WO2020159657A1

WO2020159657A1 - Methanol production process with increased energy efficiency

Info

Publication number: WO2020159657A1
Application number: PCT/US2019/069062
Authority: WO
Inventors: Arwa RABIE; Vijayanand RAJAGOPALAN; Faisal ALAHMADI
Original assignee: Sabic Global Technologies, B.V.
Priority date: 2019-01-29
Filing date: 2019-12-31
Publication date: 2020-08-06

Abstract

A system for producing methanol comprising a catalytic partial oxidation (CPO) reactor operable to produce, from a CPO reactant mixture, a first syngas characterized by an M ratio defined as (H2-CO2)/(CO+CO2); a first hydrogen recovery unit operable to produce a first hydrogen stream and a first residual gas stream from a first portion of the first syngas; a methanol reactor operable to produce a methanol reactor effluent from at least a portion of a methanol reactor feed comprising at least a portion of the first hydrogen stream, a second portion of the first syngas, and at least a portion of a recycle vapor stream; a separator operable to produce a crude methanol stream and a vapor stream from at least a portion of the methanol reactor effluent; and a recycle line operable to introduce a portion of the vapor stream to the methanol reactor as the recycle vapor stream.

Description

METHANOL PRODUCTION PROCESS WITH INCREASED ENERGY EFFICIENCY

TECHNICAL FIELD

[0001] The present disclosure relates to systems and methods for producing methanol from synthesis gas produced via catalytic partial oxidation (CPO); more specifically, the present disclosure relates to systems and methods for producing methanol that employ hydrogen recovery upstream of a methanol synthesis loop; still more specifically, the present disclosure relates to systems and methods of producing methanol that provide a synthesis gas feed having a desired composition within the methanol synthesis loop via a combination of a first hydrogen recovery upstream of the methanol synthesis loop and a second hydrogen recovery within the methanol synthesis loop, downstream of a methanol synthesis reactor(s).

BACKGROUND

[0002] Synthesis gas (syngas) is a mixture comprising carbon monoxide (CO) and hydrogen (¾), as well as small amounts of carbon dioxide (C0₂), water (H₂0), and unreacted methane (CH₄). Syngas is generally used as an intermediate in the production of methanol and ammonia, as well as an intermediate in creating synthetic petroleum to use as a lubricant or fuel.

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

[0004] In an autothermal reforming (ATR) process, a portion of the natural gas is burned as fuel to drive the conversion of natural gas to syngas resulting in relatively low hydrogen and high C0₂ concentrations. Conventional methanol production plants utilize a combined reforming (CR) technology that pairs SMR with autothermal reforming (ATR) to reduce the amount of hydrogen present in syngas. ATR produces a syngas with a hydrogen content lower than that required 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 that required for methanol synthesis. Furthermore, SMR is a highly endothermic process, and the endothermicity of the SMR technology requires burning fuel to drive the syngas synthesis. Consequently, the SMR technology reduces the energy efficiency of the methanol synthesis process.

[0005] Syngas can also be produced (non-commercially) by catalytic partial oxidation (CPO or CPOx) of natural gas. CPO processes employ partial oxidation of hydrocarbon feeds to syngas comprising CO and H₂. The CPO process is exothermic, thus eliminating the need for external heat supply. However, the composition of the produced syngas is not suitable for methanol synthesis, for example, owing to a reduced hydrogen content. Thus, there is an ongoing need for the development of systems and methods for methanol synthesis that utilize syngas produced via CPO processes. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0007] Figure 1 is a schematic of a system I for a methanol synthesis process, according to embodiments of this disclosure; and

[0008] Figure 2 is a plot of ethanol production as a function of M value, as described in Example 1.

DETAILED DESCRIPTION

[0009] Herein disclosed are a system and process for methanol synthesis using syngas from catalytic partial oxidation (CPO) of, for example, natural gas (which may also be referred to herein as‘CPO syngas’). The herein disclosed system and process adjust the composition of the CPO syngas by using an energy efficient unit operation (e.g., hydrogen recovery) that reduces unwanted carbon dioxide (C0 ) formation. Furthermore, the herein disclosed methanol synthesis system ad process provide for a reduction in the formation of byproducts, such as higher (e.g., C2+) alcohols. This results in higher carbon and energy efficiency, in embodiments.

[0010] Conventional processes to produce syngas for methanol synthesis utilize standalone Steam Reforming (SMR) technology or combined reforming (CR) technology. Both of these conventional processes utilize endothermic steam reforming (SMR) to produce syngas with the required composition for methanol synthesis. The SMR reaction is a highly endothermic unit operation that is also high in capital expenses (CAPEX). Conventional best in class methanol plants utilize a combined reforming (CR) technology that consists of an SMR reactor and an Auto Thermal Reformer (ATR) to reduce the energy intensity of the syngas production, and thus of the overall methanol synthesis process. The CR process reduces the fuel consumption of the SMR unit by introducing an ATR to reform part of the natural gas feed. The natural gas feed (e.g., the volumetric flowrate) to the SMR and the ATR is adjusted to achieve an overall syngas composition (e.g., a syngas with an M value, as described further hereinbelow, of from about 2.0 to 2.06) produced by the CR technology.

[0011] The endothermicity of the SMR technology requires burning of a fuel to drive the reactions. Consequently, the SMR technology reduces the energy efficiency of a methanol synthesis process employing SMR to provide the synthesis gas feed to the methanol synthesis.

[0012] The herein disclosed system and process utilize a standalone CPO process to produce syngas with the required composition for downstream methanol synthesis without the need of an endothermic, and CAPEX intensive SMR. Moreover, the herein disclosed methanol synthesis system and process enable the production of syngas with a composition that limits unwanted byproduct (e.g., higher alcohol) formation. The herein disclosed methanol synthesis system and process are energy efficient and can be utilized in a retrofit of an existing inefficient methanol production plant, in embodiments.

[0013] In embodiments, a CPO syngas exiting a CPO reactor, and having an M value in a range of from 1.5 to 1.95 is produced by operating the CPO reactor between 2 and 30 bar, utilizing oxygen for the CPO reactor at a carbon to oxygen ratio between 2.2 and 1.7, utilizing steam in the CPO reactor at a steam to carbon ratio between 0.2 and 1.5, and/or preheating the natural gas to a temperature in a range of from 150 °C to 520 °C. Hydrogen recovery units, such as, without limitation, a pressure swing adsorption (PSA) unit or a membrane unit, are employed prior to the methanol loop and/or both prior to and in the methanol loop to recover hydrogen. In embodiments, hydrogen recovery units are employed prior to the methanol loop and/or both prior to and in the methanol loop to recover hydrogen from 50 to 90 mole percent (mol%) of the hydrogen at a hydrogen purity of from 65 to 99.9 mol%.

[0014] Prior to the methanol loop, a syngas slip stream with a split fraction from 0.1 to 25 mol% of the CPO or‘first’ syngas produced from the CPO reactor is sent to a (first) hydrogen recovery unit (e.g., a PSA or membrane unit). The recovered hydrogen is mixed with the remaining CPO syngas prior to syngas compression. A residual gas or tail gas from the (first) hydrogen recovery unit containing unrecovered hydrogen, methane, CO, and C0 can be utilized as fuel (e.g., for process steam production), in embodiments.

[0015] A portion of a recycle syngas exiting the methanol reactor of the methanol loop is purged to reduce the buildup of inerts in the methanol synthesis loop. In embodiments, a second hydrogen recovery unit (e.g., a PSA or membrane) is employed to recover hydrogen from the purge stream, which is combined with the syngas prior to the methanol loop to increase the hydrogen content thereof. In embodiments, from 3 to 20 mole percent of the recycle syngas is purged. Again, the residual or tail gas from the second hydrogen recovery unit will contain unrecovered hydrogen, methane, CO, and C0 , and can be utilized as fuel (e.g., for process steam production), in embodiments.

[0016] Implementing a hydrogen recovery unit (e.g., a first hydrogen recovery unit, as described further hereinbelow) prior to the methanol synthesis loop and optionally also implementing a hydrogen recovery unit (e.g., a second hydrogen recovery unit, as described further hereinbelow) within the methanol synthesis loop in a standalone CPO process can be utilized as described herein to enhance the syngas M value prior to the methanol loop to an M value in the range of 1.7 to 2.2, and can alternatively or additionally be utilized to enhance the syngas M value within the methanol synthesis loop to an M value from 2.0 to 13.0.

[0017] 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. [0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] As used herein, the term“effective,” means adequate to accomplish a desired, expected, or intended result.

[0023] 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.

[0024] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art.

[0025] 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, -CFiO is attached through the carbon of the carbonyl group.

[0026] As used herein, the terms“C_x hydrocarbons” and“C_xs” are interchangeable and refer to any hydrocarbon having x number of carbon atoms (C). For example, the terms“C₄ hydrocarbons” and“C₄s” both refer to any hydrocarbons having exactly 4 carbon atoms, such as n-butane, iso-butane, cyclobutane, 1- butene, 2-butene, isobutylene, butadiene, and the like, or combinations thereof.

[0027] 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 ₊ hydrocarbons” refers to any hydrocarbons having 2 or more carbon atoms, such as ethane, ethylene, C₃s, C₄s, C₅s, etc. [0028] As utilized herein, the‘methanol synthesis loop’ or‘methanol loop’ refers to the methanol synthesis section of a plant, comprising the methanol synthesis reactor(s).

[0029] As utilized herein, the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂).

[0030] Referring to Figure 1, a methanol production system I is disclosed. The methanol production system I generally comprises a catalytic partial oxidation (CPO or CPOx) reactor 10; a compressor 30; a methanol reactor 40; a gas-liquid separator 50; a distillation unit 60; a first hydrogen (H₂) recovery unit 20 A; and (optionally) a second hydrogen recovery unit 20B. As will be appreciated by one of skill in the art, and with the help of this disclosure, methanol production system components shown in Figure 1 can be in fluid communication with each other (as represented by the connecting lines indicating a direction of fluid flow) through any suitable conduits (e.g., pipes, streams, etc.).

[0031] In an embodiment, a process as disclosed herein can comprise a step of (a) feeding a catalytic partial oxidation (CPO) reactant mixture 5 to a CPO reactor 10; wherein the CPO reactant mixture 5 comprises hydrocarbons, oxygen, and optionally steam; wherein at least a portion of the CPO reactant mixture 5 reacts, via a CPO reaction, in the CPO reactor 10 to produce a first syngas 15A; wherein the CPO reactor 10 comprises a CPO catalyst; wherein the first syngas 15A comprises hydrogen (F12), carbon monoxide (CO), carbon dioxide (C0 ), and hydrocarbons, and wherein the first syngas 15A is characterized by an M ratio of the first syngas 15 A, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ).

[0032] Generally, the CPO reaction is based on partial combustion of fuels, such as various hydrocarbons, and in the case of methane, CPO can be represented by equation (1):

CH₄ + 1/2 0₂ ® C0 + 2 H₂ (1)

Without wishing to be limited by theory, side reactions can take place along with the CPO reaction depicted in equation (1); and such side reactions can produce carbon dioxide (C0 ) and water (H 0), for example via hydrocarbon combustion, which is an exothermic reaction. As will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, the CPO reaction as represented by equation (1) can yield a syngas with a hydrogen to carbon monoxide (H /CO) molar ratio having the theoretical stoichiometric limit of 2.0. Without wishing to be limited by theory, the theoretical stoichiometric limit of 2.0 for the H /CO molar ratio means that the CPO reaction as represented by equation (1) yields 2 moles of H for every 1 mole of CO, i.e., H /CO molar ratio of (2 moles H /l mole CO) = 2. As will be appreciated by one of skill in the art, and with the help of this disclosure, the theoretical stoichiometric limit of 2.0 for the H /CO molar ratio in a CPO reaction cannot be achieved practically because reactants (e.g., hydrocarbons, oxygen) as well as products (e.g., H , CO) undergo side reactions at the conditions used for the CPO reaction. As will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, in the presence of oxygen, CO and F1 can be oxidized to C0 and H 0, respectively. The relative amounts (e.g., composition) of CO, H , 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 reactor 10 can have a direct impact on the M ratio of the produced syngas (e.g., first syngas 15 A), wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ). In the absence of any side reaction (theoretically), the CPO reaction as represented by equation (1) results in a syngas with an M ratio of 2.0. However, the presence of side reactions (practically) reduces ¾ and increases C0 , thereby resulting in a syngas 15A with an M ratio below 2.0.

[0033] Further, without wishing to be limited by theory, the CPO reaction as depicted in equation (1) is an exothermic heterogeneous catalytic reaction (i.e., a mildly exothermic reaction) and it occurs in a single reactor unit, such as the CPO reactor 10 (as opposed to more than one reactor unit as is the case in conventional processes for syngas production, such as steam methane reforming (SMR) - autothermal reforming (ATR) combinations). While it is possible to conduct partial oxidation of hydrocarbons as a homogeneous reaction, in the absence of a catalyst, homogeneous partial oxidation of hydrocarbons process entails excessive temperatures, long residence times, as well as excessive coke formation, which strongly reduce the controllability of the partial oxidation reaction, and may not produce syngas of the desired quality in a single reactor unit.

[0034] 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 CH₄-rich feed).

[0035] In an embodiment, the hydrocarbons suitable for use in a CPO reaction as disclosed herein can include methane (CH₄), natural gas, natural gas liquids, liquefied petroleum gas (LPG), associated gas, well head gas, enriched gas, paraffins, shale gas, shale liquids, fluid catalytic cracking (FCC) off gas, refinery process gases, refinery off gases, stack gases, fuel gas from a fuel gas header, and the like, or combinations thereof. The hydrocarbons can include any suitable hydrocarbons source, and can contain Ci-C₆ hydrocarbons, as well some heavier hydrocarbons.

[0036] In an embodiment, the CPO reactant mixture 5 can comprise natural gas. Generally, natural gas is composed primarily of methane, but can also contain ethane, propane and heavier hydrocarbons (e.g., iso-butane, n-butane, iso-pentane, n-pentane, hexanes, etc.), as well as very small quantities of nitrogen, oxygen, carbon dioxide, sulfur compounds, and/or water. The natural gas can be provided from a variety of sources including, but not limited to, gas fields, oil fields, coal fields, fracking of shale fields, biomass, landfill gas, and the like, or combinations thereof. In some embodiments, the CPO reactant mixture 5 can comprise CH₄ and 0 .

[0037] 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% carbon dioxide, and less than about 15 mol% nitrogen.

[0038] In an embodiment, natural gas can comprise CH₄ in an amount of equal to or greater than about 45 mol%, alternatively equal to or greater than about 50 mol%, alternatively equal to or greater than about 55 mol%, alternatively equal to or greater than about 60 mol%, alternatively equal to or greater than about 65 mol%, alternatively equal to or greater than about 70 mol%, alternatively equal to or greater than about 75 mol%, alternatively equal to or greater than about 80 mol%, alternatively equal to or greater than about 82 mol%, alternatively equal to or greater than about 84 mol%, alternatively equal to or greater than about 86 mol%, alternatively equal to or greater than about 88 mol%, alternatively equal to or greater than about 90 mol%, alternatively equal to or greater than about 91 mol%, alternatively equal to or greater than about 92 mol%, alternatively equal to or greater than about 93 mol%, alternatively equal to or greater than about 94 mol%, alternatively equal to or greater than about 95 mol%, alternatively equal to or greater than about 96 mol%, alternatively equal to or greater than about 97 mol%, alternatively equal to or greater than about 98 mol%, or alternatively equal to or greater than about 99 mol%.

[0039] In some embodiments, the hydrocarbons suitable for use in a CPO reaction as disclosed herein can comprise Ci-C₆ hydrocarbons, nitrogen (e.g., from about 0.1 mol% to about 15 mol%, alternatively from about 0.5 mol% to about 11 mol%, alternatively from about 1 mol% to about 7.5 mol%, or alternatively from about 1.3 mol% to about 5.5 mol%), and carbon dioxide (e.g., from about 0.1 mol% to about 2 mol%, alternatively from about 0.2 mol% to about 1 mol%, or alternatively from about 0.3 mol% to about 0.6 mol%). For example, the hydrocarbons suitable for use in a CPO reaction as disclosed herein can comprise Ci hydrocarbon (about 89 mol% to about 92 mol%); C hydrocarbons (about 2.5 mol% to about 4 mol%); C₃ hydrocarbons (about 0.5 mol% to about 1.4 mol%); C₄ hydrocarbons (about 0.5 mol% to about 0.2 mol%); C₅ hydrocarbons (about 0.06 mol%); and C₆ hydrocarbons (about 0.02 mol%); and optionally nitrogen (about 0.1 mol% to about 15 mol%), carbon dioxide (about 0.1 mol% to about 2 mol%), or both nitrogen (about 0.1 mol% to about 15 mol%) and carbon dioxide (about 0.1 mol% to about 2 mol%).

[0040] The oxygen used in the CPO reactant mixture 10 can comprise 100% oxygen (substantially pure 0 ), oxygen gas (which may be obtained via a membrane separation process), technical oxygen (which may contain some air), air, oxygen enriched air, oxygen-containing gaseous compounds (e.g., NO), oxygen-containing mixtures (e.g., 0 /C0 , 0 /H 0, 0 /H 0 /H 0), oxy radical generators (e.g., CH₃OH, CH 0), hydroxyl radical generators, and the like, or combinations thereof.

[0041] In an embodiment, the CPO reactant mixture 5 can be characterized by a carbon to oxygen (C/O) molar ratio of less than about 3 :1, alternatively less than about 2.6:1, alternatively less than about 2.4:1, alternatively less than about 2.2:1, alternatively less than about 2:1, alternatively less than about 1.9:1, alternatively equal to or greater than about 2:1, alternatively equal to or greater than about 2.2:1, alternatively equal to or greater than about 2.4:1, alternatively equal to or greater than about 2.6:1, alternatively from about 0.5:1 to about 3:1, alternatively from about 0.7:1 to about 2.5:1, alternatively from about 0.9:1 to about 2.2:1, alternatively from about 1 :1 to about 2:1, alternatively from about 1.1 :1 to about 1.9:1, alternatively from about 2:1 to about 3:1, alternatively from about 2.2:1 to about 3:1, alternatively from about 2.4:1 to about 3 :1, or alternatively from about 2.6:1 to about 3:1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0 ) in the reactant mixture. [0042] For example, when the only source of carbon in the CPO reactant mixture 5 is CH₄, the CH4/O2 molar ratio is the same as the C/O molar ratio. As another example, when the CPO reactant mixture 5 contains other carbon sources besides CH₄, such as ethane (C H₆), propane (C₃H₈), butanes (C₄H_I0), etc., the C/O molar ratio accounts for the moles of carbon in each compound (e.g., 2 moles of C in 1 mole of C₂H₆, 3 moles of C in 1 mole of C₃H₈, 4 moles of C in 1 mole of C₄H_I0, etc.). As will be appreciated by one of skill in the art, and with the help of this disclosure, the C/O molar ratio in the CPO reactant mixture 5 can be adjusted along with other reactor process parameters (e.g., temperature, pressure, flow velocity, etc.) to provide for a syngas with a desired composition (e.g., a syngas with a desired H₂/CO molar ratio; a syngas with a desired C0₂ content; etc.). The C/O molar ratio in the CPO reactant mixture 5 can be adjusted to provide for a decreased amount of unconverted hydrocarbons in the syngas. The C/O molar ratio in the CPO reactant mixture 5 can be adjusted based on the CPO effluent temperature in order to decrease (e.g., minimize) the unconverted hydrocarbons content of the first syngas 15 A. 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.

[0043] In an embodiment, a CPO reactor suitable for use in the present disclosure (e.g., CPO reactor 10) can comprise a tubular reactor, a continuous flow reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a circulating fluidized bed reactor (e.g., a riser type reactor), a bubbling bed reactor, an ebullated bed reactor, a rotary kiln reactor, and the like, or combinations thereof. In some embodiments, the CPO reactor 10 can comprise a circulating fluidized bed reactor, such as a riser type reactor.

[0044] In some embodiments, the CPO reactor 10 can be characterized by at least one CPO operational parameter selected from the group consisting of a CPO reactor temperature (e.g., CPO catalyst bed temperature); CPO feed temperature (e.g., CPO reactant mixture temperature); target CPO effluent temperature; a CPO pressure (e.g., CPO reactor pressure); a CPO contact time (e.g., CPO reactor contact time); a C/O molar ratio in the CPO reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture, wherein the S/C molar ratio refers to the total moles of water (H₂0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof. For purposes of the disclosure herein, the CPO effluent temperature is the temperature of the syngas (e.g., syngas effluent; first syngas 15A) measured at the point where the syngas exits the CPO reactor (CPO reactor 10), e.g., a temperature of the syngas measured at a CPO reactor outlet, a temperature of the syngas effluent, a temperature of the exit syngas effluent. For purposes of the disclosure herein, the CPO effluent temperature (e.g., target CPO effluent temperature) is considered an operational parameter. As will be appreciated by one of skill in the art, and with the help of this disclosure, the choice of operational parameters for the CPO reactor such as CPO feed temperature; CPO pressure; CPO contact time; C/O molar ratio in the CPO reactant mixture; S/C molar ratio in the CPO reactant mixture; etc. determines the temperature of the syngas effluent (e.g., first syngas 15A), as well as the composition of the syngas effluent (e.g., first syngas 15 A). Further, and as will be appreciated by one of skill in the art, and with the help of this disclosure, monitoring the CPO effluent temperature can provide feedback for changing other operational parameters (e.g., CPO feed temperature; CPO pressure; CPO contact time; C/O molar ratio in the CPO reactant mixture; S/C molar ratio in the CPO reactant mixture; etc.) as necessary for the CPO effluent temperature to match the target CPO effluent temperature. Furthermore, and as will be appreciated by one of skill in the art, and with the help of this disclosure, the target CPO effluent temperature is the desired CPO effluent temperature, and the CPO effluent temperature (e.g., measured CPO effluent temperature, actual CPO effluent temperature) may or may not coincide with the target CPO effluent temperature. In 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; etc.) can be adjusted (e.g., modified) in order for the CPO effluent temperature to match (e.g., be the same with, coincide with) the target CPO effluent temperature. The CPO reactor 10 can be operated under any suitable operational parameters that can provide for a syngas with a desired composition (e.g., a syngas with a desired H₂/CO molar ratio; a syngas with a desired C0₂ content; etc.).

[0045] The CPO reactor 10 can be characterized by a CPO feed temperature of from about 25 °C to about 600 °C, alternatively from about 25 °C to about 500 °C, alternatively from about 25 °C to about 400 °C, alternatively from about 50 °C to about 400 °C, or alternatively from about 100 °C to about 400 °C.

[0046] The CPO reactor 10 can be characterized by a CPO effluent temperature (e.g., target CPO effluent temperature) of greater than or equal to about 300 °C, greater than or equal to about 600 °C, alternatively greater than or equal to about 700 °C, alternatively greater than or equal to about 750 °C, alternatively greater than or equal to about 800 °C, alternatively greater than or equal to about 850 °C, alternatively from about 300 °C to about 1,600 °C, alternatively from about 600 °C to about 1,400 °C, alternatively from about 600 °C to about 1,300 °C, alternatively from about 700 °C to about 1,200 °C, alternatively from about 750 °C to about 1,150 °C, alternatively from about 800 °C to about 1,125 °C, or alternatively from about 850 °C to about 1,100 °C.

[0047] In an embodiment, the CPO reactor 10 can be characterized by any suitable reactor temperature and/or catalyst bed temperature. For example, the CPO reactor 10 can be characterized by a reactor temperature and/or catalyst bed temperature of greater than or equal to about 300 °C, alternatively greater than or equal to about 600 °C, alternatively greater than or equal to about 700 °C, alternatively greater than or equal to about 750 °C, alternatively greater than or equal to about 800 °C, alternatively greater than or equal to about 850 °C, alternatively from about 300 °C to about 1,600 °C, , alternatively from about 600 °C to about 1,400 °C, alternatively from about 600 °C to about 1,300 °C, alternatively from about 700 °C to about 1,200 °C, alternatively from about 750 °C to about 1,150 °C, alternatively from about 800 °C to about 1,125 °C, or alternatively from about 850 °C to about 1,100 °C.

[0048] The CPO reactor 10 can be operated under any suitable temperature profile that can provide for a syngas with a desired composition (e.g., a syngas with a desired I¾/CO molar ratio; a syngas with a desired C0₂ content; etc.). The CPO reactor 10 can be operated under adiabatic conditions, non-adiabatic conditions, isothermal conditions, near-isothermal conditions, etc. For purposes of the disclosure herein, the term“non-adiabatic conditions” refers to process conditions wherein a reactor is subjected to external heat exchange or transfer (e.g., the reactor is heated; or the reactor is cooled), which can be direct heat exchange and/or indirect heat exchange. As will be appreciated by one of skill in the art, and with the help of this disclosure, the terms“direct heat exchange” and“indirect heat exchange” are known to one of skill in the art. By contrast, the term“adiabatic conditions” refers to process conditions wherein a reactor is not subjected to external heat exchange (e.g., the reactor is not heated; or the reactor is not cooled). Generally, external heat exchange implies an external heat exchange system (e.g., a cooling system; a heating system) that requires energy input and/or output. External heat transfer can also result from heat loss from the catalyst bed (or reactor) due to radiation, conduction or convection. For example, this heat exchange from the catalyst bed can be to the external environment or to the reactor zones before and after the catalyst bed.

[0049] For purposes of the disclosure herein, the term“isothermal conditions” refers to process conditions (e.g., CPO operational parameters) that allow for a substantially constant temperature of the reactor and/or catalyst bed (e.g., isothermal temperature) that can be defined as a temperature that varies by less than about + 10 °C, alternatively less than about + 9 °C, alternatively less than about + 8 °C, alternatively less than about + 7 °C, alternatively less than about + 6 °C, alternatively less than about + 5 °C, alternatively less than about + 4 °C, alternatively less than about + 3 °C, alternatively less than about + 2 °C, or alternatively less than about + 1 °C across the reactor and/or catalyst bed, respectively.

[0050] Further, for purposes of the disclosure herein, the term“isothermal conditions” refers to process conditions (e.g., CPO operational parameters) effective for providing for a syngas with a desired composition (e.g., a desired H /CO molar ratio; a desired C0 content; etc.), wherein the isothermal conditions comprise a temperature variation of less than about + 10 °C across the reactor and/or catalyst bed. In embodiments, CPO reactor 10 can be operated under any suitable operational parameters that can provide for isothermal conditions.

[0051] For purposes of the disclosure herein, the term“near-isothermal conditions” refers to process conditions (e.g., CPO operational parameters) that allow for a fairly constant temperature of the reactor and/or catalyst bed (e.g., near- isothermal temperature), which can be defined as a temperature that varies by less than about + 100 °C, alternatively less than about + 90 °C, alternatively less than about + 80 °C, alternatively less than about + 70 °C, alternatively less than about + 60 °C, alternatively less than about + 50 °C, alternatively less than about + 40 °C, alternatively less than about + 30 °C, alternatively less than about + 20 °C, alternatively less than about + 10 °C, alternatively less than about + 9 °C, alternatively less than about + 8 °C, alternatively less than about + 7 °C, alternatively less than about + 6 °C, alternatively less than about + 5 °C, alternatively less than about + 4 °C, alternatively less than about + 3 °C, alternatively less than about + 2 °C, or alternatively less than about + 1 °C across the reactor and/or catalyst bed, respectively. In some embodiments, near-isothermal conditions allow for a temperature variation of less than about + 50 °C, alternatively less than about + 25 °C, or alternatively less than about + 10 °C across the reactor and/or catalyst bed. Further, for purposes of the disclosure herein, the term“near-isothermal conditions” is understood to include“isothermal” conditions.

[0052] 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 H /CO molar ratio; a desired C0 content; etc.), wherein the near-isothermal conditions comprise a temperature variation of less than about + 100 °C across the reactor and/or catalyst bed.

[0053] 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 the reactor and/or catalyst bed. In embodiments, the CPO reactor 10 can be operated under any suitable operational parameters that can provide for near- isothermal conditions.

[0054] Near-isothermal conditions can be provided by a variety of process and catalyst variables, such as temperature (e.g., heat exchange or heat transfer), pressure, gas flow rates, reactor configuration, catalyst bed configuration, catalyst bed composition, reactor cross sectional area, feed gas staging, feed gas injection, feed gas composition, and the like, or combinations thereof. Generally, and without wishing to be limited by theory, the terms“heat transfer” or“heat exchange” refer to thermal energy being exchanged or transferred between two systems (e.g., two reactors, such as a CPO reactor and a cracking reactor), and the terms“heat transfer” or“heat exchange” are used interchangeably for purposes of the disclosure herein.

[0055] In some embodiments, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by heat exchange or heat transfer. The heat exchange can comprise heating the reactor; or cooling the reactor. In an embodiment, achieving a target CPO effluent temperature and/or near- isothermal conditions can be provided by cooling the reactor. In another embodiment, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by heating the reactor.

[0056] In some embodiments, 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.

[0057] The heat exchange can comprise external heat exchange, external coolant fluid cooling, reactive cooling, liquid nitrogen cooling, cryogenic cooling, electric heating, electric arc heating, microwave heating, radiant heating, natural gas combustion, solar heating, infrared heating, use of a diluent in the CPO reactant mixture, and the like, or combinations thereof. For example, reactive cooling can be effected by carrying out an endothermic reaction in a cooling coil/jacket associated with (e.g., located in) the reactor.

[0058] 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 reactor. In other embodiments, achieving a target CPO effluent temperature and/or near-isothermal conditions can be provided by supplying heat to the CPO reactor. As will be appreciated by one of skill in the art, and with the help of this disclosure, a CPO reactor may need to undergo both heating and cooling in order to achieve a target CPO effluent temperature and/or near-isothermal conditions. [0059] In an embodiment, the heat exchange or heat transfer can comprise introducing a cooling agent, such as a diluent, into the reactor (e.g., CPO reactor 10), to decrease the reactor temperature and/or the catalyst bed temperature, while increasing a temperature of the cooling agent and/or changing the phase of the cooling agent. The cooling agent can be reactive or non-reactive. The cooling agent can be in liquid state and/or in vapor state. As will be appreciated by one of skill in the art, and with the help of this disclosure, the cooling agent can act as a flammability retardant; for example by reducing the temperature inside the reactor, by changing the gas mixture composition, by reducing the combustion of hydrocarbons to carbon dioxide; etc.

[0060] In some embodiments, the CPO reactant mixture 5 can further comprise a diluent, wherein the diluent contributes to achieving a target CPO effluent temperature and/or near-isothermal conditions via heat exchange, as disclosed herein. The diluent can comprise water, steam, inert gases (e.g., argon), nitrogen, carbon dioxide, and the like, or combinations thereof. Generally, the diluent is inert with respect to the CPO reaction, e.g., the diluent does not participate in the CPO reaction. However, and as will be appreciated by one of skill in the art, and with the help of this disclosure, some diluents (e.g., water, steam, carbon dioxide, etc.) might undergo chemical reactions other than the CPO reaction within the reactor, and can change the composition of the resulting syngas, as will be described in more detail later herein; while other diluents (e.g., nitrogen (N₂), argon (Ar)) might not participate in reactions that change the composition of the resulting syngas. As will be appreciated by one of skill in the art, and with the help of this disclosure, the diluent can be used to vary the composition of the resulting syngas (e.g., first syngas 15 A). The diluent can be present in the CPO reactant mixture 5 in any suitable amount.

[0061] The CPO reactor 10 can be characterized by a CPO pressure (e.g., reactor pressure measured at the reactor exit or outlet) of greater than or equal to about 1 barg, alternatively greater than or equal to about 10 barg, alternatively greater than or equal to about 20 barg, alternatively greater than or equal to about 25 barg, alternatively greater than or equal to about 30 barg, alternatively greater than or equal to about 35 barg, alternatively greater than or equal to about 40 barg, alternatively greater than or equal to 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.

[0062] The CPO reactor 10 can be characterized by a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s), alternatively from about 0.001 ms to about 1 s, alternatively from about 0.001 ms to about 100 ms, alternatively from about 0.001 ms to about 10 ms, alternatively from about 0.001 ms to about 5 ms, or alternatively from about 0.01 ms to about 1.2 ms. Generally, the contact time of a reactor comprising a catalyst refers to the average amount of time that a compound (e.g., a molecule of that compound) spends in contact with the catalyst (e.g., within the catalyst bed), e.g., the average amount of time that it takes for a compound (e.g., a molecule of that compound) to travel through the catalyst bed. In some embodiments, the CPO reactor 10 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.

[0063] 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 (e.g., of first syngas 15A) , such as a syngas with a desired composition (e.g., a syngas with a desired H /CO molar ratio; a syngas with a desired C0 content; etc.). For example, the CPO operational parameters can be adjusted to provide for an increased H content of the syngas. As another example, the CPO operational parameters can be adjusted to provide for a decreased C0₂ content of the syngas. As yet another example, the CPO operational parameters can be adjusted to provide for a decreased unreacted hydrocarbons (e.g., unreacted CH₄) content of the syngas.

[0064] In embodiments, the CPO reactor 10 is characterized by at least one CPO operational parameter selected from the group consisting of a CPO inlet temperature of from about 150 °C to about 520 °C; a CPO outlet temperature of from about 600 °C to about 1,400 °C; a CPO pressure of from about 2 barg to about 30 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture 5 of from about 1.5:1 to about 2.2:1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0 ) in the reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.2:1 to about 1.5:1, wherein the S/C molar ratio refers to the total moles of water (H 0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof.

[0065] In embodiments, the CPO reactor 10 is characterized by at least one CPO operational parameter selected from the group consisting of a CPO inlet temperature of from about 200 °C to about 400 °C; a CPO outlet temperature of from about 800 °C to about 1,100 °C; a CPO pressure of from about 10 barg to about 25 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture 5 of from about 1.5:1 to about 1.9:1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0 ) in the reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.2:1 to about 0.6:1, wherein the S/C molar ratio refers to the total moles of water (H 0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] In some embodiments, the support comprises an inorganic oxide, alpha, beta or theta alumina (A1 0₃), activated A1 0₃, silicon dioxide (Si0 ), titanium dioxide (Ti0 ), magnesium oxide (MgO), zirconium oxide (Zr0 ), lanthanum (III) oxide (La 0₃), yttrium (III) oxide (Y 0₃), cerium (IV) oxide (Ce0 ), zeolites, ZSM-5, perovskite oxides, hydrotalcite oxides, and the like, or combinations thereof.

[0071] Without limitation, CPO processes, CPO reactors, CPO catalysts, and CPO catalyst bed configurations suitable for use in the present disclosure are described in more detail in U.S. Provisional Patent Application No. 62/522,910 filed June 21, 2017 (International Application No. PCT/IB2018/054475 filed June 18, 2018) and entitled“Improved Reactor Designs for Heterogeneous Catalytic Reactions;” and U.S. Provisional Patent Application No. 62/521,831 filed June 19, 2017 (International Application No. PCT/IB2018/054470 filed June 18, 2018) and entitled“An Improved Process for Syngas Production for Petrochemical Applications;” each of which is hereby incorporated herein by reference in its entirety for purposes not contrary to this disclosure.

[0072] In an embodiment, a first syngas 15A can be recovered from the CPO reactor 10, wherein the first syngas 15A comprises hydrogen, carbon monoxide, water, carbon dioxide, and unreacted hydrocarbons. In embodiments, a process for producing methanol as disclosed herein can comprise a step of recovering a CPO reactor effluent from the CPO reactor 10, wherein the CPO reactor effluent comprises H , CO, C0 , water, and hydrocarbons; and removing at least a portion of the water from the CPO reactor effluent to produce the first syngas 15 A. [0073] In an embodiment, the first syngas 15A can be characterized by an M ratio of greater than or equal to about 1.5, alternatively greater than or equal to about 1.6, alternatively greater than or equal to about 1.7, alternatively greater than or equal to about 1.8, alternatively greater than or equal to about 1.84, alternatively greater than or equal to about 1.9, alternatively from about 1.5 to about 1.95, alternatively from about 1.7 to about 2.3, alternatively from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.2.

[0074] The first syngas 15A as disclosed herein can be characterized by a H₂/CO molar ratio of greater than about 1.7, alternatively greater than about 1.8, alternatively greater than about 1.9, alternatively greater than about 2.0, or alternatively greater than about 2.1. In some embodiments, the first syngas 15A as disclosed herein can be characterized by a H /CO molar ratio of from about 1.7 to about 2.3, alternatively from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.1.

[0075] In an embodiment, the first syngas 15A can have a C0 content of less than about 10 mol%, less than about 9 mol%, less than about 8 mol%, less than about 7 mol%, alternatively less than about 6 mol%, alternatively less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively greater than about 0.1 mol%, alternatively greater than about 0.25 mol%, alternatively greater than about 0.5 mol%, alternatively from about 0.1 mol% to about 7 mol%, alternatively from about 0.25 mol% to about 6 mol%, or alternatively from about 0.5 mol% to about 5 mol%.

[0076] In embodiments, water can be condensed and separated from at least a portion of the first syngas 15A and/or a second syngas 15B (described further below), e.g., in a condenser. In embodiments, the first syngas 15A and/or the second syngas 15B can be subjected to processing, such as the recovery of unreacted hydrocarbons, diluent, water, etc. In an embodiment, a process as disclosed herein can further comprise: (i) recovering at least a portion of the unreacted hydrocarbons from the first syngas 15A and/or the second syngas 15B to yield recovered hydrocarbons, and (ii) recycling at least a portion of the recovered hydrocarbons to the CPO reactor 10. As will be appreciated by one of skill in the art, and with the help of this disclosure, although fairly high conversions can be achieved in CPO processes (e.g., conversions of equal to or greater than about 90%), the unconverted hydrocarbons could be recovered and recycled back to the CPO reactor 10.

[0077] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of introducing a first portion 15 A' of the first syngas 15A to a first hydrogen recovery unit 20 A to produce a first hydrogen stream 16A (that comprises at least a portion of the hydrogen of the first portion 15 A' of first syngas stream 15 A) and a first residual gas stream 25 A. The first residual gas stream 25A comprises CO, C0 , hydrocarbons, and optionally H . First hydrogen recovery unit 20A can be any hydrogen recovery unit known on the art to be suitable for the separation of hydrogen from a syngas stream. For example, first hydrogen recovery unit 20A can comprise a PSA unit, a membrane separation unit, a cryogenic separation unit, and the like, or combinations thereof. In embodiments, the first portion 15 A' of the first syngas 15A is from about 1 mol% to about 25 mol%, from about 10 mol% to about 25 mol%, or from about 5 mol% to about 20 mol% of the first syngas 15A. In embodiments, the first hydrogen stream 16A comprises from about 70 mol% to about 95 mol%, from about 75 mol% to about 95 mol%, from about 70 mol% to about 90 mol%, or greater than or equal to about 40, 50, or 60 mol% of the H₂ of the first portion 15A' of the first syngas 15A. In embodiments, the first hydrogen stream 16A comprises a hydrogen purity of greater than or equal to about 60, 65, or 70 mol% H . In some embodiments, at least a portion of the first residual gas stream 25A can be purged. In other embodiments, at least a portion of the first residual gas stream 25A can be used as fuel, for example to generate steam for powering the steam-driven compressor 30.

[0078] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of contacting at least a portion of the first hydrogen stream 16A with a second portion 15A" of the first syngas 15A to yield a second syngas 15B, wherein the second syngas comprises H₂, CO, C0₂, and hydrocarbons. In embodiments, the second portion 15A" of the first syngas 15A is from about 75 mol% to about 99 mol%, from about 75 mol% to about 90 mol%, or from about 80 mol% to about 99 mol% of the first syngas 15 A.

[0079] In embodiments, the second syngas 15B is characterized by an M ratio that is greater than the M ratio of the first syngas 15A. In an embodiment, the second syngas 15B can be characterized by an M ratio of greater than or equal to about 1.7, alternatively greater than or equal to about 1.8, alternatively greater than or equal to about 1.9, alternatively greater than or equal to about 2.0, alternatively greater than or equal to about 2.1, alternatively greater than or equal to about 2.2, alternatively from about 1.7 to about 2.2, alternatively from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.2.

[0080] The second syngas 15B as disclosed herein can be characterized by a 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, or alternatively greater than about 2.1. In some embodiments, the second syngas 15B as disclosed herein can be characterized by a H /CO molar ratio of from about 1.7 to about 2.3, alternatively from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.1.

[0081] In an embodiment, the second syngas 15B can have a C0 content substantially the same as that of the first syngas 15A. In an embodiment, the second syngas 15B can have a C0 content of less than about 10 mol%, less than about 9 mol%, less than about 8 mol%, less than about 7 mol%, alternatively less than about 6 mol%, alternatively less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively greater than about 0.1 mol%, alternatively greater than about 0.25 mol%, alternatively greater than about 0.5 mol%, alternatively from about 0.1 mol% to about 7 mol%, alternatively from about 0.25 mol% to about 6 mol%, or alternatively from about 0.5 mol% to about 5 mol%.

[0082] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of contacting at least a portion of the second syngas 15B with a fourth hydrogen stream 16D to yield a third syngas 15C, wherein the third syngas 15C comprises H , CO, C0 , and hydrocarbons. As discussed further hereinbelow, fourth hydrogen stream 16D can comprise, consist, or consist essentially of hydrogen in a second hydrogen stream 16B recovered from a second hydrogen recovery unit 20B and/or hydrogen in a third hydrogen stream 16C from an alternate source.

[0083] In embodiments, the third syngas 15C is characterized by an M ratio that is greater than the M ratio of the second syngas 15B. In an embodiment, the third syngas 15C can be characterized by an M ratio of greater than or equal to about 2, alternatively greater than or equal to about 3, alternatively greater than or equal to about 4, alternatively greater than or equal to about 5, alternatively greater than or equal to about 6, alternatively greater than or equal to about 7, alternatively greater than or equal to about 8, alternatively greater than or equal to about 9, alternatively greater than or equal to about 10, alternatively greater than or equal to about 11, alternatively greater than or equal to about 12, alternatively greater than or equal to about 13, alternatively from about 2 to about 13, alternatively from about 5 to about 13, alternatively from about 5 to about 10, or alternatively from about 4 to about 13.

[0084] The third syngas 15C as disclosed herein can be characterized by a 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, or alternatively greater than about 2.1. In some embodiments, the second syngas 15B as disclosed herein can be characterized by a H /CO molar ratio of from about 1.7 to about 2.3, alternatively from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.1.

[0085] In an embodiment, the third syngas 15C can have a C0 content substantially the same as that of the first syngas 15A and/or the second syngas 15B. In an embodiment, the third syngas 15C can have a C0 content of less than about 10 mol%, less than about 9 mol%, less than about 8 mol%, less than about 7 mol%, alternatively less than about 6 mol%, alternatively less than about 5 mol%, alternatively less than about 4 mol%, alternatively less than about 3 mol%, alternatively less than about 2 mol%, alternatively less than about 1 mol%, alternatively greater than about 0.1 mol%, alternatively greater than about 0.25 mol%, alternatively greater than about 0.5 mol%, alternatively from about 0.1 mol% to about 7 mol%, alternatively from about 0.25 mol% to about 6 mol%, or alternatively from about 0.5 mol% to about 5 mol%.

[0086] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of feeding at least a portion of the third syngas 15C to a methanol synthesis reactor or‘methanol reactor’ 40 to produce a methanol reactor effluent stream 45. The methanol reactor effluent stream 45 comprises methanol, water, H , CO, C0 , and hydrocarbons. The methanol synthesis reactor 40 can comprise any reactor suitable for a methanol synthesis reaction from CO and H₂, such as for example a trickle bed reactor, a fluidized bed reactor, a slurry reactor, a loop reactor, a cooled multi tubular reactor, and the like, or combinations thereof.

[0087] Generally, CO and H can be converted into methanol (CH₃OH), for example as represented by equation (2):

CO + ¾ CH₃OH (2)

C0 and H can also be converted to methanol, for example as represented by equation (3):

C0₂ + 3H₂ CH₃OH + H₂0 (3) Without wishing to be limited by theory, the lower the C0 content of the third syngas 15C, the lower the amount of water produced in the methanol reactor 40. As will be appreciated by one of skill in the art, and with the help of this disclosure, syngas produced by SMR has a fairly high content of hydrogen (as compared to the hydrogen content of syngas produced by CPO), and a syngas with an elevated hydrogen content can promote the C0 conversion to methanol, for example as represented by equation (3), which in turn can lead to an increased water content in a crude methanol stream (e.g., crude methanol stream 45).

[0088] Methanol synthesis from CO, C0₂ and H₂ is a catalytic process, and is most often conducted in the presence of copper based catalysts. The methanol synthesis reactor 40 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 40 in the current disclosure include Cu, Cu/ZnO, Cu/Th0 , Cu/Zn/Al 0₃, Cu/Zn0/Al 0₃, Cu/Zr, and the like, or combinations thereof.

[0089] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of compressing at least a portion of the third syngas 15C in a compressor 30 to yield a third compressed syngas 15C, and at least a portion of the third compressed syngas 15C is fed to the methanol reactor 40. In embodiments, the compressor 30 is a steam-driven compressor, and at least a portion of the first residual gas stream 25A and/or at least a portion of the second residual gas stream 25B (described further hereinbelow) is used as fuel to generate steam for powering the steam-driven compressor.

[0090] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of introducing at least a portion of the methanol reactor effluent stream 45 to a separator 50 to produce a crude methanol stream 55 and a vapor stream 56, wherein the crude methanol stream 55 comprises methanol and water, and wherein the vapor stream 56 comprises H , CO, C0 , and hydrocarbons. The methanol reactor effluent stream 45 can be separated into the crude methanol stream 55 and the vapor stream 56 in the gas-liquid separator 50, such as a vapor-liquid separator, flash drum, knock-out drum, knock-out pot, compressor suction drum, etc.

[0091] 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 55 in a distillation unit 60 into a methanol stream 65 and a water stream 66. The distillation unit 60 can comprise one or more distillation columns. The water stream 66 comprises water and residual methanol. Generally, the one or more distillation columns can separate components of the crude methanol stream 55 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 55, the more distillation columns are necessary to purify the methanol.

[0092] In an embodiment, the methanol stream 65 can comprise methanol in an amount of greater than or equal to about 95 wt.%, alternatively greater than or equal to about 97.5 wt.%, alternatively greater than or equal to about 99 wt.%, or alternatively greater than or equal to about 99.9 wt.%, based on the total weight of the methanol stream 65. [0093] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of introducing a first portion 56' of the vapor stream 56 to a second hydrogen recovery unit 20B to produce a second hydrogen stream 16B (that comprises at least a portion of the hydrogen of the first portion 56' of vapor stream 56) and a second residual gas stream 25B, wherein the second residual gas stream 25B comprises CO, C0 , hydrocarbons, and optionally H . In embodiments, the second hydrogen stream 16B comprises from about 70 mol% to about 95 mol%, from about 75 mol% to about 95 mol%, from about 70 mol% to about 90 mol%, or greater than or equal to about 40, 50, or 60 mol% of the ¾ of the first portion 56' of the vapor stream 56. In embodiments, the second hydrogen stream 16B comprises a hydrogen purity of greater than or equal to about 60, 65, or 70 mol% H . In some embodiments, at least a portion of the second residual gas stream 25B can be purged. In other embodiments, at least a portion of the second residual gas stream 25B can be used as fuel, for example to generate steam for powering the steam-driven compressor 30.

[0094] In embodiments, at least a portion of the second hydrogen stream 16B is combined with the second syngas 15B (e.g., via fourth hydrogen stream 16D) to provide the third syngas stream 15C. Second hydrogen recovery unit 20B can be as described hereinabove for first hydrogen recovery unit 20A. For example, second hydrogen recovery unit 20B can comprise a PSA unit, a membrane separation unit, a cryogenic separation unit, and the like, or combinations thereof. In embodiments, the first portion 56' of the vapor stream 56 is from about 3 mol% to about 20 mol%, from about 7 mol% to about 17 mol%, or from about 5 mol% to about 20 mol% of the vapor stream 56.

[0095] In an embodiment, a process for producing methanol as disclosed herein can comprise a step of recycling a second portion 56" of the vapor stream 56 to the methanol reactor 40, for example via combination with compressed third syngas stream 15C. In embodiments, the second portion 56" of the vapor stream 56 is from about 80 mol% to about 97 mol%, from about 83 mol% to about 93 mol%, or from about 80 mol% to about 95 mol% of the vapor stream 56.

[0096] In embodiments, a process for producing methanol as disclosed herein can advantageously display improvements in one or more process characteristics when compared to conventional processes. In embodiments, a carbon efficiency is increased and/or an inert concentration within the methanol synthesis loop is decreased relative to a process absent the first hydrogen recovery unit 20A.

[0097] 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 utilizing CPO syngas as disclosed herein can advantageously generate less C0 through fuel burning, when compared to steam reforming.

[0098] Additional advantages of the processes for the production methanol as disclosed herein can be apparent to one of skill in the art viewing this disclosure. EXAMPLES

[0099] The embodiments having been generally described, the following examples are given as particular embodiments of the disclosure and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims in any manner.

[00100] Example 1: Table 1 shows the results for a standalone CPO process I, according to this disclosure, utilizing two PSA units for hydrogen recovery, including a first hydrogen recovery unit 20A prior to the methanol loop, and a second hydrogen recovery unit 20B within the methanol loop for recovering hydrogen from the purge/vapor stream 56.

[00101]

[00102] To optimize overall carbon efficiency of the standalone CPO process a syngas slip stream (e.g., first portion 15A' of first syngas 15A comprising a fraction of the total syngas (e.g., first syngas 15A) produced from CPO reactor 10) produced from the standalone CPO reactor 10 of 14 mole percent is sent to a PSA unit (e.g., to first hydrogen removal unit 20A) where hydrogen (e.g., first hydrogen stream 16A) is recovered and mixed with the remaining syngas (e.g., with second portion 15A" of first syngas 15 A). The unrecovered first residual gas stream 25A comprising CO, C0₂, H₂, and CH₄ can be used as fuel to generate process steam requirements. A PSA unit (e.g., second hydrogen recovery unit 20B) is also utilized to recover hydrogen from the methanol loop purge stream (e.g., first portion 56' of vapor stream 56). In this example, the purge quantity has been optimized, in order to achieve the required syngas composition within the methanol synthesis loop.

[00103] The makeup syngas composition or M value of 2.19 (e.g., of second syngas 15B) and an M value of methanol loop syngas of 5.3 (e.g., of third syngas 15C) were achieved. The volumetric flowrate of the slip stream (e.g., first portion 15 A' of first syngas 15 A) prior to the loop and the flowrate of the purge stream (e.g., first portion 56' of vapor stream 56) were both optimized to increase carbon efficiency and reduce byproduct formation. It is noted that the relationship between the volumetric flowrate of the slip stream prior to the loop (e.g., first portion 15 A' of first syngas 15 A), the purge stream flowrate (e.g., of first portion 56' of vapor stream 56), and the impact on the overall carbon efficiency is not linear. For example, increasing the volumetric flowrate of the slip stream sent to the PSA for hydrogen recovery loop (e.g., first portion 15 A' of first syngas 15 A) does not have the same impact on the overall system carbon efficiency as increasing the volumetric flowrate of the purge stream (e.g., of first portion 56' of vapor stream 56) by the same quantity. This is due to the difference in composition of the syngas slip stream (e.g., first portion 15A' of first syngas 15 A) prior to the loop and the recycle syngas stream (purge, e.g., first portion 56' of vapor stream 56) within the methanol loop. Tables 2 and 3 provide the absolute and normalized compositions of the syngas slipstream prior to the loop (e.g., first portion 15 A' of first syngas 15 A) and of the purge stream (e.g., of first portion 56' of vapor stream 56) for this Example.

[00104]

[00105]

[00106] Based on the results depicted above, it is apparent that it may be desirable to purge just enough syngas (e.g., via first portion 56' of vapor stream 56) to reduce inert build up in the methanol loop. Implementing a hydrogen recovery unit such as a membrane or PSA to recover hydrogen from the purge stream is efficient and will reduce the slip stream volumetric flowrate requirement. Moreover, the slip stream to the PSA or membrane for hydrogen recovery can be optimized to achieve the composition of third syngas 15C required for efficient methanol production while achieving good carbon efficiency.

[00107] The syngas M value impacts by-product formation. The by-product is represented by ethanol in the modeling studies. Figure 2 is a schematic of ethanol production as a function of methanol loop syngas M Value (e.g., M value of third syngas 15C) for various slip values (e.g., ratios of flow rate of first portion 15 A' to first syngas 15 A). Figure 2 illustrates the impact the syngas M value has on ethanol formation.

[00108] As illustrated in Figure 2, the M value of the third syngas 15C sent to the methanol reactor 40 is directly related to ethanol formation. Ethanol formation is unwanted due to increasing the energy requirement of distillation, and reducing the carbon efficiency of methanol formation. Conventional methanol plants that utilize only SMR have a high M value (e.g., greater than 10) in the methanol loop and therefore produce minimal ethanol. Fiowever, these methanol plants are not energy efficient due to the endothermcity of the SMR. The replacement of SMR with CR, or standalone CPO, or ATR will improve the energy efficiency of the methanol production plant, but will lower the methanol loop M value to below 10. These simulations show that the optimal operation of the methanol loop will change depending on the loop M value. With M-values between 5 and 10 plus, the ethanol formation decreases with increasing M value for a given slip stream (e.g., fraction of the first syngas 15A produced from CPO reactor 10 sent to PSA unit (e.g., first hydrogen recovery unit 20A) for hydrogen recovery). Fiowever, the trend unexpectedly reverses when the M value is lower than 5. As depicted by the slip values below about 0.12, an increase in M value results in higher ethanol formation instead of reducing it. The loop M value depends on the M value of the makeup syngas (e.g., second syngas 15B) and the M value of the recycle syngas (e.g., third syngas 15C) in the loop.

[00109] In this example, the carbon efficiency of the plant was found to be 70%. This is competitive when compared to standalone SMR methanol production plants. Consequently, the herein disclosed standalone CPO system and process for producing syngas for methanol synthesis can be utilized to retrofit an existing inefficient methanol production plant, or to develop a new methanol synthesis plant.

[00110] While various embodiments have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the disclosure. The embodiments described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the subject matter disclosed herein are possible and are within the scope of the disclosure. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, whenever a numerical range with a lower limit, R_L and an upper limit, R_w is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=R_L+k*(Ru-R_L), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, ... 50 percent, 51 percent, 52 percent, ... , 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. Moreover, any numerical range defined by two R numbers as defined in the above is also specifically disclosed. Use of the term "optionally" with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, etc.

[00111] 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 disclosure. Thus, the claims are a further description and are an addition to the embodiments of the present disclosure. The discussion of a reference is not an admission that it is prior art to the present disclosure, especially any reference that may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural, or other details supplementary to those set forth herein.

ADDITIONAL DESCRIPTION

[00112] The particular embodiments disclosed above are illustrative only, as the present disclosure may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present disclosure. Alternative embodiments that result from combining, integrating, and/or omitting features of the embodiment(s) are also within the scope of the disclosure. While compositions and methods are described in broader terms of "having”,“comprising," "containing," or "including" various components or steps, the compositions and methods can also "consist essentially of’ or "consist of’ the various components and steps. Use of the term“optionally” with respect to any element of a claim means that the element is required, or alternatively, the element is not required, both alternatives being within the scope of the claim.

[00113] Numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range are specifically disclosed. In particular, every range of values (of the form, "from about a to about b," or, equivalently, "from approximately a to b," or, equivalently, "from approximately a-b") disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Moreover, the indefinite articles "a" or "an", as used in the claims, are defined herein to mean one or more than one of the element that it introduces. If there is any conflict in the usages of a word or term in this specification and one or more patent or other documents, the definitions that are consistent with this specification should be adopted.

[00114] Embodiments disclosed herein include:

[00115] A: A process for producing methanol comprising: (a) feeding a catalytic partial oxidation (CPO) reactant mixture to a CPO reactor; wherein the CPO reactant mixture comprises hydrocarbons, oxygen, and optionally steam; wherein at least a portion of the CPO reactant mixture reacts, via a CPO reaction, in the CPO reactor to produce a first syngas; wherein the CPO reactor comprises a CPO catalyst; wherein the first syngas comprises hydrogen (¾), carbon monoxide (CO), carbon dioxide (C0₂), and hydrocarbons, and wherein the first syngas is characterized by an M ratio of the first syngas, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂); (b) introducing a first portion of the first syngas to a first hydrogen recovery unit to produce a first hydrogen stream and a first residual gas stream, wherein the first residual gas stream comprises CO, C0₂, hydrocarbons, and optionally H₂; (c) contacting at least a portion of the first hydrogen stream with a second portion of the first syngas to yield a second syngas, wherein the second syngas comprises H₂, CO, C0₂, and hydrocarbons, wherein the second syngas is characterized by an M ratio of the second syngas, and wherein the M ratio of the second syngas is greater than the M ratio of the first syngas; (d) contacting at least a portion of the second syngas with a hydrogen stream to yield a third syngas, wherein the third syngas comprises H₂, CO, C0₂, and hydrocarbons, wherein the third syngas is characterized by an M ratio of the third syngas, and wherein the M ratio of the third syngas is greater than the M ratio of the second syngas; (e) feeding at least a portion of the third syngas to a methanol reactor to produce a methanol reactor effluent stream; wherein the methanol reactor effluent stream comprises methanol, water, H₂, CO, C0₂, and hydrocarbons; (1) introducing at least a portion of the methanol reactor effluent stream to a separator to produce a crude methanol stream and a vapor stream; wherein the crude methanol stream comprises methanol and water; wherein the vapor stream comprises H₂, CO, C0₂, and hydrocarbons; (g) introducing a first portion of the vapor stream to a second hydrogen recovery unit to produce a second hydrogen stream and a second residual gas stream, wherein the second residual gas stream comprises CO, C0₂, hydrocarbons, and optionally H₂, and wherein at least a portion of the second hydrogen stream is contacted with the second syngas in step (d); and (h) recycling a second portion of the vapor stream to the methanol reactor.

[00116] B: A process for producing methanol comprising: (a) feeding a catalytic partial oxidation (CPO) reactant mixture to a CPO reactor; wherein the CPO reactant mixture comprises hydrocarbons, oxygen, and optionally steam; wherein at least a portion of the CPO reactant mixture reacts, via a CPO reaction, in the CPO reactor to produce a first syngas; wherein the CPO reactor comprises a CPO catalyst; wherein the first syngas comprises hydrogen (¾), carbon monoxide (CO), carbon dioxide (C0₂), and hydrocarbons, and wherein the first syngas is characterized by an M ratio of the first syngas, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂); (b) introducing a first portion of the first syngas to a first hydrogen recovery unit to produce a first hydrogen stream and a first residual gas stream, wherein the first residual gas stream comprises CO, C0₂, hydrocarbons, and optionally H₂; and wherein the first portion of the first syngas is from about 10 mol% to about 25 mol% of the first syngas; (c) contacting at least a portion of the first hydrogen stream with a second portion of the first syngas to yield a second syngas, wherein the second syngas comprises H₂, CO, C0₂, and hydrocarbons, wherein the second syngas is characterized by an M ratio of the second syngas, wherein the M ratio of the second syngas is greater than the M ratio of the first syngas, and wherein the second portion of the first syngas is from about 75 mol% to about 90 mol% of the first syngas; (d) contacting at least a portion of the second syngas with a hydrogen stream to yield a third syngas, wherein the third syngas comprises H₂, CO, C0₂, and hydrocarbons, wherein the third syngas is characterized by an M ratio of the third syngas, and wherein the M ratio of the third syngas is greater than the M ratio of the second syngas; (e) optionally compressing at least a portion of the third syngas in a steam-driven compressor to yield a third compressed syngas; (f) feeding at least a portion of the third syngas and/or at least a portion of the third compressed syngas to a methanol reactor to produce a methanol reactor effluent stream; wherein the methanol reactor effluent stream comprises methanol, water, H₂, CO, C0₂, and hydrocarbons; (g) introducing at least a portion of the methanol reactor effluent stream to a gas-liquid separator to produce a crude methanol stream and a vapor stream; wherein the crude methanol stream comprises methanol and water; wherein the vapor stream comprises H₂, CO, C0₂, and hydrocarbons; (h) introducing a first portion of the vapor stream to a second hydrogen recovery unit to produce a second hydrogen stream and a second residual gas stream, wherein the second residual gas stream comprises CO, C0₂, hydrocarbons, and optionally H₂, wherein the first portion of the vapor stream is from about 7 mol% to about 17 mol% of the vapor stream, and wherein at least a portion of the second hydrogen stream is contacted with the second syngas in step (d); (i) recycling a second portion of the vapor stream to the methanol reactor, wherein the second portion of the vapor stream is from about 83 mol% to about 93 mol% of the vapor stream; and (j) separating at least a portion of the crude methanol stream in a distillation unit into a methanol stream and a water stream.

[00117] C: A system for producing methanol, the system comprising: (a) a catalytic partial oxidation CPO reactor comprising a CPO catalyst and operable to produce a first syngas from a CPO reactant mixture comprising hydrocarbons, oxygen, and optionally steam via a CPO reaction whereby at least a portion of the CPO reactant mixture reacts in the CPO reactor to produce the first syngas, wherein the first syngas comprises hydrogen (¾), carbon monoxide (CO), carbon dioxide (C0 ), and hydrocarbons, and wherein the first syngas is characterized by an M ratio of the first syngas, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂); (b) a first hydrogen recovery unit operable to produce a first hydrogen stream and a first residual gas stream from a first portion of the first syngas, wherein the first residual gas stream comprises CO, C0 , hydrocarbons, and optionally H ; (c) a methanol synthesis reactor operable to produce a methanol reactor effluent stream from at least a portion of a methanol synthesis reactor feed comprising at least a portion of the first hydrogen stream, a second portion of the first syngas, and at least a portion of a recycle vapor stream; wherein the methanol reactor effluent stream comprises methanol, water, H₂, CO, C0₂, and hydrocarbons; (d) a separator fluidly connected with the methanol synthesis reactor and operable to produce a crude methanol stream and a vapor stream from at least a portion of the methanol reactor effluent stream; wherein the crude methanol stream comprises methanol and water; and wherein the vapor stream comprises H , CO, C0 , and hydrocarbons; and (e) a recycle line operable to introduce a portion of the vapor stream to the methanol synthesis reactor as the recycle vapor stream of the methanol synthesis reactor feed.

[00118] D: A system for producing methanol, the system comprising: (a) a catalytic partial oxidation CPO reactor comprising a CPO catalyst and operable to produce a first syngas from a CPO reactant mixture comprising hydrocarbons, oxygen, and optionally steam via a CPO reaction whereby at least a portion of the CPO reactant mixture reacts in the CPO reactor to produce the first syngas, wherein the first syngas comprises hydrogen (H ), carbon monoxide (CO), carbon dioxide (C0 ), and hydrocarbons, and wherein the first syngas is characterized by an M ratio of the first syngas, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 ); (b) a first hydrogen recovery unit operable to produce a first hydrogen stream and a first residual gas stream from a first portion of the first syngas, wherein the first residual gas stream comprises CO, C0 , hydrocarbons, and optionally H ; (c) a line configured for combining at least a portion of the first hydrogen stream with a second portion of the first syngas to yield a second syngas, wherein the second syngas comprises H , CO, C0 , and hydrocarbons, wherein the second syngas is characterized by an M ratio of the second syngas, and wherein the M ratio of the second syngas is greater than the M ratio of the first syngas; (d) a line configured for carrying a third syngas comprising a combination of at least a portion of the second syngas and a hydrogen stream, wherein the third syngas comprises H , CO, C0 , and hydrocarbons, wherein the third syngas is characterized by an M ratio of the third syngas, and wherein the M ratio of the third syngas is greater than the M ratio of the second syngas and is in a range of from about 5 to 10; (e) a methanol synthesis reactor fluidly connected with the line configured for carrying the third syngas and operable to produce a methanol reactor effluent stream from at least a portion of the third syngas; wherein the methanol reactor effluent stream comprises methanol, water, H , CO, C0 , and hydrocarbons; (f) a separator fluidly connected with the methanol synthesis reactor and operable to produce a crude methanol stream and a vapor stream from at least a portion of the methanol reactor effluent stream; wherein the crude methanol stream comprises methanol and water; and wherein the vapor stream comprises H , CO, C0 , and hydrocarbons; (g) a second hydrogen recovery unit fluidly connected with the separator and operable to produce a second hydrogen stream and a second residual gas stream from a portion of the vapor stream, wherein the second residual gas stream comprises CO, C0 , hydrocarbons, and optionally ¾; (h) a line fluidly connecting the second hydrogen recovery unit and the line configured for carrying the third syngas, whereby the hydrogen stream of the third syngas comprises at least a portion of the second hydrogen stream; and (i) a recycle line operable to introduce another portion of the vapor stream to the methanol synthesis reactor via the line configured for carrying the third syngas stream.

[00119] Each of embodiments A, B, C, and D may have one or more of the following additional elements: Element 1 : wherein the first portion of the first syngas is from about 1 mol% to about 25 mol% of the first syngas; and wherein the second portion of the first syngas is from about 75 mol% to about 99 mol% of the first syngas. Element 2: wherein the first portion of the vapor stream is from about 3 mol% to about 20 mol% of the vapor stream; and wherein the second portion of the vapor stream is from about 80 mol% to about 97 mol% of the vapor stream. Element 3: further comprising after step (a) and before step (b) recovering a CPO reactor effluent from the CPO reactor, wherein the CPO reactor effluent comprises H₂, CO, C0₂, water, and hydrocarbons; and removing at least a portion of the water from the CPO reactor effluent to produce the first syngas. Element 4: wherein at least a portion of the third syngas is compressed in a compressor to yield a third compressed syngas; and wherein at least a portion of the third compressed syngas is fed to the methanol reactor in step (e). Element 5: wherein the compressor is a steam-driven compressor, and wherein at least a portion of the first residual gas stream and/or at least a portion of the second residual gas stream is used as fuel to generate steam for powering the steam-driven compressor. Element 6: wherein the M ratio of the first syngas is from about 1.5 to about 1.95; and wherein the first syngas comprises less than about 10 mol% C0 . Element 7: wherein the M ratio of the second syngas is from about 1.7 to about 2.2. Element 8: wherein the M ratio of the third syngas is from about 2 to about 13. Element 9: wherein the first hydrogen stream comprises equal to or greater than about 50 mol% of the El of the first portion of the first syngas. Element 10: wherein the second hydrogen stream comprises equal to or greater than about 50 mol% of the I¾ of the first portion of the vapor stream. Element 11 : wherein the first hydrogen stream and/or the second hydrogen stream comprise equal to or greater than about 65 mol% I¾. Element 12: wherein each of the first hydrogen recovery unit and the second hydrogen recovery unit can independently comprise a pressure swing adsorption (PSA) unit, a membrane separation unit, a cryogenic separation unit, or combinations thereof. Element 13: wherein the CPO reactor is characterized by at least one CPO operational parameter selected from the group consisting of a CPO inlet temperature of from about 150 °C to about 520 °C; a CPO outlet temperature of from about 600 °C to about 1,400 °C; a CPO pressure of from about 2 barg to about 30 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture of from about 1.5:1 to about 2.2:1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0 ) in the reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.2:1 to about 1.5:1, wherein the S/C molar ratio refers to the total moles of water (I¾0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof. Element 14: wherein the hydrocarbons comprise methane, natural gas, natural gas liquids, liquefied petroleum gas (LPG), associated gas, well head gas, enriched gas, paraffins, shale gas, shale liquids, fluid catalytic cracking (FCC) off gas, refinery process gases, refinery off gases, stack gases, fuel gas from a fuel gas header, or combinations thereof. Element 15: further comprising separating at least a portion of the crude methanol stream in a distillation unit into a methanol stream and a water stream, wherein the distillation unit comprises one or more distillation columns. Element 16: wherein (1) the first hydrogen stream comprises from about 70 mol% to about 95 mol% of the Ef of the first portion of the first syngas, and/or (2) the second hydrogen stream comprises from about 70 mol% to about 95 mol% of the Ef of the first portion of the vapor stream; wherein the M ratio of the first syngas is from about 1.5 to about 1.95; wherein the first syngas comprises less than about 7 mol% C0 ; wherein the M ratio of the second syngas is from about 1.7 to about 2.2; and wherein the M ratio of the third syngas is from about 2 to about 13. Element 17: wherein at least a portion of the first residual gas stream and/or at least a portion of the second residual gas stream is used as fuel to generate steam for powering the steam-driven compressor. Element 18: wherein the CPO reactor is characterized by at least one CPO operational parameter selected from the group consisting of a CPO inlet temperature of from about 200 °C to about 400 °C; a CPO outlet temperature of from about 800 °C to about 1,100 °C; a CPO pressure of from about 10 barg to about 25 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture of from about 1.5:1 to about 1.9:1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0₂) in the reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.2:1 to about 0.6:1, wherein the S/C molar ratio refers to the total moles of water (H 0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof. Element 19: further comprising: (f) a second hydrogen recovery unit fluidly connected with the separator and operable to produce a second hydrogen stream and a second residual gas stream from another portion of the vapor stream, wherein the second residual gas stream comprises CO, C0 , hydrocarbons, and optionally El ; and (g) a line fluidly connecting the second hydrogen recovery unit with the methanol synthesis reactor, whereby at least a portion of the second hydrogen stream can be introduced into the methanol synthesis reactor as a further component of the methanol synthesis reactor feed. Element 20: wherein the first portion of the first syngas is from about 1 mol% to about 25 mol% of the first syngas; and wherein the second portion of the first syngas is from about 75 mol% to about 99 mol% of the first syngas. Element 21 : (i) wherein the portion of the vapor stream is from about 3 mol% to about 20 mol% of the vapor stream, (ii) wherein the another portion of the vapor stream is from about 80 mol% to about 97 mol% of the vapor stream, or (iii) both (i) and (ii).

[00120] 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. [00121] 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.

Claims

CLAIMS What is claimed is:

1. A process for producing methanol comprising:

(a) feeding a catalytic partial oxidation (CPO) reactant mixture to a CPO reactor; wherein the CPO reactant mixture comprises hydrocarbons, oxygen, and optionally steam; wherein at least a portion of the CPO reactant mixture reacts, via a CPO reaction, in the CPO reactor to produce a first syngas; wherein the CPO reactor comprises a CPO catalyst; wherein the first syngas comprises hydrogen (¾), carbon monoxide (CO), carbon dioxide (C0₂), and hydrocarbons, and wherein the first syngas is characterized by an M ratio of the first syngas, wherein the M ratio is a molar ratio defined as (H₂-ϋ0₂)/(ϋ0+ϋ0₂);

(b) introducing a first portion of the first syngas to a first hydrogen recovery unit to produce a first hydrogen stream and a first residual gas stream, wherein the first residual gas stream comprises CO, C0₂, hydrocarbons, and optionally H₂;

(c) contacting at least a portion of the first hydrogen stream with a second portion of the first syngas to yield a second syngas, wherein the second syngas comprises H₂, CO, C0₂, and hydrocarbons, wherein the second syngas is characterized by an M ratio of the second syngas, and wherein the M ratio of the second syngas is greater than the M ratio of the first syngas;

(d) contacting at least a portion of the second syngas with a hydrogen stream to yield a third syngas, wherein the third syngas comprises H₂, CO, C0₂, and hydrocarbons, wherein the third syngas is characterized by an M ratio of the third syngas, and wherein the M ratio of the third syngas is greater than the M ratio of the second syngas;

(e) feeding at least a portion of the third syngas to a methanol reactor to produce a methanol reactor effluent stream; wherein the methanol reactor effluent stream comprises methanol, water, H₂, CO, C0₂, and hydrocarbons;

(f) introducing at least a portion of the methanol reactor effluent stream to a separator to produce a crude methanol stream and a vapor stream; wherein the crude methanol stream comprises methanol and water; wherein the vapor stream comprises H₂, CO, C0₂, and hydrocarbons;

(g) introducing a first portion of the vapor stream to a second hydrogen recovery unit to produce a second hydrogen stream and a second residual gas stream, wherein the second residual gas stream comprises CO, C0₂, hydrocarbons, and optionally H₂, and wherein at least a portion of the second hydrogen stream is contacted with the second syngas in step (d); and

(h) recycling a second portion of the vapor stream to the methanol reactor.

2. The process of claim 1, wherein the first portion of the first syngas is from about 1 mol% to about 25 mol% of the first syngas; and wherein the second portion of the first syngas is from about 75 mol% to about 99 mol% of the first syngas.

3. The process of claim 1, wherein the first portion of the vapor stream is from about 3 mol% to about 20 mol% of the vapor stream; and wherein the second portion of the vapor stream is from about 80 mol% to about 97 mol% of the vapor stream.

4. The process of claim 1 further comprising after step (a) and before step (b) recovering a CPO reactor effluent from the CPO reactor, wherein the CPO reactor effluent comprises H , CO, C0 , water, and hydrocarbons; and removing at least a portion of the water from the CPO reactor effluent to produce the first syngas.

5. The process of claims 1, wherein at least a portion of the third syngas is compressed in a compressor to yield a third compressed syngas; and wherein at least a portion of the third compressed syngas is fed to the methanol reactor in step (e).

6. The process of claim 5, wherein the compressor is a steam-driven compressor, and wherein at least a portion of the first residual gas stream and/or at least a portion of the second residual gas stream is used as fuel to generate steam for powering the steam-driven compressor.

7. The process of claim 1, wherein the M ratio of the first syngas is from about 1.5 to about 1.95; wherein the first syngas comprises less than about 10 mol% C0₂; wherein the M ratio of the second syngas is from about 1.7 to about 2.2; wherein the M ratio of the third syngas is from about 2 to about 13, or a combination thereof.

8. The process of claim 1, wherein the first hydrogen stream comprises equal to or greater than about 50 mol% of the H₂ of the first portion of the first syngas.

9. The process of claim 1, wherein the second hydrogen stream comprises greater than or equal to about 50 mol% of the H of the first portion of the vapor stream; wherein the first hydrogen stream and/or the second hydrogen stream comprise greater than or equal to about 65 mol% H _; or a combination thereof.

10. The process of claim 1, wherein each of the first hydrogen recovery unit and the second hydrogen recovery unit can independently comprise a pressure swing adsorption (PSA) unit, a membrane separation unit, a cryogenic separation unit, or combinations thereof.

11. The process of claim 1 , wherein the CPO reactor is characterized by at least one CPO operational parameter selected from the group consisting of a CPO inlet temperature of from about 150 °C to about 520 °C; a CPO outlet temperature of from about 600 °C to about 1,400 °C; a CPO pressure of from about 2 barg to about 30 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture of from about 1.5:1 to about 2.2:1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0 ) in the reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.2:1 to about 1.5:1, wherein the S/C molar ratio refers to the total moles of water (H 0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof.

12. The process of claim 1, wherein the hydrocarbons comprise methane, natural gas, natural gas liquids, liquefied petroleum gas (LPG), associated gas, well head gas, enriched gas, paraffins, shale gas, shale liquids, fluid catalytic cracking (FCC) off gas, refinery process gases, refinery off gases, stack gases, fuel gas from a fuel gas header, or combinations thereof.

13. A process for producing methanol comprising:

(a) feeding a catalytic partial oxidation (CPO) reactant mixture to a CPO reactor; wherein the CPO reactant mixture comprises hydrocarbons, oxygen, and optionally steam; wherein at least a portion of the CPO reactant mixture reacts, via a CPO reaction, in the CPO reactor to produce a first syngas; wherein the CPO reactor comprises a CPO catalyst; wherein the first syngas comprises hydrogen (¾), carbon monoxide (CO), carbon dioxide (C0₂), and hydrocarbons, and wherein the first syngas is characterized by an M ratio of the first syngas, wherein the M ratio is a molar ratio defined as (H₂-C0₂)/(C0+C0₂);

(b) introducing a first portion of the first syngas to a first hydrogen recovery unit to produce a first hydrogen stream and a first residual gas stream, wherein the first residual gas stream comprises CO, C0₂, hydrocarbons, and optionally H₂; and wherein the first portion of the first syngas is from about 10 mol% to about 25 mol% of the first syngas;

(c) contacting at least a portion of the first hydrogen stream with a second portion of the first syngas to yield a second syngas, wherein the second syngas comprises H₂, CO, C0₂, and hydrocarbons, wherein the second syngas is characterized by an M ratio of the second syngas, wherein the M ratio of the second syngas is greater than the M ratio of the first syngas, and wherein the second portion of the first syngas is from about 75 mol% to about 90 mol% of the first syngas;

(e) optionally compressing at least a portion of the third syngas in a steam-driven compressor to yield a third compressed syngas;

(f) feeding at least a portion of the third syngas and/or at least a portion of the third compressed syngas to a methanol reactor to produce a methanol reactor effluent stream; wherein the methanol reactor effluent stream comprises methanol, water, H₂, CO, C0₂, and hydrocarbons;

(g) introducing at least a portion of the methanol reactor effluent stream to a gas-liquid separator to produce a crude methanol stream and a vapor stream; wherein the crude methanol stream comprises methanol and water; wherein the vapor stream comprises H₂, CO, C0₂, and hydrocarbons;

(h) introducing a first portion of the vapor stream to a second hydrogen recovery unit to produce a second hydrogen stream and a second residual gas stream, wherein the second residual gas stream comprises CO, C0₂, hydrocarbons, and optionally H₂, wherein the first portion of the vapor stream is from about 7 mol% to about 17 mol% of the vapor stream, and wherein at least a portion of the second hydrogen stream is contacted with the second syngas in step (d);

(i) recycling a second portion of the vapor stream to the methanol reactor, wherein the second portion of the vapor stream is from about 83 mol% to about 93 mol% of the vapor stream; and

(j) separating at least a portion of the crude methanol stream in a distillation unit into a methanol stream and a water stream.

14. The process of claim 13, wherein (1) the first hydrogen stream comprises from about 70 mol% to about 95 mol% of the ¾ of the first portion of the first syngas, and/or (2) the second hydrogen stream comprises from about 70 mol% to about 95 mol% of the H₂ of the first portion of the vapor stream; wherein the M ratio of the first syngas is from about 1.5 to about 1.95; wherein the first syngas comprises less than about 7 mol% C0 ; wherein the M ratio of the second syngas is from about 1.7 to about 2.2; and wherein the M ratio of the third syngas is from about 2 to about 13.

15. The process of claim 13, wherein the CPO reactor is characterized by at least one CPO operational parameter selected from the group consisting of a CPO inlet temperature of from about 200 °C to about 400 °C; a CPO outlet temperature of from about 800 °C to about 1,100 °C; a CPO pressure of from about 10 barg to about 25 barg; a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the CPO reactant mixture of from about 1.5:1 to about 1.9:1, wherein the C/O molar ratio refers to the total moles of carbon (C) of hydrocarbons in the reactant mixture divided by the total moles of oxygen (0₂) in the reactant mixture; a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.2:1 to about 0.6:1, wherein the S/C molar ratio refers to the total moles of water (H 0) in the reactant mixture divided by the total moles of carbon (C) of hydrocarbons in the reactant mixture; and combinations thereof.

16. A system for producing methanol, the system comprising:

(a) a catalytic partial oxidation CPO reactor comprising a CPO catalyst and operable to produce a first syngas from a CPO reactant mixture comprising hydrocarbons, oxygen, and optionally steam via a CPO reaction whereby at least a portion of the CPO reactant mixture reacts in the CPO reactor to produce the first syngas, wherein the first syngas comprises hydrogen (H ), carbon monoxide (CO), carbon dioxide (C0 ), and hydrocarbons, and wherein the first syngas is characterized by an M ratio of the first syngas, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 );

(b) a first hydrogen recovery unit operable to produce a first hydrogen stream and a first residual gas stream from a first portion of the first syngas, wherein the first residual gas stream comprises CO, C0 , hydrocarbons, and optionally H ;

(c) a methanol synthesis reactor operable to produce a methanol reactor effluent stream from at least a portion of a methanol synthesis reactor feed comprising at least a portion of the first hydrogen stream, a second portion of the first syngas, and at least a portion of a recycle vapor stream; wherein the methanol reactor effluent stream comprises methanol, water, H , CO, C0 , and hydrocarbons; (d) a separator fluidly connected with the methanol synthesis reactor and operable to produce a crude methanol stream and a vapor stream from at least a portion of the methanol reactor effluent stream; wherein the crude methanol stream comprises methanol and water; and wherein the vapor stream comprises H , CO, C0 , and hydrocarbons; and

(e) a recycle line operable to introduce a portion of the vapor stream to the methanol synthesis reactor as the recycle vapor stream of the methanol synthesis reactor feed.

17. The system of claim 16 further comprising:

(f) a second hydrogen recovery unit fluidly connected with the separator and operable to produce a second hydrogen stream and a second residual gas stream from another portion of the vapor stream, wherein the second residual gas stream comprises CO, C0 , hydrocarbons, and optionally H ; and

(g) a line fluidly connecting the second hydrogen recovery unit with the methanol synthesis reactor, whereby at least a portion of the second hydrogen stream can be introduced into the methanol synthesis reactor as a further component of the methanol synthesis reactor feed.

18. A system for producing methanol, the system comprising:

(a) a catalytic partial oxidation CPO reactor comprising a CPO catalyst and operable to produce a first syngas from a CPO reactant mixture comprising hydrocarbons, oxygen, and optionally steam via a CPO reaction whereby at least a portion of the CPO reactant mixture reacts in the CPO reactor to produce the first syngas, wherein the first syngas comprises hydrogen (H ), carbon monoxide (CO), carbon dioxide (C0₂), and hydrocarbons, and wherein the first syngas is characterized by an M ratio of the first syngas, wherein the M ratio is a molar ratio defined as (H -C0 )/(C0+C0 );

(c) a line configured for combining at least a portion of the first hydrogen stream with a second portion of the first syngas to yield a second syngas, wherein the second syngas comprises H , CO, C0 , and hydrocarbons, wherein the second syngas is characterized by an M ratio of the second syngas, and wherein the M ratio of the second syngas is greater than the M ratio of the first syngas;

(d) a line configured for carrying a third syngas comprising a combination of at least a portion of the second syngas and a hydrogen stream, wherein the third syngas comprises H , CO, C0 , and hydrocarbons, wherein the third syngas is characterized by an M ratio of the third syngas, and wherein the M ratio of the third syngas is greater than the M ratio of the second syngas and is in a range of from about 5 to 10;

(e) a methanol synthesis reactor fluidly connected with the line configured for carrying the third syngas and operable to produce a methanol reactor effluent stream from at least a portion of the third syngas; wherein the methanol reactor effluent stream comprises methanol, water, H , CO, C0 , and hydrocarbons;

(f) a separator fluidly connected with the methanol synthesis reactor and operable to produce a crude methanol stream and a vapor stream from at least a portion of the methanol reactor effluent stream; wherein the crude methanol stream comprises methanol and water; and wherein the vapor stream comprises H , CO, C0 , and hydrocarbons;

(g) a second hydrogen recovery unit fluidly connected with the separator and operable to produce a second hydrogen stream and a second residual gas stream from a portion of the vapor stream, wherein the second residual gas stream comprises CO, C0 , hydrocarbons, and optionally H ;

(h) a line fluidly connecting the second hydrogen recovery unit and the line configured for carrying the third syngas, whereby the hydrogen stream of the third syngas comprises at least a portion of the second hydrogen stream; and

(i) a recycle line operable to introduce another portion of the vapor stream to the methanol synthesis reactor via the line configured for carrying the third syngas stream.

19. The system of claim 16, wherein the first portion of the first syngas is from about 1 mol% to about 25 mol% of the first syngas; and wherein the second portion of the first syngas is from about 75 mol% to about 99 mol% of the first syngas.

20. The system of claim 17, wherein the portion of the vapor stream is from about 3 mol% to about 20 mol% of the vapor stream, wherein the another portion of the vapor stream is from about 80 mol% to about 97 mol% of the vapor stream, or both.