EA044713B1 - METHOD FOR PRODUCING METHANOL WITH INCREASED ENERGY EFFICIENCY - Google Patents

Description

Field of technology

The invention relates to systems and methods for producing synthesis gas through catalytic partial oxidation (CPO), and producing methanol from it; More specifically, the present invention relates to systems and methods for methanol production that utilize steam methane reforming (SMR) and catalytic partial oxidation (CPO) to produce synthesis gas for methanol production; Even more specifically, the present invention relates to systems and methods for producing methanol that provide synthesis gas having the desired composition to the methanol synthesis loop through a combination of CPO and SMR without the use of additional hydrogen enrichment, for example, through WGS, and/or removal carbon dioxide (CO2).

State of the art

Synthesis 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). Syngas is typically used as an intermediate in the production of methanol and ammonia, and as an intermediate in the production 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 offgas, naphtha feedstocks, heavy hydrocarbons, coal, biomass, etc. can be used to produce syngas. SMR is an endothermic process and requires a significant supply of energy to propel the reaction forward. Conventional endothermic technologies such as SMR produce syngas with a hydrogen content higher than that required for methanol synthesis. Typically, SMR produces syngas with an M ratio ranging from 2.6 to 2.98, where the M ratio is a molar ratio defined as (H ₂ CO2)/(CO+CO2).

In the autothermal reforming (ATR) process, a portion of the natural gas is burned as fuel to convert the natural gas into syngas, resulting in relatively low hydrogen content and high CO ₂ concentrations. Traditional methanol plants use combined reforming (CR) technology, which combines SMR with autothermal reforming (ATR), reducing the amount of hydrogen present in the syngas. ATR produces syngas with less hydrogen than required for methanol synthesis. Typically, ATR produces syngas with an M ratio ranging from 1.7 to 1.84. In CR technology, the volumetric flow rate for supplying natural gas to the SMR and ATR can be adjusted to achieve an overall syngas M ratio of 2.0 to 2.06. In addition, the syngas produced by CR has a hydrogen content that is higher than the hydrogen content required for methanol synthesis. Moreover, SMR is a highly endothermic process, and the endothermic nature of SMR technology requires combustion of fuel to enable syngas synthesis. Consequently, SMR technology reduces the energy efficiency of the methanol synthesis process.

Syngas can also be produced (non-commercially) through the catalytic partial oxidation (CPO or CPOx) of natural gas. CPO processes use the partial oxidation of hydrocarbon feedstocks into a syngas containing CO and H2. The CPO process is exothermic, thus eliminating the need for external heat. However, the composition of the resulting syngas is not fully suitable for various downstream synthesis processes (eg methanol synthesis) due to the reduced hydrogen content. Thus, there remains a continuing need to develop systems and processes that utilize CPO processes to produce synthesis gas suitable for downstream chemical synthesis (eg, methanol synthesis).

Brief description of the figures

For a detailed description of preferred embodiments of the described processes, reference is made to the accompanying drawing, where:

The figure is a system diagram for I for a synthesis gas and methanol synthesis process in accordance with embodiments of the present invention.

Detailed description

Described herein is a system and method for producing syngas and optionally subsequently synthesizing methanol from it using catalytic partial oxidation (CPO), for example, natural gas in combination with SMR.

Traditional syngas production methods for methanol synthesis use independent steam reforming (SMR) technology or combined reforming (CR) technology. Both of these traditional processes use endothermic steam reforming (SMR) to produce syngas with the desired composition for methanol synthesis. The SMR reaction is a highly endothermic typical process that also has a high capital cost (CAPEX). Traditional best-in-class methanol plants use combined reformer (CR) technology, which consists of an SMR reactor and

- 1 044713 autothermal reforming (ATR) units to reduce energy consumption in the production of syngas, and thus in the process of methanol synthesis in general. The CR method reduces the fuel consumption of the SMR element by engaging ATR to reform a portion of the natural gas feed. The natural gas feed (e.g., volumetric flow rate) to the SMR and ATR is adjusted to achieve the final syngas composition (e.g., syngas with an M value, as further described hereinbelow, of approximately 2.0 to 2.06) provided by the technology CR.

The endothermic nature of SMR technology requires combustion of fuel to power the reactions. Therefore, SMR technology reduces the energy efficiency of the methanol synthesis process using SMR to provide feedstock synthesis gas for methanol synthesis.

The system and method described herein uses the CPO process in conjunction with SMR to produce hydrogen-enriched syngas with the desired composition for subsequent methanol synthesis without the need for additional hydrogen enrichment, such as through water gas shifting (WGS), and/or carbon dioxide removal ( CO ₂ ). In accordance with the present invention, a catalytic partial oxidation (CPO) reactor can be installed in parallel with a steam methane reformer (SMR) with the hydrocarbon feed to the process divided so that from about 10 to about 70 wt.% or from about 20 to about 60 wt.% was sent to the CPO reactor, and the remainder (from about 30 to about 90 wt.% or from about 40 to about 80 wt.%) was sent to the SMR reactor. The methanol synthesis system and method described herein are energy efficient and can be used, in some embodiments, to retrofit an existing methanol production facility. Using CPO, together with SMR and/or thermal integration, the system and method described herein can reduce energy use with minimal capital investment.

In some embodiments, the energy consumption of an existing methanol production plant can be reduced in accordance with the present invention by upgrading the existing plant. Alternatively, in accordance with the present invention, a new methanol plant can be designed that has reduced energy consumption relative to a similar plant that does not have CPO. Energy consumption is minimized in accordance with the present invention by combining catalytic partial oxidation with SMR, providing similar or higher levels of methanol production with similar product quality. In some embodiments, the energy consumption of a methanol production plant (e.g., a new or existing plant retrofitted in accordance with the present invention) is reduced from an index value of 90,100 MMBTU/ton of methanol produced, to an index value of less than about 55-85 MMBTU/ton of methanol produced, which represents a decline of more than approximately 15-45%. In some embodiments, the energy consumption of a methanol production unit is reduced by the system and method of the invention by at least 5, 10, 15, 20, 25, 30, 35, 40 or 45% relative to conventional methanol production by SMR without CPO. In some embodiments, the energy consumption of a methanol production plant (e.g., a new or existing plant retrofitted in accordance with the present invention) is reduced to an index value of less than or equal to about 90, 85, 80, 75, 70, 65, 60, or 55 MMBTU/ton methanol produced by the system and method of the present invention.

Except in working examples or where otherwise indicated, all numbers or expressions regarding amounts of ingredients, reaction conditions, and the like used in the present specification and claims are intended to be modified in all cases by the term approximately. Various numerical ranges are disclosed herein. Because these ranges are continuous, they include every value between the minimum and maximum values. The endpoints of all ranges indicating the same characteristic or component are independently combinable and include the specified endpoints. Unless otherwise expressly stated, the various numerical ranges stated herein are approximations. The endpoints of all ranges that refer to the same component or property include endpoints and can be combined independently. The term greater than 0 to some amount means that the named component is present in some amount greater than 0, up to and including the higher named amount.

The singular form is not intended to indicate a limitation in quantity, but rather to indicate the presence of at least one of the entities referred to. As used within the scope of the invention, the singular form includes the plural of the entities referred to.

As used within the scope of the invention, the expression combination thereof includes one or more of the specified elements, optionally together with an element that is not specified, for example, including a combination of one or more named components, optionally with one or more other components not specifically named, which have essentially the same function. How

- 2 044713 is used within the scope of the invention, the term combination includes combinations, mixtures, alloys, reaction products, etc.

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

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

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

As used herein, the terms containing (and any form of the term containing, such as contain and contains), having (and any form of the term having, such as have and has), including (and any form of the term including, such as include and include ) or containing (and any form of containing, such as contain and contains) are inclusive or open-ended and do not exclude additional unspecified elements or process steps.

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

The compounds are described herein using standard nomenclature. For example, any position not substituted in any of these groups is meant to have its valency occupied by a bond as indicated or by a hydrogen atom. A bar (-) that is not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is bonded through the carbon atom of the carbonyl group.

As used herein, the terms C _x hydrocarbons and C _x s 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 s refer to any hydrocarbons having exactly 4 carbon atoms, such as n-butane, isobutane, cyclobutane, 1-butene, 2-butene, isobutylene, butadiene, and the like. , or their combinations.

As used herein, the term Cx+ hydrocarbons refers to any hydrocarbon having more than or exactly x 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.

As used herein, a methanol synthesis loop or methanol loop refers to the portion of the plant in which methanol synthesis occurs, including the methanol synthesis reactor(s).

As used herein, the ratio M is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ).

Referring to the figure, a system I for producing syngas and methanol is disclosed. System I for producing syngas and methanol typically includes a catalytic partial oxidation (CPO or CPOx) reactor 10; steam methane reforming (SMR) reactor 20; compressor 30; methanol synthesis reactor 40; a gas-liquid separator 50 and a distillation unit 60. In some embodiments, the system I for synthesizing syngas and methanol I may further include a desulfurization element 6, and one or more heat exchangers, as a first heat exchanger HE1, a second heat exchanger HE2, and a third heat exchanger HE3. As will be appreciated by one skilled in the art and with the benefit of the present description, the components of the syngas and methanol production system illustrated in the figure may be hydraulically coupled to each other (as indicated by connecting lines indicating the direction of fluid flow) through any suitable passages (eg , pipes, streams, etc.).

In some embodiments, the method described herein may include the step of (a) feeding a mixture of catalytic partial oxidation (CPO) reactants into the CPO reactor 10; wherein the CPO reactant mixture includes oxygen, the first hydrocarbon portion 8A, and optionally steam; wherein at least a portion of the CPO reactant mixture is reacted by a CPO reaction in the CPO reactor 10 to form a CPO reactor effluent stream 15A; wherein the CPO reactor 10 contains a CPO catalyst; wherein the CPO reactor effluent stream 15A contains hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons, wherein the CPO reactor effluent stream 15A is characterized by a molar ratio of hydrogen to carbon monoxide ( _H2 /CO) of the CPO reactor effluent stream 15A, and wherein the CPO reactor effluent stream 15A is characterized by the ratio M of the CPO reactor effluent stream 15A, wherein the ratio M

- 3 044713 is a molar ratio defined as (H2-CO ₂ )/(CO+CO2). As further described below, the CPO reactant mixture may include oxygen in line 12 and/or steam in line 11A in combination with the first hydrocarbon portion 8A.

In addition, the method includes (b) supplying a steam methane reforming (SMR) reactant mixture to the SMR reactor 20, where the SMR reactant mixture includes steam and a second hydrocarbon portion 8B; wherein at least a portion of the SMR reactant mixture is reacted by an SMR reaction in the SMR reactor 20 to form an SMR reactor effluent stream 15B; wherein the SMR reactor effluent stream 15B includes hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), water and unreacted hydrocarbons; wherein the SMR reactor effluent stream 15B has an H2/CO molar ratio of the SMR reactor effluent stream 15B that is greater than the H2/CO molar ratio of the CPO reactor effluent stream 15A; and wherein the SMR reactor effluent stream 15B has a ratio M of the SMR reactor effluent stream 15B that is greater than the M ratio of the CPO reactor effluent stream 15A. As further described herein below, the SMR reactant mixture may include steam in line 11A and/or 11C in combination with a second hydrocarbon portion 8B.

Typically, the CPO reaction is based on the partial combustion of fuels such as various hydrocarbons, and, in the case of methane, CPO may correspond to equation (1):

CHI 2O2 ^> CO ^, 2H2 (1)

Without being limited by theory, side reactions may occur during the CPO reaction shown in equation (1); and such reactions can produce carbon dioxide (CO ₂ ) and water (H ₂ O), for example from the combustion of hydrocarbons, which is an exothermic reaction. As will be appreciated by one skilled in the art both by the present description and without being limited by theory, the CPO reaction corresponding to equation (1) can result in a syngas with a hydrogen to carbon monoxide (H2/CO) molar ratio having a theoretical stoichiometric limit of 2. 0. Without being limited by theory, the theoretical stoichiometric limit of 2.0 for the H2/CO molar ratio means that the CPO reaction corresponding to equation (1) provides 2 mol H ₂ for every 1 mol CO, i.e. H2/CO molar ratio (2 mol H2/1 mol CO) = 2. As will be appreciated by one skilled in the art and with the benefit of this disclosure, the theoretical stoichiometric limit of 2.0 for the _H2 /CO molar ratio in the CPO reaction cannot be achieved practically, since reactants (eg hydrocarbons, oxygen) as well as products (eg H ₂ , CO) undergo side reactions under the conditions used for the CPO reaction. As will be appreciated by one of ordinary skill in the art, both by use of the present disclosure and without being limited by 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 changed through the equilibrium of the water gas shift (WGS) reaction, which is discussed in more detail below herein. Side reactions that may occur in the CPO reactor 10 may have a direct effect on the M ratio of the resulting syngas (e.g., syngas in the CPO reactor effluent stream 15A), where the M ratio is a molar ratio defined as (H ₂ -CO ₂ ) /(CO+CO ₂ ). In the absence of any side reaction (theoretical), the CPO reaction corresponding to equation (1) provides syngas with an M ratio of 2.0. However, the presence of side reactions (virtually) reduces the H ₂ content and increases the CO ₂ content, thereby providing syngas in the CPO reactor effluent stream 15A with an M ratio of less than 2.0.

Moreover, without being limited by theory, the CPO reaction as presented in equation (1) is an exothermic heterogeneous catalytic reaction (i.e., a weakly exothermic reaction) and occurs in a single reactor unit such as a 10 CPO reactor (as opposed to more than one reactor plant, as is the case with conventional syngas production processes such as steam methane reforming (SMR) - autothermal reforming (ATR) combinations). While it is possible to carry out the partial oxidation of hydrocarbons as a homogeneous reaction in the absence of a catalyst, the process of homogeneous partial oxidation of hydrocarbons involves excessive temperatures, long residence times, as well as excessive coke formation, which significantly reduces the controllability of the partial oxidation reaction, and cannot provide the desired syngas quality in one reactor plant.

Moreover, without being limited by theory, the CPO reaction is quite resistant to chemical poisoning and as such allows the use of a wide variety of hydrocarbon feedstocks, including some sulfur-containing hydrocarbon feedstocks; which in some cases can increase the lifetime and performance of the catalyst. In contrast, conventional ATR processes have more restrictive feedstock requirements, for example in terms of feed impurity content (e.g. ATR feedstock is desulfurized) and also in terms of hydrocarbon composition (e.g. ATR primarily uses _CH4 -rich raw materials).

Steam can react with methane, for example, as shown in equation (2):

CH ₄ +H ₂ O^ CO+3H2 (2)

- 4 044713

The SMR reactor effluent stream 15B may be produced by reacting, via an SMR reaction (eg, the reaction corresponding to equation (2)), a mixture of SMR reactants containing a second hydrocarbon portion 8B and steam 11B and/or 11C in the SMR reactor 20 to produce effluent stream 15B from the SMR reactor; wherein the SMR reactant mixture thus includes methane and steam; and wherein the effluent stream 15B from the SMR reactor includes hydrogen, carbon monoxide, carbon dioxide, water and unreacted methane.

Generally, SMR refers to the catalytic reaction of methane and steam to produce carbon monoxide and hydrogen according to the reaction corresponding to equation (2). The steam reforming catalysts used in the SMR reactor 20 may include any suitable commercially available steam reforming catalyst; nickel (Ni) and/or rhodium (Rh) as active metal(s) on alumina; or combinations thereof. SMR uses significantly increased S/C molar ratios compared to the S/C molar ratios used in CPO. For example, SMR reactor 20 may have an S/C molar ratio of the SMR reactant mixture greater than or equal to about 1.5:1, alternatively greater than or equal to about 2:1, alternatively greater than or equal to about 2.5:1, alternatively greater than or equal to about 2.7:1, alternatively greater than or equal to about 3.0:1, or in the range of about 1.5:1 to 3.5:1, about 1.5:1 to 3:1, or from about 1.5:1 to about 2.5:1. Additionally, the SMR reactor effluent stream 15B may have an H ₂ /CO molar ratio greater than or equal to about 2.5, alternatively greater than or equal to about 2.7, or alternatively greater than or equal to about 2.9. As will be appreciated by one of ordinary skill in the art, both from the present description and without being limited by theory, the SMR reaction corresponding to equation (2) can provide syngas with a H2/CO molar ratio having a theoretical stoichiometric limit of 3.0 (i.e., the reaction The SMR corresponding to equation (2) provides 3 mol H2 for every 1 mol CO). As will be appreciated by one skilled in the art and with the benefit of the present disclosure, the theoretical stoichiometric limit of 3.0 for the H2/CO molar ratio in the SMR reaction cannot be achieved because the reactants undergo side reactions under the conditions used for the SMR reaction. The M ratio of the SMR reactor effluent stream 15B is greater than the M ratio of the CPO reactor effluent stream 15A.

In some embodiments, the hydrocarbon feedstock 5 further includes one or more sulfur-containing compounds, and at least a portion of the sulfur-containing compounds is removed from the processing portion 5A of the hydrocarbon feedstock 5 before feeding the hydrocarbons into the CPO reactor 10 as a component of the CPO reactant mixture or in SMR reactor 20 as a component of the SMR reagent mixture. In such embodiments, the process portion 5A (optionally after heat exchange therewith of a CPO reactor effluent stream 15A, an SMR reactor effluent stream 15B, or a combined syngas stream comprising at least a portion of the CPO reactor effluent stream 15A and at least a portion of the CPO reactor effluent stream 15B SMR reactor providing a heat-exchanged hydrocarbon processing portion 5A', which is described herein below), the hydrocarbon feedstock 5 may be supplied to the desulfurization element 6 to remove one or more sulfur-containing compounds therefrom. Any suitable desulfurization element 6 known to those skilled in the art may be used. For example, in some embodiments, the desulfurization element 6 includes a hydrodesulfurization (HDS) element 6, and hydrogen is supplied to the desulfurization element 6 via a hydrogen line 7. The desulfurized hydrocarbon stream 8 may be removed from the desulfurization element 6. The desulfurized hydrocarbon stream 8 may be separated into a first hydrocarbon portion 8A which is supplied to the CPO reactor 10 as a component of the CPO reactant mixture (optionally after being heat exchanged therewith to provide a heat exchanged desulfurized first hydrocarbon portion 8A' which is further described herein below). ), and a second hydrocarbon portion 8B which is supplied to the SMR reactor 20 as a component of the SMR reactant mixture.

In embodiments, the weight ratio of the first hydrocarbon portion 8A to the second hydrocarbon portion 8B is from about 1:9 to about 9:1, from about 1:9 to about 8:1, or from about 2:9 to about 9:1. In some embodiments, the first hydrocarbon portion 8A constitutes more than or exactly about 10, 20, 30, 40, 50, or 60 weight percent of the total hydrocarbons 8 (e.g., all hydrocarbons being the sum of the first hydrocarbon portion 8A and the second hydrocarbon portion 8B). In some embodiments, the second hydrocarbon portion 8B represents less than or exactly about 90, 80, 70, 60, 50, or 40 weight percent of the total hydrocarbons 8 (eg, all hydrocarbons are the sum of the first hydrocarbon portion 8A and the second hydrocarbon portion 8B).

In some embodiments, hydrocarbons (e.g., in hydrocarbon feed 5) suitable for use in the CPO and SMR reaction as described herein may include methane (CH ₄ ), natural gas, natural gas liquids, liquefied petroleum gas (LPG), associated gas, gas cap gas, enriched gas, paraffinic hydrocarbons, shale gas, shale liquids,

- 5 044713 fluid catalytic cracking (FCC) off-gas, oil refining process gas, oil refining off-gas, flue gases, fuel gas from a fuel gas header, etc., or combinations thereof. Hydrocarbons may include any suitable source of hydrocarbons and may include C ₁ -C ₆ hydrocarbons as well as some heavier hydrocarbons.

In some embodiments, the CPO reactant mixture in the CPO reactor 10 and the SMR reactant mixture in the SMR reactor 20 may contain hydrocarbons from hydrocarbon feedstock 5, which may contain, consist essentially of, or consist of natural gas. The process portion 5A of the hydrocarbon feedstock 5 may be used as a process gas (for example, PNG process natural gas)) and may be sent to the CPO reactor 10 or the SMR reactor 20, while the fuel portion 5B of the hydrocarbon feedstock 5 may be used as the fuel gas. (e.g., fuel natural gas (FNG)), and sent to other parts of the system 1 for use as a fuel (e.g., to burn to produce steam, e.g., to produce high pressure (HP) steam to run a turbine, e.g. to start steam compressor turbine 30 and/or to generate heat for heating the SMR reactor 20). In some embodiments, the hydrocarbons of the fuel portion 5B of the hydrocarbon feedstock 5 used as fuel are from about 5 to about 20, from about 5 to about 15, from about 6 to about 12 weight percent, or less than about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1 wt.% of all hydrocarbons of hydrocarbon feedstock 5 based on the total mass of hydrocarbons in the hydrocarbon feed 5, where the total hydrocarbons consist of the sum of the hydrocarbons fed to the CPO reactor 10 or the SMR process reactor 20 through the process portion 5A and the hydrocarbons sent as fuel through the fuel portion 5B.

Typically, natural gas consists primarily of methane, but may also contain ethane, propane and heavier hydrocarbons (e.g. isobutane, n-butane, isopentane, n-pentane, hexane, etc.), as well as very small amounts nitrogen, oxygen, carbon dioxide, sulfur compounds and/or water. Natural gas can be provided from a variety of sources, including, but not limited to, gas fields, oil fields, coal fields, fracking shale gas fields, biomass, landfill gas, and the like, or combinations thereof. In some embodiments, the CPO reactant mixture and the SMR reactant mixture may include CH ₄ and O2.

Natural gas may contain any suitable amount of methane. In some embodiments, the natural gas may comprise biogas. For example, natural gas may contain from about 45 mol% to about 80 mol% methane, from about 20 mol% to about 55 mol% carbon dioxide, and less than about 15 mol% nitrogen.

In some embodiments, the natural gas (or hydrocarbon stream 5) may include CH4 in an amount greater than or equal to about 45 mol%, alternatively greater than or equal to about 50 mol%, alternatively greater than or equal to about 55 mol%, alternatively greater than or equal to about 60 mol.%, alternatively greater than or equal to about 65 mol.%, alternatively greater than or equal to about 70 mol.%, alternatively greater than or equal to about 75 mol.%, alternatively greater than or equal to about 80 mol.%, alternatively greater than or equal to about 82 mol.%, alternatively greater than or equal to about 84 mol.%, alternatively greater than or equal to about 86 mol.%, alternatively greater than or equal to about 88 mol.%, alternatively greater than or equal to about 90 mol.%, alternatively greater than or equal to about 91 mol.%, alternatively greater than or equal to about 92 mol.%, alternatively greater than or equal to about 93 mol.%, alternatively greater than or equal to about 94 mol.%, alternatively greater than or equal to about 95 mol.%, alternatively greater than or equal to about 96 mol.%, alternatively greater than or equal to about 97 mol.%, alternatively greater than or equal to about 98 mol.%, or alternatively greater than or equal to about 99 mol.%.

In some embodiments, the hydrocarbon feedstock 5 suitable for use in the CPO and SMR reaction as described herein may contain C ₁ -C ₆ hydrocarbons, nitrogen (for example, from about 0.1 mol.% to about 15 mol.% , alternatively from about 0.5 mol.% to about 11 mol.%, alternatively from about 1 mol.% to about 7.5 mol.%, or alternatively from about 1.3 mol.% to about 5.5 mol.%. %) and carbon dioxide (for example, from about 0.1 mol.% to about 2 mol.%, alternatively from about 0.2 mol.% to about 1 mol.%, or alternatively from about 0.3 mol.% to approximately 0.6 mol.%). For example, hydrocarbons suitable for use in the CPO reaction as described herein may comprise C ₁ hydrocarbon (from about 89 mol.% to about 92 mol.%); C2 hydrocarbons (from about 2.5 mol.% to about 4 mol.%); ^-hydrocarbons (from approximately 0.5 mol.% to

- 6 044713 approximately 1.4 mol.%); C ₄ -hydrocarbons (from about 0.5 mol.% to about 0.2 mol.%); ^-hydrocarbons (approximately 0.06 mol.%); and C ₆ hydrocarbons (approximately 0.02 mol%); and optionally nitrogen (from about 0.1 mol.% to about 15 mol.%), carbon dioxide (from about 0.1 mol.% to about 2 mol.%), or as nitrogen (about 0.1 mol.% to about 15 mol.%), and carbon dioxide (from about 0.1 mol.% to about 2 mol.%). Thus, the CPO reactant mixture and the SMR reactant mixture may contain such hydrocarbons that can be supplied to the CPO reactor 10 and the SMR reactor 20 by the hydrocarbon feedstock process portion 5A 5, and the first hydrocarbon portion 8A or the second hydrocarbon portion 8B, respectively, or separately.

Oxygen used in the 10-reagent mixture for CPO may include 100% oxygen (substantially pure O ₂ ), gaseous oxygen (which can be obtained through membrane separation), industrial oxygen (which may contain some air), oxygen-enriched air air, oxygen-containing gaseous compounds (for example, NO), oxygen-containing mixtures (for example, O2/CO2, O2/H2O, O2/H2O2/H2O), hydroxy radical generators (for example, CH ₃ OH, CH2O), hydroxyl radical generators, etc. ., or combinations thereof. Oxygen may be supplied to the CPO reactor 10 through the oxygen line 12, in some embodiments, or in another way (eg, along with the first hydrocarbon portion 8A or the heat-exchanged first portion 8A').

In some embodiments, the CPO reactant mixture in CPO reactor 10 may have a carbon to oxygen (C/O) molar ratio of less than or equal to about 5:1, alternatively less than or equal to about 4:1; alternatively less than or equal to about 3:1; alternatively less than or equal to about 2.6:1, alternatively less than or equal to about 2.4:1, alternatively less than or equal to about 2.2:1, alternatively less than or equal to about 2:1, alternatively less than or equal to about 1.9 :1, alternatively less than or equal to about 1.8:1, alternatively less than or equal to about 1.75:1, alternatively greater than or equal to about 1.4:1; alternatively greater than or equal to about 2:1, alternatively greater than or equal to about 2.2:1, alternatively greater than or equal to about 2.4:1, alternatively greater than or equal to about 2.6:1, alternatively from about 0.5:1 up to approximately 5:1; alternatively from about 1.4:1 to about 5:1; alternatively from about 0.5:1 to about 3:1, alternatively from about 0.7:1 to about 2.5:1, alternatively from about 0.9:1 to about 2.2:1, alternatively from about 1 :1 to about 2:1, alternatively from about 1.1:1 to about 1.9:1, alternatively from about 1.5:1 to about 2.5:1, alternatively from about 1.6:1 to about 2.5:1, alternatively from about 2:1 to about 3:1, alternatively from about 2.2:1 to about 3:1, alternatively from about 2.4:1 to about 3:1, or alternatively from about 2.6:1 to about 3:1, where the C/O molar ratio refers to the total moles of carbon (C) in the hydrocarbons in the reactant mixture divided by the total moles of oxygen (O ₂ ) in the reactant mixture.

For example, when the only source of carbon in the CPO reactant mixture in the CPO reactor 10 is CH ₄ (for example, supplied through the first hydrocarbon portion 8A of hydrocarbons in the process portion 5A), the molar ratio of CH ₄ /O ₂ is the same as the molar ratio of C /O. As another example, when _the CPO reactant mixture contains, in addition to CH4, _other carbon sources such as ethane (C2H6), propane ( _C3H8 ), butane ( _C4H10 ), etc., the molar ratio C/O takes into account the number of moles _{of carbon in each compound (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 one skilled in the art will appreciate and with the benefit of this disclosure, the C/O molar ratio of the CPO reactant mixture can be adjusted, as well as other reactor process parameters (e.g., temperature, pressure, flow rate, etc.) to providing syngas with the desired composition (eg, syngas with the desired H2/CO molar ratio; syngas with the desired CO2 content; etc.). The C/O molar ratio of the CPO reactant mixture can be adjusted to provide the desired amount of unconverted hydrocarbons in the syngas. The C/O molar ratio of the CPO reactant mixture can be adjusted based on the CPO outlet temperature to reduce (eg, minimize) the unconverted hydrocarbon content of the syngas in the CPO reactor effluent stream 15A. As will be appreciated by one skilled in the art and with the benefit of the present disclosure, when syngas is further used in a methanol production process, unconverted hydrocarbons present in the syngas may undesirably accumulate in the methanol synthesis reaction loop, thereby reducing the efficiency of the methanol production process.

In some embodiments, a CPO reactor 10 suitable for use with the present invention (e.g., a CPO reactor 10) may include a tubular reactor, a continuous flow reactor, a fixed bed reactor, a fluidized bed reactor, a

- 7 044713 moving bed, circulating fluidized bed reactor (eg riser type reactor), foam bed reactor, fluidized bed reactor, rotary drying oven reactor, etc., or combinations thereof. In some embodiments, the CPO reactor 10 may include a circulating fluidized bed reactor, such as an elevator reactor.

In some embodiments, the CPO reactor 10 may be characterized by at least one CPO operating parameter selected from the group consisting of CPO reactor temperature (eg, CPO catalyst bed temperature); temperature of the CPO feedstock (for example, temperature of the CPO reagent mixture); target CPO effluent temperature; CPO pressure (eg CPO reactor pressure); CPO contact time (eg reactor contact time for CPO); C/O molar ratio in the reagent mixture for CPO; the molar ratio of steam to carbon (S/C) in the reactant mixture for CPO, where the molar ratio S/C refers to the total moles of water (H2O) in the reactant mixture divided by the total moles of carbon (C) in the hydrocarbons in the reaction mixture; and their combinations. For purposes of the present invention, the temperature of the CPO effluent stream is the temperature of the syngas (e.g., the effluent syngas stream; first syngas 15A) measured at the point where the syngas exits the CPO reactor (CPO reactor 10), e.g., the temperature of the syngas measured at the outlet CPO reactor, temperature of the effluent syngas stream, temperature of the effluent syngas stream at the outlet. For purposes of the present invention, the CPO effluent temperature (eg, the target CPO effluent temperature) is considered an operating parameter. As will be appreciated by one skilled in the art and with the benefit of the present disclosure, the selection of process parameters for the CPO reactor, such as CPO feed temperature; CPO pressure; CPO contact time; C/O molar ratio in the reagent mixture for CPO; molar ratio of S/C in a mixture of reagents for CPO, etc. determines the temperature of the syngas effluent stream (eg, the syngas effluent stream 15A from the CPO reactor), as well as the composition of the syngas effluent stream (eg, the syngas in the CPO reactor effluent stream 15A). Additionally, and as will be appreciated by one skilled in the art and with the benefit of this disclosure, monitoring the CPO effluent temperature can provide feedback to change other operating parameters (e.g., CPO feed temperature; CPO pressure; CPO contact time; molar C/O ratio of the CPO reactant mixture, S/C molar ratio of the CPO reactant mixture, etc.) as necessary to match the CPO effluent temperature to the target CPO effluent temperature. Moreover, and as will be appreciated by one skilled in the art and with the aid of the present disclosure, the target CPO effluent temperature is the desired CPO effluent temperature, and the CPO effluent temperature (e.g., measured CPO effluent temperature, actual temperature CPO effluent) may or may not be the same as the target CPO effluent temperature. In embodiments where the CPO effluent temperature differs from the target CPO effluent temperature, one or more CPO operating parameters (e.g., CPO feed temperature; CPO pressure; CPO contact time; C/O molar ratio of reactant mixture for CPO; the S/C molar ratio of the CPO reactant mixture; etc.) can be adjusted (e.g., modified) so that the CPO effluent temperature matches (e.g., is the same as, the same as) the target effluent temperature from CPO. The CPO reactor 10 may be operated at any suitable operating parameters that can provide syngas with a desired composition (eg, syngas with a desired H2/CO molar ratio; syngas with a desired CO2 content; etc.).

The CPO reactor 10 may have a CPO feed temperature of from about 25°C to about 600°C, alternatively from about 25°C to about 500°C, alternatively from about 25°C to about 400°C, alternatively from about 50°C up to about 400°C, alternatively from about 100°C to about 400°C, or alternatively less than or exactly about 550, 540 or 535°C.

The CPO reactor 10 may have a CPO effluent temperature (e.g., a target CPO effluent temperature) greater than or equal to about 300°C, greater than or equal to about 600°C, alternatively greater than or equal to about 700°C, alternatively greater than or equal to about 750°C, alternatively greater than or equal to about 800°C, alternatively greater than or equal to about 850°C, alternatively from about 300°C to about 1600°C, alternatively from about 600°C to about 1400°C, alternatively from about 600°C to about 1300°C, alternatively from about 700°C to about 1200°C, alternatively from about 750°C to about 1150°C, alternatively from about 800°C to about 1125°C, or alternatively from about 850 °C to approximately 1100°C.

- 8 044713

In some embodiments, the CPO reactor 10 may be characterized by any suitable reactor temperature and/or catalyst bed temperature. For example, CPO reactor 10 may have a reactor temperature and/or catalyst bed temperature greater than or equal to about 300°C, alternatively greater than or equal to about 600°C, alternatively greater than or equal to about 700°C, alternatively greater than or equal to about 750°C , alternatively greater than or equal to about 800°C, alternatively greater than or equal to about 850°C, alternatively from about 300°C to about 1600°C, alternatively from about 600°C to about 1400°C, alternatively from about 600°C to about about 1300°C, alternatively from about 700°C to about 1200°C, alternatively from about 750°C to about 1150°C, alternatively from about 800°C to about 1125°C, or alternatively from about 850°C to about 1100°C.

The CPO reactor 10 can be operated at any suitable temperature profile that can provide syngas with a desired composition (eg, syngas with a desired H2/CO molar ratio; syngas with a desired CO2 content; etc.). The CPO reactor 10 can be operated under adiabatic conditions, non-adiabatic conditions, isothermal conditions, near-isothermal conditions, etc. For purposes of the present invention, the term non-adiabatic conditions refers to process conditions where the reactor is subject to external heat exchange or heat transfer (eg, the reactor is heated; or the reactor is cooled), which may be direct heat exchange and/or indirect heat transfer. As will be appreciated by one skilled in the art and with the benefit of the present 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 where the reactor is not subject to external heat exchange (eg, the reactor is not heated; or the reactor is not cooled). Generally, external heat exchange refers to an external heat exchange system (eg, cooling system; heating system) that requires the input and/or removal of energy. External heat transfer can also result from heat loss from the catalyst bed (or reactor) due to radiation, conduction, or convection. For example, this heat exchange from the catalyst bed can be carried out to the external environment or to the reactor zones before and after the catalyst bed.

For purposes of the present invention, the term isothermal conditions refers to process conditions (eg, CPO process parameters) that provide a substantially constant temperature of the reactor and/or catalyst bed (eg, isothermal temperature), which can be defined as a temperature that varies less than by about +10°C, alternatively by less than about +9°C, alternatively by less than about +8°C, alternatively by less than about +7°C, alternatively by less than about +6°C, alternatively by less than about at +5°C, alternatively less than about +4°C, alternatively less than about +3°C, alternatively less than about +2°C, or alternatively less than about +1°C in the reactor and/ or a catalyst layer, respectively.

Additionally, for purposes of the present invention, the term isothermal conditions refers to process conditions (e.g., CPO process parameters) effective to provide syngas with the desired composition (e.g., desired H2/CO molar ratio; desired CO2 content; etc.) where isothermal conditions include a temperature variation of less than about +10°C in the reactor and/or catalyst bed. In some embodiments, the CPO reactor 10 may be operated at any suitable process parameters that can provide isothermal conditions.

For purposes of the present invention, the term substantially isothermal conditions refers to process conditions (eg, CPO process parameters) that provide a fairly constant temperature of the reactor and/or catalyst bed (eg, substantially isothermal temperature), which can be defined as a temperature that varies less than alternatively less than about +100°C, alternatively less than about +90°C, alternatively less than about +80°C, alternatively less than about +70°C, alternatively less than about +60°C, alternatively less alternatively less than about +50°C, alternatively less than about +40°C, alternatively less than about +30°C, alternatively less than about +20°C, alternatively less than about +10°C, alternatively less alternatively less than about +9°C, alternatively less than about +8°C, alternatively less than about +7°C, alternatively less than about +6°C, alternatively less than about +5°C, alternatively less alternatively less than about +4°C, alternatively less than about +3°C, alternatively less than about +2°C, or alternatively less than about +1°C in the reactor and/or catalyst bed, respectively. In some embodiments, substantially isothermal conditions provide a temperature variation of less than about +50°C, alternatively less than about +25°C,

- 9 044713 or alternatively less than approximately +10°C in the reactor and/or catalyst bed. Additionally, for purposes of the present invention, the term substantially isothermal conditions is intended to include isothermal conditions.

Moreover, for purposes of the present invention, the term near-isothermal conditions refers to process conditions (e.g., operating parameters for CPO) effective to provide syngas with the desired composition (e.g., desired H2/CO molar ratio; desired CO2 content; etc.) where near isothermal conditions include a temperature variation of less than about +100°C in the reactor and/or catalyst bed.

In some embodiments, the method as described herein may include conducting the CPO reaction under near-isothermal conditions to produce syngas, wherein the near-isothermal conditions include varying the temperature by less than about +100°C in the reactor and/or catalyst bed. In some embodiments, the CPO reactor 10 may be operated at any suitable parameters that can provide near isothermal conditions.

Near-isothermal conditions can be achieved by various process and catalyst variables, such as temperature (e.g., heat exchange or heat transfer), pressure, gas flow rate, reactor configuration, catalyst bed configuration, catalyst bed composition, reactor cross-sectional area, feed gas staging, supply gas injection, supply gas composition, etc., or combinations thereof. Generally, and without being limited by theory, the terms heat transfer or heat exchange refer to thermal energy exchanged or transferred between two systems (eg, two reactors, such as a CPO reactor and a cracker), and the terms heat transfer or heat exchange are used interchangeably for purposes of this description.

In some embodiments, achieving a target CPO effluent temperature and/or near isothermal conditions may be achieved through heat exchange or heat transfer. Heat exchange may include heating the reactor or cooling the reactor. In some embodiments, achieving a target CPO effluent temperature and/or near isothermal conditions can be achieved by cooling the reactor. In another embodiment, achieving a target CPO effluent temperature and/or near isothermal conditions can be achieved by heating the reactor.

In some embodiments, achieving a target CPO effluent temperature and/or near isothermal conditions may be achieved through direct heat exchange and/or indirect heat exchange. As will be appreciated by one skilled in the art and with the benefit of the present description, the terms direct heat transfer and indirect heat transfer are known to one skilled in the art.

Heat exchange may include external heat exchange, external coolant cooling, jet cooling, liquid nitrogen cooling, cryogenic cooling, electrical heating, electric arc heating, microwave heating, radiation heating, natural gas combustion, solar heating, infrared heating, use diluent in a mixture of CPO reagents, etc., or a combination thereof. For example, reactive cooling can be achieved by conducting an endothermic reaction in a refrigeration coil/shell associated with (eg, located in) the reactor.

In some embodiments, achieving a target CPO effluent temperature and/or near isothermal conditions can be achieved through process heat from the CPO reactor. In other embodiments, achieving a target CPO effluent temperature and/or near isothermal conditions can be achieved by applying heat to the CPO reactor. As one skilled in the art will appreciate and with the benefit of this disclosure, the CPO reactor may need to be heated and cooled to achieve a target CPO effluent temperature and/or near isothermal conditions.

In some embodiments, the heat exchange or heat transfer may include introducing a cooling agent, such as a diluent, into a reactor (e.g., CPO reactor 10) to reduce the reactor temperature and/or catalyst bed temperature while increasing the temperature of the cooling agent and/or changing the phase of the cooling agent . The coolant may be reactive or non-reactive. The coolant may be in a liquid and/or vapor state. As will be appreciated by one skilled in the art and with the benefit of the present disclosure, the coolant can act as a flammability inhibitor; for example, by reducing the temperature inside the reactor, by changing the composition of the gas mixture, by reducing the combustion of hydrocarbons to carbon dioxide, etc.

In some embodiments, the CPO reactant mixture in CPO reactor 10 may further comprise a diluent, wherein the diluent is involved in achieving a target CPO effluent temperature and/or near isothermal conditions through heat exchange, as described herein. The diluent may include water, steam, inert gases (for example,

- 10 044713 argon), nitrogen, carbon dioxide, etc., or combinations thereof. Typically, the diluent is inert to the CPO reaction, eg, the diluent does not participate in the CPO reaction. However, and as will be appreciated by one skilled in the art and with the benefit of this disclosure, some diluents (e.g., water, steam, carbon dioxide, etc.) may undergo different chemical reactions than the CPO reaction in the reactor and may change the composition of the final product. syngas, as described in more detail below herein; while other diluents (eg nitrogen (N2), argon (Ar)) may not participate in reactions that change the composition of the final syngas. As one skilled in the art will appreciate and with the benefit of this disclosure, a diluent can be used to vary the composition of the final syngas (eg, the syngas in CPO effluent stream 15A). The diluent may be present in the CPO reagent mixture in any suitable amount.

The CPO reactor 10 may have a CPO pressure (eg, reactor pressure measured at the outlet of the CPO reactor or at its outlet) greater than or equal to approximately 1 bar i.d. (gauge pressure), alternatively greater than or equal to about 10 barg, alternatively greater than or equal to about 20 barg, alternatively greater than or equal to about 25 barg, alternatively greater than or equal to about 30 barg. alternatively greater than or equal to about 35 barg, alternatively greater than or equal to about 40 barg, alternatively greater than or equal to about 50 barg, alternatively less than about 30 barg, alternatively less than about 25 bar i.d., alternatively less than about 20 bar i.d., alternatively less than about 10 bar i.d., alternatively from about 1 bar i.d. up to approximately 90 bar i.d., alternatively from approximately 1 bar i.d. up to approximately 70 bar i.d., alternatively from approximately 1 bar i.d. up to approximately 40 bar i.d., alternatively from approximately 1 bar i.d. up to approximately 30 bar i.d., alternatively from approximately 1 bar i.d. up to approximately 25 bar i.d., alternatively from approximately 1 bar i.d. up to approximately 20 bar i.d., alternatively from approximately 1 bar i.d. up to approximately 10 bar i.d., alternatively from approximately 20 bar i.d. up to approximately 90 bar i.d., alternatively from approximately 25 bar i.d. to approximately 85 bar i.d., or alternatively from approximately 30 bar i.d. up to approximately 80 bar i.d.

The CPO reactor 10 may have a CPO contact time of from about 0.001 milliseconds (ms) to about 5 seconds (s), alternatively from about 0.001 ms to about 1 s, alternatively from about 0.001 ms to about 100 ms, alternatively from about 0.001 ms to about 100 ms. about 10 ms, alternatively from about 0.001 ms to about 5 ms, or alternatively from about 0.01 ms to about 1.2 ms. Typically, the contact time of 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., in a catalyst bed), e.g., the average amount of time it takes for the compound to pass through ( for example, molecules of this compound) through a catalyst layer. In some embodiments, the CPO reactor 10 may have a contact time of from about 0.001 ms to about 5 ms, or alternatively from about 0.01 ms to about 1.2 ms.

All CPO performance parameters described herein are applicable to all of the embodiments described herein unless otherwise noted. As one skilled in the art will appreciate and with the benefit of the present disclosure, each CPO operating parameter can be adjusted to provide a desired quality of syngas (e.g., CPO reactor effluent stream 15A), such as a syngas of a desired composition (e.g., syngas with a desired molar ratio H/CO; syngas with desired CO content; etc.). For example, CPO operating parameters can be adjusted to provide increased H2 content in the syngas. As another example, CPO operating parameters can be adjusted to provide reduced CO ₂ content in the syngas. As another example, CPO operating parameters may be adjusted to ensure a reduction in unreacted hydrocarbons (eg, unreacted CH ₄ ) in the syngas.

In some embodiments, the CPO reactor 10 is characterized by at least one CPO operating parameter selected from the group consisting of a CPO inlet temperature of about 200°C to about 550°C; CPO outlet temperatures from approximately 600°C to approximately 1400°C; pressure in CPO from approximately 1 bar i.d. up to approximately 90 bar i.d.; contact time in CPO from approximately 0.001 milliseconds (ms) to approximately 5 seconds (s); molar ratio of carbon to oxygen (C/O) in the reactant mixture for CPO from about 1.4:1 to about 5:1, where the molar ratio C/O refers to the total moles of carbon (C) hydrocarbons in the reactant mixture divided by the total number of moles of oxygen (O2) in the mixture of reagents; molar ratio of steam to carbon (S/C) in the reactant mixture for CPO from about 0 to about 2:1, where the molar ratio S/C refers to the total moles of water (H ₂ O) in the reactant mixture divided by the total moles carbon (C)

- 11 044713 hydrocarbons in a mixture of reagents; and their combinations. In some embodiments, reactor 10

CPO is characterized by a steam to carbon (S/C) molar ratio in the CPO reactant mixture of about 0.05:1 to about 1:1, about 0.1:1 to about 2:1, about 0.1:1 up to approximately 2:1, or equal to approximately 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7,

0.8, 0.9 or 1.0.

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, i.e. a metal active in catalyzing the CPO reaction. The catalytically active metal may include a noble metal (eg, Pt, Rh, Ir, Pd, Ru, Ag, etc., or combinations thereof); base metal (eg 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 benefit of the present disclosure, the components of a CPO catalyst (eg, metals such as noble metals, base metals, rare earth metals) can either be separated into phases or combined in a single phase.

In some embodiments, CPO catalysts suitable for use in the present invention may be supported catalysts and/or unsupported catalysts. In some embodiments, supported catalysts may include 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 a metal mesh or wire screen (eg, Pt mesh or wire screen); monolithic catalyst based on a catalytically active metal, etc. In other embodiments, supported catalysts may comprise a support, where the support may be a catalytically inactive support (eg, the support cannot catalyze a CPO reaction), such as SiO ₂ ; silicon carbide (SiC); aluminum oxide; catalytically inactive monolithic substrate, etc. In other embodiments, supported catalysts may include a catalytically active support and a catalytically inactive support.

In some embodiments, the CPO catalyst may be applied as a thin coating to a support, where the support may be catalytically active or inactive, and where the support may be a monolith, a foam, a complex catalyst particle, etc.

In some embodiments, the CPO catalyst may be a monolith, foam, powder, particle, etc. Non-limiting examples of CPO catalyst particle shapes suitable for use with the present invention include cylindrical, disk-shaped, spherical, sheet-shaped, ellipsoidal, isometric, irregular, cubic, acicular, and the like, or combinations thereof.

In some embodiments, the support includes inorganic oxide, alpha, beta, or theta aluminum oxide (Al ₂ O ₃ ), activated Al ₂ O, silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), magnesium oxide (MgO), oxide zirconium (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, oxides hydrotalcite oxides, etc., or combinations thereof.

Without limitation, CPO processes, CPO reactors, CPO catalysts, and CPO catalyst bed configurations suitable for use with the present invention are described in more detail in U.S. Provisional Patent Application No. 62/522,910, filed June 21, 2017 (International Application No. PCT/ IB2018/054475, filed June 18, 2018) and entitled Improved Reactor Designs for Heterogeneous Catalytic Reactions; and Provisional Patent Application No. 62/521831, filed June 19, 2017 (International Application No. PCT/IB2018/054470, filed June 18, 2018) entitled An Improved Process for Syngas Production for Petrochemical Applications; each of which is incorporated herein by reference in its entirety for purposes not inconsistent with this specification.

In accordance with the present invention, the CPO reactor effluent stream 15A can be recovered from the CPO reactor 10, the CPO reactor effluent stream 15A including hydrogen, carbon monoxide, water, carbon dioxide and unreacted hydrocarbons (eg, methane). In some embodiments, the CPO reactor effluent stream 15A may have an M ratio greater than or equal to about 1.5, alternatively greater than or equal to about 1.6, alternatively greater than or equal to about 1.7, alternatively greater than or equal to about 1.8, alternatively greater than or equal to about 1.84, alternatively greater than or equal to about 1.9, alternatively from about 1.5 to about 1.95, alternatively from about 1.7 to about 2.3, alternatively from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.2.

- 12 044713

The CPO reactor effluent stream 15A as described herein may have an H/CO molar ratio of greater than about 1.7, alternatively greater than about 1.8, alternatively greater than about 1.9, alternatively greater than about 2.0 , or alternatively more than about 2.1. In some embodiments, the effluent syngas 15A from a CPO reactor as described herein may have an H ₂ /CO molar ratio of from about 1.7 to about 2.3, alternatively from about 1.75 to about 1.81, alternatively from from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.1.

In some embodiments, the CPO reactor effluent stream 15A may have a CO content of less than about 10 mol%, less than about 9 mol%, less than about 8 mol%, less than about 7 mol%, alternatively less than about 6 mol.%, alternatively less than about 5 mol.%, alternatively less than about 4 mol.%, alternatively less than about 3 mol.%, alternatively less than about 2 mol.%, alternatively less than about 1 mol.%, alternatively more than about 0.1 mol.%, alternatively more than about 0.25 mol.%, alternatively more than about 0.5 mol.%, alternatively from about 0.1 mol.% to about 7 mol.%, alternatively from about 0.25 mol% to about 6 mol%, or alternatively from about 0.5 mol% to about 5 mol%.

In accordance with the present invention, the SMR reactor effluent stream 15B can be recovered from the SMR reactor 20, where the SMR reactor effluent stream 15B includes hydrogen, carbon monoxide, water, carbon dioxide, and unreacted hydrocarbons (eg, methane). The SMR reactor effluent stream 15B has a H2/CO molar ratio of the SMR reactor effluent stream 15B that is greater than the H2/CO molar ratio of the CPO reactor effluent stream 15A; and the SMR reactor effluent stream 15B has an M ratio of the SMR reactor effluent stream 15B that is greater than the M ratio of the CPO reactor effluent stream 15A. In some embodiments, the SMR reactor effluent stream 15B may have an M ratio greater than or equal to about 1.5, alternatively greater than or equal to about 1.6, alternatively greater than or equal to about 1.7, alternatively greater than or equal to about 1.8, alternatively greater than or equal to about 1.84, alternatively greater than or equal to about 1.9, alternatively from about 1.5 to about 1.95, alternatively from about 1.7 to about 2.3, alternatively from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.2.

The effluent stream 15B from the SMR reactor as described herein may have a H2/CO molar ratio of greater than about 1.7, alternatively greater than about 1.8, alternatively greater than about 1.9, alternatively greater than about 2.0 , or alternatively more than about 2.1. In some embodiments, the SMR reactor effluent stream 15B as described herein may have an H ₂ /CO molar ratio of from about 1.7 to about 2.3, alternatively from about 1.75 to about 1.81, alternatively from from about 1.8 to about 2.2, or alternatively from about 1.9 to about 2.1.

In some embodiments, the SMR reactor effluent stream 15B may have a CO2 content of less than about 10 mol%, less than about 9 mol%, less than about 8 mol%, less than about 7 mol%, alternatively less than about 6 mol.%, alternatively less than about 5 mol.%, alternatively less than about 4 mol.%, alternatively less than about 3 mol.%, alternatively less than about 2 mol.%, alternatively less than about 1 mol.%, alternatively more than about 0.1 mol.%, alternatively more than about 0.25 mol.%, alternatively more than about 0.5 mol.%, alternatively from about 0.1 mol.% to about 7 mol.%, alternatively from about 0.25 mol% to about 6 mol%, or alternatively from about 0.5 mol% to about 5 mol%.

The method of the present invention may include (c) contacting at least a portion of the CPO reactor effluent stream 15A with at least a portion of the SMR reactor effluent stream 15B to produce a combined syngas 15C (optionally either upstream or downstream of the first heat exchanger HE1 and/or or a third heat exchanger HE3), wherein the combined syngas of the combined effluent streams 15A and 15B from the CPO and SMR reactors, respectively, is characterized by the H2/CO molar ratio of the combined syngas, and where the combined syngas is characterized by the M ratio of the syngas. The H2/CO molar ratio of the combined syngas 15C is greater than the H2/CO molar ratio of the CPO reactor effluent 15A and is less than the H2/CO molar ratio of the SMR reactor effluent 15B. The M ratio of the combined syngas 15C is greater than the M ratio of the CPO reactor effluent 15A and is less than the M ratio of the SMR reactor effluent 15B.

- 13 044713

Thus, the system may comprise one or more flow lines arranged to combine at least a portion of the CPO reactor effluent stream 15A with at least a portion of the SMR reactor effluent stream 15B to produce a combined syngas stream

15C. In some embodiments, one or more flow lines may be located above or below the first heat exchanger HE1 and/or the third heat exchanger HE3.

In some embodiments, the combination syngas 15C (and syngas 15D, 15E, and 15E, further described herein below) may have an M ratio greater than or equal to about 1.9, 1.95, or 2.0, from about 1.9 to about 2.5, alternatively from about 1.9 to about 2.2, alternatively from about 1.95 to about 2.1, or alternatively from about 2 to about 2.1. In some embodiments, the 15C/15D/15E/15E' combination syngas may have an H ₂ /CO molar ratio greater than or equal to about 1.8, 1.9, or 2, or from about 1.8 to about 2, alternatively from about 1.9 to about 2, or alternatively from about 1.8 to about 2.5.

In some embodiments, water may be condensed and separated from at least a portion of the CPO reactor effluent stream 15A, at least a portion of the SMR reactor effluent stream 15B, or a combination thereof (e.g., a combined syngas stream 15C comprising at least a portion of the SMR reactor effluent stream 15C). 15A from the CPO reactor and at least a portion of the effluent stream 15B from the SMR reactor), for example, in a condenser. In some embodiments, the CPO reactor effluent stream 15A and/or the SMR reactor effluent stream 15B may be subjected to processing, such as recovery of unreacted hydrocarbons, diluent, water, etc. In some embodiments, the method as described herein may further include: (i) recovering at least a portion of the unreacted hydrocarbons from the CPO reactor effluent stream 15A and/or the SMR reactor effluent stream 15B to produce recovered hydrocarbons, and (ii) recycling at least a portion of the recovered hydrocarbons to the CPO reactor 10 and/or the SMR reactor 20. As will be appreciated by one skilled in the art and with the benefit of the present disclosure, although fairly high conversions can be achieved in the CPO and SMR processes (e.g., CPO conversion greater than or equal to approximately 90%), in some embodiments, unconverted hydrocarbons can be recovered and recycled back to a 10 CPO reactor and/or a 20 SMR reactor.

In some embodiments, the method of the invention further includes cooling the CPO reactor effluent stream 15A, the SMR reactor effluent stream 15B, or the combined syngas stream 15C by heating the hydrocarbons of the first hydrocarbon portion 8A, the hydrocarbons of the second hydrocarbon portion 8B, or the hydrocarbon stream 8 containing a first hydrocarbon portion 8A and a second hydrocarbon portion 8B before separating them for supply to the CPO reactor 10 and the SMR reactor 20, while cooling the CPO reactor effluent stream 15A, the SMR reactor effluent stream 15B, or the combined syngas stream 15C, respectively, by heat exchange in the first heat exchanger HE1 to produce heated hydrocarbons and a first cooled reactor effluent stream 15D. In some embodiments, heated hydrocarbons (eg, heated first hydrocarbon portion 8A, heated second hydrocarbon portion 8B) are fed directly to CPO reactor 10 and/or SMR reactor 20, respectively. In some embodiments, the combined hydrocarbon stream 5A is heated to produce a heated hydrocarbon stream 5A', which is separated to produce a first hydrocarbon portion 8A and a second hydrocarbon portion 8B, which are fed directly to the CPO reactor 10 and the SMR reactor 20, respectively. In alternative embodiments, process hydrocarbons 5A are heated to produce heated process hydrocarbons 5A' before desulfurizing them. In some embodiments, the heated process hydrocarbons 5A' contain one or more sulfur-containing compounds, and the process includes removing at least a portion of the sulfur-containing compounds from the heated process hydrocarbons 5A' to produce a desulphurized hydrocarbon process stream 8, which can be separated to produce a first hydrocarbon portion 8A and a second hydrocarbon portion 8B. In some embodiments, the first hydrocarbon portion 8 is supplied directly to the CPO reactor 10, while in alternative embodiments, the first hydrocarbon portion 8A is supplied to the CPO reactor 10 after heat exchange in the second heat exchanger HE2, as further described below. Thus, in some embodiments, heating water while cooling the CPO reactor effluent stream 15A and/or the SMR reactor effluent stream 15B (eg, combined syngas 15C) through heat exchange in the first heat exchanger HE1 provides a (first) cooled reactor effluent stream 15D.

In some embodiments, the process described herein further includes cooling at least a portion (e.g., the first hydrocarbon portion 8A) of the desulfurized hydrocarbons 8. For example, in some embodiments, at least

At least a portion of the desulfurized hydrocarbons 8 is cooled by heating water 9 while cooling the desulfurized hydrocarbons 8 (eg, the first hydrocarbon portion 8A) by heat exchange in a second heat exchanger HE2 to produce steam 11 and a cooled desulfurized first hydrocarbon portion 8A'. In some embodiments, at least a portion of the cooled desulfurized hydrocarbon portion 8A' and optionally at least a portion 11A of stream 11 is supplied to CPO reactor 10 in step (a). In some embodiments, at least a portion 11B of stream 11 is supplied to SMR reactor 20 in step (b).

In some embodiments, cooling the CPO reactor effluent stream 15A, the SMR reactor effluent stream 15B, or the combined syngas 15C further includes heating water 16 while cooling the first cooled reactor effluent stream 15D through heat exchange in a third heat exchanger HE3 to produce steam 17 and a second cooled reactor effluent stream 15E. In some embodiments, at least a portion of the second cooled reactor effluent stream 15E is supplied to a downstream methanol synthesis reactor 40, as further described herein below. Steam 17 may be high pressure steam. In some embodiments, at least a portion 17A of steam 17 is used to drive a steam compressor, such as compressor 30, further described herein below.

In some embodiments, a method for producing methanol as described herein may include the step of feeding at least a portion of the syngas 15E to a methanol synthesis reactor or methanol reactor 40 to produce a methanol reactor effluent stream 45. The methanol reactor effluent stream 45 contains methanol, water, H ₂ , CO, CO ₂ and hydrocarbons. The methanol synthesis reactor 40 may include any reactor suitable for the reaction of methanol synthesis from CO and H2, for example, such as a trickle bed reactor, a fluidized bed reactor, a slurry reactor, a loop reactor, a cooled multi-tubular reactor, and the like, or their combinations.

Typically, CO and _H2 can be converted to methanol (CH3OH), for example as given in equation (3):

CO+H2-CH3OH (3)

CO ₂ and H ₂ can also be converted to methanol, for example as given in equation (4): CO ₂ +3H ₂ -CH ₃ OH+H ₂ O (4)

Without being limited by theory, the lower the CO2 content of the syngas 15E, the lower the amount of water produced in the methanol synthesis reactor 40. As will be appreciated by one skilled in the art and with the benefit of the present description, syngas produced by SMR has a fairly high hydrogen content (compared to the hydrogen content of syngas produced by CPO), and syngas with increased hydrogen content can facilitate the conversion of CO2 to methanol , for example, as indicated in equation (4), which in turn can lead to increased water content in the crude methanol stream (for example, crude methanol stream 55 described herein below).

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 synthesis reactor 40 may include a methanol production catalyst, such as any suitable commercial catalyst used for methanol synthesis. Non-limiting examples of methanol catalysts suitable for use in the methanol synthesis reactor 40 of the present invention include Cu, Cu/ZnO, Cu/ThO ₂ , Cu/Zn/Al ₂ O, Cu/ZnO/Al ₂ O, Cu /Zr, etc., or combinations thereof.

In some embodiments, a method for producing methanol as described herein may include the step of compressing at least a portion of the syngas 15E in a syngas compressor 30 to produce compressed syngas 15E', and supplying at least a portion of the compressed syngas 15E' to a synthesis reactor 40 methanol. In some embodiments, compressor 30 is a steam compressor, and at least a portion 17A (eg, HP) of steam 17 is used in a turbine of the steam compressor. In some embodiments, the compressor 30 is a steam compressor, and at least a portion of the fuel portion 5B of the hydrocarbon feedstock 5 is used to provide steam to drive the steam compressor. In some embodiments, steam (eg, supplemental or alternative steam) is generated by burning alternative hydrocarbons, and the steam is further used to drive a steam compressor. As noted above, in some embodiments, the syngas 15E and/or the compressed syngas 15E' fed to the methanol synthesis reactor 40 has a H2/CO molar ratio greater than or equal to about 1.8 and/or an M ratio greater than or equal to approximately 1.9, 1.95 or 2.0.

In some embodiments, methanol reactor 40 uses a series (eg, 3, 4, or 5) cooled bed reactors and cold feed is mixed with the effluent gas from each bed to reduce the gas temperature before feeding the feed to the next bed. Due to increased

- 15 044713 concentration of carbon monoxide in the methanol reactor loop in accordance with the present invention, the temperature of the exit gas from each layer can be higher than in methanol synthesis plants using only SMR. Thus, in some embodiments, the temperature of the cold feed streams injected between the beds may be reduced until adiabatic operation is achieved in the methanol synthesis reactor 40.

In some embodiments, a method for producing methanol as described herein may include the step of feeding at least a portion of the methanol reactor effluent stream 45 to a separator 50 to produce a crude methanol stream 55 and a steam stream 56, wherein the crude methanol stream 55 contains methanol. and water, and wherein the steam stream 56 contains H2, CO, CO2 and hydrocarbons. The methanol reactor effluent stream 45 may be separated into a crude methanol stream 55 and a vapor stream 56 in a gas-liquid separator 50, such as a vapor-liquid separator, a flash drum, a drain drum, a drain tank, a compressor vacuum drum, etc.

In some embodiments, a method for producing methanol as described herein may include the step of separating at least a portion of the crude methanol stream 55 in the distillation unit 60 into a methanol stream 65 and a water stream 66. Distillation unit 60 may include one or more distillation columns. Water stream 66 includes water and residual methanol. Typically, one or more distillation columns may separate components of the crude methanol stream 55 based on their boiling points. As one skilled in the art will appreciate and with the benefit of the present disclosure, the higher the water content of the crude methanol stream 55, the more distillation columns are needed to purify the methanol.

In some embodiments, methanol stream 65 may contain methanol in an amount greater than or equal to about 95 weight percent, alternatively greater than or equal to about 97.5 weight percent, alternatively greater than or equal to about 99 weight percent, or alternatively greater than or equal to about 99.9 wt.%, based on the total mass of the methanol stream 65.

In some embodiments, a method for producing methanol as described herein may include the step of purging and/or fueling a first portion 56' of steam stream 56, and recycling a second portion 56 of steam stream 56 to a methanol synthesis reactor 40. In some embodiments, the second portion 56 of steam stream 56 is from about 90 weight percent (wt%) to about 99 wt%, from about 94 wt% to about 97 wt%, or from about 91 wt% to approximately 98 wt.% of the steam stream 56, based on the total weight of the steam stream 56. In some embodiments, the first portion 56' of the steam stream 56 that is purged (or directed for use as a fuel) is from about 1 weight percent (wt.%) to about 10 wt.%, from about 2 wt.% to about 9 wt.%, or from about 3 wt.% to about 6 wt.% of the steam stream 56.

The first portion 56' of the vapor stream 56 may be divided into a first first portion 56'A and a second first portion 56'B. At least a portion of the first first portion 56'A may be recycled to the CPO reactor 10, for example through the hydrocarbon feedstock process portion 5A 5 and/or the first hydrocarbon portion 8A. At least a portion of the second first portion 56'B may be used as fuel to heat the SMR reactor 20 and/or generate steam. The first first portion 56'A may be from 0 to 100% of the flow of the first portion 56'; the second first portion 56'B may be from 0 to 100% of the flow of the first portion 56'. For example, in some embodiments, the flow of the first first part 56'A is 0, 25, 60, or 100% of the flow of the first part 56', and the flow of the second first part 56'B is the remaining 100, 75, 40, or 0% of the flow of the first parts 56'.

In some embodiments, the syngas and/or methanol synthesis system and method does not include an additional step or apparatus for hydrogen enrichment (eg, WGS) and/or CO ₂ removal prior to subsequent chemical synthesis (eg, methanol). In some embodiments, methanol synthesis reactor 40 has a reactor volume that is reduced (e.g., for the same methanol yield) compared to the volume of a methanol synthesis reactor used for an otherwise similar process that produces methanol from syngas produced by SMR reactor without CPO reactor; wherein the syngas produced by the SMR reactor without the CPO reactor has an H ₂ /CO molar ratio that is greater than the H 2 /CO molar ratio of the syngas in step (c) (eg, 15C combination syngas).

In some embodiments, methanol synthesis reactor 40 has a methanol synthesis reactor volume that is the same as the volume of a methanol synthesis reactor used for an otherwise similar process that produces methanol from syngas produced by an SMR reactor without a CPO reactor ; wherein the syngas produced by the SMR reactor without the CPO reactor has an H ₂ /CO molar ratio that is greater than the H ₂ /CO molar ratio of the syngas in step (c) (eg, 15C combination syngas), and in

- 16 044713 the process described in the present description produces a larger amount of methanol for a given amount of hydrocarbon feedstock 5.

In some embodiments, a method for producing methanol as described herein may advantageously demonstrate an improvement in one or more process characteristics over conventional processes. In some embodiments, the methanol synthesis method of the present invention provides increased carbon efficiency, reduced methanol synthesis reactor size due to lower syngas flow (or increased methanol yield for the same methanol synthesis reactor size), reduced energy consumption, higher overall efficiency, higher chemical carbon efficiency, reduced syngas compressor load, higher methanol synthesis loop efficiency, reduced steam use, or a combination thereof relative to an otherwise similar process that uses only SMR to produce methanol synthesis syngas.

By using CPO together with SMR, rather than SMR alone (together with thermal integration (e.g., via heat exchangers HE1, HE2 and/or HE3)) to produce synthesis gas suitable for subsequent methanol synthesis, the system and method described herein allows for reduction in energy consumption with minimal capital investment for new or improved applications. In some embodiments, the methanol synthesis plant of the present invention provides a reduction in energy consumption from an index value of about 90-100 MMBTU/ton of methanol produced, to an index value of less than about 55-85 MMBTU/ton of methanol produced, representing a reduction of more than about 15- 45%. In some embodiments, CPO and SMR are used together to provide syngas suitable for subsequent methanol synthesis (or synthesis of other chemical compound for which a reduced H ₂ /CO molar ratio is desired) without the use of a hydrogen enrichment mechanism (for example, without water gas shifting). WGS)) and/or without the use of a CO2 removal mechanism (for example, without a CO ₂ separator, for example, after a WGS reactor).

The method of the present invention can generate higher heat from the methanol synthesis reactor 40, which can be used in the process (for example, to provide a boiling-feed water reactor and/or to heat the process portion 5A of the hydrocarbon feed 5 before desulfurization in the desulfurization element 6 ).

As will be appreciated by one skilled in the art and with the benefit of the present disclosure, since the CPO reaction is exothermic, very little heat input in the form of fuel combustion is required (eg, to preheat the reactants in the reaction mixture that is fed to the syngas generation compartment) compared to with conventional steam reforming. As such, a process for producing methanol using CPO syngas as described herein can advantageously produce less CO2 due to fuel combustion compared to using steam reforming alone.

Additional advantages of the methods for producing methanol as described herein may become apparent to one skilled in the art upon consideration of the present disclosure.

Examples

Having described the embodiments generally, the following examples are provided as specific embodiments of the invention and to demonstrate its practical application and advantages. It is understood that the examples are provided by way of illustration and are not intended to limit the description or claims in any way.

Example 1: The table shows the results of the existing methanol synthesis method including SMR (comparative example) and the methanol synthesis methods of the present invention (methods A, B and C of the invention), where 20, 40 or 60 wt.%, respectively, of the process hydrocarbon feedstock (5A) is converted to syngas through the CPO reactor 10, while the remaining 80, 60 or 40 wt.%, respectively, is converted to syngas in the SMR reactor 20. In the methods of the invention, the index separation of fuel natural gas (eg, fuel portion 5B of hydrocarbon feedstock 5 (eg, natural gas) used as fuel) was 79.72, 70.86 and 53.14 wt.% of the total hydrocarbon feedstock 5, for inventive processes A, B and C, respectively. Purge gas recovery was 102.4, 101.87, and 101.87 for Invention Processes A, B, and C, respectively. The energy consumption index (El) as MMBTU per ton of methanol produced decreased from 100 MMBTU/ton of methanol produced to 83.47, 75.58 and 67.11 MMBTU/ton of methanol produced for inventive processes A, B and C, respectively. The loop efficiency index remained essentially unchanged for inventive methods A, B and C, relative to the comparative method. As can be seen from the table, overall efficiency index, carbon chemical efficiency index, crude methanol production index (e.g. crude methanol stream 55 in the figure), dimethyl ether by-product formation

- 17 044713 (DME), the small boiler performance index, the air separation unit (ASU) performance, and the inert gas concentration index in the methanol synthesis loop increased for inventive methods A, B and C relative to the comparative method. As can be seen in the table, the operating index of the methanol synthesis reactor 40, the total steam utilization index, and the total load index of the syngas compressor 30 were reduced for inventive methods A, B, and C, relative to the comparative method.

Example 1 data

Position Existing method (comparative example) Feed 20 wt.% in CPOX (method A according to the invention) Feed 40 wt.% in CPOX (method A according to the invention) Feed 60 wt.% into CPOX (method A according to invention) Fuel natural gas department (index) 100 79.72 70.86 53.14 Purge gas separation (index) 100 102.40 101.87 101.87 EI (MMBTU/ton MeOH) (index) 100 83.47 75.58 67.11 Circuit efficiency (index) 100 102.20 100.82 99.03 Overall efficiency (index) 100 107.00 109.52 113.21 Chemical efficiency according to carbon (index) 100 104.82 105.88 106.54 Value M of raw materials (56 + 15E') 12.52 14.42 8.76 5.30 M, fresh (15A) 3.01 2.71 2.46 2.21 Yield of crude substance (tons) MeOH/day) (index) 100 106.96 109.47 113.19 MeOH synthesis reactor load (MMBTU/h) (index) -100 -103 -125.4 -143.8 Small Boiler Load (MMBTU/h) (index) 100 206.01 296.46 400.89 ASU load (MMBTU/ton MeOH) (index) 100 135.36 170.01 204.37 Concentration of inert substance in the circuit, mol% (index) 100 117.43 119.28 122.6 DME production (kmol/h) 100 124 140.3 172.5 Total amount of steam used (ton/h) (index) 100 97.61 96.41 95.22 Total load syngas compressor (MMBTU/h) (index) 100 96.31 91.80 89.16 Total load circulator (MMBTU/h) (index) 100 124.93 85.11 62.03

While various embodiments have been shown and described, modifications thereof may be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are only

- 18 044713 are illustrative and not intended to be limiting. Many variations and modifications to the subject matter described herein are possible and are within the scope of the invention. When numerical ranges and limits are expressly stated, such express ranges or limits are to be understood to include iterative ranges or limits of similar magnitude within the expressly stated ranges or limits (e.g., from about 1 to about 10 includes 2, 3, 4, etc. .d.; more than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, when given a numeric range with an upper limit, R _L , and an upper limit, R , any number included in the range is specifically disclosed. In particular, the following numbers in the range are specifically disclosed: R=R _L +k*(Ru-R _L ), where k represents a variable ranging from 1 percent to 100 percent in 1 percent increments, i.e., k represents 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,... 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent or 100 percent. Moreover, any numerical range defined by two R numbers, as defined above, is also specifically disclosed. It is intended that the use of the term optional in relation to any element of a claim means that the element in question is required or alternatively not required. Both alternatives are intended to be within the scope of this claim. It should be understood that the use of broader terms such as contains, includes, having, etc. justifies narrower terms such as consisting of, essentially consisting of, essentially containing, etc.

Thus, the scope of protection is not limited to the description above, but is limited only by the claims that follow, 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 provide further description and complement the embodiments of the present invention. A discussion of a source of literature is not an admission that it is prior art of the present invention, especially any source of literature that may have a publication date after the priority date of this application. The contents of all patents, patent applications and publications cited herein are incorporated herein by reference to the extent that they provide illustrative, methodological or other details in addition to those set forth herein.

Additional Description

The specific embodiments described above are illustrative only, as the present invention may be modified and practiced in a different but equivalent manner known to those skilled in the art, taking into account the teachings described herein. Moreover, no limitation is intended on the details of the design or model presented herein other than as described in the claims below. Thus, it will be appreciated that the specific illustrative embodiments described above may be changed or modified, and all such variations are considered to be within the scope and spirit of the present invention. Also included within the scope of the present invention are alternative embodiments that result from combining, combining, and/or eliminating features of the embodiment(s). While compositions and processes are described in broader terms as having, containing, containing, or including various components or steps, compositions and methods may also essentially consist of or consist of various components and steps. The use of the term optional in relation to any element of a claim means that the element is required, or alternatively that the element is not required, both alternatives being within the scope of the claim.

The numbers and ranges described above may vary by some amount. When a numeric range with a lower limit and an upper limit is disclosed, any number and any included range included within that range are specifically disclosed. In particular, each range of values (in the form of about a to about b, or equivalently about a to b or equivalently about a-b) disclosed herein is intended to indicate each number and range covered by the broader range of values. Also, the terms in the claims have their direct ordinary meaning, unless the applicant expressly and explicitly defines otherwise. Moreover, the singular form used in the claims is defined herein to mean one or more of the elements to which it refers. If there is any conflict in the use of a word or term in this specification and in one or more patent or other documents, the definitions that are consistent with the specification should be used.

Embodiments described herein include:

A: A method for producing syngas, comprising: (a) feeding a mixture of catalytic partial oxidation (CPO) reactants into a CPO reactor; wherein the CPO reactant mixture contains oxygen, a first portion of hydrocarbons, and optionally steam; wherein at least a portion of the CPO reactant mixture reacts, via a CPO reaction, in a CPO reactor to form a reactor effluent

- 19 044713

CPO; wherein the CPO reactor contains a CPO catalyst; wherein the CPO reactor effluent includes hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons, wherein the CPO reactor effluent is characterized by the hydrogen to carbon monoxide molar ratio (H2/CO) of the CPO reactor effluent a CPO reactor, and wherein the CPO reactor effluent is characterized by the ratio M of the CPO reactor effluent, wherein the ratio M is a molar ratio defined as (H2- _CO2 )/(CO+CO2); (b) supplying a steam methane reforming (SMR) reactant mixture to the SMR reactor, wherein the SMR reactant mixture includes steam and a second portion of hydrocarbons; wherein at least a portion of the SMR reactant mixture is reacted by an SMR reaction in an SMR reactor to form an SMR reactor effluent; wherein the effluent from the SMR reactor includes hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons; wherein the SMR reactor effluent has a H2/CO molar ratio of the SMR reactor effluent that is greater than the H2/CO molar ratio of the CPO reactor effluent; and wherein the SMR reactor effluent has a ratio M of the SMR reactor effluent that is greater than the M ratio of the CPO reactor effluent; (c) contacting at least a portion of the CPO reactor effluent with at least a portion of the SMR reactor effluent to produce syngas, where the syngas is characterized by a syngas H ₂ /CO molar ratio, and where the syngas is characterized by a syngas M ratio; and (d) cooling the syngas; wherein cooling the syngas includes heating a first portion of hydrocarbons and/or a second portion of hydrocarbons while cooling the syngas by heat exchange in a first heat exchanger to produce a heated first portion of hydrocarbons and/or a heated second portion of hydrocarbons, respectively, and a first cooled syngas; and wherein the heated first portion of hydrocarbons is supplied to the CPO reactor in step (a) and/or the heated second portion of hydrocarbons is supplied to the SMR reactor in step (b), respectively.

B: A process for producing methanol, comprising: (a) heating a feed stream comprising hydrocarbons to produce heated hydrocarbons; (b) optionally removing one or more sulfur-containing compounds from the heated hydrocarbons when present; (c) separating the heated hydrocarbons into a first hydrocarbon portion and a second hydrocarbon portion; (d) supplying a mixture of catalytic partial oxidation (CPO) reactants to the CPO reactor; wherein the CPO reactant mixture contains oxygen, a first portion of hydrocarbons, and optionally steam; wherein at least a portion of the CPO reactant mixture is reacted, through a CPO reaction, in a CPO reactor to form a CPO reactor effluent; wherein the CPO reactor contains a CPO catalyst; wherein the CPO reactor effluent includes hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons, wherein the CPO reactor effluent is characterized by the hydrogen to carbon monoxide molar ratio (H2/CO) of the CPO reactor effluent a CPO reactor, and wherein the CPO reactor effluent is characterized by the ratio M of the CPO reactor effluent, wherein the ratio M is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ); (e) supplying a steam methane reforming (SMR) reactant mixture to the SMR reactor, wherein the SMR reactant mixture contains steam and a second portion of hydrocarbons; wherein at least a portion of the SMR reactant mixture is reacted by an SMR reaction in an SMR reactor to form an SMR reactor effluent; wherein the effluent from the SMR reactor includes hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), water and unreacted hydrocarbons; wherein the SMR reactor effluent has an _H2 /CO molar ratio of the SMR reactor effluent that is greater than the H2/CO molar ratio of the CPO reactor effluent; wherein the SMR reactor effluent has a ratio M of the SMR reactor effluent that is greater than the M ratio of the CPO reactor effluent; and wherein the weight ratio of the first hydrocarbon portion to the second hydrocarbon portion is from about 1:4 to about 3:1; (f) contacting at least a portion of the CPO reactor effluent with at least a portion of the SMR reactor effluent to form syngas; (g) heating water while cooling the syngas by heat exchange in a heat exchanger to produce steam and cooled syngas; (h) driving the steam compressor with at least a portion of the steam; (i) compressing at least a portion of the cooled syngas in a steam compressor to produce compressed syngas; (j) supplying at least a portion of the compressed syngas to the methanol synthesis reactor to obtain an effluent stream from the methanol synthesis reactor; wherein the effluent from the methanol synthesis reactor contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; (k) separating at least a portion of the methanol synthesis reactor effluent into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; and wherein the vapor stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and (l) recycling from about 90 wt.% to about 99 wt.% of the steam stream based on the total weight of the steam stream to the methanol synthesis reactor.

C: A system comprising: (a) a catalytic partial oxidation (CPO) reactor operating by converting at least a portion of a CPO reactant mixture containing oxygen, a first

- 20 044713 a portion of hydrocarbons and optionally steam, through a CPO reaction, into a CPO reactor effluent containing hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons, wherein the CPO reactor effluent is characterized the molar ratio of hydrogen and carbon monoxide (H2/CO) and the ratio M, where the ratio M is a molar ratio defined as (H2- _CO2 )/(CO+CO2); (b) a steam methane reforming (SMR) reactor operating by converting at least a portion of the SMR reactant mixture containing steam and a second portion of hydrocarbons, through an SMR reaction, into an SMR reactor effluent containing hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons; wherein the SMR reactor effluent has an H2/CO molar ratio that is greater than the H2/CO molar ratio of the CPO reactor effluent and an M ratio that is greater than the M ratio of the CPO reactor effluent; (c) one or more flow lines arranged to combine at least a portion of the CPO reactor effluent with at least a portion of the SMR reactor effluent to produce a combined syngas stream above or below the heat exchanger; and (d) a heat exchanger operating by transferring heat from at least a portion of the CPO reactor effluent, at least a portion of the SMR reactor effluent, or a combined syngas stream to a first hydrocarbon portion, a second hydrocarbon portion, or a combined hydrocarbon stream, comprising a first hydrocarbon portion and a second hydrocarbon portion to produce a heated first hydrocarbon portion, a heated second hydrocarbon portion, or a heated combined hydrocarbon stream, respectively, wherein the combined syngas stream has an M ratio greater than or equal to about 1.7 and/or an H2/molar ratio CO greater than or equal to approximately 1.8.

Each of embodiments A, B and C may have one or more of the following additional elements: Element 1: wherein step (d) of cooling the syngas further includes heating water while cooling the first cooled syngas by heat exchange in a third heat exchanger to produce steam and a second cooled syngas wherein at least a portion of the steam is used to drive a steam compressor. Element 2: wherein at least a portion of the first cooled syngas and/or at least a portion of the second cooled syngas is supplied to a steam compressor to form compressed syngas. Element 3: further comprising (i) supplying at least a portion of the compressed gas to the methanol synthesis reactor to obtain an effluent stream from the methanol synthesis reactor; wherein the effluent from the methanol synthesis reactor contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and (ii) separating at least a portion of the methanol synthesis reactor effluent into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; and wherein the vapor stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons. Element 4: where the first part of the steam stream is recycled to the methanol synthesis reactor; and wherein the second portion of the steam stream is used for purge, recycled to the CPO reactor as a component of the CPO reactant mixture, and/or used as fuel. Element 5: wherein 0 to 100% of the second portion of the steam stream is recycled to the CPO reactor as a component of the CPO reactant mixture and the remainder of the second portion of the steam stream is used as fuel to heat the SMR reactor and/or to generate steam. Element 6: wherein the methanol synthesis reactor is characterized by a volume of the methanol synthesis reactor that is reduced compared to the volume of the methanol synthesis reactor used for an otherwise similar process in which methanol is produced from syngas produced by an SMR reactor without a CPO reactor; wherein the syngas produced by the SMR reactor without the CPO reactor has an H2/CO molar ratio that is greater than the H2/CO molar ratio of the syngas in step (c). Element 7: Where hydrocarbons include methane, natural gas, natural gas liquids, associated gas, cap gas, enriched gas, paraffinic hydrocarbons, shale gas, shale liquids, fluid catalytic cracking (FCC) offgas, petroleum refining process gas, flue gases or combinations thereof. Element 8: wherein the hydrocarbons additionally contain one or more sulfur-containing compounds. Element 9: wherein at least a portion of the sulfur-containing compounds is removed from the heated second hydrocarbon portion to form a desulfurized second hydrocarbon portion, and wherein the desulfurized second hydrocarbon portion is supplied to the SMR reactor in step (b). Element 10: wherein at least a portion of the sulfur-containing compounds is removed from the heated first hydrocarbon portion to form a desulfurized first hydrocarbon portion, and wherein the desulfurized first hydrocarbon portion is supplied to the CPO reactor in step (a). Element 11: further comprising cooling the desulphurized first portion of the hydrocarbons. Element 12: wherein cooling the desulfurized first hydrocarbon portion includes heating water while cooling the desulfurized first hydrocarbon portion by heat exchange in a second heat exchanger to produce steam and a cooled desulfurized first hydrocarbon portion, and wherein at least a portion of the cooled desulfurized first hydrocarbon portion is supplied to a CPO reactor at

- 21 044713 stages (a). Element 13: wherein at least a portion of the steam produced by the second heat exchanger is supplied to the CPO reactor in step (a) and/or the SMR reactor in step (b). Element 14: further comprising (1) heating the hydrocarbon-containing feed stream to produce heated hydrocarbons; (2) optionally removing one or more sulfur-containing compounds from the heated hydrocarbons when present; and (3) separating the heated hydrocarbons into a first hydrocarbon portion and a second hydrocarbon portion. Element 15: wherein the weight ratio of the first hydrocarbon portion to the second hydrocarbon portion is from about 1:9 to about 9:1. Element 16: wherein the CPO reactor is characterized by at least one CPO operating parameter selected from the group consisting of a CPO inlet temperature of from about 200°C to about 550°C; CPO outlet temperature from approximately 600°C to approximately 1400°C; pressure in CPO from approximately 1 bar i.d. up to approximately 90 bar i.d.; contact time at CPO from approximately 0.001 milliseconds (ms) to approximately 5 seconds (s); a molar ratio of carbon to oxygen (C/O) in the CPO reactant mixture of from about 1.5:1 to about 2.5:1, where the molar ratio C/O refers to the total moles of carbon (C) hydrocarbons in the reactant mixture, divided by the total number of moles of oxygen (O2) in the mixture of reagents; The steam to carbon (S/C) molar ratio in the CPO reactant mixture is from about 0 to about 2:1, where the S/C molar ratio refers to the total moles of water (H2O) in the reactant mixture. divided by the total number of moles of carbon (C) hydrocarbons in the reactant mixture; and their combinations. Element 17: where (1) the syngas ratio M is equal to or greater than about 1.7; and/or (2) the H2/CO molar ratio of the syngas is equal to or greater than about 1.8. Element 18: wherein the SMR reactor has an S/C molar ratio of the SMR reactant mixture equal to or greater than about 1.5:1. Element 19: further comprising (1) withdrawing a third portion of hydrocarbons from the feed stream prior to step (a), wherein the third portion of hydrocarbons constitutes from about 5 wt.% to about 15 wt.% of the total hydrocarbons of the feed stream based on the total weight of total hydrocarbons , and where the total hydrocarbons consist of the sum of the first part of hydrocarbons, the second part of hydrocarbons and the third part of hydrocarbons; and (2) burning a third of the hydrocarbons to generate heat to heat the SMR reactor and/or generate additional steam, and wherein at least a portion of the additional steam is used to drive a steam compressor. Element 20: further comprising a methanol synthesis reactor operable to produce an effluent stream from the methanol synthesis reactor containing methanol from at least a portion of the combined syngas stream. Element 21: further including another heat exchanger downstream of said heat exchanger, operable to generate steam by heat exchange with the combined syngas stream. Element 22: further including a steam compressor upstream of the methanol synthesis reactor and operating to compress at least a portion of the combined syngas stream, wherein at least a portion of the steam for driving the steam compressor turbine includes steam produced by heat exchange with the combined syngas stream.

While preferred embodiments of the invention are shown and described, modifications thereof may be made by one skilled in the art without departing from the teachings of the present invention. The embodiments described herein are illustrative only and are not intended to be limiting. Many changes and modifications of the invention described in the present description are possible and are within the scope of the invention.

Numerous other modifications, equivalents and alternatives will become apparent to those skilled in the art upon full consideration of the above description. The following claims are intended to be interpreted as covering all such modifications, equivalents and alternatives, where applicable. Thus, the scope of protection is not limited to the description given above, but is limited only by the claims that follow, 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 further describe and supplement the detailed description of the present invention. The contents of all patents, patent applications and publications cited herein are incorporated herein by reference.

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Claims (15)

CLAIM 1. A method for producing syngas, including: (a) feeding a mixture of reagents for catalytic partial oxidation (CPO) into the CPO reactor; where the mixture of reagents for SRO contains oxygen, the first part of hydrocarbons; wherein at least a portion of the mixture of SRO reactants is reacted, through an SRO reaction, in an SRO reactor to form an effluent stream from the SRO reactor; where the SRO reactor contains an SRO catalyst; wherein the effluent from the SRO reactor includes hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons, wherein the effluent from the SRO reactor is characterized by the molar ratio of hydrogen to carbon monoxide (H2/CO) of the effluent from an SRO reactor, and wherein the effluent stream from the SRO reactor is characterized by the ratio M of the effluent stream from the SRO reactor, where the ratio M is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ); (b) supplying a steam methane reforming (SMR) reactant mixture to the SMR reactor, wherein the SMR reactant mixture includes steam and a second portion of hydrocarbons; wherein at least a portion of the SMR reactant mixture is reacted by an SMR reaction in an SMR reactor to form an SMR reactor effluent; wherein the effluent from the SMR reactor includes hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), water and unreacted hydrocarbons; wherein the SMR reactor effluent has a H2/CO molar ratio of the SMR reactor effluent that is greater than the H2/CO molar ratio of the SRO reactor effluent; and wherein the SMR reactor effluent has a ratio M of the SMR reactor effluent that is greater than the M ratio of the SRO reactor effluent; (c) contacting at least a portion of the CPO reactor effluent with at least a portion of the SMR reactor effluent to produce syngas, wherein the syngas is characterized by a syngas H2/CO molar ratio, and wherein the syngas is characterized by a syngas M ratio; and (d) cooling the syngas; wherein cooling the syngas includes heating a first portion of hydrocarbons and/or a second portion of hydrocarbons while cooling the syngas by heat exchange in a first heat exchanger to produce a heated first portion of hydrocarbons and/or a heated second portion of hydrocarbons, respectively, and a first cooled syngas; and wherein the heated first portion of hydrocarbons is fed to the SMR reactor in step (a) and/or the heated second portion of hydrocarbons is fed to the SMR reactor in step (b), respectively, wherein step (d) of cooling the syngas further includes heating water while cooling the first cooled syngas by heat exchange in a third heat exchanger to produce steam and a second cooled syngas, wherein at least a portion of the steam is used to drive a steam compressor, wherein at least a portion of the first cooled syngas and/or at least a portion of the second cooled syngas is supplied to the steam compressor with formation of compressed syngas. 2. The method of claim 1, further comprising (i) supplying at least a portion of the compressed syngas to a methanol synthesis reactor to obtain an effluent stream from the methanol synthesis reactor; wherein the effluent from the methanol synthesis reactor contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and (ii) separating at least a portion of the methanol synthesis reactor effluent into a crude methanol stream and a steam stream; wherein the crude methanol stream includes methanol and water; and wherein the vapor stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons. 3. The method according to claim 2, where the first part of the steam stream is recycled into a reactor for methanol synthesis; and where the second part of the steam stream is used for purging and/or as fuel. 4. The method of claim 2, wherein the methanol synthesis reactor has a methanol synthesis reactor volume that is reduced compared to the volume of a methanol synthesis reactor used for an otherwise similar process in which methanol is produced from syngas produced by an SMR reactor without SRO reactor; wherein the syngas produced in the SMR reactor without the SRO reactor has an H ₂ /CO molar ratio that is greater than the H ₂ /CO molar ratio of the syngas in step (c). 5. The method according to any one of claims 1 to 4, where the hydrocarbons include methane, natural gas, gas condensate liquids, associated gas, gas cap gas, rich gas, paraffinic hydrocarbons, shale gas, shale liquids, fluid catalytic cracking offgas (FCC) ), oil refining process gas, flue gases, fuel gas from a fuel gas header, or combinations thereof. 6. The method of claim 5, wherein the hydrocarbons further include one or more sulfur-containing compounds, and where the method further includes removing at least a portion of the sulfur-containing compounds from the heated first hydrocarbon portion to produce a desulfurized first hydrocarbon portion, and wherein the desulfurized first hydrocarbon portion is fed to SRO reactor at stage (a); and/or - 23 044713 wherein the method further includes removing at least a portion of the sulfur-containing compounds from the heated second hydrocarbon portion to produce a desulfurized second hydrocarbon portion, and wherein the desulfurized second hydrocarbon portion is fed to the SMR reactor in step (b). 7. The method of claim 6, where the method includes removing at least a portion of the sulfur-containing compounds from the heated first hydrocarbon portion to produce a desulfurized first hydrocarbon portion, and wherein the desulfurized first hydrocarbon portion is fed to the SRO reactor in step (a), and where the method further includes cooling of the desulphurized first part of the hydrocarbons. 8. The method of claim 7, wherein cooling the desulfurized first portion of hydrocarbons includes heating water while cooling the desulfurized first portion of hydrocarbons by heat exchange in a second heat exchanger to form steam and the cooled desulfurized first portion of hydrocarbons, and wherein at least a portion of the cooled desulfurized first portion of hydrocarbons is supplied into the SRO reactor at stage (a); and wherein at least a portion of the steam generated in the second heat exchanger is optionally supplied to the SRO reactor in step (a) and/or to the SMR reactor in step (b). 9. The method of claim 1, further comprising (1) heating a feed stream containing hydrocarbons to produce heated hydrocarbons; (2) optionally removing one or more sulfur-containing compounds from the heated hydrocarbons when present; and (3) separating the heated hydrocarbons into a first hydrocarbon portion and a second hydrocarbon portion. 10. The method according to any one of claims 1 to 9, wherein the weight ratio of the first hydrocarbon portion to the second hydrocarbon portion is from about 1:9 to about 9:1. 11. The method according to any one of claims 1-10, where the SRO reactor is characterized by at least one SRO operational parameter selected from the group consisting of an SRO inlet temperature from about 200°C to about 550°C; SRO outlet temperature from approximately 600°C to approximately 1400°C; pressure in the SRO from approximately 1 bar i.d. up to approximately 90 bar i.d.; SRO contact time from approximately 0.001 milliseconds (ms) to approximately 5 seconds (s); a carbon to oxygen (C/O) molar ratio in the FRO reactant mixture of from about 1.4:1 to about 5:1, where the C/O molar ratio refers to the total moles of carbon (C) hydrocarbons in the reactant mixture divided by the total number of moles of oxygen (O ₂ ) in the mixture of reagents; the molar ratio of steam to carbon (S/C) in the CPO reactant mixture is from about 0 to about 2:1, where the molar ratio S/C refers to the total moles of water (H ₂ O) in the reactant mixture divided by the total moles carbon (C) hydrocarbons in a mixture of reagents; and their combinations. 12. The method according to any one of claims 1 to 11, where (1) the M ratio for syngas is greater than or equal to approximately 1.7; (2) the H2/CO molar ratio for the syngas is greater than or equal to approximately 1.8; and/or (3) the SMR reactor has an S/C molar ratio of the SMR reactant mixture greater than or equal to about 1.5:1. 13. A method for producing methanol, including: (a) heating the feed stream comprising hydrocarbons to produce heated hydrocarbons; (b) removing one or more sulfur-containing compounds from the heated hydrocarbons when present; (c) separating the heated hydrocarbons into a first hydrocarbon portion and a second hydrocarbon portion; (d) supplying a mixture of catalytic partial oxidation (CPO) reactants to the CPO reactor; where the mixture of reagents for SRO contains oxygen, the first part of hydrocarbons; wherein at least a portion of the mixture of SRO reactants is reacted, through an SRO reaction, in an SRO reactor to form an effluent stream from the SRO reactor; where the SRO reactor contains an SRO catalyst; wherein the effluent from the SRO reactor includes hydrogen ( _H2 ), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons, wherein the effluent from the SRO reactor is characterized by the molar ratio of hydrogen to carbon monoxide (H2/CO) of the effluent from the SRO reactor, and wherein the effluent stream from the SRO reactor is characterized by the ratio M of the effluent stream from the SRO reactor, where the ratio M is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ); (e) supplying a steam methane reforming (SMR) reactant mixture to the SMR reactor, wherein the SMR reactant mixture contains steam and a second portion of hydrocarbons; wherein at least a portion of the SMR reactant mixture is reacted by an SMR reaction in an SMR reactor to form an SMR reactor effluent; wherein the effluent from the SMR reactor includes hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons; wherein the SMR reactor effluent has a H2/CO molar ratio of the SMR reactor effluent that is greater than the H2/CO molar ratio of the SRO reactor effluent; wherein the SMR reactor effluent has a ratio M of the SMR reactor effluent that is greater than the M ratio of the SRO reactor effluent; and where the mass ratio of the first part of hydrocarbons and the second part of hydrocarbons is from 1:4 to 3:1; (f) contacting at least a portion of the CPO reactor effluent with at least a portion of the SMR reactor effluent to form syngas; - 24 044713 (g) heating water while cooling syngas by means of heat exchange in a heat exchanger to form steam and cooled syngas; (h) driving the steam compressor with at least a portion of the steam; (i) compressing at least a portion of the cooled syngas in a steam compressor to produce compressed syngas; (j) supplying at least a portion of the compressed syngas to the methanol synthesis reactor to obtain an effluent stream from the methanol synthesis reactor; wherein the effluent from the methanol synthesis reactor contains methanol, water, hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; (k) separating at least a portion of the methanol synthesis reactor effluent into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; and wherein the vapor stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and (l) recycling from 90 wt.% to 99 wt.% of the steam stream based on the total mass of the steam stream to the methanol synthesis reactor. 14. The method of claim 13, further comprising (1) removing a third portion of the hydrocarbons from the feed stream prior to step (a), wherein the third portion of the hydrocarbons constitutes from 5 wt.% to 15 wt.% of all hydrocarbons in the feed stream based on the total the mass of total hydrocarbons, and where the total hydrocarbons consist of the sum of the first part of hydrocarbons, the second part of hydrocarbons and the third part of hydrocarbons; and (2) burning a third of the hydrocarbons to generate heat to heat the SMR reactor and/or generate additional steam, and wherein at least a portion of the additional steam is used to drive a steam compressor. 15. A system for producing synthesis gas through incomplete catalytic oxidation and producing methanol from it, including: (a) a catalytic partial oxidation (CPO) reactor operating by converting at least a portion of the CPO reactant mixture containing oxygen, a first portion of hydrocarbons, through a CPO reaction, into a CPO reactor effluent containing hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons, where the effluent from the SRO reactor is characterized by the molar ratio of hydrogen to carbon monoxide (H ₂ /CO) and the ratio M, where the ratio M is the molar ratio defined as (H ₂ CO2ISO+CO2); (b) a steam methane reforming (SMR) reactor operable to convert at least a portion of the SMR reactant mixture comprising steam and a second portion of hydrocarbons, through an SMR reaction, into an SMR reactor effluent containing hydrogen (H2), carbon monoxide ( CO), carbon dioxide (CO2), water and unreacted hydrocarbons; wherein the SMR reactor effluent has a H2/CO molar ratio that is greater than the H2/CO molar ratio of the SRO reactor effluent and an M ratio that is greater than the M ratio of the SRO reactor effluent; (c) one or more flow lines arranged to combine at least a portion of the CPO reactor effluent with at least a portion of the SMR reactor effluent to produce a combined syngas stream above or below the heat exchanger; and (d) a heat exchanger operating by transferring heat from at least a portion of the CPO reactor effluent, at least a portion of the SMR reactor effluent, or a combined syngas stream to a first hydrocarbon portion, a second hydrocarbon portion, or a combined hydrocarbon stream, comprising a first hydrocarbon portion and a second hydrocarbon portion, to produce a heated first hydrocarbon portion, a heated second hydrocarbon portion, or a heated combined hydrocarbon stream, respectively, wherein the combined syngas stream has an M ratio greater than or equal to 1.7 and/or an H2/molar ratio CO greater than or equal to 1.8, the system further includes a methanol synthesis reactor operable to produce a methanol synthesis reactor effluent stream from at least a portion of the combined syngas stream; another heat exchanger below said heat exchanger generating steam by heat exchange with the combined syngas stream; a steam compressor upstream of the methanol synthesis reactor, and operating to compress at least a portion of the combined syngas stream, wherein at least a portion of the steam for driving the steam compressor turbine includes steam produced by heat exchange with the combined syngas stream. -