WO2020142595A1

WO2020142595A1 - Catalyst activity management in catalytic partial oxidation

Info

Publication number: WO2020142595A1
Application number: PCT/US2020/012036
Authority: WO
Inventors: Sivadinarayana Chinta; Narayanaswamy RAVICHANDER; Atul Pant
Original assignee: SABIC Global Technologies BV
Current assignee: SABIC Global Technologies BV
Priority date: 2019-01-02
Filing date: 2020-01-02
Publication date: 2020-07-09
Anticipated expiration: 2021-07-02

Abstract

A process for producing syngas comprising reacting, via a catalytic partial oxidation (CPO) reaction, a CPO reactant mixture in a CPO reactor to produce the syngas; wherein the CPO reactant mixture comprises hydrocarbons and oxygen; wherein the CPO reactor comprises a CPO catalyst; wherein a portion of the hydrocarbons in the CPO reactant mixture undergo decomposition to carbon and hydrogen; wherein the syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; wherein the CPO catalyst is characterized by a catalyst productivity variation within about <u>+</u> 20% of a target catalyst productivity over a time period of equal to or greater than about 500 hours (h), and wherein catalyst productivity is defined as the amount of syngas recovered from the CPO reactor divided by the amount of hydrocarbons introduced to the CPO reactor.

Description

CATALYST ACTIVITY MANAGEMENT IN CATALYTIC PARTIAL OXIDATION

TECHNICAL FIELD

[0001] The present disclosure relates to methods of producing syngas, more specifically methods of producing syngas by catalytic partial oxidation (CPO) of hydrocarbons, while maintaining CPO catalyst activity.

BACKGROUND

[0002] Synthesis gas (syngas) is a mixture comprising carbon monoxide (CO) and hydrogen (H₂), as well as small amounts of carbon dioxide (C0₂), water (H₂0), and unreacted methane (CEE). 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.

[0003] Syngas is produced conventionally by steam reforming of natural gas (steam methane reforming or SMR), although other hydrocarbon sources can be used for syngas production, such as refinery off-gases, naphtha feedstocks, heavy hydrocarbons, coal, biomass, etc. SMR is an endothermic process and requires significant energy input to drive the reaction forward. Conventional endothermic technologies such as SMR produce syngas with a hydrogen content greater than the required content for methanol synthesis. Generally, SMR produces syngas with an M ratio ranging from 2.6 to 2.98, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂).

[0004] In an autothermal reforming (ATR) process, a portion of the natural gas is burned as fuel to drive the conversion of natural gas to syngas resulting in relatively low hydrogen and high C0₂ concentrations. Conventional methanol production plants utilize a combined reforming (CR) technology that pairs SMR with autothermal reforming (ATR) to reduce the amount of hydrogen present in syngas. ATR produces a syngas with a hydrogen content lower than the required content for methanol synthesis. Generally, ATR produces syngas with an M ratio ranging from 1.7 to 1.84. In the CR technology, the natural gas feed volumetric flowrate to the SMR and the ATR can be adjusted to achieve an overall syngas M ratio of 2.0 to 2.06. Further, CR syngas has a hydrogen content greater than the required content for methanol synthesis. Furthermore, SMR is a highly endothermic process, and the endothermicity of the SMR technology requires burning fuel to drive the syngas synthesis. Consequently, the SMR technology reduces the energy efficiency of the methanol synthesis process.

[0005] Syngas can also be produced (non-commercially) by catalytic partial oxidation (CPO or CPOx) of natural gas. CPO processes employ partial oxidation of hydrocarbon feeds to syngas comprising CO and H₂. The CPO process is exothermic, thus eliminating the need for external heat supply. However, the composition of the produced syngas is not suitable for methanol synthesis, for example, owing to a reduced hydrogen content. Further, maintaining a desired catalyst activity and productivity can be challenging in a CPO process, owing to elevated or run-away CPO temperatures leading to catalyst deactivation. The CPO reaction is exothermic, and can lead to a high temperature increase in a CPO catalyst bed, which can in turn lead to catalyst deactivation. Furthermore, coke deposition on the CPO catalyst can lead to catalyst deactivation. Thus, there is an ongoing need for the development of syngas production processes via CPO processes that can maintain catalyst activity and productivity.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] For a detailed description of the preferred aspects of the disclosed methods, reference will now be made to the accompanying drawing in which:

[0007] The Figure displays a schematic of a system for a methanol production process.

DETAILED DESCRIPTION

[0008] Disclosed herein are processes for producing syngas comprising reacting, via a catalytic partial oxidation (CPO) reaction, a CPO reactant mixture in a CPO reactor to produce the syngas; wherein the CPO reactant mixture comprises hydrocarbons and oxygen; wherein the CPO reactor comprises a CPO catalyst; wherein a portion of the hydrocarbons in the CPO reactant mixture undergo decomposition to carbon and hydrogen; wherein the syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; wherein the CPO catalyst is characterized by a catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 hours (h), and wherein catalyst productivity is defined as the amount of syngas recovered from the CPO reactor divided by the amount of hydrocarbons introduced to the CPO reactor. In an aspect, the CPO reactant mixture further comprises carbon dioxide and water (e.g., steam). In an aspect, the CPO reactor can be operated under near- isothermal conditions, wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the CPO reactor and/or a catalyst bed thereof, and wherein the catalyst bed comprises the CPO catalyst. In an aspect, carbon (e.g., coke) can deposit onto the CPO catalyst to produce a spent CPO catalyst, wherein a portion of the spent CPO catalyst can be removed from the CPO reactor, and wherein additional CPO catalyst (e.g., active CPO catalyst) can be introduced to the CPO reactor. The hydrocarbons used for syngas production can 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, fuel gas from fuel gas header, and the like, or combinations thereof. The syngas can be further used in a methanol production process.

[0009] Other than in the operating examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as modified in all instances by the term“about.” Various numerical ranges are disclosed herein. Because these ranges are continuous, they include every value between the minimum and maximum values. The endpoints of all ranges reciting the same characteristic or component are independently combinable and inclusive of the recited endpoint. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations. The endpoints of all ranges directed to the same component or property are inclusive of the endpoint and independently combinable. The term“from more than 0 to an amount” means that the named component is present in some amount more than 0, and up to and including the higher named amount.

[0010] The terms“a,”“an,” and“the” do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. As used herein the singular forms“a,”“an,” and“the” include plural referents.

[0011] As used herein,“combinations thereof’ is inclusive of one or more of the recited elements, optionally together with a like element not recited, e.g., inclusive of a combination of one or more of the named components, optionally with one or more other components not specifically named that have essentially the same function. As used herein, the term“combination” is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0012] Reference throughout the specification to“an aspect,”“another aspect,”“other aspects,”“some aspects,” and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the aspect is included in at least an aspect described herein, and may or may not be present in other aspects. In addition, it is to be understood that the described element(s) can be combined in any suitable manner in the various aspects.

[0013] As used herein, 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.

[0014] As used herein, the term“effective,” means adequate to accomplish a desired, expected, or intended result.

[0015] As used herein, 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.

[0016] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art.

[0017] Compounds are described herein using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash (“-”) that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through the carbon of the carbonyl group.

[0018] As used herein, the terms“C_x hydrocarbons” and“C_xs” are interchangeable and refer to any hydrocarbon having x number of carbon atoms (C). For example, the terms“C hydrocarbons” and“C₄s” both refer to any hydrocarbons having exactly 4 carbon atoms, such as n-butane, iso-butane, cyclobutane, 1 - butene, 2-butene, isobutylene, butadiene, and the like, or combinations thereof.

[0019] As used herein, the term“C_x+ hydrocarbons” refers to any hydrocarbon having equal to or greater than x carbon atoms (C). For example, the term“C₂₊ hydrocarbons” refers to any hydrocarbons having 2 or more carbon atoms, such as ethane, ethylene, C₃s, C s, C₅s, etc.

[0020] Referring to the Figure, a methanol production system 1000 is disclosed. The methanol production system 1000 generally comprises a catalytic partial oxidation (CPO or CPOx) reactor 100; a methanol reactor 200; a gas-liquid separator 300; a distillation unit 400; a hydrogen (H₂) recovery unit 500; and a carbon dioxide (C0₂) separator 600. As will be appreciated by one of skill in the art, and with the help of this disclosure, methanol production system components shown in the Figure can be in fluid communication with each other (as represented by the connecting lines indicating a direction of fluid flow) through any suitable conduits (e.g., pipes, streams, etc.).

[0021] In an aspect, a process as disclosed herein can comprise a step of reacting, via a CPO reaction, a CPO reactant mixture 10 in the CPO reactor 100 to produce syngas 15; wherein the CPO reactant mixture 10 comprises hydrocarbons and oxygen; wherein the CPO reactor 100 comprises a CPO catalyst; and wherein the syngas 15 comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons.

[0022] Generally, the 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):

CH₄ + 1/2 0₂ C0 + 2 H₂ (1)

Without wishing to be limited by theory, side reactions can take place along with the CPO reaction depicted in equation (1); and such side reactions can produce carbon dioxide (C0₂) and water (H₂0), for example via hydrocarbon combustion, which is an exothermic reaction. As will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, the CPO reaction as represented by equation (1) can yield a syngas with a hydrogen to carbon monoxide (H₂/CO) molar ratio having the theoretical stoichiometric limit of 2.0. Without wishing to be limited by theory, the theoretical stoichiometric limit of 2.0 for the H₂/CO molar ratio means that the CPO reaction as represented by equation (1) yields 2 moles of H₂ for every 1 mole of CO, i.e., H₂/CO molar ratio of (2 moles H₂/l mole CO) = 2. As will be appreciated by one of skill in the art, and with the help of this disclosure, the theoretical stoichiometric limit of 2.0 for the H₂/CO molar ratio in a CPO reaction cannot be achieved practically because reactants (e.g., hydrocarbons, oxygen) as well as products (e.g., H₂, CO) undergo side reactions at the conditions used for the CPO reaction. As will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, in the presence of oxygen, CO and H₂ can be oxidized to C0₂ and H₂0, respectively. The relative amounts (e.g., composition) of CO, H₂, C0₂ and H₂0 can be further altered by the equilibrium of the water-gas shift (WGS) reaction, which will be discussed in more detail later herein. The side reactions that can take place in the CPO reactor 100 can have a direct impact on the M ratio of the produced syngas (e.g., syngas 15), wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂). In the absence of any side reaction (theoretically), the CPO reaction as represented by equation (1) results in a syngas with an M ratio of 2.0. However, the presence of side reactions (practically) reduces H₂ and increases C0₂, thereby resulting in a syngas with an M ratio below 2.0.

[0023] Further, without wishing to be limited by theory, the CPO reaction as depicted in equation (1) is an exothermic heterogeneous catalytic reaction (i.e., a mildly exothermic reaction) and it occurs in a single reactor unit, such as the CPO reactor 100 (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). While it is possible to conduct partial oxidation of hydrocarbons as a homogeneous reaction, in the absence of a catalyst, 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.

[0024] Furthermore, without wishing to be limited by theory, 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. By contrast, conventional ATR processes have more restrictive feed requirements, for example in terms of content of impurities in the feed (e.g., feed to ATR is desulfurized), as well as hydrocarbon composition (e.g., ATR primarily uses a CH -rich feed).

[0025] In an aspect, the hydrocarbons suitable for use in a CPO reaction as disclosed herein can include methane (CTf), 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, fuel gas from fuel gas header, and the like, or combinations thereof. The hydrocarbons can include any suitable hydrocarbons source, and can contain Ci-C₆ hydrocarbons, as well some heavier hydrocarbons.

[0026] In an aspect, the CPO reactant mixture 10 can comprise natural gas. Generally, natural gas is composed primarily of methane, but can also contain ethane, propane and heavier hydrocarbons (e.g., iso butane, n-butane, iso-pentane, n-pentane, hexanes, etc.), as well as very small quantities of nitrogen, oxygen, carbon dioxide, sulfur compounds, and/or water. The natural gas can be provided from a variety of sources including, but not limited to, gas fields, oil fields, coal fields, fracking of shale fields, biomass, landfill gas, and the like, or combinations thereof. In some aspects, the CPO reactant mixture 10 can comprise CH₄ and 0₂. [0027] The natural gas can comprise any suitable amount of methane. In some aspects, the natural gas can comprise biogas. For example, the natural gas can comprise from about 45 mol% to about 80 mol% methane, from about 20 mol% to about 55 mol% carbon dioxide, and less than about 15 mol% nitrogen.

[0028] In an aspect, natural gas can comprise CH₄ in an amount of equal to or greater than about 45 mol%, alternatively equal to or greater than about 50 mol%, alternatively equal to or greater than about 55 mol%, alternatively equal to or greater than about 60 mol%, alternatively equal to or greater than about 65 mol%, alternatively equal to or greater than about 70 mol%, alternatively equal to or greater than about 75 mol%, alternatively equal to or greater than about 80 mol%, alternatively equal to or greater than about 82 mol%, alternatively equal to or greater than about 84 mol%, alternatively equal to or greater than about 86 mol%, alternatively equal to or greater than about 88 mol%, alternatively equal to or greater than about 90 mol%, alternatively equal to or greater than about 91 mol%, alternatively equal to or greater than about 92 mol%, alternatively equal to or greater than about 93 mol%, alternatively equal to or greater than about 94 mol%, alternatively equal to or greater than about 95 mol%, alternatively equal to or greater than about 96 mol%, alternatively equal to or greater than about 97 mol%, alternatively equal to or greater than about 98 mol%, or alternatively equal to or greater than about 99 mol%.

[0029] In some aspects, the hydrocarbons suitable for use in a CPO reaction as disclosed herein can comprise C C₆ hydrocarbons, nitrogen (e.g., from about 0.1 mol% to about 15 mol%, alternatively from about 0.5 mol% to about 11 mol%, alternatively from about 1 mol% to about 7.5 mol%, or alternatively from about 1.3 mol% to about 5.5 mol%), and carbon dioxide (e.g., from about 0.1 mol% to about 2 mol%, alternatively from about 0.2 mol% to about 1 mol%, or alternatively from about 0.3 mol% to about 0.6 mol%). For example, the hydrocarbons suitable for use in a CPO reaction as disclosed herein can comprise Ci hydrocarbon (about 89 mol% to about 92 mol%); C₂ hydrocarbons (about 2.5 mol% to about 4 mol%); C₃ hydrocarbons (about 0.5 mol% to about 1.4 mol%); C₄ hydrocarbons (about 0.5 mol% to about 0.2 mol%); C₅ hydrocarbons (about 0.06 mol%); and C₆ hydrocarbons (about 0.02 mol%); and optionally nitrogen (about 0.1 mol% to about 15 mol%), carbon dioxide (about 0.1 mol% to about 2 mol%), or both nitrogen (about 0.1 mol% to about 15 mol%) and carbon dioxide (about 0.1 mol% to about 2 mol%).

[0030] The oxygen used in the CPO reactant mixture 10 can comprise 100% oxygen (substantially pure 0₂), 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., 0₂/C0₂, 0₂/H₂0, 0₂/H₂0₂/H₂0), oxy radical generators (e.g., CH₃OH, CH₂0), hydroxyl radical generators, and the like, or combinations thereof. [0031] In an aspect, the CPO reactant mixture 10 can be characterized by a carbon to oxygen (C/O) molar ratio of less than about 3 : 1, alternatively less than about 2.6: 1, alternatively less than about 2.4: 1, alternatively less than about 2.2: 1, alternatively less than about 2: 1, alternatively less than about 1.9: 1, alternatively equal to or greater than about 2: 1, alternatively equal to or greater than about 2.2: 1, alternatively equal to or greater than about 2.4: 1, alternatively equal to or greater than about 2.6: 1, alternatively from about 0.5: 1 to about 3 : 1, alternatively from about 0.7: 1 to about 2.5: 1, alternatively from about 0.9: 1 to about 2.2: 1, alternatively from about 1 : 1 to about 2: 1, alternatively from about 1.1 : 1 to about 1.9: 1, alternatively from about 2: 1 to about 3 : 1, alternatively from about 2.2: 1 to about 3: 1, alternatively from about 2.4: 1 to about 3: 1, or alternatively from about 2.6: 1 to about 3: 1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0₂) in the reactant mixture.

[0032] For example, when the only source of carbon in the CPO reactant mixture 10 is CH₄, the CH₄/O₂ molar ratio is the same as the C/O molar ratio. As another example, when the CPO reactant mixture 10 contains other carbon sources besides CH₄, such as ethane (C₂H₆), propane (C H₈), butanes (C₄H₁₀), etc., the C/O molar ratio accounts for the moles of carbon in each compound (e.g., 2 moles of C in 1 mole of C₂H₆, 3 moles of C in 1 mole of C H₈, 4 moles of C in 1 mole of C₄H₁₀, etc.). As will be appreciated by one of skill in the art, and with the help of this disclosure, the C/O molar ratio in the CPO reactant mixture 10 can be adjusted along with other reactor process parameters (e.g., temperature, pressure, flow velocity, etc.) to provide for a syngas with a desired composition (e.g., a syngas with a desired H₂/CO molar ratio; a syngas with a desired C0₂ content; etc.). The C/O molar ratio in the CPO reactant mixture 10 can be adjusted to provide for a decreased amount of unconverted hydrocarbons in the syngas. The C/O molar ratio in the CPO reactant mixture 10 can be adjusted based on the CPO effluent temperature in order to decrease (e.g., minimize) the unconverted hydrocarbons content of the syngas 15. As will be appreciated by one of skill in the art, and with the help of this disclosure, when the syngas is further used in a methanol production process, unconverted hydrocarbons present in the syngas can undesirably accumulate in a methanol reaction loop, thereby decreasing the efficiency of the methanol production process.

[0033] In an aspect, a CPO reactor suitable for use in the present disclosure (e.g., CPO reactor 100) can comprise a tubular reactor, a continuous flow reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a circulating fluidized bed reactor (e.g., a riser type reactor), a bubbling bed reactor, an ebullated bed reactor, a rotary kiln reactor, and the like, or combinations thereof. In some aspects, the CPO reactor can comprise a circulating fluidized bed reactor, such as a riser type reactor.

[0034] In some aspects, the CPO reactor 100 can be characterized by at least one CPO operational parameter selected from the group consisting of a CPO reactor temperature (e.g., CPO catalyst bed temperature); CPO feed temperature (e.g., CPO reactant mixture temperature); target CPO effluent temperature; a CPO pressure (e.g., CPO reactor pressure); a CPO contact time (e.g., CPO reactor contact time); a C/O molar ratio in the CPO reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture, wherein the S/C molar ratio refers to the total moles of water (H₂0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof. For purposes of the disclosure herein, the CPO effluent temperature is the temperature of the syngas (e.g., syngas effluent; syngas 15) measured at the point where the syngas exits the CPO reactor (CPO reactor 100), e.g., a temperature of the syngas measured at a CPO reactor outlet, a temperature of the syngas effluent, a temperature of the exit syngas effluent. For purposes of the disclosure herein, the CPO effluent temperature (e.g., target CPO effluent temperature) is considered an operational parameter. As will be appreciated by one of skill in the art, and with the help of this disclosure, the choice of operational parameters for the CPO reactor such as CPO feed temperature; CPO pressure; CPO contact time; C/O molar ratio in the CPO reactant mixture; S/C molar ratio in the CPO reactant mixture; etc. determines the temperature of the syngas effluent (e.g., syngas 15), as well as the composition of the syngas effluent (e.g., syngas 15). Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, monitoring the CPO effluent temperature can provide feedback for changing other operational parameters (e.g., CPO feed temperature; CPO pressure; CPO contact time; C/O molar ratio in the CPO reactant mixture; S/C molar ratio in the CPO reactant mixture; etc.) as necessary for the CPO effluent temperature to match the target CPO effluent temperature. Furthermore, and as will be appreciated by one of skill in the art, and with the help of this disclosure, the target CPO effluent temperature is the desired CPO effluent temperature, and the CPO effluent temperature (e.g., measured CPO effluent temperature, actual CPO effluent temperature) may or may not coincide with the target CPO effluent temperature. In aspects where the CPO effluent temperature is different from the target CPO effluent temperature, one or more CPO operational parameters (e.g., CPO feed temperature; CPO pressure; CPO contact time; C/O molar ratio in the CPO reactant mixture; S/C molar ratio in the CPO reactant mixture; etc.) can be adjusted (e.g., modified) in order for the CPO effluent temperature to match (e.g., be the same with, coincide with) the target CPO effluent temperature. The CPO reactor 100 can be operated under any suitable operational parameters that can provide for a syngas with a desired composition (e.g., a syngas with a desired Ffi/CO molar ratio; a syngas with a desired C0₂ content; etc.).

[0035] The CPO reactor 100 can be characterized by a CPO feed temperature of from about 25 °C to about 600 °C, alternatively from about 25 °C to about 500 °C, alternatively from about 25 °C to about 400 °C, alternatively from about 50 °C to about 400 °C, or alternatively from about 100 °C to about 400 °C. In aspects where the CPO reactant mixture comprises steam, the CPO feed temperature can be as high as about 600 °C, alternatively about 575 °C, alternatively about 550 °C, or alternatively about 525 °C. In aspects where the CPO reactant mixture does not comprise steam, the CPO feed temperature can be as high as about 450 °C, alternatively about 425 °C, alternatively about 400 °C, or alternatively about 375 °C.

[0036] The CPO reactor 100 can be characterized by a CPO effluent temperature (e.g., target CPO effluent temperature) of equal to or greater than about 300 °C, alternatively equal to or greater than about 600 °C, alternatively equal to or greater than about 700 °C, alternatively equal to or greater than about 750 °C, alternatively equal to or greater than about 800 °C, alternatively equal to or greater than about 850 °C, alternatively from about 300 °C to about 1,600 °C, alternatively from about 600 °C to about 1,400 °C, alternatively from about 600 °C to about 1,300 °C, alternatively from about 700 °C to about 1,200 °C, alternatively from about 750 °C to about 1,150 °C, alternatively from about 800 °C to about 1,125 °C, or alternatively from about 850 °C to about 1,100 °C.

[0037] In an aspect, the CPO reactor 100 can be characterized by any suitable reactor temperature and/or catalyst bed temperature. For example, the CPO reactor 100 can be characterized by a reactor temperature and/or catalyst bed temperature of equal to or greater than about 300 °C, alternatively equal to or greater than about 600 °C, alternatively equal to or greater than about 700 °C, alternatively equal to or greater than about 750 °C, alternatively equal to or greater than about 800 °C, alternatively equal to or greater than about 850 °C, alternatively from about 300 °C to about 1,600 °C, , alternatively from about 600 °C to about 1,400 °C, alternatively from about 600 °C to about 1,300 °C, alternatively from about 700 °C to about 1,200 °C, alternatively from about 750 °C to about 1,150 °C, alternatively from about 800 °C to about 1,125 °C, or alternatively from about 850 °C to about 1,100 °C.

[0038] The CPO reactor 100 can be operated under any suitable temperature profde that can provide for a syngas with a desired composition (e.g., a syngas with a desired H₂/CO molar ratio; a syngas with a desired C0₂ content; etc.). The CPO reactor 100 can be operated under adiabatic conditions, non-adiabatic conditions, isothermal conditions, near-isothermal conditions, etc. For purposes of the disclosure herein, the term“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. As will be appreciated by one of skill in the art, and with the help of this disclosure, the terms“direct heat exchange” and“indirect heat exchange” are known to one of skill in the art. By contrast, the term“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). Generally, external heat exchange implies an external heat exchange system (e.g., a cooling system; a heating system) that requires energy input and/or output. As will be appreciated by one of skill in the art, and with the help of this disclosure, external heat transfer can also result from heat loss from the catalyst bed (or reactor) owing to radiation heat transfer, conduction heat transfer, convection heat transfer, and the like, or combinations thereof. For example, the catalyst bed can participate in heat exchange with the external environment, and/or with reactor zones upstream and/or downstream of the catalyst bed.

[0039] For purposes of the disclosure herein, the term “isothermal conditions” refers to process conditions (e.g., CPO operational parameters) that allow for a substantially constant temperature of the reactor and/or catalyst bed (e.g., isothermal 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 across the reactor and/or catalyst bed, respectively.

[0040] Further, for purposes of the disclosure herein, the term“isothermal conditions” refers to process conditions (e.g., CPO operational parameters) effective for providing for a syngas with a desired composition (e.g., a desired H₂/CO molar ratio; a desired C0₂ content; etc.), wherein the isothermal conditions comprise a temperature variation of less than about + 10 °C across the reactor and/or catalyst bed.

[0041] The CPO reactor 100 can be operated under any suitable operational parameters that can provide for isothermal conditions.

[0042] For purposes of the disclosure herein, the term“near-isothermal conditions” refers to process conditions (e.g., CPO operational parameters) that allow for a fairly constant temperature of the reactor and/or catalyst bed (e.g., near-isothermal temperature), 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 + 1 °C across the reactor and/or catalyst bed, respectively. In some aspects, near-isothermal conditions allow for a temperature variation of less than about + 50 °C, alternatively less than about + 25 °C, or alternatively less than about + 10 °C across the reactor and/or catalyst bed. Further, for purposes of the disclosure herein, the term“near-isothermal conditions” is understood to include“isothermal” conditions.

[0043] Furthermore, for purposes of the disclosure herein, the term“near-isothermal conditions” refers to process conditions (e.g., CPO operational parameters) effective for providing for a syngas with a desired composition (e.g., a desired H₂/CO molar ratio; a desired C0₂ content; etc.), wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the reactor and/or catalyst bed. [0044] In an aspect, a process as disclosed herein can comprise conducting the CPO reaction under near-isothermal conditions to produce syngas, wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the reactor and/or catalyst bed.

[0045] The CPO reactor 100 can be operated under any suitable operational parameters that can provide for near-isothermal conditions.

[0046] Near-isothermal conditions can be provided by a variety of process and catalyst variables, such as temperature (e.g., heat exchange or heat transfer), 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. Generally, and without wishing to be limited by theory, the terms“heat transfer” or“heat exchange” refer to thermal energy being exchanged or transferred between two systems (e.g., two reactors, such as a CPO reactor and a cracking reactor), and the terms“heat transfer” or“heat exchange” are used interchangeably for purposes of the disclosure herein.

[0047] In some aspects, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by heat exchange or heat transfer. The heat exchange can comprise heating the reactor; or cooling the reactor. In an aspect, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by cooling the reactor. In another aspect, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by heating the reactor.

[0048] In some aspects, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by direct heat exchange and/or indirect heat exchange. As will be appreciated by one of skill in the art, and with the help of this disclosure, the terms“direct heat exchange” and“indirect heat exchange” are known to one of skill in the art.

[0049] The heat exchange can comprise 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, use of a diluent in the CPO reactant mixture, and the like, or combinations thereof. For example, reactive cooling can be effected by carrying out an endothermic reaction in a cooling coil/jacket associated with (e.g., located in) the reactor.

[0050] In some aspects, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by removal of process heat from the CPO reactor. In other aspects, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by supplying heat to the CPO reactor. As will be appreciated by one of skill in the art, and with the help of this disclosure, a CPO reactor may need to undergo both heating and cooling in order to achieve a target CPO effluent temperature and/or near-isothermal conditions.

[0051] In an aspect, the heat exchange or heat transfer can comprise introducing a cooling agent, such as a diluent, into the reactor (e.g., CPO reactor 100), to decrease the reactor temperature and/or the catalyst bed temperature, while increasing a temperature of the cooling agent and/or changing the phase of the cooling agent. The cooling agent can be reactive or non-reactive. The cooling agent can be in liquid state and/or in vapor state. As will be appreciated by one of skill in the art, and with the help of this disclosure, the cooling agent can act as a flammability retardant; for example by reducing the temperature inside the reactor, by changing the gas mixture composition, by reducing the combustion of hydrocarbons to carbon dioxide; etc.

[0052] In some aspects, the CPO reactant mixture 10 can further comprise a diluent, wherein the diluent contributes to achieving a target CPO effluent temperature and/or near-isothermal conditions via 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. Generally, the diluent is inert with respect to the CPO reaction, e.g., the diluent does not participate in the CPO reaction. However, and as will be appreciated by one of skill in the art, and with the help of this disclosure, some diluents (e.g., water, steam, carbon dioxide, etc.) might undergo chemical reactions other than the CPO reaction within the reactor, and can change the composition of the resulting syngas, as will be described in more detail later herein; while other diluents (e.g., nitrogen (N₂), argon (Ar)) might not participate in reactions that change the composition of the resulting syngas. As will be appreciated by one of skill in the art, and with the help of this disclosure, the diluent can be used to vary the composition of the resulting syngas. The diluent can be present in the CPO reactant mixture 10 in any suitable amount.

[0053] In an aspect, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by removal of process heat (Q_out) from the CPO reactor 100, e.g., cooling the CPO reactor 100, for example by heating a cracking reactor and/or heating water to produce steam. As will be appreciated by one of skill in the art, and with the help of this disclosure, a positive Q going“out” (by the direction of the arrows 13, 14) represents that heat is being transferred from that particular reactor, e.g., that particular reactor is being cooled. For example, Q_out 13 and/or Q_out 14 in The Figure indicate that heat is being transferred from the CPO reactor 100 (e.g., the CPO reactor 100 is being cooled), for example to a cracking process and/or a steam production process, respectively. The heat transfer can comprise cooling the CPO reactor 100 while heating a cracking reactor, wherein the cracking reactor can optionally produce ethylene by ethane cracking. In an aspect, a cracking feed can be fed to the cracking reactor, wherein the cracking feed comprises alkanes (e.g., ethane, propane, butanes, naphtha, and the like, or combinations thereof); wherein at least a portion of the alkanes undergoes an endothermic cracking reaction in the cracking reactor to produce a cracking reactor product stream; and wherein the cracking reactor product stream comprises olefins (e.g., ethylene), hydrogen, and unreacted alkanes. The heat transfer can comprise cooling the CPO reactor 100 while heating water to produce steam. In some aspects, the CPO reactor 100 can comprise a water-cooled reactor. The CPO reactor 100 can have internal and/or external cooling elements for water to steam conversion. For example, conduits for water to steam conversion can be used as internal cooling elements in the CPO reactor 100, wherein a portion of the process heat from the CPO reaction heats the water inside such conduits, thereby converting the water to steam. As another example, a cooling external jacket can be used for water to steam conversion.

[0054] In some aspects, the heat transfer (e.g., heat transfer that provides for achieving a target CPO effluent temperature and/or near-isothermal conditions) excludes heat transfer with the syngas effluent (e.g., syngas 15) subsequent to the syngas effluent (e.g., syngas 15) exiting the CPO reactor (e.g., CPO reactor 100). In other aspects, the heat transfer (e.g., heat transfer that provides for achieving a target CPO effluent temperature and/or near-isothermal conditions) can comprise heat transfer with the syngas effluent (e.g., syngas 15) subsequent to the syngas effluent (e.g., syngas 15) exiting the CPO reactor (e.g., CPO reactor 100).

[0055] The CPO reactor 100 can be characterized by a CPO pressure (e.g., reactor pressure measured at the reactor exit or outlet) of equal to or greater than about 1 barg, alternatively equal to or greater than about 10 barg, alternatively equal to or greater than about 20 barg, alternatively equal to or greater than about 25 barg, alternatively equal to or greater than about 30 barg, alternatively equal to or greater than about 35 barg, alternatively equal to or greater than about 40 barg, alternatively equal to or greater than about 50 barg, alternatively less than about 30 barg, alternatively less than about 25 barg, alternatively less than about 20 barg, alternatively less than about 10 barg, alternatively from about 1 barg to about 90 barg, alternatively from about 1 barg to about 70 barg, alternatively from about 1 barg to about 40 barg, alternatively from about 1 barg to about 30 barg, alternatively from about 1 barg to about 25 barg, alternatively from about 1 barg to about 20 barg, alternatively from about 1 barg to about 10 barg, alternatively from about 20 barg to about 90 barg, alternatively from about 25 barg to about 85 barg, or alternatively from about 30 barg to about 80 barg.

[0056] The CPO reactor 100 can be characterized by a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s), alternatively from about 0.001 ms to about 1 s, alternatively from about 0.001 ms to about 100 ms, alternatively from about 0.001 ms to about 10 ms, alternatively from about 0.001 ms to about 5 ms, or alternatively from about 0.01 ms to about 1.2 ms. Generally, the contact time of a reactor comprising a catalyst refers to the average amount of time that a compound (e.g., a molecule of that compound) spends in contact with the catalyst (e.g., within the catalyst bed), e.g., the average amount of time that it takes for a compound (e.g., a molecule of that compound) to travel through the catalyst bed. For purposes of the disclosure herein the contact time of less than about 5 ms can be referred to as“millisecond regime” (MSR); and a CPO process or CPO reaction as disclosed herein characterized by a contact time of less than about 5 ms can be referred to as“millisecond regime”- CPO (MSR-CPO) process or reaction, respectively. [0057] In some aspects, the CPO reactor 100 can be characterized by a contact time of from about 0.001 ms to about 5 ms, or alternatively from about 0.01 ms to about 1.2 ms.

[0058] All of the CPO operational parameters disclosed herein are applicable throughout all of the embodiments disclosed herein, unless otherwise specified. As will be appreciated by one of skill in the art, and with the help of this disclosure, each CPO operational parameter can be adjusted to provide for a desired syngas quality, such as a syngas with a desired composition (e.g., a syngas with a desired H₂/CO molar ratio; a syngas with a desired C0₂ content; etc.). For example, the CPO operational parameters can be adjusted to provide for an increased H₂ content of the syngas. As another example, the CPO operational parameters can be adjusted to provide for a decreased C0₂ content of the syngas. As yet another example, the CPO operational parameters can be adjusted to provide for a decreased unreacted hydrocarbons (e.g., unreacted CH₄) content of the syngas.

[0059] 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. 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. Generally, a noble metal is a metal that resists corrosion and oxidation in a water-containing environment. As will be appreciated by one of skill in the art, and with the help of this disclosure, the components of the CPO catalyst (e.g., metals such as noble metals, non-noble metals, rare earth elements) can be either phase segregated or combined within the same phase.

[0060] In an aspect, the CPO catalysts suitable for use in the present disclosure can be supported catalysts and/or unsupported catalysts. In some aspects, the supported catalysts can comprise a support, wherein the support can be catalytically active (e.g., the support can catalyze a CPO reaction). For example, 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. In other aspects, 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 Si0₂; silicon carbide (SiC); alumina; a catalytically inactive monolithic support; etc. In yet other aspects, the supported catalysts can comprise a catalytically active support and a catalytically inactive support.

[0061] In some aspects, 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. [0062] In some aspects, the CPO catalyst can be a monolith, a foam, a powder, a particle, etc. Nonlimiting examples of 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.

[0063] In some aspects, the support comprises an inorganic oxide, alpha, beta or theta alumina (A1₂0 ), activated A1₂0₃, silicon dioxide (Si0₂), titanium dioxide (Ti0₂), magnesium oxide (MgO), zirconium oxide (Zr0₂), lanthanum (III) oxide (La₂0₃), yttrium (III) oxide (Y₂0₃), cerium (IV) oxide (Ce0₂), zeolites, ZSM- 5, perovskite oxides, hydrotalcite oxides, and the like, or combinations thereof.

[0064] CPO processes, CPO reactors, CPO catalysts, and CPO catalyst bed configurations suitable for use in the present disclosure are described in more detail in U.S. Provisional Patent Application No. 62/522,910 filed June 21, 2017 (International Application No. PCT/IB2018/054475 filed June 18, 2018) and entitled“Improved Reactor Designs for Heterogeneous Catalytic Reactions;” and U.S. Provisional Patent Application No. 62/521,831 filed June 19, 2017 (International Application No. PCT/IB2018/054470 filed June 18, 2018) and entitled“An Improved Process for Syngas Production for Petrochemical Applications;” each of which is incorporated by reference herein in its entirety.

[0065] In an aspect, the CPO catalyst can be characterized by a catalyst productivity variation within about + 20%, alternatively within about + 17.5%, alternatively within about + 15%, alternatively within about + 12.5%, alternatively within about + 10%, alternatively within about + 7.5%, alternatively within about + 5%, alternatively within about + 2.5%, or alternatively within about + 1% of a target catalyst productivity over a time period of equal to or greater than about 500 hours (h), alternatively equal to or greater than about 1,000 h, alternatively equal to or greater than about 2,500 h, alternatively equal to or greater than about 5,000 h, alternatively equal to or greater than about 7,500 h, or alternatively equal to or greater than about 10,000 h; wherein catalyst productivity is defined as the amount of syngas 15 recovered from the CPO reactor 100 divided by the amount of hydrocarbons introduced to the CPO reactor 100. As will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, catalyst productivity is a quantitative measure of catalyst activity, wherein the catalyst activity refers to the ability of a catalyst (e.g., CPO catalyst) to increase the rate of a chemical reaction (e.g., CPO reaction) under a given set of reaction conditions (e.g., CPO operational parameters). For purposes of the disclosure herein, a CPO catalyst having a productivity variation greater than about + 20% can be referred to as a“spent CPO catalyst” (as opposed to an active CPO catalyst). As used herein, the target catalyst productivity is associated with an active CPO catalyst (e.g., fresh CPO catalyst and/or regenerated CPO catalyst). For purposes of the disclosure herein, the term“fresh CPO catalyst” refers to a CPO catalyst that has not been used in a CPO process. As will be appreciated by one of skill in the art, and with the help of this disclosure, an active CPO catalyst displays optimum (e.g., maximum) catalyst activity with respect to a chemical reaction (e.g., CPO reaction) under a given set of reaction conditions (e.g., CPO operational parameters). Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, the target catalyst productivity is the maximum catalyst productivity of an active CPO catalyst (e.g., fresh CPO catalyst and/or regenerated CPO catalyst) under a given set of reaction conditions (e.g., CPO operational parameters). Furthermore, and as will be appreciated by one of skill in the art, and with the help of this disclosure, the terms“catalyst productivity” and“target catalyst productivity” are used in the context of steady-state operation of the CPO reactor (e.g., CPO reactor 100).

[0066] As will be appreciated by one of skill in the art, and with the help of this disclosure, catalyst activity (e.g., CPO catalyst activity) can vary (e.g., decay, decrease) over time, for a variety of reasons, such as poisoning (e.g., feed contaminants), fouling (e.g., coking by carbon produced by cracking/condensation/decomposition reactions of hydrocarbon reactants, intermediates, and/or products), thermal degradation (e.g., collapse of support structure, solid-state reactions, attrition), active component leaching, migration of active components within and/or outside catalyst particles, side reactions, attrition/crushing, and the like, or combinations thereof. Decay in catalyst activity leads to spent catalysts (e.g., spent CPO catalysts). In some aspects, spent catalysts can be regenerated and returned to a production process, as will be described in more detail later herein.

[0067] In an aspect, a portion of the hydrocarbons (e.g., methane) in the CPO reactant mixture 10 can undergo a thermal decomposition reaction to carbon (C) and H₂, for example as represented by equation (2):

CH₄ C + 2 H₂ (2)

The decomposition reaction of hydrocarbons, such as methane, is facilitated by elevated temperatures, and increases the hydrogen content in the syngas 15. However, the carbon produced by the decomposition reaction of hydrocarbons (e.g., a decomposition reaction as represented by equation (2)) can lead to coking of the CPO catalyst via carbon deposition onto the CPO catalyst, thereby producing a spent CPO catalyst. As will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, while the percentage of hydrocarbons in the CPO reactant mixture 10 that undergoes a decomposition reaction (e.g., a decomposition reaction as represented by equation (2)) increases with increasing the C/O molar ratio in the CPO reactant mixture 10, a portion of hydrocarbons can undergo a decomposition reaction to C and H₂ even at relatively low C/O molar ratios in the CPO reactant mixture 10 (e.g., a C/O molar ratio in the CPO reactant mixture 10 of less than about 1 : 1). Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, the quality of the hydrocarbon feed to the CPO reactor 100 can influence coking. For example, higher hydrocarbons (e.g., hydrocarbons having equal to or greater than 2 C atoms) can produce more coke than methane, owing to having a higher carbon content than methane. [0068] In an aspect, maintaining the catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 h can be provided by introducing water and C0₂ to the CPO reactor 100.

[0069] In an aspect, the CPO reactant mixture 10 can further comprise a diluent, such as water and/or steam, and C0₂. The CPO reactor 100 can be operated under any suitable operational conditions (e.g., CPO operational parameters) that can provide for a syngas with a desired composition (e.g., a desired H₂/CO molar ratio; a desired C0₂ content; etc.); for example, the CPO reactor 100 can be operated with introducing water and/or steam, and C0₂ to the CPO reactor 100.

[0070] When carbon is present in the reactor (e.g., coke; C produced as a result of a decomposition reaction as represented by equation (2)), water and/or steam diluent can react with the carbon and generate additional CO and H₂, for example as represented by equation (3):

C + H₂0 C0 + H₂ (3)

As will be appreciated by one of skill in the art, and with the help of this disclosure, the presence of water and/or steam in the CPO reactor 100 can decrease the amount of coke in the CPO reactor 100 (e.g., the amount of coke deposited on the CPO catalyst, the amount of spent CPO catalyst present in the CPO reactor 100), thereby providing for maintaining the catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 h.

[0071] Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, water and/or steam can be used to vary the composition of the resulting syngas 15. Steam can react with methane, for example as represented by equation (4):

CH₄ + H₂0 CO + 3 H₂ (4)

[0072] In an aspect, a diluent comprising water and/or steam can increase a hydrogen content of the resulting syngas 15. For example, in aspects where the CPO reactant mixture 10 comprises water and/or steam diluent, the resulting syngas 15 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. Without wishing to be limited by theory, the reforming reaction (e.g., as represented by equation (4)) is an endothermic reaction. The reforming reaction as represented by equation (4) can remove a portion of the process heat (e.g., heat produced by the exothermic CPO reaction, for example as represented by equation (1)).

[0073] In the presence of water and/or steam in the CPO reactor 100, carbon monoxide can react with the water and/or steam to form carbon dioxide and hydrogen via a water-gas shift (WGS) reaction, for example as represented by equation (5):

CO + H₂0 C0₂ + H₂ (5) While the WGS reaction can increase the H₂/CO molar ratio of the syngas produced by the CPO reactor 100, it also produces C0₂.

[0074] In an aspect, the CPO reactor 100 can be operated at an S/C molar ratio in the CPO reactant mixture 10 of less than about 2.4: 1, alternatively less than about 2: 1, alternatively less than about 1.5: 1, alternatively less than about 1: 1, alternatively less than about 0.8: 1, alternatively less than about 0.5:1, alternatively from about 0.01 : 1 to less than about 2.4: 1, alternatively from about 0.05: 1 to about 2: 1, alternatively from about 0.1 : 1 to about 1.5: 1, alternatively from about 0.15: 1 to about 1 : 1, or alternatively from about 0.2: 1 to about 0.8: 1. As will be appreciated by one of skill in the art, and with the help of this disclosure, the steam that is introduced to the CPO reactor for use as a diluent in a CPO reaction as disclosed herein is present in significantly smaller amounts than the amounts of steam utilized in steam reforming (e.g., SMR) 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.

[0075] The S/C molar ratio in the CPO reactant mixture 10 can be adjusted based on the desired CPO effluent temperature (e.g., target CPO effluent temperature) in order to increase (e.g., maximize) the H₂ content of the produced syngas (e.g., syngas 15). As will be appreciated by one of skill in the art, and with the help of this disclosure, the reaction (4) that consumes steam in the CPO reactor is preferable over the water-gas shift (WGS) reaction (5) in the CPO reactor 100, as reaction (4) allows for increasing the H₂ content of the produced syngas (e.g., syngas 15), as well as the M ratio of the produced syngas (e.g., syngas 15), wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂). Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, reaction (4) converts water and CO to both H₂ and C0₂.

[0076] In an aspect, the amount of methane that reacts according to reaction (3) in the CPO reactor 100 is less than the amount of methane that reacts according to reaction (1) in the CPO reactor 100. In an aspect, less than about 50 mol%, alternatively less than about 40 mol%, alternatively less than about 30 mol%, alternatively less than about 20 mol%, or alternatively less than about 10 mol% of hydrocarbons (e.g., methane) react with steam in the CPO reactor 100.

[0077] Without wishing to be limited by theory, the presence of water and/or steam in the CPO reactor 100 changes the flammability of the CPO reactant mixture 10, thereby providing for a wider practical range of C/O molar ratios in the CPO reactant mixture 10. Further, and without wishing to be limited by theory, the presence of water and/or steam in the CPO reactor 100 allows for the use of lower C/O molar ratios in the CPO reactant mixture 10. Furthermore, and without wishing to be limited by theory, the presence of water and/or steam in the CPO reactor 100 allows for operating the CPO reactor 100 at relatively high pressures [0078] As will be appreciated by one of skill in the art, and with the help of this disclosure, the introduction of water and/or steam in the CPO reactor 100 can lead to increasing the amount of unreacted hydrocarbons in the syngas 15. Further, as will be appreciated by one of skill in the art, and with the help of this disclosure, methanol production processes typically tolerate limited amounts of unreacted hydrocarbons in the syngas.

[0079] In some aspects, the syngas 15 can comprise less than about 7.5 mol%, alternatively less than about 5 mol%, or alternatively less than about 2.5 mol% hydrocarbons (e.g., unreacted hydrocarbons, unreacted CH ). In such aspects, the syngas 15 can be produced in a CPO process that employs water and/or steam. In such aspects, the syngas 15 can be used for methanol synthesis.

[0080] Further, since oxygen is present in the CPO reactant mixture 10, the carbon present in the reactor (e.g., coke; C produced as a result of a decomposition reaction as represented by equation (2)) can also react with oxygen, for example as represented by equation (6):

C + 0₂ C0₂ (6)

[0081] When carbon is present in the reactor (e.g., coke; C produced as a result of a decomposition reaction as represented by equation (2)), C0₂ (e.g., introduced to the CPO reactor 100 as part of the CPO reactant mixture 10 and/or produced by the reaction represented by equation (6)) can react with the carbon, for example as represented by equation (7):

C + C0₂ 2 CO (7) thereby decreasing the amount of C0₂ in the resulting syngas 15. As will be appreciated by one of skill in the art, and with the help of this disclosure, the presence of C0₂ in the CPO reactor 100 can decrease the amount of coke in the CPO reactor 100 (e.g., the amount of coke deposited on the CPO catalyst, the amount of spent CPO catalyst present in the CPO reactor 100), thereby providing for maintaining the catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 h.

[0082] Furthermore, C0₂ can react with methane in a dry reforming reaction, for example as represented by equation (8):

CH₄ + C0₂ 2 CO + 2 H₂ (8) thereby decreasing the amount of C0₂ in the resulting syngas 15. Without wishing to be limited by theory, the dry reforming reaction (e.g., as represented by equation (8)) is an endothermic reaction (e.g., highly endothermic reaction). The dry reforming reaction can remove a portion of the process heat (e.g., heat produced by the exothermic CPO reaction, for example as represented by equation (1)).

[0083] In an aspect, a diluent comprising carbon dioxide can increase a carbon monoxide content of the resulting syngas. For example, in aspects where the CPO reactant mixture 10 comprises carbon dioxide diluent, the syngas 15 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. Without wishing to be limited by theory, carbon dioxide can react with coke inside the CPO reactor 100 and generate additional CO, for example as represented by equation (7). Further, and without wishing to be limited by theory, carbon dioxide can participate in a dry reforming of methane reaction, thereby generating additional CO and H₂, for example as represented by equation (8). 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.

[0084] In an aspect, the CPO reactant mixture 10 can comprise carbon dioxide in an amount effective to provide for less than about 7 mol%, alternatively less than about 6 mol%, alternatively less than about 5 mol%, alternatively from about 0.1 mol% to about 7 mol%, alternatively from about 0.25 mol% to about 6 mol%, or alternatively from about 0.5 mol% to about 5 mol% carbon dioxide in the syngas 15, based on the total weight of the syngas 15. The carbon dioxide of the CPO reactant mixture 10 can be C0₂ from natural gas sources, wherein the C0₂ is introduced to the CPO reactor 100 with the hydrocarbons; and/or additional or supplemental C0₂, for example C0₂ recovered as a process stream and recycled to the CPO reactor 100 (e.g., C0₂ stream 61).

[0085] As will be appreciated by one of skill in the art, and with the help of this disclosure, a C0₂- lean syngas has a higher M ratio than a C0₂-rich syngas: the lower the C0₂ content of the syngas, the higher the M ratio of the syngas. The C0₂ content of the syngas can be adjusted as described in more detail in the co-pending U.S. Provisional Patent Application No. 62/787,574 filed January 2, 2019 and entitled “Hydrogen Enrichment in Syngas Produced via Catalytic Partial Oxidation”); which is incorporated by reference herein in its entirety.

[0086] In an aspect, maintaining the catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 h can be provided by heat management of the CPO reactor 100; for example by achieving a target CPO effluent temperature and/or near-isothermal conditions, as disclosed herein. As will be appreciated by one of skill in the art, and with the help of this disclosure, run-away temperatures (e.g., uncontrolled temperatures that run relatively high, for example greater than about 1,600 °C) can lead to the thermal deactivation of the catalyst (e.g., CPO catalyst), thereby resulting in a spent catalyst (e.g., spent CPO catalyst). Thermal deactivation can involve a variety of distinct processes, such as coking (e.g., agglomeration of material such as carbon deposits on a catalyst surface); sintering of catalytically active sites (e.g., agglomeration of catalytically active sites with a reduction in catalytically active surface area); fusing of catalytically active sites to a non-active catalyst phase; evaporation of catalytically active sites from the catalyst; and the like; or combinations thereof. As such, achieving a target CPO effluent temperature and/or employing near- isothermal conditions, can provide for maintaining the catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 h can be provided by heat management of the CPO reactor.

[0087] In an aspect, maintaining the catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 h can be provided by replenishing the active CPO catalyst in the CPO reactor.

[0088] In an aspect, at least a portion of the CPO spent catalyst can be removed 11 from the reactor. The spent CPO catalyst can be regenerated to produce a regenerated CPO catalyst, for example by combusting the coke deposited onto the CPO catalyst. Regenerating the spent CPO catalyst can generally restore catalyst activity. A regenerated CPO catalyst can be characterized by a catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 h. In an aspect, a CPO catalyst (e.g., active CPO catalyst; fresh CPO catalyst) and/or a regenerated CPO catalyst can be characterized by a carbon content that is less than a carbon content of the spent CPO catalyst. The regenerated CPO catalyst and/or fresh CPO catalyst can be reintroduced 12 to the CPO reactor 100.

[0089] In aspects where the CPO reactor 100 comprises a fixed catalyst bed, the catalyst bed comprising the spent CPO catalyst can be removed from the CPO reactor, wherein the spent CPO catalyst can be regenerated to produce a regenerated CPO catalyst, and wherein a fixed bed comprising regenerated CPO catalyst and/or fresh CPO catalyst (e.g., additional CPO catalyst) can be subsequently placed in the reactor. Generally, the reactor has to be shut down and taken off-line for the removal and/or regeneration of the catalyst bed, wherein the reactor can be reintroduced on-line subsequent to reintroducing the regenerated CPO catalyst and/or fresh CPO catalyst fixed bed in the reactor. In some aspects, the spent CPO catalyst can be regenerated inside the reactor, such as for example in the case of a fixed bed reactor, or a fluidized bed reactor without a catalyst recirculation loop; once the reactor has been taken off-line. In such aspects, the process can comprise operating two or more reactors in parallel, wherein at any time there is a reactor ready to undergo or already undergoing the CPO reaction, thereby providing for a continuous process.

[0090] In aspects where the CPO reactor 100 comprises a moving catalyst bed and/or a fluidized catalyst bed (e.g., a fluidized bed reactor with a recirculation loop, a moving bed reactor, a riser type reactor, and the like, or combinations thereof), a portion of the spent CPO catalyst can be removed 11 from the CPO reactor 100 either continuously or discontinuously. In such aspects, the CPO reactor 100 can operate continuously. As will be appreciated by one of skill in the art, and with the help of this disclosure, a moving catalyst bed and/or a fluidized catalyst bed can be removed entirely from the reactor, although the removal of the entire CPO catalyst bed entails shutting down the reactor and taking it off- line (similarly to the case of fixed catalyst beds). The spent CPO catalyst can be regenerated to produce a regenerated CPO catalyst. The regenerated CPO catalyst and/or fresh CPO catalyst can be reintroduced 12 to the CPO reactor 100.

[0091] In aspects where the CPO reactor 100 comprises a moving catalyst bed and/or a fluidized catalyst bed, additional CPO catalyst (e.g., regenerated CPO catalyst and/or fresh CPO catalyst) can be introduced to the CPO reactor either continuously (e.g., constant catalyst addition) or discontinuously (e.g., periodic or intermittent catalyst addition). Continuous catalyst addition can lead to an elevated substantially constant catalyst activity (e.g., catalyst productivity). Periodic catalyst addition can lead to spikes or boosts in catalyst activity (e.g., catalyst productivity) followed by a decay in catalyst activity.

[0092] In an aspect, a syngas 15 can be recovered from the CPO reactor 100, wherein the syngas 15 comprises hydrogen, carbon monoxide, water, carbon dioxide, and unreacted hydrocarbons.

[0093] In some aspects, the syngas 15 can be used in a downstream process (e.g., methanol production) without further processing to enrich the hydrogen content of the syngas 15. The syngas 15 as disclosed herein can be characterized by a H₂/CO molar ratio of greater than about 1.7, alternatively greater than about 1.8, alternatively greater than about 1.9, alternatively greater than about 2.0, or alternatively greater than about 2.1. In some aspects, the syngas 15 as disclosed herein can be characterized by a H₂/CO molar ratio of from about 1.7 to about 2.3, alternatively from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.1.

[0094] In an aspect, the syngas 15 can be characterized by an M ratio of equal to or greater than about 1.5, alternatively equal to or greater than about 1.6, alternatively equal to or greater than about 1.7, alternatively equal to or greater than about 1.8, alternatively equal to or greater than about 1.84, alternatively equal to or greater than about 1.9, alternatively from about 1.5 to about 1.84, alternatively from about 1.7 to about 2.3, alternatively from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.2.

[0095] In other aspects, the syngas 15 can be further processed prior to using syngas 15 in a downstream process, such as methanol production. The syngas 15 can be processed to enrich its hydrogen content; for example by contacting the syngas 15 with additional (e.g., supplemental) hydrogen (e.g., hydrogen stream 51).

[0096] As will be appreciated by one of skill in the art, and with the help of this disclosure, although the syngas 15 can be characterized by a H₂/CO molar ratio of greater than about 1.8, which can be appropriate for methanol synthesis, the syngas 15 can be processed to further increase its hydrogen content. Further, as will be appreciated by one of skill in the art, and with the help of this disclosure, the syngas 15 can be subjected to minimal processing, such as the recovery of unreacted hydrocarbons, diluent, water, etc., without substantially changing the H₂/CO molar ratio of the syngas 15. For example, water can be condensed and separated from the syngas 15, e.g., in a condenser.

[0097] In an aspect, a process as disclosed herein can further comprise (i) recovering at least a portion of the unreacted hydrocarbons from the syngas 15 to yield recovered hydrocarbons, and (ii) recycling at least a portion of the recovered hydrocarbons to the CPO reactor 100. As will be appreciated by one of skill in the art, and with the help of this disclosure, although fairly high conversions can be achieved in CPO processes (e.g., conversions of equal to or greater than about 90%), the unconverted hydrocarbons could be recovered and recycled back to the CPO reactor 100.

[0098] In an aspect, the syngas 15 can have a C0₂ content of less than about 7 mol%, alternatively less than about 6 mol%, alternatively less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively greater than about 0.1 mol%, alternatively greater than about 0.25 mol%, alternatively greater than about 0.5 mol%, alternatively from about 0.1 mol% to about 7 mol%, alternatively from about 0.25 mol% to about 6 mol%, or alternatively from about 0.5 mol% to about 5 mol%. For example, side reactions as represented by equations (7) and/or (8) could lead to a syngas 15 that has a C0₂ content of less than about 7 mol%, alternatively less than about 6 mol%, alternatively less than about 5 mol%, alternatively from about 0.1 mol% to about 7 mol%, alternatively from about 0.25 mol% to about 6 mol%, or alternatively from about 0.5 mol% to about 5 mol%.

[0099] In aspects where the syngas 15 is characterized by an M ratio of from about 1.8 to about 2.2, the syngas 15 can be further used for methanol production.

[00100] In an aspect, a process for producing methanol as disclosed herein can comprise a step of introducing at least a portion of the syngas 15 to the methanol reactor 200 to produce a methanol reactor effluent stream 30; wherein the methanol reactor effluent stream 30 comprises methanol, water, hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons. The methanol reactor 200 can comprise any reactor suitable for a methanol synthesis reaction from CO and H₂, such as for example 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.

[00101] Generally, CO and H₂ can be converted into methanol (CH OH), for example as represented by equation (9):

CO + H₂ CH₃OH (9)

C0₂ and H₂ can also be converted to methanol, for example as represented by equation (10):

C0₂ + 3H₂ CH₃OH + H₂0 (10)

Without wishing to be limited by theory, the lower the C0₂ content of the syngas 15, the lower the amount of water produced in the methanol reactor 200. As will be appreciated by one of skill in the art, and with the help of this disclosure, syngas produced by SMR has a fairly high content of hydrogen (as compared to the hydrogen content of syngas produced by CPO), and a syngas with an elevated hydrogen content can promote the C0₂ conversion to methanol, for example as represented by equation (10), which in turn can lead to an increased water content in a crude methanol stream (e.g., crude methanol stream 40).

[00102] Methanol synthesis from CO, C0₂ and H₂ is a catalytic process, and is most often conducted in the presence of copper based catalysts. The methanol reactor 200 can comprise a methanol production catalyst, such as any suitable commercial catalyst used for methanol synthesis. Nonlimiting examples of methanol production catalysts suitable for use in the methanol reactor 200 in the current disclosure include Cu, Cu/ZnO, Cu/Th0₂, Cu/Zn/Al₂0 , Cu/Zn0/Al₂0₃, Cu/Zr, and the like, or combinations thereof.

[00103] In an aspect, a process for producing methanol as disclosed herein can comprise a step of separating at least a portion of the methanol reactor effluent stream 30 into a crude methanol stream 40 and a vapor stream 50; wherein the crude methanol stream 40 comprises methanol and water; wherein the vapor stream 50 comprises hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons. The methanol reactor effluent stream 30 can be separated into the crude methanol stream 40 and the vapor stream 50 in the gas-liquid separator 300, such as a vapor-liquid separator, flash drum, knock-out drum, knock-out pot, compressor suction drum, etc.

[00104] In an aspect, a process for producing methanol as disclosed herein can comprise a step of separating at least a portion of the crude methanol stream 40 in the distillation unit 400 into a methanol stream 45 and a water stream 46, wherein the distillation unit 400 comprises one or more distillation columns. The water stream 46 comprises water and residual methanol. Generally, the one or more distillation columns can separate components of the crude methanol stream 40 based on their boiling points. As will be appreciated by one of skill in the art, and with the help of this disclosure, the higher the water content of the crude methanol stream 40, the more distillation columns are necessary to purify the methanol.

[00105] In an aspect, the methanol stream 45 can comprise methanol in an amount of equal to or greater than about 95 wt.%, alternatively equal to or greater than about 97.5 wt.%, alternatively equal to or greater than about 99 wt.%, or alternatively equal to or greater than about 99.9 wt.%, based on the total weight of the methanol stream 45.

[00106] In an aspect, a process for producing methanol as disclosed herein can comprise a step of separating at least a portion of the vapor stream 50 into a hydrogen stream 51 and a residual gas stream 52, wherein the hydrogen stream 51 comprises at least a portion of the hydrogen of the vapor stream 50, and wherein the residual gas stream 52 comprises carbon monoxide, carbon dioxide, and hydrocarbons. The vapor stream 50 can be separated into the hydrogen stream 51 and the residual gas stream 52 in a hydrogen recovery unit 500, such as a PSA unit, a membrane separation unit, a cryogenic separation unit, and the like, or combinations thereof.

[00107] In an aspect, a process for producing methanol as disclosed herein can comprise recycling at least a portion 51 a of the hydrogen stream 51 to the methanol reactor 200; for example via syngas 15.

[00108] In an aspect, a process for producing methanol as disclosed herein can comprise a step of separating at least a portion of the residual gas stream 52 in a C0₂ separator 600 (e.g., C0₂ scrubber) into a C0₂ stream 61 and a purge gas stream 60; wherein the C0₂ stream 61 comprises at least a portion of the C0₂ of the residual gas stream 52; and wherein the purge gas stream 60 comprises carbon monoxide and hydrocarbons.

[00109] The C0₂ separator 600 can comprise C0₂ removal by amine (e.g., monoethanolamine) absorption (e.g., amine scrubbing), pressure swing adsorption (PSA), temperature swing adsorption, gas separation membranes (e.g., porous inorganic membranes, palladium membranes, polymeric membranes, zeolites, etc.), cryogenic separation, and the like, or combinations thereof. In an aspect, the C0₂ separator 600 can comprise C0₂ removal by amine absorption.

[00110] In some aspects, at least a portion of the purge gas stream 60 can be purged. In other aspects, at least a portion of the purge gas stream 60 can be used as fuel, for example for pre-heating the CPO reactant mixture 10.

[00111] In an aspect, at least a portion 61a of the C0₂ stream 61 can be recycled to the CPO reactor 100. The C0₂ introduced to the CPO reactor via the C0₂ stream 61 can provide for C0₂ that can further reduce or eliminate coke deposits on the CPO catalysts, for example by participating in the reaction represented by equation (7). Further, C0₂ introduced to the CPO reactor 100 via the C0₂ stream 61 can provide for C0₂ that can be converted to useful syngas components, such as CO and H₂, for example by participating in the dry reforming reaction represented by equation (8).

[00112] As will be appreciated by one of skill in the art, and with the help of this disclosure, the reactions represented by equations (7) and (8) reduce the amount of C0₂ that will be present in the syngas 15. Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, while the H₂/CO molar ratio of the syngas does not change by changing the carbon dioxide content of the syngas, the concentration of hydrogen increases in the syngas by decreasing the amount of carbon dioxide in the syngas. However, the M ratio of the syngas changes with changing the carbon dioxide content of the syngas.

[00113] In an aspect, the M ratio of the syngas 15 can be greater than the M ratio of a syngas produced in an otherwise similar process that does not introduce C0₂ to the CPO reactor 100. [00114] In an aspect, a process for producing methanol can comprise the steps of (a) reacting under near-isothermal conditions, via a CPO reaction, a CPO reactant mixture 10 in a CPO reactor 100 to produce syngas 15; wherein the CPO reactant mixture 10 comprises hydrocarbons, oxygen, water and carbon dioxide; wherein the CPO reactor 100 comprises a CPO catalyst; wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the CPO reactor 100 and/or a catalyst bed thereof, wherein the catalyst bed comprises the CPO catalyst; wherein a portion of the hydrocarbons in the CPO reactant mixture 10 undergo decomposition to carbon and hydrogen; wherein a portion of the carbon is optionally deposited on the CPO catalyst to produce a spent CPO catalyst; wherein the syngas 15 comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; wherein the syngas 15 is characterized by an M ratio of the syngas of equal to or greater than about 1.5, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂); wherein the CPO catalyst is characterized by a catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 hours (h), and wherein catalyst productivity is defined as the amount of syngas recovered from the CPO reactor divided by the amount of hydrocarbons introduced to the CPO reactor; (b) optionally removing 11 a portion of the spent CPO catalyst from the CPO reactor 100, wherein at least a portion of the spent CPO catalyst is optionally regenerated by removal of at least a portion of the deposited carbon from the spent CPO catalyst to produce regenerated CPO catalyst; (c) optionally introducing 12 additional CPO catalyst to the CPO reactor 100, wherein the additional CPO catalyst comprises fresh CPO catalyst and/or regenerated CPO catalyst; (d) introducing at least a portion of the syngas 15 to a methanol reactor 200 to produce a methanol reactor effluent stream 30; wherein the methanol reactor effluent stream 30 comprises methanol, water, hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons; (e) separating at least a portion of the methanol reactor effluent stream 30 in a gas-liquid separator 300 into a crude methanol stream 40, and a vapor stream 50; wherein the crude methanol stream 40 comprises methanol and water; and wherein the vapor stream 50 comprises hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons; (f) separating at least a portion of the vapor stream 50 into a hydrogen stream 51 and a residual gas stream 52; wherein the hydrogen stream 51 comprises at least a portion of the hydrogen of the vapor stream 50; and wherein the residual gas stream 52 comprises carbon monoxide, carbon dioxide, and hydrocarbons; (g) separating at least a portion of the residual gas stream 52 in a C0₂ separator 600 into a C0₂ stream 61 and a purge gas stream 60; wherein the C0₂ stream 61 comprises at least a portion of the C0₂ of the residual gas stream 52; (h) optionally feeding at least a portion 61a of the C0₂ stream 61 to the CPO reactor 100 in step (a); (i) recycling at least a portion 51a of the hydrogen stream 51 to the methanol reactor 200; and (j) separating at least a portion of the crude methanol stream 40 into a methanol stream 45 and a water stream 46. In such aspect, the near-isothermal conditions can be provided by heat transfer, wherein the heat transfer excludes heat transfer with the syngas 15 subsequent to the syngas 15 exiting the CPO reactor 100, wherein the heat transfer comprises cooling the CPO reactor 100 while heating an ethane cracking reactor and/or while heating water to produce steam. In such aspect, the CPO reactor 100 can be characterized by at least one CPO operational parameter selected from the group consisting of a CPO feed temperature of from about 25 °C to about 400 °C; a CPO effluent temperature of from about 600 °C to about 1,400 °C; a CPO pressure of from about 1 barg to about 70 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a C/O molar ratio in the CPO reactant mixture 10 of from about 1 : 1 to about 2: 1 ; a S/C molar ratio in the CPO reactant mixture 10 of from about 0.01 : 1 to less than about 1 : 1 ; and combinations thereof.

[00115] In an aspect, 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 maintain the CPO catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 h. The process as disclosed herein can advantageously increase the overall efficiency of the process by maintaining the catalyst activity in a desired range.

[00116] In an aspect, a process for producing syngas as disclosed herein can advantageously provide for an on-stream factor of the CPO reactor that is greater than the on-stream factor of a CPO reactor in an otherwise similar process that has to shut-down the CPO reactor to regenerate the CPO catalyst. For purposes of the disclosure herein the on-stream factor is defined as the ratio of the number of days in a year that a reactor is actively producing a desired product to the number of days in a calendar year. The CPO catalyst can be advantageously regenerated in a continuous manner, as disclosed herein, thereby advantageously allowing for continuous production of syngas.

[00117] As will be appreciated by one of skill in the art, and with the help of this disclosure, since the CPO reaction is exothermic, very little heat supply in the form of fuel combustion is needed (e.g., for pre heating reactants in the reaction mixture that is supplied to a syngas generation section), when compared to conventional steam reforming. As such, the process for producing syngas as disclosed herein can advantageously generate less C0₂ through fuel burning, when compared to steam reforming.

[00118] The syngas production as disclosed herein can advantageously employ achieving a target CPO effluent temperature and/or near-isothermal conditions, thereby decreasing the CPO catalyst deactivation (e.g., thermal deactivation). The CPO process can be advantageously integrated with a cracking process and/or a steam production process for achieving a target CPO effluent temperature and/or near-isothermal conditions (e.g., via heat transfer).

[00119] In an aspect, the use of water and/or steam diluent can advantageously lead to a decreased amount of coke, thus decreasing catalyst deactivation (e.g., maintaining the catalyst in an active state). [00120] The syngas production as disclosed herein can advantageously employ carbon dioxide diluent. In such aspect, 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). Generally, by using carbon dioxide to produce syngas, carbon dioxide emissions can advantageously be reduced.

[00121] The use of carbon dioxide in the CPO reactant mixture 10 can advantageously decrease the amount of hydrocarbons converted to C0₂ in the CPO reactor 100, for example via a combustion reaction. Without wishing to be limited by theory, and according to Le Chatelier's Principle, the equilibrium of hydrocarbons dry reforming reaction will be shifted towards consuming C0₂ with increasing the amount of C0₂ in the reactant mixture, thereby allowing for a higher amount of hydrocarbons to convert to syngas. Additional advantages of the processes for the production of syngas and/or methanol as disclosed herein can be apparent to one of skill in the art viewing this disclosure.

ADDITIONAL DISCLOSURE

[00122] A first aspect, which is a process for producing syngas comprising reacting, via a catalytic partial oxidation (CPO) reaction, a CPO reactant mixture in a CPO reactor to produce the syngas; wherein the CPO reactant mixture comprises hydrocarbons and oxygen; wherein the CPO reactor comprises a CPO catalyst; wherein a portion of the hydrocarbons in the CPO reactant mixture undergo decomposition to carbon and hydrogen; wherein the syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; wherein the CPO catalyst is characterized by a catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 hours (h), and wherein catalyst productivity is defined as the amount of syngas recovered from the CPO reactor divided by the amount of hydrocarbons introduced to the CPO reactor.

[00123] A second aspect, which is the process of the first aspect, 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, fuel gas from fuel gas header, or combinations thereof.

[00124] A third aspect, which is the process of any one of the first and the second aspects, wherein the CPO reactor is characterized by at least one CPO operational parameter selected from the group consisting of a CPO feed temperature of from about 25 °C to about 600 °C; a CPO effluent temperature of from about 300 °C to about 1,600 °C; a CPO pressure of from about 1 barg to about 90 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture of from about 0.5: 1 to about 3: 1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0₂) in the reactant mixture; and combinations thereof. [00125] A fourth aspect, which is the process of the third aspect, wherein the CPO reactant mixture further comprises water and carbon dioxide.

[00126] A fifth aspect, which is the process of the fourth aspect, wherein the at least one CPO operational parameter comprises a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.01 : 1 to less than about 2.4: 1, wherein the S/C molar ratio refers to the total moles of water (H₂0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture.

[00127] A sixth aspect, which is the process of the fourth aspect, wherein at wherein at least a portion of the water reacts with at least a portion of the carbon in the CPO reactor to produce carbon monoxide and hydrogen.

[00128] A seventh aspect, which is the process of the fourth aspect, wherein the CPO reactant mixture comprises carbon dioxide in an amount effective to provide for from about 0.1 mol% to about 7 mol% carbon dioxide in the syngas.

[00129] An eighth aspect, which is the process of the fourth aspect, wherein at least a portion of the carbon dioxide reacts with at least a portion of the carbon in the CPO reactor to produce carbon monoxide.

[00130] A ninth aspect, which is the process of any of the first through the eighth aspects, wherein the CPO reactor is operated under near-isothermal conditions, wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the CPO reactor and/or a catalyst bed thereof, and wherein the catalyst bed comprises the CPO catalyst.

[00131] A tenth aspect, which is the process of the ninth aspect, wherein the near-isothermal conditions are provided by heat transfer, and wherein the heat transfer excludes heat transfer with the syngas subsequent to the syngas exiting the reactor.

[00132] An eleventh aspect, which is the process of the tenth aspect, wherein the heat transfer comprises cooling the CPO reactor while heating a cracking reactor, wherein the cracking reactor optionally produces ethylene by ethane cracking.

[00133] A twelfth aspect, which is the process of the tenth aspect, wherein the heat transfer comprises cooling the CPO reactor while heating water to produce steam.

[00134] A thirteenth aspect, which is the process of any of the first through the twelfth aspects, wherein a portion of the carbon is deposited on the CPO catalyst to produce a spent CPO catalyst; wherein at least a portion of the spent CPO catalyst is optionally regenerated by removal of at least a portion of the deposited carbon from the spent CPO catalyst to produce regenerated CPO catalyst; wherein additional CPO catalyst is introduced to the CPO reactor continuously or discontinuously, and wherein the additional CPO catalyst comprises fresh CPO catalyst and/or regenerated CPO catalyst. [00135] A fourteenth aspect, which is the process of thirteenth aspect, wherein the CPO reactor comprises a fluidized bed reactor, a moving bed reactor, a riser type reactor, or combinations thereof.

[00136] A fifteenth aspect, which is the process of any of the first through the fourteenth aspects, wherein the syngas is characterized by an M ratio of the syngas of equal to or greater than about 1.5, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂).

[00137] A sixteenth aspect, which is the process of the fifteenth aspect further comprising introducing at least a portion of the syngas to a methanol reactor to produce a methanol reactor effluent stream; wherein the methanol reactor effluent stream comprises methanol, water, hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons.

[00138] A seventeenth aspect, which is the process of the sixteenth aspect further comprising (i) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream, a hydrogen stream, a C0₂ stream, and a purge gas stream; wherein the crude methanol stream comprises methanol and water; wherein the purge gas stream comprises carbon monoxide and hydrocarbons; and wherein the C0₂ stream comprises at least a portion of the carbon dioxide of the methanol reactor effluent stream; and (ii) recycling at least a portion of the C0₂ stream to the CPO reactor.

[00139] An eighteenth aspect, which is a process for producing methanol comprising (a) reacting under near-isothermal conditions, via a catalytic partial oxidation (CPO) reaction, a CPO reactant mixture in a CPO reactor to produce syngas; wherein the CPO reactant mixture comprises hydrocarbons, oxygen, water and carbon dioxide; wherein the CPO reactor comprises a CPO catalyst; wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the CPO reactor and/or a catalyst bed thereof, wherein the catalyst bed comprises the CPO catalyst; wherein a portion of the hydrocarbons in the CPO reactant mixture undergo decomposition to carbon and hydrogen; wherein a portion of the carbon is optionally deposited on the CPO catalyst to produce a spent CPO catalyst; wherein the syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; wherein the syngas is characterized by an M ratio of the syngas of equal to or greater than about 1.5, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂); wherein the CPO catalyst is characterized by a catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 hours (h), and wherein catalyst productivity is defined as the amount of syngas recovered from the CPO reactor divided by the amount of hydrocarbons introduced to the CPO reactor; (b) optionally removing a portion of the spent CPO catalyst from the CPO reactor, wherein at least a portion of the spent CPO catalyst is optionally regenerated by removal of at least a portion of the deposited carbon from the spent CPO catalyst to produce regenerated CPO catalyst; (c) optionally introducing additional CPO catalyst to the CPO reactor, wherein the additional CPO catalyst comprises fresh CPO catalyst and/or regenerated CPO catalyst; (d) introducing at least a portion of the syngas to a methanol reactor to produce a methanol reactor effluent stream; wherein the methanol reactor effluent stream comprises methanol, water, hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons; (e) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream, and a vapor stream; wherein the crude methanol stream comprises methanol and water; and wherein the vapor stream comprises hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons; (f) optionally recovering a C0₂ stream from at least a portion of the vapor stream; (g) optionally feeding at least a portion of the C0₂ stream to the CPO reactor in step (a); and (h) separating at least a portion of the crude methanol stream into a methanol stream and a water stream.

[00140] A nineteenth aspect, which is the process of the eighteenth aspect, wherein the CPO reactant mixture comprises carbon dioxide in an amount effective to provide for from about 0.5 mol% to about 5 mol% carbon dioxide in the syngas.

[00141] A twentieth aspect, which is the process of any one of the eighteenth and the nineteenth aspects, wherein the near-isothermal conditions are provided by heat transfer, wherein the heat transfer excludes heat transfer with the syngas subsequent to the syngas exiting the CPO reactor, wherein the heat transfer comprises cooling the CPO reactor while heating an ethane cracking reactor and/or while heating water to produce steam; and wherein the CPO reactor is characterized by at least one CPO operational parameter selected from the group consisting of a CPO feed temperature of from about 25 °C to about 600 °C; a CPO effluent temperature of from about 600 °C to about 1 ,400 °C; a CPO pressure of from about 1 barg to about 70 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture of from about 1 : 1 to about 2: 1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0₂) in the reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.01 : 1 to less than about 1 : 1, wherein the S/C molar ratio refers to the total moles of water (H₂0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof.

[00142] For the purpose of any U.S. national stage filing from this application, all publications and patents mentioned in this disclosure are incorporated herein by reference in their entireties, for the purpose of describing and disclosing the constructs and methodologies described in those publications, which might be used in connection with the methods of this disclosure. Any publications and patents discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.

[00143] In any application before the United States Patent and Trademark Office, the Abstract of this application is provided for the purpose of satisfying the requirements of 37 C.F.R. § 1.72 and the purpose stated in 37 C.F.R. § 1.72(b)“to enable the United States Patent and Trademark Office and the public generally to determine quickly from a cursory inspection the nature and gist of the technical disclosure.” Therefore, the Abstract of this application is not intended to be used to construe the scope of the claims or to limit the scope of the subject matter that is disclosed herein. Moreover, any headings that can be employed herein are also not intended to be used to construe the scope of the claims or to limit the scope of the subject matter that is disclosed herein. Any use of the past tense to describe an example otherwise indicated as constructive or prophetic is not intended to reflect that the constructive or prophetic example has actually been carried out.

[00144] While embodiments of the disclosure have been shown and described, modifications thereof can be made without departing from the spirit and teachings of the invention. The embodiments and examples described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention.

[00145] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the detailed description of the present invention. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference.

Claims

CLAIMS What is claimed is:

1. A process for producing syngas comprising reacting, via a catalytic partial oxidation (CPO) reaction, a CPO reactant mixture in a CPO reactor to produce the syngas; wherein the CPO reactant mixture comprises hydrocarbons and oxygen; wherein the CPO reactor comprises a CPO catalyst; wherein a portion of the hydrocarbons in the CPO reactant mixture undergo decomposition to carbon and hydrogen; wherein the syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; wherein the CPO catalyst is characterized by a catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 hours (h), and wherein catalyst productivity is defined as the amount of syngas recovered from the CPO reactor divided by the amount of hydrocarbons introduced to the CPO reactor.

2. The process of claim 1, 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, fuel gas from fuel gas header, or combinations thereof.

3. The process of claim 1, wherein the CPO reactor is characterized by at least one CPO operational parameter selected from the group consisting of a CPO feed temperature of from about 25 °C to about 600 °C; a CPO effluent temperature of from about 300 °C to about 1,600 °C; a CPO pressure of from about 1 barg to about 90 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture of from about 0.5: 1 to about 3: 1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0₂) in the reactant mixture; and combinations thereof.

4. The process of claim 3, wherein the CPO reactant mixture further comprises water and carbon dioxide.

5. The process of claim 4, wherein the at least one CPO operational parameter comprises a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.01 : 1 to less than about 2.4: 1, wherein the S/C molar ratio refers to the total moles of water (H₂0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture.

6. The process of claim 4, wherein at wherein at least a portion of the water reacts with at least a portion of the carbon in the CPO reactor to produce carbon monoxide and hydrogen.

7. The process of claim 4, wherein the CPO reactant mixture comprises carbon dioxide in an amount effective to provide for from about 0.1 mol% to about 7 mol% carbon dioxide in the syngas.

8. The process of claim 4, wherein at least a portion of the carbon dioxide reacts with at least a portion of the carbon in the CPO reactor to produce carbon monoxide.

9. The process of claim 1, wherein the CPO reactor is operated under near-isothermal conditions, wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the CPO reactor and/or a catalyst bed thereof, and wherein the catalyst bed comprises the CPO catalyst.

10. The process of claim 9, wherein the near-isothermal conditions are provided by heat transfer, and wherein the heat transfer excludes heat transfer with the syngas subsequent to the syngas exiting the reactor.

11. The process of claim 10, wherein the heat transfer comprises cooling the CPO reactor while heating a cracking reactor, wherein the cracking reactor optionally produces ethylene by ethane cracking.

12. The process of claim 10, wherein the heat transfer comprises cooling the CPO reactor while heating water to produce steam.

13. The process of claim 1, wherein a portion of the carbon is deposited on the CPO catalyst to produce a spent CPO catalyst; wherein at least a portion of the spent CPO catalyst is optionally regenerated by removal of at least a portion of the deposited carbon from the spent CPO catalyst to produce regenerated CPO catalyst; wherein additional CPO catalyst is introduced to the CPO reactor continuously or discontinuously, and wherein the additional CPO catalyst comprises fresh CPO catalyst and/or regenerated CPO catalyst.

14. The process of claim 13, wherein the CPO reactor comprises a fluidized bed reactor, a moving bed reactor, a riser type reactor, or combinations thereof.

15. The process of claim 1 , wherein the syngas is characterized by an M ratio of the syngas of equal to or greater than about 1.5, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂).

16. The process of claim 15 further comprising introducing at least a portion of the syngas to a methanol reactor to produce a methanol reactor effluent stream; wherein the methanol reactor effluent stream comprises methanol, water, hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons.

17. The process of claim 16 further comprising (i) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream, a hydrogen stream, a C0₂ stream, and a purge gas stream; wherein the crude methanol stream comprises methanol and water; wherein the purge gas stream comprises carbon monoxide and hydrocarbons; and wherein the C0₂ stream comprises at least a portion of the carbon dioxide of the methanol reactor effluent stream; and (ii) recycling at least a portion of the C0₂ stream to the CPO reactor.

18. A process for producing methanol comprising:

(a) reacting under near-isothermal conditions, via a catalytic partial oxidation (CPO) reaction, a CPO reactant mixture in a CPO reactor to produce syngas; wherein the CPO reactant mixture comprises hydrocarbons, oxygen, water and carbon dioxide; wherein the CPO reactor comprises a CPO catalyst; wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the CPO reactor and/or a catalyst bed thereof, wherein the catalyst bed comprises the CPO catalyst; wherein a portion of the hydrocarbons in the CPO reactant mixture undergo decomposition to carbon and hydrogen; wherein a portion of the carbon is optionally deposited on the CPO catalyst to produce a spent CPO catalyst; wherein the syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; wherein the syngas is characterized by an M ratio of the syngas of equal to or greater than about 1.5, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂); wherein the CPO catalyst is characterized by a catalyst productivity variation within about + 20% of a target catalyst productivity over a time period of equal to or greater than about 500 hours (h), and wherein catalyst productivity is defined as the amount of syngas recovered from the CPO reactor divided by the amount of hydrocarbons introduced to the CPO reactor;

(b) optionally removing a portion of the spent CPO catalyst from the CPO reactor, wherein at least a portion of the spent CPO catalyst is optionally regenerated by removal of at least a portion of the deposited carbon from the spent CPO catalyst to produce regenerated CPO catalyst;

(c) optionally introducing additional CPO catalyst to the CPO reactor, wherein the additional CPO catalyst comprises fresh CPO catalyst and/or regenerated CPO catalyst;

(d) introducing at least a portion of the syngas to a methanol reactor to produce a methanol reactor effluent stream; wherein the methanol reactor effluent stream comprises methanol, water, hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons;

(e) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream, and a vapor stream; wherein the crude methanol stream comprises methanol and water; and wherein the vapor stream comprises hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons;

(f) optionally recovering a C0₂ stream from at least a portion of the vapor stream;

(g) optionally feeding at least a portion of the C0₂ stream to the CPO reactor in step (a); and

(h) separating at least a portion of the crude methanol stream into a methanol stream and a water stream.

19. The process of claim 18, wherein the CPO reactant mixture comprises carbon dioxide in an amount effective to provide for from about 0.5 mol% to about 5 mol% carbon dioxide in the syngas.

20. The process of claim 18, wherein the near-isothermal conditions are provided by heat transfer, wherein the heat transfer excludes heat transfer with the syngas subsequent to the syngas exiting the CPO reactor, wherein the heat transfer comprises cooling the CPO reactor while heating an ethane cracking reactor and/or while heating water to produce steam; and wherein the CPO reactor is characterized by at least one CPO operational parameter selected from the group consisting of a CPO feed temperature of from about 25 °C to about 600 °C; a CPO effluent temperature of from about 600 °C to about 1,400 °C; a CPO pressure of from about 1 barg to about 70 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture of from about 1 : 1 to about 2: 1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0₂) in the reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.01 : 1 to less than about 1 : 1, wherein the S/C molar ratio refers to the total moles of water (H₂0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof.