US20190263659A1 - Integration of a hot oxygen burner with an auto thermal reformer - Google Patents

Integration of a hot oxygen burner with an auto thermal reformer Download PDF

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US20190263659A1
US20190263659A1 US15/905,292 US201815905292A US2019263659A1 US 20190263659 A1 US20190263659 A1 US 20190263659A1 US 201815905292 A US201815905292 A US 201815905292A US 2019263659 A1 US2019263659 A1 US 2019263659A1
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Prior art keywords
stream
hydrocarbon
hot oxygen
fuel
syngas
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US15/905,292
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English (en)
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Minish Mahendra Shah
Lawrence Bool
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Praxair Technology Inc
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Praxair Technology Inc
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Priority to US15/905,292 priority Critical patent/US20190263659A1/en
Assigned to PRAXAIR TECHNOLOGY, INC. reassignment PRAXAIR TECHNOLOGY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOOL, LAWRENCE, SHAH, MINISH MAHENDRA
Priority to ES19705658T priority patent/ES2964329T3/es
Priority to BR112020015822-4A priority patent/BR112020015822A2/pt
Priority to EP19705658.3A priority patent/EP3759047B1/en
Priority to KR1020207025726A priority patent/KR102493874B1/ko
Priority to CN201980012639.2A priority patent/CN111699154A/zh
Priority to KR1020237003017A priority patent/KR102650849B1/ko
Priority to CA3090983A priority patent/CA3090983C/en
Priority to MX2020008307A priority patent/MX2020008307A/es
Priority to PCT/US2019/015989 priority patent/WO2019164649A1/en
Publication of US20190263659A1 publication Critical patent/US20190263659A1/en
Priority to US17/211,148 priority patent/US12006214B2/en
Abandoned legal-status Critical Current

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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
    • 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
    • C01B3/36—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 oxygen or mixtures containing oxygen as gasifying agents
    • C01B3/363—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 oxygen or mixtures containing oxygen as gasifying agents characterised by the burner used
    • 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
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • 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
    • C01B2203/1241—Natural gas or methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention relates to a novel system and process for integrating a hot oxygen burner with an auto thermal reformer for reducing capital expenditure as compared to existing partial oxidation and autothermal reformer systems.
  • the system also reduces oxygen utilization and soot formation as compared to existing partial oxidation system and keeps soot formation to at or below the levels in existing autothermal reformer system.
  • the system reduces the sizes of pre-reformer and fired heater or eliminates the need for pre-reformers and/or fired heater entirely.
  • the system further enables the use of ‘opportunity fuels’ (as defined below) in the ATR.
  • Hydrocarbons such as natural gas, naphtha, or liquefied petroleum gas (LPG) can be catalytically converted with steam to obtain a synthesis gas (i.e., a mixture of hydrogen (H 2 ) and carbon monoxide (CO), commonly referred to as synthesis gas or syngas.
  • a synthesis gas i.e., a mixture of hydrogen (H 2 ) and carbon monoxide (CO), commonly referred to as synthesis gas or syngas.
  • This reforming process could be done through the use of a so-called steam methane reforming, or alternatively, partial oxidation and auto thermal reforming processes.
  • These generation systems are known, and are typically utilized to obtain syngas which may be ultimately utilized in the production of hydrogen, methanol, ammonia, or other chemicals.
  • Hydrocarbon feedstock stream ( 1 ) is mixed with hydrogen ( 2 ) and then pre-heated to a temperature ranging from 600-725° F. in heating coils ( 102 ) and then preheated hydrocarbon stream ( 5 ) is fed to desulfurizer ( 105 ).
  • Amount of hydrogen mixed with hydrocarbon is generally in 2-3% of hydrocarbon feed on a volumetric basis and it is used for aiding reactions within desulfurizer.
  • Desulfurized hydrocarbon stream ( 8 ) is mixed with steam ( 35 ) and a mixed feed ( 10 ) is preheated to 700 to 950° F. in heating coils ( 107 ).
  • Pre-heated mixed feed ( 12 ) is fed to a pre-reformer ( 110 ), where any C 2 + hydrocarbons are reacted with steam so as to convert them into mixture of H 2 , CO and CH 4 .
  • Pre-reformed feed stream ( 14 ) is further heated to 1000-1200° F. in heating coils ( 112 ) within fired heater ( 100 ) and then fed to ATR ( 120 ) as pre-heated pre-reformed feed ( 16 ).
  • Oxygen needed in the ATR is produced by air separation unit (“ASU”) ( 130 ).
  • Air feedstock stream ( 21 ) is separated into oxygen stream ( 24 ) and nitrogen ( 31 ) in ASU ( 130 ).
  • Oxygen is pre-heated to a temperature ranging from 200 to 400° F. in oxygen preheater ( 135 ) and preheated oxygen ( 25 ) is also fed to the ATR ( 120 ).
  • An ATR unit operation ( 120 ) that combines a partial oxidation (POx) step and a catalytic reforming step.
  • preheated pre-reformed feed ( 16 ) and oxygen ( 25 ) react to produce a syngas mixture ( 20 ) comprising H 2 , CO, CO 2 , steam, any unconverted CH 4 and other trace components.
  • the feed ( 16 ) first reacts with oxygen ( 25 ) in a POx step to consume all the oxygen and release heat.
  • the remaining hydrocarbons in the feed are then reformed autothermally (not catalytically) with CO 2 and H 2 O present in the mixture. Since the reforming reactions are endothermic this non-catalytic reforming results in a reduction in gas temperature.
  • the rates of reaction (“kinetics”) slow down causing a kinetic limit to the achievable hydrocarbon conversion.
  • the still hot, reactive, mixture is fed to a catalyst which promotes reforming to achieve a near equilibrium degree of reforming. Due to the nature of the catalyst bed, it is critical that soot not enter the catalyst as it could cause fouling.
  • the conditions in the non-catalytic zone of the reactor must be maintained to prevent soot at the entrance to the catalyst. This can be accomplished by preventing soot from forming in the first place, or by promoting soot gasification reactions that would consume any soot formed before the gas reaches the catalyst. For this reason a conventional ATR requires a pre-reformer ( 110 ) to convert higher hydrocarbons, which may be prone to sooting in the POx step, to methane. Further the ATR may use steam injection at higher levels than needed in the catalytic reforming step just to reduce soot formation and enhance soot oxidation.
  • Syngas ( 20 ) exits the ATR at a temperature of 1800-1900° F. and at pressure ranging from 350-550 psia. Syngas ( 20 ) is then passed through process gas boiler ( 150 ) boiler feed water heater ( 155 ) and water heater ( 160 ) in sequence to recover thermal energy contained in syngas for steam generation. Temperature of syngas exiting the process gas boiler ranges from 550 to 700° F. Steam is typically generated at 350 to 750 psia, however, it can be generated at higher pressure if desired. Finally, syngas is cooled to 80 to 110° F. in a cooler ( 165 ) and sent to a condensate separator ( 170 ) to separate any condensate.
  • Syngas ( 32 ) is then routed to a downstream process for either making chemicals such as methanol or Fischer Trope liquids or sent to a purification process for separating syngas into hydrogen and carbon monoxide. Any residual fuel stream from the downstream process is combined with make-up hydrocarbon fuel stream to form a fuel stream for the fired heater. Burning of fuel in the fired heater provides heat for various heating coils disposed within the fired heater. Process water ( 50 ) is combined with condensate ( 52 ) and heated in water heater ( 160 ) to a temperature of 200-210° F. Heated water is fed to deaerator ( 140 ) to remove any dissolved gases.
  • Process water ( 50 ) is combined with condensate ( 52 ) and heated in water heater ( 160 ) to a temperature of 200-210° F. Heated water is fed to deaerator ( 140 ) to remove any dissolved gases.
  • Boiler feed water ( 55 ) from deaerator ( 140 ) is pumped to desired pressure (generally >450 psia) and heated to temperature that is 10 to 50° F. below the boiling point of water and sent to steam drum ( 125 ).
  • Hot boiler feed water stream ( 60 ) from steam drum ( 125 ) is circulated through process gas boiler ( 150 ) to generate steam.
  • a portion of saturated steam ( 62 ) from steam drum is superheated in heating coils ( 114 ).
  • the superheated steam ( 35 ) is used in the reforming process.
  • the remainder of saturated steam ( 70 ) is exported.
  • FIG. 2 a related art partial oxidation process for generating syngas is depicted.
  • Hydrocarbon feedstock stream ( 1 ) is mixed with hydrogen ( 2 ) and pre-heated to 450-725° F. in hydrocarbon heating device ( 104 ) and the preheated hydrocarbon stream ( 5 ) is fed to desulfurizer device ( 105 ).
  • Desulfurized hydrocarbon stream ( 8 ) along with oxygen stream ( 24 ) from the ASU ( 130 ) is fed to the POx reactor ( 115 ).
  • Syngas ( 20 ) from the POx reactor exits at a temperature of 2500 to 2700° F. and at pressure ranging from 350-550 psia.
  • Syngas stream ( 20 ) may contain some soot due to cracking of hydrocarbons within the POx reactor. Due to high temperature and potential presence of soot, a specialized boiler called syngas cooler ( 152 ) is required to cool syngas and generate steam. If steam has no value, syngas cooler can be replaced by quench vessel (not shown) to cool syngas using direct contact with water. Partially cooled syngas ( 22 ) at 550 to 750° F. from syngas cooler ( 152 ) is used to preheat hydrocarbon feedstock in the hydrocarbon heating device ( 104 ). Syngas stream ( 23 ) is then routed and processed in a soot scrubber ( 154 ).
  • the soot scrubber includes a venturi scrubber for contacting syngas with large quantity of water, a contact tower for additional scrubbing section to remove residual soot from syngas and separating soot containing water from syngas and pump for circulating water.
  • Soot free syngas ( 26 ) at 275 to 350° F. is then routed through a water heater ( 160 ) and cooler ( 165 ) to cool the syngas ( 30 ) to 80-110° F. and sent to the condensate separator ( 170 ).
  • the syngas product ( 32 ) from condensate separator is sent to the downstream process.
  • Process water ( 50 ) is combined with condensate ( 52 ) and heated in water heater device ( 160 ) to a temperature ranging from 200-210° F. Heated water is fed to deaerator ( 140 ) to remove any dissolved gases.
  • Boiler feed water ( 55 ) is pumped to desired pressure (generally >450 psia) and sent to syngas cooler ( 152 ) to generate steam.
  • desired pressure generally >450 psia
  • syngas cooler 152
  • boiler feed water can be heated (not shown) close to its boiling point against partially cooled syngas prior to feeding it to syngas cooler.
  • the oxygen consumption in the POx reactor is about 25% higher than the ATR system for a comparable quantity of syngas.
  • High grade heat at the exit of the POx reactor is either used for steam generation or rejected to atmosphere via quench cooling. Therefore, in order to take advantage of the high temperatures ( ⁇ 2600° F.) at the exit of the POx reactor, an expensive boiler (i.e., syngas cooler) is necessary.
  • the burner In a conventional ATR the burner is designed to rapidly mix the feed(s) and oxygen, often using swirl and other mixing enhancement strategies. These strategies make staging the burner difficult, if not impossible.
  • all the feed streams are rapidly mixed with the oxygen without the ability to feed different streams into different parts of the flame.
  • this rapid mixing was used to mix the hot oxygen-containing gas with the hydrocarbon feed to reduce the mixture temperature below the ignition temperature without igniting the mixture, thereby feeding an oxygen and hydrocarbon containing mixture to the catalyst bed.
  • the HOB/ATR reactor of the integrated system of the invention uses a different mixing strategy.
  • a portion of the fuel is burned in an oxygen stream upstream of a nozzle.
  • the resulting ‘hot oxygen’ stream exits the nozzle and mixes quickly with surroundings. Since the mixing method is that of a simple reacting jet, it is possible to control how different streams get mixed into the reactive portion.
  • the HOB/ATR reactor ignites the oxygen and hydrocarbon containing mixture to perform partial oxidation reactions prior to the mixture entering the catalyst bed. Therefore, the HOB is designed to mix the streams more slowly than that in the related art to ensure ignition and avoid soot formation.
  • unit operation within a system for generating syngas includes: a hot oxygen burner assembly integrated with an auto thermal reactor for receiving a first stream of fuel and oxygen in the hot oxygen burner to combust said fuel and generate a hot oxygen jet; introducing a hydrocarbon stream in proximity to the exit of the hot oxygen burner wherein said exit is disposed within the auto thermal reactor; igniting the hydrocarbon stream with hot oxygen, performing partial reforming of the hydrocarbon in a non-catalytic zone of the auto thermal reactor, and completing the reforming in a catalytic reaction zones of the of the auto thermal reactor, thereby forming a syngas which exits the reactor at a temperature below 2000° F. and with minimal soot formation.
  • an integrated system for generating syngas including:
  • an integrated system for generating syngas which includes:
  • an integrated system for generating syngas includes:
  • FIG. 1 is a process flow diagram for a related art ATR reactor based system for generating syngas
  • FIG. 2 process flow diagram for a related art POx reactor based system for generating syngas
  • FIG. 3 depicts a process flow diagram of the present invention where an HOB is integrated with the ATR based reactor system for generating syngas.
  • the system generates syngas without employing pre-reformers and fired heater.
  • FIG. 3A depicts a sketch of an HOB/ATR reactor used for the process shown in FIG. 3 .
  • FIG. 4 depicts a process flow diagram of another embodiment of the present invention where an HOB is integrated with the ATR based reactor system for generating syngas.
  • the system generates syngas without employing pre-reformers and fired heater and two hydrocarbon containing streams are introduced in two different locations of an HOB/ATR reactor.
  • FIG. 4A depicts a sketch of an HOB/ATR reactor used for the process shown in FIG. 4 .
  • FIG. 5 depicts a process flow diagram of another embodiment of the present invention where an HOB is integrated with the ATR based reactor system for generating syngas, wherein fuel for HOB bypasses pre-reformer and fired heater.
  • FIG. 5A depicts a sketch of an HOB/ATR reactor used for the process shown in FIG. 5 .
  • FIG. 6 depicts a process flow diagram of another embodiment of the present invention where an HOB is integrated with the ATR based reactor system for generating syngas, wherein fuel for HOB and first hydrocarbon feed bypass pre-reformer and fired heater.
  • FIG. 6A depicts a sketch of an HOB/ATR reactor used for the process shown in FIG. 6 .
  • FIG. 7 depicts a process flow diagram of another embodiment of the present invention where an HOB is integrated with the ATR based reactor system for generating syngas, wherein fuel for HOB and first hydrocarbon feed bypass pre-reformer and fired heater and pre-reformed second feed for an HOB/ATR reactor bypasses fired heater.
  • the present invention provides for a system and method of integrating an HOB, such as the one developed by the assignee of the current invention, into an ATR reactor to design a syngas generation system that minimizes capital expenditure by either eliminating some of the process units or by reducing the sizing thereof.
  • the “HOB/ATR,” as utilized herein, will be understood to be a single unit operation, which is at times referred to as a hot oxygen burner assembly integrated with an auto thermal reformer or simply as an HOB-based reactor.
  • the HOB's ability to control mixing in the ATR reactor such that ignition of the oxygen-containing and hydrocarbon containing streams and subsequent partial oxidation reactions are achieved and soot formation is minimized is leveraged by integrating it into the ATR reactor.
  • the system developed does not require a pre-reformer and a fired heater, thereby simplifying the syngas generation system.
  • the utilization of a catalyst bed to reform a portion of hydrocarbon feed by employing high grade heat results in a reduction of oxygen consumption per unit volume of syngas generated compared to the related art POx system.
  • hydrocarbon shall be understood to mean a natural gas feed, or a refinery-off gas containing various hydrocarbons as well as hydrogen, CO and CO 2 or the like.
  • the exit temperature from an HOB/ATR reactor is below ⁇ 2000° F. and advantageously the syngas generation system utilizes a far less expensive process gas boiler.
  • total stoichiometric ratio shall mean moles of oxygen supplied to process/moles of oxygen required to completely combust hydrocarbons supplied for syngas conversion.
  • burner stoichiometric ratio or “burner SR” shall mean moles of oxygen supplied to burner/moles of oxygen required to completely combust hydrocarbons supplied to the burner.
  • FIG. 3A shows a sketch of an HOB/ATR reactor ( 118 ) to show non-catalytic and catalytic reaction zones of the reactor and entry locations of various feeds to the reactor.
  • This embodiment has several advantages over the related art discussed above.
  • the design of process gas boiler is simplified due to lower inlet temperature ( ⁇ 1900° F. vs. 2600° F.) and minimization of soot in the syngas.
  • the soot scrubber is not needed due to minimization of soot formation.
  • the fired heater and pre-reformer are not needed due to unique design of burner used in the HOB/ATR reactor that minimizes soot formation without the use of pre-reforming.
  • hydrocarbon feedstock stream ( 1 ) is pre-heated to 450-725° F. in hydrocarbon heating device ( 104 ) and the preheated hydrocarbon stream ( 5 ) is routed to desulfurizer device ( 105 ) to form hydrocarbon feed stream ( 8 ).
  • main hydrocarbon feed stream ( 8 ) is split into two separate streams referred to as fuel stream ( 9 ) and feed stream ( 11 ).
  • Fuel stream ( 9 ) usually amounting to about 5-10% of main feed stream ( 8 ), is combusted with oxygen ( 24 ) by HOB ( 180 ) to generate a reactive hot oxygen jet.
  • the amount of fuel ( 9 ) fed to HOB is such that burner SR value is between 3 and 6.
  • the combustion product from HOB is a hot oxygen jet that contains mainly oxygen, CO 2 and H 2 O.
  • the feed stream ( 11 ) is combined with a steam stream ( 68 ) from the steam drum ( 125 ) and the combined mixed feed ( 15 ) is introduced in close proximity to the HOB ( 180 ).
  • One way to ensure that mixed feed ( 15 ) is introduced in close proximity to the HOB is by providing an annular section around HOB as shown in FIG. 3A .
  • Other option is to provide feed ports in the HOB/ATR reactor close to where HOB penetrates the reactor (not shown).
  • the amount of oxygen is adjusted such that total SR for the reactor is between 0.28 and 0.33.
  • oxygen supplied is 0.28 to 0.33 times the amount needed for complete combustion of stream 8 .
  • the reaction between hot oxygen jet and combined mixed feed ( 15 ) in a non-catalytic zone of the reactor generates syngas. Mixing the streams in the non-catalytic zone in this manner, the streams ( 9 ) and ( 15 ) are mixed sufficiently quick to avoid soot formation by the hydrocarbons in the reactor, but sufficiently slow to avoid soot formation by cracking of the hydrocarbons in the hot gas stream.
  • the syngas than enters the catalyst bed where further reforming takes place.
  • the syngas ( 20 ) exits the reactor at about 1800 to 1900° F. and at about 350 to 550 psia.
  • the syngas composition depends on relative amounts of hydrocarbon feed stream ( 8 ), oxygen ( 24 ) and steam stream ( 68 ) are supplied in the system.
  • the range of concentrations of various components on a molar basis could be ranging from 40 to 60% for hydrogen, 20 to 35% for CO, 10 to 25% for H 2 O, 1 to 7% for CO 2 , 0 to 2% of CH 4 and ⁇ 1% other components including nitrogen, argon, NH 3 , and HCN.
  • the lower exit temperature from the reactor ( 118 ) enables use of a steam generation system comprising process gas reboiler ( 150 ) and steam drum ( 125 ) that is similar to that in embodiment of FIG.
  • syngas cooler ( 152 ) 1 and significantly less expensive compared to more expensive syngas cooler ( 152 ) of the embodiment of the related art shown in FIG. 2 .
  • it eliminates the need of pre-reformer ( 110 ) or the fired heater ( 100 ) of the related art embodiments in FIG. 1 or the soot scrubber ( 154 ) in the related art embodiment of FIG. 2 , thereby reducing capital expenditure.
  • Partially cooled syngas ( 22 ) at 550 to 750° F., from process gas boiler ( 150 ) is used to preheat hydrocarbon feed in the hydrocarbon heating device ( 104 ).
  • Syngas stream ( 27 ) is then routed to a boiler feed water heater ( 155 ) to preheat boiler feed water to about 10 to 50° F. below its boiling point.
  • Syngas is further cooled through water heater ( 160 ) and cooler ( 165 ).
  • the cooled syngas ( 30 ) is separated in a condensate separator to generate syngas product ( 32 )
  • FIG. 4 depicts an alternative exemplary embodiment, in which main hydrocarbon feed stream ( 8 ) is split into three fractions.
  • One fraction forms first fuel stream ( 9 ) with flow ranging from about 5-10% of the main hydrocarbon feed flow of stream ( 8 ).
  • a second fraction forms a first feed stream ( 11 ) for reactor with flow of 50 to 85% of main hydrocarbon feed stream ( 8 ).
  • the third fraction forms a second feed stream ( 18 ) with flow of sufficient quantity to achieve the total SR desired by the operator.
  • This second feed is combined with steam ( 68 ) to form a second feed stream ( 15 ) for the reactor.
  • First fuel stream ( 9 ) is introduced into the HOB along with oxygen ( 24 ) to form a hot oxygen stream and first feed stream ( 11 ) is introduced into a section closest to the nozzle of the HOB ( 180 ) in reactor ( 118 ) such that this first feed stream ( 11 ) is preferentially entrained into the hot gas jet over second feed stream ( 15 ).
  • the first feed stream ( 11 ) is ignited by the hot oxygen stream to create a reactive jet, partially reforming the hydrocarbon in a non-catalytic zone of the auto thermal reactor.
  • the second feed stream ( 15 ) is introduced after first feed stream ( 11 ) has been predominantly entrained into the reactive jet.
  • One option for introducing second feed stream ( 15 ) is just upstream of catalyst bed in the HOB/ATR reactor ( 118 ) as shown in FIG. 4A .
  • the total SR value in the non-catalytic reaction zone of the reactor would be similar to a conventional HOB reactor at 0.35 to 0.37 and syngas exiting the non-catalytic reaction zone would contain minimal soot.
  • the soot is minimized by mixing the streams sufficiently quick to avoid soot formation by hydrocarbons in the reactor, but slow enough to avoid soot formation by cracking of the hydrocarbons in the hot gas stream, as described in detail in U.S. Pat. No. 9,540,240 B2, which is incorporated herein in its entirety.
  • the syngas temperature toward the end of the non-catalytic zone would be 2500 to 2700° F.
  • This syngas and second feed stream ( 18 ) are mixed just upstream of the catalyst bed and temperature of the syngas decreases to below 2100° F. as a result.
  • This syngas then enters the catalyst zone, where thermal energy from the syngas aids in endothermic reforming of hydrocarbons in the second feed ( 18 ).
  • the syngas exiting the reactor ( 118 ) is similar in temperature, pressure and composition to those described earlier for FIG. 3 .
  • the total SR value for the entire reactor (non-catalytic and catalytic zones) when all the hydrocarbon containing stream ( 9 ), ( 11 ) and ( 18 ) are considered would be similar to that of embodiment of FIG. 3 at 0.28 to 0.33.
  • FIGS. 3 and 4 are envisioned where the system configuration for the embodiments of FIGS. 3 and 4 , steam generation equipment process gas boiler ( 150 ) and steam drum ( 125 ) are replaced by a quench vessel (not shown), which utilizes direct contact with water.
  • Partially cooled syngas ( 22 ) at 550 to 750° F., from process gas boiler ( 150 ) is used to preheat hydrocarbon feed in the hydrocarbon heating device ( 104 ).
  • Syngas stream ( 27 ) is then routed to a boiler feed water heater ( 155 ) to preheat boiler feed water to about 10 to 50° F. below its boiling point.
  • Syngas is further cooled through water heater ( 160 ) and cooler ( 165 ).
  • the cooled syngas ( 30 ) is separated in a condensate separator to generate syngas product ( 32 ) for further use in a downstream process.
  • FIGS. 3 and 4 shows embodiments with significant simplifications in systems of prior art
  • the HOB/ATR reactor can be deployed in a conventional ATR like system of FIG. 1 to achieve improvements over the related art.
  • an alternative exemplary embodiment depicts a system/process configuration change to that of related art system of FIG. 1 .
  • FIG. 5A a sketch of an HOB/ATR reactor ( 118 ) including HOB assembly ( 180 ) is depicted. Since the ‘fuel’ fed to the HOB ( 180 ) is completely combusted before it enters HOB/ATR ( 118 ) it is possible to use non-pre-reformed feed, or opportunity fuels as a fuel stream in HOB.
  • “opportunity fuels” will be understood to mean any hydrocarbon that can provide an economic advantage, including but not limited to refinery off-gases, tail gases, and other associated gases. As shown in FIG.
  • a portion of desulfurized NG ( 8 ) is split as a slip stream of hydrocarbon fuel ( 9 ), which bypasses pre-reformer ( 110 ) and is fed directly to HOB/ATR ( 118 ), specifically into HOB assembly ( 180 ). This would reduce the need for prereforming this portion of the total feed and associated heating duty within fired heater.
  • FIG. 6 a variation in the system of FIG. 5 is provided.
  • the mixing can be carefully controlled within HOB assembly ( 180 ), it is possible to introduce a specific portion of the feed as first feed stream ( 19 ) a hydrocarbon gas split from the hydrocarbon main stream ( 8 ) is routed near the burner such that this feed is entrained into the jet prior to introducing the second feed stream ( 16 ) which consists of pre-reformed natural gas. Since reactions in this portion of the jet are fuel lean enough to avoid soot formation, it can be possible to feed unreformed feed into this region without forming soot.
  • desulfurized hydrocarbon main stream ( 8 ) is split into three fractions: hydrocarbon fuel stream ( 9 ) which is fed to HOB/ATR ( 118 ) to support the fuel lean combustion, specifically into HOB assembly ( 180 ); stream of hydrocarbon ( 19 ) which is fed as first feed to HOB/ATR ( 118 ), specifically into close proximity of HOB assembly ( 180 ) and a stream of desulfurized hydrocarbon ( 18 ), which is first routed through fired heater ( 100 ).
  • Desulfurized hydrocarbon feedstock stream ( 18 ) is mixed with steam stream ( 35 ) and processed through pre-reformer ( 110 ) and fired heater ( 100 ) as described with respect to the embodiment of FIG. 1 to generate pre-heated pre-reformed feed stream ( 16 ), which is fed to HOB/ATR ( 118 ) as second feed stream.
  • pre-reformer 110
  • fired heater 100
  • pre-heated pre-reformed feed stream 16
  • HOB/ATR 118
  • the reaction of the hydrocarbon fuel stream ( 9 ) and the fuel lean combustion product from the HOB assembly ( 180 ) are not likely to form soot.
  • the pre-reformer duty can be reduced, and in some situations alternative fuels from within or outside the integrated system could be used, in essence reducing the size of the fired heater and/or the pre-reformer and enabling use of lower cost fuel and/or refinery off-gas streams.
  • pre-reformed hydrocarbon feed ( 14 ) is directly fed to HOB/ATR ( 118 ) a second feed.
  • eliminating the preheating of this steam reduces the duty of the fired heater.
  • the total SR is increased, thereby reducing the soot forming potential.
  • Table 2 summarizes key comparative parameters of syngas generation systems in the embodiments of FIGS. 1 through 7 , detailed above. All the embodiments of this invention ( FIGS. 3 through 7 ) achieves H2/CO ratio of between 2.2 to 2.4.
  • Embodiments of FIGS. 3 and 4 consume about the same NG while consuming ⁇ 10% less oxygen in comparison to relate art embodiment of FIG. 2 . This improved performance is achieved by embodiments of FIGS. 3 and 4 while simultaneously reducing process complexity by eliminating soot scrubber and using a lower cost boiler when compared to FIG. 2 .
  • the embodiments described with respect to FIGS. 3 and 4 consume slightly less NG and ⁇ 22% more oxygen while significantly lowering process complexity by eliminating fired heater and pre-reformer.
  • FIG. 1 FIG. 2 (related (related Emodiment art) art)
  • FIG. 3 FIG. 4
  • FIG. 5 FIG. 6
  • FIG. 7 H2 + CO in SG
  • 20 20 20 20 20 20 20 20 20 20 MMscfd NG/(H2 + CO) 0.388 0.380 0.377 0.382 0.391 0.396 0.395 O2/(H2 + CO) 0.200 0.272 0.245 0.246 0.204 0.209 0.226 H2/CO ratio 2.4 1.6 2.2 2.2 2.4 2.4 2.4
  • Steam export, 27584 44281 30668 31068 29921 29738 29589 lb/hr
  • Prereformer size 1 n/a n/a n/a 0.95 0.68 0.68
  • Fired heater size 1 n/a n/a n/a 0.98 0.89 0.56
  • Embodiments of FIGS. 5, 6 and 7 consumes slightly more NG and oxygen compared to the related art embodiment of FIG. 1 while achieving size reduction for the fired heater between 5% and 32% and that for the pre-reformer between 2% and 44%.

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US15/905,292 US20190263659A1 (en) 2018-02-26 2018-02-26 Integration of a hot oxygen burner with an auto thermal reformer
PCT/US2019/015989 WO2019164649A1 (en) 2018-02-26 2019-01-31 Integration of a hot oxygen burner with an auto thermal reformer
KR1020207025726A KR102493874B1 (ko) 2018-02-26 2019-01-31 고온 산소 버너와 자열 개질기의 통합
BR112020015822-4A BR112020015822A2 (pt) 2018-02-26 2019-01-31 Operação unitária dentro de um sistema para gerar gás de síntese, e, sistema integrado para gerar gás de síntese.
EP19705658.3A EP3759047B1 (en) 2018-02-26 2019-01-31 Integration of a hot oxygen burner with an auto thermal reformer
ES19705658T ES2964329T3 (es) 2018-02-26 2019-01-31 Integración de un quemador de oxígeno caliente con un reformador autotérmico
CN201980012639.2A CN111699154A (zh) 2018-02-26 2019-01-31 热氧燃烧器与自热重整器的集成
KR1020237003017A KR102650849B1 (ko) 2018-02-26 2019-01-31 고온 산소 버너와 자열 개질기의 통합
CA3090983A CA3090983C (en) 2018-02-26 2019-01-31 Integration of a hot oxygen burner with an auto thermal reformer
MX2020008307A MX2020008307A (es) 2018-02-26 2019-01-31 Integracion de quemador de oxigeno caliente con reformador autotermico.
US17/211,148 US12006214B2 (en) 2018-02-26 2021-03-24 Integration of a hot oxygen burner with an auto thermal reformer

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US20210206633A1 (en) 2021-07-08
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CN111699154A (zh) 2020-09-22
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