WO2015034556A1 - Procédé et système d'obtention d'un gaz de synthèse à l'aide d'un système de reformage à base de membrane transporteuse d'oxygène à reformage secondaire et source de chaleur auxiliaire - Google Patents

Procédé et système d'obtention d'un gaz de synthèse à l'aide d'un système de reformage à base de membrane transporteuse d'oxygène à reformage secondaire et source de chaleur auxiliaire Download PDF

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WO2015034556A1
WO2015034556A1 PCT/US2014/035430 US2014035430W WO2015034556A1 WO 2015034556 A1 WO2015034556 A1 WO 2015034556A1 US 2014035430 W US2014035430 W US 2014035430W WO 2015034556 A1 WO2015034556 A1 WO 2015034556A1
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Prior art keywords
stream
reforming
oxygen
transport membrane
reactor
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PCT/US2014/035430
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English (en)
Inventor
Shrikar Chakravarti
Ines C. STUCKERT
Raymond F. Drnevich
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Praxair Technology, Inc.
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Priority to CA2920197A priority Critical patent/CA2920197A1/fr
Priority to CN201480048887.XA priority patent/CN105517950B/zh
Publication of WO2015034556A1 publication Critical patent/WO2015034556A1/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
    • C01B3/382—Multi-step processes
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0457—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being placed in separate reactors
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00256—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • 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
    • C01B2203/025—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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • C01B2203/1623—Adjusting the temperature

Definitions

  • the present invention relates to a method and system for producing a synthesis gas in an oxygen transport membrane based reforming system, and more particularly, a method and system for producing a synthesis gas in an oxygen transport membrane based reforming system that provides both primary and secondary reforming and an auxiliary heat source.
  • Synthesis gas containing hydrogen and carbon monoxide is used for a variety of industrial applications, for example, the production of hydrogen, chemicals and synthetic fuel production.
  • the synthesis gas is produced in a fired reformer in which natural gas and steam is reformed in nickel catalyst containing reformer tubes at high temperatures (e.g., 850 °C to 1000 °C) and moderate pressures (e.g., 16 to 30 bar) to produce the synthesis gas.
  • the endothermic heating requirements for steam methane reforming reactions occurring within the reformer tubes are provided by burners firing into the furnace that are fueled by part of the natural gas.
  • the synthesis gas can be subjected to water-gas shift reactions to react residual steam in the synthesis gas with the carbon monoxide.
  • a well established alternative to steam methane reforming is the non-catalytic partial oxidation process (POx) whereby a sub -stoichiometric amount of oxygen is allowed to react with the natural gas feed creating steam and carbon dioxide at high temperatures.
  • the high temperature residual methane is reformed through reactions with the high temperature steam and carbon dioxide.
  • ATR autothermal reforming
  • Pre-reforming is a catalyst based process for converting higher hydrocarbons to methane, hydrogen, carbon monoxide and carbon dioxide.
  • the reactions involved in pre-reforming are generally endothermic.
  • the secondary reforming process is essentially an autothermal process that is fed the product from a SMR process.
  • the feed to a secondary reforming process is primarily synthesis gas from steam methane reforming.
  • some natural gas may bypass the SMR process and be directly introduced into the secondary reforming step.
  • the SMR may operate at a lower temperature, e.g. 650°C to 825°C versus 850°C to 1000°C.
  • a typical oxygen transport membrane has a dense layer that, while being impervious to air, will transport oxygen ions when subjected to an elevated operational temperature and a difference in oxygen partial pressure across the membrane.
  • oxygen transport membrane based reforming systems used in the production of synthesis gas can be found in United States Patent Nos. 6,048,472; 6,110,979; 6,114,400; 6,296,686; 7,261,751; 8,262,755; and 8,419,827.
  • There is an operational problem with all of these oxygen transport membrane based systems because such oxygen transport membranes need to operate at high temperatures of around 900 °C to 1100 °C.
  • hydrocarbons such as methane and higher order hydrocarbons are subjected to such high temperatures within the oxygen transport membrane, excessive carbon formation occurs, especially at high pressures and low steam to carbon ratios.
  • the carbon formation problems are particularly severe in the above-identified prior art oxygen transport membrane based systems.
  • the present invention addresses the aforementioned problems by providing an improved process for making synthesis gas using a reactively-driven oxygen transport membrane based system, which consists of two reactors that can be in the form of sets of catalyst containing tubes - reforming reactor and oxygen transport membrane reactor. Partial oxidation and some reforming occurs at the permeate (i.e. catalyst containing) side of the oxygen transport membranes and a reforming process facilitated by a reforming catalyst occurs in the reforming reactor in close proximity to the oxygen transport membrane reactor.
  • improvements to the reactively-driven oxygen transport membrane based system include modifications to the reactively-driven oxygen transport membrane based system to carry out both a primary reforming process in a catalyst filled reforming reactor as well as a secondary reforming process within the catalyst containing oxygen transport membrane reactor and to provide a source of auxiliary heat to balance the reforming duty between the oxygen transport membrane reactor and the auxiliary heat source.
  • the present invention may be characterized as a method for producing a synthesis gas in an oxygen transport membrane based reforming system, which may comprise at least two reactors that can be in the form of sets of catalyst containing tubes, including a reforming reactor and an oxygen transport membrane reactor, the method comprising the steps of: (i) reforming a hydrocarbon containing feed stream in a reforming reactor in the presence of a reforming catalyst disposed in the reforming reactor and heat to produce a reformed synthesis gas stream; (ii) feeding the reformed synthesis gas stream to a reactant side of a reactively driven and catalyst containing oxygen transport membrane reactor, wherein the oxygen transport membrane reactor includes at least one oxygen transport membrane element configured to separate oxygen from an oxygen containing stream at the oxidant side of the reactively driven and catalyst containing oxygen transport membrane reactor and transport the separated oxygen to the reactant side through oxygen ion transport when subjected to an elevated operational temperature and a difference in oxygen partial pressure across the at least one oxygen transport membrane element; (iii) reacting a portion
  • a first portion of the heat required for the initial or primary reforming step is provided by the reactively driven and catalyst containing oxygen transport membrane reactor and a second portion of the heat required for the primary reforming step is transferred from an auxiliary heat source disposed proximate the reforming reactor.
  • the invention may also be characterized as an oxygen transport membrane based reforming system comprising: (a) a reactor housing; (b) a reforming reactor disposed in the reactor housing and configured to reform a hydrocarbon containing feed stream in the presence of a reforming catalyst disposed in the reforming reactor and heat to produce a reformed synthesis gas stream; (c) a reactively driven oxygen transport membrane reactor disposed in the reactor housing proximate the reforming reactor and configured to receive the reformed synthesis gas stream and react a portion of the reformed synthesis gas stream with permeated oxygen and generate reaction products and heat, including a first portion of the heat required by the reforming reactor; and (d) an auxiliary heat source disposed in the reactor housing proximate the reforming reactor and configured to supply a second portion of the heat required by the reforming reactor to produce the reformed synthesis gas stream.
  • the reactively driven oxygen transport membrane reactor is further configured to reform any unreformed hydrocarbon gas in the reformed synthesis gas stream in the presence of one or more catalysts and some of the heat generated by the reaction of the reformed synthesis gas stream and permeated oxygen to produce a synthesis gas product stream.
  • the module of the synthesis gas product stream is between about 1.85 and 2.15 or more and is dependent on the amount of heat supplied to the reforming reactor from the auxiliary heat source.
  • the module of the synthesis gas product stream rises from a minimum of about 1.85 when the percentage of heat supplied to the reforming reactor from the auxiliary heat source is less than 15% to a maximum of about 2.15 when the percentage of heat supplied to the reforming reactor from the auxiliary heat source is greater than about 85%.
  • the module of the synthesis gas product stream will be between about 1.85 and 2.00 when the second portion of heat supplied to the reforming reactor from the auxiliary heat source is 50% or less of the total required heat to be supplied to the reforming reactor and between about 2.00 and 2.15 when the second portion of heat supplied to the reforming reactor from the auxiliary heat source is more than 50% of the total required heat to be supplied to the reforming reactor.
  • the actual module of the synthesis gas product stream is also dependent on the reforming temperatures within the oxygen transport membrane based reforming system, and in particular, the temperature at the exit of the reforming reactor.
  • the range of module for the synthesis gas product stream would be expected to increase to perhaps between about 1.90 to 2.25 or more depending on the amount of heat supplied to the reforming reactor from the auxiliary heat source.
  • the hydrogen to carbon monoxide ratio (H 2 /CO) of the synthesis gas product stream is also varied slightly between about 2.95 and 3.10 at a reforming reactor exit temperature of about 730 °C and depending on the amount of heat supplied to the reforming reactor from the auxiliary heat source.
  • the carbon monoxide to carbon dioxide ratio (CO/C02) of the synthesis gas product stream also varies between about 2.50 and 3.30 at an exit temperature of about 730 °C and depending on the reforming duty split between the first portion of heat and the second portion of heat.
  • the auxiliary heat source may be designed to provide between about 15% and 85% of the heat required for the reforming of the hydrocarbon containing feed stream.
  • the auxiliary heat source may be in the form of one or more auxiliary oxygen transport membrane reactors or one or more ceramic burners disposed within the reactor housing and in close proximity to the reforming reactor.
  • FIG. 1 is a schematic illustration of an embodiment of an oxygen transport membrane based reforming system designed to carry out both a primary reforming process and a secondary reforming process within the oxygen transport membrane reactor using an auxiliary heat source comprising a second oxygen transport membrane reactor;
  • FIG. 2 is a schematic illustration of the oxygen transport membrane based reforming system of Fig. 1 tailored for and integrated with a methanol production process;
  • FIG. 3 is a schematic illustration of an alternate embodiment of an oxygen transport membrane based reforming system designed to carry out both a primary reforming process and a secondary reforming process within the oxygen transport membrane reactor using an auxiliary heat source comprising one or more ceramic burners;
  • Fig. 4 is a graph that depicts the module of the synthesis gas produced in the oxygen transport membrane based reforming system as a function of the percent of primary reforming duty attributable to the auxiliary heat source;
  • Fig. 5 is a graph that depicts the hydrogen to carbon monoxide ratio (H 2 /CO) of the synthesis gas produced in the oxygen transport membrane based reforming system as a function of the percent of primary reforming duty attributable to the auxiliary heat source; and
  • Fig. 6 is a graph that depicts the carbon monoxide to carbon dioxide ratio (CO/C02) of the synthesis gas produced in the oxygen transport membrane based reforming system as a function of the percent of primary reforming duty attributable to the auxiliary heat source.
  • FIG. 1 provides a schematic illustration of an embodiment of an oxygen transport membrane based reforming system 100 in accordance with the present invention.
  • an oxygen containing stream 110 such as air
  • FD forced draft
  • Heat exchanger 113 is preferably a high efficiency, cyclic and continuously rotating ceramic regenerator disposed in operative association with the oxygen containing feed stream 110 and a heated oxygen depleted retentate stream 124.
  • the incoming air feed stream 110 is heated in the ceramic regenerator 113 to a temperature in the range of about 850 °C to 1050 °C to produce a heated air feed stream 115.
  • the oxygen depleted air leaves the oxygen transport membrane reforming tubes as heated oxygen depleted retentate stream 124 at the same or slightly higher temperature than the heated air feed stream 115.
  • Any temperature increase typically less than about 30 °C, is attributable to the portion of energy generated by oxidizing reaction of hydrogen and carbon monoxide in the oxygen transport membrane tubes and transferred by convection to the oxygen depleted retentate stream 124.
  • This oxygen depleted retentate stream 124 is heated back to a temperature between about 1050 °C and 1200 °C prior to being directed to the heat exchanger or ceramic regenerator 113.
  • This increase in temperature of the oxygen depleted retentate stream 124 is preferably accomplished by use of a duct burner 126, which facilitates combustion of a supplemental fuel stream 128 using some of the residual oxygen in the retentate stream 124 as the oxidant.
  • an alternative means is to combust the supplemental fuel stream 128 with a separate air stream in duct burner 126 and then mix the hot flue gas with the oxygen depleted retentate stream 124.
  • the heated, oxygen depleted retentate stream 124 provides the energy to raise the temperature of the incoming feed air stream 110 from ambient temperature to a temperature between about 850 °C to 1050 °C.
  • the resulting cold retentate stream exiting the ceramic heat exchanger typically containing less than about 5% oxygen, leaves the oxygen transport membrane based reforming system 100 system as exhaust gas 131 at a temperature of around 150 °C.
  • an alternate embodiment of the oxygen transport membrane based reforming system 100 could dispose the duct burner and supplemental fuel stream upstream of the reactors in intake duct 116. Such arrangement would allow use of a smaller ceramic regenerator 113 and less severe operating conditions for the ceramic regenerator 113.
  • the hydrocarbon containing feed stream 130 preferably natural gas, to be reformed is typically mixed with a small amount of hydrogen or hydrogen-rich gas 132 to form a combined hydrocarbon feed 133 and then preheated to around 370 °C in heat exchanger 134 that serves as a feed pre-heater, as described in more detail below.
  • natural gas typically contains unacceptably high level of sulfur species
  • a small amount of hydrogen or hydrogen- rich gas 132 is added to facilitate desulfurization.
  • the heated feed stream 136 undergoes a sulfur removal process via device 140 such as hydro-treating to reduce the sulfur species to H 2 S, which is subsequently removed in a guard bed using material like ZnO and/or CuO.
  • the hydro-treating step also saturates any alkenes present in the hydrocarbon containing feed stream.
  • the natural gas feed stream is preferably pre-reformed in an adiabatic pre- reformer, which converts higher hydrocarbons to methane, hydrogen, carbon monoxide, and carbon dioxide.
  • the pre-reformer is a heated pre-reformer that may be thermally coupled with oxygen transport membrane based reforming system.
  • Superheated steam 150 is added to the pre -treated natural gas and hydrogen feed stream 141, as required, to produce a mixed feed stream 160 with a steam to carbon ratio between about 1.0 and 2.5, and more preferably between about 1.2 and 2.2.
  • the superheated steam 150 is preferably between about 15 bar and 80 bar and between about 300 °C and 600 °C and generated in a fired heater 170 using a source of process steam 172.
  • the fired heater 170 is configured to combust a supplemental fuel stream 174 and optionally a portion of the off-gas 229 produced by the oxygen transport membrane based reforming system using air 175 as the oxidant to heat the process steam 172 to superheated steam 150.
  • a source of air 175 is heated in the fired heater 170 to produce a heated air stream 176 to be used as the oxidant in the fired heated 170.
  • the mixed feed stream 160 is also heated in the fired heater 170 producing a heated mixed feed stream 180.
  • the heated mixed feed stream 180 has a temperature preferably between about 450 °C and 650 °C and more preferably a temperature between about 500 °C and 600 °C.
  • the illustrated embodiment of the oxygen transport membrane based reforming system 100 comprises three reactors (200, 210, 220) disposed in a single reactor housing 201.
  • the first reactor is a reforming reactor 200 which comprises reforming catalyst containing tubes configured to reform the heated mixed feed stream 180 containing a hydrocarbon feed and steam in the presence of a conventional reforming catalyst disposed in the reforming tubes and heat to produce a reformed synthesis gas stream 205.
  • the first reactor is a reforming reactor 200 which comprises reforming catalyst containing tubes configured to reform the heated mixed feed stream 180 containing a hydrocarbon feed and steam in the presence of a conventional reforming catalyst disposed in the reforming tubes and heat to produce a reformed synthesis gas stream 205.
  • temperature of the reformed hydrogen-rich synthesis gas stream is typically designed to be between 650 °C and 850 °C.
  • the reformed synthesis gas stream 205 is then fed as an influent to the second reactor which is an oxygen transport membrane reactor 210. More particularly, reformed synthesis gas stream 205 is fed to a reactant side of a reactively driven and catalyst containing oxygen transport membrane reactor 210.
  • the reactively driven, oxygen transport membrane reactor 210 includes one or more oxygen transport membrane elements or tubes each having an oxidant side and a reactant side that are disposed proximate to the reforming tubes. Each of the oxygen transport membrane elements or tubes are configured to separate oxygen from the heated oxygen containing stream 115 contacting the oxidant side to the reactant side through oxygen ion transport.
  • the oxygen ion transport occurs when the oxygen transport membrane elements or tubes are subjected to elevated operational temperatures and there is a difference in oxygen partial pressure across the oxygen transport membrane elements or tubes.
  • a portion of the reformed synthesis gas stream 205 fed to the reactant side of the oxygen transport membrane reactor 210 immediately reacts with oxygen permeated through the oxygen transport membrane elements or tubes to produce the difference in oxygen partial pressure across the oxygen transport membrane elements or tubes which drives the oxygen ion transport and separation. This reaction produces reaction products and heat.
  • a portion of the heat produced by the reaction the reformed synthesis gas stream 205 and the permeated oxygen is transferred via convection to the oxygen depleted retentate stream and another portion of the heat is transferred via radiation to the reforming reactor 200.
  • the oxygen transport membrane reactor 210 is further configured to reform unreformed hydrocarbon gas in the reformed synthesis gas stream 205 and produce a synthesis gas product stream 215. This secondary reforming occurs in the presence of one or more reforming catalysts contained in the oxygen transport membrane elements or tubes, reaction products (e.g. from the reaction of a portion of the reformed synthesis gas stream 205 and oxygen permeate) and the third portion of the energy or heat produced by the same reaction.
  • the synthesis gas product stream 215 leaving the oxygen transport membrane reactor 210 is preferably at a temperature between about 900 °C and 1050 °C.
  • the third reactor in the illustrated embodiment is an auxiliary oxygen transport membrane reactor 220 that is configured to provide an auxiliary source of radiant heat to the reforming reactor 200.
  • This auxiliary reactor 220 or heat source preferably provides between about 15% and 85% of the heat required for the initial reforming of the heated mixed feed stream 180 that occurs in the reforming reactor 200.
  • the auxiliary oxygen transport membrane reactor 220 is also a reactively driven oxygen transport membrane reactor 220 that comprises a plurality of oxygen transport membrane elements or tubes disposed proximate to or in a juxtaposed orientation with respect to the reforming reactor 200.
  • the auxiliary oxygen transport membrane reactor 220 is configured to also separate or permeate oxygen from the oxygen containing stream 115 contacting the oxidant side of the oxygen transport membrane elements or tubes to the reactant side of the oxygen transport membrane elements or tubes through oxygen ion transport.
  • the permeated oxygen reacts with a low pressure hydrogen containing stream 222, preferably less than about 3 bar, that is fed via a valve 221 to the reactant side of the oxygen transport membrane elements or tubes to produce the difference in oxygen partial pressure across the oxygen transport membrane element and to produce an auxiliary reaction product stream 225 and heat.
  • the low pressure hydrogen containing stream 222 is a hydrogen and light hydrocarbon containing stream that preferably includes a recirculated portion 226 of the synthesis gas product stream and optionally a supplementary fuel 224.
  • a portion of the reaction product stream 225 exiting the reactant side of the oxygen transport membrane elements or tubes of the oxygen transport membrane reactor 220 is an off-gas 227 that may be mixed with a supplementary natural gas fuel 228 to the duct burner 126.
  • Another portion of the reaction product stream 225 exiting the reactant side of the oxygen transport membrane elements or tubes is an off-gas 229 that may be mixed with a supplementary natural gas fuel 174 to fired heater 170.
  • the reforming reactor 200 and the oxygen transport membrane reactor 210 are arranged as sets of closely packed tubes in close proximity to one another.
  • the reforming reactor 200 generally consists of reforming tubes.
  • Oxygen transport membrane reactor 210 as well as the auxiliary oxygen transport membrane reactor 220 comprise a plurality of ceramic oxygen transport membrane tubes.
  • the oxygen transport membrane tubes are preferably configured as multilayered ceramic tubes capable of conducting oxygen ions at an elevated operational temperature, wherein the oxidant side of the oxygen transport membrane tubes is the exterior surface of the ceramic tubes exposed to the heated oxygen containing stream and the reactant side or permeate side is the interior surface of the ceramic tubes.
  • Within each of the oxygen transport membrane tubes are one or more catalysts that facilitate partial oxidation and/or reforming, as applicable.
  • the oxygen transport membrane elements or tubes used in the embodiments disclosed herein preferably comprise a composite structure that incorporates a dense layer, a porous support and an intermediate porous layer located between the dense layer and the porous support.
  • Each of the dense layer and the intermediate porous layer are capable of conducting oxygen ions and electrons at elevated operational temperatures to separate the oxygen from the incoming air stream.
  • the porous support layer would thus form the reactant side or permeate side.
  • the dense layer and the intermediate porous layer preferably comprise a mixture of an ionic conductive material and an electrically conductive material to conduct oxygen ions and electrons, respectively.
  • the intermediate porous layer preferably has a lower permeability and a smaller average pore size than the porous support layer to distribute the oxygen separated by the dense layer towards the porous support layer.
  • the preferred oxygen transport membrane tubes also include a mixed phase oxygen ion conducting dense ceramic separation layer comprising a mixture of a zirconia based oxygen ion conducting phase and a predominantly electronic conducting perovskite phase. This thin, dense separation layer is implemented on the thicker inert, porous support.
  • Oxidation catalyst particles or a solution containing precursors of the oxidation catalyst particles are optionally located in the intermediate porous layer and/or in the thicker inert, porous support adjacent to the intermediate porous layer.
  • the oxidation catalyst particles contain an oxidation catalyst, such as gadolinium doped ceria, are selected to promote oxidation of the partially reformed synthesis gas stream in the presence of the permeated oxygen when introduced into the pores of the porous support, on a side thereof opposite to the intermediate porous layer.
  • the endothermic heating requirements of the reforming process occurring in the reforming reactor 200 is supplied through radiation of some of the heat from the oxygen transport membrane reactor 210 and auxiliary oxygen transport membrane reactor 220 together with the convective heat transfer provided by heated oxygen depleted retentate stream .
  • Sufficient thermal coupling or heat transfer between the heat-releasing ceramic oxygen transport membrane tubes and the heat-absorbing catalyst containing reformer tubes must be enabled within the design of the present reforming system.
  • a portion of the heat transfer between the ceramic oxygen transport membrane tubes and the adjacent or juxtaposed reforming catalyst containing reformer tubes is through the radiation mode of heat transfer whereby surface area, surface view factor, surface emissivity, and non-linear temperature difference between the tubes (e.g., T otm 4 -T reformer 4 ) , are critical elements to achieve the desired thermal coupling.
  • Surface emissivity and temperatures are generally dictated by tube material and reaction requirements.
  • the surface area and surface view factor are generally dictated by tube arrangement or configuration within each module and the entire reactor.
  • the module of the synthesis gas product stream produced from the disclosed embodiments of the oxygen transport membrane based reforming system varies depending on the exit stream temperatures and the amount of heat supplied to the reforming reactor from the auxiliary heat source.
  • the module of the synthesis gas product stream produced from the disclosed embodiments when the temperature at the exit of the reforming reactor is about 730 °C and the temperature at the exit of the OTM reactor is about 995 °C, is between about 1.85 and 2.15 or more and is a function of the amount of heat supplied to the reforming reactor from the auxiliary heat source presented as a percentage of total primary reforming duty that comes from the auxiliary heat source.
  • Fig. 4 the module of the synthesis gas product stream produced from the disclosed embodiments, when the temperature at the exit of the reforming reactor is about 730 °C and the temperature at the exit of the OTM reactor is about 995 °C, is between about 1.85 and 2.15 or more and is a function of the amount of heat supplied to the reforming reactor from the auxiliary heat source presented as a percentage of
  • the hydrogen to carbon monoxide ratio (H 2 /CO) of the synthesis gas product stream is maintained with a small band generally between about 2.95 and 3.10 depending on the amount of heat supplied to the reforming reactor from the auxiliary heat source.
  • the amount of heat supplied to the reforming reactor from the auxiliary heat source is depicted in Fig. 5 as a percentage of total primary reforming duty that comes from the auxiliary heat source.
  • the carbon monoxide to carbon dioxide ratio (CO/C02) of the synthesis gas product stream ranges between about 2.50 and 3.30 depending on the amount of heat supplied to the reforming reactor from the auxiliary heat source.
  • the actual module, H 2 /CO ratio and CO/C02 ratio of the synthesis gas product stream is very much dependent on the exit temperatures realized within the oxygen transport membrane based reforming system.
  • the graphs of Figs. 4-6 represent a temperature of about 730 °C at the exit of the reforming reactor. If this temperature is raised to a temperature of between about 800 °C and 900 °C, the range of module for the synthesis gas product stream would be expected to also increase, perhaps to between about 1.90 to 2.25 or more depending on the amount or percentage of reforming duty heat supplied to the reforming reactor from the auxiliary heat source. Increasing the temperature at the exit of the OTM reactor typically results in a decrease in the module of the synthesis gas.
  • the auxiliary heat source is configured, or more preferably designed, to provide between about 15% and 85% of the total heat required for the primary reforming of the hydrocarbon containing feed stream in the reforming reactor.
  • the auxiliary heat source may be an auxiliary oxygen transport membrane reactor as shown in Figs. 1 and 2 or may comprise one or more ceramic burners as shown, for example, in Fig. 3 described in more detail below.
  • the module of the synthesis gas product stream is around 1.90 whereas at the higher end of the range, the module of the synthesis gas product stream is between about 2.10 and 2.15 or more.
  • the module of the synthesis gas product stream is between about 1.85 and 2..00 when the heat supplied from the auxiliary heat source to the reforming reactor is 50% or less of the total required heat to be supplied to the reforming reactor, and between about 2.00 and 2.15 or more when the heat supplied to the reforming reactor from the auxiliary heat source is more than 50% of the total required heat to the reforming reactor.
  • the temperature at the exit of the reforming reactor is raised, one would expect a corresponding increase in module of the synthesis gas product to 2.25 or more depending on the amount of heat supplied to the reforming reactor from the auxiliary heat source.
  • the synthesis gas stream 215 produced by the oxygen transport membrane reactor 210 generally contains hydrogen, carbon monoxide, unconverted methane, steam, carbon dioxide and other constituents.
  • a significant portion of the sensible heat from the synthesis gas stream 215 can be recovered using a heat exchange section or recovery train 250.
  • Heat exchange section 250 is designed to cool the produced synthesis gas stream 215 exiting the oxygen transport membrane reactor 210.
  • the heat exchange section 250 is also designed such that in cooling the synthesis gas stream 215, process steam 172 is generated, the combined hydrocarbon feed stream 133 is preheated, and boiler feed water 255 and feed water 259 are heated.
  • the hot synthesis gas product stream 215, preferably at a temperature between about 900 °C and 1050 °C is cooled to a temperature of about 400 °C or less in a Process Gas (PG) Boiler 252.
  • the initially cooled synthesis gas product stream 254 is then used to preheat the mixture of natural gas and hydrogen feed stream 133 in a feed pre-heater 134 and subsequently to preheat boiler feed water 255 in the economizer 256 and to heat the feed water stream 259.
  • the boiler feed water stream 255 is preferably pumped using a feed water pump (not shown), heated in economizer 256 and sent to steam drum 257 while the heated feed water stream is sent to a de-aerator (not shown) that provides boiler feed water 255.
  • Synthesis gas leaving the feed water heater 258 is preferably around 150 °C. It is cooled down to about 40 °C using a fin-fan cooler 261 and a synthesis gas cooler 264 fed by cooling water 266.
  • the cooled synthesis gas 270 then enters a knock-out drum 268 where water is removed from the bottoms as process condensate stream 271 which, although not shown, is recycled for use as feed water, and the cooled synthesis gas 272 is recovered overhead.
  • the final synthesis gas product 276 is obtained from the compression of the cooled synthesis gas stream 273 in a synthesis gas compressor 274. Depending on the application, multiple stages of compression may be required. The inter-stage cooling and condensate knock out is not shown in Fig. 1. Prior to such compression, however, a portion of the cooled synthesis gas stream 226 may optionally be recirculated to the reactor housing to form all or part of the low pressure hydrogen containing stream 222. Depending on the operating pressures of the oxygen transport membrane based reforming system, pressure of the recovered synthesis gas is preferably in the range of about 10 bar and 35 bar and more preferably in the range of 12 bar and 30 bar.
  • the module of the final synthesis gas product produced in the described embodiment is typically about 1.8 to 2.3.
  • FIG. 2 is a schematic illustration of the oxygen transport membrane based reforming system of Fig. 1 tailored for and integrated with a methanol production process.
  • this embodiment is similar to the embodiment of Fig. 1 and, for sake of brevity, the description of the common aspects of the two embodiments will not be repeated here, rather, the following discussion shall focus on the differences.
  • the syngas is typically compressed to between about 80 and 100 bar in syngas compressor 274.
  • the final synthesis gas product 276 is mixed with a methanol loop recycle stream 310.
  • This mixed stream 320 of compressed synthesis gas and methanol loop recycle is indirectly heated in heat exchanger 322 by the synthesized methanol stream 324 to a temperature between about 175°C and 300°C.
  • the heated stream 326 is directed to the methanol synthesis reactor 330.
  • the exact heat arrangement will vary depending on the type of methanol synthesis reactor, technology vendor and approach to overall process integration, i.e. integrating with the front-end or syngas generation section.
  • hydrogen, carbon monoxide and carbon dioxide are consumed to produce methanol and water in an exothermic process through the following reactions:
  • the heat generated in the methanol synthesis reaction is used for steam production and/or for preheating of the synthesis gas feed.
  • Temperature at the outlet of the methanol reactor is typically between about 200°C and about 260°C.
  • This methanol synthesis stream 324 is cooled down to about 38°C in heat exchanger 322 and cooler 332 before entering a separator 334 where the crude methanol stream 340 containing mostly methanol, water and trace amounts of other species (e.g. dimethyl ether, ethanol and higher alcohols), is separated in the bottoms and sent to further distillation steps for final purification.
  • other species e.g. dimethyl ether, ethanol and higher alcohols
  • Most of the overhead stream 336 from the separator 334 is a methanol loop recycle stream 344 sent back to the methanol synthesis reactor 330 via recycle compressor 345 to increase the carbon conversion to methanol.
  • the recycle compressor 345 is required to compensate for pressure drop across the methanol synthesis reactor 330 and associated equipment, e.g. heat
  • a small portion of the overhead stream 336, typically between about 1% and 5% is purged from the methanol synthesis loop 300 to prevent buildup of inerts in the methanol synthesis loop 300.
  • the typical composition of the purge stream 350 is as follows: 75% hydrogen, 3% carbon dioxide, 12% carbon dioxide, 3% nitrogen, and 7% methane, with a higher heating value of about 325 BTU/scf.
  • the methanol loop purge stream 350 is then split into two streams, namely methanol purge stream 350A which is directed back to the auxiliary oxygen transport membrane reactor 220 as the hydrogen containing feed and methanol purge stream 350B which forms the hydrogen-rich gas that is combined with the hydrocarbon containing feed stream to form a combined hydrocarbon feed 133.
  • methanol purge stream 350A which is directed back to the auxiliary oxygen transport membrane reactor 220 as the hydrogen containing feed
  • methanol purge stream 350B which forms the hydrogen-rich gas that is combined with the hydrocarbon containing feed stream to form a combined hydrocarbon feed 133.
  • the low pressure hydrogen containing stream 222 is a mixture of a portion of the methanol purge stream 350A and a supplemental natural gas fuel stream 224.
  • Fig. 3 is a schematic illustration of an alternate embodiment of an oxygen transport membrane based reforming system designed to carry out both a primary reforming process and a secondary reforming process within the oxygen transport membrane reactor using an auxiliary heat source comprising one or more ceramic burners.
  • this embodiment is similar to the embodiment of Fig. 2 and, for sake of brevity, the description of the common aspects of the two embodiments will not be repeated here, rather, the following discussion shall focus only on the differences.
  • the one or more ceramic burners 555 are preferably configured to burn a light hydrocarbon containing stream using air or enriched air as the oxidant.
  • a porous ceramic burner as the auxiliary heat source it is important to design the spatial arrangement of the ceramic burners vis-a-vis the oxygen transport membrane reactor and reforming reactor so as to maximize the thermal coupling and system efficiency while minimizing the mechanical complexity of the system.
  • the use of porous ceramic burners within the reactor housing requires other design challenges and modifications of the system to fully integrate the burners as the auxiliary heat source.
  • Such challenges and modifications may include providing a separate oxidant stream and/or a separate fuel source for the porous ceramic burners.
  • start-up procedures as well as the exhaust manifolding differences between the embodiments using the low pressure oxygen transport membrane reactor and those embodiments using one or more porous ceramic burners would be potentially significant and must taken into consideration.
  • the porous ceramic or flameless burners may preferably be radiant tube type burners having a similar tubular or cylindrical configuration as the oxygen transport membrane reactor tubes depicted in Figs. 1 and 2 with combustion occurring on the interior of the tube.
  • Yet another ceramic burner configuration is to arrange a plurality of porous tubular ceramic burners with the fuel transport from the interior of the tube to the exterior surface with the combustion occurring on the outside surface using the oxygen depleted retentate stream as the oxidant.
  • Still other contemplated arrangements of the auxiliary heat source may include a radial or circumferential ceramic burner arrangement or perhaps even a circumferential arrangement of the burner.
  • duct burner 126 A is disposed upstream of the reactor housing 201 in intake duct 116 and coupled to a supplemental fuel stream and/or the recirculated methanol purge stream 350B.
  • the operating conditions for the ceramic regenerator 113 are less severe and would save capital expense by allowing use of a smaller ceramic regenerator 113.
  • the duct burner 126 A could instead be placed downstream of reactor housing 201 as in Fig. 2.

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Abstract

L'invention porte sur un procédé et sur un système d'obtention d'un gaz de synthèse, dans un système de reformage à base de membrane transporteuse d'oxygène, qui effectuent un processus de reformage primaire au sein d'un réacteur de reformage et un processus de reformage secondaire au sein d'un réacteur à membrane transporteuse d'oxygène et en présence de chaleur générée par un réacteur à membrane transporteuse d'oxygène et une source auxiliaire de chaleur. La source auxiliaire de chaleur est disposée à l'intérieur de l'enveloppe du réacteur à proximité des réacteurs de reformage et peut comprendre un réacteur auxiliaire à membrane transporteuse d'oxygène entraîné par réaction ou un brûleur céramique.
PCT/US2014/035430 2013-09-05 2014-04-25 Procédé et système d'obtention d'un gaz de synthèse à l'aide d'un système de reformage à base de membrane transporteuse d'oxygène à reformage secondaire et source de chaleur auxiliaire WO2015034556A1 (fr)

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CA2920197A CA2920197A1 (fr) 2013-09-05 2014-04-25 Procede et systeme d'obtention d'un gaz de synthese a l'aide d'un systeme de reformage a base de membrane transporteuse d'oxygene a reformage secondaire et source de chaleur auxiliaire
CN201480048887.XA CN105517950B (zh) 2013-09-05 2014-04-25 用于使用具有二级重整和辅助热源的基于氧传输膜的重整系统来生产合成气的方法和系统

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