less steep curve (e.g., smaller slope) going through the data point corresponding to an M ratio of 1.7 and 1,100 °C, indicating that a variation in temperature around the value of 1,100 °C will cause a smaller deviation from a target M ratio value (e.g., M ratio of 1.7) of the resulting syngas when operating under near-isothermal conditions around the value of 1,100
  • option (1) has a steeper curve (e.g., greater slope) going through the data point corresponding to an M ratio of 2.0 and 700 °C, indicating that a variation in temperature around the value of 700 °C will cause a larger deviation from a target M ratio value (e.g., M ratio of 2.0) of the resulting syngas when operating under near- isothermal conditions around the value of 700 °C; when compared to option (2) which has a less steep curve (e.g., smaller slope) going through the data point corresponding to an M ratio of 2.0 and 1 ,070 °C, indicating that a deviation from isothermal temperature around the value of 1 ,070 °C will cause a smaller deviation from a target M ratio value (e.g., M ratio of 2.0) of the resulting syngas when operating under near-isothermal conditions around the value of 1,070 °C.
  • a target M ratio value e.g., M ratio of 2.0
  • the data provided in Figure 2 can be used for considering the magnitude of the heat transfer required for maintaining the reactor at a given temperature (near- isothermal temperature) given a particular set of process parameters. For example, option (1) requires more heat transfer in terms of cooling to maintain 700 °C than option (2) requires as heat transfer in terms of heating for maintaining 1,070 °C.
  • Option (1) displays a slope of about 0 (zero) over a fairly wide temperature range (about 740 °C to about 1,000 °C), corresponding to an M ratio of 2.1, indicating that a temperature variation within the range of from about 740 °C to about 1,000 °C would not alter the M ratio.
  • Option (2) displays a slope of about 0 (zero) over a more narrow temperature range (about 1,275 °C to about 1,325 °C), when compared to option (1), corresponding to an M ratio of 2.1, indicating that a temperature variation within the range of from about 1,275 °C to about 1,325 °C would not alter the M ratio.
  • the data provided in Figure 2 (corresponding to the data in Figure 1) can be used for considering the magnitude of the heat transfer required for maintaining the reactor at a given temperature (near-isothermal temperature) given a particular set of process parameters.
  • a fourth aspect which is the process of the third aspect, wherein the indirect heat exchange comprises external heat exchange, external coolant fluid cooling, reactive cooling, liquid nitrogen cooling, cryogenic cooling, electric heating, electric arc heating, microwave heating, radiant heating, natural gas combustion, solar heating, infrared heating, or combinations thereof.
  • a fifth aspect which is the process of any one of the first through the fourth aspects, wherein the reactant mixture further comprises a diluent, and wherein the diluent contributes to the near-isothermal conditions via direct heat exchange.
  • a sixth aspect which is the process of the fifth aspect, wherein the diluent comprises water, steam, inert gases, nitrogen, carbon dioxide, or combinations thereof.
  • a seventh aspect which is the process of any one of the first through the sixth aspects, wherein the diluent contributes to the near-isothermal conditions by phase change.
  • An eighth aspect which is the process of any one of the first through the seventh aspects, wherein the reactor comprises an isothermal reactor.
  • a ninth aspect which is the process of the eighth aspect, wherein the isothermal reactor comprises a fixed catalyst bed, and wherein the fixed catalyst bed comprises the CPO catalyst.
  • a tenth aspect which is the process of any one of the first through the ninth aspects, wherein the reactor is characterized by a near-isothermal temperature of from about 300 °C to about 1,600 °C.
  • An eleventh aspect which is the process of any one of the first through the tenth aspects, wherein the reactor is characterized by a near-isothermal temperature of from about 300 °C to about 1 ,200 °C, and wherein the near-isothermal conditions are provided by removal of process heat from the reactor.
  • a twelfth aspect which is the process of any one of the first through the tenth aspects, wherein the reactor is characterized by a near-isothermal temperature of from about 800 °C to about 1 ,600 °C, and wherein the near-isothermal conditions are provided by supplying heat to the reactor.
  • a fourteenth aspect which is the process of any one of the first through the thirteenth aspects, wherein the reactant mixture is characterized by a methane to oxygen (CH 4 /O 2 ) molar ratio of from about 1 : 1 to about 3:1.
  • CH 4 /O 2 methane to oxygen
  • a fifteenth aspect which is the process of any one of the first through the fourteenth aspects, wherein the syngas is characterized by an M ratio that varies by less than about 20% from a desired M ratio under the near-isothermal conditions for a given set of reactor operating conditions, and wherein the M ratio is a molar ratio defined as (H 2 -C0 2 )/(CO+C0 2 ).
  • a seventeenth aspect which is the process of any one of the first through the sixteenth aspects, wherein the reactant mixture further comprises water and/or steam diluent, and wherein the syngas is characterized by a hydrogen to carbon monoxide molar ratio that is increased when compared to a hydrogen to carbon monoxide molar ratio of a syngas produced by an otherwise similar process conducted with a reactant mixture comprising hydrocarbons and oxygen without the water and/or steam diluent.
  • An eighteenth aspect which is the process of any one of the first through the seventeenth aspects, wherein the reactant mixture further comprises carbon dioxide diluent, and wherein the syngas is characterized by a hydrogen to carbon monoxide molar ratio that is decreased when compared to a hydrogen to carbon monoxide molar ratio of a syngas produced by an otherwise similar process conducted with a reactant mixture comprising hydrocarbons and oxygen without the carbon dioxide diluent.
  • a nineteenth aspect which is the process of any one of the first through the eighteenth aspects, wherein the hydrocarbons comprise methane, natural gas, natural gas liquids, associated gas, well head gas, enriched gas, paraffins, shale gas, shale liquids, fluid catalytic cracking (FCC) off gas, refinery process gases, stack gases, or combinations thereof.
  • the hydrocarbons comprise methane, natural gas, natural gas liquids, associated gas, well head gas, enriched gas, paraffins, shale gas, shale liquids, fluid catalytic cracking (FCC) off gas, refinery process gases, stack gases, or combinations thereof.

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Abstract

Un procédé de production de gaz de synthèse comprend la réaction dans des conditions non adiabatiques et quasi-isothermes, par l'intermédiaire d'une réaction d'oxydation partielle catalytique (CPO), d'un mélange de réactifs dans un réacteur pour produire du gaz de synthèse; le mélange de réactifs comprenant des hydrocarbures et de l'oxygène; le réacteur comprenant un catalyseur CPO; le réacteur étant caractérisé par un temps de contact allant d'environ 0,001 millisecondes (ms) à environ 5 s; et le gaz de synthèse comprenant de l'hydrogène, du monoxyde de carbone, du dioxyde de carbone, de l'eau et des hydrocarbures n'ayant pas réagi.
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US12006280B2 (en) 2019-01-21 2024-06-11 Eni S.P.A. Methanol production process with higher carbon utilization by CO2 recycle
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US11932537B2 (en) 2019-02-26 2024-03-19 Eni S.P.A. Integrated indirect heat transfer process for the production of syngas and olefins by catalytic partial oxidation and cracking
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