EA044653B1 - PRODUCTION OF SYNTHESIS GAS AND METHANOL - Google Patents

Description

Field of technology

The present invention relates to systems and methods for producing synthesis gas by catalytic partial oxidation (CPO) and producing methanol therefrom; More specifically, the present invention relates to systems and methods for producing methanol that utilize water gas shifting (WGS) and/or carbon dioxide (CO2) separation after CPO and prior to methanol production; More specifically, the present invention relates to methanol production systems and methods that provide synthesis gas having a desired composition to a methanol synthesis loop through the combination of CPO and WGS, CO2 separation and/or thermal integration.

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 for the production of methanol and ammonia, and as an intermediate for 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 involve 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. The system and process described modify the composition of the CPO reactor effluent using water gas shift (WGS) and carbon dioxide (CO2) removal, and utilize thermal integration for energy efficiency.

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 high capital costs

- 1 044653 (CAPEX). Traditional best-in-class methanol plants use combined reformer (CR) technology, which consists of an SMR reactor and an autothermal reformer (ATR) to reduce energy consumption in syngas production, and thus the overall methanol synthesis process. 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 herein below, 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 a stand-alone CPO process in conjunction with WGS, CO ₂ removal and/or thermal integration to produce hydrogen-enriched synthesis gas of the desired composition for downstream methanol synthesis without the need for endothermic and high CAPEX SMR. 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. By using CPO together with WGS, CO2 removal and/or thermal integration instead of SMR, the system and process described herein allows for reduced 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 production plant can be designed that has reduced energy consumption relative to a traditional methanol synthesis plant that uses SMR or CR. Energy consumption is minimized in accordance with the present invention by combining catalytic partial oxidation with optional WGS, CO2 removal and/or process heat integration, providing similar or higher levels of methanol production with similar product quality. In some embodiments, the energy consumption of a methanol production plant (eg, a new or existing plant retrofitted in accordance with the present invention) is reduced from an index value of 100 to approximately 90, 80, or 70 MMBTU/ton of methanol produced. In some embodiments, energy consumption for methanol production is reduced by the system and method of the invention by at least 10, 30, or 50% relative to conventional methanol production. 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 approximately 40, 50, 60, 70, or 80 MMBTU/ton of methanol produced by the system and the 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. As used herein, the term combination includes combinations, mixtures, alloys, reaction products, and the like.

Reference in the present description to an embodiment, another embodiment, other embodiments, some embodiments, etc. means that a specific

- 2044653 The element (eg, feature, structure, property and/or characteristic) described in relation to 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 uC _x s are interchangeable and refer to any hydrocarbon having x number of carbon atoms (C). For example, both the terms C4 hydrocarbons and _C4s 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 to combinations thereof.

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; water gas shift (WGS) reactor 20; carbon dioxide (CO2) separator 25; compressor 30 and methanol synthesis circuit 40. In some embodiments, the system I for synthesizing syngas and methanol I may further include a desulfurization element 6, a hydrogen separation element 70, and a distillation element 60, and one or more heat exchangers, as first heat exchanger HE1, second heat exchanger HE2, third heat exchanger HE3 , a fourth heat exchanger HE4 and/or a fifth heat exchanger (eg electric heater) HE5. 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 FIG. can be hydraulically connected to each other (as indicated by connecting lines indicating the direction of fluid flow) through any suitable passages ( e.g. pipes, streams, etc.).

In some embodiments, the method described herein may include the step of (a) reacting, through a catalytic partial oxidation (CPO) reaction, a mixture of CPO reactants in a CPO reactor 10 to produce a CPO reactor effluent stream 15 containing syngas; wherein the CPO reactant mixture includes hydrocarbons, oxygen and optionally water; wherein the CPO reactor 10 contains a CPO catalyst; wherein the CPO reactor effluent stream 15 contains hydrogen ( _H2 ), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons, wherein the CPO reactor effluent stream 15 is characterized by a molar ratio of hydrogen to carbon monoxide (H2/CO) the CPO reactor effluent stream 15, and wherein the CPO reactor effluent stream 15 is characterized by the ratio M of the CPO reactor effluent stream, wherein the ratio M is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ). As further described below, the CPO reactant mixture may include a combination of oxygen in line 12, steam in line 11A, and a first hydrocarbon portion 5A of hydrocarbon feedstock 5 optionally heat exchanged in a second heat exchanger HE2 to produce a heat exchanged first portion 5A'.

- 3 044653 desulfurized in the desulfurization element 6 to obtain a desulfurized first part in line 8, and/or subjected to heat exchange in a fourth heat exchanger HE4 to obtain a heat-exchanged desulfurized first part 8'.

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 (CO2) and water (H2O), 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 H ₂ can be oxidized to CO 2 and H 2 O, 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 15), 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 15 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 feedstock ).

In some embodiments, hydrocarbons (eg, in hydrocarbon feed 5) suitable for use in the CPO 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, fluid catalytic cracking (FCC) off-gas, oil refining process gas, oil refining off-gas, flue gas, fuel gas from fuel gas header, etc. etc., or combinations thereof. Hydrocarbons may include any suitable source of hydrocarbons and may include C1-C6 hydrocarbons as well as some heavier hydrocarbons.

In some embodiments, the CPO reactant mixture in CPO reactor 10 may contain hydrocarbons from hydrocarbon feed 5, which may contain, consist essentially of, or consist of natural gas. The first portion 5A of the hydrocarbon feedstock 5 may be used as a process gas (e.g., PNG process natural gas)) and may be sent to the CPO reactor 10, while the second portion 5B of the hydrocarbon feedstock 5 may be used as a fuel gas (e.g., fuel natural gas (FNG)), and sent to other parts of the system 1 for use as fuel (e.g. to produce steam, e.g.

- 4 044653 obtaining high pressure steam (HP) to start a turbine, for example, to start a compressor turbine 30). In some embodiments, the second portion 5B of hydrocarbons used as fuel is less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt.% of the total hydrocarbon feedstock 5 based on the total weight all hydrocarbons, where the total hydrocarbons consist of the sum of the hydrocarbons supplied to the CPO reactor 10 in step (a) through the first part 5A, and the hydrocarbons sent as fuel through the second part 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 may include CH4 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 mole% to about 80 mole% methane, from about 20 mole% to about 55 mole% carbon dioxide, and less than about 15 mole% nitrogen.

In some embodiments, the natural gas (or hydrocarbon feedstock 5) may include CH4 in an amount greater than or equal to about 45 mole%, alternatively greater than or equal to about 50 mole%, alternatively greater than or equal to about 55 mole%, 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 hydrocarbons in hydrocarbon feed 5 suitable for use in the CPO reaction as described herein may include C1-C6 hydrocarbons, nitrogen (e.g., from about 0.1 mol.% to about 15 mol.%, alternatively from about 0.5 mol.% to about 11 mol.%, alternatively from about 1 mol.% to about 7.5 mol.%, or alternatively from about 1.3 mol.% to about 5.5 mol.%) and carbon dioxide (e.g., from about 0.1 mole% to about 2 mole%, alternatively from about 0.2 mole% to about 1 mole%, or alternatively from about 0.3 mole% to about 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.%); C ₂ hydrocarbons (from about 2.5 mol.% to about 4 mol.%); C ₃ hydrocarbons (from about 0.5 mol.% to about 1.4 mol.%); C ₄ hydrocarbons (from about 0.5 mol.% to about 0.2 mol.%); C ₅ 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 may contain such hydrocarbons that can be supplied to the CPO reactor 10 through the first portion 5A of the hydrocarbon feedstock 5, or separately.

Oxygen used in the 10-reagent mixture for CPO may include 100% oxygen (essentially pure O2), gaseous oxygen (which can be obtained through membrane separation), industrial oxygen (which may contain some air), air, oxygen-enriched 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, CH3OH, CH2O), hydroxyl radical generators, etc., or their combinations. Oxygen may be supplied to the CPO reactor 10 through oxygen line 12, in some embodiments, or in another way (eg, together with the first part 8 or the heat-exchanged desulphurized first part 8').

- 5 044653

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 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 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 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 about 2.2:1 to about 3:1, alternatively about 2.4:1 to about 3:1, or alternatively 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 (eg, supplied through the first portion 5A of the hydrocarbon stream 5), the CH4/O2 molar ratio is the same as the C/O molar ratio. 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 the C/O ratio 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 may 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 15. 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, the hydrocarbon feedstock 5 further contains one or more sulfur-containing compounds, and at least a portion of the sulfur-containing compounds is removed from the first portion 5A of the hydrocarbon feedstock 5 before feeding the hydrocarbons into the CPO reactor 10 as a component of the CPO reactant mixture. In such embodiments, the first portion 5A (optionally after heat exchange of the CPO reactor effluent stream 15 therewith to produce a heat-exchanged first hydrocarbon portion 5A', which is further described below) of the hydrocarbon feedstock 5 may be supplied to the desulfurization element 6 to remove one or more containing sulfur compounds from it. 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 element (FIDS) 6, and hydrogen is supplied to the desulfurization element 6 through a hydrogen line 7. The desulfurized first hydrocarbon portion 8 can be removed from the desulfurization element 6. The desulfurized first hydrocarbon portion 8 may be fed to the CPO reactor (optionally after being heat exchanged therewith to provide a heat exchanged desulfurized first hydrocarbon portion 8', which is further described below).

In some embodiments, a CPO reactor 10 suitable for use with the present invention may include a tubular reactor, a continuous flow reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a circulating fluidized bed reactor (e.g., a lift reactor type), 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 a riser 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); feed temperatures for CPO (e.g.

- 6 044653 temperature of the reagent mixture for CPO); 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 stream of the syngas; the effluent stream 15 from the CPO reactor) 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 of the CPO reactor, the temperature of the effluent syngas stream, the 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 15 from the CPO reactor), as well as the composition of the syngas effluent stream (eg, the syngas in the CPO reactor effluent stream 15). 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 600, 500 or 400°C.

The CPO reactor 10 may have a temperature of the CPO effluent stream (e.g., the target temperature of the CPO reactor effluent stream 15) 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 approximately 850°C to approximately 1100°C.

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,

- 7 044653 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, or alternatively less than about +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 would 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 at

- 8 044653 reactor and/or catalyst layer. 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 may 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, heat exchange or heat transfer may include introducing a cooling agent, such as a diluent, into a reactor (eg, 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 (eg, 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 chemical reactions different from 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 15). The diluent may be present in the CPO reagent mixture in any suitable amount.

- 9 044653

The CPO reactor 10 may have a CPO pressure (e.g., the reactor pressure measured at the outlet of the CPO reactor or at its outlet) greater than or equal to about 1 barg, alternatively greater than or equal to about 10 barg, alternatively greater than or equal to about 20 barg, alternatively greater than or equal to about 25 barg, alternatively greater than or equal to about 30 barg, alternatively greater than or equal to about 35 barg, alternatively greater than or equal to about 40 barg, alternatively greater than or equal to about 50 barg, alternatively less than about 30 barg, alternatively less than about 25 barg, alternatively less than about 20 barg, and .d., alternatively less than about 10 bar id., alternatively from about 1 bar id. 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 15), 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 H ₂ 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); 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; 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) hydrocarbons in a mixture of reagents; and their combinations. In some embodiments, the CPO reactor 10 has a steam to carbon (S/C) molar ratio of the CPO reactant mixture of from about 0.05:1 to about 1:1, from about 0.1:1 to about 2:1, from about 0.1:1 to about 2:1, or equal to about 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. Typically, a noble metal is

- 10 044653 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 SiO2; 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 ( _Al2O3 ), activated Al2O, silicon dioxide (SiO2), titanium dioxide (TiO2), magnesium oxide (MgO), zirconium oxide (ZrO2) , lanthanum (III) oxide (La ₂ O ₃ ), yttrium (III) oxide (Y ₂ O ₃ ), cerium (IV) oxide (CeO ₂ ), zeolites, ZSM-5, perovskite oxides, hydrotalcite oxides, etc. 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 embodiments of the present invention, the CPO reactor effluent stream 15 is recovered from the CPO reactor 10, the CPO reactor effluent stream 15 including hydrogen, carbon monoxide, water, carbon dioxide and unreacted hydrocarbons. In some embodiments, the CPO reactor effluent stream 15 may have a 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 CPO reactor effluent 15 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 CPO reactor effluent stream 15 as described herein may have an H2/CO molar ratio of from about 1.7 to about 2.3, alternatively from about 1.75 to about 1.81, alternatively from about 1.75 to about 1.81, alternatively from about 1.75 to about 1.81, alternatively 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 15 may have a CO content of less than about 10 mole%, less than about 9 mole%, less than about 8 mole%, less than about 7 mole%, alternatively less than about 6 mole%, alternatively less than about 5 mole%, alternatively less than about 4 mole%, alternatively less than about 3 mole%, alternatively less than about

- 11 044653 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.%, alternative 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 some embodiments, water may be condensed and separated from at least a portion of the CPO reactor effluent 15, such as in a condenser. In some embodiments, the CPO reactor effluent stream 15 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 15 to produce recovered hydrocarbons, and (ii) recycling at least a portion of the recovered hydrocarbons into the 10 CPO reactor. As will be appreciated by one of ordinary skill in the art and with the benefit of the present disclosure, although fairly high conversions can be achieved in CPO processes (eg, conversion greater than or equal to approximately 90%), unconverted hydrocarbons can be recovered and recycled back to the CPO reactor 10.

In some embodiments, the method of the present invention further includes cooling the CPO reactor effluent stream 15 by heating the hydrocarbons of the first portion 5A while cooling the CPO reactor effluent stream 15. Cooling the CPO reactor effluent stream 15 by heating the hydrocarbons of the first portion 5A while cooling the CPO reactor effluent stream 15 may involve heat exchange between the CPO reactor effluent stream 15 and a heat transfer fluid 18 (e.g., water or low pressure (LP) steam) in the first heat exchanger HE1 to obtain the first cooled effluent stream 15A from the CPO reactor; heating the hydrocarbons while further cooling the first cooled CPO reactor effluent stream 15A by heat exchange therebetween in a second heat exchanger HE2 to produce heated hydrocarbons 5A' and a second cooled CPO reactor effluent stream 15B and LP steam, medium pressure (MP) steam and/or steam high pressure (HP). In some embodiments, the method further includes optionally preheating the hydrocarbons by an electrical heater or heat exchanger HE5 before the second heat exchanger HE2.

In some embodiments, the heated first portion of hydrocarbons 5A' is fed directly to the CPO reactor 10. In alternative embodiments, the first hydrocarbon portion 5A is heated prior to desulfurization. In some embodiments, the heated first hydrocarbon portion 5A' contains one or more sulfur-containing compounds, the method includes removing at least a portion of the sulfur-containing compounds from the heated first hydrocarbon portion 5A' to produce a desulfurized first hydrocarbon portion 8, which can be fed directly to the CPO reactor 10 or may be supplied to the CPO reactor 10, followed by heat exchange in the fourth heat exchanger E1E4, as further described below.

In some embodiments, the method described herein includes cooling the desulfurized first hydrocarbon portion 8. For example, in some embodiments, the desulfurized first hydrocarbon portion 8 is cooled by heating water 9 while cooling the desulfurized first hydrocarbon portion 8 by heat exchange in a fourth heat exchanger E1E4 to produce steam 11 (eg LP steam) and cooled desulfurized first portion of 8' hydrocarbons. In some embodiments, at least a portion of the cooled desulfurized first hydrocarbon portion 8' and optionally at least a portion 11A of steam 11 is supplied to the CPO reactor 10 as a component of the CPO reactant mixture in step (a).

In some embodiments, cooling the CPO reactor effluent stream 15 further includes heating water 16 while cooling a second cooled CPO reactor effluent stream 15B through heat exchange in a third heat exchanger HE3 to produce a stream 17 (e.g., including boiled water and/or LP steam) and a third cooled 15C effluent from the CPO reactor. In some embodiments, at least a portion of the third cooled CPO reactor effluent stream 15C is supplied to WGS reactor 20 in step (b), further described herein below. Stream 17 may be low pressure steam. In some embodiments, at least the steam portion 21 (17/19) is used to drive a steam compressor, such as the syngas compressor 30 further described herein below.

As noted herein above, in some embodiments, the method of the present invention further includes (b) feeding at least a portion of the CPO reactor effluent stream 15 to a water gas shift (WGS) reactor 20 to produce a rich reactor effluent stream 15D, wherein a portion of the carbon monoxide of the CPO reactor effluent stream 15 reacts with water through a WGS reaction to produce hydrogen and carbon dioxide, wherein the hydrogen-enriched reactor effluent stream 15D has a molar ratio

- 12 044653

H ₂ /CO of the hydrogen-rich reactor effluent and the M ratio of the hydrogen-rich reactor effluent, and wherein the H ₂ /CO molar ratio of the hydrogen-rich reactor effluent 15D is greater than the H2/CO molar ratio of the CPO reactor effluent 15. As described herein above, the effluent stream 15 from the CPO reactor may be used to preheat the first portion 5A of the hydrocarbon feedstock 5 to produce a heated first hydrocarbon portion 5A' in the first heat exchanger HE1, and/or to produce steam (e.g., high pressure steam ( HP) in the steam stream 17 HP) from water and steam 16 through the third heat exchanger HE3 before entering the WGS reactor 20. Thus, in some embodiments, the method of the present invention includes supplying at least a portion of the cooled CPO reactor effluent stream (e.g., the first cooled CPO reactor effluent stream 15B and/or the second cooled CPO reactor effluent stream 15C) to the conversion reactor 20 water gas (WGS) to produce a hydrogen-enriched reactor effluent stream 15D, wherein a portion of the carbon monoxide of the cooled CPO reactor effluent reacts with water through a WGS reaction to produce hydrogen and carbon dioxide, wherein the hydrogen-enriched reactor effluent stream 15D is characterized by a molar ratio of H ₂ /CO of the hydrogen-rich reactor effluent stream 15D, wherein the hydrogen-rich reactor effluent stream 15D is characterized by the M ratio of the hydrogen-rich reactor effluent stream 15D, and where the H ₂ /CO molar ratio of the hydrogen-rich reactor effluent stream 15D is greater than the H ₂ molar ratio /CO of the CPO reactor effluent stream 15, the first cooled CPO reactor effluent stream 15B, and/or the second cooled CPO reactor effluent stream 15C.

In the water gas shift (WGS) reactor 20, a portion of the carbon monoxide of the CPO reactor effluent stream 15 reacts with water through the WGS reaction to produce hydrogen and carbon dioxide and thereby provides hydrogen-rich syngas as the hydrogen-rich reactor effluent stream 15D. Basically, the WGS reaction describes the catalytic reaction of carbon monoxide and water vapor to produce carbon dioxide and hydrogen, for example, as presented in equation (2):

CO + H ₂ O^CO ₂ + H ₂ ⁽²⁾

The WGS reaction can be used to increase the H2/CO molar ratio of gas streams including carbon monoxide and hydrogen. WGS catalysts may include any suitable WGS catalysts, such as commercial WGS catalysts; iron-based catalysts reinforced with chromium or copper; catalysts based on copper-zinc-aluminum, etc.; or combinations thereof.

A portion of the carbon monoxide in the CPO reactor may undergo a WGS reaction (as represented in equation (2)) in the CPO reactor 10, thereby increasing the amount of hydrogen in the CPO reactor effluent stream 15.

In some embodiments, a method for producing syngas as described herein may further include recovering a hydrogen-enriched effluent stream 15D from WGS reactor 20, wherein the hydrogen-enriched reactor effluent stream 15D includes hydrogen, carbon monoxide, carbon dioxide, water, and unreacted hydrocarbons, and wherein the H2/CO molar ratio of the hydrogen-rich WGS reactor effluent stream 15D is greater than the H2/CO molar ratio of the CPO reactor effluent stream 15.

In some embodiments, the hydrogen-enriched WGS reactor effluent stream 15D may be used as syngas in a downstream process without further processing the WGS reactor effluent stream. In other embodiments, the hydrogen-enriched effluent stream 15D from the WGS reactor may be further processed prior to subsequent chemical synthesis (eg, methanol). For example, in some embodiments, the hydrogen-enriched WGS reactor effluent stream 15D may be further processed in carbon dioxide separator 25 to reduce its carbon dioxide content.

In some embodiments, the method of the present invention further includes removing a portion of the CO ₂ from the hydrogen-rich reactor effluent stream 15D in a CO ₂ separator 25 to form syngas 15E. The resulting syngas 15E is characterized by a syngas ratio M where the M ratio of the syngas 15E is greater than the M ratio of the CPO reactor effluent 15, and where the M ratio of the syngas 15E is greater than the M ratio of the hydrogen-rich reactor effluent 15D.

In some embodiments, the CPO reactor effluent stream 15 is further processed to form hydrogen-rich syngas 15E by removing at least a portion of the carbon dioxide from the CPO reactor effluent stream 15 and/or the hydrogen-rich WGS reactor effluent stream 15D to form hydrogen-enriched syngas 15E . As will be appreciated by one skilled in the art, both by use of the present invention and without being limited by theory, while the H ₂ /CO molar ratio of syngas does not change as a result of carbon dioxide removal

- 13 044653 from syngas, the hydrogen concentration increases in the syngas by removing carbon dioxide from the syngas. However, the M ratio of the syngas changes with the carbon dioxide content of the syngas, where the M ratio is a molar ratio defined as (H2- _CO2 )/(CO+CO2). The CPO reactor effluent stream 15 is characterized by the ratio M of the CPO reactor effluent stream. Hydrogen-rich syngas 15E is characterized by the ratio M of hydrogen-rich syngas. The hydrogen-enriched syngas 15E has an M ratio that is greater than the M ratio of the CPO reactor effluent 15 and also greater than the M ratio of the hydrogen-enriched WGS reactor effluent 15D. As one skilled in the art will appreciate, and with the aid of the present invention, CO ₂ -lean syngas has a higher M ratio than CO ₂ -rich syngas: the lower the CO 2 content of the syngas, the higher the M ratio in the syngas.

In some embodiments, at least a portion of the carbon dioxide may be removed from the hydrogen-rich WGS reactor effluent stream 15D to form syngas 15E suitable for further chemical synthesis. Since syngas 15E is hydrogen-rich relative to the CPO reactor effluent 15, it may also be referred to herein as hydrogen-rich syngas. By reducing the carbon dioxide content in the CO2 separator 25, the resulting syngas 15E has an M ratio greater than the M ratio of the hydrogen-rich WGS reactor effluent 15D.

In some embodiments, the hydrogen enriched syngas 15E may have an M ratio greater than or equal to about 1.7, 1.9, 2.1, 2.3, or 2.5, from about 1.9 to about 2.2, alternatively from about 1.95 to about 2.1, or alternatively from about 1.98 to about 2.06. In some embodiments, the hydrogen-enriched syngas 15E may have a H2/CO molar ratio greater than or equal to about 1.8, 2.0, 2.2, 2.5, 2.8, or 3, or from about 1.5 to about 3 .5, alternatively from about 2 to about 3, or alternatively from about 2.25 to about 2.75. The H2/CO molar ratio of the hydrogen-rich WGS reactor effluent 15D and the hydrogen-rich syngas 15E may be substantially the same.

The CO2 separator 25 may include any CO2 separator known to those skilled in the art to operate by removing _CO2 from the hydrogen-rich reactor effluent stream 15D to form syngas 15E. The CO ₂ separator 25 may include CO ₂ removal via amine absorption (eg, monoethanolamine) (eg, amine scrubbing), pressure swing adsorption (PSA), temperature swing adsorption, gas separation membranes (eg, porous inorganic membranes, palladium membranes, polymer membranes, zeolites, etc.), cryogenic separation, etc., or combinations thereof. In some embodiments, the step of removing at least a portion of carbon dioxide from the CPO reactor effluent stream 15 and/or the hydrogen-rich WGS reactor effluent stream 15D to form the hydrogen-rich syngas 15E may include removing CO ₂ by amine absorption. For example, CO2 separator 25 may include a CO2 absorber such as an amine element. In some embodiments, less than about 50, 45, 40, 35, or 30 mole percent of the CO2 in the hydrogen-rich WGS reactor effluent stream 15D is removed in CO2 separator ₂₅ to form syngas 15E.

In some embodiments, a first portion of the CPO reactor effluent stream 15 may be fed to the WGS reactor 20 to form a hydrogen-rich WGS reactor effluent stream 15D. In such embodiments, at least a portion of the hydrogen-rich WGS reactor effluent stream 15D may be contacted with a second portion of the CPO reactor effluent stream 15 to form a hydrogen-rich syngas. In such embodiments, the CPO reactor effluent stream (eg, the first portion of the CPO reactor effluent stream 15, the second portion of the CPO reactor effluent stream 15) and/or the hydrogen-enriched WGS reactor effluent stream 15D may be subjected to a carbon dioxide removal step. For example, the first portion of the CPO reactor effluent stream 15 that may be fed to the WGS reactor 20 to form a hydrogen-rich WGS reactor effluent stream 15D may range from about 0.01 vol.% to about 100 vol.%, alternatively from about 0.01 vol.% to about 100 vol.%, alternatively from about 0.01 vol. ,1 vol.% to about 90 vol.%, alternatively from about 1 vol.% to about 80 vol.%, alternatively from about 10 vol.% to about 75 vol.%, alternatively from about 20 vol.% to about 60 vol.%, alternatively from about 25 vol.% to about 50 vol.%, alternatively more than or exactly about 5 vol.%, alternatively more than or exactly about 10 vol.%, alternatively more than or exactly about 15 vol.% , alternatively more than or exactly about 20 vol.%, or alternatively more than or exactly about 25 vol.% based on the total volume of the CPO reactor effluent stream 15.

In some embodiments, a second portion of the CPO reactor effluent stream 15 may be brought into contact with at least a portion of the hydrogen-enriched CPO reactor effluent stream 15D.

- 14 044653 WGS reactor with the formation of a combined effluent stream, where the combined effluent stream is characterized by the ratio M of the combined effluent stream; wherein at least a portion of the carbon dioxide may be removed from the combined effluent stream in CO ₂ separator 25 to form syngas 15E, and wherein syngas 15E has an M ratio that is greater than the M ratio of the combined effluent stream. For example, the second portion of the CPO reactor effluent stream 15, which may be contacted with at least a portion of the hydrogen-rich WGS reactor effluent stream 15D to form a combined effluent stream, may be from about 0.01 vol.% to about 99.99 vol.%, alternatively from about 10 vol.% to about 99.9 vol.%, alternatively from about 20 vol.% to about 99 vol.%, alternatively from about 25 vol.% to about 90 vol.%, alternatively from about 40 vol.% to about 80 vol.%, alternatively from about 50 vol.% to about 75 vol.%, alternatively less than about 95 vol.%, alternatively less than about 90 vol.%, alternatively less than about 85 vol. .%, alternatively less than about 80 vol.%, or alternatively less than about 75 vol.% based on the total volume of the CPO reactor effluent stream 15.

In some embodiments, a method for producing syngas as described herein may include the step of removing carbon dioxide from one or more streams; for example, carbon dioxide may be removed from at least a portion of the CPO reactor effluent stream 15, from at least a portion of the hydrogen-rich WGS reactor effluent stream 15D, from at least a portion of the combined effluent stream, etc. For example, carbon dioxide may be removed from at least a portion of the CPO reactor effluent stream 15 and/or from at least a portion of the hydrogen-rich WGS reactor effluent stream 15D to form syngas 15E; carbon dioxide may be removed from either at least a portion of the CPO reactor effluent stream 15 or from at least a portion of the hydrogen-enriched WGS reactor effluent stream 15D prior to combining the CPO reactor effluent stream 15 and the hydrogen-enriched WGS reactor effluent stream 15D with the formation of syngas 15E; carbon dioxide may be removed from the combined effluent to form syngas 15E or the like; or combinations thereof.

Methanol synthesis can be carried out in methanol synthesis loop 40. The methanol synthesis loop 40 may include any methanol synthesis loop known in the art and by the present invention as being suitable for producing a crude methanol stream 55 and a purge gas stream 56. For example, methanol synthesis loop 40 may include one or more methanol synthesis reactors, one or more gas-liquid separators, one or more heat exchangers, one or more recycle streams, and/or one or more steam drums. In some embodiments, a method for producing methanol as described herein may include the step of supplying at least a portion of the syngas 15E to the methanol synthesis loop 40. The methanol synthesis loop 40 operates to produce a crude methanol stream 55 and a purge gas stream 56. The methanol synthesis loop includes a methanol synthesis reactor or methanol reactor operating by producing a methanol reactor effluent. The methanol reactor effluent includes methanol, water, H ₂ , CO, CO 2 and hydrocarbons. The methanol synthesis loop 40 may include any reactor suitable for reacting the synthesis of methanol from CO and H ₂ , 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)

CO2 and H2 can also be converted to methanol, for example as given in equation (4): CO2+3H2-CH3OH+H2O (4)

Without being limited by theory, the lower the CO ₂ content of the 15E syngas, the lower the amount of water produced in the methanol synthesis reactor. As will be appreciated by one skilled in the art and with the benefit of this disclosure, 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 help convert CO ₂ to methanol, for example, as indicated in equation (4), which in turn can lead to increased water content in the crude methanol stream (eg, 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. The methanol synthesis reactor may include a catalyst for producing methanol, such as any suitable commercial catalyst used for methanol synthesis. Non-limiting examples of methanol catalysts suitable for use in the methanol synthesis reactor in methanol synthesis loop 40 in

- 15 044653 within the scope of the present invention include Cu, Cu/ZnO, Cu/ThO2, Cu/Zn/Al2O, Cu/ZnO/Al2O, 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 a compressed syngas 15E', and at least a portion of the compressed syngas 15E' is supplied to a methanol synthesis loop 40 . 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, compressor 30 is a steam compressor, and at least a portion of the second portion 5B of 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' supplied to the methanol synthesis loop 40 has a H2/CO molar ratio greater than or equal to about 1.8, 2.0, 2.2, 2 .5, 2.8 or 3, and/or an M ratio greater than or equal to approximately 1.7, 1.9, 2.1, 2.3 or 2.5.

In some embodiments, methanol synthesis loop 40 utilizes 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 temperature of the gas before feeding the feed to the next bed. Due to the increased concentration of carbon monoxide in the methanol reactor loop of the present invention, the temperature of the exit gas from each bed can be higher than in SMR-only methanol synthesis plants. 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.

In some embodiments, a method for producing methanol as described herein may include the step of feeding at least a portion of the methanol synthesis reactor effluent stream to a separator to produce a crude methanol stream 55 and a steam stream, wherein the crude methanol stream 55 includes methanol and water, and wherein the steam stream 56 contains H ₂ , CO, CO 2 and hydrocarbons. The methanol reactor effluent may be separated into a crude methanol stream 55 and a vapor stream in a gas-liquid separator, 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 from the methanol synthesis loop 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 recycling a first portion of the steam stream to methanol synthesis loop 40 (e.g., its methanol synthesis reactor), and supplying a second portion of the steam stream as purge gas stream 56 to a hydrogen separation element 70 to form a hydrogen stream 71 and a residual gas stream 72. In some embodiments, the second portion (e.g., purge gas stream 56) of the vapor stream is from about 90 weight percent (wt%)% to about 99 wt%, from about 94 wt% to about 97 wt%, or from about 92 wt.% to about 99 wt.% steam stream based on the total weight of the steam stream. In some embodiments, the first portion of the vapor stream recycled to methanol synthesis loop 40 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.% steam flow.

The hydrogen separator 70 may be any device known in the art to operate by separating a substantially pure (eg, pure) hydrogen stream 71 from the purge gas stream 56 supplied thereto. The hydrogen separator 70 may partially or completely remove hydrogen from the purge gas stream 56 supplied thereto. In some embodiments, the hydrogen stream 71 is split, with at least a portion of the hydrogen stream 71

- 16 044653 hydrogen can be recycled as a first recycle 71A to the CPO reactor 10 (for example, above HDS 6, for example, through a heat-exchanged first portion 5A') and/or at least a portion of the hydrogen stream 71 can be recycled as a second recycle 71B into methanol synthesis loop 40 (eg, methanol synthesis reactor(s)) with reformed synthesis gas (eg, syngas 15E). In some embodiments, the residual gas stream 72 is separated, wherein at least a portion of the residual gas stream 72 may be recycled as a residual gas recycle 72B to the CPO reactor 10 (e.g., above HDS 6, e.g., via a heat-exchanged first portion 5A') and/ or at least a portion of the residual gas stream 72 may be used in the form of remaining residual gas stream 72A as fuel.

In some embodiments, the system and method for synthesizing syngas and/or methanol of the invention does not include a steam methane reforming (SMR) reactor. In some embodiments, methanol synthesis loop 40 has a methanol synthesis reactor volume that is smaller than the volume of a methanol synthesis reactor used for an otherwise similar process that produces (same product) methanol from syngas produced by an SMR steam methane reformer without CPO reactor. In some embodiments, the methanol synthesis reactor has a methanol synthesis reactor volume that is the same as the methanol synthesis reactor volume used for an otherwise similar process in which methanol is produced by a steam methane reforming reactor (SMR) without a CPO reactor, and in The process described herein produces more 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 SMR to produce methanol synthesis syngas.

By using CPO together with WGS, CO ₂ removal and/or thermal integration (e.g. via heat exchangers HE1, HE2, E1E3, E1E4 and/or HE5), instead of SMR, to produce synthesis gas suitable for subsequent methanol synthesis, described in The present description of the system and method allows for reduced 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 20-50 MMBTU/ton of methanol produced, representing a reduction of more than about 40- 80%. In some embodiments, CPO, WGS, and/or CO ₂ removal are used in conjunction with thermal integration (e.g., via heat exchangers HE1, HE2, HE3, HE4, and/or HE5) to produce syngas suitable for subsequent methanol synthesis (or other chemical synthesis , for which a reduced H2/CO molar ratio is desired without the use of SMR. In some embodiments, the CPO process described herein allows for a reduction in the overall energy consumption or carbon efficiency of a methanol production facility (e.g., by about 5 to about 15%) compared to prior art methanol production technologies (e.g., which use combined reforming , ATR and ATR+gas heated reforming (GHR)).

The method of the present invention can generate more heat in the methanol synthesis reactor of the methanol synthesis loop 40, which can be used in the method (eg, additional medium pressure or low pressure steam used in the method).

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, in a methanol production process using CPO syngas as described herein, less CO2 may advantageously be generated due to fuel combustion compared to steam reforming.

- 17 044653

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.

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 illustrative only and are 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 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 provide additional 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 description and in

- 18 044653 one or more patent or other documents, definitions that correspond to the description should be used.

Embodiments described herein include:

A: A method for producing syngas, comprising: (a) reacting, by a catalytic partial oxidation (CPO) reaction, a mixture of CPO reactants in a CPO reactor to produce an effluent stream from the CPO reactor; wherein the CPO reactant mixture contains hydrocarbons, oxygen and optionally water; wherein the CPO reactor contains a CPO catalyst; wherein the CPO reactor effluent contains 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) passing at least a portion of the CPO reactor effluent to a water gas shift (WGS) reactor to produce a hydrogen-enriched reactor effluent, wherein a portion of the carbon monoxide of the CPO reactor effluent is reacted with water through a WGS reaction to produce hydrogen and dioxide carbon, wherein the hydrogen-enriched reactor effluent is characterized by the H ₂ /CO molar ratio of the hydrogen-enriched reactor effluent, wherein the hydrogen-enriched reactor effluent is characterized by the M ratio of the hydrogen-enriched reactor effluent, and where the H ₂ /CO molar ratio of the hydrogen-enriched reactor effluent is the reactor effluent exceeds the H ₂ /CO molar ratio of the CPO reactor effluent; and (c) removing a portion of the CO2 from the hydrogen-enriched reactor effluent in a CO2 separator to produce syngas, wherein the syngas has a syngas ratio M, and wherein the syngas ratio M is greater than the M ratio of the CPO reactor effluent, and wherein the synthase ratio M is greater than the M ratio hydrogen-rich reactor effluent.

B: A method for producing methanol, comprising: (a) reacting, by a catalytic partial oxidation (CPO) reaction, a mixture of CPO reactants in a CPO reactor to produce an effluent stream from the CPO reactor; wherein the CPO reactant mixture includes hydrocarbons, oxygen and optionally water; 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 molar ratio of hydrogen to carbon monoxide (H2/CO) effluent the CPO reactor effluent, and wherein the CPO reactor effluent is characterized by the ratio M of the CPO reactor effluent, wherein the M ratio is a molar ratio defined as (H2-CO2)/(CO+CO2); (b) heating water while cooling the CPO reactor effluent by heat exchange in a heat exchanger to form steam and the cooled CPO reactor effluent; (c) supplying at least a portion of the cooled CPO reactor effluent to a water gas shift (WGS) reactor to form a hydrogen-enriched reactor effluent, wherein a portion of the carbon monoxide of the cooled CPO reactor effluent reacts with water through a WGS reaction to produce hydrogen and carbon dioxide, wherein the hydrogen-enriched reactor effluent is characterized by the H ₂ /CO molar ratio of the hydrogen-enriched reactor effluent, wherein the hydrogen-enriched reactor effluent is characterized by the M ratio of the hydrogen-enriched reactor effluent, and where the molar ratio of H2/CO enriched the hydrogen content of the reactor effluent exceeds the H2/CO molar ratio of the CPO reactor effluent and/or the cooled CPO reactor effluent; (d) removing a portion of the CO2 from the hydrogen-enriched reactor effluent in a CO2 separator to produce syngas, wherein the syngas is characterized by a syngas M ratio, and where the syngas M ratio exceeds the M ratio of the CPO reactor effluent, and where the syngas M ratio exceeds the M enriched ratio hydrogen from the reactor effluent; (e) driving the steam compressor using at least a portion of the steam; (f) compressing at least a portion of the syngas in a steam compressor to produce compressed syngas; (g) supplying at least a portion of the compressed syngas to the methanol synthesis loop to produce a crude methanol stream and a purge gas stream; wherein the crude methanol stream includes methanol and water; and wherein the purge gas stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and (h) optionally producing additional steam by combustion of hydrocarbons, where the additional steam is further used to drive a steam compressor.

C: A system comprising: (a) a catalytic partial oxidation (CPO) reactor operating by producing, through reaction of CPO, a CPO reactor effluent comprising hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons from a mixture of CPO reagents including hydrocarbons, oxygen and optionally water; wherein the CPO reactor effluent is characterized by a carbon monoxide molar ratio (H ₂ /CO) and an M ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ); (b) water gas shift reactor

- 19 044653 (WGS) for producing, through a WGS reaction, a hydrogen-enriched reactor effluent from at least a portion of the CPO reactor effluent, wherein the hydrogen-enriched reactor effluent has a H2/CO molar ratio greater than the H2/CO molar ratio effluent from the CPO reactor; and (c) a CO ₂ separator operating by removing a portion of the CO ₂ from the hydrogen-enriched reactor effluent to form syngas, wherein the syngas has an M ratio that is greater than the M ratio of the CPO reactor effluent and greater than the M ratio of the hydrogen-enriched reactor effluent .

Each of embodiments A, B and C may have one or more of the following additional elements: element 1: wherein hydrocarbons include methane, natural gas, natural gas liquids, associated gas, gas cap gas, rich gas, paraffinic hydrocarbons, shale gas, shale liquids, fluid catalytic cracking (FCC) offgas, petroleum refining process gas, flue gases, or combinations thereof. Element 2: where the hydrocarbons further include one or more sulfur-containing compounds and where at least a portion of the sulfur-containing compounds is removed from the hydrocarbons before feeding the hydrocarbons into the CPO reactor. Element 3: 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 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 carbon to oxygen (C/O) molar ratio in the CPO reactant mixture of from about 1.5:1 to about 2.5:1, 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 (O2) in the mixture of reagents; the molar ratio of steam to carbon (S/C) in the reactant mixture for CPO 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) in hydrocarbon mixtures of reagents; and their combinations. Element 4: where the syngas ratio M is greater than or equal to approximately 1.7. Element 5: wherein less than about 50 mole percent of the CO2 in the hydrogen-enriched reactor effluent is removed in a _CO2 separator to form syngas. Element 6: further including cooling the CPO reactor effluent. Element 7: further comprising cooling the CPO reactor effluent and heating the hydrocarbons by: (i) exchanging heat between the CPO reactor effluent and a heat transfer fluid in the first heat exchanger to produce a first cooled CPO reactor effluent; (ii) heating the hydrocarbons while further cooling the first cooled CPO reactor effluent stream by heat exchange therebetween in a second heat exchanger to produce heated hydrocarbons and a second cooled CPO reactor effluent stream, wherein the heated hydrocarbons include one or more sulfur-containing compounds and wherein at least a portion of sulfur-containing compounds are removed from heated hydrocarbons to form desulfurized hydrocarbons; and (iii) optionally heating the hydrocarbons before (ii) by means of an electrical heater. Element 8: further comprising cooling the desulfurized hydrocarbons. Element 9: wherein cooling the desulfurized hydrocarbons includes heating water while cooling the desulfurized hydrocarbons through heat exchange in a third heat exchanger to produce steam and cooled desulfurized hydrocarbons, wherein at least a portion of the cooled desulfurized hydrocarbons and optionally at least a portion of the steam are supplied to the CPO reactor in step (a ). Element 10: further comprising heating water while cooling the second cooled CPO reactor effluent by heat exchange in a third heat exchanger to produce a third cooled CPO reactor effluent, wherein at least a portion of the third cooled CPO reactor effluent is supplied to the WGS reactor in step ( b). Element 11: wherein at least a portion of the steam produced in the first heat exchanger and/or the third heat exchanger is optionally used to drive the steam compressor. Element 12: wherein at least a portion of the syngas is supplied to a steam compressor to form compressed syngas, and further comprising (i) supplying at least a portion of the compressed syngas to a methanol synthesis loop to form a crude methanol stream and a purge gas stream; wherein the crude methanol stream includes methanol and water; and wherein the purge gas stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons. Element 13: further comprising: supplying at least a portion of the purge gas stream to the hydrogen separation element to form a hydrogen stream and a residual gas stream; recycling at least a portion of the residual gas stream to the CPO reactor and/or using at least a portion of the residual gas stream as fuel; and recycling at least a portion of the hydrogen stream to the methanol synthesis loop and/or recycling at least a portion of the hydrogen stream to the CPO reactor. Element 14: wherein the methanol synthesis loop includes a methanol synthesis reactor, which is characterized by a volume of the methanol synthesis reactor that is reduced compared to the volume of the methanol reactor,

-

Claims (16)

used for an otherwise similar process that produces methanol from syngas produced through a steam methane reformer (SMR) without a CPO reactor. Item 15: does not include a steam methane reformer (SMR). Element 16: wherein the hydrocarbons burned in step (h) constitute less than about 10 wt.% of all hydrocarbons based on the total weight of all hydrocarbons, and where all hydrocarbons are determined by the sum of hydrocarbons fed to the CPO reactor in step (a), and hydrocarbons burned in step (h). Element 17: wherein the CPO reactor is characterized by a steam to carbon (S/C) molar ratio in the CPO reactant mixture of from about 0.05:1 to about 1:1, wherein the S/C molar ratio refers to the total moles of water (H2O) in mixture of reactants divided by the total number of moles of carbon (C) hydrocarbons in the mixture of reactants; and wherein the syngas and/or compressed syngas has a H2/CO molar ratio greater than or equal to about 1.8. Element 18: wherein the ratio M of syngas and/or compressed syngas is greater than or equal to approximately 2.0. Element 19: further comprising a methanol synthesis loop operating by producing a crude methanol stream and a purge gas stream; wherein the crude methanol stream includes methanol and water; and wherein the purge gas stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons. Element 20: further including a heat exchanger operating by transferring heat from the CPO reactor effluent to heat the CPO reactant mixture, and/or a heat exchanger operating by transferring heat from the CPO reactor effluent to generate steam. 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 to the invention described herein 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. CLAIM 1. A method for producing syngas, including: (a) reacting, through a catalytic partial oxidation (CPO) reaction, a mixture of CPO reactants in a CPO reactor to form an effluent stream from the CPO reactor; where the mixture of reagents for SRO includes hydrocarbons, oxygen and water; where the SRO reactor contains an SRO catalyst; where the effluent from the SRO reactor includes hydrogen (H2), 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 and 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) passing at least a portion of the CPO reactor effluent to a water gas shift (WGS) reactor to produce a hydrogen-enriched reactor effluent, wherein a portion of the carbon monoxide of the CPO reactor effluent is reacted with water through a WGS reaction to produce hydrogen and dioxide carbon, wherein the hydrogen-enriched reactor effluent is characterized by the _H2 /CO molar ratio of the hydrogen-enriched reactor effluent, wherein the hydrogen-enriched reactor effluent is characterized by the M ratio of the hydrogen-enriched reactor effluent, and where the H2/CO molar ratio of the hydrogen-enriched reactor effluent is the flow from the reactor exceeds the molar ratio of H2/CO of the effluent from the SRO reactor; and (c) removing a portion of the CO2 from the hydrogen-enriched reactor effluent in a CO2 separator to produce syngas, wherein the syngas has a syngas ratio M, and where the syngas ratio M is greater than the M ratio of the CPO reactor effluent, and where the syngas ratio M is greater than the M ratio. a hydrogen-enriched reactor effluent; wherein the method further includes cooling the CPO reactor effluent and heating the hydrocarbons by: (i) exchanging heat between the CPO reactor effluent and a coolant fluid in a first heat exchanger to form a first cooled effluent - 21 044653 from the SRO reactor; (ii) heating the hydrocarbons while further cooling the first cooled SRO reactor effluent by heat exchange therebetween in a second heat exchanger to form heated hydrocarbons and a second cooled SRO reactor effluent; and (iii) heating the hydrocarbons before (ii) using an electrical heater, wherein the heated hydrocarbons include one or more sulfur-containing compounds and wherein at least a portion of the sulfur-containing compounds is removed from the heated hydrocarbons to form desulfurized hydrocarbons; wherein the method further includes heating water while cooling the second cooled CPO reactor effluent by heat exchange in a third heat exchanger to produce a third cooled CPO reactor effluent, wherein at least a portion of the third cooled CPO reactor effluent is supplied to the WGS reactor in step (b) ), and wherein at least a portion of the steam produced in the first heat exchanger and/or the third heat exchanger is used to drive the steam compressor. 2. The method according to claim 1, where the hydrocarbons include methane, natural gas, gas condensate liquids, associated gas, gas cap gas, enriched gas, paraffinic hydrocarbons, shale gas, shale liquids, fluid catalytic cracking (FCC) offgas, process gas oil refining, oil refining off-gas, flue gases, fuel gas from a fuel gas header, or combinations thereof. 3. The method of claim 1 or claim 2, wherein the hydrocarbons further include one or more sulfur-containing compounds, and wherein at least a portion of the sulfur-containing compounds is removed from the hydrocarbons before feeding the hydrocarbons into the SRO reactor. 4. The method according to any one of claims 1-3, 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; SRO pressure from approximately 1 bar i.d. up to approximately 90 bar i.d.; contact time for SRO from approximately 0.001 milliseconds (ms) to approximately 5 seconds (s); a molar ratio of carbon to oxygen (C/O) in the FRO reactant mixture of from about 1:1 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 amount mole 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 3:1, 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) in hydrocarbon mixtures of reagents; and their combinations. 5. The process according to any one of claims 1 to 4, wherein the M ratio of the syngas is greater than or equal to about 1.7 and/or wherein less than about 50 mol.% CO ₂ in the hydrogen-rich reactor effluent is removed in a CO 2 separator to form syngas . 6. The method according to any one of claims 1 to 5, further comprising cooling the desulfurized hydrocarbons, wherein cooling the desulfurized hydrocarbons optionally includes heating water while cooling the desulfurized hydrocarbons through heat exchange in a third heat exchanger to produce steam and cooled desulfurized hydrocarbons, wherein at least a portion of the cooled desulfurized hydrocarbons and optionally at least a portion of the steam are supplied to the SRO reactor in step (a). 7. The method according to any one of claims 1 to 5, wherein at least a portion of the syngas is supplied to a compressor to form a compressed syngas and further comprising (i) supplying at least a portion of the compressed syngas to a methanol synthesis loop to form a crude methanol stream and a stream purge gas; wherein the crude methanol stream includes methanol and water; and wherein the purge gas stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons. 8. The method according to claim 7, additionally including: supplying at least a portion of the purge gas stream to the hydrogen separation element to form a hydrogen stream and a residual gas stream; recycling at least a portion of the residual gas stream to the SRO reactor and/or using at least a portion of the residual gas stream as fuel; and recycling at least a portion of the hydrogen stream to the methanol synthesis loop and/or recycling at least a portion of the hydrogen stream to the SRO reactor. 9. The method according to any one of claims 1 to 8, not including a steam methane reforming reactor (SMR). 10. A method for producing methanol, including: (a) reacting, through a catalytic partial oxidation (CPO) reaction, a mixture of CPO reactants in a CPO reactor to produce an effluent stream from the CPO reactor; where the mixture of reagents for SRO includes hydrocarbons, oxygen and water; where the SRO reactor contains an SRO catalyst; where the effluent stream from the SRO reactor includes hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons, where the effluent stream from the SRO reactor is characterized by the molar ratio of hydrogen and carbon monoxide (H ₂ /CO) of the effluent stream from the SRO reactor, and where are you - 22 044653 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 (H2-CO ₂ )/(CO+CO2); (b) heating water while cooling the SRO reactor effluent by heat exchange in a heat exchanger to produce steam and cooled SRO reactor effluent; (c) supplying at least a portion of the cooled CPO reactor effluent to a water gas shift (WGS) reactor to produce a hydrogen-enriched reactor effluent, wherein a portion of the carbon monoxide in the cooled CPO reactor effluent reacts with water through a WGS reaction to form hydrogen and carbon dioxide, wherein the hydrogen enriched reactor effluent is characterized by the H2/CO molar ratio of the hydrogen enriched reactor effluent, where the hydrogen enriched reactor effluent is characterized by the M ratio of the hydrogen enriched reactor effluent, and where the molar ratio of H2/CO enriched the hydrogen content of the reactor effluent exceeds the H2/CO molar ratio of the SRO reactor effluent and/or the cooled SRO reactor effluent; (d) removing a portion of the CO2 from the hydrogen-enriched reactor effluent in a CO ₂ separator to form syngas, wherein the syngas is characterized by a syngas M ratio and where the syngas M ratio exceeds the M ratio of the CPO reactor effluent, and where the syngas M ratio exceeds the M rich ratio hydrogen from the reactor effluent; (e) driving the steam compressor using at least a portion of the steam; (f) compressing at least a portion of the syngas in a steam compressor to form compressed syngas; (g) supplying at least a portion of the compressed syngas to the methanol synthesis loop to form a crude methanol stream and a purge gas stream; wherein the crude methanol stream includes methanol and water; and wherein the purge gas stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons; and (h) generating additional steam by combustion of hydrocarbons, where the additional steam is further used to drive a steam compressor. 11. The process of claim 10, wherein the hydrocarbons burned in step (h) constitute less than about 10 wt.% of all hydrocarbons based on the total weight of all hydrocarbons, and wherein all hydrocarbons are determined by the sum of hydrocarbons fed to the SRO reactor at stage (a), and hydrocarbons burned in stage (n). 12. The method according to any one of claims 10-11, where the SRO reactor is characterized by a molar ratio of steam to carbon (S/C) in the mixture of SRO reagents from about 0.05:1 to about 1:1, where the molar ratio S/C refers to to the total moles of water (H2O) in the reactant mixture divided by the total moles of carbon (C) hydrocarbons in the reactant mixture; and wherein the syngas and/or compressed syngas has a H2/CO molar ratio greater than or equal to about 1.8. 13. Method according to any one of claims 10 to 12, wherein the ratio M of syngas and/or compressed syngas is greater than or equal to approximately 2.0. 14. System for producing syngas, containing: (a) a catalytic partial oxidation (CPO) reactor operating by producing, through a CPO reaction, an effluent from the CPO reactor comprising hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), water and unreacted hydrocarbons from a mixture of reactants SRO, including hydrocarbons, oxygen and water; where the effluent from the SRO reactor is characterized by the molar ratio of hydrogen and carbon monoxide (H2/CO) and the ratio M, defined as (H2-CO2)/(CO+CO2); (b) a water gas shift (WGS) reactor configured to produce, through the WGS reaction, a hydrogen-enriched reactor effluent from at least a portion of the effluent from the CPO reactor, wherein the hydrogen-enriched reactor effluent has a molar ratio of H2/CO greater than H2/CO ratio of the effluent from the SRO reactor; and (c) a CO ₂ separator operating by removing a portion of the CO ₂ from the hydrogen-enriched reactor effluent to form syngas, wherein the syngas has an M ratio that is greater than the M ratio of the SRO reactor effluent and greater than the M ratio of the hydrogen-enriched reactor effluent ; wherein the system further comprises a heat exchanger operating by transferring heat from the effluent stream from the SRO reactor to heat the mixture of reactants for the SRO, and/or a heat exchanger operating by transferring heat from the effluent stream from the SRO reactor to produce steam; and where the system further comprises a steam compressor. 15. The system of claim 14, excluding the steam methane reformer (SMR). 16. The system of claim 14 or claim 15, further comprising a methanol synthesis loop operating by producing a crude methanol stream and a purge gas stream; wherein the crude methanol stream includes methanol and water; and wherein the purge gas stream includes hydrogen, carbon monoxide, carbon dioxide and hydrocarbons. -