PRODUCTION OF METHANOL AND OLEFINS BY CATALYTIC PARTIAL OXIDATION AND CATALYTIC SELECTIVE DEHYDROGENATION

TECHNICAL FIELD

[0001] The present disclosure relates to methods of producing methanol, more specifically methods of producing methanol from syngas produced by catalytic partial oxidation (CPO) of hydrocarbons, such as methane, integrated with dehydrogenation such that at least a portion of the heat needed for the dehydrogenation is provided by the CPO.

BACKGROUND

[0002] Synthesis gas (syngas) is a mixture comprising carbon monoxide (CO) and hydrogen (¾), as well as small amounts of carbon dioxide (C0 ₂ ), water (¾0), and unreacted methane (CH ₄ ). Syngas is generally used as an intermediate in the production of methanol and ammonia, as well as an intermediate in creating synthetic petroleum to use as a lubricant or fuel. Syngas is produced conventionally by steam reforming of natural gas (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 ₂ -C0 ₂ )/(C0+C0 ₂ ).

[0003] 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 ₂ 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.

[0004] 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. Further, maintaining a desired catalyst activity and productivity can be challenging in a CPO process, owing to elevated or run-away CPO temperatures leading to catalyst deactivation. The CPO reaction is exothermic, and can lead to a high temperature increase in a CPO catalyst bed, which can in turn lead to catalyst deactivation. Thus, there is an ongoing need for the development of syngas production via CPO processes that manage the reaction temperature, as well as produce a syngas that is suitable for a methanol production process.

BRIEF DESCRIPTION OF THE DRAWINGS

[0005] For a detailed description of the preferred embodiments of the disclosed methods, reference will now be made to the accompanying drawing in which:

[0006] Figure 1 displays a schematic of a system for a methanol production process;

[0007] Figure 2 displays a schematic of an arrangement of a CPO reaction zone and a dehydrogenation zone, according to embodiments of this disclosure; and

[0008] Figure 3 displays a schematic of a separation unit, according to embodiments of this disclosure.

DETAILED DESCRIPTION

[0009] Disclosed herein are processes for producing syngas and olefins comprising: (a) feeding a catalytic partial oxidation (CPO) reactant mixture to a CPO reaction zone; wherein the CPO reactant mixture comprises oxygen, first hydrocarbons, and optionally steam; wherein at least a portion of the CPO reactant mixture reacts, via an exothermic CPO reaction, in the CPO reaction zone to produce a CPO reaction zone effluent; wherein the CPO reaction zone comprises a CPO catalyst; wherein the CPO reaction zone effluent comprises hydrogen (¾), carbon monoxide (CO), carbon dioxide (C0 ), water, and unreacted first hydrocarbons; and wherein the CPO reaction zone effluent is characterized by a CPO effluent temperature; (b) feeding a dehydrogenation zone reactant mixture to a dehydrogenation zone, wherein the dehydrogenation zone reactant mixture comprises at least a portion of the CPO reaction zone effluent and second hydrocarbons; wherein a portion of the dehydrogenation zone reactant mixture reacts, via an endothermic catalytic dehydrogenation reaction, in the dehydrogenation zone to produce a combined effluent; wherein the dehydrogenation zone comprises a dehydrogenation catalyst; wherein the dehydrogenation zone is characterized by a dehydrogenation zone temperature; wherein the CPO effluent temperature is greater than the dehydrogenation zone temperature; wherein the first hydrocarbons and the second hydrocarbons are the same or different; wherein the combined effluent comprises ¾, CO, C0 , water, olefins, unreacted first hydrocarbons, and unreacted second hydrocarbons; (c) cooling the CPO reaction zone effluent; wherein cooling the CPO reaction zone effluent comprises heating the second hydrocarbons to the dehydrogenation zone temperature while cooling the CPO reaction zone effluent by heat transfer (e.g., direct heat transfer) between the CPO reaction zone effluent and the second hydrocarbons; (d) removing at least a portion of the water from the combined effluent to produce a dehydrated combined effluent; and (e) separating at least a portion of the dehydrated combined effluent into syngas, an olefins stream, and an alkanes stream; wherein the syngas comprises H , CO, C0 , and methane (CH ₄ ); wherein the olefins stream comprises at least a portion of the olefins in the dehydrated combined effluent; and wherein the alkanes stream comprises at least a portion of the C ₊ alkanes in the dehydrated combined effluent. The process can further comprise: (f) introducing at least a portion of the syngas to a methanol reactor to produce methanol.

[0010] In embodiments, the syngas is characterized by an M ratio of equal to or greater than about 1.8, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ); the syngas is characterized by a hydrogen to carbon monoxide (H /CO) molar ratio of greater than about 2.0; the dehydrogenation zone reactant mixture comprises an amount of second hydrocarbons effective to provide for a syngas characterized by a hydrogen to carbon monoxide (¾/CO) molar ratio of greater than about 2.0; and/or the syngas is characterized by an M ratio and/or a H /CO molar ratio that is greater than an M ratio and/or a H /CO molar ratio, respectively of a syngas produced in an otherwise similar process without feeding the CPO reaction zone effluent to a dehydrogenation zone. In embodiments, the process can further comprise optionally recycling at least a portion of the C ₊ hydrocarbons stream and/or at least a portion of the alkanes stream to the dehydrogenation zone in step (b) and/or to the CPO reaction zone in step (a).

[0011] The first hydrocarbons and/or the second hydrocarbons can comprise methane, ethane, propane, butanes, naphtha, 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. In embodiments, the second hydrocarbons comprise ethane, propane, butane, naphtha, optionally methane, or combinations thereof; and the olefins comprise ethylene.

[0012] Run-away temperatures in the CPO reaction zone can be avoided by utilizing heat from the exothermic CPO reaction in the CPO reaction zone to provide heat for endothermic catalytic dehydrogenation of the dehydrogenation zone reactant mixture comprising the dehydrogenation zone feed via direct heat exchange between the CPO reaction zone effluent and the second hydrocarbons.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] Reference throughout the specification to “an embodiment,” “another embodiment,” “other embodiments,”“some embodiments,” and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least an embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described element(s) can be combined in any suitable manner in the various embodiments.

[0017] 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.

[0018] As used herein, the term“effective,” means adequate to accomplish a desired, expected, or intended result.

[0019] 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.

[0020] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art. 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. 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. 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.

[0021] Referring to Figure 1, a methanol production system 1000 is disclosed. The methanol production system 1000 generally comprises a catalytic partial oxidation (CPO or CPOx) reaction zone 100; a methanol reactor 200; a gas-liquid separator 300; a distillation unit 400; a hydrogen (H ) recovery unit 500; a dehydrogenation zone 650; and a separation apparatus comprising separation unit 700 and separator 800. Common reference numerals refer to common components present in one or more of the Figures, and the description of a particular component is generally applicable across respective Figures wherein the component is present, except as otherwise indicated herein.

[0022] In an embodiment, a process as disclosed herein can comprise a step of reacting, via a CPO reaction, a CPO reactant mixture 10 in the CPO reaction zone 100 to produce a CPO reaction zone effluent 15; wherein the CPO reactant mixture 10 comprises oxygen, hydrocarbons (e.g., first hydrocarbons) and optionally steam; wherein the CPO reaction zone 100 comprises a CPO catalyst; and wherein the CPO reaction zone effluent 15 comprises hydrogen (H ), carbon monoxide (CO), carbon dioxide (C0 ), water, and unreacted first hydrocarbons. As will be appreciated by one of skill in the art, and with the help of this disclosure, depending on the composition of the CPO reactant mixture 10, the composition of the resulting CPO reaction zone effluent 15 recovered from the CPO reaction zone 100 can vary. [0023] 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 ® C0 + 2 H ₂ (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 C0 and water (¾0), 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 CO (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., ¾, 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 ¾ can be oxidized to C0 and H 0, respectively. The relative amounts (e.g., composition) of CO, ¾, C0 and H 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 reaction zone 100 can have a direct impact on the M ratio of the produced CPO reaction zone effluent 15, wherein the M ratio is a molar ratio defined as (H ₂ -C0 ₂ )/(C0+C0 ₂ ). 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.

[0024] Further, without wishing to be limited by theory, the CPO reaction as depicted in equation (1) is an exothermic heterogeneous catalytic reaction (i.e., a mildly exothermic reaction) and it occurs in a single reactor unit, such as the CPO reaction zone 100 (as opposed to more than one reactor unit as is the case in conventional processes for syngas production, such as steam methane reforming (SMR) - autothermal reforming (ATR) combinations). While it is possible to conduct partial oxidation of hydrocarbons as a homogeneous reaction, in the absence of a catalyst, homogeneous partial oxidation of hydrocarbons process entails excessive temperatures, long residence times, as well as excessive coke formation, which strongly reduce the controllability of the partial oxidation reaction, and may not produce syngas of the desired quality in a single reaction zone.

[0025] Furthermore, without wishing to be limited by theory, the CPO reaction is fairly resistant to chemical poisoning, and as such it allows for the use of a wide variety of hydrocarbon feedstocks, including some sulfur containing hydrocarbon feedstocks; which, in some cases, can enhance catalyst life-time and productivity. By contrast, conventional ATR processes have more restrictive feed requirements, for example in terms of content of impurities in the feed (e.g., feed to ATR is desulfurized), as well as hydrocarbon composition (e.g., ATR primarily uses a CH ₄ -rich feed). [0026] In an embodiment, the hydrocarbons (e.g., first hydrocarbons) suitable for use in a CPO reaction as disclosed herein can include methane (CH ₄ ), ethane, propane, butanes, naphtha, 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 (e.g., first hydrocarbons) can include any suitable hydrocarbons source, and can contain Ci-C ₆ hydrocarbons, as well as some heavier hydrocarbons.

[0027] In an embodiment, the CPO reactant mixture 10 can comprise natural gas. Generally, natural gas is composed primarily of methane, but can also contain ethane, propane and heavier hydrocarbons (e.g., iso butane, n-butane, iso-pentane, n-pentane, hexanes, etc.), as well as very small quantities of nitrogen, oxygen, C0 , 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 embodiments, the CPO reactant mixture 10 can comprise CH ₄ and 0 .

[0028] The natural gas can comprise any suitable amount of methane. In some embodiments, 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% C0 , and less than about 15 mol% nitrogen.

[0029] In an embodiment, natural gas can comprise CH ₄ in an amount of equal to or greater than about 45 mol%, about 50 mol%, about 55 mol%, about 60 mol%, about 65 mol%, about 70 mol%, about 75 mol%, about 80 mol%, about 82 mol%, about 84 mol%, about 86 mol%, about 88 mol%, about 90 mol%, about 91 mol%, about 92 mol%, about 93 mol%, about 94 mol%, about 95 mol%, about 96 mol%, about 97 mol%, about 98 mol%, or about 99 mol%.

[0030] In some embodiments, the hydrocarbons (e.g., first 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 C0 (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 (e.g., first 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%), C0 (about 0.1 mol% to about 2 mol%), or both nitrogen (about 0.1 mol% to about 15 mol%) and C0 (about 0.1 mol% to about 2 mol%).

[0031] In an aspect, the CPO reactant mixture 10 can comprise any suitable amount of C0 . In an aspect, the CPO reactant mixture 10 can comprise an amount of C0 effective to provide for a CPO reaction zone effluent 15 with a desired composition (e.g., a CPO reaction zone effluent with a desired H /CO molar ratio; a CPO reaction zone effluent with a desired M ratio; a CPO reaction zone effluent with a desired C0 content; etc.). In some aspects, the CPO reactant mixture 10 can comprise C0 in an amount of from about 0.01 mol% to about 5 mol%, alternatively 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%. In other aspects, the CPO reactant mixture 10 can comprise C0 in an amount of equal to or greater than about equal to or greater than about 5 mol%, alternatively equal to or greater than about 10 mol%, or alternatively equal to or greater than about 15 mol%.

[0032] In some aspects, the CPO reactant mixture 10 can comprise any suitable amount of hydrocarbons. The hydrocarbons (e.g., first hydrocarbons) suitable for use in a CPO reaction as disclosed herein can comprise Ci-C ₆ hydrocarbons (optionally including some amount of C ₇₊ hydrocarbons), optionally nitrogen (e.g., from 0 wt.% to about 10 wt.%, alternatively from about 0.1 wt.% to about 5 wt.%, alternatively from about 0.2 wt.% to about 2.5 wt.%, or alternatively from about 0.25 wt.% to about 1 wt.%, based on the total weight of the hydrocarbons), and C0 (e.g., from about 0.01 wt.% to about 5 wt.%, alternatively from about 0.02 wt.% to about 1 wt.%, or alternatively from about 0.025 wt.% to about 0.5 wt.%, based on the total weight of the hydrocarbons). For example, the hydrocarbons (e.g., first hydrocarbons) suitable for use in a CPO reaction as disclosed herein can comprise Ci hydrocarbon (about 0.01 wt.% to about 10 wt.%, alternatively about 0.05 wt.% to about 5 wt.%, or alternatively about 0.1 wt.% to about 1 wt.%, based on the total weight of the hydrocarbons); C hydrocarbons (about 15 wt.% to about 75 wt.%, alternatively about 20 wt.% to about 60 wt.%, or alternatively about 25 wt.% to about 50 wt.%, based on the total weight of the hydrocarbons); C ₃ hydrocarbons (about 15 wt.% to about 50 wt.%, alternatively about 20 wt.% to about 40 wt.%, or alternatively about 25 wt.% to about 35 wt.%, based on the total weight of the hydrocarbons); C ₄ hydrocarbons, such as normal-C ₄ and/or iso-C ₄ (about 5 wt.% to about 40 wt.%, alternatively about 10 wt.% to about 30 wt.%, or alternatively about 15 wt.% to about 25 wt.%, based on the total weight of the hydrocarbons); C ₅ hydrocarbons, such as normal-C ₅ and/or iso-C ₅ (about 1 wt.% to about 20 wt.%, alternatively about 2.5 wt.% to about 15 wt.%, or alternatively about 5 wt.% to about 10 wt.%, based on the total weight of the hydrocarbons); and C ₆ hydrocarbons, including C ₆₊ hydrocarbons (about 1 wt.% to about 15 wt.%, alternatively about 1.5 wt.% to about 10 wt.%, or alternatively about 2.5 wt.% to about 7.5 wt.%, based on the total weight of the hydrocarbons); and optionally nitrogen (from 0 wt.% to about 10 wt.%, based on the total weight of the hydrocarbons) and/or C0 (from about 0.01 wt.% to about 5 wt.%, based on the total weight of the hydrocarbons).

[0033] The oxygen used in the CPO reactant mixture 10 can comprise 100% oxygen (substantially pure 0 ₂ ), oxygen gas (which may be obtained via a membrane separation process), technical oxygen (which may contain some air), air, oxygen enriched air, oxygen-containing gaseous compounds (e.g., NO), oxygen- containing mixtures (e.g., 0 /C0 , 0 /H 0, 0 /H 0 /H 0), oxy radical generators (e.g., CFfrOH, CH 0), hydroxyl radical generators, and the like, or combinations thereof.

[0034] In an embodiment, the CPO reactant mixture 10 can be characterized by a carbon to oxygen (C/O) molar ratio of less than about 3 :1, about 2.6:1, about 2.4: 1, about 2.2:1, about 2:1, or 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 ₂ ) in the reactant mixture. For example, when the only source of carbon in the CPO reactant mixture 10 is CH ₄ , the CH4/O2 molar ratio is the same as the C/O molar ratio. As another example, when the CPO reactant mixture 10 contains other carbon sources besides CH ₄ , such as ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), butanes (C ₄ HI ₀ ), 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 ₂ H ₆ , 3 moles of C in 1 mole of C ₃ H ₈ , 4 moles of C in 1 mole of C ₄ HI ₀ , etc.). As will be appreciated by one of skill in the art, and with the help of this disclosure, the C/O molar ratio in the CPO reactant mixture 10 can be adjusted along with other reactor process parameters (e.g., temperature, pressure, flow velocity, etc.) to provide for a syngas with a desired composition (e.g., a syngas with a desired H ₂ /CO molar ratio; a syngas with a desired C0 ₂ content; etc.). The C/O molar ratio in the CPO reactant mixture 10 can be adjusted to provide for a decreased amount of unconverted hydrocarbons in the CPO reaction zone effluent 15. The C/O molar ratio in the CPO reactant mixture 10 can be adjusted based on the CPO effluent temperature in order to decrease (e.g., minimize) the unconverted hydrocarbons content of the CPO reaction zone effluent 15. As will be appreciated by one of skill in the art, and with the help of this disclosure, when the syngas is further used in a methanol production process, unconverted hydrocarbons present in the syngas can undesirably accumulate in a methanol reaction loop, thereby decreasing the efficiency of the methanol production process.

[0035] In an embodiment, a portion of the hydrocarbons (e.g., first hydrocarbons) in CPO reactant mixture 10 can undergo a thermal decomposition reaction to C and H ₂ , for example as represented by eqn. (2):

CH ₄ ® C + 2 H ₂ (2)

[0036] The decomposition reaction of hydrocarbons, such as methane, is facilitated by elevated temperatures, and increases the hydrogen content in the CPO reaction zone effluent 15. As will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, while the percentage of hydrocarbons in the CPO reactant mixture 10 that undergoes a decomposition reaction (e.g., a decomposition reaction as represented by equation (2)) increases with increasing the C/O molar ratio in the CPO reactant mixture 10, a portion of hydrocarbons can undergo a decomposition reaction to C and H ₂ even at relatively low C/O molar ratios in the CPO reactant mixture 10 (e.g., a C/O molar ratio in the CPO reactant mixture 10 of less than about 2:1).

[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 embodiment, the CPO catalysts suitable for use in the present disclosure can be supported catalysts and/or unsupported catalysts. In some embodiments, 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 embodiments, 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 embodiments, the supported catalysts can comprise a catalytically active support and a catalytically inactive support.

[0039] In some embodiments, 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. In some embodiments, 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. In some embodiments, 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.

[0040] CPO processes, CPO reactors, CPO catalysts, CPO reaction zones, 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.

[0041] In an embodiment, a CPO reactor suitable for use in the present disclosure (e.g., comprising CPO reaction zone 100) can comprise a tubular reactor, a continuous flow reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a riser type reactor, a bubbling bed reactor, a circulating bed reactor, an ebullated bed reactor, a rotary kiln reactor, and the like, or combinations thereof.

[0042] In some embodiments, the CPO reaction zone 100 can be characterized by at least one CPO operational parameter selected from the group consisting of a CPO reaction zone 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 reaction zone pressure); a CPO contact time (e.g., CPO reaction zone 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 CPO reaction zone effluent 15 measured at the point where the syngas exits the CPO reaction zone 100, e.g., a temperature of the CPO reaction zone effluent 15 measured at an exit of the CPO reaction zone 100. 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 reaction zone 100 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; a flow rate of a dehydrogenation zone feed 61, as described further hereinbelow; etc. determines the temperature of the CPO reaction zone effluent 15, as well as the composition of the CPO reaction zone effluent 15. Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, monitoring the CPO effluent temperature can provide feedback for changing other operational parameters (e.g., CPO feed temperature; CPO pressure; CPO contact time; C/O molar ratio in the CPO reactant mixture; S/C molar ratio in the CPO reactant mixture; flow rate of dehydrogenation zone feed 61; 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 embodiments 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; flow rate of dehydrogenation zone feed 61 ; 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 reaction zone 100 can be operated under any suitable operational parameters that can provide for a CPO reaction zone effluent 15 with a desired composition (e.g., a syngas with a desired F^/CO molar ratio; a syngas with a desired C0 ₂ content; etc.).

[0043] The CPO reaction zone 100 can be characterized by a CPO feed temperature of from about 25 °C to about 600 °C, about 25 °C to about 500 °C, about 25 °C to about 400 °C, about 50 °C to about 400 °C, or about 100 °C to about 400 °C. In embodiments 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 embodiments 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.

[0044] The CPO reaction zone 100 can be characterized by a CPO effluent temperature (e.g., target CPO effluent temperature; (target) CPO reaction zone effluent 15 temperature) of equal to or greater than about 400 °C, about 500 °C, about 600 °C, about 700 °C, about 750 °C, about 800 °C, or about 850 °C, alternatively from about 400 °C to about 1,600 °C, about 600 °C to about 1,400 °C, about 600 °C to about 1,300 °C, about 700 °C to about 1,200 °C, about 750 °C to about 1,150 °C, about 800 °C to about 1,125 °C, about 850 °C to about 1,600 °C, or about 850 °C to about 1 ,100 °C.

[0045] In an embodiment, the CPO reaction zone 100 can be characterized by any suitable reactor temperature and/or catalyst bed temperature. For example, the CPO reaction zone 100 can be characterized by a reactor temperature and/or catalyst bed temperature of equal to or greater than about 400 °C, about 500 °C, about 600 °C, about 700 °C, about 750 °C, about 800 °C, or about 850 °C, alternatively from about 400 °C to about 1,600 °C, about 600 °C to about 1,400 °C, about 600 °C to about 1,300 °C, about 700 °C to about 1,200 °C, about 750 °C to about 1,150 °C, about 800 °C to about 1, 125 °C, or about 850 °C to about 1,100 °C.

[0046] The CPO reaction zone 100 can be operated under any suitable temperature profile that can provide for a CPO reaction zone effluent 15 with a desired composition (e.g., a desired H /CO molar ratio; a desired C0 content; etc.). The CPO reaction zone 100 can be operated under 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 reaction zone is subjected to external heat exchange or transfer (e.g., the reaction zone is heated; or the reaction zone 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 reaction zone is not subjected to external heat exchange (e.g., the reaction zone is not heated; or the reaction zone 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.

[0047] 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 reaction zone and/or catalyst bed (e.g., isothermal temperature) that can be defined as a temperature that varies by less than about + 10 °C, about + 9 °C, about + 8 °C, about + 7 °C, about + 6 °C, about + 5 °C, about + 4 °C, about + 3 °C, about + 2 °C, or about + 1 °C across the reaction zone and/or catalyst bed, respectively. 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 CPO reaction zone 15 with a desired composition (e.g., a desired I¾/CO molar ratio; a desired C0 content; etc.), wherein the isothermal conditions comprise a temperature variation of less than about + 10 °C across the reaction zone and/or catalyst bed. In embodiments, the CPO reaction zone 100 can be operated under any suitable operational parameters that can provide for isothermal conditions.

[0048] 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 reaction zone 100 and/or catalyst bed (e.g., near-isothermal temperature), which can be defined as a temperature that varies by less than about + 100 °C, about + 90 °C, about + 80 °C, about + 70 °C, about + 60 °C, about + 50 °C, about + 40 °C, about + 30 °C, about + 20 °C, about + 10 °C, about + 9 °C, about + 8 °C, about + 7 °C, about + 6 °C, about + 5 °C, about + 4 °C, about + 3 °C, about + 2 °C, or about + 1 °C across the reactor and/or catalyst bed, respectively. In some embodiments, near-isothermal conditions allow for a temperature variation of less than about + 50 °C, about + 25 °C, or 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. 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 F^/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 reaction zone and/or catalyst bed. In an embodiment, 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 CPO reaction zone 100 and/or catalyst bed. In embodiments, CPO reaction zone 100 can be operated under any suitable operational parameters that can provide for near-isothermal conditions.

[0049] Near-isothermal conditions can be provided by a variety of process and catalyst variables, such as temperature (e.g., heat exchange or heat transfer), pressure, gas flow rates, reactor configuration, catalyst bed configuration, catalyst bed composition, reactor cross sectional area, feed gas staging, feed gas injection, feed gas composition, and the like, or combinations thereof. Generally, and without wishing to be limited by theory, the terms“heat transfer” or“heat exchange” refer to thermal energy being exchanged or transferred between two systems (e.g., two reaction zones and/or reactors, such as a CPO reaction zone and/or CPO reactor and a dehydrogenation zone and/or dehydrogenation reactor), and the terms“heat transfer” or“heat exchange” are used interchangeably for purposes of the disclosure herein.

[0050] According to this disclosure, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by heat exchange or heat transfer. The heat exchange can comprise heating the reaction zone; and/or cooling the reaction zone. In an embodiment, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by cooling the CPO reaction zone 100. In another embodiment, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by heating the CPO reaction zone 100.

[0051] According to this disclosure, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by direct heat exchange and/or indirect heat exchange. As will be appreciated by one of skill in the art, and with the help of this disclosure, the terms“direct heat exchange” and“indirect heat exchange” are known to one of skill in the art. As utilized herein, heating of a stream (e.g., a dehydrogenation zone feed stream), a reaction zone (e.g., a dehydrogenation zone), or a reactor (e.g., a dehydrogenation reactor) via indirect heat transfer between the stream, the reaction zone, or the reactor and another stream (e.g., a CPO reaction zone effluent), another reaction zone (e.g., a CPO reaction zone), or another reactor (e.g., a CPO reactor) indicates heating without direct contact of the contents of the stream, the reaction zone, or the reactor with the contents of the another stream, the another reaction zone, or the another reactor, while heating of a stream (e.g., a dehydrogenation zone feed stream), a reaction zone (e.g., a dehydrogenation zone), or a reactor (e.g., a dehydrogenation reactor) via direct heat transfer between the stream, the reaction zone, or the reactor and another stream (e.g., a CPO reaction zone effluent), another reaction zone (e.g., a CPO reaction zone), or another reactor (e.g., a CPO reactor) indicates heating with direct contact of the contents of the stream, the reaction zone, or the reactor with the contents of the another stream, the another reaction zone, or the another reactor. According to this disclosure, achieving a target CPO effluent temperature, a target combined stream (described further hereinbelow) temperature, and/or near-isothermal conditions is provided, at least in part, by direct heat exchange between the CPO reaction zone effluent 15 and the dehydrogenation zone 650 (e.g., the second hydrocarbons), as detailed further hereinbelow.

[0052] The heat exchange can comprise external heat exchange, external coolant fluid cooling, reactive cooling, liquid nitrogen cooling, cryogenic cooling, electric heating, electric arc heating, microwave heating, radiant heating, natural gas combustion, solar heating, infrared heating, use of a diluent in the CPO reactant mixture, and the like, or combinations thereof. For example, reactive cooling can be effected by carrying out an endothermic reaction in a cooling coi l/jackct associated with (e.g., located in) a CPO reactor comprising the CPO reaction zone 100.

[0053] In some embodiments, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by removal of process heat from the CPO reaction zone. In other embodiments, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by supplying heat to the CPO reaction zone. As will be appreciated by one of skill in the art, and with the help of this disclosure, a CPO reaction zone may need to undergo both heating and cooling in order to achieve a target CPO effluent temperature and/or near-isothermal conditions.

[0054] In an embodiment, the heat exchange or heat transfer can comprise introducing a cooling agent, such as a diluent, into CPO reaction zone 100, to decrease the reactor temperature and/or the catalyst bed temperature, while increasing a temperature of the cooling agent and/or changing the phase of the cooling agent. The cooling agent can be reactive or non-reactive. The cooling agent can be in liquid state and/or in vapor state. As will be appreciated by one of skill in the art, and with the help of this disclosure, the cooling agent can act as a flammability retardant; for example by reducing the temperature inside the reaction zone, by changing the gas mixture composition, by reducing the combustion of hydrocarbons to C0 ; etc.

[0055] In some embodiments, the CPO reactant mixture 10 can further comprise a diluent, wherein the diluent contributes to achieving a target CPO effluent temperature and/or near-isothermal conditions via heat exchange, as disclosed herein. The diluent can comprise water, steam, inert gases (e.g., argon), nitrogen, C0 , and the like, or combinations thereof. Generally, the diluent is inert with respect to the CPO reaction, e.g., the diluent does not participate in the CPO reaction. However, and as will be appreciated by one of skill in the art, and with the help of this disclosure, some diluents (e.g., water, steam, C0 , etc.) might undergo chemical reactions other than the CPO reaction within the CPO reaction zone 100, and can change the composition of the resulting CPO reaction zone effluent 15, as will be described in more detail later herein; while other diluents (e.g., nitrogen (N ), argon (Ar)) might not participate in reactions that change the composition of the resulting syngas. As will be appreciated by one of skill in the art, and with the help of this disclosure, the diluent can be used to vary the composition of the resulting CPO reaction zone effluent 15. The diluent can be present in the CPO reactant mixture 10 in any suitable amount.

[0056] According to this disclosure, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided, at least in part, by the removal of process heat (Q) (indicated at arrow 13) from the CPO reaction zone 100, e.g., cooling the CPO reaction zone 100, by heating a dehydrogenation zone 650. As will be appreciated by one of skill in the art, and with the help of this disclosure, a positive Q going“out” (by the direction of the arrow 13) represents that heat is being transferred from that particular reaction zone, e.g., that particular reaction zone is being cooled. For example, Q in Figure 1 indicates that heat is being transferred from the CPO reaction zone 100 (e.g., the CPO reaction zone 100 is being cooled), to the dehydrogenation process in dehydrogenation zone 650. As will be appreciated by one of skill in the art, and with the help of this disclosure, a positive Q going“in” (by the direction of the arrow 13) represents that heat is being transferred to that particular reaction zone, e.g., that particular reaction zone is being heated.

[0057] According to this disclosure and detailed further hereinbelow, the heat transfer comprises cooling the CPO reaction zone 100 while heating the dehydrogenation zone 650 (e.g., second hydrocarbons of the dehydrogenation zone feed 61). In embodiments, the dehydrogenation zone 650 can optionally produce ethylene by ethane dehydrogenation. In an embodiment, a dehydrogenation zone reactant mixture can be fed to the dehydrogenation zone 650, wherein the dehydrogenation zone reactant mixture comprises at least a portion of the CPO reaction zone effluent 15, and a dehydrogenation zone feed 61 comprising second hydrocarbons (e.g., such as alkanes, ethane, propane, butanes, naphtha, and the like, or combinations thereof), and optionally steam; wherein a portion of the dehydrogenation zone reactant mixture reacts, via an endothermic catalytic dehydrogenation reaction in the dehydrogenation zone 650 to produce a combined effluent 68; wherein the combined effluent 68 comprises H ₂ , CO, C0 , H ₂ ). olefins (e.g., ethylene), unreacted first hydrocarbons, and unreacted second hydrocarbons. Fleat transfer integration of a CPO process with an endothermic process (e.g., cracking process) is described in more detail in the co-pending U.S. Provisional Patent Application No. 62/787,620 filed January 2, 2019 and entitled“Catalyst Activity Management in Catalytic Partial Oxidation” and U.S. Provisional Patent Application No. 62/793,606 filed January 17, 2019 and entitled“Methanol Production Process from Syngas Produced by Catalytic Partial Oxidation Integrated with Cracking”, the disclosure of each of which is hereby incorporated herein by reference in its entirety for purposes not contrary to this disclosure. Fleat transfer integration of a CPO process with a dehydrogenation process is described in U.S. Provisional Patent Application No. 62/810,633 filed February 26, 2019 and entitled,“Integrated Indirect Fleat Transfer Process for the Production of Syngas and Olefins by Catalytic Partial Oxidation and Catalytic Selective Dehydrogenation”, while heat transfer integration of a CPO process with a cracking process is described in U.S. Provisional Patent Application Nos. 62/810,629 filed February 26, 2019 and entitled“An Integrated Indirect Fleat Transfer Process for the Production of Syngas and Olefins by Catalytic Partial Oxidation and Cracking” and 62/820,397 filed on March 19, 2019 and entitled“An Integrated Direct Fleat Transfer Process for the Production of Methanol and Olefins by Catalytic Partial Oxidation and Cracking”, and the disclosure of each of which is hereby incorporated herein by reference in its entirety for purposes not contrary to this disclosure.

[0058] In some embodiments, the heat transfer (e.g., heat transfer that provides for achieving a target CPO effluent 15 temperature and/or near-isothermal conditions) excludes heat transfer with the syngas effluent subsequent to the effluent 15 exiting a common housing 150 in which the CPO reaction zone 100 is housed. In other embodiments, the heat transfer (e.g., heat transfer that provides for achieving a target CPO effluent 15 temperature and/or near-isothermal conditions) can comprise heat transfer with the CPO reaction zone effluent 15 subsequent to the CPO reaction zone effluent 15 exiting the common housing 150.

[0059] The CPO reaction zone 100 can be characterized by a CPO pressure (e.g., reaction zone pressure measured at the reaction zone exit or outlet) of equal to or greater than about 1 barg, alternatively equal to or greater than about 10 barg, alternatively equal to or greater than about 20 barg, alternatively equal to or greater than about 25 barg, alternatively equal to or greater than about 30 barg, alternatively equal to or greater than about 35 barg, alternatively equal to or greater than about 40 barg, alternatively equal to or greater than about 50 barg, alternatively less than about 30 barg, alternatively less than about 25 barg, alternatively less than about 20 barg, alternatively less than about 10 barg, alternatively from about 1 barg to about 90 barg, alternatively from about 1 barg to about 70 barg, alternatively from about 1 barg to about 40 barg, alternatively from about 1 barg to about 30 barg, alternatively from about 1 barg to about 25 barg, alternatively from about 1 barg to about 20 barg, alternatively from about 1 barg to about 10 barg, alternatively from about 20 barg to about 90 barg, alternatively from about 25 barg to about 85 barg, or alternatively from about 30 barg to about 80 barg.

[0060] The CPO reaction zone 100 can be characterized by a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s), alternatively from about 0.001 ms to about 1 s, alternatively from about 0.001 ms to about 100 ms, alternatively from about 0.001 ms to about 10 ms, alternatively from about 0.001 ms to about 5 ms, or alternatively from about 0.01 ms to about 1.2 ms. Generally, the contact time of a reaction zone 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. In some embodiments, the CPO reaction zone 100 can be characterized by a contact time of from about 0.001 ms to about 5 ms, or alternatively from about 0.01 ms to about 1.2 ms.

[0061] 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 I¾ content of the CPO reaction zone effluent 15. As another example, the CPO operational parameters can be adjusted to provide for a decreased C0 content of the CPO reaction zone effluent 15. As yet another example, the CPO operational parameters can be adjusted to provide for a decreased unreacted hydrocarbons (e.g., unreacted CFfr) content of the CPO reaction zone effluent 15.

[0062] In an embodiment, the CPO reactant mixture 10 can further comprise a diluent, such as water and/or steam, C0 , nitrogen, argon, etc. The CPO reaction zone 100 can be operated under any suitable operational conditions (e.g., CPO operational parameters) that can provide for a CPO reaction zone effluent 15 with a desired composition (e.g., a desired I¾/CO molar ratio; a desired C0 content; etc.); for example, the CPO reaction zone 100 can be operated with introducing water and/or steam, and optionally C0 to the CPO reaction zone 100.

[0063] When carbon is present in the reaction zone (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 (3):

C + H ₂ 0 C0 + H ₂ (3)

As will be appreciated by one of skill in the art, and with the help of this disclosure, the presence of water and/or steam in the CPO reaction zone 100 can decrease the amount of coke in the CPO reaction zone 100.

[0064] Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, water and/or steam can be used to vary the composition of the resulting CPO reaction zone effluent 15. Steam can react with methane, for example as represented by equation (4):

CH ₄ + H ₂ 0 ^ C0 + 3 H ₂ (4)

[0065] In an embodiment, a diluent comprising water and/or steam can increase a hydrogen content of the resulting CPO reaction zone effluent 15. For example, in embodiments where the CPO reactant mixture 10 comprises water and/or steam diluent, the resulting CPO reaction zone effluent 15 can be characterized by a hydrogen to CO molar ratio that is increased when compared to a hydrogen to CO molar ratio of a CPO reaction zone effluent 15 produced by an otherwise similar process conducted with a reactant mixture comprising hydrocarbons and oxygen without the water and/or steam diluent. Without wishing to be limited by theory, the reforming reaction (e.g., as represented by equation (4)) is an endothermic reaction. The reforming reaction as represented by equation (4) can remove a portion of the process heat (e.g., heat produced by the exothermic CPO reaction, for example as represented by equation (1)).

[0066] In the presence of water and/or steam in the CPO reaction zone 100, CO can react with the water and/or steam to form C0 and hydrogen via a water-gas shift (WGS) reaction, for example as represented by equation (5):

CO + H ₂ 0 C0 ₂ + ¾ (5)

While the WGS reaction can increase the H ₂ /CO molar ratio of the syngas produced by the CPO reaction zone 100, it also produces C0 .

[0067] In an embodiment, the CPO reaction zone 100 can be operated at an S/C molar ratio in the CPO reactant mixture 10 of less than about 2.4:1, alternatively less than about 2:1, alternatively less than about 1.5:1, alternatively less than about 1 :1, alternatively less than about 0.8:1, alternatively less than about 0.5:1, alternatively from about 0.01 :1 to less than about 2.4: 1, alternatively from about 0.05:1 to about 2:1 , alternatively from about 0.1 : 1 to about 1.5:1, alternatively from about 0.15:1 to about 1 :1, or alternatively from about 0.2: 1 to about 0.8: 1. As will be appreciated by one of skill in the art, and with the help of this disclosure, the steam that is introduced to the CPO reaction zone 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. [0068] The S/C molar ratio in the CPO reactant mixture 10 can be adjusted based on the desired CPO effluent temperature (e.g., target CPO effluent temperature) in order to increase (e.g., maximize) the ¾ content of the CPO reaction zone effluent 15. As will be appreciated by one of skill in the art, and with the help of this disclosure, the reaction (4) that consumes steam in the CPO reaction zone 100 is preferable over the water-gas shift (WGS) reaction (5) in the CPO reaction zone 100, as reaction (4) allows for increasing the ¾ content of the CPO reaction zone effluent 15, as well as the M ratio of the CPO reaction zone effluent 15, wherein the M ratio is a molar ratio defined as (H ₂ -C0 ₂ )/(C0+C0 ). Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, reaction (4) converts water and CO to both ¾ and C0 .

[0069] In an embodiment, the amount of methane that reacts according to reaction (3) in the CPO reaction zone 100 is less than the amount of methane that reacts according to reaction (1) in the CPO reaction zone 100. In an embodiment, 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 reaction zone 100.

[0070] Without wishing to be limited by theory, the presence of water and/or steam in the CPO reaction zone 100 changes the flammability of the CPO reactant mixture 10, thereby providing for a wider practical range of C/O molar ratios in the CPO reactant mixture 10. Further, and without wishing to be limited by theory, the presence of water and/or steam in the CPO reaction zone 100 allows for the use of lower C/O molar ratios in the CPO reactant mixture 10. Furthermore, and without wishing to be limited by theory, the presence of water and/or steam in the CPO reaction zone 100 allows for operating the CPO reaction zone 100 at relatively high pressures.

[0071] 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 reaction zone 100 can lead to increasing the amount of unreacted hydrocarbons in the CPO reaction zone effluent 15. Further, as will be appreciated by one of skill in the art, and with the help of this disclosure, methanol production processes typically tolerate limited amounts of unreacted hydrocarbons in the syngas.

[0072] In some embodiments, the CPO reaction zone effluent 15 (and/or syngas stream 78) 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 CIT ₄ ). In such embodiments, the CPO reaction zone effluent 15 can be produced in a CPO process that employs water and/or steam.

[0073] Further, since oxygen is present in the CPO reactant mixture 10, the carbon present in the reaction zone (e.g., coke; C produced as a result of a decomposition reaction as represented by equation (2)) can also react with oxygen, for example as represented by equation (6):

C + 0 ₂ ® C0 ₂ (6)

[0074] When carbon is present in the reaction zone (e.g., coke; C produced as a result of a decomposition reaction as represented by equation (2)), C0 (e.g., introduced to the CPO reaction zone 100 as part of the CPO reactant mixture 10 and/or produced by the reaction represented by equation (6)) can react with the carbon, for example as represented by equation (7):

C + C0 ₂ 2 CO (7) thereby decreasing the amount of C0 in the resulting CPO reaction zone effluent 15. As will be appreciated by one of skill in the art, and with the help of this disclosure, the presence of C0 in the CPO reaction zone 100 can decrease the amount of coke in the CPO reaction zone 100.

[0075] Furthermore, C0 can react with methane in a dry reforming reaction, for example as represented by equation (8):

CH ₄ + C0 ₂ 2 CO + 2 ¾ (8) thereby decreasing the amount of C0 in the resulting CPO reaction zone effluent 15. Without wishing to be limited by theory, the dry reforming reaction (e.g., as represented by equation (8)) is an endothermic reaction (e.g., highly endothermic reaction). The dry reforming reaction can remove a portion of the process heat (e.g., heat produced by the exothermic CPO reaction, for example as represented by equation (1)).

[0076] In an embodiment, a diluent comprising C0 can increase a CO content of the resulting CPO reaction zone effluent 15. For example, in embodiments where the CPO reactant mixture 10 comprises C0 diluent, the CPO reaction zone effluent 15 can be characterized by a hydrogen to CO molar ratio that is decreased when compared to a hydrogen to CO molar ratio of a CPO reaction zone effluent (e.g., syngas) produced by an otherwise similar process conducted with a reactant mixture comprising hydrocarbons and oxygen without the C0 diluent. Without wishing to be limited by theory, C0 can react with coke inside the CPO reaction zone 100 and generate additional CO, for example as represented by equation (7). Further, and without wishing to be limited by theory, C0 can participate in a dry reforming of methane reaction, thereby generating additional CO and H , for example as represented by equation (8). Dry reforming of methane is generally accompanied by a reaction between C0 and hydrogen which results in the formation of additional CO and water.

[0077] The use of C0 ₂ in the CPO reactant mixture 10 can advantageously decrease the amount of hydrocarbons converted to C0 in the CPO reaction zone 100, for example via a combustion reaction. Without wishing to be limited by theory, and according to Le Chatelier's Principle, the equilibrium of hydrocarbons dry reforming reaction will be shifted towards consuming C0 with increasing the amount of C0 in the reactant mixture, thereby allowing for a higher amount of hydrocarbons to convert to syngas.

[0078] 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, increasing the amount of C0 in the CPO reactant mixture 10 can lead to an increased amount of CO in the CPO reaction zone effluent 15, and thus to a lowered IT ₂ /CO molar ratio and/or a lowered M ratio of the CPO reaction zone effluent 15. In some aspects, the CPO reactant mixture 10 can comprise an amount of C0 ₂ effective to provide for a CPO reaction zone effluent 15 with a desired composition (e.g., a syngas with a desired I¾/CO molar ratio; a syngas with a desired M ratio; a syngas with a desired C0 content; etc.). In aspects where the CPO reaction zone effluent 15 has a I¾/CO molar ratio and/or an M ratio lower or much lower than the desired I¾/CO molar ratio and/or the desired M ratio, respectively, the cracking zone 600 can be operated under conditions effective to provide for an increased amount of hydrogen in the combined effluent 67; i.e., an amount of hydrogen effective to provide for a syngas 78 with a desired composition (e.g., a syngas with a desired IT /CO molar ratio; a syngas with a desired M ratio; a syngas with a desired C0 content; etc.). In aspects where the CPO reaction zone effluent 15 has a I¾/CO molar ratio and/or an M ratio lower or slightly lower than the desired ¾/CO molar ratio and/or the desired M ratio, respectively, the cracking zone 600 can be operated under conditions effective to provide for a decreased amount of hydrogen in the combined effluent 67; i.e., an amount of hydrogen effective to provide for a syngas 78 with a desired composition (e.g., a syngas with a desired H /CO molar ratio; a syngas with a desired M ratio; a syngas with a desired C0 content; etc.).

[0079] In aspects where the CPO reactant mixture 10 comprises both steam and C0 , the CPO reaction zone 100 can be operated at a steam to C0 (S/C0 ) molar ratio in the CPO reactant mixture 10 of less than about 100,000:1 , alternatively less than about 50,000:1, alternatively less than about 10,000: 1, alternatively less than about 5,000:1, alternatively less than about 1,000: 1, alternatively less than about 500: 1, alternatively from about 0.1 :1 to about 100,000:1, alternatively from about 0.2:1 to about 50,000: 1, alternatively from about 1 :1 to about 10,000: 1, alternatively from about 5:1 to about 5,000:1, alternatively from about 10: 1 to about 1,000:1, or alternatively from about 25:1 to about 500:1.

[0080] As will be appreciated by one of skill in the art, and with the help of this disclosure, a C0 ₂ -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. The C0 ₂ content of the CPO reaction zone effluent 15 can be adjusted as described in more detail in the co-pending U.S. Provisional Patent Application 62/787,574 filed January 2, 2019 and entitled “Hydrogen Enrichment in Syngas Produced via Catalytic Partial Oxidation”); which is hereby incorporated herein by reference in its entirety for purposes not contrary to this disclosure.

[0081] In an embodiment, a CPO reaction zone effluent 15 from the CPO reaction zone 100 comprises hydrogen, CO, water, C0 ₂ , and unreacted hydrocarbons (e.g., unreacted first hydrocarbons, unreacted methane, optionally unreacted second hydrocarbons (e.g., recycled via alkanes stream 84)). The CPO reaction zone effluent 15 as disclosed herein can be characterized by a H ₂ /CO molar ratio of greater than about 1.3, alternatively greater than about 1.4, alternatively greater than about 1.5, alternatively greater than about 1.6, alternatively greater than about 1.7, alternatively greater than about 1.8, alternatively greater than about 1.9, or alternatively greater than about 2.0. In some embodiments, the CPO reaction zone effluent 15 as disclosed herein can be characterized by a H ₂ /CO molar ratio of from about 1.3 to about 2.3, alternatively from about 1.4 to about 2.3, alternatively from about 1.5 to about 2.3, alternatively from about 1.6 to about 2.3, alternatively from about 1.7 to about 2.2, or alternatively from about 1.8 to about 2.1. In an embodiment, the CPO reaction zone effluent 15 can be characterized by an M ratio of equal to or greater than about 1.3, alternatively equal to or greater than about 1.4, alternatively equal to or greater than about 1.5, alternatively equal to or greater than about 1.6, alternatively equal to or greater than about 1.7, alternatively equal to or greater than about 1.8, from about 1.3 to about 2.3, alternatively from about 1.4 to about 2.3, alternatively from about 1.5 to about 2.3, alternatively from about 1.6 to about 2.3, alternatively from about 1.7 to about 2.2, or alternatively from about 1.8 to about 2.2.

[0082] In an embodiment, the CPO reaction zone effluent 15 can have a C0 content of less than about 7 mol%, alternatively less than about 6 mol%, alternatively less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively from about 0.1 mol% to about 7 mol%, alternatively from about 0.25 mol% to about 5 mol%, or alternatively from about 0.5 mol% to about 3 mol%. For example, side reactions as represented by equations (7) and/or (8) could lead to a CPO reaction zone effluent 15 that has a C0 content of from about 0.1 mol% to about 7 mol%.

[0083] In an embodiment, the CPO reaction zone effluent 15 can have a hydrocarbon content of less than about 10 mol%, alternatively less than about 7.5 mol%, alternatively less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively less than about 0.1 mol%, or alternatively less than about 0.01 mol%.

[0084] As depicted in the embodiment of Figure 1, a process as disclosed herein comprises a step of feeding a dehydrogenation zone reactant mixture comprising at least a portion of the CPO reaction zone effluent 15, and a dehydrogenation zone reactant feed 61 comprising second hydrocarbons, and optionally steam to a dehydrogenation zone 650, wherein at least a portion of the dehydrogenation zone reactant mixture reacts, via an endothermic dehydrogenation reaction, in the dehydrogenation zone 650 to produce a combined effluent 68 comprising H ₂ , CO, C0 , water, olefins, unreacted first hydrocarbons, and unreacted second hydrocarbons.

[0085] The dehydrogenation zone 650 can comprise any suitable dehydrogenation zone configured to convert saturated hydrocarbons (e.g., alkanes) into olefins. For example, the dehydrogenation zone 650 can comprise any suitable dehydrogenation zone configured to convert the dehydrogenation zone reactant mixture into the combined effluent 68 comprising olefins. Nonlimiting examples of dehydrogenation zones suitable for use in the present disclosure include a catalytic dehydrogenation zone. As will be appreciated by one of skill in the art, and with the help of this disclosure, dehydrogenation processes are known to one of skill in the art.

[0086] With reference back to the embodiment of Figure 1, a process as disclosed herein comprises a step of feeding a dehydrogenation zone reactant mixture comprising at least a portion of the CPO reaction zone effluent 15 and a dehydrogenation zone feed 61 comprising second hydrocarbons to a dehydrogenation zone 650 to produce a combined effluent 68. The combined effluent 68 can comprise H ₂ , CO, C0 , water, olefins, such as ethylene, propene, butenes, and the like, alkanes (e.g., unreacted first and/or second hydrocarbons) or combinations thereof. The combined effluent 68 can comprise other unsaturated hydrocarbons, such as butadiene, C _5.6 olefins, C _6.8 aromatic hydrocarbons, etc. The dehydrogenation zone 650 can comprise any suitable dehydrogenation zone configured to convert saturated hydrocarbons (e.g., alkanes) into olefins. For example, the dehydrogenation zone 650 can comprise any suitable dehydrogenation zone configured to convert the dehydrogenation zone reactant mixture into combined effluent 68 comprising olefins. By way of nonlimiting example, in embodiments, dehydrogenation zone 650 comprises a catalytic selective dehydrogenation zone. As will be appreciated by one of skill in the art, and with the help of this disclosure, catalytic selective dehydrogenation processes are known to one of skill in the art.

[0087] Without wishing to be limited by theory, dehydrogenation refers to the endothermic reaction that converts alkanes into olefins and hydrogen. Generally, and as will be appreciated by one of skill in the art, and with the help of this disclosure, heat (e.g., thermal energy) has to be supplied to the dehydrogenation zone to enable the dehydrogenation reaction that produces olefins. According to this disclosure, at least a portion of the heat Q that is used by the dehydrogenation zone 650 is supplied by the CPO reaction zone 100, as disclosed herein. As will be appreciated by one of skill in the art, and with the help of this disclosure, the process heat from the CPO reaction zone 100 may not be enough to supply all the heat necessary for the dehydrogenation zone 650. In an embodiment, a fuel stream can be combusted to supply the additional heat necessary for the dehydrogenation zone 650.

[0088] Catalytic dehydrogenation of alkanes, e.g., ethane, proceeds according to the following reaction (9):

C„H _2n+2 ® C _n H _2n + H ₂ (9)

[0089] However, this dehydrogenation reaction (e.g., dehydrogenation reaction (9)) cannot be carried out easily, due to its strong endothermicity (e.g., DH° = 124 kJ.mol ¹ for propane dehydrogenation), and the necessity to heat at around 500-600 °C for propane dehydrogenation in the presence of certain catalysts. 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 dehydrogenation temperature can vary significantly based on the catalyst choice and/or based on the composition of the feed subjected to dehydrogenation. In an aspect, any suitable dehydrogenation catalyst can be used in dehydrogenation zone 650. In embodiments, a noble metal dehydrogenation catalyst is utilized in dehydrogenation zone 650. Nonlimiting examples of dehydrogenation catalysts suitable for use in the present disclosure in dehydrogenation zone 650 include noble metal (e.g., Pt, Pd, Rh, Re, Ir, Ru, Ag, and the like, or combinations thereof) based catalysts (e.g., Pt based catalysts, Pd based catalysts, Rh based catalysts, Re based catalysts, Ir based catalysts, etc.); chromium based catalysts (e.g., chromium(III)oxide); Sn based catalysts; and the like; or combinations thereof. The dehydrogenation catalysts suitable for use in the present disclosure in dehydrogenation zone 650 can comprise a support, such as alumina, silica, carbon, and the like, or combinations thereof.

[0090] The dehydrogenation reaction (e.g., dehydrogenation reaction (9)) can be oxidative or not, depending on the use of 0 in the feed flow. In embodiments, endothermic dehydrogenation in dehydrogenation zone 650 comprises selective non-oxidative dehydrogenation. In embodiments, endothermic dehydrogenation in dehydrogenation zone 650 comprises oxidative dehydrogenation, which may be carried out at lower temperatures than non-oxidative dehydrogenation. However, in such embodiments, increased byproducts can be formed during the dehydrogenation due to nonselective oxidation.

[0091] In an embodiment, the second hydrocarbons suitable for feeding to a dehydrogenation zone 650 as disclosed herein can comprise saturated hydrocarbons, such as alkanes. Nonlimiting examples of second hydrocarbons suitable for feeding to a dehydration zone as disclosed herein can include alkanes, ethane, propane, butanes, naphtha, and the like, or combinations thereof. In some embodiments, the first hydrocarbons and the second hydrocarbons can be the same. For example, a naphtha feed can be introduced to a dehydration one 650 as well as to a CPO reaction zone 100. In other embodiments, the first hydrocarbons and the second hydrocarbons can be different. As another example, ethane (e.g., second hydrocarbons) can be introduced to a dehydrogenation zone 650 and methane (e.g., first hydrocarbons) can be introduced to a CPO reaction zone 100

[0092] In embodiments, heating the second hydrocarbons to the dehydrogenation zone temperature comprises (i) introducing liquid second hydrocarbons to the dehydrogenation zone 650; (ii) heating the liquid second hydrocarbons to vaporize at least a portion thereof and to form gaseous second hydrocarbons; and (iii) heating the gaseous second hydrocarbons to the dehydrogenation zone temperature.

[0093] In an embodiment, the second hydrocarbons suitable for feeding to a dehydrogenation zone 650 as disclosed herein can comprise saturated hydrocarbons, such as alkanes. Nonlimiting examples of second hydrocarbons suitable for feeding to a dehydrogenation zone 650 as disclosed herein can include C ₅ _ hydrocarbons, such as, without limitation, alkanes, ethane, propane, and butanes, naphtha, and the like, or combinations thereof. In some embodiments, the first hydrocarbons and the second hydrocarbons can be the same. For example, a naphtha feed can be introduced to a dehydrogenation zone 650, as well as to a CPO reaction zone 100. In other embodiments, the first hydrocarbons and the second hydrocarbons can be different. As another example, ethane (e.g., second hydrocarbons) can be introduced to a dehydrogenation zone 650 and methane (e.g., first hydrocarbons) can be introduced to a CPO reaction zone 100.

[0094] As will now be described with reference to the embodiment of Figure 2, in embodiments, a common housing 150 comprises both the CPO reaction zone 100 (such that the CPO catalyst is disposed within the common housing 150) and the dehydrogenation zone 650. As depicted in the embodiment of Figure 2, in embodiments, dehydrogenation zone 650 comprises a catalytic dehydrogenation zone, and a bed of dehydrogenation catalyst is positioned within dehydrogenation zone 650. The dehydrogenation zone feed 61 can be introduced into the common housing 150, wherein it is combined with the CPO reaction zone effluent 15 to provide the dehydrogenation zone reactant mixture. The dehydrogenation zone feed 61 can, in embodiments, be introduced above the bed of dehydrogenation catalyst. Although not depicted as such in the Figures, a mixed bed comprising both the CPO catalyst and the dehydrogenation catalyst can be utilized, in embodiments.

[0095] The combined effluent 68 can be removed from dehydrogenation zone 650 (and/or common housing 150), as indicated in Figure 2. The dehydrogenation zone feed (e.g., the second hydrocarbons) can be introduced to the dehydrogenation zone 650 via a nozzle, a spray nozzle, an atomization nozzle, an injector, a spray injector, an atomization injector, a steam atomization injector, a quill, a distributor, a distributor plate, or a combination thereof.

[0096] In embodiments, the common housing 150 further comprises a furnace zone wherein a fuel stream can be combusted in the furnace zone to provide for additional heat for the endothermic catalytic dehydrogenation reaction. In embodiments, heating the dehydrogenation zone 650 comprises heating the dehydrogenation zone feed 61 (e.g., the second hydrocarbons) within common housing 150.

[0097] In embodiments, the dehydrogenation zone reactant mixture comprises an amount of second hydrocarbons effective to provide for cooling the CPO reaction zone effluent 15 to the dehydrogenation zone temperature while heating the dehydrogenation zone feed 61 (e.g., the second hydrocarbons) to the dehydrogenation zone temperature. In embodiments, the combined effluent 68 is characterized by a combined effluent temperature, wherein the dehydrogenation zone reactant mixture comprises an amount of second hydrocarbons effective to provide for a combined effluent temperature variation within less than about + 10% of a target combined effluent temperature. [0098] A flow control valve can be utilized to introduce the CPO reactant mixture 10 to CPO reaction zone 100 and/or a flow control valve can be utilized to introduce the dehydrogenation zone feed 61 to dehydrogenation zone 650. The flow of the dehydrogenation zone feed 61 can be regulated by a set temperature of the CPO reaction zone 100 and/or of the combined effluent 68. Should the temperature of the CPO reaction zone 100 and/or the combined effluent 68 increase above the set temperature, flow of dehydrogenation zone feed 61 can be increased via the flow control valve on the dehydrogenation zone feed 61 to provide enhanced heat removal from the CPO reaction zone 100 (e.g., a CPO catalyst bed of CPO reaction zone 100), whereby the temperature of the CPO reaction zone 100 and/or the combined effluent 68 can be returned to the set temperature. Should the temperature of CPO reaction zone 100 and/or the combined effluent 68 be less than the set temperature of the CPO reaction zone 100 and/or the combined effluent 68, respectively, the flow control valve on the dehydrogenation zone feed 61 can be closed, to reduce or eliminate the flow of the dehydrogenation zone feed 61 to dehydrogenation zone 650. In this manner, potential runaway of the CPO reaction zone 100 can be prevented, and, in embodiments, near-isothermal conditions within the CPO reaction zone 100 and/or of the combined effluent 68 can be maintained. In embodiments, the dehydrogenation zone 650 is characterized by a dehydrogenation zone temperature in the range of from about 200 °C to about 800 °C, alternatively from about 300 °C to about 800 °C, alternatively from about 400 °C to about 800 °C, alternatively from about 500 °C to about 800 °C, alternatively from about 500 °C to about 700 °C, or alternatively from about 500 °C to about 600 °C. In some aspects, the dehydrogenation zone 650 is characterized by a dehydrogenation zone temperature in the range of from about 500 °C to about 800 °C. In some aspects, the dehydrogenation zone 650 is characterized by a dehydrogenation zone temperature of less than or equal to about 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, or 200 °C.

[0099] A method of this disclosure further comprises: (d) removing at least a portion of the water from the combined effluent to produce a dehydrated combined effluent; and (e) separating at least a portion of the dehydrated combined effluent into syngas and a C ₊ hydrocarbons stream, wherein the syngas comprises ¾, CO, C0 ₂ , and methane (CH ₄ ), and wherein the C ₂₊ hydrocarbons stream comprises C ₂₊ olefins and C ₂₊ alkanes. A separation unit 700 of a separation apparatus of this disclosure operable to provide steps (d) and (e) can be configured to separate a liquid stream 71, a syngas stream 78, and a C ₊ hydrocarbons stream 77 from at least a portion of the combined effluent 68, while a separator 800 of the separation apparatus can be configured to separate at least a portion 77a of the C ₊ hydrocarbons stream into an olefins stream 83 and an alkanes stream 84, wherein the olefins stream 83 comprises at least a portion of the olefins in the C ₊ hydrocarbons stream 77, and wherein the alkanes stream 84 comprises at least a portion of the alkanes in the C ₊ hydrocarbons stream 77. As discussed further hereinbelow, a process of this disclosure can further comprise optionally recycling at least a portion of the C ₊ hydrocarbons stream 77 and/or at least a portion of the alkanes stream 84 to the dehydrogenation zone 650 in step (b) and/or to the CPO reaction zone 100 in step (a).

[00100] In embodiments, the separation unit 700 can comprise a gas-liquid separation unit, a pressure swing adsorption (PSA) unit, a membrane separation unit, a cryogenic separation unit, an oil scrubber separation unit, a size exclusion unit, or combinations thereof. In embodiments, separation unit 700 comprises an oil scrubber separation unit and a size exclusion unit. Such a separation unit 700 can further comprise a cooler, a gas-liquid separator, an oil regenerator, and/or a low temperature condenser. For example, in the embodiment of Figure 3, a separation unit 700' comprises a cooler Cl, a gas-liquid separator 710, an oil scrubber separation unit 720, an oil regenerator 730, a low temperature condenser 740 and a size exclusion unit 750. In such embodiments, at least a portion of combined effluent 68 (e.g., comprising H , CO, C0 , water, olefins, alkanes (e.g., unreacted first and/or second hydrocarbons), etc.) can be scrubbed in oil scrubber separation unit 720. The combined effluent 68 can be cooled in cooler Cl (e.g., to a temperature of less than or equal to about 100 °C, alternatively less than or equal to about 80 °C, alternatively less than or equal to about 60 °C, alternatively from about 20 °C to about 100 °C, alternatively from about 30 °C to about 80 °C, or alternatively from about 40 °C to about 60 °C) to provide cooled, combined effluent stream 701. Cooled, combined effluent stream 701 can be introduced into gas-liquid separator 710, wherein liquid stream 71 can be separated from the cooled, combined effluent stream 701 to provide dehydrated combined effluent stream 712.

[00101] The gas-liquid separator 710 of separation unit 700/700' can comprise any suitable gas-liquid separator configured to separate the cooled, combined effluent stream 701 into a liquid stream 71 comprising water and a dehydrated combined effluent stream 712, comprising a reduced water content relative to that of cooled, combined effluent stream 701. For example, gas-liquid separator 710 can comprise a vapor-liquid separator, flash drum, knock-out drum, knock-out pot, compressor suction drum, etc. Liquid stream 71 can be recovered from the gas-liquid separator 710 as a bottoms stream. Liquid stream 71 recovered from the gas- liquid separator 710 can comprise water, C ₅₊ hydrocarbons, such as pentane, pentenes, hexanes, hexenes, benzene, toluene, xylene, and the like, or combinations thereof. As will be appreciated by one of skill in the art, and with the help of this disclosure, liquid stream 71 recovered from the gas-liquid separator 710 can further comprise trace amounts of C ₄ _ hydrocarbons, such as butanes, butenes, butadiene, etc. The dehydrated combined effluent stream 712 can comprise less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively less than about 0.5 mol%, alternatively less than about 0.1 mol%, alternatively less than about 0.05 mol%, or alternatively less than about 0.01 mol% water, in addition to hydrocarbons (e.g., C , C ₃ , and C ₄ hydrocarbons, with some optional trace amounts of C ₅ hydrocarbons), including olefins, methane, ethane, propane, unreacted second hydrocarbons, unreacted first hydrocarbons, hydrogen, CO, and/or C0 .

[00102] In some aspects, the liquid stream 71 can be further introduced to a liquid-liquid separator, wherein the liquid-liquid separator can comprise any suitable liquid-liquid separator configured to separate the liquid stream 71 into an aqueous phase stream comprising water, and an oil phase stream comprising hydrocarbons. For example, the liquid-liquid separator can comprise a horizontal gravity settling tank, a vertical gravity settling tank, a coalescer, a membrane separator, and the like, or combinations thereof. In some aspects, the aqueous phase stream can comprise water, and traces of C ₄ _ hydrocarbons, such as butanes, butenes, butadiene, and the like, or combinations thereof. The oil phase stream can comprise C ₅₊ hydrocarbons, such as pentane, pentenes, hexanes, hexenes, benzene, toluene, xylene, and the like, or combinations thereof; and traces of water and/or C ₄ _ hydrocarbons, such as butanes, butenes, butadiene, etc.

[00103] In some aspects, the gas-liquid separator 710 can comprise a gas-liquid-liquid separator. The gas- liquid-liquid separator can comprise any suitable gas-liquid-liquid separator configured to separate the cooled, cracking zone product stream 701 into a dehydrated cracking zone product stream 712, an aqueous phase stream comprising water, and an oil phase stream comprising hydrocarbons. For example, the gas-liquid-liquid separator can comprise a gas-liquid separator (e.g., a vapor-liquid separator, flash drum, knock-out drum, knock-out pot, compressor suction drum, etc.) integrated with a liquid-liquid separator (e.g., a horizontal gravity settling tank, a vertical gravity settling tank, a coalescer, a membrane separator, and the like, or combinations thereof). The dehydrated cracking zone product stream 712 recovered from the gas-liquid-liquid separator can comprise less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively less than about 0.5 mol%, alternatively less than about 0.1 mol%, alternatively less than about 0.05 mol%, or alternatively less than about 0.01 mol% water, in addition to cracking zone product hydrocarbons, including olefins, methane, ethane, propane, unreacted second hydrocarbons, hydrogen, CO, and/or C0 . The aqueous phase stream recovered from the gas-liquid-liquid separator can comprise water, and traces of C ₄ _ hydrocarbons, such as butanes, butenes, butadiene, and the like, or combinations thereof. The oil phase stream recovered from the gas-liquid-liquid separator can comprise C ₅₊ hydrocarbons, such as pentane, pentenes, hexanes, hexenes, benzene, toluene, xylene, and the like, or combinations thereof; and traces of water and/or C ₄ _ hydrocarbons, such as butanes, butenes, butadiene, etc.

[00104] Within oil scrubber separation unit 720, the combined effluent 68 or the dehydrated combined effluent 712 is contacted with a scrubbing oil in oil stream 733 to provide a syngas containing stream 722 and a scrubbed oil stream 721 comprising spent oil (e.g., scrubbing oil and C ₊ hydrocarbons scrubbed from combined effluent 68 or dehydrated combined effluent stream 712 introduced thereto. The syngas containing stream 722 can comprise trace amounts of C ₊ hydrocarbons, along with H , CO, C0 , and CH ₄ .

[00105] An oil regenerator 730 can be utilized to separate a regenerated oil stream 731 from C ₊ hydrocarbons stream 77, comprising C ₊ olefins and C ₊ alkanes. The regenerated oil stream 731 can be reintroduced into oil scrubber separation unit 720, for example, via oil stream 733.

[00106] Remaining hydrocarbons can be removed from syngas containing stream 722, to provide syngas 78. For example, in embodiments, syngas containing stream 722 can be subjected to low temperature (e.g., less than or equal to about 10 °C, alternatively less than or equal to about 5 °C, alternatively less than or equal to about 0 °C, alternatively from about -40 °C to about 10 °C, alternatively from about -32 °C to about 5 °C, or alternatively from about -20 °C to about 0 °C) condensing in a low temperature condenser 740, to separate a C ₊ stream 742 from a C ₊ -reduced syngas stream 741. C ₊ -reduced syngas stream 741 can be subjected to size exclusion in a size exclusion unit 750, to provide syngas stream 78 comprising H ₂ , CO, C0 , and/or CIT ₄ , and another C ₊ stream 752. Low temperature condenser 740 and size exclusion unit 750 can comprise any low temperature condenser and size exclusion unit known to those of skill in the art, and with the help of this disclosure, to be operable to provide the noted separations of the C ₊ streams 742 and 752, respectively. For example, size exclusion unit 750 can comprise any suitable number of size exclusion units, such as 1, 2, 3, 4, 5, or more size exclusion units. In embodiments, the C ₊ streams 742 and/or 752 can be combined with C ₊ hydrocarbons stream 77, for example, prior to subsequent processing and/or utilization of C ₊ hydrocarbons stream 77. [00107] In an embodiment, the C ₊ hydrocarbons stream 77 can be further subjected to one or more separation steps to recover the olefins. For example, ethylene can be recovered from the C ₊ hydrocarbons stream 77, wherein ethylene can be further used, for example, in a polymerization process. In an embodiment, with reference back to Figure 1, at least a portion 77a of the C ₊ hydrocarbons stream 77 is introduced into separator 800, which is configured to separate the at least a portion 77a of the C ₊ hydrocarbons stream 77 into an olefin stream 83, wherein the olefins stream 83 comprises at least a portion of the olefins in the C ₊ hydrocarbons stream 77 (e.g., ethylene, propylene, butenes) and an alkanes stream 84, wherein the alkanes stream 84 comprises at least a portion of the alkanes (e.g., unreacted first and/or second hydrocarbons) in the C ₊ hydrocarbons stream 77. In embodiments, the olefins stream 83 can comprise olefins, such as ethylene and/or propylene. In an embodiment, the alkanes stream 84 can comprise methane, ethane, propane, and the like, or combinations thereof. Separator 800 can effect the separation via any suitable separation technique, such as, without limitation, distillation, cryogenic distillation, extractive distillation, selective adsorption, selective absorption, and the like, or combinations thereof.

[00108] As will be appreciated by one of skill in the art, and with the help of this disclosure, the composition of combined effluent 68, the composition of C ₂₊ hydrocarbons stream 77, the composition of syngas stream 78, the composition of alkanes stream 84, and the composition of olefins stream 83 are all dependent on a variety of factors, such as the composition of CPO reactant mixture 10, the CPO reaction zone catalyst, the operating conditions for CPO reaction zone 100, the composition of dehydrogenation zone feed 61, the dehydrogenation catalyst utilized in dehydrogenation zone 650, the operating conditions for dehydrogenation zone 650, etc.

[00109] Syngas stream 78 comprises H and CO, and optionally C0 , CH ₄ , and/or trace hydrocarbons. In embodiments, the syngas stream 78 is characterized by an M ratio of equal to or greater than about 1.8, alternatively equal to or greater than about 2.0, alternatively equal to or greater than about 2.1, alternatively greater than about 2.2, alternatively greater than about 2.3, alternatively greater than about 2.4, alternatively greater than about 2.5, alternatively from about 1.8 to about 2.5, alternatively from about 1.8 to about 2.4, alternatively from about 1.9 to about 2.3, or alternatively from about 2.0 to about 2.2, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ). In embodiments, the syngas 78 is characterized by a hydrogen to CO (H /CO) molar ratio of greater than about 1.7, alternatively greater than about 1.8, alternatively greater than about 1.9, alternatively greater than about 2.0, alternatively greater than about 2.1, alternatively greater than about 2.2, alternatively greater than about 2.3, alternatively greater than about 2.4, or alternatively greater than about 2.5. In embodiments, the syngas 78 is characterized by an M ratio and/or a H /CO molar ratio that is greater than an M ratio and/or a H /CO molar ratio, respectively of a syngas produced in an otherwise similar process without feeding the CPO reaction zone effluent 15 to a dehydrogenation zone 650. In embodiments, the dehydrogenation zone reactant mixture comprises an amount of second hydrocarbons (e.g., provided by dehydrogenation zone feed 61) effective to provide for a syngas 78 characterized by a hydrogen to CO (H /CO) molar ratio of greater than about 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5.

[00110] In an embodiment, the syngas 78 as disclosed herein can comprise C0 in an amount of an amount of less than about 7 mol%, alternatively less than about 6 mol%, alternatively less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively from about 0.1 mol% to about 7 mol%, alternatively from about 0.25 mol% to about 5 mol%, or alternatively from about 0.5 mol% to about 3 mol%. The amount of C0 in the syngas 78 can be less than the amount of C0 in the CPO reaction zone effluent 15. As will be appreciated by one of skill in the art, and with the help of this disclosure, the syngas stream 78 recovered from the dehydrogenation zone 650 can have a reduced C0 content, as compared to an effluent stream from the CPO reaction zone 100.

[00111] In an embodiment, the syngas 78 as disclosed herein can comprise hydrocarbons in an amount of an amount of less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively less than about 0.1 mol%, or alternatively less than about 0.01 mol%. The amount of hydrocarbons in the syngas 78 can be less than the amount of hydrocarbons in the CPO reaction zone effluent 15.

[00112] In embodiments where the syngas 78 is characterized by an M ratio of from about 1.8 to about 2.2, the syngas can be further used for methanol production, as described further hereinbelow.

[00113] In embodiments, a process of this disclosure comprises recycling at least a portion of C ₊ hydrocarbons stream 77, at least a portion of C ₂₊ stream 742, at least a portion of C ₂₊ stream 752, and/or at least a portion of alkanes stream 84 to dehydrogenation zone 650 and/or to CPO reaction zone 100.

[00114] In embodiments, at least a portion of the alkanes stream 84 is introduced into the dehydrogenation zone 650, at least a portion of the alkanes stream 84 is introduced into the CPO reaction zone 100, at least a portion of the alkanes stream 84 is utilized as a fuel to heat the dehydrogenation zone 650 (e.g., is introduced into a furnace within common housing 150), and/or at least a portion of alkanes stream 84 is utilized as a fuel to heat the CPO reactant mixture 10.

[00115] In an embodiment, at least a portion of the C ₊ hydrocarbons stream 77 can be fed to the CPO reaction zone 100, for example via the CPO reactant mixture 10. In an embodiment, at least a portion of the C ₊ hydrocarbons stream 77 can be used as fuel (e.g., to preheat the CPO reactant mixture; to heat the dehydrogenation zone 650) and/or fed to the dehydrogenation zone 650. The C ₊ hydrocarbons stream 77 can provide for additional (e.g., supplemental) hydrocarbons to undergo a CPO reaction in the CPO reaction zone 100

[00116] In embodiments where a portion of the alkanes 84 and/or a portion of the C ₊ hydrocarbons stream 77 is introduced to the CPO reaction zone 100, the M ratio and/or the H /CO molar ratio of the CPO reaction zone effluent 15 can be greater than the M ratio and/or the H /CO molar ratio, respectively of a CPO reaction zone effluent produced by an otherwise similar process that feeds a CPO reactant mixture without the portion of the alkanes and/or the C ₊ hydrocarbons stream to a CPO reaction zone 100. In embodiments, at least a portion of the C ₊ hydrocarbons stream 77 and/or at least a portion of the alkanes 84 can be used as fuel (e.g., to preheat the CPO reactant mixture 10; to heat the dehydrogenation zone 650) and/or fed to the dehydrogenation zone 650.

[00117] In an embodiment, at least a portion of the alkanes 84 and/or at least a portion of the C ₂₊ hydrocarbons stream 77 can be recycled to the dehydrogenation zone 650, for example via the dehydrogenation zone feed 61. In an embodiment, at least a portion of alkanes 84 and/or at least a portion of the C ₊ hydrocarbons stream 77 can be used as fuel, for example for heating the dehydrogenation zone 650 and/or preheating the CPO reactant mixture 10.

[00118] In some embodiments, syngas 78 can be used in a downstream process (e.g., methanol production) without further processing to enrich the hydrogen content thereof In other embodiments, the syngas 78 can be further processed prior to use thereof in a downstream process, such as methanol production. As will be appreciated by one of skill in the art, and with the help of this disclosure, although the syngas 78 can be characterized by a H /CO molar ratio of greater than about 2.0, which can be appropriate for methanol synthesis, the syngas 78 can be processed to further increase its hydrogen content.

[00119] In an embodiment, a process for producing methanol and olefins as disclosed herein can comprise a step of introducing at least a portion of the syngas 78 to a methanol reactor 200 to produce a methanol reactor effluent 30, wherein the methanol reactor effluent stream 30 comprises methanol, water, hydrogen, CO, C0 , CH ₄ , and optionally C alcohols. The methanol reactor 200 can comprise any reactor suitable for a methanol synthesis reaction from CO and H , such as for example a trickle bed reactor, a fluidized bed reactor, a slurry reactor, a loop reactor, a cooled multi tubular reactor, and the like, or combinations thereof.

[00120] Generally, CO and ¾ can be converted into methanol (CH ₃ OH), for example as represented by equation (10):

CO + H ₂ CH ₃ OH (10)

C0 and H can also be converted to methanol, for example as represented by equation (11):

C0 ₂ + 3H ₂ C¾OH + H ₂ 0 (11)

Without wishing to be limited by theory, the lower the C0 content of the syngas 78, the lower the amount of water produced in the methanol reactor 200. As will be appreciated by one of skill in the art, and with the help of this disclosure, syngas produced by SMR has a fairly high content of hydrogen (as compared to the hydrogen content of syngas produced by CPO), and a syngas with an elevated hydrogen content (such as syngas 78) can promote the C0 conversion to methanol, for example as represented by equation (11), which in turn can lead to an increased water content in a crude methanol stream (e.g., crude methanol stream 40).

[00121] Methanol synthesis from CO, C0 and ¾ is a catalytic process, and is most often conducted in the presence of copper based catalysts. The methanol reactor 200 can comprise a methanol production catalyst, such as any suitable commercial catalyst used for methanol synthesis. Nonlimiting examples of methanol production catalysts suitable for use in the methanol reactor 200 in the current disclosure include Cu, Cu/ZnO, Cu/Th0 , Cu/Zn/Al 0 ₃ , Cu/Zn0/Al 0 ₃ , Cu/Zr, and the like, or combinations thereof

[00122] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of separating at least a portion of the methanol reactor effluent stream 30 into a crude methanol stream 40 and a vapor stream 50; wherein the crude methanol stream 40 comprises methanol and water; wherein the vapor stream 50 comprises hydrogen, CO, C0 , CH ₄ , and optionally Ci_ alcohols. The methanol reactor effluent stream 30 can be separated into the crude methanol stream 40 and the vapor stream 50 in the gas-liquid separator 300, such as a vapor- liquid separator, flash drum, knock-out drum, knock-out pot, compressor suction drum, etc. [00123] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of separating at least a portion of the crude methanol stream 40 in the distillation unit 400 into a methanol stream

45 and a water stream 46, wherein the distillation unit 400 comprises one or more distillation columns. The water stream 46 comprises water and residual methanol. Generally, the one or more distillation columns can separate components of the crude methanol stream 40 based on their boiling points. As will be appreciated by one of skill in the art, and with the help of this disclosure, the higher the water content of the crude methanol stream 40, the more distillation columns are necessary to purify the methanol.

[00124] In an embodiment, the methanol stream 45 can comprise methanol in an amount of equal to or greater than about 95 wt.%, alternatively equal to or greater than about 97.5 wt.%, alternatively equal to or greater than about 99 wt.%, or alternatively equal to or greater than about 99.9 wt.%, based on the total weight of the methanol stream 45.

[00125] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of separating at least a portion of the vapor stream 50 into a hydrogen stream 51 and a residual gas stream 52, wherein the hydrogen stream 51 comprises at least a portion of the hydrogen of the vapor stream 50, and wherein the residual gas stream 52 comprises CO, C0 , CH ₄ , and optionally Ci_ ₂ alcohols. The vapor stream 50 can be separated into the hydrogen stream 51 and the residual gas stream 52 in the hydrogen recovery unit 500, such as a PSA unit, a membrane separation unit, a cryogenic separation unit, and the like, or combinations thereof.

[00126] In an embodiment, a process for producing methanol as disclosed herein can comprise recycling at least a portion 51a of the hydrogen stream 51 to the methanol reactor 200; for example via a syngas feed to the methanol reactor 200. In some aspects, at least a portion 51a of the hydrogen stream 51 can be contacted with at least a portion of the syngas 78 to yield a methanol reactor feed stream 21, wherein at least a portion of the methanol reactor feed stream 21 can be introduced to the methanol reactor 200 to produce methanol. In such aspects, the methanol reactor feed stream 21 can be characterized by an M ratio of from about 4 to about 17, alternatively from about 5 to about 15, alternatively from about 6 to about 12, or alternatively from about 7 to about 10.

[00127] In some embodiments, at least a portion of the residual gas stream 52 can be purged. In other embodiments, at least a portion of the residual gas stream 52 can be used as fuel, for example for pre -heating the CPO reactant mixture 10, heating the dehydrogenation zone 650, and the like, or combinations thereof. In other embodiments, at least a portion 52a of the residual gas stream 52 can be fed to the CPO reaction zone 100. In yet other embodiments, at least a portion 52b of the residual gas stream 52 can be fed to the dehydrogenation zone 650.

[00128] In an embodiment, a process for producing methanol and olefins (e.g., ethylene) comprises: (a) feeding a catalytic partial oxidation (CPO) reactant mixture 10 to a CPO reaction zone 100; wherein the CPO reactant mixture 10 comprises oxygen, first hydrocarbons, and optionally steam; wherein at least a portion of the CPO reactant mixture reacts, via an exothermic CPO reaction, in the CPO reaction zone 100 to produce a CPO reaction zone effluent 15; wherein the CPO reaction zone 100 comprises a CPO catalyst; wherein the CPO reaction zone effluent 15 comprises ¾, CO, C0 , water, and unreacted first hydrocarbons; and wherein the CPO reaction zone effluent 15 is characterized by a CPO effluent temperature; (b) feeding a dehydrogenation zone reactant mixture to a dehydrogenation zone 650, wherein the dehydrogenation zone reactant mixture comprises at least a portion of the CPO reaction zone effluent 15 and a dehydrogenation zone feed 61 comprising second hydrocarbons (e.g., ethane); wherein a portion of the dehydrogenation zone reactant mixture reacts, via an endothermic catalytic dehydrogenation reaction, in the dehydrogenation zone 650 to produce a combined effluent 68; wherein the dehydrogenation zone 650 comprises a dehydrogenation catalyst; wherein the dehydrogenation zone 650 is characterized by a dehydrogenation zone temperature; wherein the CPO effluent temperature is greater than the dehydrogenation zone temperature; wherein the combined effluent 68 comprises ¾, CO, C0 , water, olefins (e.g., ethylene), unreacted first hydrocarbons, and unreacted second hydrocarbons (e.g., unreacted ethane); (c) cooling the CPO reaction zone effluent 15; wherein cooling the CPO reaction zone effluent 15 comprises heating the second hydrocarbons (e.g., ethane) to the dehydrogenation zone temperature while cooling the CPO reaction zone effluent 15 by heat transfer (e.g., direct heat transfer) between the CPO reaction zone effluent 15 and the second hydrocarbons of the dehydrogenation zone feed 61 (e.g., ethane); (d) removing at least a portion of the water (e.g., liquid stream 71) from the combined effluent 68 (e.g., in separation unit 700/700') to produce a dehydrated combined effluent 712, wherein the dehydrated combined effluent 712 comprises ¾, CO, C0 , olefins (e.g., ethylene), unreacted first hydrocarbons, and unreacted second hydrocarbons (e.g., unreacted ethane); (e) separating (e.g., in separation apparatus comprising separation unit 700/700' and/or separator 800) at least a portion of the dehydrated combined effluent 712 into syngas 78, an olefins stream 83 and an alkanes stream 84; wherein the syngas 78 comprises H ₂ , CO, C0 ₂ , and methane (CH ₄ ); wherein the syngas 78 is characterized by a hydrogen to CO (H /CO) molar ratio of greater than about 2.0; wherein the olefins stream 83 comprises at least a portion of the olefins (e.g., ethylene) in the dehydrated combined effluent 712; and wherein the alkanes stream 84 comprises at least a portion of the C ₊ alkanes in the dehydrated combined effluent 712; (f) introducing at least a portion of the syngas 78 to a methanol reactor 200 to produce a methanol reactor effluent stream 30; wherein the methanol reactor effluent stream 30 comprises methanol, water, hydrogen, CO, C0 ₂ , methane (CH ₄ ), and optionally C ₂ alcohols; (g) separating at least a portion of the methanol reactor effluent stream 30 into a crude methanol stream 40 and a vapor stream 50, wherein the crude methanol stream 40 comprises methanol and water, and wherein the vapor stream 50 comprises hydrogen, CO, C0 , CH ₄ , and optionally Ci_ alcohols; (h) separating at least a portion of the vapor stream 50 into a hydrogen stream 51 and a residual gas stream 52, wherein the hydrogen stream 51 comprises at least a portion of the hydrogen of the vapor stream 50, and wherein the residual gas stream 52 comprises CO, C0 , CH ₄ , and optionally Ci_ alcohols; (i) recycling at least a portion 51a of the hydrogen stream 51 to the methanol reactor 200; and (j) optionally recycling at least a portion 52a, 52b, respectively, of the residual gas stream 52 and/or at least a portion of the alkanes stream 84 to the dehydrogenation zone in step (b) and/or to the CPO reaction zone in step (a). In such embodiment, the M ratio of the syngas 78 can be equal to or greater than about 1.8, and the H ₂ /CO molar ratio of the syngas 78 can be greater than about 2.0. In such embodiment, the second hydrocarbons can comprise ethane, the dehydrogenation zone 650 can comprises an ethane dehydrogenation zone, and the olefins 83 can comprise ethylene. [00129] In an embodiment, a process for producing methanol and olefins as disclosed herein can advantageously display improvements in one or more process characteristics when compared to an otherwise similar process that does not integrate a CPO reaction zone with a dehydrogenation zone. The process as disclosed herein can advantageously utilize syngas 78 separated from the combined effluent 68, having an increased hydrogen content relative to a hydrogen content of the CPO reaction zone effluent 15 for downstream methanol synthesis.

[00130] As will be appreciated by one of skill in the art, and with the help of this disclosure, since the CPO reaction is exothermic, very little heat supply in the form of fuel combustion is needed (e.g., for pre -heating reactants in the reaction mixture that is supplied to a syngas generation section), when compared to conventional steam reforming. As such, the process for producing methanol and olefins as disclosed herein can advantageously generate less C0 through fuel burning, when compared to process that utilize steam reforming to produce syngas.

[00131] Further, the process as disclosed herein utilizes at least a portion of the process heat from the CPO reaction zone 100 to heat the dehydrogenation zone 650, thereby preventing run-away temperatures in the CPO reaction zone 100 (e.g., in a CPO catalyst bed), which could lead to catalyst de-activation. As will be appreciated by one of skill in the art, and with the help of this disclosure, operating the CPO reaction zone 100 at a relatively low C/O ratio (e.g., less than about 2:1) can lead to run-away temperatures, and thus removing heat from the CPO reaction zone 100 can advantageously enable operating the CPO reaction zone at relatively low C/O ratios.

[00132] In an embodiment, at least a portion of the C ₊ hydrocarbons stream 77 and/or the alkanes stream 84 can be advantageously mixed into the CPO reactant mixture 10 such that the resulting CPO reactant mixture 10 has a hydrogen content of less than about 20 mol%, or alternatively less than about 14 mol%, which allows for the hydrocarbons therein to be utilized in the CPO reaction. Additional advantages of the processes for the production of syngas, olefins, and/or methanol as disclosed herein can be apparent to one of skill in the art viewing this disclosure.

[00133] While preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the teachings of this disclosure. The embodiments 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.

[00134] Numerous other modifications, equivalents, and alternatives, will become apparent to those skilled in the art once the above disclosure is fully appreciated. It is intended that the following claims be interpreted to embrace all such modifications, equivalents, and alternatives where applicable. 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.