EA044126B1 - METHOD OF METHANOL PRODUCTION - Google Patents

Description

Field of technology

The present invention relates to methods for producing methanol, and more particularly to methods for producing methanol from synthesis gas produced by the catalytic partial oxidation of hydrocarbons such as methane.

State of the art

Synthetic gas (syngas) is a mixture containing carbon monoxide (CO) and hydrogen ( _H2 ), as well as small amounts of carbon dioxide (CO2), water (H2O) and unreacted methane ( _CH4 ). Synthesis gas is commonly used as an intermediate in the production of methanol and ammonia, and as an intermediate in the creation of synthetic petroleum for use as a lubricant or fuel.

Syngas is typically produced by steam reforming natural gas (steam methane reforming or SMR), although other hydrocarbon sources such as refinery off-gases, naphtha feedstocks, heavy hydrocarbons, coal, biomass and etc. PRM is an endothermic process and requires significant energy input to promote the reaction. Traditional endothermic technologies, such as PRM, produce synthesis gas with a hydrogen content greater than that required for methanol synthesis. Typically, PRM produces synthesis gas with an M ratio of 2.6 to 2.98, where the M ratio is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ).

In the autothermal reforming (ATR) process, a portion of the natural gas is burned as fuel to convert the natural gas into synthesis gas, resulting in relatively low concentrations of hydrogen and high concentrations of CO2. Conventional methanol plants use combined reforming (CR) technology, which combines ATR with autothermal reforming (ATR) to reduce the amount of hydrogen present in the synthesis gas. ATP produces synthesis gas with a hydrogen content lower than that required for methanol synthesis. Typically, ATP produces synthesis gas with an M ratio of 1.7 to 1.84. In CR technology, the volumetric flow rate of natural gas supplied to the PRM and ATP can be adjusted to achieve an overall synthesis gas M ratio of 2.0 to 2.06. In addition, the KR synthesis gas has a hydrogen content greater than that required for methanol synthesis. Moreover, PRM is a highly endothermic process, and the endothermic nature of PRM technology requires combustion of fuel to promote syngas synthesis. Consequently, the PRM technology reduces the energy efficiency of the methanol synthesis process.

Synthesis gas can also be produced (not industrially) by catalytic partial oxidation (CPO (SRO) or KCHOk (SPOx)) of natural gas. COC processes use partial oxidation of hydrocarbon feedstock to synthesis gas containing CO and H ₂ . The CPO process is exothermic, eliminating the need for external heat input. However, the composition of the produced synthesis gas is not suitable for methanol synthesis, for example due to the reduced hydrogen content.

In addition, in traditional methanol synthesis methods, purification (eg distillation) of the produced methanol requires large amounts of energy. Purification (eg, distillation) during the methanol production process is primarily used to remove water from crude methanol. Traditional methanol synthesis processes use multiple distillation lines to remove water and purify the methanol, making the entire process energy-intensive. Thus, there is a continuing need to develop methanol production processes that can control the composition of the crude methanol produced, for example by controlling the composition of the synthesis gas used to produce the methanol.

Brief description of the drawing

For a detailed description of preferred aspects of the disclosed methods, reference is made to the accompanying drawing.

The drawing shows a system diagram of a method for producing methanol.

Detailed description

Disclosed herein are methods for producing methanol, including a method for producing methanol comprising: (a) reacting, through a catalytic partial oxidation (CPO) reaction, a mixture of CPO reagents in a CPO reactor to produce synthesis gas; where the mixture of CPO reagents contains hydrocarbons and oxygen; where the CPO reactor contains a CPO catalyst; and wherein the synthesis gas contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted hydrocarbons; (b) introducing at least a portion of the synthesis gas into the methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and (c) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; wherein the steam stream contains hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and wherein the crude methanol stream contains water in an amount of less than about 10 wt.% based on the total weight of the crude methanol stream, in which the synthesis gas contains carbon dioxide in an amount of from about 0.1 to 5 mol.%.

Hydrocarbons used to produce synthesis gas may include methane, natural gas, liquefied natural gas, associated gas, wellhead gas, enriched gas, waxes, shale gas,

- 1 044126 shale fluids, fluid catalytic cracking off-gas (FCC), process gases from oil refining, flue gases, fuel gas from a fuel gas header, etc., or combinations thereof.

Except for working examples or other indications, all numbers or expressions referring to quantities of ingredients, reaction conditions, etc., used in the description and claims are to be understood as modified in all cases by the term approximately. The invention discloses different numerical intervals. Because these intervals are continuous, they include every value between the minimum and maximum values. The endpoints of all intervals that list the same characteristic or component can be combined independently to include the specified endpoint. Unless specifically stated otherwise, the various numerical ranges given in this invention are approximate. The endpoints of all intervals that refer to the same component or property include the endpoint and are combined independently. The term greater than 0 to an amount means that the named component is present in an amount greater than 0 and up to and including said higher amount.

The terms a, an and the do not denote a limitation in quantity, but rather denote the presence of at least one of the mentioned elements. As used here, the singular forms a, an, and the include references to the plural.

As used herein, combinations thereof include one or more of the listed elements, optionally together with a similar element that is not listed, for example, includes a combination of one or more named components, optionally with one or more other components not specifically named, which essentially have the same function. As used herein, the term combination includes mixtures, alloys, reaction products, and the like.

Reference in the description to an aspect, another aspect, other aspects, some aspects, and so on means that the particular element (e.g., characteristic, structure, property and/or characteristic) described in connection with the aspect is included in at least the aspect described herein and may or may not be present in other aspects. In addition, it should be understood that the described element(s) can be combined in any suitable manner in various aspects.

As used herein, the terms inhibition, or reduction, or prevention, or elimination, or any variation of these terms include any measurable reduction or complete inhibition to achieve a desired result.

As used herein, the term effective means adequate to achieve the desired, expected or intended result.

As used herein, the terms containing (and any form of content such as contain and includes), having (and any form of having such as have and has), including (and any form of inclusion such as include and includes) or consisting of (and any form of composition such as consist of and consists of) are inclusive and open-ended and do not exclude additional, unlisted elements or method steps.

Unless otherwise specified, technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art.

The compounds are described in the invention using standard nomenclature. For example, any position unsubstituted by any specified group is understood to have its valence filled by a bond or hydrogen atom. A dash (-) that is not between two letters or symbols is used to show the attachment point for a substituent. For example, the CHO group is attached through the carbon atom of the carbonyl group.

As used herein, the terms C _x hydrocarbons and C _x are used interchangeably and refer to any hydrocarbon having x number of carbon atoms (C). For example, both the terms C ₄ hydrocarbons and C ₄ refer to any hydrocarbons having exactly 4 carbon atoms, such as n-butane, isobutane, cyclobutane, 1-butene, 2-butene, isobutylene, butadiene, etc., or their combinations.

As used herein, the term C _x+ hydrocarbons refers to any hydrocarbon having equal to or greater than x number of carbon atoms (C). For example, the term C2 ₊ hydrocarbons refers to any hydrocarbons having 2 or more carbon atoms, such as ethane, ethylene, _C3 , _C4 , _C5 , etc.

With respect to the figure, the figure discloses a methanol production system 1000. The methanol production system 1000 typically includes a catalytic partial oxidation reactor (CPR or CPR) 100; optional steam methane reforming reactor (SMR) 110; optional carbon dioxide (CO ₂ ) separator 150; methanol reactor 200; gas-liquid separator 300; distillation unit 400; and a hydrogen (H ₂ ) recovery unit 500. As will be appreciated by one skilled in the art and with the benefit of this description, the components of the methanol production system shown in the drawing may be in fluid communication with each other (as illustrated by the connecting lines indicating the direction of fluid flow) through any suitable conduits (for example, pipes, streams, etc.).

In one aspect, a method for producing methanol disclosed herein may include the step of reacting by reacting a mixture of reactants of a CPO 10 in a CPO reactor 100 to produce a synthesis gas (eg, the effluent from a CPO reactor 15); where the mixture of reagents KCHO 10 contains hydrocarbons, oxygen and optionally water vapor; where the KChO reactor 100 contains the KChO catalyst; and wherein the synthesis gas contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted hydrocarbons.

Typically, the CPR reaction is based on the partial combustion of fuels such as various hydrocarbons, and in the case of methane, the CPR can be represented by equation (1):

CH ₄ +1/2O ₂ CO + 2H ₂ (1)

Without intending to be bound by any theory, it should be noted that side reactions may occur along with the COC reaction depicted in equation (1); and such side reactions can produce carbon dioxide (CO2) and water (H2O), for example, through the combustion of hydrocarbons, which is an exothermic reaction. As will be appreciated by one skilled in the art and by the use of this description, and without intending to be bound by any theory, the CPO reaction represented by equation (1) can produce synthesis gas with a molar ratio of hydrogen to carbon monoxide (H2/ CO), having a theoretical stoichiometric limit of 2.0. Without intending to be bound by any theory, it should be noted that the theoretical stoichiometric limit of 2.0 for the H2/CO molar ratio means that the CCO reaction represented by equation (1) produces 2 mol H2 for every 1 mol CO, that is, molar ratio of H ₂ /CO (2 mol H ₂ /mol CO) is 2. As will be appreciated by one skilled in the art and from this description, the theoretical stoichiometric limit is 2.0 for the molar ratio of H ₂ /CO in the CPO reaction practically cannot be achieved, since reactants (for example, hydrocarbons, oxygen), as well as products (for example, H ₂ , CO) undergo side reactions under the conditions used for the CPO reaction. As will be appreciated by one skilled in the art and by this description, and without intending to be bound by any theory, in the presence of oxygen, CO and H2 can be oxidized to CO2 and H2O, respectively. The relative amounts (eg composition) of CO, _H2 , _CO2 and _H2O can be further altered by shifting the equilibrium of the water gas shift (WGS) reaction, which will be discussed in more detail later. Side reactions that may occur in the KCHO 100 reactor can have a direct effect on the M ratio of the synthesis gas produced, where the M ratio is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ). In the absence of any side reaction (theoretically), the CPO reaction represented by equation (1) results in synthesis gas with an M ratio of 2.0. However, the presence of side reactions (in practice) reduces _H2 and increases _CO2 , resulting in synthesis gas with an M ratio below 2.0.

Additionally, without intending to be bound by any theory, it should be noted that the CPO reaction shown in equation (1) is an exothermic heterogeneous catalytic reaction (i.e., a moderately exothermic reaction) and it occurs in a single reactor unit (e.g. at one stage of the process in one reaction zone), such as the KChO 100 reactor (as opposed to more than one reactor block, as in the case of traditional synthesis gas production processes, such as combinations of steam methane reforming (SMR) with autothermal reforming (ATR) )). Although it is possible to carry out partial oxidation of hydrocarbons as a homogeneous reaction in the absence of a catalyst, the process of homogeneous partial oxidation of hydrocarbons entails excessive temperatures, long residence times, and excessive coke formation, which greatly reduces the controllability of the partial oxidation reaction and may not produce the desired synthesis gas quality in one reactor unit (for example, at one process stage in one reaction zone).

In addition, without intending to be bound by any theory, it should be noted that the CPO reaction is quite resistant to chemical poisoning, and as such it allows the use of a wide range of hydrocarbon feedstocks, including some sulfur-containing hydrocarbon feedstocks; this can in some cases increase catalyst life and performance. In contrast, traditional ATP processes have more stringent requirements for raw materials, for example, in terms of the content of impurities in the feedstock (for example, the ATP feedstock is subjected to desulfurization), as well as the hydrocarbon composition (for example, CH ₄ -enriched feedstock is predominantly used in the ATP).

In one aspect, hydrocarbons suitable for use in the CSF reaction described herein may include methane (CH ₄ ), natural gas, liquefied natural gas, petroleum field gas, associated gas, rich gas, waxes, shale gas, shale fluids, fluid catalytic cracking (FCC) off-gas, refinery process gases, flue gases, fuel gas from a fuel gas header, etc., or combinations thereof. Hydrocarbons may include any suitable hydrocarbon source and may include C ₁ -C ₆ hydrocarbons as well as some heavier hydrocarbons.

In one aspect, the reactant mixture CCO 10 may comprise natural gas. Typically, natural gas consists predominantly of methane, but may also contain ethane, propane and heavier hydrocarbons (for example, isobutane, n-butane, isopentane, n-pentane, hexanes, etc.), as well as very small

- 3 044126 amounts of nitrogen, oxygen, carbon dioxide, sulfur compounds and/or water. Natural gas may be provided from a number of sources, including, but not limited to, gas fields, oil fields, coal fields, hydraulic fracturing fields, biomass, landfill gas, and the like, or combinations thereof. In some aspects, the mixture of reagents

KCHO 10 may contain CH ₄ and O2.

Natural gas may contain any suitable amount of methane. In some aspects, natural gas may contain biogas. For example, natural gas may contain about 45 to 80 mole% methane, about 20 to 55 mole% carbon dioxide, and about 15 mole% nitrogen.

In one aspect, the natural gas may contain CH4 in an amount equal to or greater than about 45 mole%, or equal to or greater than about 50 mole%, or equal to or greater than about 55 mole%, or equal to or greater than about 60 mol.%, or equal to or greater than about 65 mol.%, or equal to or greater than about 70 mol.%, or equal to or greater than about 75 mol.%, or equal to or greater than about 80 mol.%, or equal to or greater than about 82 mol.%, or equal to or greater than about 84 mol.%, or equal to or greater than about 86 mol.%, or equal to or greater than about 88 mol.%. %, or equal to or greater than about 90 mol.%, or equal to or greater than about 91 mol.%, or equal to or greater than about 92 mol.%, or equal to or greater than about 93 mol.%, or equal to or greater than about 94 mol.%, or equal to or greater than about 95 mol.%, or equal to or greater than about 96 mol.%, or equal to or greater than about 97 mol.%, or equal to or greater than about 98 mol.%, or equal to or greater than about 99 mol.%.

In some aspects, hydrocarbons suitable for use in the CPO reaction described herein may contain C ₁ -C ₆ hydrocarbons, nitrogen (for example, from about 0.1 to 15 mol.%, or from about 0.5 to 11 mol.%, or about 1 to 7.5 mol.%, or about 1.3 to 5.5 mol.%), and carbon dioxide (for example, about 0.1 to 2 mol.% , or about 0.2 to 1 mol.%, or about 0.3 to 0.6 mol.%). For example, hydrocarbons suitable for use in the CPO reaction described herein may contain C1 hydrocarbon (about 89 to 92 mol%); C ₂ hydrocarbons (approximately 2.5 to 4 mol%); C3 hydrocarbons (about 0.5 to 1.4 mol%); C ₄ hydrocarbons (about 0.5 to 0.2 mol%); C ₅ hydrocarbons (approximately 0.06 mol%); and C6 hydrocarbons (approximately 0.02 mol%); and optionally nitrogen (about 0.1 to 15 mol.%), carbon dioxide (about 0.1 to 2 mol.%), or both nitrogen (about 0.1 to 15 mol.%) and carbon dioxide ( approximately 0.1 to 2 mol.%).

The oxygen used in the KCHO 10 reagent mixture may contain 100% oxygen (essentially pure O2), oxygen gas (which can be obtained through a membrane separation process), technical oxygen (which may contain some air), oxygen-enriched air, oxygen-containing gaseous compounds (for example, NO), oxygen-containing mixtures (for example, O ₂ /CO ₂ , O ₂ /H ₂ O, O ₂ /H ₂ O ₂ /H ₂ O), oxy-radical generators (for example, CH ₃ OH , CH2O), hydroxyl radical generators, etc., or combinations thereof.

In one aspect, the CCO reactant mixture 10 may have a carbon to oxygen (C/O) molar ratio of less than about 3:1, or less than about 2.6:1, or less than about 2.4:1, or less than about 2.2:1, or less than about 2:1, or less than about 1.9:1, or equal to or greater than about 2:1, or equal to or greater than about 2.2 :1, or equal to or greater than about 2.4:1, or equal to or greater than about 2.6:1, or from about 0.5:1 to 3:1, or from about 0.7:1 to 2.5:1, or from about 0.9:1 to 2.2:1, or from about 1:1 to 2:1, or from about 1.1:1 to 1.9:1 , or about 2:1 to 3:1, or about 2.2:1 to 3:1, or about 2.4:1 to 3:1, or about 2.6:1 to 3:1, where the C/O molar ratio refers to all moles of carbon (C) hydrocarbons in the reactant mixture divided by all moles of oxygen (O ₂ ) in the reactant mixture.

For example, when the only source of carbon in a mixture of CCHO 10 reagents is CH ₄ , the CH ₄ /O ₂ molar ratio is the same as the C/O molar ratio. As another example, when the mixture of reagents KCHO 10 contains other carbon sources in addition to CH ₄ , such as ethane (C ₂ H ₆ ), propane (C3H8), butanes (C ₄ H ₁₀ ), etc., the C/O molar ratio takes into account moles of carbon in each component (for example, 2 mol C in ₁ mol _C2H6 , 3 mol C in 1 mol C3H8, 4 mol C in 1 _{mol C4H10} , etc.). As will be appreciated by one skilled in the art and by reference to this description, the C/O molar ratio in the CPO 10 reactant mixture can be adjusted along with other reactor process parameters (e.g., temperature, pressure, flow rate, etc.) to obtain synthesis gas of the desired composition (eg, synthesis gas with a desired CO ₂ content, such as synthesis gas with a CO ₂ content of about 0.1 to 5 mol.%). The C/O molar ratio in the CPO reagent mixture can be adjusted to provide a reduced amount of unreacted hydrocarbons in the synthesis gas. The C/O molar ratio of the CPO reactant mixture 10 can be adjusted based on the temperature of the CPO effluent stream to reduce (eg, minimize) the unreacted hydrocarbon content of the produced synthesis gas. As will be appreciated by one skilled in the art and with the help of this description, the C/O molar ratio can be adjusted along with other reactor process parameters (e.g., temperature, pressure, flow rate, etc.) to provide the synthesis gas of the desired composition (eg, synthesis gas with a desired CO2 content, such as synthesis gas with a CO2 content of approximately 0.1 to 5 mol.%).

The CPO reaction is an exothermic reaction (eg, heterogeneous catalytic reaction; exothermic heterogeneous catalytic reaction) which is typically carried out in the presence of a CPO catalyst containing a catalytically active metal, that is, a metal active in catalyzing the CPO reaction. The catalytically active metal may comprise a noble metal (eg, Pt, Rh, Ir, Pd, Ru, Ag, etc., or combinations thereof); base metal (for example, Ni, Co, V, Mo, P, Fe, Cu, etc., or combinations thereof); rare earth elements (eg La, Ce, Nd, Eu, etc., or combinations thereof); their oxides; and so on.; or combinations thereof. Generally, a noble metal is a metal that is resistant to corrosion and oxidation in a water-containing environment. As will be appreciated by one skilled in the art and with the help of this description, the components of the CPO catalyst (eg, metals, such as noble metals, base metals, rare earth elements) can be phase separated or combined in the same phase.

In one aspect, CPO catalysts suitable for use in the present invention may be supported catalysts and/or unsupported catalysts. In some aspects, supported catalysts may comprise a support, where the support may be catalytically active (eg, the support may catalyze a CPO reaction). For example, the catalytically active support may include metal fabric or wire mesh (eg, Pt fabric or wire mesh); catalytically active metal monolithic catalyst; and others. In other aspects, supported catalysts may comprise supports where the support may be catalytically inactive (eg, the support cannot catalyze the CPO reaction), such as SiO ₂ , silicon carbide (SiC), alumina, catalytically inactive monolithic support; and others. In yet other aspects, supported catalysts may comprise a catalytically active support and a catalytically inactive support.

In some aspects, the CPO catalyst may be thinly coated on a support, wherein the support may be catalytically active or inactive, and where the support may be a monolith, foam, irregularly shaped catalyst particles, etc.

In some aspects, the CPO catalyst may be a monolith, foam, powder, particle, etc. Non-limiting examples of shapes for CPO catalyst particles suitable for use in the present invention include cylindrical, disk-shaped, spherical, plate-shaped, ellipsoidal, equal-area, irregular, cubic, needle-shaped, etc., or combinations thereof.

In some aspects, the support comprises an inorganic oxide, alpha, beta or theta aluminum oxide (Al ₂ O ₃ ), activated Al ₂ O ₃ , silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), magnesium oxide (MgO) , zirconium oxide (ZrO ₂ ), lanthanum (III) oxide (La ₂ O ₃ ), yttrium (III) oxide (Y ₂ O ₃ ), cerium (IV) oxide (CeO ₂ ), zeolites, ZSM-5, perovskite oxides , hydrotalcite oxides, etc., or combinations thereof.

CSF processes, CSF reactor, CSF catalysts, and CSF catalyst bed configurations suitable for use in the present invention are described in more detail in US Provisional Patent Application No. 62/522910, filed June 21, 2017 (International Application No. PCT/IB2018/054475 , filed June 18, 2018) entitled Improved Reactor Designs for Heterogeneous Catalytic Reactions, and in US Provisional Patent Application No. 62/521831, filed June 19, 2017 (International Application No. PCT/1B2O18/O5447O, filed June 18, 2018 d) entitled An Improved Process for Syngas Production for Petrochemical Applications, each of which is incorporated herein by reference in its entirety.

In one aspect, a CPO reactor suitable for use in the present invention (e.g., a CPO 100 reactor) may include a tubular reactor, a continuous flow reactor, an isothermal reactor, an adiabatic reactor, a fixed bed reactor, a fluidized bed reactor, a bubble bed reactor , circulating bed reactor, fluidized bed reactor, rotary kiln type reactor, etc., or combinations thereof.

In some aspects, the CPO reactor 100 may be characterized by at least one CPO operating parameter selected from the group consisting of CPO reactor temperature (eg, CPO catalyst bed temperature); the temperature of the CCHO supply (for example, the temperature of the mixture of CCHO reagents); target temperature of the CCH outlet stream; pressure of the reactor (for example, the pressure in the reactor of the reactor); CWC contact time (for example, contact time in the CWC reactor); molar C/O ratio in the mixture of CCHO reagents; the molar ratio of water vapor to carbon (P/C) in a mixture of reagents CWC, where the molar ratio P/C refers to the total number of moles of water (H ₂ O) in the mixture of reagents divided

- 5 044126 per total number of moles of carbon (C) hydrocarbons in the reaction mixture; and their combinations. As used herein, the temperature of the CPO effluent stream is the temperature of the synthesis gas (e.g., the synthesis gas effluent stream) measured at the point where the synthesis gas leaves the CPO reactor (the CPO 100 reactor), e.g., the temperature of the synthesis gas measured at exit from the CCHO reactor, temperature of the outlet synthesis gas stream, temperature of the outlet of the outlet synthesis gas stream. For purposes of the present disclosure, the CSF effluent temperature (eg, the target CSF effluent temperature) is considered an operating parameter. As will be understood by one skilled in the art and with the help of this description, the selection of operating parameters for the CSF reactor, such as CSF feed temperature, CSF pressure, CSF contact time, C/O molar ratio in the CSF reactant mixture, P/ molar ratio C in the mixture of CPO reactants, etc., determines the temperature of the CPO reactor effluent (for example, synthesis gas), as well as the composition of the CPO reactor effluent (for example, synthesis gas). In addition, as one skilled in the art will appreciate and with the help of this description, monitoring the temperature of the CSF effluent stream can provide feedback for changes in other operating parameters (e.g., CSF feed temperature, CSF pressure, CSF contact time, C molar ratio /O in the mixture of CSC reagents, the P/C molar ratio in the mixture of CSC reagents, etc.) as necessary, so that the temperature of the CSC effluent stream coincides with the target temperature of the CSC effluent stream. Moreover, as one skilled in the art will appreciate and with the help of this description, the target CSF effluent temperature is the desired CSF effluent temperature, and the CSF effluent temperature (e.g., the measured CSF effluent temperature, the actual effluent temperature) CCHO flow) may or may not coincide with the target temperature of the CCHO outlet stream. In aspects where the temperature of the CSF effluent stream differs from the target temperature of the CSF effluent stream, one or more operating parameters of the CSF (e.g., CSF supply temperature, CSF pressure, CSF contact time, C/O molar ratio of the CSF reagent mixture, P/M molar ratio C in the mixture of CSC reagents, etc.) can be adjusted (for example, changed) so that the temperature of the CSC outlet stream corresponds to (for example, is the same, coincides with) the target temperature of the CSC outlet stream. The CPO reactor 100 can be operated at any suitable operating parameters that can provide synthesis gas of the desired composition (eg, synthesis gas with a desired CO2 content, such as synthesis gas with a CO2 content of about 0.1 to 5 mole percent).

The CPO 100 reactor may have a CPO feed temperature of about 25 to 600°C, or about 25 to 500°C, or about 25 to 400°C, or about 50 to 400°C, or about from 100 to 400°C. In aspects where the CSC reactant mixture includes steam, the CSC feed temperature may reach about 600°C, or about 575°C, or about 550°C, or about 525°C. In aspects where the CPO reactant mixture does not contain steam, the CPO feed temperature may reach about 450°C, or about 425°C, or about 400°C, or about 375°C.

The CSF reactor 100 may be characterized by a CSF effluent temperature (e.g., a target CSF effluent temperature) equal to or greater than about 300°C, or equal to or greater than about 600°C, or equal to or greater than about 700°C , or equal to or greater than about 750°C, or equal to or greater than about 800°C, or equal to or greater than about 850°C, or from about 300 to 1600°C, or from about 600 to 1400°C, or approximately 600 to 1300°C, or approximately 700 to 1200°C, or approximately 750 to 1150°C, or approximately 800 to 1125°C, or, on the other hand, approximately from 850 to 1100°C.

In one aspect, the CPO reactor 100 can be characterized by any suitable reactor temperature and/or catalyst bed temperature. For example, the CPO reactor 100 may have a reactor temperature and/or catalyst bed temperature equal to or greater than about 300°C, or equal to or greater than about 600°C, or equal to or greater than about 700°C, or equal to or greater than about 750°C, or equal to or greater than about 800°C, or equal to or greater than about 850°C, or from about 300 to 1600°C, or from about 600 to 1400°C, or from about 600 to 1300°C, or from about 700 to 1200°C, or from about 750 to 1150°C, or from about 800 to 1125°C, or, on the other hand, from about 850 to 1100 °C.

The KCHO reactor 100 can be operated at any suitable temperature condition that can provide synthesis gas with the desired composition (for example, synthesis gas with a desired CO2 content, such as synthesis gas with a CO ₂ content of less than about 5 mol.%, or less than about 4 mol.%, or less than about 3 mol.%, or less than about 2 mol.%, or less than about 1 mol.%, or about 0.1 to 5 mol.% , or from about 0.25 to 4 mol.% or, on the other hand, from about 0.5 to 3 mol.%). The KChO 100 reactor can operate under adiabatic conditions, non-adiabatic conditions, isothermal conditions, nearly isothermal conditions, etc. As used herein, the term non-adiabatic conditions refers to process conditions in which the reactor is subjected to external heat exchange or

- 6 044126 heat transfer (eg 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 skilled in the art and from this description, the terms direct heat transfer and indirect heat transfer are known to one skilled in the art. In contrast, the term adiabatic conditions refers to process conditions in which the reactor is not subject to external heat exchange (eg, the reactor is not heated or the reactor is not cooled). Typically, external heat exchange refers to an external heat exchange system (eg, cooling system, heating system) that requires energy input and/or output. As one skilled in the art will appreciate and with the benefit of this description, external heat transfer can also result from heat loss from the catalyst (or reactor) bed due to radiative heat transfer, conduction, convection heat transfer, and the like, or combinations thereof. For example, the catalyst bed may participate in heat exchange with the external environment and/or with the reactor zones upstream and/or downstream of the catalyst bed.

As used herein, the term isothermal conditions refers to process conditions (e.g., CPO operating parameters) that allow the temperature of the reactor and/or catalyst bed to be maintained substantially constant (e.g., isothermal temperature), which can be defined as a temperature that varies approximately less than by ±10°C, or by approximately less than ±9°C, or by approximately less than ±8°C, or by approximately less than ±7°C, or by approximately less than ±6°C, or by approximately less than ±5°C, or by approximately less than ±4°C, or by approximately less than ±3°C, or by approximately less than ±2°C, or by approximately less than ±1°C throughout the reactor and/or catalyst bed, respectively.

Additionally, as used herein, the term isothermal conditions refers to process conditions (e.g., CPO operating parameters) effective to produce synthesis gas of the desired composition (e.g., desired H ₂ /CO molar ratio, desired CO ₂ content, etc. .), where isothermal conditions include a temperature change of approximately less than ±10°C throughout the reactor and/or catalyst bed.

The KCHO 100 reactor can be operated at any suitable operating parameters that can provide isothermal conditions.

As used herein, the term near-isothermal conditions refers to process conditions (e.g., CPO operating parameters) that allow the temperature of the reactor and/or catalyst bed to be maintained nearly constant (e.g., near-isothermal temperature), which can be defined as a temperature that varies approximately less than ±100°C, or approximately less than ±90°C, or approximately less than ±80°C, or approximately less than ±70°C, or approximately less than ±60° C, or approximately less than ±50°C, or approximately less than ±40°C, or approximately less than ±30°C, or approximately less than ±20°C, or approximately less by less than ±10°C, or by approximately less than ±9°C, or by approximately less than ±8°C, or by approximately less than ±7°C, or by approximately less than ±6°C, or by approximately less than ±5°C, or approximately less than ±4°C, or approximately less than ±3°C, or approximately less than ±2°C, or approximately less than ±1°C the entire reactor and/or catalyst bed, respectively. In some aspects, near-isothermal conditions allow a temperature variation of less than about ±50°C, or less than about ±25°C, or less than about ±10°C throughout the reactor and/or catalyst bed . Additionally, as used herein, the term near-isothermal conditions should be understood to include isothermal conditions.

Additionally, as used herein, the term near-isothermal conditions refers to process conditions (e.g., CPO operating parameters) effective to produce synthesis gas of the desired composition (e.g., desired H2/CO molar ratio, desired CO2 content, etc.) , where near isothermal conditions include a temperature change of approximately less than ±100°C throughout the reactor and/or catalyst bed.

In one aspect, the method disclosed herein may include conducting a CPO reaction under near-isothermal conditions to produce synthesis gas, wherein the near-isothermal conditions include a temperature change of less than approximately ±100°C throughout the reactor and/or catalyst bed.

The KCHO 100 reactor can be operated at any suitable operating parameters that can provide near isothermal conditions.

The CPR reactor 100 may be characterized by a CPR pressure (e.g., reactor pressure measured at the outlet or outlet of the reactor) equal to or greater than about 1 barg, or equal to or greater than about 10 barg, or equal to or greater than about 20 barg, or equal to or greater than about 25 barg, or equal to or

- 7 044126 greater than approximately 30 barg, or equal to or greater than approximately 35 barg, or equal to or greater than approximately 40 barg, or equal to or greater than approximately 50 barg (g), or less than about 30 barg, or less than about 25 barg, or less than about 20 barg, or less than about 10 barg. ), or from about 1 to 90 bar(g), or from about 1 to 40 bar, or from about 1 to 30 bar, or from about 1 to 25 bar, or from about 1 to 20 bar, or from about 1 to 10 bar, or from about 20 to 90 bar, or from about 25 to 85 bar, or, on the other hand, from about 30 to 80 bar.

The CCO reactor 100 may have a CCO contact time of about 0.001 milliseconds (ms) to 5 seconds (s), or about 0.001 ms to 1 s, or about 0.001 to 100 ms, or about 0.001 to 10 ms , or about 0.001 to 5 ms, or, on the other hand, about 0.01 to 1.2 ms. Typically, contact time in a reactor containing 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., a catalyst bed), e.g., the average amount of time it takes a compound (e.g., a molecule of that compound) to of this compound) to pass through the catalyst bed. As used herein, contact times of less than about 5 ms may be referred to as millisecond mode (MSR); and the CSF method or CSF reaction described herein, characterized by a contact time of less than about 5 ms, may be referred to as a millisecond mode CSF method or reaction (MSR-MCR), respectively.

In some aspects, the CPO reactor 100 may have a contact time of about 0.001 to 5 ms, or, alternatively, about 0.01 to 1.2 ms.

All operating parameters of the CFC disclosed in the invention are applicable in all embodiments disclosed in the invention, unless otherwise indicated. As will be appreciated by one skilled in the art and with the help of this description, each operating parameter of the CPR can be adjusted to produce a desired quality of synthesis gas, such as synthesis gas of a desired composition (e.g., synthesis gas with a desired CO ₂ content, such as synthesis gas with a CO ₂ content of approximately 0.1 to 5 mol.%). For example, the operating parameters of the CPO can be adjusted to ensure a reduced CO ₂ content in the synthesis gas. As another example, the operating parameters of the CPO can be adjusted to provide increased H ₂ content in the synthesis gas. As another example, the operating parameters of the CPO can be adjusted to produce a reduced content of unreacted hydrocarbons (eg, unreacted CH ₄ ) in the synthesis gas.

In one aspect, the effluent from CPR reactor 15 may be recovered from CPR reactor 100, wherein the effluent from CPR reactor 15 contains hydrogen, carbon monoxide, water, carbon dioxide, and unreacted hydrocarbons.

In some aspects, the effluent of the CPO reactor 15 (for example, after cooling and removing water from the synthesis gas and/or after adjusting the pressure and/or temperature of the synthesis gas) can be used as synthesis gas 20 in a downstream process (for example, in the production methanol) without further processing to increase the hydrogen content and/or reduce the CO ₂ content in the effluent stream of the KCHO 15 reactor. In such aspects, the effluent stream of the KCHO 15 reactor is the same stream as the synthesis gas 20, with the molar ratio of H ₂ /CO in the effluent stream of the reactor KChO 15 is the same as the molar ratio of H ₂ /CO in the synthesis gas 20. The effluent stream of the reactor KCHO 15 and/or synthesis gas 20, as described herein, can be characterized by the molar ratio H2/ CO is greater than about 1.7, or greater than about 1.8, or greater than about 1.9, or greater than about 2.0, or greater than about 2.2, or greater than about 2 .5, or greater than about 2.7, or greater than about 3.0. In some aspects, the CPO reactor effluent 15 and/or synthesis gas 20, as disclosed herein, can be characterized by an H2/CO molar ratio of about 1.7 to 2.3, or alternatively from about 1.8 to 2.2 or, on the other hand, approximately 1.9 to 2.1.

In other aspects, the effluent from CPO reactor 15 may be further processed to produce synthesis gas 20, which synthesis gas 20 may be further used to produce methanol. The effluent of the KChO 15 reactor can be processed to enrich it with hydrogen. In such aspects, the H ₂ /CO molar ratio in the synthesis gas 20 is greater than the H ₂ /CO molar ratio in the KCHO reactor effluent 15.

As will be appreciated by one skilled in the art and by reference to this description, although synthesis gas 20 may have a H2/CO molar ratio greater than about 1.8, which may be acceptable for methanol synthesis, synthesis gas 20 may be processed to further reduce the CO2 content to provide a synthesis gas of the desired composition (eg, a synthesis gas with a desired CO2 content, such as a synthesis gas with a CO2 content of about 0.1 to 5 mole percent).

In addition, as one skilled in the art will appreciate and with the help of this description, the effluent of the CPO reactor 15 and/or the synthesis gas 20 may be subjected to minimal

- 8 044126 processing, such as recovery of unreacted hydrocarbons, diluent, water, etc., without significantly changing the H2/CO molar ratio in the KCHO reactor effluent 15 and/or in the synthesis gas 20, respectively. For example, water can be condensed and separated from the effluent of the reactor 15 and/or synthesis gas 20, for example, in a condenser.

In one aspect, a method for producing methanol disclosed herein may further comprise (i) recovering at least a portion of the unreacted hydrocarbons from the effluent of the CPO reactor 15 and/or synthesis gas 20 to produce recovered hydrocarbons, and (ii) recycling at least at least a portion of the recovered hydrocarbons into the CPO reactor 100. As will be appreciated by one skilled in the art and with the benefit of this description, although fairly high conversions (e.g., conversions equal to or greater than about 90%) can be achieved in CPO processes, unreacted hydrocarbons can be removed and returned back to the KChO 100 reactor.

The KCHO 100 reactor can be operated at any suitable operating parameters that can provide synthesis gas of the desired composition (for example, synthesis gas with a desired CO ₂ content, such as synthesis gas with a CO 2 content of approximately 0.1 to 5 mol %) ; for example, the CPR reactor 100 may be operated at a relatively low pressure and optionally at a relatively low C/O molar ratio in the COC reactant mixture 10. Without intending to be bound by any theory, it is believed that for a given COC effluent temperature (e.g., target temperature output stream of CPO) and a given molar C/O ratio in the mixture of CPO reagents, the molar ratio of H ₂ /CO in the resulting synthesis gas increases with decreasing pressure. In addition, without intending to be bound by any theory and in accordance with Le Chatelier's principle, the equilibrium of the reforming reaction represented by equation (3) with decreasing pressure will be shifted towards the production of H ₂ and CO: the reforming reaction proceeds from 2 moles of reactants (CH4 and H2O) to 4 mol of products ( _H2 and CO), and a decrease in pressure will contribute to a shift in the equilibrium of the reaction towards the formation of _H2 and CO. The reforming reaction represented by Equation (3) can result in a synthesis gas having an H ₂ /CO molar ratio of 3, which is greater than the H ₂ /CO molar ratio of 2 for the synthesis gas produced according to the CPO reaction , represented by equation (1).

In one aspect, the CPO reactor 100 can be operated at a CPO pressure of less than about 30 barg, or less than about 25 barg, or less than about 20 barg, or less than about 10 bar(g), or approximately 1 to 30 bar(g), or approximately 1 to 25 bar(g), or approximately 1 to 20 bar(g), or, on the other hand, sides, approximately 1 to 10 bar(g). In such an aspect, the CSF reactor 100 may be operated at (i) a CSF effluent temperature (e.g., a target CSF effluent temperature) equal to or greater than about 750°C, or equal to or greater than about 800°C, or equal to or greater than about 850°C, or from about 750 to 1150°C, or from about 800 to 1125°C, or, on the other hand, from about 850 to 1100°C; and/or when (ii) the C/O molar ratio in the mixture of reagents CCO 10 is less than about 2.2:1, or less than about 2:1, or less than about 1.9:1, or about 0. 9:1 to 2.2:1, or about 1:1 to 2:1 or, on the other hand, about 1.1:1 to 1.9:1.

In some aspects, the CSF reactor 100 can be operated at a CSF pressure of less than about 30 bar(g), with a CSF effluent temperature (e.g., a target CSF effluent temperature) equal to or greater than about 750° C., at a molar ratio of C/ The O in the CCO 10 reagent mixture is approximately less than 2.2:1 and the P/S molar ratio in the CCO reagent mixture is approximately 0.2:1 to 0.8:1.

The CPO reactor can be operated at any suitable operating parameters that can produce synthesis gas of the desired composition (for example, synthesis gas with a desired CO ₂ content, such as synthesis gas with a CO ₂ content of approximately 0.1 to 5 mol %) ; for example, the reactor KCHO 100 can operate at a relatively high molar ratio of C/O in the mixture of reactants KCHO 10 and optionally at a relatively low pressure.

When an excess of hydrocarbons (e.g. methane) is present, some of the hydrocarbons may undergo a thermal decomposition reaction, for example, as represented by equation (2):

CH ₄ C + 2H ₂ (2).

The decomposition reaction of hydrocarbons, such as methane, is enhanced at elevated temperatures and increases the hydrogen content in the effluent stream of the CCHO reactor 15 and/or the synthesis gas 20. As will be understood by one skilled in the art, also by this description and without the intention of being bound by By any theory, although the percentage of hydrocarbons in a KChO 10 reagent mixture that undergoes a decomposition reaction (e.g., the decomposition reaction represented by equation (2)) increases with increasing C/O molar ratio in the KChO 10 reagent mixture, some of the hydrocarbons may undergo decomposition reactions to carbon (C) and H ₂ even at relatively low C/O molar ratios in the KCHO 10 reagent mixture (for example, the C/O molar ratio in the KCHO 10 reagent mixture is approximately less than 2:1).

In one aspect, the KCHO 100 reactor can be operated at a C/O molar ratio of the reactant mixture

- 9 044126

NOR 10 equal to or greater than about 2:1, or equal to or greater than about 2.2:1, or equal to or greater than about 2.4:1, or equal to or greater than about 2.6:1 , or from about 2:1 to 3:1, or from about 2.2:1 to 3:1, or from about 2.4:1 to 3:1, or, on the other hand, from about 2, 6:1 to 3:1. In such an aspect, the CPO reactor 100 may be operated at (i) a CPO pressure of less than about 30 barg, or less than about 25 barg, or less than about 20 barg, or less than about 10 barg, or about 1 to 30 barg, or about 1 to 25 barg, or about 1 to 20 barg, or from approximately 1 to 10 bar(g); and/or at (ii) a CSF effluent temperature (e.g., a target CSF effluent temperature) equal to or greater than about 750°C, or equal to or greater than about 800°C, or equal to or greater than about 850° C, or from about 750 to 1150°C, or from about 800 to 1125°C, or, on the other hand, from about 850 to 1100°C.

In some aspects, the CSF reactor 100 can be operated at a CSF pressure of less than about 30 bar(g), at a CSF effluent temperature (e.g., a target CSF effluent temperature) equal to or greater than about 750° C., and at a molar ratio of C /O in the mixture of reagents is KCHO 10, equal to or greater than approximately 2:1.

In one aspect, the CPO reagent mixture 10 may further comprise a diluent such as water and/or steam. The KCHO reactor 100 can be operated at any suitable operating parameters that can produce synthesis gas of the desired composition (eg, synthesis gas with a desired CO ₂ content, such as synthesis gas with a CO 2 content of approximately 0.1 to 5 mol%); for example, the KCHO reactor 100 can operate by introducing water and/or steam into the KCHO reactor 100.

Typically, the diluent is inert to the COC reaction, for example, the diluent does not participate in the COC reaction (eg, the COC reaction represented by equation (1)). However, as one skilled in the art will appreciate and with the help of this description, some diluents (e.g., water, steam, etc.) may undergo chemical reactions other than the CPO reaction within the CPO reactor 100, and may change the composition of the resulting synthesis gas (for example, the outlet stream of the KChO reactor 15 and/or synthesis gas 20). As will be appreciated by one skilled in the art and by reference to this description, water and/or steam can be used to change the composition of the synthesis gas produced. Steam can react with methane, for example, as shown in equation (3):

CH ₄ + H ₂ O o CO + ZN ₂ (3)

In one aspect, a diluent containing water and/or steam can increase the hydrogen content of the resulting synthesis gas (eg, in the effluent of the CPO reactor 15 and/or in the synthesis gas 20). For example, in aspects where the reactant mixture of the CHO 10 includes a diluent of water and/or steam, the resulting synthesis gas (e.g., the effluent of the reactor CCO 15 and/or synthesis gas 20) may be characterized by a molar ratio of hydrogen to carbon monoxide, which increases when compared with the molar ratio of hydrogen to carbon monoxide in synthesis gas produced by an otherwise similar process carried out with a reactant mixture containing hydrocarbons and oxygen, without the diluent of water and/or steam.

In addition, in the presence of water and/or steam in the reactor KCHO 100, carbon monoxide can react with water and/or steam to form carbon dioxide and hydrogen through a water gas shift (WGS) reaction, for example as represented by equation (4):

CO + H ₂ O θ CO ₂ + H ₂ (4)

Although the WGS reaction can increase the H ₂ /CO molar ratio in the synthesis gas produced in the KCHO 200 reactor, it also produces CO ₂ .

When carbon is present in the reactor (for example, coke; C produced by the decomposition reaction represented by equation (2)), dilute water and/or steam can react with the carbon and produce additional amounts of CO and H ₂ , for example, as represented by equation (5):

C+H ₂ O CO+H ₂ (5)

In addition, since oxygen is present in the reactant mixture of KCHO 10, carbon present in the reactor (for example, coke; C produced by the decomposition reaction represented by equation (2)) can also react with oxygen, for example, as represented by equation (6 ):

C+O ₂ CO ₂ (6)

In addition, CO ₂ can react with carbon (for example, with coke C formed as a result of the decomposition reaction represented by equation (2)), for example as represented by equation (7): C + CO ₂ o 2CO (7), thereby reducing the amount of CO ₂ in the resulting synthesis gas (for example, in the effluent of the KCHO reactor 15 and/or in the synthesis gas 20).

Moreover, CO2 can react with methane in a dry reforming reaction, for example, as represented by equation (8):

CH ₄ +CO ₂ θ 2СО+2Н ₂ (8),

- 10 044126 thereby reducing the amount of CO2 in the resulting synthesis gas (for example, in the outlet stream of the KCHO reactor 15 and/or in the synthesis gas 20).

In one aspect, the CPO reactor 100 can be operated at a molar ratio of steam to carbon (S/C) in the CPO reactant mixture of less than about 2.4:1, or less than about 2:1, or less than about 1.5 :1, or less than about 1:1, or less than about 0.8:1, or less than about 0.5:1, or from about 0.01:1 to less than 2.4: 1, or about 0.05:1 to 2:1, or about 0.1:1 to 1.5:1, or about 0.15:1 to 1:1, or on the other hand , from approximately 0.2:1 to 0.8:1, where the P/C molar ratio means the total moles of water (H2O) in the reactant mixture divided by the total moles of carbon (C) hydrocarbons in the reactant mixture. As will be appreciated by one skilled in the art and by reference to this description, the steam that is introduced into the reactor for use as a diluent in the CPO reaction disclosed in the invention is present in significantly smaller quantities than the quantities of steam used in the processes steam reforming (eg, SMR), and as such, the method for producing synthesis gas disclosed herein can produce synthesis gas with smaller amounts of hydrogen compared to the amounts of hydrogen in synthesis gas produced by steam reforming.

The P/S molar ratio of the CPO reactant mixture 10 can be adjusted based on the desired temperature of the CPO effluent stream (eg, the target temperature of the CPO effluent stream) to increase (eg, maximize) the H ₂ content of the resulting synthesis gas. As will be appreciated by one skilled in the art and from this description, reaction (3) which consumes water vapor in the CPO 100 reactor is preferred over the water gas shift (WGS) reaction (4) in the CPO 100 reactor. since reaction (3) increases the H ₂ content of the resulting synthesis gas, as well as the M ratio of the resulting synthesis gas, where the M ratio is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ).

In one aspect, the amount of methane that reacts according to reaction (3) in the CPO 100 reactor is less than the amount of methane that reacts according to reaction (1) in the CPO 100 reactor. In one aspect, it is less than about 50 mol.%, or about less than 40 mol.%, or approximately less than 30 mol.%, or less than approximately 20 mol.%, or less than approximately 10 mol.% hydrocarbons (for example, methane) react with water vapor in the KCHO 100 reactor.

Without intending to be bound by any theory, it is believed that the presence of water and/or steam in the KCHO 100 reactor changes the flammability of the KCHO 10 reactant mixture, thereby providing a wider practical range of C/O molar ratios in the KCHO 10 reactant mixture. In addition, It is believed, without intending to be bound by any theory, that the presence of water and/or steam in the KChO 100 reactor allows the use of lower C/O molar ratios in the KChO 10 reactant mixture. Moreover, without intending to be bound by any theory, it is believed that the presence of water and/or water vapor in the KChO 100 reactor allows the KChO 100 reactor to be operated at relatively high pressures.

In one aspect, the CPO reactor 100 can be operated in the presence of water and/or steam at a CPO pressure equal to or greater than about 10 bar(g), or equal to or greater than about 20 bar(g), or equal to or greater than about 25 barg, or equal to or greater than about 30 barg, or equal to or greater than about 35 barg, or equal to or greater than about 40 barg , or equal to or greater than approximately 50 bar(g)

In one aspect, the CPO reactor 100 can be operated in the presence of water and/or steam at a C/O molar ratio of the CPO reactant mixture 10 of less than about 2.2:1, or less than about 2:1, or less than about 1 .9:1, or from about 0.9:1 to 2.2:1, or from about 1:1 to 2:1, or, on the other hand, from about 1.1:1 to 1.9: 1.

As will be appreciated by one skilled in the art and by reference to this description, the introduction of water and/or steam into the CPO reactor 100 may result in an increase in the amount of unreacted hydrocarbons in the CPO reactor effluent 15 and/or in the synthesis gas 20. In addition As will be appreciated by one skilled in the art and from this description, methanol production processes typically tolerate limited amounts of unreacted hydrocarbons in the synthesis gas.

In some aspects, the CPO reactor effluent 15 and/or synthesis gas 20 may contain less than about 7.5 mol.%, or less than about 5 mol.%, or, on the other hand, less than about 2.5 mol.% .% hydrocarbons (eg, unreacted hydrocarbons, unreacted CH ₄ ). In such aspects, the CPO reactor effluent 15 and/or synthesis gas 20 can be produced in a CPO process that uses water and/or steam. In such aspects, the CPO reactor effluent 15 and/or synthesis gas 20 can be used to synthesize methanol.

In some aspects, the CPO 100 reactor can be operated at a P/S molar ratio of the CPO reactant mixture of less than about 1:1, a CPO pressure of less than about 30 barg, and a C/O molar ratio of the CPO reactant mixture 10 of about less than than 2.2:1.

- 11 044126

In one aspect, a method for producing methanol disclosed herein may include (i) recovering the effluent of a CPO reactor 15 from a CPO reactor 100, wherein the effluent of the CPO reactor 15 contains hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons; and (ii) processing at least a portion of the effluent from the KCHO reactor 15 to produce synthesis gas 20; where (1) the CO ₂ content in the synthesis gas 20 is lower than the CO ₂ content in the effluent of the KChO reactor 15; and/or (2) the H ₂ content in the synthesis gas 20 is greater than the H ₂ content in the effluent stream of the CCHO reactor 15. As will be appreciated by one skilled in the art, and also by this description, even if the effluent stream from the reactor (eg, the effluent of the KChO 15 reactor) extracted from the KChO 100 reactor is characterized by (1) a CO2 content of from about 0.1 to 5 mol%. and/or (2) an H2/CO molar ratio greater than about 1.9, the reactor effluent can be further processed to reduce the CO2 content and/or increase the hydrogen content of the reactor effluent to produce synthesis gas of the desired composition.

In one aspect, the step of processing at least a portion of the effluent stream of the CPO reactor 15 to produce synthesis gas 20 may include removing at least a portion of carbon dioxide from the effluent stream of the CPO reactor 15 to produce synthesis gas 20. As will be appreciated by one skilled in the art. and by this description, and without intending to be bound by any theory, although the H ₂ /CO molar ratio in the synthesis gas does not change when carbon dioxide is removed from the synthesis gas, the hydrogen concentration in the synthesis gas increases due to the removal of carbon dioxide carbon from synthesis gas. However, the M ratio of the synthesis gas changes with the carbon dioxide content of the synthesis gas, and the M ratio is a molar ratio defined as (H ₂ CO ₂ )/(CO+CO ₂ ). The effluent stream of the CPO reactor 15 is characterized by the ratio M of the effluent stream of the CPO reactor 15. Synthesis gas 20 is characterized by the ratio M of the synthesis gas 20. In aspects where the synthesis gas 20 is produced by removing at least a portion of carbon dioxide from the effluent stream of the CPO reactor 15, synthesis gas 20 can be characterized by a ratio M that is greater than the ratio M of the effluent stream of the reactor KCHO 15.

In one aspect, the effluent of the CPO reactor 15 may have an M ratio of about 1.2 to 1.8, or about 1.6 to 1.78, or, alternatively, about 1.7 to 1.78.

In some aspects, at least a portion of the effluent from the CPO reactor 15 may be introduced into a CO2 separator (e.g., a CO2 scrubber) to produce synthesis gas 20, wherein the synthesis gas 20 may have an M ratio that is greater than the M ratio in the effluent reactor stream 15. The CO2 separator 150 may include CO2 removal by amine (e.g., monoethanolamine) absorption (e.g., amine scrubbing), pressure swing adsorption (PSA), temperature swing adsorption, gas separation membranes (e.g., porous inorganic membranes) , palladium membranes, polymer membranes, zeolites, etc.), by cryogenic separation, etc., or combinations thereof. In one aspect, the step of removing at least a portion of the carbon dioxide from the effluent of the CPO reactor 15 to produce synthesis gas 20 may include removing CO2 by amine absorption. As will be appreciated by one skilled in the art and from this description, CO ₂ -depleted synthesis gas has a higher M ratio than CO ₂ -rich synthesis gas because the lower the CO ₂ content of the synthesis gas , the higher the M ratio of synthesis gas.

In one aspect, synthesis gas 20 may have an M ratio of about 1.9 to 2.2, or about 1.95 to 2.1, or about 1.98 to 2.06.

As will be appreciated by one of ordinary skill in the art and with the aid of this description, if the effluent stream of the CPO reactor 15 has a CO2 content of from about 0.1 to 5 mol.%, the step of removing at least a portion of the carbon dioxide from the effluent stream of the CPO reactor 15 to produce synthesis gas 20 can be performed, but is not required. For example, the side reactions represented by equations (7) and/or (8) may result in an effluent from the CPO reactor 15 that has a CO2 content of approximately 0.1 to 5 mol%.

In one aspect, the CPO reactor effluent 15 and/or synthesis gas 20 may have a CO2 content of less than about 5 mole%, or less than about 4 mole%, or less than about 3 mole%, or about less than 2 mol.%, or about less than 1 mol.%, or from about 0.1 to 5 mol.%, or from about 0.25 to 4 mol.%, or, on the other hand, from about 0.5 to 3 mol.%.

In one aspect, the CPO reactor effluent 15 and/or synthesis gas 20 may be characterized by a carbon monoxide to carbon dioxide (CO/CO2) molar ratio of equal to or greater than about 5, or equal to or greater than about 7.5, or equal to or greater than about 10, or equal to or greater than about 12.5, or, on the other hand, equal to or greater than about 15.

The CO2 content of the synthesis gas (e.g., the KCHO reactor effluent 15 and/or the synthesis gas 20) can be controlled, as described in more detail in co-pending US Provisional Patent Application No. 62/787574 entitled Hydrogen Enrichment in Syngas Produced via Catalytic Partial Oxidation), which is incorporated herein by reference at

- 12 044126 in its entirety.

In one aspect, the step of processing at least a portion of the effluent stream of the CPO reactor 15 to produce synthesis gas 20 may include contacting the effluent stream of the synthesis gas of the PRM reactor 12 with at least a portion of the effluent stream of the CPO reactor 15 and/or, according to with at least a portion of the synthesis gas 20 before introducing the effluent of the CPO reactor 15 and/or the synthesis gas 20 into the methanol reactor 200, respectively; in this case, the outlet synthesis gas stream of the PRM reactor 12 can increase the H2 content in the outlet stream of the KChO reactor 15 and/or in the synthesis gas 20, respectively.

In one aspect, at least a portion 12a of the synthesis gas effluent stream of the PRM reactor 12 can be contacted with at least a portion of the effluent stream of the CPO reactor 15 to produce synthesis gas 20.

In one aspect, at least a portion 12c of the synthesis gas effluent stream of the PRM reactor 12 can be contacted with at least a portion of the CO ₂ separator effluent stream to produce synthesis gas 20.

The synthesis gas effluent of PRM reactor 12 can be obtained by reacting, through a PRM reaction (eg, the reaction represented by equation (3)), a mixture of the reactants of PRM 11 in reactor PRM 110 to produce the synthesis gas effluent stream of PRM reactor 12; where the mixture of reagents PRM 11 contains methane and water vapor; and wherein the synthesis gas effluent of the PRM 12 reactor contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted methane. Typically, the PRM describes the catalytic reaction of methane and water vapor to produce carbon monoxide and hydrogen according to the reaction represented by equation (3). The steam reforming catalysts may include any suitable commercially available steam reforming catalyst; nickel (Ni) and/or rhodium (Rh) as active metals on alumina; or combinations thereof. PRM uses rather elevated P/S molar ratios compared to the P/S molar ratios used in CPR. For example, the PMR may be characterized by a P/S molar ratio equal to or greater than about 2.5, or equal to or greater than about 2.7, or equal to or greater than about 3.0. In addition, the effluent synthesis gas stream of the PRM 12 reactor may be characterized by an H ₂ /CO molar ratio equal to or greater than about 2.5, or equal to or greater than about 2.7, or, on the other hand, equal to or greater than approximately 2.9. As will be appreciated by one skilled in the art and by the use of this description, and without intending to be bound by any theory, the PRM reaction represented by equation (3) can produce synthesis gas with a H ₂ /CO molar ratio having the theoretical the stoichiometric limit is 3.0 (that is, the PRM reaction represented by equation (3) produces 3 mol H ₂ for every 1 mol CO). As will be appreciated by one skilled in the art and from this description, the theoretical stoichiometric limit of 3.0 for the H ₂ /CO molar ratio in the PRM reaction cannot be achieved because the reactants undergo side reactions under the conditions used for the PRM reaction. The M ratio of the outlet synthesis gas stream of the PRM 12 reactor is greater than the M ratio of the outlet stream of the KChO 15 reactor.

In some aspects, at least a portion 12b of the PRM reactor 12 synthesis gas effluent stream may be supplied to the CPO reactor 100 to produce the CPO reactor effluent 15. In such aspects, the PRM reactor 12 synthesis gas effluent stream contains unreacted hydrocarbons (e.g., CH4) , which can participate in the CPO reaction represented by equation (1). Because the PRM 12 reactor synthesis gas effluent stream has a fairly high H ₂ /CO molar ratio (e.g., equal to or greater than about 2.5), the synthesis gas recovered from the CPO reactor may have an H 2 /CO molar ratio that is greater , than the H2/CO molar ratio in the synthesis gas obtained using an otherwise similar KChO process without feeding the PRM 12 reactor synthesis gas effluent into the KChO 100 reactor.

In aspects where the CPO reactor effluent 15 and/or synthesis gas 20 has an M ratio of about 1.8 to 2.2, the CPO reactor effluent 15 and/or synthesis gas 20 may also be used to produce methanol.

In one aspect, a method for producing methanol disclosed herein may include the step of introducing at least a portion of the effluent of CPO reactor 15 and/or synthesis gas 20 into a methanol reactor 200 to produce a methanol reactor effluent 30; wherein the effluent stream of methanol reactor 30 contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons. The methanol reactor 200 may be any reactor suitable for the synthesis reaction of methanol from CO and H ₂ , such as, for example, an isothermal reactor, an adiabatic reactor, a thin trickle bed reactor, a fluidized bed reactor, a slurry reactor, a loop reactor, etc. etc., cooled multi-tube reactor, etc., or combinations thereof.

Typically, CO and _H2 can be converted to methanol ( _CH3OH ), for example, as represented by equation (9):

CO+H ₂ θ CH3OH (9)

- 13 044126

Also CO2 and _H2 can also be converted into methanol, for example, as represented by equation (10):

CO ₂ + ZN ₂ o CH ₃ OH + H ₂ O (10)

Without intending to be bound by any theory, it is believed that the lower the CO2 content in the CPO reactor effluent 15 and/or synthesis gas 20, the lower the amount of water produced in the methanol reactor 200. As will be appreciated by one skilled in the art, and also by this description, synthesis gas produced by PRM has a fairly high hydrogen content (compared to the hydrogen content of synthesis gas produced by CPO), and synthesis gas with increased hydrogen content can help convert CO ₂ into methanol, for example, as represented by equation (10), which in turn may result in increased water content in the crude methanol stream (eg, crude methanol stream 40).

The synthesis of methanol from CO, CO2 and H2 is a catalytic process and is most often carried out in the presence of copper-based catalysts. Methanol reactor 200 may contain a catalyst for the production of methanol, such as any suitable commercial catalyst used for the synthesis of methanol. Non-limiting examples of methanol production catalysts suitable for use in the methanol reactor 200 in the present invention include Cu, Cu/ZnO, Cu/ThO ₂ , Cu/Zn/Al ₂ O ₃ , Cu/ZnO/Al ₂ O ₃ , Cu/ Zr, etc., or combinations thereof.

In one aspect, a method for producing methanol disclosed herein may include the step of separating at least a portion of the effluent stream of methanol reactor 30 into a crude methanol stream 40 and a steam stream 50; wherein the crude methanol stream 40 contains methanol and water; wherein the steam stream 50 contains hydrogen, carbon monoxide, carbon dioxide and hydrocarbons. The effluent stream of methanol reactor 30 may be separated into a crude methanol stream 40 and a vapor stream 50 in a gas-liquid separator 300, such as a vapor-liquid separator, a flash drum, a gas separator, a condensate collector, a compressor suction separator, etc.

In one aspect, the crude methanol stream 40 may contain water in an amount of less than about 10 wt.%, or less than about 8 wt.%, or less than about 6 wt.%, or less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.%, or, on the other hand, less than about 1 wt.% based on the total weight of the crude methanol stream 40.

In one aspect, the crude methanol stream 40 may contain methanol in an amount equal to or greater than about 90 wt.%, or equal to or greater than about 92 wt.%, or equal to or greater than about 94 wt.%, or equal to or greater than about 96 wt.%, or equal to or greater than about 97 wt.%, or equal to or greater than about 98 wt.%, or, on the other hand, equal to or greater than about 99 wt.% of the total mass of crude methanol flow 40.

In one aspect, a method for producing methanol disclosed herein may include the step of separating at least a portion of a crude methanol stream 40 in a distillation unit 400 into a methanol stream 45 and a water stream 46, wherein the distillation unit 400 includes one or more distillation columns. Water stream 46 contains water and residual methanol. Typically, one or more distillation columns may separate components of the crude methanol stream 40 based on their boiling points. As will be appreciated by one skilled in the art and by reference to this description, the higher the water content in the crude methanol stream 40, the more energy will be expended in the distillation unit to purify the methanol.

In one aspect, methanol stream 45 may contain methanol in an amount equal to or greater than about 95 weight percent, or equal to or greater than about 97.5 weight percent, or equal to or greater than about 99 weight percent, or, on the other hand, equal to or greater than about 99.9 wt.% based on the total weight of the methanol stream 45.

In one aspect, a method for producing methanol disclosed herein may include the step of separating at least a portion of the steam stream 50 into a hydrogen stream 51 and a tail gas stream 52, wherein the hydrogen stream 51 contains at least a portion of the hydrogen of the steam stream 50, wherein the tail gas stream gas 52 contains carbon monoxide, carbon dioxide and hydrocarbons. The steam stream 50 may be divided into a hydrogen stream 51 and a residual gas stream 52 in a hydrogen recovery unit 500, such as a PSA unit, a membrane separation unit, a cryogenic separation unit, and the like, or combinations thereof.

In one aspect, at least a portion of the residual gas stream 52 may be withdrawn. In one aspect, at least a portion of the residual gas stream 52 can be used as fuel, for example, to preheat the reactant mixture of the CCH 10 and/or the PRM reactor 110.

In one aspect, the methanol production method disclosed herein may include recycling at least a portion 51a of the hydrogen stream 51 to the methanol reactor 200, for example, using the effluent of the CPO reactor 15 and/or synthesis gas 20.

In one aspect, a method for producing methanol may include the steps of (a) reacting, through a catalytic partial oxidation (CPO) reaction, a mixture of CPO reagents 10 in a CPO reactor

- 14 044126

100 to obtain the output stream of the KChO 15 reactor; where the mixture of reagents KCHO 10 contains hydrocarbons, oxygen and optionally water vapor; where the KChO reactor 100 contains the KChO catalyst; where the effluent of the reactor KCHO 15 contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted hydrocarbons; (b) cooling at least a portion of the CPO reactor effluent 15 to produce cooled CPO reactor effluent and process heat (eg, which can be recovered and used as thermal energy); (c) removing at least a portion of the water from the cooled CPO reactor effluent to produce a dehydrated CPO reactor effluent, wherein the dehydrated CPO reactor effluent contains _H2 , CO, CO2, and unreacted hydrocarbons; (d) removing at least a portion of the carbon dioxide from the dehydrated effluent of the CPO reactor in CO2 separator 150 to produce synthesis gas 20, wherein synthesis gas 20 contains carbon dioxide in an amount of from about 0.1 to 5 mole percent; (e) introducing at least a portion of the synthesis gas 20 into the methanol reactor 200 to produce an effluent stream from the methanol reactor 30; wherein the effluent stream of methanol reactor 30 contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; (f) separating at least a portion of the effluent stream of methanol reactor 30 in gas-liquid separator 300 into a crude methanol stream 40 and a steam stream 50, wherein the crude methanol stream 40 contains methanol and water, the steam stream 50 contains hydrogen, carbon monoxide, carbon dioxide and hydrocarbons ; and wherein the crude methanol stream 40 contains water in an amount of less than about 5 wt.% based on the total weight of the crude methanol stream 40; (g) separating at least a portion of the crude methanol stream 40 in the distillation unit 400 into a methanol stream 45 and a water stream 46, where the distillation unit includes one or more distillation columns; (h) separating at least a portion of the steam stream 50 in the hydrogen recovery unit 500 into a hydrogen stream 51 and a tail gas stream 52, wherein the hydrogen stream 51 contains at least a portion of the hydrogen of the steam stream 50, and where the tail gas stream 52 contains carbon monoxide, carbon dioxide and hydrocarbons; and (i) recycling at least a portion 51a of the hydrogen stream 51 to the methanol reactor 200. In such an aspect, the CPO reactor 100 has a P/S molar ratio of the CPO reactant mixture 10 of less than approximately 0.5:1; wherein a portion of the hydrocarbons in the KChO 10 reactant mixture is decomposed to carbon and hydrogen, wherein at least a portion of the carbon reacts with carbon dioxide in the KChO 100 reactor to form carbon monoxide, and/or where at least a portion of the carbon reacts with water in the KChO reactor 100 to form carbon monoxide and hydrogen.

In one aspect, the methanol production method disclosed herein may advantageously exhibit improvements in one or more process characteristics compared to another similar process in which a synthesis gas containing carbon dioxide in an amount equal to or greater than about 5% is introduced into the methanol reactor. mol.%. The methanol production method disclosed herein can advantageously reduce the overall energy consumption of methanol production by reducing the water content of the crude methanol. The methanol production method disclosed herein can advantageously reduce the water content of the crude methanol by reducing the CO ₂ content of the synthesis gas that is introduced into the methanol reactor.

As will be appreciated by one skilled in the art and with the help of this description, the quality of the synthesis gas (e.g., the composition of the synthesis gas) that is fed to a particular process (e.g., a methanol production process) can have a strong impact on the flow rates, and also on the selectivity of the product. For example, in the case of a methanol production process, the composition of the synthesis gas used to produce methanol may change the composition of the crude methanol recovered from the methanol production reactor (e.g., a loop reactor), where the crude methanol may be enriched with methanol (as opposed to water), thereby most advantageously changing the process downstream of the methanol reactor due to reduced recycle streams (due to the presence of only the required amount of hydrogen in the synthesis gas), as well as the reduced amount of water in the crude methanol product. Thus, the methanol production process can be more energy efficient due to lower energy consumption in the methanol purification area. As the amount of CO ₂ in the synthesis gas is reduced (for example, compared to synthesis gas containing carbon dioxide in an amount equal to or greater than about 5 mol.%), the recycle loops will be smaller and smaller recycle gas compressors will be required. volume flow and therefore consuming less electricity. The methanol production process can be more carbon efficient by saving the hydrocarbon feedstock (eg natural gas) used in producing the synthesis gas (eg less carbon is converted to CO2). As used herein, carbon efficiency is defined as the ratio of the number of moles of carbon present in a methanol stream (eg, methanol stream 45) to the number of moles of carbon in the CPO reactant mixture (eg, CPO 10 reactant mixture).

In one aspect, the methanol production method disclosed herein advantageously can produce a methanol reactor throughput ratio that is greater than the methanol reactor throughput ratio in an otherwise similar process in which carbon dioxide-containing synthesis gas is introduced into the methanol reactor. in an amount equal to

- 15044126 or more than about 5 mol.%. As used herein, the flow rate is defined as the ratio of the number of days per year during which the reactor is actively producing the desired product to the number of days in the calendar year.

In one aspect, the methanol production method disclosed herein may advantageously control the composition of the synthesis gas produced by the CSF (e.g., by adjusting the operating parameters of the CSF), which in turn may advantageously result in a reduction in the water content of the stream. crude methanol.

In some aspects, PRM can be advantageously used in combination with the CPO disclosed herein to produce synthesis gas having a composition that can advantageously result in a reduced water content in the crude methanol stream.

As will be appreciated by one skilled in the art and from this description, since the CPO reaction is exothermic, no additional heat input in the form of combustion of fuel is required (other than preheating the reactants in the reaction mixture, which is supplied to the synthesis gas production site ) compared to conventional steam reforming. Thus, the synthesis gas production method described in the invention can advantageously generate less CO2 through fuel combustion compared to steam reforming. Additional advantages of the methanol production methods described herein may be apparent to one skilled in the art considering the present invention.

Examples

Since the subject matter of the invention has been described in general, the following examples are given as specific embodiments of the invention and demonstrate its practical application and advantages. It is understood that the examples are given for illustration purposes and are not intended to limit in any way the description of the appended claims.

Example.

The water content of a methanol production system was studied based on the composition of the synthesis gas used for methanol synthesis. The traditional method of producing synthesis gas using combined reforming (CR) technology, which combines steam reforming of methane (SMR) with autothermal reforming (ATR), is compared with the method of producing synthesis gas through CCR, where each type of synthesis gas (i.e., from KR and KChO) are then converted into methanol.

In the case of CR technology, synthesis gas is produced in a traditional way.

In the case of CPO, synthesis gas is obtained with two different preheating temperatures of the reactant mixture. Process conditions are varied as understood by one skilled in the art. For example, the reaction temperature is from about 800 to 1100°C.

Methanol is produced using traditional technology, and the water content of the crude methanol stream is shown in the table for all three cases._________________________________________________

PRM +ATR KChO Preheating temperature of the reagent mixture 350°C KChO Preheating temperature of the reagent mixture 520°C Efficiency across all carbon 77% 88% 91% P/S ratio for synthesis gas production 1.5 0.2 0.2 Gas consumption (million stub. m/hour) 0.6 0.46 0.47 Total CO ₂ emissions 23% 12% 9% Water in MeOH (wt.%) 20% 4% 3% CO ₂ in synthesis gas (% mol.) 7% 3% 2.5% Molar ratio of CO/CO ₂ synthesis gas 3 10 12 M value synthesis gas 2.5 1.82 1.83

The data in the table shows that when using CPO for the production of synthesis gas, the water content in the crude methanol stream can be reduced from 20 wt.% (CR) to 3-4 wt.% (CPO). The decrease in water content correlates with a decrease in the CO2 content in the synthesis gas from 7 mol.% (CR) to 2.5-3 mol.% (NOC), respectively. In addition, the overall carbon efficiency increases with decreasing CO ₂ content in the synthesis gas.

For the purposes of filing this application nationally in the United States, all publications and patents mentioned in this specification are hereby incorporated by reference in their entirety to describe and disclose the designs and methodologies described in these publications that may be used in connection with the methods of this invention. Any publications and patents discussed herein are provided solely for their disclosure prior to the filing date of this application. Nothing in this document is

- 16 044126 should be construed as recognizing that inventors are not entitled to backdate such disclosure based on a prior invention.

Any application filed with the United States Patent and Trademark Office shall provide an abstract of this invention to satisfy the requirements of 37 CFR § 1.72 and the purpose of 37 CFR § 1.72(b) to enable the United States Patent and Trademark Office and the public In general, quickly determine, based on a quick review, the nature and essence of the technical disclosure. Accordingly, the abstract of this invention is not intended to be used in interpreting the scope of the claims or to limit the scope of the subject matter disclosed herein. Moreover, any headings that may be used herein are also not intended to be used to construe the scope of the claims or to limit the scope of the subject matter disclosed herein. Any use of the past tense to describe an example otherwise designated as constructive or prophetic is not intended to reflect that the constructive or prophetic example was actually brought to pass.

Additional Description

The following are non-limiting specific embodiments in accordance with the present invention.

The first embodiment, which is a method for producing methanol, comprising (a) reacting, through a catalytic partial oxidation (CPO) reaction, a mixture of CPO reagents in a CPO reactor to produce synthesis gas; where the mixture of CPO reagents contains hydrocarbons and oxygen; where the CPO reactor contains a CPO catalyst; and wherein the synthesis gas contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted hydrocarbons, (b) introducing at least a portion of the synthesis gas into a methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent stream contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons, and (c) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; wherein the steam stream contains hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and wherein the crude methanol stream contains water in an amount of less than about 10% by weight based on the total weight of the crude methanol stream.

A second embodiment, which is a method of the first embodiment, wherein the synthesis gas contains carbon dioxide in an amount of about 0.1 to 5 mol%.

The third embodiment, which is a method of any of the first to second embodiments, wherein the synthesis gas has a molar ratio of carbon monoxide to carbon dioxide (CO/CO ₂ ) equal to or greater than about 5.

A fourth embodiment, which is a method of any of the first to third embodiments, wherein the hydrocarbons include methane, natural gas, liquefied natural gas, associated gas, wellhead gas, rich gas, waxes, shale gas, shale liquids, waste gas fluid - catalytic cracking (FCC), process gases from oil refining, flue gases, fuel gas from the fuel gas collector, or combinations thereof.

A fifth embodiment, which is a method of any of embodiments one through four, wherein the CPO reactor has a water vapor to carbon (W/C) molar ratio of the CPO reactant mixture of about 0.01:1 to less than 2.4 :1.

A sixth embodiment, which is a method of any of embodiments one through five, also comprising (i) recovering the CPO reactor effluent from the CPO reactor, wherein the CPO reactor effluent contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted hydrocarbons, and where the amount of carbon dioxide in the effluent of the CPO reactor is greater than the amount of carbon dioxide in the synthesis gas; and (ii) removing at least a portion of the carbon dioxide from the CPO reactor effluent to produce synthesis gas.

The seventh embodiment, which is the method of the sixth embodiment, in which the CPO reactor effluent is characterized by the ratio M of the CPO reactor effluent, where the ratio M is a molar ratio defined as (H ₂ CO ₂ )/(CO+CO ₂ ); where the synthesis gas is characterized by a ratio M that is greater than the ratio M of the effluent stream of the CPO reactor.

An eighth embodiment, which is a method of the seventh embodiment, further comprising reacting, through a steam methane reforming (SMR) reaction, a mixture of SMR reactants in a SMR reactor to produce an effluent synthesis gas stream of the SMR reactor; where the mixture of PRM reagents includes methane and water vapor; wherein the effluent synthesis gas stream of the PRM reactor contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted methane; and where the ratio M of the output stream of synthesis gas of the PRM reactor is greater than the ratio of M of the output stream of the CCHO reactor.

A ninth embodiment, which is a method of the eighth embodiment, further comprising contacting at least a portion of the PMR reactor synthesis gas effluent with at least a portion of the CPO reactor effluent to produce synthesis gas.

The tenth embodiment, which is a method of the eighth embodiment, further comprising introducing at least a portion of the effluent synthesis gas stream of the PMR reactor into the CPO reactor.

An eleventh embodiment, which is a method of the eighth embodiment, in which the P/S molar ratio in the PRM reactant mixture is greater than the P/S molar ratio in the CCO reactant mixture, where the P/S molar ratio means the total number of moles of water (H2O) in the reaction mixture divided by the total moles of carbon (C) hydrocarbons in the reaction mixture.

A twelfth embodiment, which is a method of any of the first to eleventh embodiments, wherein the CSF reactor is characterized by at least one CSF operating parameter selected from the group consisting of a CSF feed temperature of about 25 to 600° C.; temperature of the CCHO outlet stream is approximately from 300 to 1600°C; pressure CCH from approximately 1 to 90 bar (g); CFC contact time is approximately from 0.001 milliseconds (ms) to 5 s; the molar ratio of carbon to oxygen (C/O) in a mixture of COC reagents is from approximately 0.5:1 to 3:1, where the molar ratio C/O means the total number of moles of carbon (C) hydrocarbons in the reaction mixture divided by the total number of moles oxygen (02) in the reaction mixture; and their combinations.

A thirteenth embodiment, which is a method of the twelfth embodiment, wherein the at least one operating parameter includes a water vapor to carbon (W/C) molar ratio in the CWC reactant mixture of less than about 1:1, wherein the W/C molar ratio means the total number of moles of water (H ₂ O) in the reactant mixture divided by the total number of moles of carbon (C) hydrocarbons in the reactant mixture.

A fourteenth embodiment, which is a method of any of embodiments twelve through thirteen, wherein the at least one operating parameter includes a CPR pressure of approximately less than 30 bar(g)

A fifteenth embodiment, which is a method of any of embodiments twelve through fourteen, wherein the at least one operating parameter includes a CPO effluent temperature equal to or greater than about 750° C. and/or a C/O molar ratio of the reactant mixture NER is approximately less than 2.2:1.

A sixteenth embodiment, which is a method of any of embodiments one through fifteen, wherein a portion of the hydrocarbons in the CPO reactant mixture is decomposed to carbon and hydrogen, and wherein at least a portion of the carbon is reacted with carbon dioxide in a CPO reactor to produce monoxide carbon.

A seventeenth embodiment, which is a method of any of the first to sixteenth embodiments, further comprising (i) separating at least a portion of the steam stream into a hydrogen stream and a tail gas stream, wherein the hydrogen stream contains at least a hydrogen portion of the vapor stream, wherein the residual gas stream contains carbon monoxide, carbon dioxide and hydrocarbons; and (ii) recycling at least a portion of the hydrogen stream to the methanol reactor.

An eighteenth embodiment, which is a method for producing methanol, comprising (a) reacting, through a catalytic partial oxidation (CPO) reaction, a mixture of CPO reactants in a CPO reactor to produce a CPO reactor effluent; where the mixture of CPO reagents contains hydrocarbons and oxygen; where the CPO reactor contains a CPO catalyst; wherein the CPO reactor effluent contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted hydrocarbons, (b) removing at least a portion of the carbon dioxide from the CPO reactor effluent in a carbon dioxide separator to produce synthesis gas, wherein the synthesis gas contains dioxide carbon in an amount of from about 0.1 to 5 mol.%, (c) introducing at least a portion of the synthesis gas into the methanol reactor to obtain a methanol reactor effluent; wherein the methanol reactor effluent stream comprises methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons, (d) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream, wherein the crude methanol stream comprises methanol and water, wherein the steam stream contains hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and wherein the crude methanol stream contains water in an amount of less than about 5 wt.% based on the total weight of the crude methanol stream, (e) separating at least a portion of the crude methanol stream in the distillation unit into a methanol stream and a water stream, where the distillation unit includes one or more distillation columns, (f) separating at least a portion of the steam stream into a hydrogen stream and a tail gas stream, where the hydrogen stream contains at least a portion of the hydrogen of the steam stream, and where the tail gas stream contains carbon monoxide, carbon dioxide and hydrocarbons, and (g) recycling at least a portion of the hydrogen stream to the methanol reactor.

A nineteenth embodiment, which is a method of the eighteenth embodiment, in which the CPO reactor has a molar ratio of water vapor to carbon (W/C) in the CPO reactant mixture of approximately less than 0.5:1, where the molar ratio of P/C

-

Claims (19)

means the total moles of water (H2O) in the reactant mixture divided by the total moles of carbon (C) hydrocarbons in the reactant mixture; wherein a portion of the hydrocarbons in the CPO reactant mixture undergoes decomposition to carbon and hydrogen, wherein at least a portion of the carbon reacts with carbon dioxide in the CPO reactor to form carbon monoxide, and/or where at least a portion of the carbon reacts with water in the CPO reactor to produce carbon monoxide and hydrogen. A twentieth embodiment, which is a method of any of embodiments eighteen to nineteen, further comprising (1) cooling at least a portion of the CPO reactor effluent to obtain a cooled CPO reactor effluent; (2) removing at least a portion of the water from the cooled CPO reactor effluent to produce a dehydrated CPO reactor effluent, wherein the dehydrated CPO reactor effluent contains hydrogen, carbon monoxide, carbon dioxide, and unreacted hydrocarbons; and (3) feeding at least a portion of the dehydrated effluent of the CPO reactor to a carbon dioxide separator in step (b). While embodiments of the invention have been presented and described, modifications may be made without departing from the spirit and ideas of the invention. The embodiments and examples described herein are illustrative only and are not intended to be limiting. Many variations and modifications of the disclosed invention are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the above description, but is limited only by the claims below, which scope includes all equivalents of the subject matter of the claims. Each claim is included in the description as an embodiment of the present invention. Thus, the claims are intended to further describe and supplement the detailed description of the present invention. The descriptions of all patents, patent applications and publications cited herein are incorporated herein by reference. CLAIM 1. A method for producing methanol, comprising (a) reacting through a catalytic partial oxidation (CPO) reaction of a mixture of CPO reagents in a CPO reactor to produce synthesis gas; where the mixture of CPO reagents contains hydrocarbons and oxygen; where the CPO reactor contains a CPO catalyst; and wherein the synthesis gas contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted hydrocarbons; (b) introducing at least a portion of the synthesis gas into the methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and (c) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; wherein the steam stream contains hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and wherein the crude methanol stream contains water in an amount of less than about 10 wt.% based on the total weight of the crude methanol stream, in which the synthesis gas contains carbon dioxide in an amount of from about 0.1 to 5 mol.%. 2. The method of claim 1, wherein the synthesis gas has a molar ratio of carbon monoxide to carbon dioxide (CO/CO ₂ ) equal to or greater than about 5. 3. The method of claim 1, wherein the hydrocarbons include methane, natural gas, liquefied natural gas, associated gas, wellhead gas, rich gas, paraffins, shale gas, shale fluids, fluid catalytic cracking waste gas (FCC) , refinery process gases, flue gases, fuel gas from a fuel gas manifold, or combinations thereof. 4. The method of claim 1, wherein the CPO reactor is characterized by a molar ratio of water vapor to carbon (W/C) in the CPO reactant mixture from about 0.01:1 to less than 2.4:1. 5. The method of claim 1, further comprising (i) recovering the CPO reactor effluent from the CPO reactor, wherein the CPO reactor effluent contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted hydrocarbons and wherein the amount of carbon dioxide in the CPO reactor effluent stream is greater than the amount of carbon dioxide in the synthesis gas; and (ii) removing at least a portion of the carbon dioxide from the CPO reactor effluent to produce synthesis gas. 6. The method according to claim 5, in which the effluent stream of the CPO reactor is characterized by the ratio M of the effluent stream of the CPO reactor, where the ratio M means a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ); and where the synthesis gas has an M ratio that is greater than the M ratio of the CPO reactor effluent. 7. The method of claim 6, further comprising reacting, through a steam methane reforming (SMR) reaction, a mixture of SMR reagents in a SMR reactor to produce an effluent synthesis gas stream of the SMR reactor; where the mixture of PRM reagents contains methane and water vapor; wherein the effluent synthesis gas stream of the PRM reactor contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted methane; and where the ratio M of the output stream of synthesis gas of the PRM reactor is greater than the ratio of M of the output stream of the CCHO reactor. - 19 044126 8. The method of claim 7, further comprising contacting at least a portion of the PRM reactor effluent synthesis gas stream with at least a portion of the CPO reactor effluent stream to produce synthesis gas. 9. The method according to claim 7, also including introducing at least a portion of the effluent synthesis gas stream of the PRM reactor into the CPO reactor. 10. The method according to claim 7, wherein the P/S molar ratio in the PRM reagent mixture is greater than the P/S molar ratio in the CCHO reagent mixture, where the P/S molar ratio means the total number of moles of water (H2O) in the reagent mixture, divided by the total number of moles of carbon (C) hydrocarbons in the reactant mixture. 11. The method according to claim 1, in which the CPO reactor is characterized by at least one CPO operating parameter selected from the group consisting of a CPO supply temperature of approximately 25 to 600°C; temperature of the CCHO outlet stream is approximately from 300 to 1600°C; pressure CCH from approximately 1 to 90 bar (g); CFC contact time is approximately from 0.001 milliseconds (ms) to 5 s; the molar ratio of carbon to oxygen (C/O) in a mixture of COC reagents is from approximately 0.5:1 to 3:1, where the molar ratio C/O means the total number of moles of carbon (C) hydrocarbons in the reaction mixture divided by the total number of moles oxygen (O ₂ ) in the reaction mixture; and their combinations. 12. The method of claim 11, wherein the at least one operating parameter comprises a molar ratio of water vapor to carbon (W/C) in the CWC reactant mixture of less than approximately 1:1, wherein the molar ratio of W/C means the total number of moles of water (H ₂ O) in the reactant mixture divided by the total moles of carbon (C) hydrocarbons in the reactant mixture. 13. The method of claim 11, wherein the at least one operating parameter comprises a pressure of the CPO of less than approximately 30 bar(g) 14. The method of claim 11, wherein the at least one operating parameter includes a temperature of the CPO effluent stream equal to or greater than about 750°C, and/or a C/O molar ratio of the CPO reagent mixture of less than about 2.2: 1. 15. The method of claim 1, wherein a portion of the hydrocarbons in the CPO reactant mixture is decomposed to carbon and hydrogen, and wherein at least a portion of the carbon reacts with carbon dioxide in the CPO reactor to form carbon monoxide. 16. The method of claim 1, further comprising (i) separating at least a portion of the steam stream into a hydrogen stream and a tail gas stream, wherein the hydrogen stream contains at least a portion of the hydrogen of the steam stream and where the tail gas stream contains carbon monoxide, carbon dioxide and hydrocarbons; and (ii) recycling at least a portion of the hydrogen stream to the methanol reactor. 17. A method for producing methanol, comprising (a) reacting, through a catalytic partial oxidation (CPO) reaction, a mixture of CPO reagents in a CPO reactor to produce a CPO reactor effluent; where the mixture of CPO reagents contains hydrocarbons and oxygen; where the CPO reactor contains a CPO catalyst; wherein the effluent stream of the CPO reactor contains hydrogen, carbon monoxide, carbon dioxide, water and unreacted hydrocarbons; (b) removing at least a portion of the carbon dioxide from the CPO reactor effluent in a carbon dioxide separator to produce synthesis gas, wherein the synthesis gas contains carbon dioxide in an amount of from about 0.1 to 5 mole percent; (c) introducing at least a portion of the synthesis gas into the methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; (d) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream, where the crude methanol stream contains methanol and water, where the steam stream contains hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and wherein the crude methanol stream contains water in an amount of less than about 5 wt.% based on the total weight of the crude methanol stream; (e) separating at least a portion of the crude methanol stream in the distillation unit into a methanol stream and a water stream, where the distillation unit includes one or more distillation columns; (f) separating at least a portion of the steam stream into a hydrogen stream and a residual gas stream, where the hydrogen stream contains at least a portion of the hydrogen of the steam stream and where the residual gas stream contains carbon monoxide, carbon dioxide and hydrocarbons; and (g) recycling at least a portion of the hydrogen stream to the methanol reactor. 18. The method of claim 17, wherein the CWC reactor is characterized by a molar ratio of water vapor to carbon (W/C) in the CWC reactant mixture of approximately less than 0.5:1, wherein the molar ratio of P/C means the total number of moles of water (H2O ) in a mixture of reagents, divided by the total number of moles of carbon (C) hydrocarbons in the mixture of reagents; wherein a portion of the hydrocarbons in the CPO reactant mixture is decomposed to carbon and hydrogen, wherein at least a portion of the carbon reacts with carbon dioxide in the CPO reactor to form carbon monoxide and/or wherein at least a portion of the carbon reacts with water in the CPO reactor to produce carbon monoxide carbon and hydrogen. 19. The method of claim 17, further comprising (1) cooling at least a portion of the effluent stream -