VIA 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 of hydrocarbons, such as methane.

BACKGROUND

[0002] Synthesis gas (syngas) is a mixture comprising carbon monoxide (CO) and hydrogen (H ₂ ), as well as small amounts of carbon dioxide (C0 ), water (H 0), and unreacted methane (CH ₄ ). Syngas is generally used as an intermediate in the production of methanol and ammonia, as well as an intermediate in creating synthetic petroleum to use as a lubricant or fuel.

[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 (H -C0 )/(C0+C0 ).

[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 C0 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 H ₂ . 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. Thus, there is an ongoing need for the development of syngas production processes that can control the composition of the produced syngas, as well as produce a syngas that could be suitable for downstream processes, such as methanol synthesis.

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] Figure 1 displays a graph of the variation of syngas M ratio ((H ₂ -C0 ₂ )/(C0+C0 ₂ )) with the pressure;

[0008] Figure 2 displays a graph of the variation of syngas FF/CO molar ratio with the pressure;

[0009] Figure 3 displays a graph of the variation of syngas M ratio with the feed carbon to oxygen (C/O) molar ratio;

[0010] Figure 4 displays a graph of the variation of syngas FF/CO ratio with the feed C/O molar ratio;

[0011] Figure 5 displays a graph of the variation of syngas M ratio with the feed steam to carbon (S/C) molar ratio; and

[0012] Figure 6 displays a graph of the variation of syngas M ratio with the amount of syngas that is further processed in a water-gas shift reaction.

DETAILED DESCRIPTION

[0013] Disclosed herein are processes for producing hydrogen enriched syngas comprising reacting, via a catalytic partial oxidation (CPO or CPOx) reaction, a CPO reactant mixture in a CPO reactor to produce the hydrogen enriched syngas; wherein the CPO reactant mixture comprises hydrocarbons and oxygen; wherein the CPO reactor comprises a CPO catalyst; wherein the hydrogen enriched syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; and wherein the hydrogen enriched syngas is characterized by a hydrogen to carbon monoxide (FF/CO) molar ratio of greater than about 2.0. The hydrocarbons 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.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] As used herein, the term“effective,” means adequate to accomplish a desired, expected, or intended result.

[0020] 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.

[0021] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art.

[0022] 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.

[0023] As used herein, the terms“C _x hydrocarbons” and“C _x s” are interchangeable and refer to any hydrocarbon having x number of carbon atoms (C). For example, the terms“C ₄ hydrocarbons” and“C ₄ s” 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.

[0024] 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“C ₂₊ hydrocarbons” refers to any hydrocarbons having 2 or more carbon atoms, such as ethane, ethylene, C ₃ s, C ₄ s, C ₅ s, etc.

[0025] In an aspect, a process for producing hydrogen enriched syngas as disclosed herein can comprise reacting, via a catalytic partial oxidation (CPO or CPOx) reaction, a CPO reactant mixture in a CPO reactor to produce a hydrogen enriched syngas, wherein the CPO reactant mixture comprises hydrocarbons and oxygen.

[0026] 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):

CH ₄ + 1/2 0 ₂ CO + 2 ¾ (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 (C0 ) and water (H 0), 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 (H /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 H /CO molar ratio means that the CPO reaction as represented by equation (1) yields 2 moles of H for every 1 mole of CO, i.e., H /CO molar ratio of (2 moles H /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 H /CO molar ratio in a CPO reaction cannot be achieved practically because reactants (e.g., hydrocarbons, oxygen) as well as products (e.g., H , 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 H can be oxidized to C0 and H 0, respectively. The relative amounts (e.g., composition) of CO, H , C0 ₂ and H ₂ 0 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 can have a direct impact on the M ratio of the produced syngas (e.g., hydrogen enriched syngas), wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ). 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 H and increases C0 , thereby resulting in a syngas with an M ratio below 2.0.

[0027] 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 a CPO reactor (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.

[0028] 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 CH ₄ -rich feed).

[0029] In an aspect, the hydrocarbons suitable for use in a CPO reaction as disclosed herein can include methane (CH ₄ ), 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 C _r C ₆ hydrocarbons, as well some heavier hydrocarbons.

[0030] In an aspect, the CPO reactant mixture 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 can comprise CH ₄ and 0 ₂ .

[0031] 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.

[0032] In an aspect, natural gas can comprise CIT ₄ 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%.

[0033] In some aspects, the hydrocarbons suitable for use in a CPO reaction as disclosed herein can comprise Ci-C ₆ 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%); C hydrocarbons (about 2.5 mol% to about 4 mol%); C ₃ hydrocarbons (about 0.5 mol% to about 1.4 mol%); C ₄ hydrocarbons (about 0.5 mol% to about 0.2 mol%); C ₅ hydrocarbons (about 0.06 mol%); and C ₆ 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%). [0034] The oxygen used in the CPO reactant mixture can comprise 100% oxygen (substantially pure 0 ), oxygen gas (which may be obtained via a membrane separation process), technical oxygen (which may contain some air), air, oxygen enriched air, oxygen-containing gaseous compounds (e.g., NO), oxygen- containing mixtures (e.g., 0 ₂ /C0 ₂ , 0 ₂ /H ₂ 0, 0 ₂ /H ₂ 0 ₂ /H ₂ 0), oxy radical generators (e.g., CH ₃ OH, CH ₂ 0), hydroxyl radical generators, and the like, or combinations thereof.

[0035] In an aspect, the CPO reactant mixture 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 (0 ) in the reactant mixture.

[0036] For example, when the only source of carbon in the CPO reactant mixture is CH ₄ , the CH ₄ /0 molar ratio is the same as the C/O molar ratio. As another example, when the CPO reactant mixture contains other carbon sources besides CH ₄ , such as ethane (C H ₆ ), propane (C ₃ H ₈ ), butanes (C ₄ H _I0 ), 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 C H ₆ , 3 moles of C in 1 mole of C ₃ H ₈ , 4 moles of C in 1 mole of C ₄ H _I0 , 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 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 H /CO molar ratio, such as a hydrogen enriched syngas with a H /CO molar ratio of greater than about 2.0). The C/O molar ratio in the CPO reactant mixture 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 can be adjusted based on the CPO effluent temperature in order to decrease (e.g., minimize) the unconverted hydrocarbons content of the produced syngas (e.g., hydrogen enriched syngas). As will be appreciated by one of skill in the art, and with the help of this disclosure, when the syngas (e.g., hydrogen enriched 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.

[0037] 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.

[0038] 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 Si0 ; 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.

[0039] 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.

[0040] 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.

[0041] In some aspects, the support comprises an inorganic oxide, alpha, beta or theta alumina (A1 0 ₃ ), activated A1 0 ₃ , silicon dioxide (Si0 ), titanium dioxide (Ti0 ), magnesium oxide (MgO), zirconium oxide (Zr0 ), lanthanum (III) oxide (La 0 ₃ ), yttrium (III) oxide (Y 0 ₃ ), cerium (IV) oxide (Ce0 ), zeolites, ZSM- 5, perovskite oxides, hydrotalcite oxides, and the like, or combinations thereof.

[0042] 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.

[0043] In an aspect, a CPO reactor suitable for use in the present disclosure can comprise a tubular reactor, a continuous flow reactor, an isothermal reactor, an adiabatic reactor, a fixed bed reactor, a fluidized bed reactor, a bubbling bed reactor, a circulating bed reactor, an ebullated bed reactor, a rotary kiln reactor, and the like, or combinations thereof.

[0044] In some aspects, the CPO reactor 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 (H 0) 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; hydrogen enriched syngas effluent) measured at the point where the syngas exits the CPO reactor, 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 CPO reactor effluent (e.g., hydrogen enriched syngas), as well as the composition of the CPO reactor effluent (e.g., hydrogen enriched syngas). 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 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 H /CO molar ratio, such as a hydrogen enriched syngas with a H /CO molar ratio of greater than about 2.0; a hydrogen enriched syngas with an M ratio of greater than about 1.2).

[0045] The CPO reactor 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. [0046] The CPO reactor 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.

[0047] In an aspect, the CPO reactor can be characterized by any suitable reactor temperature and/or catalyst bed temperature. For example, the CPO reactor 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.

[0048] The CPO reactor can be operated under any suitable temperature profile that can provide for a syngas with a desired composition (e.g., a syngas with a desired H /CO molar ratio, such as a hydrogen enriched syngas with a H /CO molar ratio of greater than about 2.0). The CPO reactor 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.

[0049] 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.

[0050] 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 H /CO molar ratio; a desired C0 content; etc.), wherein the isothermal conditions comprise a temperature variation of less than about + 10 °C across the reactor and/or catalyst bed.

[0051] The CPO reactor can be operated under any suitable operational parameters that can provide for isothermal conditions.

[0052] 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.

[0053] 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 Fl /CO molar ratio; a desired C0 content; etc.), wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the reactor and/or catalyst bed.

[0054] 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.

[0055] The CPO reactor can be operated under any suitable operational parameters that can provide for near-isothermal conditions.

[0056] The CPO reactor 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, from about 1 barg to about 90 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.

[0057] The CPO reactor 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.

[0058] In some aspects, the CPO reactor 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.

[0059] 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 H /CO molar ratio; a syngas with a desired C0 content; etc.). For example, the CPO operational parameters can be adjusted to provide for an increased H content of the syngas. As another example, the CPO operational parameters can be adjusted to provide for a decreased C0 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 CH ₄ ) content of the syngas.

[0060] In an aspect, a CPO reactor effluent can be recovered from the CPO reactor, wherein the CPO reactor effluent comprises hydrogen, carbon monoxide, water, carbon dioxide, and unreacted hydrocarbons.

[0061] In some aspects, the CPO reactor effluent can be used as syngas in a downstream process without further processing to enrich the hydrogen content of the CPO reactor effluent. In such aspects, the CPO reactor effluent is the hydrogen enriched syngas, wherein the H /CO molar ratio of the CPO reactor effluent is the same as the H /CO molar ratio of the hydrogen enriched syngas.

[0062] The hydrogen enriched syngas as disclosed herein can be characterized by a H /CO molar ratio of greater than about 2.0, alternatively greater than about 2.2, alternatively greater than about 2.5, alternatively greater than about 2.7, or alternatively greater than about 3.0. For purposes of the disclosure herein, when the CPO reactor effluent is characterized by a H /CO molar ratio of greater than about 2.0, the CPO reactor effluent can be referred to as“hydrogen enriched syngas,” given that the CPO reaction represented by equation (1) can only produce a gas mixture (e.g., syngas) having a H ₂ /CO molar ratio with a theoretical stoichiometric limit of 2.0.

[0063] In other aspects, the CPO reactor effluent can be further processed to produce the hydrogen enriched syngas, wherein the hydrogen enriched syngas can be used in a downstream process. The CPO reactor effluent can be processed to enrich its hydrogen content. In such aspects, the H /CO molar ratio of the hydrogen enriched syngas is greater than the H /CO molar ratio of the CPO reactor effluent.

[0064] As will be appreciated by one of skill in the art, and with the help of this disclosure, although the hydrogen enriched syngas is characterized by a H ₂ /CO molar ratio of greater than about 2.0, the hydrogen enriched syngas can be processed to further increase its hydrogen content, to provide for a syngas with a desired composition.

[0065] Further, as will be appreciated by one of skill in the art, and with the help of this disclosure, the CPO reactor effluent and/or hydrogen enriched syngas can be subjected to minimal processing, such as the recovery of unreacted hydrocarbons, diluent, water, etc., without substantially changing the IT /CO molar ratio of the CPO reactor effluent and/or hydrogen enriched syngas, respectively. For example, water can be condensed and separated from the syngas, e.g., in a condenser.

[0066] In an aspect, a process for producing hydrogen enriched syngas as disclosed herein can further comprise (i) recovering at least a portion of the unreacted hydrocarbons from the CPO reactor effluent and/or hydrogen enriched syngas to yield recovered hydrocarbons, and (ii) recycling at least a portion of the recovered hydrocarbons to the CPO reactor. 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.

[0067] The CPO reactor can be operated under any suitable operational parameters that can provide for a syngas with a desired composition (e.g., a hydrogen enriched syngas with a I¾/CO molar ratio of greater than about 2.0); for example, the CPO reactor can be operated at relatively low pressure, and optionally at relatively low C/O molar ratio in the CPO reactant mixture. Without wishing to be limited by theory, for a given CPO effluent temperature (e.g., target CPO effluent temperature) and a given C/O molar ratio in the CPO reactant mixture, the I¾/CO molar ratio of the produced syngas increases with decreasing the pressure. Further, without wishing to be limited by theory, and according to Le Chatelier's Principle, the equilibrium of the reforming reaction represented by equation (3) will be shifted towards producing IT and CO with decreasing the pressure: the reforming reaction goes from 2 moles reactants (CFft and I¾0) to 4 moles of products (IT and CO), and a decrease in pressure will favor the equilibrium of the reaction to be shifted towards the production of IT and CO. The reforming reaction represented by equation (3) can lead to a syngas having a I¾/CO molar ratio of 3, which is greater than the IT ₂ /CO molar ratio of 2 for the syngas produced according to the CPO reaction as represented by equation (1). [0068] In an aspect, the CPO reactor can be operated at a CPO pressure of 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 30 barg, alternatively from about 1 barg to about 25 barg, alternatively from about 1 barg to about 20 barg, or alternatively from about 1 barg to about 10 barg. In such aspect, the CPO reactor can be operated at (i) a CPO effluent temperature (e.g., target CPO effluent temperature) of 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 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; and/or (ii) a C/O molar ratio in the CPO reactant mixture of less than about 2.2:1, alternatively less than about 2:1, alternatively less than about 1.9:1, alternatively from about 0.9:1 to about 2.2:1, alternatively from about 1 :1 to about 2:1, or alternatively from about 1.1 :1 to about 1.9:1.

[0069] In some aspects, the CPO reactor can be operated at a CPO pressure of less than about 30 barg, at a CPO effluent temperature (e.g., target CPO effluent temperature) of equal to or greater than about 750 °C, and at a C/O molar ratio in the CPO reactant mixture of less than about 2.2:1.

[0070] The CPO reactor can be operated under any suitable operational parameters that can provide for a syngas with a desired composition (e.g., a hydrogen enriched syngas with a H /CO molar ratio of greater than about 2.0); for example, the CPO reactor can be operated at a relatively high C/O molar ratio in the CPO reactant mixture, and optionally at relatively low pressure. Without wishing to be limited by theory, and according to Le Chatelier's Principle, the equilibrium of the CPO reaction represented by equation (1) will be shifted towards producing ¾ and CO with increasing the concentration of one of the reactants (e.g., CH ₄ ).

[0071] When excess hydrocarbons (e.g., methane) are present, a portion of hydrocarbons can undergo a thermal decomposition reaction, for example as represented by equation (2):

CH ₄ C + 2 H ₂ (2)

The decomposition reaction of hydrocarbons, such as methane, is facilitated by elevated temperatures, and increases the hydrogen content in the CPO reactor effluent and/or hydrogen enriched syngas. 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 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, a portion of hydrocarbons can undergo a decomposition reaction to carbon (C) and H even at relatively low C/O molar ratios in the CPO reactant mixture (e.g., a C/O molar ratio in the CPO reactant mixture of less than about 2: 1).

[0072] In an aspect, the CPO reactor can be operated at a C/O molar ratio in the CPO reactant mixture of 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 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. In such aspect, the CPO reactor can be operated at (i) a CPO pressure of 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 30 barg, alternatively from about 1 barg to about 25 barg, alternatively from about 1 barg to about 20 barg, or alternatively from about 1 barg to about 10 barg; and/or (ii) a CPO effluent temperature (e.g., target CPO effluent temperature) of 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 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.

[0073] In some aspects, the CPO reactor can be operated at a CPO pressure of less than about 30 barg, at a CPO effluent temperature (e.g., target CPO effluent temperature) of equal to or greater than about 750 °C, and at a C/O molar ratio in the CPO reactant mixture of equal to or greater than about 2:1.

[0074] In an aspect, the CPO reactant mixture can further comprise a diluent, such as water and/or steam. The CPO reactor can be operated under any suitable operational parameters that can provide for a syngas with a desired composition (e.g., a hydrogen enriched syngas with a H /CO molar ratio of greater than about 2.0); for example, the CPO reactor can be operated with introducing water and/or steam to the CPO reactor.

[0075] Generally, a diluent is inert with respect to the CPO reaction, e.g., the diluent does not participate in the CPO reaction (e.g., a CPO reaction as represented by equation (1)). 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, etc.) might undergo chemical reactions other than the CPO reaction within the CPO reactor, and can change the composition of the resulting syngas (e.g., hydrogen enriched syngas). 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. Steam can react with methane, for example represented by equation (3):

CH ₄ + H ₂ 0 C0 + 3 H ₂ (3)

[0076] In an aspect, a diluent comprising water and/or steam can increase a hydrogen content of the resulting syngas (e.g., hydrogen enriched syngas). For example, in aspects where the CPO reactant mixture comprises water and/or steam diluent, the resulting syngas (e.g., hydrogen enriched syngas) can be characterized by a hydrogen to carbon monoxide molar ratio that is increased when compared to a hydrogen to carbon monoxide molar ratio of a syngas produced by an otherwise similar process conducted with a reactant mixture comprising hydrocarbons and oxygen without the water and/or steam diluent.

[0077] 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 H , for example as represented by equation (4):

C + H ₂ 0 ^ C0 + H ₂ (4)

[0078] Further, since oxygen is present in the CPO reactant mixture, 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 (5):

C + 0 ₂ C0 ₂ (5) [0079] In an aspect, the CPO reactor can be operated at an S/C molar ratio in the CPO reactant mixture 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 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 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.

[0080] The S/C molar ratio in the CPO reactant mixture can be adjusted based on the desired CPO effluent temperature (e.g., target CPO effluent temperature) in order to increase (e.g., maximize) the ¾ content of the produced syngas (e.g., hydrogen enriched syngas). As will be appreciated by one of skill in the art, and with the help of this disclosure, the reaction (3) that consumes steam in the CPO reactor is preferable over the water-gas shift (WGS) reaction (6) in the CPO reactor, as reaction (3) allows for increasing the ¾ content of the produced syngas (e.g., hydrogen enriched syngas), as well as the M ratio of the produced syngas (e.g., hydrogen enriched syngas), wherein the M ratio is a molar ratio defined as (H ₂ -C0 ₂ )/(C0+C0 ₂ ).

[0081] In an aspect, the amount of methane that reacts according to reaction (3) in the CPO reactor is less than the amount of methane that reacts according to reaction (1) in the CPO reactor. 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.

[0082] Without wishing to be limited by theory, the presence of water and/or steam in the CPO reactor changes the flammability of the CPO reactant mixture, thereby providing for a wider practical range of C/O molar ratios in the CPO reactant mixture. Further, and without wishing to be limited by theory, the presence of water and/or steam in the CPO reactor allows for the use of lower C/O molar ratios in the CPO reactant mixture. Furthermore, and without wishing to be limited by theory, the presence of water and/or steam in the CPO reactor allows for operating the CPO reactor at relatively high pressures.

[0083] In an aspect, the CPO reactor can be operated in the presence of water and/or steam at a CPO pressure of 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.

[0084] In an aspect, the CPO reactor can be operated in the presence of water and/or steam at a C/O molar ratio in the CPO reactant mixture of less than about 2.2:1, alternatively less than about 2:1, alternatively less than about 1.9:1, alternatively from about 0.9:1 to about 2.2:1, alternatively from about

1 : 1 to about 2:1, or alternatively from about 1.1 :1 to about 1.9: 1. [0085] 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 can lead to increasing the amount of unreacted hydrocarbons in the CPO reactor effluent and/or hydrogen enriched syngas. Further, as will be appreciated by one of skill in the art, and with the help of this disclosure, some downstream processes, such as methanol production processes, can tolerate limited amounts of unreacted hydrocarbons in the syngas.

[0086] In some aspects, the hydrogen enriched syngas 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 ₄ ). In such aspects, the hydrogen enriched syngas can be produced in a CPO process that employs water and/or steam. In such aspects, the hydrogen enriched syngas can be used for methanol synthesis.

[0087] In some aspects, the CPO reactor can be operated at an S/C molar ratio in the CPO reactant mixture of from about 0.01 :1 to less than about 2.4:1, at a CPO pressure of equal to or greater than about 10 barg, and at a C/O molar ratio in the CPO reactant mixture of less than about 2.2:1.

[0088] In an aspect, a process for producing hydrogen enriched syngas as disclosed herein can comprise (i) recovering a CPO reactor effluent from the CPO reactor, wherein the CPO reactor effluent comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; and (ii) processing at least a portion of the CPO reactor effluent to produce the hydrogen enriched syngas, wherein the H /CO molar ratio of the hydrogen enriched syngas is greater than the H /CO molar ratio of the CPO reactor effluent. As will be appreciated by one of skill in the art, and with the help of this disclosure, even if the reactor effluent (e.g., CPO reactor effluent, hydrogen enriched syngas) recovered from the CPO reactor is characterized by a H /CO molar ratio of the CPO reactor effluent of greater than about 2.0, the reactor effluent can be further processed to enrich the hydrogen content of the reactor effluent (i.e., to increase the H /CO molar ratio of the CPO reactor effluent) to provide for a syngas with a desired composition.

[0089] In an aspect, the step of processing at least a portion of the CPO reactor effluent to produce the hydrogen enriched syngas can comprise contacting an SMR reactor syngas effluent with at least a portion of the CPO reactor effluent to yield the hydrogen enriched syngas; wherein the H /CO molar ratio of the SMR reactor syngas effluent is greater than the H /CO molar ratio of the CPO reactor effluent. The SMR reactor syngas effluent can be produced by reacting, via an SMR reaction (e.g., a reaction represented by equation (3)), an SMR reactant mixture in an SMR reactor to produce an SMR reactor syngas effluent; wherein the SMR reactant mixture comprises methane and steam; and wherein the SMR reactor syngas effluent comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted methane. Generally, SMR describes the catalytic reaction of methane and steam to form carbon monoxide and hydrogen according to the reaction represented by equation (3). Steam reforming catalysts can comprise any suitable commercially available steam reforming catalyst; nickel (Ni) and/or rhodium (Rh) as active metal(s) on alumina; or combinations thereof. SMR employs fairly elevated S/C molar ratios when compared to the S/C molar ratios used in CPO. For example, SMR can be characterized by an S/C molar ratio of equal to or greater than about 2.5, alternatively equal to or greater than about 2.7, or alternatively equal to or greater than about 3.0. Further, the SMR reactor syngas effluent can be characterized by a H ₂ /CO molar ratio of equal to or greater than about 2.5, alternatively equal to or greater than about 2.7, or alternatively equal to or greater than about 2.9. 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 SMR reaction as represented by equation (3) can yield a syngas with a H /CO molar ratio having the theoretical stoichiometric limit of 3.0 (i.e., SMR reaction as represented by equation (3) yields 3 moles of H for every 1 mole of CO). As will be appreciated by one of skill in the art, and with the help of this disclosure, the theoretical stoichiometric limit of 3.0 for the H ₂ /CO molar ratio in an SMR reaction cannot be achieved because reactants undergo side reactions at the conditions used for the SMR reaction.

[0090] In some aspects, an SMR reactor syngas effluent can be fed to the CPO reactor to produce the hydrogen enriched syngas. In such aspects, the SMR reactor syngas effluent comprises unreacted hydrocarbons (e.g., CH ₄ ) that can participate in the CPO reaction as represented by equation (1). Since the SMR reactor syngas effluent has a fairly high H ₂ /CO molar ratio (e.g., equal to or greater than about 2.5), the syngas recovered from the CPO reactor can have a H /CO molar ratio that is greater than the H /CO molar ratio of a syngas produced via an otherwise similar CPO process without feeding an SMR reactor syngas effluent to the CPO reactor.

[0091] In an aspect, the step of processing at least a portion of the CPO reactor effluent to produce the hydrogen enriched syngas can comprise removing at least a portion of the carbon dioxide from the CPO reactor effluent to yield the hydrogen enriched syngas. 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 H /CO molar ratio of the syngas does not change by removing carbon dioxide from the syngas, the concentration of hydrogen increases in the syngas by removing carbon dioxide from the syngas. However, the M ratio of the syngas changes with changing the carbon dioxide content of the syngas, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ). The CPO reactor effluent is characterized by an M ratio of the CPO reactor effluent. The hydrogen enriched syngas is characterized by an M ratio of the hydrogen enriched syngas. In aspects where the hydrogen enriched syngas is produced by removing at least a portion of the carbon dioxide from the CPO reactor effluent, the hydrogen enriched syngas can be characterized by an M ratio that is greater than the M ratio of the CPO reactor effluent. As will be appreciated by one of skill in the art, and with the help of this disclosure, a C0 -lean syngas has a higher M ratio than a C0 -rich syngas: the lower the C0 content of the syngas, the higher the M ratio of the syngas.

[0092] In an aspect, the CPO reactor effluent can be characterized by an M ratio of from about 1.2 to about 1.8, alternatively from about 1.6 to about 1.78, or alternatively from about 1.7 to about 1.78.

[0093] In some aspects, at least a portion of the CPO reactor effluent can be introduced to a C0 separator (e.g., C0 ₂ scrubber) to yield the hydrogen enriched syngas, wherein the hydrogen enriched syngas can be characterized by an M ratio that is greater than the M ratio of the CPO reactor effluent. The C0 separator can comprise C0 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 step of removing at least a portion of the carbon dioxide from the CPO reactor effluent to yield the hydrogen enriched syngas can comprise C0 removal by amine absorption.

[0094] In an aspect, the hydrogen enriched syngas can be characterized by an M ratio of from about 1.9 to about 2.2, alternatively from about 1.95 to about 2.1, or alternatively from about 1.98 to about 2.06.

[0095] In an aspect, the step of processing at least a portion of the CPO reactor effluent to produce the hydrogen enriched syngas can comprise feeding at least a portion of the CPO reactor effluent to a water- gas shift (WGS) reactor to produce the hydrogen enriched syngas, wherein a portion of the carbon monoxide of the CPO reactor effluent reacts with water via a WGS reaction to produce hydrogen and carbon dioxide. Generally, the WGS reaction describes the catalytic reaction of carbon monoxide and water vapor to form carbon dioxide and hydrogen, for example as represented by equation (6):

CO + H ₂ 0 C0 ₂ + ¾ (6)

The WGS reaction can be used to increase the H /CO molar ratio of gas streams comprising carbon monoxide and hydrogen. WGS catalysts can comprise any suitable WGS catalysts, such as commercial WGS catalysts; chromium or copper promoted iron-based catalysts; copper-zinc-aluminum catalyst; and the like; or combinations thereof.

[0096] In an aspect, a portion of the carbon monoxide in the CPO reactor can undergo a WGS reaction (as represented by equation (6)), thereby increasing the amount of hydrogen in the CPO reactor effluent and/or the hydrogen enriched syngas.

[0097] In an aspect, a process for producing hydrogen enriched syngas as disclosed herein can further comprise recovering a WGS reactor effluent from the WGS reactor, wherein the WGS reactor effluent comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons, and wherein the H /CO molar ratio of the WGS reactor effluent is greater than the H /CO molar ratio of the CPO reactor effluent.

[0098] In some aspects, the WGS reactor effluent can be used as syngas in a downstream process without further processing the WGS reactor effluent. In such aspects, the WGS reactor effluent is the hydrogen enriched syngas, wherein the H /CO molar ratio of the WGS reactor effluent is the same as the H /CO molar ratio of the hydrogen enriched syngas. For purposes of the disclosure herein, when the WGS reactor effluent is characterized by a H /CO molar ratio of greater than about 2.0, the WGS reactor effluent can be referred to as“hydrogen enriched syngas.”

[0099] In other aspects, the WGS reactor effluent can be further processed to produce the hydrogen enriched syngas, wherein the hydrogen enriched syngas can be used in a downstream process. The WGS reactor effluent can be further processed to enrich its hydrogen content.

[00100] In an aspect, at least a portion of the carbon dioxide can be removed from the WGS reactor effluent to yield the hydrogen enriched syngas, and wherein the hydrogen enriched syngas is characterized by an M ratio that is greater than the M ratio of the WGS reactor effluent. The WGS reactor effluent can be introduced to a C0 separator (e.g., C0 scrubber) to yield the hydrogen enriched syngas, as previously described herein for the CPO reactor effluent.

[00101] In an aspect, a first portion of the CPO reactor effluent can be introduced to the WGS reactor to produce the WGS reactor effluent. In such aspect, at least a portion of the WGS reactor effluent can be contacted with a second portion of the CPO reactor effluent to yield the hydrogen enriched syngas. In such aspect, the CPO reactor effluent (e.g., first portion of the CPO reactor effluent, second portion of the CPO reactor effluent) and/or the WGS reactor effluent can be subjected to a step of carbon dioxide removal. For example, the first portion of the CPO reactor effluent that can be introduced to the WGS reactor to produce the WGS reactor effluent can be from about 0.01 vol.% to about 100 vol.%, alternatively from about 0.1 vol.% to about 90 vol.%, alternatively from about 1 vol.% to about 80 vol.%, alternatively from about 10 vol.% to about 75 vol.%, alternatively from about 20 vol.% to about 60 vol.%, alternatively from about 25 vol.% to about 50 vol.%, alternatively equal to or greater than about 5 vol.%, alternatively equal to or greater than about 10 vol.%, alternatively equal to or greater than about 15 vol.%, alternatively equal to or greater than about 20 vol.%, or alternatively equal to or greater than about 25 vol.%, based on the total volume of the CPO reactor effluent.

[00102] In some aspects, a second portion of the CPO reactor effluent can be contacted with at least a portion of the WGS reactor effluent to produce a combined effluent stream, wherein the combined effluent stream is characterized by an M ratio of the combined effluent stream; wherein at least a portion of the carbon dioxide can be removed from the combined effluent stream to yield the hydrogen enriched syngas, and wherein the hydrogen enriched syngas is characterized by an M ratio that is greater than the M ratio of the combined effluent stream. For example, the second portion of the CPO reactor effluent that can be contacted with at least a portion of the WGS reactor effluent to produce a combined effluent stream can be from about 0.01 vol.% to about 99.99 vol.%, alternatively from about 10 vol.% to about 99.9 vol.%, alternatively from about 20 vol.% to about 99 vol.%, alternatively from about 25 vol.% to about 90 vol.%, alternatively from about 40 vol.% to about 80 vol.%, alternatively from about 50 vol.% to about 75 vol.%, alternatively less than about 95 vol.%, alternatively less than about 90 vol.%, alternatively less than about 85 vol.%, alternatively less than about 80 vol.%, or alternatively less than about 75 vol.%, based on the total volume of the CPO reactor effluent.

[00103] In an aspect, a process for producing hydrogen enriched syngas as disclosed herein can comprise a step of removing carbon dioxide from one or more streams; e.g., carbon dioxide can be removed from at least a portion of the CPO reactor effluent, from at least a portion of the WGS reactor effluent, from at least a portion of the combined effluent stream, etc. For example, carbon dioxide can be removed from at least a portion of the CPO reactor effluent and from at least a portion of the WGS reactor effluent, prior to combining the CPO reactor effluent and the WGS reactor effluent to yield the hydrogen enriched syngas; carbon dioxide can be removed from either at least a portion of the CPO reactor effluent or from at least a portion of the WGS reactor effluent, prior to combining the CPO reactor effluent and the WGS reactor effluent to yield the hydrogen enriched syngas; carbon dioxide can be removed from the combined effluent stream to yield the hydrogen enriched syngas; and the like; or combinations thereof.

[00104] In an aspect, at least a portion of the CPO reactor effluent can be contacted with a hydrogen stream to yield the hydrogen enriched syngas. In some aspects, the hydrogen stream can be recovered from a methanol production process.

[00105] In aspects where the hydrogen enriched syngas is characterized by an M ratio of from greater than about 2.0 to about 2.2, the hydrogen enriched syngas can be further used for methanol production. In an aspect, at least a portion of the hydrogen enriched syngas can be introduced 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. The methanol reactor can comprise any reactor suitable for a methanol synthesis reaction from CO and H ₂ , such as for example an isothermal reactor, an adiabatic reactor, a trickle bed reactor, a fluidized bed reactor, a slurry reactor, a loop reactor, a cooled multi tubular reactor, and the like, or combinations thereof.

[00106] Generally, CO and ¾ can be converted into methanol (CH ₃ OH), for example as represented by equation (7):

CO + H ₂ CH ₃ OH (7)

C0 and H can also be converted to methanol, for example as represented by equation (8):

C0 ₂ + 3H ₂ CH ₃ OH + H ₂ 0 (8)

Methanol synthesis from CO, C0 and H is a catalytic process, and is most often conducted in the presence of copper based catalysts. The methanol reactor 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 in the current disclosure include Cu, Cu/ZnO, Cu/Th0 , Cu/Zn/Al 0 ₃ , Cu/Zn0/Al 0 ₃ , Cu/Zr, and the like, or combinations thereof.

[00107] In an aspect, at least a portion of the methanol reactor effluent stream can be separated 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. The methanol reactor effluent stream can be separated into a crude methanol stream and a vapor stream in a gas-liquid separator, such as a vapor-liquid separator, flash drum, knock-out drum, knock-out pot, compressor suction drum, etc. The crude methanol stream can be introduced to a distillation unit to produce a methanol stream and a water stream.

[00108] In an aspect, at least a portion of the vapor stream can be separated into a hydrogen stream and a residual gas stream, wherein the hydrogen stream comprises at least a portion of the hydrogen of the vapor stream, and wherein the residual gas stream comprises carbon monoxide, carbon dioxide, and hydrocarbons. The vapor stream can be separated into a hydrogen stream and a residual gas stream in a hydrogen recovery unit, such as a PSA unit, a membrane separation unit, a cryogenic separation unit, and the like, or combinations thereof. [00109] In an aspect, at least a portion of the residual gas stream can be purged. In an aspect, at least a portion of the residual gas stream can be used as fuel, for example for pre-heating the CPO reactant mixture and/or the SMR reactor.

[00110] The hydrogen stream can be contacted with the CPO reactor effluent to yield the hydrogen enriched syngas, wherein the hydrogen enriched syngas can be fed to the methanol reactor.

[00111] In an aspect, the hydrogen enriched syngas can be compressed in a single compression stage prior to introducing at least a portion of the hydrogen enriched syngas to the methanol reactor. Generally, the methanol reactor can operate at pressures that are greater than the operating pressure of the CPO reactor. In an aspect, the methanol reactor can be characterized by a pressure of from about 70 barg to about 100 barg, alternatively from about 75 barg to about 95 barg, or alternatively from about 80 barg to about 85 barg.

[00112] In some aspects, the natural gas feed to the CPO reactor can have a pressure of from about 35 barg to about 45 barg, wherein the CPO reactor can be operated at about 35 barg to about 45 barg. In other aspects, the natural gas feed to the CPO reactor can have a pressure of from about 35 barg to about 45 barg, wherein the CPO reactor can be operated at a pressure other than from about 35 barg to about 45 barg, and wherein the natural feed can be either compressed or expanded to meet the operational pressure requirements of the CPO reactor.

[00113] In some aspects, the natural gas feed to the CPO reactor can have a pressure of from about 15 barg to about 25 barg, wherein the CPO reactor can be operated at about 15 barg to about 25 barg. In other aspects, the natural gas feed to the CPO reactor can have a pressure of from about 15 barg to about 25 barg, wherein the CPO reactor can be operated at a pressure other than from about 15 barg to about 25 barg, and wherein the natural feed can be either compressed or expanded to meet the operational pressure requirements of the CPO reactor. For example, the natural gas feed to the CPO reactor can have a pressure of from about 15 barg to about 25 barg, wherein the CPO reactor can be operated at about 35 barg to about 45 barg, wherein the natural feed can be compressed to meet the operational pressure requirements of the CPO reactor.

[00114] In aspects where the CPO reactor operates at pressures of greater than about 30 barg to less than about 70 barg, the hydrogen enriched syngas can be compressed in a single compression stage (e.g., by using a single compressor) prior to introducing at least a portion of the hydrogen enriched syngas to the methanol reactor. In aspects where the CPO reactor operates at pressures of greater than about 70 barg, the hydrogen enriched syngas can be introduced to the methanol reactor without being additionally compressed. In aspects where the CPO reactor operates at pressures of less than about 40 barg, or alternatively less than about 30 barg, the hydrogen enriched syngas can be compressed in two or more compression stages (e.g., by using two or more compressors) prior to introducing at least a portion of the hydrogen enriched syngas to the methanol reactor.

[00115] In an aspect, a process for producing hydrogen enriched syngas as disclosed herein can advantageously display improvements in one or more process characteristics when compared to an otherwise similar process that does not employ CPO for producing syngas. The process for producing hydrogen enriched syngas as disclosed herein can advantageously utilize various qualities of natural gas, including lower qualities of natural gas (e.g.,“dirty” shale gas, sulfur-containing gas, etc.). Generally, combined reforming (CR) technology that pairs SMR with autothermal reforming (ATR) processes require higher quality natural gas than CPO.

[00116] As will be appreciated by one of skill in the art, and with the help of this disclosure, since the CPO reaction is exothermic, no additional heat supply in the form of fuel combustion is needed (except for pre-heating reactants in the CPO reactant mixture), when compared to conventional steam reforming. As such, the process for producing hydrogen enriched syngas as disclosed herein can advantageously generate less C0 ₂ through fuel burning, when compared to steam reforming.

[00117] In an aspect, a process for producing hydrogen enriched syngas as disclosed herein can advantageously employ steam, thereby reducing the flammability of the CPO reactant mixture; which in turn enables the use of a wider range of C/O molar ratios in the CPO reactant mixture, as well as the use of higher operating pressures in the CPO reactor. The steam can advantageously react with carbon produced in the reactor, thereby reducing coking of the catalyst and increasing catalyst life.

[00118] In an aspect, a process for producing hydrogen enriched syngas as disclosed herein can advantageously employ short contact times, such as the millisecond regime (MSR), which can increase selectivity to a syngas having a desired composition (e.g., syngas with specific H /CO molar ratios, with specific M ratios, with or without C0 , etc.). MSR in a syngas reactor can advantageously minimize side reactions, such as complete combustion, that could result in a decrease in selectivity to desired syngas components. Additional advantages of the processes for the production of hydrogen enriched syngas as disclosed herein can be apparent to one of skill in the art viewing this disclosure.

EXAMPLES

[00119] The subject matter having been generally described, the following examples are given as particular embodiments of the disclosure and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification of the claims to follow in any manner.

EXAMPLE 1

[00120] Syngas composition was investigated as a function of pressure for a catalytic partial oxidation

(CPO) reaction under defined process conditions. The syngas composition was calculated by using a mathematical model of the CPO reactor, and the resulting data are displayed in Figures 1 and 2. The mathematical model was developed in Aspen Plus software. The reactor was represented by a Gibbs reactor which approaches equilibrium composition for a given set of process conditions. The feed composition and reactor operating parameters were varied to obtain the change in exit stream composition. The exit stream composition was used to calculate the M ratio value. The y axis in Figure

1 plots M ratio values, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ).

[00121] For the data in Figure 1, the CPO operational parameters were: a CPO effluent temperature

(e.g., target CPO effluent temperature) of 1,000 °C, a C/O molar ratio in the CPO reactant mixture of 2, and a CPO pressure of from 1 barg to 25 barg. The produced syngas displayed a stoichiometric ratio (M) that can be sufficient for methanol production between 1 barg and 10 barg. These data indicate that hydrogen enrichment of the produced syngas can be accomplished by operating the CPO reactor at low pressures.

[00122] For the data in Figure 2, the CPO operational parameters were: a CPO effluent temperature (e.g., target CPO effluent temperature) of 1,000 °C, a C/O molar ratio in the CPO reactant mixture of 2, and a CPO pressure of from 1 barg to 25 barg. At pressures between 1 bar and 10 barg, the syngas had a hydrogen content that is sufficient for methanol production. The syngas IT2/CO molar ratio decreased with increasing the pressure.

[00123] In order to produce syngas with an enriched hydrogen content, the CPO reactor can be operated at CPO pressures less than about 15 barg, at desired CPO effluent temperatures (e.g., target CPO effluent temperatures) greater than about 850 °C, and at C/O molar ratios in the CPO reactant mixture of equal to or less than about 2.

EXAMPLE 2

[00124] Syngas composition was investigated as a function of C/O molar ratios in the CPO reactant mixture for a catalytic partial oxidation (CPO) reaction under defined process conditions. The syngas composition was calculated by using a mathematical model of the CPO reactor as described in Example 1, and the resulting data are displayed in Figures 3 and 4.

[00125] For the data in Figures 3 and 4, the CPO operational parameters were: a CPO effluent temperature (e.g., target CPO effluent temperature) of 980 °C, a CPO pressure of 5 barg, and a C/O molar ratio in the CPO reactant mixture of from 2 to 2.3. As supported by the data in Figures 3 and 4, increasing the C/O molar ratio in the CPO reactant mixture can provide for an amount of methane that can undergo decomposition to carbon (C) and hydrogen, which increases the hydrogen content of the syngas, thus providing for an increased M ratio (Figure 3), as well as an increased H ₂ /CO molar ratio (Figure 4).

EXAMPLE 3

[00126] Syngas composition was investigated as a function of S/C molar ratios in the CPO reactant mixture for a catalytic partial oxidation (CPO) reaction under defined process conditions. The syngas composition was calculated by using a mathematical model of the CPO reactor as described in Example 1, and the resulting data are displayed in Figure 5.

[00127] For the data in Figure 5, the CPO operational parameters were: a CPO pressure of 20 barg, a C/O molar ratio in the CPO reactant mixture of 1.7, and a S/C molar ratio in the CPO reactant mixture of from 0.2 to 1. As will be appreciated by one of skill in the art, and with the help of this disclosure, steam injection enriches the produced syngas with hydrogen. The H ₂ /CO molar ratio of the produced syngas increases with increasing the S/C molar ratio. Similar behavior can be also achieved at higher C/O molar ratios in the CPO reactant mixture. A preferred C/O molar ratio in the CPO reactant mixture is about 2.0 or lower. [00128] In order to produce syngas with an enriched hydrogen content, the CPO reactor can be operated at CPO pressures greater than about 15 barg, at C/O molar ratios in the CPO reactant mixture of equal to or less than about 2, at S/C molar ratios in the CPO reactant mixture of equal to or greater than about 0.2, and with a natural gas preheat temperature of less than about 550 °C. Steam injection can enrich the syngas with hydrogen.

EXAMPLE 4

[00129] Syngas composition was investigated as a function of syngas amount diverted to a water-gas shift (WGS) reaction for a catalytic partial oxidation (CPO) reaction under defined process conditions. The syngas composition was calculated by using a mathematical model of the CPO reactor as described in Example 1, and the resulting data are displayed in Figure 6.

[00130] A portion of the syngas produced by CPO can be diverted to a WGS reactor to convert CO to C0 ₂ by reaction with steam, wherein additional hydrogen is formed during WGS reaction. The C0 ₂ formed in the WGS process can be removed to further enhance the M ratio of the syngas. Figure 6 displays the increase in M value due to hydrogen enrichment that is obtained for different amounts of syngas diverted to WGS. The increase in M value at two different S/C ratios is compared to M value in syngas from CPO (dashed line). The WGS reaction can be applied to at least a portion of the syngas to augment the stoichiometric balance in favor of H , optionally followed by C0 separation.

[00131] As disclosed in Examples 1-4, the hydrogen content of the“as generated” syngas is increased when compared to syngas produced by conventional CPO processes. The produced hydrogen enriched syngas can be directly used for making methanol in conventional (commercially available) methanol loops. The hydrogen enrichment ensures that the hydrogen content is similar to the hydrogen in the makeup syngas used in current conventional methanol loops. This is important for ensuring higher M value in the combined feed for the methanol reactor, which is a requirement for current conventional methanol catalysts.

ADDITIONAL DISCLOSURE

[00132] A first aspect, which is a process for producing hydrogen enriched syngas comprising reacting, via a catalytic partial oxidation (CPO) reaction, a CPO reactant mixture in a CPO reactor to produce the hydrogen enriched syngas; wherein the CPO reactant mixture comprises hydrocarbons and oxygen; wherein the CPO reactor comprises a CPO catalyst; wherein the hydrogen enriched syngas comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; and wherein the hydrogen enriched syngas is characterized by a hydrogen to carbon monoxide (H ₂ /CO) molar ratio of greater than about 2.0.

[00133] 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. [00134] 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 (0 ) in the reactant mixture; and combinations thereof.

[00135] A fourth aspect, which is the process of the third aspect, wherein the at least one operational parameter comprises a CPO pressure of less than about 30 barg.

[00136] A fifth aspect, which is the process of the fourth aspect, wherein the at least one operational parameter further comprises a CPO effluent temperature of equal to or greater than about 750 °C and/or a C/O molar ratio in the CPO reactant mixture of less than about 2.2:1.

[00137] A sixth aspect, which is the process of the third aspect, wherein the at least one operational parameter comprises a C/O molar ratio in the CPO reactant mixture of equal to or greater than about 2:1.

[00138] A seventh aspect, which is the process of the sixth aspect, wherein the at least one operational parameter further comprises a CPO pressure of less than about 30 barg and/or a CPO effluent temperature of equal to or greater than about 750 °C.

[00139] An eighth aspect, which is the process of the third aspect, wherein the at least one 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 (H 0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture.

[00140] A ninth aspect, which is the process of the eighth aspect, wherein the at least one operational parameter further comprises a CPO pressure of equal to or greater than about 10 barg and/or a C/O molar ratio in the CPO reactant mixture of less than about 2.2:1.

[00141] A tenth aspect, which is the process of any of the first through the ninth aspects, wherein (1) the hydrogen enriched syngas comprises less than about 7.5 mol% hydrocarbons; and/or (2) the hydrogen enriched syngas is characterized by an M ratio of equal to or greater than about 1.7; wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ), and wherein at least a portion of the hydrogen enriched syngas is optionally used for methanol synthesis.

[00142] An eleventh aspect, which is the process of any of the first through the tenth aspects, wherein a portion of the hydrocarbons in the CPO reactant mixture undergo decomposition to carbon and hydrogen, and wherein at least a portion of the carbon reacts with water to produce carbon monoxide and hydrogen.

[00143] A twelfth aspect, which is the process of any of the first through the eleventh aspects, comprising (i) recovering a CPO reactor effluent from the CPO reactor, wherein the CPO reactor effluent comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; and (ii) processing at least a portion of the CPO reactor effluent to produce the hydrogen enriched syngas, wherein the H /CO molar ratio of the hydrogen enriched syngas is greater than the H /CO molar ratio of the CPO reactor effluent.

[00144] A thirteenth aspect, which is the process of the twelfth aspect, further comprising reacting, via a steam methane reforming (SMR) reaction, an SMR reactant mixture in an SMR reactor to produce an SMR reactor syngas effluent; wherein the SMR reactant mixture comprises methane and steam; wherein the SMR reactor syngas effluent comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted methane; wherein the H /CO molar ratio of the SMR reactor syngas effluent is greater than the H /CO molar ratio of the CPO reactor effluent; and wherein the step of processing at least a portion of the CPO reactor effluent to produce the hydrogen enriched syngas comprises contacting at least a portion of the SMR reactor syngas effluent with at least a portion of the CPO reactor effluent to yield the hydrogen enriched syngas.

[00145] A fourteenth aspect, which is the process of the twelfth aspect, wherein the CPO reactor effluent is characterized by an M ratio of the CPO reactor effluent, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ), wherein the step of processing at least a portion of the CPO reactor effluent to produce the hydrogen enriched syngas comprises removing at least a portion of the carbon dioxide from the CPO reactor effluent to yield the hydrogen enriched syngas, and wherein the hydrogen enriched syngas is characterized by an M ratio that is greater than the M ratio of the CPO reactor effluent.

[00146] A fifteenth aspect, which is the process of the twelfth aspect, wherein the step of processing at least a portion of the CPO reactor effluent to produce the hydrogen enriched syngas comprises feeding at least a portion of the CPO reactor effluent to a water-gas shift (WGS) reactor to produce the hydrogen enriched syngas, wherein a portion of the carbon monoxide of the CPO reactor effluent reacts with water via a WGS reaction to produce hydrogen and carbon dioxide.

[00147] A sixteenth aspect, which is the process of the fifteenth aspect further comprising (a) recovering a WGS reactor effluent from the WGS reactor, wherein the WGS reactor effluent comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons, and wherein the WGS reactor effluent is characterized by an M ratio of the WGS reactor effluent, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ); and (b) removing at least a portion of the carbon dioxide from the WGS reactor effluent to yield the hydrogen enriched syngas, and wherein the hydrogen enriched syngas is characterized by an M ratio that is greater than the M ratio of the WGS reactor effluent.

[00148] A seventeenth aspect, which is the process of the sixteenth aspect further comprising (1) contacting a portion of the CPO reactor effluent with at least a portion of the WGS reactor effluent to produce a combined effluent stream, wherein the combined effluent stream is characterized by an M ratio of the combined effluent stream; and (2) removing at least a portion of the carbon dioxide from the combined effluent stream to yield the hydrogen enriched syngas, and wherein the hydrogen enriched syngas is characterized by an M ratio that is greater than the M ratio of the combined effluent stream.

[00149] An eighteenth aspect, which is the process of any of the first through the seventeenth aspects, wherein a portion of the carbon monoxide in the CPO reactor undergoes a water-gas shift (WGS) reaction, thereby increasing the amount of hydrogen in the hydrogen enriched syngas. [00150] A nineteenth aspect, which is the process of any of the first through the eighteenth aspects further comprising (a) recovering a CPO reactor effluent from the CPO reactor, wherein the CPO reactor effluent comprises hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; (b) introducing at least a portion of the CPO reactor effluent 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; (c) 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; (d) separating at least a portion of the vapor stream into a hydrogen stream and a residual gas stream, wherein the hydrogen stream comprises at least a portion of the hydrogen of the vapor stream, and wherein the residual gas stream comprises carbon monoxide, carbon dioxide, and hydrocarbons; (e) contacting at least a portion of the hydrogen stream with the CPO reactor effluent to yield the hydrogen enriched syngas; and (f) introducing at least a portion of the hydrogen enriched syngas to the methanol reactor in step (b).

[00151] A twentieth aspect, which is the process of the nineteenth aspect, wherein the hydrogen enriched syngas is compressed in a single compression stage prior to introducing at least a portion of the hydrogen enriched syngas to the methanol reactor.

[00152] 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.

[00153] 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.

[00154] 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. [00155] 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.