EA042919B1 - METHOD FOR PRODUCING HYDROGEN-DEFERENT SYNTHESIS GAS FOR ACETIC ACID SYNTHESIS AND DIMETHYL ETHER SYNTHESIS - Google Patents

Description

The disclosure of the present invention relates to systems and methods for producing acetic acid and dimethyl ether (DME); more specifically, the disclosure of the present invention relates to systems and methods for producing acetic acid and DME from hydrogen-depleted synthesis gas, where hydrogen-depleted synthesis gas is produced by catalytic partial oxidation (CPO); even more specifically, the disclosure of the present invention relates to systems and methods for producing acetic acid and DME through the reaction of the FRO of a mixture of CRO reagents containing hydrocarbons and oxygen, where the hydrocarbons contain at least about 3 mole percent (mol.%) of higher hydrocarbons (for example, alkanes containing 2 or more carbon atoms, C ₂₊ ).

BACKGROUND OF THE INVENTION Synthesis gas (synthesis gas) is a mixture containing carbon monoxide (CO) and hydrogen (H ₂ ), as well as small amounts of carbon dioxide (CO ₂ ), water (H ₂ O) and unreacted methane (CH ₄ ). Synthesis gas is commonly used as an intermediate in a variety of synthesis processes, including, but not limited to, the synthesis of dimethyl ether (DME), alcohols such as methanol, ethanol, oxo alcohols (e.g., n-butanol, etc.), ethylene glycol, aldehydes, and the like. Syngas is traditionally produced by steam reforming of natural gas (steam methane reforming or SMR), although other sources of hydrocarbons can be used to produce synthesis gas, such as gases from facilities between plants, feed naphtha, heavy hydrocarbons, coal, biomass, and so on. . SMR is an endothermic process and requires a significant amount of energy to start the reaction. Conventional endothermic technologies, such as SMR, produce synthesis gas with an H ₂ content greater than that required for a variety of downstream chemical syntheses. In the autothermal reforming (ATR) process, a portion of the natural gas is burned as fuel to drive the conversion of the natural gas to synthesis gas, resulting in relatively low hydrogen concentrations and high CO ₂ concentrations. In conventional combined reforming (CR) technology, SMR is combined with autothermal reforming (ATR) to reduce the amount of H2 present in the synthesis gas. ATR produces synthesis gas with a lower hydrogen content. Synthesis gas in CR technology typically has a higher H ₂ content than is needed for many downstream synthesis processes. In addition, SMR is a highly endothermic process, and the endothermicity of the SMR technology requires fuel to be burned to drive syngas synthesis. Consequently, SMR technology reduces the energy efficiency of the subsequent chemical synthesis process.

Synthesis gas can also be produced (non-industrially) by catalytic partial oxidation (CPO or CPOx) of natural gas. FRO processes use the partial oxidation of hydrocarbon feedstocks to synthesis gas containing CO and H2. The FRO process is exothermic, thus eliminating the need for external heat input. Conventional partial oxidation processes do not produce an H2 depleted syngas suitable for use in downstream syntheses where hydrogen to carbon monoxide molar ratios of less than about 1.6 are required. Thus, there is an urgent need to develop systems and methods for producing acetic acid and DME from lean H ₂ syngas produced by FRO.

Brief description of the drawings

In the following, for a detailed description of the preferred embodiments of the disclosed methods, reference will be made to the accompanying drawings, in which:

in fig. 1 is a schematic representation of a system I for producing acetic acid from hydrogen-depleted synthesis gas produced by partial catalytic oxidation (CPO or CPOx), according to embodiments of the disclosure of the present invention;

in fig. 2 is a schematic representation of a system II for producing DME from hydrogen-depleted synthesis gas produced by FRO according to embodiments of the disclosure of the present invention;

in fig. 3 is a graph showing the molar ratio of carbon monoxide to hydrogen (CO/H2) in syngas resulting from FRO as a function of reactor temperature without introducing CO ₂ into the feed mixture;

in fig. 4 is a graph showing CO/H2 molar ratio in synthesis gas resulting from FRO as a function of reactor temperature with CO ₂ injection into a reactant mixture having a carbon dioxide to methane molar ratio (CO2/CH4) of 0.5;

in fig. 5 is a graph showing CO/H2 molar ratio in synthesis gas as a result of FRO as a function of reactor temperature with CO2 injection into a reactant mixture having a carbon dioxide to methane molar ratio (CO2/CH4) of 1;

in fig. 6 is a graph showing the CO2/CO mole ratio in syngas resulting from FRO as a function of reactor temperature without CO2 injection into reactant feed mixtures having CH4/O2 mole ratios of 2.2, 1.7 and pressures of 40, 100 bar;

in fig. 7 is a graph showing the CO2/CO molar ratio in synthesis gas resulting from FRO as a function of reactor temperature with CO ₂ injection into a reactant mixture having a carbon dioxide to methane molar ratio (CO ₂ /CH ₄ ) of 0.5 ;

- 1 042919 in FIG. 8 is a graph showing the molar ratio of carbon monoxide to hydrogen (H2/CO) in synthesis gas as a result of FRO as a function of conversion (%) and the molar ratio of carbon dioxide to carbon (CO ₂ /C) in the feed mixture of reactants (in conditional notation) at a pressure of 30 bar and an oxygen to carbon molar ratio (O2/C) of 0.55;

in fig. 9 is a graph showing the molar ratio of carbon monoxide to hydrogen (H ₂ /CO) in the synthesis gas as a result of FRO as a function of conversion (%) and the molar ratio of carbon dioxide to carbon (CO ₂ /C) in the feed mixture of reactants (in symbols) at a pressure of 75 bar and an oxygen to carbon molar ratio (O2/C) of 0.55;

in fig. 10 is a graph showing the molar ratio of carbon monoxide to hydrogen (H2/CO) in syngas as a result of FRO as a function of conversion (%) and the molar ratio of hydrocarbons having three carbon atoms (C ₃ ) to carbon (C ₃ / C) in a reactant feed mixture (in symbols) at a pressure of 75 bar, an oxygen to carbon molar ratio (O2/C) of 0.55, and a carbon dioxide to carbon molar ratio (CO2/C) of 0, 25;

in fig. 11 is a graph showing the molar ratio of carbon monoxide to hydrogen (H ₂ /CO) in synthesis gas as a function of conversion (%) and the molar ratio of hydrocarbons having three carbon atoms (C ₃ ) to carbon (C ₃ /C) in the feed mixture of reagents (in symbols) at a pressure of 75 bar, a molar ratio of oxygen to carbon (O ₂ /C) equal to 0.55 and without CO ₂ in the feed mixture of reagents;

in fig. 12 is a graph showing the molar ratio of carbon monoxide to hydrogen (H ₂ /CO) in syngas as a result of FRO as a function of conversion (%) and the mole ratio of hydrocarbons having two carbon atoms (C2) to carbon (C2/C ) in a reactant feed mixture (in symbols) at a pressure of 75 bar, an oxygen to carbon molar ratio (O2/C) of 0.55 and a carbon dioxide to carbon molar ratio (CO2/C) of 0.25 ;

in fig. 13 is a graph showing the molar ratio of carbon monoxide to hydrogen (H2/CO) in syngas as a result of FRO as a function of conversion (%) and the molar ratio of hydrocarbons having two carbon atoms (C ₂ ) to carbon (C ₂ / C) in the feed mixture of reagents (in symbols) at a pressure of 75 bar, an O ₂ /C molar ratio of 0.55 and no CO ₂ in the feed mixture of reagents;

in fig. 14 is a graph showing the molar ratio of carbon monoxide to hydrogen (H ₂ /CO) in syngas as a result of FRO as a function of conversion (%) and the molar ratio of hydrocarbons having four carbon atoms (C ₄ ) to carbon (C ₄ /C) in a reactant feed mixture (in symbols) at a pressure of 75 bar, an oxygen to carbon molar ratio (O2/C) of 0.55 and a carbon dioxide to carbon molar ratio (CO2/C) of 0 .25; and in FIG. 15 is a graph showing the molar ratio of carbon monoxide to hydrogen (H2/CO) in syngas as a result of FRO as a function of conversion (%) and the molar ratio of hydrocarbons having four carbon atoms (C4) to carbon (C4/C) in the reactant feed mixture (in symbols) at a pressure of 75 bar, an O2/C molar ratio of 0.55 and no CO ₂ in the reactant feed mixture.

Detailed description of the present invention

Syngas-containing feedstocks for a variety of chemical synthesis processes are required to contain H ₂ depleted synthesis gas having a molar ratio of H ₂ to carbon monoxide (H 2 /CO) of approximately 1:1. When synthesis gas is produced from conventional processes that provide synthesis gas having a higher molar ratio (e.g., about 2:1), the synthesis gas must be preheated, for example, by means of an H ₂ removal unit (e.g. pressure swing adsorption PSA), to reduce the molar ratio of H2/CO in synthesis gas. Conventional partial oxidation (POx) processes do not provide synthesis gas having an H2/CO molar ratio of approximately 1:1. The use of an intermediate H ₂ removal step (eg PSA) increases the energy and capital cost requirements.

Within the scope of the present invention, hydrogen-depleted synthesis gas (eg, synthesis gas having an H2/CO molar ratio ranging from about 0.8 to about 1.6) can be produced by a partial catalytic oxidation (CRO) process. Through the system and method embodiments disclosed herein, the FRO process can be adapted to provide hydrogen-depleted synthesis gas having a desired composition (e.g., a reduced H2/CO molar ratio compared to that of synthesis gas produced by conventional POX process). Accordingly, the systems and methods disclosed herein may make it possible to reduce the size or eliminate the hydrogen removal apparatus, thus reducing the number of individual operations, and thus may, in embodiments, also make it possible to reduce the energy requirements for the process.

In embodiments, FRO is used to produce hydrogen-depleted synthesis gas by using an FRO feed mixture that contains higher hydrocarbons and/or carbon dioxide (CO ₂ ). The use of feed mixtures of reagents containing higher hydrocarbons

- 2 042919, makes it possible to reduce the amount of CO2 required to achieve an H2/CO molar ratio of approximately 1, and at the same time allows the production of hydrogen-depleted synthesis gas having an H2/CO molar ratio of approximately 1 at a higher hydrocarbon conversion into synthesis gas.

Except in working examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and the like used in the specification and claims are to be understood as modified in all instances by the term approximately. Various numerical ranges are disclosed herein. Because these intervals are continuous, they include every value between the minimum and maximum values. The limit values of all intervals in which the same characteristic or component is given are independently combinable and include the limit value given. Unless explicitly stated otherwise, the various numerical ranges indicated in this application are approximations. The limit values of all intervals directed to the same component or property are inclusive of the limit value and can be independently combined. An expression from greater than 0 to an amount means that the named component is present in an amount greater than 0 and greater than and including the higher named amount.

The singular terms do not indicate a quantitative limitation, but rather indicate the presence of at least one of the mentioned elements. Within the scope of the present invention, the singular forms include references to the plural.

Within the scope of the present invention, combinations thereof include one or more of the listed elements, optionally together with a similar element not listed, for example, includes a combination of one or more of the named components, optionally with one or more other components not specifically named, which essentially perform the same function. Within the scope of the present invention, the term combination includes complexes, mixtures, alloys, reaction products, and the like.

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

Within the scope of the present invention, the terms inhibitory or reducing or interfering or eliminating or any variation of these terms include any measurable reduction or complete inhibition to achieve the desired result. In the context of the present invention, the term effective means an adequate action to achieve the desired, expected or intended result. Within the scope of the present invention, the terms containing (and any form of content such as includes and contains), having (and any form of possession such as have and have), including (and any form of inclusion such as include and includes) or containing (and any form of content such as contain and contains) are inclusive or non-limiting and do not exclude additional, non-listed elements or method steps.

Unless otherwise defined, technical and scientific terms used herein have the same meaning as is generally understood by a person skilled in the art. Compounds in this document are described using standard nomenclature. For example, any position not substituted by any specified group is understood to have a valency filled by the specified bond or hydrogen atom. A dash (-) that is not between two letters or symbols is used to indicate the attachment point for a substituent. For example, -CHO is attached through the carbonyl carbon. Within the scope of the present invention, the terms C _x hydrocarbons and CxS are used interchangeably and refer to any hydrocarbon having x number of carbon atoms (C). For example, the terms C ₄ hydrocarbons and C ₄ s both refer to any hydrocarbon having exactly 4 carbon atoms, such as n-butane, isobutane, cyclobutane, 1-butene, 2-butene, isobutylene, butadiene, and the like, or combinations thereof. Within the scope of the present invention, the term C _x+ hydrocarbons refers to any hydrocarbon having at least x carbon atoms (C). For example, the term C ₂₊ hydrocarbons refers to any hydrocarbon having 2 or more carbon atoms, such as ethane, ethylene, C ₃ s, C ₄ s, C ₅ s, and so on.

With reference to FIG. 1 discloses a chemical production system I. Chemical production system I typically comprises a partial catalytic oxidation (CPO or CPOx) reactor 10 and a downstream synthesis device, including an acetic acid synthesis device (FIG. 1) or a DME synthesis device (FIG. 2). It will be appreciated by those skilled in the art with the aid of this disclosure that the components of the methanol production system shown in FIG. 1 and 2 can

- 3 042919 communicate with the possibility of passing the fluid with each other (as represented by connecting lines indicating the direction of flow of the fluid) through any suitable circuits (eg, pipes, streams, and so on).

In embodiments, the method for producing DME or acetic acid disclosed herein may include the step of reacting, via a partial catalytic oxidation (CPO) reaction, a mixture of 5 CPO reactants in an CPO reactor 10 to produce hydrogen-depleted synthesis gas 15; where the mixture of 5 CPO reagents contains hydrocarbons and oxygen (O ₂ ) and optionally carbon dioxide (CO ₂ ); where the hydrocarbons contain at least about 3 mol.% With ₂₊ alkanes; where the reactor 10 FRO contains the catalyst FRO; wherein the hydrogen-depleted synthesis gas 15 contains hydrogen, carbon monoxide (CO), CO2, and unreacted hydrocarbons;

and wherein the hydrogen-depleted synthesis gas 15 has a hydrogen to carbon monoxide molar ratio (H2/CO) of about 0.8 to about 1.6.

Typically, the FRO reaction is based on the partial combustion of a fuel such as a variety of hydrocarbons, and in the case of methane, the FRO can be represented by equation (1),

CH4 + 1/2 O2 > CO + 2 H2 (1).

Without being limited by theory, the authors note that, along with the FRO reaction represented by equation (1), side reactions (1) can occur; and such side reactions can lead to the production of CO ₂ and water (H ₂ O), for example, through the combustion of hydrocarbons, which is an exothermic reaction. It will be understood by one of skill in the art with the aid of the present disclosure, and without being bound by theory, the authors note that the FRO reaction represented by equation (1) can produce synthesis gas with an H ₂ /CO molar ratio having a theoretical stoichiometric limit of 2.0. Without wishing to be bound by theory, the authors note that a theoretical stoichiometric limit of 2.0 for the H2/CO molar ratio means that the FRO reaction represented by equation (1) results in 2 moles of _H2 for every 1 mole of CO, i.e. . the molar ratio of H2/CO is (2 mol H ₂ /1 mol CO)=2. One skilled in the art will appreciate with the aid of this disclosure that the theoretical stoichiometric limit of 2.0 for the H2/CO molar ratio in the FRO reaction cannot be practically achieved because the reactants (e.g., hydrocarbons, O2) as well as the products (eg H ₂ , CO) participate in side reactions under the conditions used for the FRO reaction. One of skill in the art will appreciate with the aid of the present disclosure, and without being limited by theory, the authors note that, in the presence of O ₂ , CO and H ₂ can be oxidized to CO ₂ and H ₂ O, respectively. The relative amounts (eg, composition) of CO, H ₂ , CO ₂ and H ₂ O can be further changed by shifting the equilibrium of the water gas shift (WGS) reaction, which will be discussed in more detail below in this document. Side reactions that may occur in the FRO reactor 10 may have a direct impact on the composition of the hydrogen-depleted synthesis gas 15 which, within the scope of the present invention, contains hydrogen-depleted synthesis gas. In the absence of any side reaction (theoretically), the FRO reaction represented by equation (1) results in a synthesis gas with an H2/CO molar ratio of 2.0. However, the presence of side reactions can (virtually) decrease H2 (and increase CO2), thus resulting in syngas with a reduced _H2 /CO molar ratio.

In addition, without being limited by theory, the authors note that, the FRO reaction represented by equation (1) is an exothermic heterogeneous catalytic reaction (i.e., a moderately exothermic reaction), and it is carried out in a separate reactor unit, such as a 10 FRO reactor ( as opposed to more than one reactor plant, as is the case with conventional synthesis gas production processes such as combinations of steam methane reforming (SMR) - autothermal reforming (ATR)). 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 is associated with excessive temperatures, long contact times, and excessive coke formation, which significantly reduce the controllability of the partial oxidation reaction, and may not lead to obtaining synthesis gas of the required quality in a separate reactor plant. In addition, without being bound by theory, the authors note that, the FRO reaction is quite resistant to chemical poisoning, and thus allows the use of a wide variety of hydrocarbon feed mixtures, including some sulfur-containing hydrocarbon feed mixtures; which, in some cases, can increase catalyst life and productivity. In contrast, conventional ATR processes are characterized by more restrictive feedstock requirements, for example regarding the content of impurities in the feedstock (eg ATR feedstock is desulphurized) as well as hydrocarbon composition (eg ATR typically uses CH4 rich feedstock).

In embodiments, hydrocarbons suitable for use in the FRO reaction disclosed herein may include methane, natural gas, natural gas liquids, liquefied petroleum gas (LPG), petroleum gas, associated gas, enriched gas, waxes, shale gas, shale liquid fluids, fluid catalytic cracking (FCC) gas, process plant gases, inter-plant gases, residual gases, fuel gas from a fuel gas header, or combinations thereof. In embodiments, the amount of CO ₂ and/or CO in the 5 reactant mixture may

- 4 042919 be increased by diluting the feed mixture with gases (eg residual gases) containing CO2 and/or CO. Such gases containing CO2 and/or CO include, without limitation, tail gases, reducing gases, exhaust gases, high in CO, such as those used in metallurgy, crackers, and the like. For example, dedicated coke oven reactors can be used which, by injecting feed steam, air and CO2, deliver a continuous stream of CO into the FRO reactor 10 .

In embodiments, the reactant mixture 5 contains fuel gases from a steam cracker and the FRO reactor 10 is operated at a high CH ₄ /O ₂ molar ratio, providing autothermal operation. In embodiments, the hydrogen content of the reactant mixture 5 may be adjusted to maintain an appropriate adiabatic rise.

The hydrocarbons may include any suitable source of hydrocarbons and may contain Ci-C6 hydrocarbons as well as some heavier hydrocarbons. In embodiments, the FRO mixture 5 may contain natural gas. Natural gas typically consists primarily of methane, but may also contain ethane, propane, and heavier hydrocarbons (e.g., isobutane, nbutane, isopentane, n-pentane, hexanes, etc.) and very small amounts of nitrogen (N2) , O ₂ , CO 2 , 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, shale fracturing, biomass, landfill gas, and the like, or combinations thereof. In some aspects, the mixture of 5 CPO reagents may contain mainly CH ₄ and O ₂ .

Natural gas may contain any suitable amount of methane. In some embodiments, natural gas may contain biogas. For example, natural gas may contain from about 45 to about 80 mole% methane, from about 20 to about 55 mole% CO ₂ , and less than about 15 mole% N2.

In embodiments, natural gas may contain CH4 in an amount not less than about 45 mole%, about 50 mole%, about 55 mole%, about 60 mole%, about 65 mole%, about 70 mole%, about 75 mole%, about 80 mole%, about 82 mole%, about 84 mole%, about 86 mole%, about 88 mole%, about 90 mole%, about 91 mole%, about 92 mol%, about 93 mol%, about 94 mol%, about 95 mol%, about 96 mol%, or about 97 mol%.

Within the scope of the present invention, the hydrocarbons in the reactant feed mixture 5 contain at least about 3, 4, 5, 6, 7, 8, 9, or 10 mole % of heavier hydrocarbons, including hydrocarbons having two or more carbon atoms (e.g., C _{2 +} hydrocarbons). In embodiments, the hydrocarbons in the reactant feed mixture 5 contain at least about 3, 4, 5, 6, 7, 8, 9, or 10 mole % C ₂₊ alkanes. In embodiments, the hydrocarbons in the reactant feed mixture 5 contain ethane in an amount of at least about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mol%. In embodiments, the hydrocarbons in the reactant feed mixture 5 contain at least about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mole percent propane. In embodiments, the hydrocarbons contain butanes in an amount of at least about 3, 4, 5, 6, 7, or 8 mol%. In embodiments, the hydrocarbons in the feed mixture 5 of the reactants contain ethane in an amount of at least about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mol%, propane in an amount of at least about 4 , 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 mol.%, butanes in an amount of at least about 3, 4, 5, 6, 7 or 8 mol.%, or a combination thereof.

In embodiments, the FRO mixture 5 further comprises CO2, and the FRO mixture 5 has a molar ratio of CO2 to carbon (CO2/C) and/or CO2/CH4 in the FRO mixture 5 of at least about 0.5:1, 0.25 :1 or 0:1, where the CO2/C molar ratio refers to the total number of moles of CO2 in the reactant mixture divided by the total moles of carbon (C) in hydrocarbons in the reactant mixture.

In embodiments, the FRO mixture 5 further comprises CO ₂ and the FRO mixture 5 has a molar ratio of CO ₂ to carbon (CO ₂ /C) in the FRO mixture 5 of less than or about 10:1, 5:1, or 2:1. in embodiments, all or part of the CO ₂ in the reactant feed mixture 5 may be introduced into the reactant mixture 5 via the CO ₂ stream 7 . In embodiments, the FRO reactor 10 is operated in an autothermal operating mode with CO ₂ injection or addition via 7.

In embodiments, the amount of CO2 in the 5 CPO reactant mixture is lower than the amount of CO2 in the FRO reactant mixture according to another similar process, wherein hydrogen-depleted synthesis gas is produced from a reactant mixture containing a lower amount of C2+ alkanes hydrocarbons (e.g., where the hydrocarbons in the feed mixture 5 reagents contain less than about 3 mol% C2+alkanes). In embodiments, a portion of the CO2 in the 10 CRO reactor is subjected to a water gas shift (r-WGS) reverse reaction in the 10 CPO reactor (and/or in a separate r-WGS reactor 20 after the 10 CPO reactor), thereby reducing the amount of hydrogen in the hydrogen-depleted synthesis gas.

- 5 042919

In some embodiments, hydrocarbons suitable for use in the FRO reaction disclosed herein may contain C ₁ -C ₆ hydrocarbons (for example, including C ₂ , C ₃ and/or C ₄ as described above), N2 (for example, from about 0.1 to about 15 mole%, alternatively from about 0.5 to about 11 mole%, alternatively from about 1 to about 7.5 mole%, or alternatively from about 1.3 to about 5.5 mole .%), and CO ₂ (for example, from about 0.1 to about 2 mol.%, alternatively from about 0.2 to about 1 mol.%, or alternatively from about 0.3 to about 0.6 mol.%) . For example, hydrocarbons suitable for use in the FRO reaction disclosed herein may include C1 hydrocarbons (from about 89 to about 92 mol%); C ₂ hydrocarbons (at least about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mole %); C ₃ hydrocarbons (at least about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mole %); C ₄ hydrocarbons (at least about 3, 4, 5, 6, 7, or 8 mole %); C ₅ hydrocarbons (about 0.06 mole %); and C ₆ hydrocarbons (about 0.02 mole %); and optionally N2 (from about 0.1 to about 15 mol%), CO2 (from about 0.1 to about 2 mol%), or both N2 (from about 0.1 to about 15 mol%) and CO ₂ (from about 0.1 to about 2 mol.%).

The O ₂ used in the 5 CPO Reagent Mix may contain 100% O ₂ (essentially pure O ₂ ), gaseous O ₂ (which can be produced by a membrane separation process), technical O ₂ (which may contain some air), air enriched with O ₂ air containing O ₂ gaseous compounds (for example, NO) containing O ₂ mixtures (for example, O ₂ /CO ₂ , O ₂ /H ₂ O, O ₂ /H ₂ O ₂ /H ₂ O) , oxygen radical generators (eg, CH ₃ OH, CH ₂ O), hydroxyl radical generators, and the like, or combinations thereof.

In embodiments, the FRO reagent mixture 5 may have a carbon to oxygen (C/O) or CH ₄ /O ₂ molar ratio of less than about 3:1, about 2.6:1, about 2.4:1, about 2.2: 1, about 2:1 or about 1.9:1, alternatively not less than about 0.1:1, about 0.2:1, about 0.3:1, about 0.4:1, or about 0.5: 1, alternatively from about 0.5:1 to about 0.6:1, alternatively from about 0.55:1 to about 0.6:1, 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 1.5:1 to about 1.9:1, alternatively from about 2:1 to about 3:1, alternatively from about 2.2:1 to about 3:1, alternatively from about 2.4:1 to about 3:1, or alternatively from from about 2.6:1 to about 3:1, where the C/O mole ratio refers to the total moles (C) of hydrocarbons in the 5 reactant mixture divided by the total moles of O2 in the 5 reactant mixture.

Since the mixture of 5 CPO reagents according to the present disclosure contains other carbon sources other than CH ₄ such as ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), butanes (C ₄ H ₁₀ ) and so on, the C/O molar ratio takes into account moles of carbon in each compound (for example, 2 moles of C in 1 mole of C2H6, 3 moles of C in 1 mole of C ₃ H ₈ , 4 moles of C in 1 mole of C ₄ H ₁₀ , and so on). One skilled in the art will appreciate with the aid of this disclosure that the C/O molar ratio in the 5 CPO reactant mixture can be controlled along with other process parameters in the reactor (e.g., temperature, pressure, flow rate, etc.) to produce a hydrogen-depleted synthesis. -gas described in the framework of the present invention. The molar ratio C/O in the mixture of 5 CPO reagents can be adjusted to obtain a reduced amount of unchanged hydrocarbons in the synthesis gas. The C/O molar ratio of the FRO reactant mixture 5 can be adjusted based on the temperature of the FRO effluent to reduce (eg, minimize) the unchanged hydrocarbon content of the hydrogen-depleted synthesis gas 15, which is a hydrogen-depleted synthesis gas.

In embodiments, an FRO reactor suitable for use in the present disclosure (e.g., a 10 FRO reactor) may be a tubular reactor, a continuous reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a circulating fluidized bed reactor. (eg, column reactor), fluidized bed reactor, fluidized bed reactor with catalyst circulation, rotary kiln reactor, and the like, or combinations thereof. In some embodiments, the FRO reactor may comprise a circulating fluidized bed reactor, such as a column reactor.

In some embodiments, the FRO reactor 10 may differ in at least one FRO operating parameter selected from the group consisting of FRO reactor temperature (eg, FRO catalyst bed temperature); FRO feed mixture temperature (e.g., FRO reactant mixture temperature 5; target hydrogen-depleted synthesis gas temperature 15; FRO pressure (e.g., FRO reactor pressure 10); FPO reaction contact time (e.g., FRO reactor contact time 10); molar molar ratio of water vapor to carbon (S/C) in the mixture of 5 CPO reagents, where the molar ratio S/C refers to the total number of moles of water (H ₂ O) in the mixture of 5 reagents divided by per total number of moles of carbon (C) hydrocarbons in a mixture of 5 reactants, and combinations thereof For purposes of this disclosure,

- 6 042919 the temperature of the outlet stream after the FRO is the temperature of the synthesis gas (for example, hydrogen-depleted synthesis gas 15), measured at the moment when the synthesis gas leaves the FRO reactor (for example, the reactor 10 FRO), for example, the temperature of the synthesis gas , measured at the outlet of the FRO reactor, the temperature of the outlet stream from the synthesis gas reactor, the temperature of the outlet synthesis gas stream at the outlet. For the purposes of this disclosure, the post-CPO outlet temperature (eg, the target post-CPO outlet temperature) is considered to be an operating parameter. One skilled in the art will appreciate with the aid of this disclosure that the choice of operating parameters for an FRO reactor, such as the temperature of the FRO feed mixture; pressure in the FRO reaction; contact time in the FRO reaction; the molar ratio C/O in the mixture of CPO reagents; the molar ratio S/C in the mixture of CPO reagents; and so on determines the temperature of the hydrogen-depleted synthesis gas 15 as well as the composition of the effluent synthesis gas stream (eg, the hydrogen-depleted synthesis gas 15). In addition, as one of skill in the art will appreciate with the aid of this disclosure, monitoring the temperature of the effluent after the FRO can provide feedback to change other operating parameters (e.g., FRO feed mixture temperature; FRO reaction pressure; FRO reaction contact time; molar C/O ratio in the CPO reagent mixture; S/C molar ratio in the CPO reagent mixture; and so on) if you want the temperature of the effluent after the CPO to match the target temperature of the effluent after the CPO. In addition, as will be appreciated by one of ordinary skill in the art with the help of this disclosure, the target temperature of the effluent after CRO is the desired effluent temperature after CRO, and the temperature of the effluent after CRO (e.g., measured effluent temperature after CRO, actual effluent temperature after CRO, CRO) may or may not match the target outlet temperature after CRO. In embodiments where the FRO effluent temperature is different from the target FRO effluent temperature, one or more FRO operating parameters (e.g., FRO feed mixture temperature; FRO reaction pressure; FRO reaction contact time; C/O molar ratio in mixture of CPO reactants; the S/C molar ratio of the mixture of CPO reactants; and so on) can be adjusted (e.g., changed) so that the temperature of the effluent stream after the CPO matches (for example, is the same, the same as) the target effluent temperature after SRO. The FRO reactor 10 may be operated with any suitable operating parameters described herein that can provide hydrogen-depleted syngas 15 with an H2/CO molar ratio ranging from about 0.8 to 1.6, from about 0.8 to 1.5, about 0.8 to 1.4, about 0.8 to 1.3, about 0.8 to about 1.2, about 0.9 to about 1.1, or about 1. In embodiments, hydrogen-depleted syngas 15 has an H2/CO molar ratio ranging from about 0.7, 0.8, or 0.9 to about 1.1, 1.2, 1.3, 1.4, 1.5, or 1 ,6.

The FRO reactor 10 may vary in FRO reactant feed temperature from about 25 to about 600°C, alternatively from about 25 to about 500°C, alternatively from about 25 to about 400°C, alternatively from about 50 to about 400°C, alternatively from about 100 to about 400°C; or alternatively from about 100 to about 500°C. In embodiments, the FRO reactor 10 may be characterized by an FRO reactor temperature of less than 1200, 1100, or 1000°C.

The FRO reactor 10 may be characterized by a post-FRO effluent temperature (e.g., a target post-FRO effluent temperature) of at least about 300°C, about 600°C, about 700°C, about 750°C, about 800°C, or about 850°C. C, alternatively from about 300 to about 1600°C, alternatively from about 600 to about 1400°C, alternatively from about 600 to about 1300°C, alternatively from about 700 to about 1200°C, alternatively from about 750 to about 1150°C C, alternatively from about 800 to about 1125°C, or alternatively from about 850 to about 1100°C.

In embodiments, the FRO reactor 10 may be any suitable reactor temperature and/or catalyst bed temperature. For example, the SPO reactor 10 may vary in reactor temperature and/or catalyst bed temperature of at least about 300°C, about 600°C, about 700°C, about 750°C, about 800°C, or about 850°C, alternatively from about 300 to about 1600°C, alternatively from about 600 to about 1400°C, alternatively from about 600 to about 1300°C, alternatively from about 700 to about 1200°C, alternatively from about 750 to about 1150°C, alternatively from about 800 to about 1125°C, or alternatively from about 850 to about 1100°C.

The FRO reactor 10 can be operated with any suitable temperature profile that the hydrogen-depleted synthesis gas described in the present invention can provide. The FRO reactor 10 can be operated under adiabatic, non-adiabatic, isothermal, near isothermal conditions, autothermal conditions, and so on, for the purposes of this disclosure, the term non-adiabatic conditions refers to process conditions where the reactor is subjected to

- 7 042919 heat exchange or external heat transfer (for example, the reactor is heated; or the reactor is cooled), which may be direct heat exchange and/or indirect heat exchange. Those skilled in the art will appreciate with the aid of this disclosure that the terms direct heat transfer and indirect heat transfer are known to those skilled in the art. In contrast, the term adiabatic conditions refers to process conditions where the reactor is not subjected to external heat exchange (eg, the reactor is not heated; or the reactor is not cooled). Typically, external heat exchange refers to an external heat exchange system (eg, cooling system; heating system) that requires input and/or output of energy. External heat transfer can also be the result of heat loss from the catalyst bed (or reactor) due to radiation, conduction, or convection. For example, this heat exchange from the catalyst bed can take place to the outside environment or to the reactor zones before and after the catalyst bed.

For the purposes of this disclosure, the term isothermal conditions refers to process conditions (e.g., CPO operating conditions) that provide a substantially constant reactor and/or catalyst bed temperature (e.g., isothermal temperature), which can be defined as a temperature that less than about +10°C, about +9°C, about +8°C, about +7°C, about +6°C, about +5°C, about +4°C, about +3°C , approximately +2°C or approximately +1°C throughout the reactor and/or catalyst bed, respectively. In addition, for the purposes of this disclosure, the term isothermal conditions includes temperature fluctuations of less than about +10° C. throughout the reactor and/or catalyst bed. In embodiments, the FRO reactor 10 may be operated with any suitable operating parameters that can provide isothermal conditions.

For the purposes of this disclosure, the term near-isothermal conditions refers to process conditions (e.g., CRO operating conditions) that provide a sufficiently constant reactor and/or catalyst bed temperature (e.g., near-isothermal temperature), which can be defined as a temperature that varies less than approximately +100°C, approximately +90°C, approximately +80°C, approximately +70°C, approximately +60°C, approximately +50°C, approximately +40°C, approximately +30°C, approx. +20°C, approx. +10°C, approx. +9°C, approx. +8°C, approx. +7°C, approx. +6°C, approx. +5°C, approx. +4°C, approx. + 3°C, approximately +2°C or approximately +1°C throughout the reactor and/or catalyst bed, respectively. In some embodiments, nearly isothermal conditions provide a temperature swing of less than about +50°C, alternatively less than about +25°C, or alternatively less than about +10°C throughout the reactor and/or catalyst bed. Furthermore, for the purposes of this disclosure, the term near isothermal conditions is meant to encompass isothermal conditions. In addition, for the purposes of this disclosure, the term near isothermal conditions refers to process conditions that include a temperature swing of less than about +100° C. throughout the reactor and/or catalyst bed. In embodiments, the process disclosed herein may include operating the FRO reaction under near isothermal conditions to produce hydrogen-depleted synthesis gas, where the near isothermal conditions include a temperature swing of less than about +100°C throughout the reactor and/or catalyst bed. In embodiments, the FRO reactor 10 can be operated with any suitable operating parameters that can provide near isothermal conditions. Nearly isothermal conditions can be provided by a variety of process and catalyst variables such as temperature (e.g., heat exchange or heat transfer), pressure, gas flow rates, reactor configuration, catalyst bed configuration, catalyst bed composition, reactor cross-sectional area, gas feed stages , the input of the supplied gas mixture, the composition of the supplied gas mixture, and the like, or combinations thereof. Generally, and without being bound by theory, the terms heat transfer or heat transfer refer to the exchange or transfer of thermal energy between two systems (e.g., two reactors such as an FRO reactor and a cracking reactor), and the terms heat transfer or heat transfer are used interchangeably for purposes of this disclosure. .

In some embodiments, the achievement of the target temperature of the exit stream after FRO and/or near isothermal conditions can be achieved through heat exchange or heat transfer, heat exchange may include heating the reactor; or reactor cooling. In embodiments, achieving the target effluent temperature after the FRO and/or near isothermal conditions can be achieved by cooling the reactor. In another embodiment, the achievement of the target temperature of the outlet stream after FRO and/or near isothermal conditions can be achieved by heating the reactor.

In some embodiments, the achievement of the target temperature of the exit stream after FRO and/or near isothermal conditions can be achieved by direct heat exchange and/or indirect heat exchange. A person skilled in the art with the help of this disclosure will understand that the terms direct heat transfer and indirect heat transfer are known to a person skilled in the art, warm

- 8 042919 Loop exchange may include external heat exchange, external coolant cooling, reactive cooling, liquid N2 cooling, cryogenic cooling, electrical heating, electric arc heating, microwave heating, radiation heating, natural gas combustion, solar heating, infrared heating, use of a diluent in mixtures of CPO reagents and the like, or combinations thereof. For example, reactive cooling can be accomplished by conducting an endothermic reaction in a cooling coil/jacket associated with (eg, located within) the reactor.

In some embodiments, the target FRO effluent temperature and/or near isothermal conditions can be achieved by removing process heat from the FRO reactor. In other embodiments, the target FRO effluent temperature and/or near isothermal conditions can be achieved by supplying heat to the FRO reactor. One skilled in the art will appreciate with the aid of this disclosure that the FRO reactor may need to be subjected to both heating and cooling to achieve the target temperature of the effluent after FRO and/or near isothermal conditions.

In embodiments, the heat exchange or heat transfer may include introducing a coolant, such as a diluent, into the reactor (e.g., CPO reactor 10) to lower the reactor temperature and/or catalyst bed temperature while raising the coolant temperature and/or changing the phase of the coolant, the coolant may be reactive or non-reactive. the refrigerant may be in a liquid state and/or in a vapor state. A person skilled in the art with the help of this disclosure will understand that the refrigerant can act as an ignition retardant; for example, by lowering the temperature inside the reactor, by changing the composition of the gas mixture, by reducing the combustion of hydrocarbons to CO ₂ ; and so on.

In some embodiments, the FRO reactant mixture 5 may further comprise a diluent, wherein the diluent assists in achieving the target FRO effluent temperature and/or near isothermal conditions through heat exchange as disclosed herein. The diluent may contain water, steam, inert gases (eg, argon (Ar)), N2, _CO2 , and the like, or combinations thereof. Typically, the diluent is inert to the FRO reaction, eg the diluent does not participate in the FRO reaction. However, as will be appreciated by one of skill in the art with the aid of this disclosure, certain diluents (e.g., water, steam, CO ₂ , etc.) may undergo chemical reactions other than the FPO reaction in the reactor and may change the composition of the resulting hydrogen-depleted synthesis gas 15, as will be described in more detail later in this document; although other diluents (e.g., N2, Ar) may not be involved in reactions that change the composition of the resulting hydrogen-depleted synthesis gas 15. It will be appreciated by one skilled in the art with the aid of this disclosure that a diluent can be used to alter the composition of the resulting hydrogen-depleted synthesis gas. -gas 15. The diluent may be present in the mixture of 5 CPO reagents in any suitable amount.

The FRO reactor 10 may be characterized by an FRO pressure (e.g., reactor pressure as measured at or at the outlet of the reactor) of at least about 1 barg, about 10 barg, about 20 barg, about 25 barg, about 30 barg, approximately 35 barg, approximately 40 barg, or approximately 50 barg, alternatively less than about 30 barg, approximately 25 barg, approximately 20 barg, or approximately 10 barg, alternatively from about 1 barg to about 90 barg, alternatively from about 1 barg to about 70 barg, alternatively from about 1 barg to about 40 barg, alternatively from about 1 barg to about 30 barg, alternatively from about 1 barg to about 25 barg, alternatively from about 1 barg to about 20 barg, alternatively from about 1 barg to about 10 barg, alternatively from about 20 barg to about 90 barg, alternatively from about 25 barg to about 85 barg, or alternatively from about 30 barg to about 80 barg.

The FPO reactor 10 may vary in FPO response contact time 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 to about 100 ms, alternatively from about 0.001 to about 10 ms, alternatively from about 0.001 to about 5 ms, or alternatively from about 0.01 to about 1.2 ms. Typically, the contact time in a reactor containing a catalyst refers to the average amount of time that a compound (e.g., a molecule of that compound) spends in contact with the catalyst (e.g., inside the catalysis bed).

- 9 042919 torus), for example, the average amount of time it takes a compound (for example, a molecule of this compound) to pass through the catalyst bed. In some embodiments, the FRO reactor 10 may vary in contact time from about 0.001 to about 5 ms, or alternatively from about 0.01 to about 1.2 ms.

All operating parameters of the SRO disclosed in the framework of the present invention are applicable when considering all embodiments disclosed within the scope of the present invention, unless otherwise indicated. One of ordinary skill in the art will appreciate with the aid of this disclosure that each operating parameter of the FRO can be controlled to produce the hydrogen-depleted synthesis gas described within the scope of the present invention. For example, the operating parameters of the FRO can be adjusted to produce an increased H ₂ content in the synthesis gas, as long as the H 2 /CO molar ratio remains in the desired range (eg, from about 0.8 to about 1.6). As another example, the operating parameters of the FRO can be adjusted to obtain a reduced content of CO2 in the hydrogen-depleted synthesis gas 15. As another example, the operating parameters of the FRO can be adjusted to obtain a reduced content of unreacted hydrocarbons (for example, unreacted CH4) in the synthesis gas 15.

In embodiments, the FRO reactor 10 is characterized by at least one FRO operating parameter selected from the group consisting of an FRO reactant mixture temperature of about 100 to about 500°C; CRO pressures from about 20 barg to about 80 barg; a contact time in the FRO reaction of from about 0.001 milliseconds (ms) to about 5 seconds (s); molar ratio of carbon to oxygen (C/O) in the CPO reactant mixture from about 0.5:1 to about 3:1, where the C/O molar ratio refers to the total number of moles (C) in hydrocarbons in the reactant mixture divided by the total the number of moles of O ₂ in the mixture of reagents; molar ratio of water vapor to carbon (S/C) in the CPO reactant mixture is less than about 0.6:1, where the S/C molar ratio refers to the total moles of water in the reactant mixture divided by the total moles of C in the hydrocarbons in the reactant mixture ; molar ratio of CO ₂ to carbon (CO ₂ /C) in the CRO reagent mixture of not less than about 0.5:1, where the CO 2 /C molar ratio refers to the total number of moles of CO ₂ in the reactant mixture divided by the total number of moles of C in hydrocarbons in a mixture of reagents; and their combinations.

In embodiments, the FRO reactor 10 is characterized by at least one FRO operating parameter selected from the group consisting of a temperature of the FRO reactant mixture of about 100 to about 500°C; CPO pressures from about 25 barg to about 80 barg; a contact time in the FRO reaction of from about 0.001 milliseconds (ms) to about 5 seconds (s); C/O molar ratio in the CPO reactant mixture from about 0.5:1 to about 2:1, where the C/O molar ratio refers to the total number of moles (C) in hydrocarbons in the reactant mixture divided by the total number of moles of O2 in the mixture reagents; S/C molar ratio in the CPO reactant mixture less than about 0.25:1, where the S/C molar ratio 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 mixture reagents; molar ratio of CO ₂ to carbon (CO 2 /C) in the mixture of CPO reagents, not less than about 0.5:1, where the molar ratio of CO ₂ /C refers to the total number of moles of CO ₂ in the mixture of reagents, divided by the total number of moles carbon (C) in hydrocarbons in the reactant mixture; and their combinations.

The FRO reaction is an exothermic reaction (eg, heterogeneous catalytic reaction; exothermic heterogeneous catalytic reaction), which is usually carried out in the presence of an FRO catalyst containing a catalytically active metal, i. e. a metal active to catalyze the FRO reaction. The catalytically active metal may contain a noble metal (eg, Pt, Rh, Ir, Pd, Ru, Ag, and the like, or combinations thereof); base metal (eg, Ni, Co, V, Mo, P, Fe, Cu, and the like, or combinations thereof); rare earth elements (eg La, Ce, Nd, Eu and the like, or combinations thereof); their oxides; etc; or their combinations. Typically, a noble metal is a metal that resists corrosion and oxidation in an environment containing water. One skilled in the art will appreciate with the aid of this disclosure that the FPO catalyst components (eg, metals such as noble metals, non-noble metals, rare earth elements) may be either phase-separated or combined in the same phase.

In embodiments, FRO catalysts suitable for use in the present disclosure may be supported and/or unsupported catalysts. In some embodiments, the supported catalysts may comprise a carrier, wherein the carrier may be catalytically active (eg, the carrier may catalyze the FRO reaction). For example, the catalytically active carrier may comprise a metal mesh or wire mesh (eg Pt mesh or wire mesh); monolithic catalytically active metal catalyst; and so on. In other embodiments, supported catalysts may comprise a support where the support may be catalytically inactive (eg, the support cannot catalyze the FRO reaction), such as SiO ₂ ; silicon carbide (SiC); aluminium oxide; catalytically

- 10 042919 inactive monolithic carrier; and so on. In still other embodiments, supported catalysts may comprise a catalytically active support and a catalytically inactive support.

In some embodiments, the FPO catalyst may be thinly coated on a support, where the support may be catalytically active or inactive, and where the support may be a monolith, foam, irregularly sized catalyst particles, and so on.

In some embodiments, the FPO catalyst may be a monolith, foam, powder, particle, and so on. Non-limiting examples of FPO catalyst particle shapes suitable for use in the present disclosure include cylindrical, discoidal, spherical, stratified, ellipsoidal, isometric, heterogeneous, cubic, acicular, and the like, or combinations thereof.

In some embodiments, the carrier comprises an inorganic oxide, alpha, beta, or theta alumina (Al ₂ O ₃ ), activated Al ₂ O ₃ , silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), magnesium oxide (MgO), oxide zirconium (ZrO ₂ ), lanthanum (III) oxide (La ₂ O ₃ ), yttrium (III) oxide (Y ₂ O ₃ ), cerium (IV) oxide (СеО ₂ ), zeolites, ZSM-5, perovskite oxides, oxides hydrotalcite; and the like, or combinations thereof.

Without limitation, FRO processes, FRO reactors, FRO catalysts, and FRO catalyst bed configurations suitable for use in the present disclosure are described in more detail in U.S. Provisional Patent Application No. 62/522,910, filed June 21, 2017, (International Patent Application No. PCT /Sh2018/05475, submitted on June 18, 2018) and the entitled Improved Reactor Designs for Heterogeneous Catalytic Reactions and preliminary patent application of the United States No. 62/521831, filed on June 19, 2017 No. RST/1V2O18/O547O, Pod June 18 2018) and entitled An Improved Process for Syngas Production for Petrochemical Applications, each of which is hereby incorporated by reference in its entirety within the scope of the present invention for purposes not inconsistent with this disclosure.

In embodiments, the FRO catalyst may vary in catalyst productivity within about +20%, about +17.5%, about +15%, about +12.5%, about +10%, about +7.5%, about + 5%, about +2.5%, or about +1% of the target catalyst productivity for a period of time not less than about 500 hours (h), about 1000 hours, about 2500 hours, about 5000 hours, about 7500 hours, or about 10000 h; where the productivity of the catalyst is defined as the amount of hydrogen-depleted synthesis gas 15 (for example, the effluent from the FRO reactor) removed from the reactor 10 FRO divided by the amount of hydrocarbons introduced into the reactor 10 FRO in the mixture of 5 FRO reactants. It will be understood by one of skill in the art with the aid of the present disclosure, without being limited by theory, that catalyst productivity is a quantitative measure of catalyst activity, where catalyst activity refers to the ability of a catalyst (e.g., FRO catalyst) to increase the rate of a chemical reaction (e.g., FRO reaction) for a given a set of reaction conditions (eg, FRO operating parameters). For purposes of this disclosure, an FRO catalyst having a performance variation of greater than about +20% can be considered a spent FRO Catalyst (as opposed to an active FRO catalyst). Within the scope of the present invention, a target catalyst performance is associated with an active FRO catalyst (eg fresh FRO catalyst and/or regenerated FRO catalyst). For the purposes of this disclosure, the term fresh FRO catalyst refers to FRO catalyst that has not been used in the FRO process. One skilled in the art will appreciate with the aid of this disclosure that an active FRO catalyst exhibits optimal (e.g., maximum) catalyst activity with respect to a chemical reaction (e.g., FRO reaction) under a given set of reaction conditions (e.g., FRO operating parameters). Furthermore, as will be appreciated by one of skill in the art with the aid of this disclosure, the target catalyst productivity is the maximum catalyst productivity of an active FRO catalyst (e.g., fresh FRO catalyst and/or regenerated FRO catalyst) for a given set of reaction conditions (e.g., FRO operating parameters ). In addition, as will be appreciated by one of skill in the art with the aid of this disclosure, the terms catalyst productivity and target catalyst productivity are used in the context of a steady state operation of an FRO reactor (eg, FRO reactor 10).

It will be appreciated by those skilled in the art with the aid of this disclosure that catalyst activity (e.g., FPO catalyst activity) may vary (e.g., drop, decline) over time for a variety of reasons, such as poisoning (e.g., by feed contaminants), fouling (e.g., coking with carbon produced by cracking/condensation/decomposition reactions of hydrocarbon reactants, intermediates and/or products), thermal degradation (e.g., disruption of the support structure, solid state reactions, wear), leaching of the active component, migration of active components inward and /or outside of the catalyst particles, side reactions, wear/destruction, and the like, or combinations thereof. A drop in catalyst activity leads to spent catalysts (for example,

- 11 042919 used SRO catalysts). In embodiments, spent catalysts may be reclaimed and returned to the production process, as will be described in more detail below within the scope of the present invention.

In embodiments, a portion of the hydrocarbons (e.g., methane) in the FRO reagent mixture 5 may undergo a thermal decomposition reaction to carbon (C) and H ₂ , for example, as represented by equation (2),

SI; >С'2Н _: (2).

Decomposition reactions of hydrocarbons such as CH ₄ are favored by elevated temperatures and the H ₂ content of the hydrogen-depleted synthesis gas is increased. However, the carbon produced by the hydrocarbon decomposition reaction (for example, the decomposition reaction as represented by equation (2)) can lead to coking of the FRO catalyst by depositing carbon on the surface of the FRO catalyst, thereby producing a spent FRO catalyst. It will be understood by one skilled in the art with the help of the present disclosure, without being limited by theory, that while the percentage of hydrocarbons in the mixture of 5 CPO reagents that undergo a decomposition reaction (e.g., a decomposition reaction as represented by equation (2)) increases with increasing molar ratio C/O in a mixture of 5 CRO reagents, some hydrocarbons can undergo a decomposition reaction to C and H ₂ even at a relatively low molar ratio C/O in a mixture of 5 CRO reagents (for example, a molar C/O ratio in a mixture of 5 CRO reagents is less than approximately 1:1). In addition, as will be appreciated by one of ordinary skill in the art with the aid of the present disclosure, coking can affect the quality of the hydrocarbon feed to the FRO reactor 10. For example, higher hydrocarbons (eg, hydrocarbons having at least 2 C, C ₂₊ atoms) can produce more coke than CH ₄ due to having a higher carbon content than CH ₄ .

In an aspect, the CPO reagent mixture 5 may further comprise a diluent such as water and/or steam and CO ₂ . The FRO reactor 10 can be operated under any suitable operating conditions (eg, FRO operating parameters) that can provide syngas with the desired composition (eg, desired H2/CO molar ratio; desired CO ₂ content; and so on); for example, the FRO reactor 10 may be operated by introducing water and/or steam and CO2 into the FRO reactor 10.

When carbon is present in the reactor (e.g., coke; C resulting from a decomposition reaction as represented by equation (2)), the water and/or steam diluent can react with the carbon and generate additional CO and H ₂ , for example, as represented by equation (3),

С+Н2О0СО+Н2 (3).

One skilled in the art will appreciate with the aid of this disclosure that the presence of water and/or steam in the FRO reactor 10 can reduce the amount of coke in the FRO reactor 10 (e.g., the amount of coke deposited on the FRO catalyst, the amount of spent FRO catalyst present in reactor 10 SRO), thereby ensuring the maintenance of the performance of the catalyst.

In addition, as will be appreciated by one of skill in the art with the aid of the present disclosure, water and/or steam can be used to alter the composition of the resulting hydrogen-depleted synthesis gas 15 in the FRO reactor effluent.

Water vapor can interact with methane, for example, as represented by equation (4), CH ₄ +H ₂ O<eSO+3H ₂ (4).

In an aspect, a diluent containing water and/or steam can increase the hydrogen content of the resulting hydrogen-depleted synthesis gas 15 in the effluent from the FRO reactor. For example, in aspects where the FRO reactant mixture 5 contains a diluent, water and/or steam, the resulting hydrogen-depleted synthesis gas 15 in the FRO reactor effluent may differ in a hydrogen to CO molar ratio that increases when compared to the hydrogen to CO molar ratio. synthesis gas obtained by another similar method, carried out with a mixture of reagents containing hydrocarbons and O ₂ without a diluent in the form of water and/or steam. Without being limited by theory, the authors note that the reforming reaction (for example, as represented by equation (4)) is an endothermic reaction. The reforming reaction as represented by equation (4) can remove part of the heat of the process (eg, the heat produced by the exothermic FRO reaction, eg as represented by equation (1)).

In the presence of water and/or steam in the SRO reactor 10, CO can react with water and/or steam to form CO ₂ and H ₂ via a water gas shift (WGS) reaction, for example, as represented by equation (5),

CO+WHO^CO+H (5).

While the WGS reaction can increase the H2/CO molar ratio of the synthesis gas produced in the CPO reactor 10, it also produces CO2.

The introduction of steam and/or water can thus be used in embodiments to increase CO production and restore the quality of the hydrogen-depleted synthesis gas 15, thereby providing a hydrogen-depleted synthesis gas 15 having a lower molar ratio

- 12 042919

H2/CO. The introduction of steam and/or water may also help maintain the activity of the FRO catalyst. In embodiments, the FRO reagent mixture 5 may have a molar ratio of water vapor to carbon (S/C) and/or water vapor to CH ₄ (S/CH4) less than or equal to 1.0, 0.9, 0.8, 0, 7, 0.6, 0.5, 0.4, 0.3, 0.2, or between about 0.1, 0.2, or 0.3 to about 0.4, 0.5, 0.6 , 0.7, 0.8, 0.9, or 1, from about 0.2 to about 1, from about 0.2 to about 0.6, or from about 0.2 to about 0.5. In embodiments, the FRO reactor 10 can be operated at a molar ratio of S/C and/or steam to CH ₄ (S/CH ₄ ) in the FRO mixture 5 of less than about 0.6:1, alternatively less than about 0.5:1, alternatively less than about 0.4:1, alternatively less than about 0.3:1, alternatively less than about 0.2:1, alternatively less than about 0.1:1, alternatively from about 0.01:1 to less than about 0.6 :1, alternatively from about 0.05:1 to about 0.6:1, alternatively from about 0.1:1 to about 0.5:1, alternatively from about 0.15:1 to about 0.6:1 or alternatively from about 0.2:1 to about 0.6:1. One skilled in the art will appreciate with the aid of this disclosure that the steam that is introduced into the FRO reactor for use as a diluent in the FRO reaction disclosed herein is present in significantly lower amounts than the amounts of steam used in the steam reforming (e.g., SMR) and as such, the process for producing synthesis gas disclosed herein can result in (e.g., hydrogen-depleted) synthesis gas with lower amounts of hydrogen when compared to the amounts of hydrogen in through steam reforming.

The S/C molar ratio of the FRO reactant mixture 5 can be adjusted based on the desired temperature of the FRO effluent (eg, target temperature of the FRO effluent) to control the H2 content of the resulting synthesis gas (eg, synthesis gas 15). A person skilled in the art with the help of this disclosure will understand that the reaction (4), which consumes water vapor in the FRO reactor may be less preferred than the reaction (5) water gas shift (WGS) in the FRO reactor 10, since the reaction ( 4) makes it possible to increase the H ₂ content of the produced synthesis gas (for example, synthesis gas 15), as well as the M-ratio of the obtained synthesis gas (for example, synthesis gas 15), where the M-ratio is a molar ratio defined as ( H ₂ CO ₂ )/(CO+CO ₂ ). In addition, as will be appreciated by one of skill in the art with the aid of the present disclosure, reaction (5) converts water and CO to both H ₂ and CO ₂ .

Without wishing to be bound by theory, the inventors note that the presence of water and/or steam in the FRO reactor 10 alters the flammability of the FRO reactant mixture 5, thereby providing a wider practical range of C/O molar ratios in the FRO reactant mixture 5. In addition, and without being bound by theory, the authors note that the presence of water and/or steam in the FRO reactor 10 allows the use of lower C/O molar ratios in the FRO reactant mixture 5. In addition, without being limited by theory, the authors note that the presence of water and/or steam in the reactor 10 FRO allows you to use the reactor 10 FRO at relatively high pressures.

One skilled in the art will appreciate with the aid of this disclosure that the introduction of water and/or steam into the FRO reactor 10 may result in an increase in the amount of unreacted hydrocarbons in the synthesis gas 15. Furthermore, one skilled in the art with the aid of this disclosure will it is understood that some chemical synthesis processes with subsequent stages allow limited amounts of unreacted hydrocarbons in the synthesis gas.

In some aspects, the hydrogen-depleted synthesis gas 15 may contain less than about 7.5 mol%, alternatively less than about 5 mol%, or alternatively less than about 2.5 mol% hydrocarbons (eg, unreacted hydrocarbons, unreacted CH ₄ ). In such aspects, synthesis gas 15 may be produced in an FRO process using water and/or steam.

In embodiments, CO2 is introduced into the FRO reactor 10 (eg, via line 7, 7A and/or 7B). Since O ₂ is present in the mixture of 5 FPO reactants, the carbon present in the reactor (e.g., coke; C resulting from the decomposition reaction, as represented by equation (2)), can also interact with O ₂ , for example, as represented by equation (6 ),

С + О2 >СО2 (6).

When carbon is present in the reactor (for example, coke; C obtained from the decomposition reaction as represented by equation (2)), CO ₂ (for example, introduced into the reactor 10 FRO as part of the mixture of 5 FRO reagents and / or obtained through the reaction represented by equation (6)), can interact with carbon, for example, as represented by equation (7),

C+COA>2CO (7), thereby reducing the amount of CO2 and increasing the amount of CO in the resulting hydrogen-depleted synthesis gas 15. The use of mixtures of reagents 5 containing higher hydrocarbons (for example, C ₂₊ ) can lead to the formation of more coke , and thus result in CO enrichment and a reduced H2/CO molar ratio in the hydrogen-depleted synthesis gas 15. It will be appreciated by those skilled in the art with the aid of the present disclosure that the presence of

- 13 042919

The CO2 in the FRO reactor 10 can reduce the amount of coke in the FRO reactor 10 (e.g., the amount of coke deposited on the FRO catalyst, the amount of spent FRO catalyst present in the FRO reactor 10), thereby maintaining catalyst performance. Introducing CO2 also provides an increase in carbon use efficiency, since the carbon in CO2 is converted into additional CO. As a result, more CO will be produced by the MMBTU of the feed mixture of reactants (eg, natural gas) according to embodiments of the disclosure of the present invention. This additional CO can increase chemical production (eg, increase production of acetic acid in the FIG. 1 process or DME in the FIG. 2 process) for the same reactant (eg, natural gas) feed volume flow rate.

In addition, CO ₂ can interact with CH ₄ in a dry reforming reaction, for example, as represented by equation (8),

CH ₄ +CO2<>CO+2H2 (8), thereby reducing the amount of CO ₂ in the resulting synthesis gas in the outlet stream 15 from the FRO reactor. Without wishing to be bound by theory, we note that a dry reforming reaction (eg, as represented by equation (8)) is an endothermic reaction (eg, a highly endothermic reaction). The dry reforming reaction may remove some of the heat from the process (eg, heat generated by the exothermic FRO reaction, eg as represented by equation (1)).

In embodiments, the _CO2- containing diluent may increase the CO content of the resulting hydrogen-depleted synthesis gas 15. For example, in embodiments where the CPO reactant mixture 5 contains CO2, the hydrogen-depleted synthesis gas 15 may differ in the molar ratio of hydrogen to CO, which is reduced in comparison with the molar ratio of hydrogen to CO in synthesis gas obtained by another similar method, carried out with a mixture of reagents containing hydrocarbons and O2 without diluent CO2. Without limiting theory, the authors note that CO ₂ can interact with the coke inside the reactor 10 FRO and generate additional CO, for example, as represented by equation (7). In addition, and without being limited by theory, the authors note that CO ₂ can participate in the dry methane reforming reaction, thereby generating additional CO and H ₂ , for example, as represented by equation (8). Dry reforming of methane is usually accompanied by a reaction between CO ₂ and hydrogen, which leads to the formation of additional CO and water.

In embodiments, the CPO reagent mixture 5 may contain an amount of CO2 effective to produce less than about 7 mole%, alternatively less than about 6 mole%, alternatively less than about 5 mole%, alternatively from about 0.1 mole% 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.% CO ₂ in hydrogen-depleted synthesis gas 15, based on the total mol. % synthesis gas. The CO ₂ of the FRO mixture 5 may be CO ₂ from natural gas sources, where the CO ₂ is introduced into the hydrocarbon FRO reactor 10; and/or additional or additional CO ₂ , eg CO ₂ recovered from the process stream and recycled to the CPO reactor 10 (eg via CO ₂ stream 7, 7A and/or 7B).

In embodiments, the hydrocarbon conversion in the FRO reactor 10 exceeds the hydrocarbon conversion in the FRO reactor according to another similar process that produces hydrogen-depleted synthesis gas from hydrocarbons containing a reduced amount of higher hydrocarbons (eg, C ₂₊ hydrocarbons). For example, in embodiments, the hydrocarbon conversion in the FRO reactor 10 of a mixture of 5 FRO reagents containing at least about 5, 4, or 3 mol% C ₂₊ alkanes exceeds the hydrocarbon conversion in the FRO reactor according to another similar process that produces hydrogen-depleted synthesis -gas from a mixture of 5 CPO reagents containing less than about 5, 4 or 3 mol.% C ₂₊ alkanes, respectively.

In embodiments, there is no provision for further control of the H ₂ /CO molar ratio of the hydrogen-depleted synthesis gas 15 prior to subsequent DME or acetic acid synthesis. Thus, the FRO system and process disclosed in the present invention can be used to produce hydrogen-depleted synthesis gas 15 having an H ₂ /CO molar ratio suitable for the subsequent production of acetic acid or DME (for example, an H ₂ /CO molar ratio in the range from about 0.8 to 1.6). Thus, in embodiments, the method disclosed in the present invention eliminates the step of introducing at least a portion of the hydrogen-depleted synthesis gas 15 to a hydrogen recovery unit to reduce the amount of hydrogen in the hydrogen-depleted synthesis gas 15. Thus, in embodiments, the method disclosed in the present invention does not include changing the H2/CO molar ratio of the hydrogen-depleted synthesis gas 15 between the FPO reactor 10 and the downstream synthesis apparatus. Thus, in embodiments, the chemical synthesis system disclosed herein does not include a device (e.g., a hydrogen remover, PSA) for changing the H ₂ /CO molar ratio of the hydrogen-depleted synthesis gas 15 between the CPO reactor 10

- 14 042919 and a device for subsequent synthesis (for example, either the device for the synthesis of acetic acid, described in the framework of the present invention below with reference to the embodiment of Fig. 1, or the device for the synthesis of DME of the embodiment of Fig. 2).

In embodiments, the method disclosed in the present invention does not include adjusting the H ₂ /CO molar ratio of the hydrogen-depleted synthesis gas 15 prior to using the hydrogen-depleted synthesis gas 15 in subsequent chemical synthesis. Thus, in embodiments, the chemical synthesis system disclosed herein does not include a device for controlling the H ₂ /CO molar ratio of the hydrogen-depleted synthesis gas 15 prior to the subsequent acetic acid synthesis or DME synthesis reactor.

In embodiments, the process disclosed herein does not include removing the hydrogen stream from the hydrogen-depleted synthesis gas 15 prior to using the hydrogen-depleted synthesis gas 15 in downstream acetic acid synthesis or DME synthesis. Thus, in embodiments, the chemical synthesis system disclosed herein does not include a device configured to remove the hydrogen stream from the hydrogen-depleted synthesis gas 15 between the CPO reactor 10 and the post-synthesis device (e.g., the DME carbonylation unit 30 30 described within the scope of the present invention below with reference to the embodiment of Fig. 1, or the DME reactor 70 described within the scope of the present invention below with reference to the embodiment of Fig. 2).

In embodiments, FRO reactor 10 may produce hydrogen-depleted synthesis gas 15 at high pressures (e.g., at least about 20, 25, 30, 35, 40, 45, 50 bar) required for subsequent chemical synthesis (e.g., acetic acid , DME), thus reducing the size or eliminating the need for one or more compressors 20 to compress the hydrogen-depleted synthesis gas 15 prior to downstream chemical synthesis. Accordingly, within the scope of the present invention, the disclosed systems and methods for producing acetic acid or DME via hydrogen-depleted synthesis gas produced by FPO may, in embodiments, further reduce the energy requirements for producing acetic acid or DME.

In embodiments, the hydrogen-depleted synthesis gas 15 may have a CO ₂ content of less than about 10 mol%, less than about 9 mol%, less than about 8 mol%, less than about 7 mol%, alternatively less than about 6 mol%, alternatively less than about 5 mole%, alternatively less than about 4 mole%, alternatively less than about 3 mole%, alternatively less than about 2 mole%, alternatively less than about 1 mole%, alternatively greater than about 0.1 mole% , alternatively greater than about 0.25 mole%, alternatively greater than about 0.5 mole%, alternatively from about 0.1 to about 7 mole%, alternatively from about 0.25 to about 6 mole%, or alternatively from about 0.5 to about 5 mol.%. For example, side reactions can result in hydrogen-depleted synthesis gas 15 that has a CO2 content of less than about 7 mole%, alternatively less than about 6 mole%, alternatively less than about 5 mole%, alternatively from about 0.1 to about 7 mol.%, alternatively from about 0.25 to about 6 mol.%, or alternatively from about 0.5 to about 5 mol.%. As noted above within the scope of the present invention, the concentration of CO ₂ in the hydrogen-depleted synthesis gas 15 can be controlled by introducing CO ₂ (for example, through the stream 7 CO ₂ ) and/or by changing the operating conditions of the reactor 10 FRO.

The amount of CO2 in the H2 depleted synthesis gas 15 can be adjusted depending on the downstream application. In such applications, the amount of CO2 in the H2-depleted synthesis gas 15 can be controlled as described above within the scope of the present invention.

In embodiments, the hydrogen-depleted synthesis gas 15 may be processed, such as recovery of unreacted hydrocarbons, diluent, water, etc. In embodiments, water may be condensed and separated from the hydrogen-depleted synthesis gas 15, for example, in a refrigerator. It will be appreciated that such processing to remove hydrocarbons, diluent, water, etc. will not change the H ₂ /CO molar ratio of the hydrogen-depleted synthesis gas stream 15 . In embodiments, the method disclosed herein may further include: (i) recovering at least a portion of the unreacted hydrocarbons from the hydrogen-depleted synthesis gas 15 to produce regenerated hydrocarbons, and (ii) recycling at least part of the regenerated hydrocarbons in the reactor 10 SRO. One of skill in the art will appreciate with the aid of this disclosure that while reasonably high conversions can be achieved in FRO processes (e.g., conversions of at least about 90%), unchanged hydrocarbons can be recovered and recycled back to reactor 10 SRO.

In embodiments, the process disclosed herein further includes producing acetic acid or DME from at least a portion of the hydrogen-depleted synthesis gas, since DME and acetic acid production selectivity is increased by synthesizing

- 15 042919 gas having a molar ratio of H2/CO equal to approximately 1:1. The term unit (eg, DME carbonylation unit or methanol synthesis unit) refers to a plant that may contain separation equipment in addition to the reactor. For simplicity, such separation equipment is not shown in FIG. 1 or 2.

In embodiments, the method disclosed herein further includes producing acetic acid from at least a portion of the hydrogen-depleted syngas 15. In embodiments, any system and method for producing acetic acid from hydrogen-depleted syngas 15 may be used downstream of the 10 CRO reactor according to this disclosure to produce acetic acid. In embodiments, the process disclosed herein includes producing acetic acid from at least a portion of the hydrogen-depleted synthesis gas 15 via intermediate methanol synthesis. When producing hydrogen-depleted synthesis gas 15 to produce acetic acid downstream, the concentration of CO2 in the hydrogen-depleted synthesis gas can be controlled (for example, by introducing CO2 and/or changing the operating conditions of the CPO reactor 10) to obtain a small amount of CO2 in the hydrogen-depleted synthesis gas 15, since such CO ₂ will increase the production of methanol, which is an intermediate in the synthesis of acetic acid, thus increasing the production of acetic acid. For example, small amounts of CO ₂ may be desirable in the hydrogen-depleted synthesis gas 15 when fed to the DME reactor 70 downstream (as described within the scope of the present invention below with reference to the FIG. 2 embodiment), where small amounts of CO ₂ in the lean hydrogen synthesis gas 15 may be desirable to increase the production of methanol (which is an intermediate in the production of acetic acid) and thus increase the synthesis of DME.

In embodiments, the method disclosed herein further includes feeding at least a portion of the hydrogen-depleted synthesis gas 15 and dimethyl ether (DME) 51 to a DME carbonylation unit 30 to produce methyl acetate 35 and hydrogen-rich synthesis gas; and feeding at least a portion of methyl acetate 35 and water 36 to a methyl acetate hydrolysis reaction zone 36 to produce acetic acid 65 and a methanol stream 45A. In embodiments, the hydrogen-rich synthesis gas 31 contains hydrogen, CO, CO ₂ and unreacted hydrocarbons, and has an H2/CO molar ratio of about 1.4, 1.5, 1.6, 1.7, or 1.8 up to about 1.8, 1.9, 2.0, 2.1, or 2.2. DME 51 may contain DME 51A from DME synthesis reaction zone 50 (described further in the context of the present invention below) and/or DME 51B from another source.

Inside the carbonylation plant 30, DME, DME 51 and CO from the hydrogen-depleted synthesis gas 15 are converted to methyl acetate. Any suitable carbonylation catalyst may be used in DME carbonylation unit 30, and DME carbonylation unit 30 may be operated under any suitable DME carbonylation reaction conditions known to those skilled in the art. In other embodiments, the carbonylation of methanol to produce acetic acid occurs in a single step.

In embodiments, the FRO reactor 10 is characterized by FRO pressure; The DME carbonylation plant 30 is characterized by a DME carbonylation pressure; and the CRO pressure is approximately equal to the DME carbonylation pressure. In alternative embodiments, the FRO reactor 10 is characterized by an FRO pressure, the DME carbonylation unit 30 is characterized by a DME carbonylation pressure that exceeds the pressure in the FRO reaction, and at least a portion of the hydrogen-depleted synthesis gas 15 is compressed in the compressor 20 to produce compressed synthesis gas 15' such that the compressed synthesis gas 15' is at a pressure that is approximately equal to the DME carbonylation pressure before at least a portion of the compressed synthesis gas 15' is supplied to the DME carbonylation unit 30.

In embodiments, compressor 20 is smaller than a compressor used to compress hydrogen-depleted synthesis gas according to another similar method, wherein (i) a hydrogen recovery unit is used to produce hydrogen-depleted synthesis gas; (ii) obtaining hydrogen-depleted synthesis gas from hydrocarbons containing less than about 3 mol.% With ₂₊ alkanes; and/or (iii) do not produce hydrogen-depleted synthesis gas by FRO.

The methyl acetate hydrolysis reaction zone 36 may be any reaction zone suitable for the production of acetic acid 65 and methanol 45A from methyl acetate 35 and water 36 and may be operated under any operating conditions suitable for the hydrolysis of methyl acetate to methanol and acetic acid.

In embodiments, the process for producing acetic acid within the scope of the present invention further includes feeding at least a portion of hydrogen-rich synthesis gas 31 to methanol synthesis unit 40 to produce another (i.e., second) methanol stream 45B and a purge gas stream 41, where the purge gas stream contains hydrogen, CO, CO2 and unreacted hydrocarbons, and where at least a portion of the purge gas stream 41 is optionally used as a fuel. The methanol synthesis unit 40 may include any suitable methanol synthesis reactor known in the art and may be operated under any reaction conditions known to those skilled in the art.

In embodiments, the method for producing acetic acid within the scope of the present invention

- 16 042919 further includes: (1) feeding at least a portion of (eg, first) methanol stream 45A and/or at least a portion of another (eg, second) methanol stream 45B to DME synthesis reaction zone 50 to receive a DME 51B stream; and (2) feeding at least a portion of the DME stream 51A to the DME carbonylation unit 30.

In embodiments, the DME synthesis reaction zone 50 is operable to produce DME via methanol dehydration. In embodiments, the conventional reactor contains both a methyl acetate hydrolysis reaction zone 60 and a DME synthesis reaction zone 50. In embodiments, at least a portion of the water produced in DME synthesis reaction zone 50 is used as feed water 36 to methyl acetate hydrolysis zone 60. In embodiments, the synthesis of methanol from synthesis gas 31 and the dehydration of methanol (45A and/or 45B) to produce DME take place in a separate process unit.

In embodiments, the amount of acetic acid produced 65 is greater than the amount of acetic acid produced by another similar method, wherein (i) a hydrogen recovery unit is used to produce hydrogen-depleted synthesis gas; (ii) obtaining hydrogen-depleted synthesis gas from hydrocarbons containing less than about 3 mol.% With ₂₊ alkanes; and/or (iii) do not produce hydrogen-depleted synthesis gas by FRO.

In embodiments such as those depicted in the embodiment of FIG. 2, the method disclosed herein further includes producing DME from at least a portion of the hydrogen-depleted synthesis gas 15. In embodiments, the method disclosed herein further includes supplying at least a portion hydrogen-depleted synthesis gas 15 to a dimethyl ether (DME) reactor 70 to produce an effluent stream 75 from the DME reactor containing DME, methanol, water, and CO2.

The DME reactor 70 is characterized by a pressure in the DME reactor, which may be the same as or different from the pressure in the FRO reactor. When the pressure of the DME exceeds the pressure in the FPO reaction, the method for producing DME may further include: (1) compressing at least a portion of the hydrogen-depleted synthesis gas 15 to obtain a compressed synthesis gas 15', where the pressure of the compressed synthesis gas is 15' approximately equal to 70 DME reactor pressure; and (2) supplying at least a portion of the compressed synthesis gas 15' to the DME reactor 70.

DME reactor 70 may be any reactor known to be suitable for converting hydrogen-depleted syngas 15 (e.g., compressed hydrogen-depleted syngas 15') into a DME reactor effluent containing DME, water, methanol and CO ₂ . and may be operated under any suitable reactor operating conditions known in the art. The DME reactor 70 may contain two catalyst systems, so that both methanol synthesis and methanol dehydration to produce DME are carried out. The method for producing DME according to embodiments of the disclosure of the present invention may further include separating at least a portion of the effluent from the DME reactor 75 into a DME stream 82, a methanol stream 81, a water stream 83, and a CO2B stream 7, and optionally recycling at least at least a portion of the methanol stream 81 to the DME reactor 70 and/or optionally recycling at least a portion of the CO ₂ stream 7B to the FRO reactor 10.

In embodiments, the method for producing DME within the scope of the present invention is to produce an amount of DME 82 that is greater than the amount of DME obtained by another similar method, wherein (i) an H ₂ recovery unit is used to produce an H ₂ depleted synthesis gas; (I) getting depleted of H ₂ synthesis gas from hydrocarbons containing less than about 3 mol.% With ₂₊ alkanes; and/or (iii) do not produce H ₂ depleted synthesis gas by FRO.

In embodiments, the method disclosed herein may advantageously exhibit improvements in one or more method differences when compared to conventional methods.

One skilled in the art will appreciate with the aid of this disclosure that because the FRO reaction is exothermic, very little heat input is required in the form of fuel combustion (e.g., to preheat the reactants in reaction mixture 5 that is fed to the FRO section to generate synthesis gas ) when compared with conventional steam reforming. As such, the hydrogen-depleted synthesis gas FRO chemical synthesis process disclosed herein can advantageously generate less CO ₂ through fuel combustion when compared to steam reforming.

The use of mixtures of CPO reagents containing higher hydrocarbons and/or CO ₂ , as described in the scope of the present invention, represents high selectivity and thus increases the overall carbon efficiency of acetic acid synthesis or DME synthesis relative to conventional methods. Because FROs can be operated at higher pressures than conventional synthesis gas synthesis (e.g., dry reforming) used to produce hydrogen-depleted synthesis gas, energy requirements (e.g., the energy required to compress the hydrogen-depleted synthesis gas before subsequent synthesis of acetic acid or synthesis of DME) can be reduced (or such compression eliminated) relative to conventional methods.

The method for the synthesis of acetic acid, disclosed in the framework of the present invention, is

- 17 042919 irradiation of hydrogen-rich synthesis gas 31 (eg from DME carbonylation plant 30) which can be used directly to produce DME in DME synthesis reaction zone 50 without adjusting the H2/CO molar ratio.

Additional advantages of the methanol processes disclosed within the scope of the present invention may be apparent to those skilled in the art considering this disclosure.

Examples

In general, the embodiments have been described, the following examples are provided as specific embodiments of the disclosure and to demonstrate their practical implementation and advantages. It should be understood that the examples are by way of illustration only and are not intended to limit the description or claims in any way.

Example. The synthesis gas process was modeled as an equilibrium reactor in the ASPEN program, in FIG. 3 is a graph showing the CO/H2 molar ratio in syngas resulting from FRO as a function of reactor temperature without CO2 addition to the feed mixture for CH ₄ /O ₂ mole ratios of 2.2 and 1.7 and pressures, equal to 40 and 100 bar, which demonstrates the molar ratios of CO/H ₂ that can be obtained in the FRO under thermodynamic conditions at various temperatures of the reactor 10 FRO. Fig. 4 is a graph showing CO/H ₂ mole ratio in synthesis gas resulting from FRO as a function of reactor temperature with CO ₂ injection into a reactant mixture having a CO ₂ /CH ₄ mole ratio of 0.5, mole ratios of CH ₄ /O ₂ equal to 2.2 and 1.7, and pressures equal to 40 and 100 bar. fig. 5 shows a plot of CO/H ₂ in syngas resulting from FRO as a function of reactor temperature with CO2 injection into a reactant mixture having a CO2/CH4 mole ratio of 1, CH4/O2 mole ratios of 2.2 and 1 ,7, and pressures equal to 40 and 100 bar.

As seen in FIG. 3, synthesis gas having an H2/CO molar ratio of less than 2 can be produced above 900° C. and at a low CH4/O2 molar ratio. From FIG. 4 and FIG. 5, it is clear that the addition of CO ₂ to the reactant feed extends the operational limits of the FRO to lower temperatures and higher CH ₄ /O ₂ molar ratios. As noted within the framework of the present invention, the introduction of CO ₂ also provides an increase in the efficiency of carbon use, since the carbon in CO ₂ is converted into additional CO. As a result, CO will be produced by the MMBTU of the feed mixture of reactants (eg, natural gas) according to embodiments of the disclosure of the present invention. This additional CO can increase the production of a chemical product (eg, acetic acid or DME) at the same feed flow rate of the reactant mixture (eg, natural gas). As seen in FIG. 3-5, the FRO reactor can produce hydrogen-depleted synthesis gas at high pressures (e.g., at least about 25, 30, 35, 40, 45, 50 bar) required for subsequent chemical synthesis (e.g., acetic acid, DME) thus reducing or eliminating the need to compress the hydrogen-depleted synthesis gas 15 prior to subsequent synthesis of acetic acid or DME.

In FIG. 6 is a graph showing the molar ratio of CO ₂ to CO (CO2/CO) in synthesis gas resulting from FRO as a function of reactor temperature without introducing CO ₂ into reactant feed mixtures having a molar ratio of methane to O ₂ (CH ₄ /O ₂ ) equal to 2.2 or 1.7, and pressures equal to 40 or 100 bar. In FIG. 7 is a graph showing the molar ratio of CO ₂ to carbon (CO ₂ /CO) in synthesis gas as a result of FRO as a function of the reactor temperature with the introduction of CO ₂ into the reactant mixture having a molar ratio of CO ₂ to methane (CO ₂ /CH ₄ ) equal to 0.5, CH4/O2 molar ratios equal to 2.2 and 1.7, and pressures equal to 40 and 100 bar.

In FIG. 8 is a graph showing the molar ratio of CO to hydrogen (H2/CO) in the synthesis gas as a function of conversion (%) and the molar ratio of CO ₂ to carbon (CO2/C) in the feed mixture (in legend) at a pressure of 30 bar and an O2 to carbon molar ratio (O2/C) of 0.55. In FIG. 9 is a graph showing the molar ratio of CO to hydrogen (H2/CO) in the synthesis gas as a function of conversion (%), and the molar ratio of CO ₂ to carbon (CO ₂ /C) in the feed mixture of reactants (in conditional notation) at a pressure of 75 bar and a molar ratio of O ₂ to carbon (O ₂ /C) of 0.55. As can be seen from FIG. 8 and 9, the CO ₂ /C molar ratio required to provide an H ₂ FRO lean synthesis gas having an H ₂ /CO molar ratio of 1 decreases as the pressure increases.

In FIG. 10 is a graph showing the molar ratio of CO to hydrogen (H ₂ /CO) in synthesis gas as a function of conversion (%) and the molar ratio of hydrocarbons having three carbon atoms (C ₃ ) to carbon (C3/C) in a reactant feed mixture (in symbols) at a pressure of 75 bar, an O2 to carbon molar ratio (O2/C) of 0.55 and a CO2 to carbon molar ratio (CO2/C) of 0.25. In FIG. 11 is a graph showing the molar ratio of CO to hydrogen (H2/CO) in synthesis gas as a function of conversion (%) and the mole ratio of hydrocarbons having three carbon atoms (C ₃ ) to carbon (C3/C) in the reactant feed mixture (in legend) at a pressure of 75 bar, an O ₂ to carbon molar ratio (O ₂ /C) of 0.55, and no CO ₂ in the reactant feed mixture.

In FIG. 12 is a graph showing the molar ratio of CO to hydrogen (H ₂ /CO) in

- 18 042919 synthesis gas as a result of FRO as a function of conversion (%) and the molar ratio of hydrocarbons having two carbon atoms (C ₂ ) to carbon (C ₂ /C) in the feed mixture of reagents (in conventional terms) at pressure, equal to 75 bar, an O ₂ to carbon molar ratio (O ₂ /C) of 0.55, and a CO ₂ to carbon molar ratio (CO 2 /C) of 0.25. In FIG. 13 is a graph showing the molar ratio of CO to hydrogen (H ₂ /CO) in synthesis gas as a function of conversion (%) and the molar ratio of hydrocarbons having two carbon atoms (C ₂ ) to carbon (C ₂ /C ) in the reactant feed mixture (in symbols) at a pressure of 75 bar, an O ₂ to carbon molar ratio (O ₂ /C) of 0.55, and no CO ₂ in the reactant feed mixture.

In FIG. 14 is a graph showing the molar ratio of CO to hydrogen (H2/CO) in synthesis gas as a function of conversion (%) and the molar ratio of hydrocarbons having four carbon atoms (C ₄ ) to carbon (C4/C) in a reactant feed mixture (in symbols) at a pressure of 75 bar, an O2 to carbon molar ratio (O2/C) of 0.55 and a _CO2 to carbon molar ratio (CO2/C) of 0.25. Fig. 15 is a graph showing the molar ratio of CO to hydrogen (H2/CO) in synthesis gas as a result of FRO as a function of conversion (%) and the molar ratio of hydrocarbons having four carbon atoms (C ₄ ) to carbon (C ₄ /C ) in the reactant feed mixture (in symbols) at a pressure of 75 bar, an O ₂ to carbon molar ratio (O2/C) of 0.55, and no CO ₂ in the reactant feed mixture.

As seen in FIG. 10-15, the use of reactant mixtures 5 containing higher hydrocarbons (eg, C ₂ , C ₃ and/or C ₄ ) reduces the amount of CO ₂ used to achieve a molar ratio of hydrogen to CO (H ₂ /CO) of approximately 1 , and provides a hydrogen-depleted synthesis gas having an H2/CO molar ratio of approximately 1 at a higher conversion of hydrocarbon to synthesis gas.

While various embodiments have been shown and described, modifications may be made by one skilled in the art without departing from the spirit and teachings of the disclosure. The embodiments described within the scope of the present invention are illustrative only and are not intended to be limiting. Many variations and modifications of the object of the invention disclosed in the framework of the present invention are possible and are within the scope of the disclosure. Where numerical intervals or limits are explicitly stated, such expressed intervals or limits are to be understood as including iteration intervals or limits of similar magnitude falling within the explicitly stated intervals or limits (e.g., from about 1 to about 10 includes, 2, 3 , 4, and so on; more than 0.10 includes 0.11, 0.12, 0.13, and so on). For example, whenever a number range with a lower limit R _L and an upper limit Ru is disclosed, any number falling within the interval is specifically disclosed. In particular, the following numbers within the interval are specifically disclosed: R=R _L +k*(R _u -R _L ), where k is a variable between 1 percent and 100 percent in increments of 1 percent, i. 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. In addition, any number range defined by two R numbers as defined above is also specifically disclosed. The use of the term optionally with respect to any element of a claim is intended to mean that the element in question is required or, alternatively, not required. It is understood that both alternatives are within the scope of the claim. The use of broader terms such as includes, includes, having, etc. should be understood as providing confirmation for narrower terms such as consisting of, consisting essentially of, composed essentially of, and so on.

Accordingly, the scope of legal protection is not limited to the description given above, but is only limited to the following claims, the scope of which includes all equivalents of the subject matter of the claims. Any and every claim is included in the description as an embodiment of the present disclosure. Thus, the claims are a further description and are in addition to the embodiments of the present disclosure. Discussion of a reference is not an admission that it is prior art to the present disclosure, especially any reference that may have a publication date after the priority date for the present application. The disclosures of all patents, patent applications, and publications cited within the scope of the present invention are incorporated herein by reference, to the extent that they provide illustrative, methodological, or other details in addition to those set forth within the scope of the present invention.

Additional description of the present invention

The specific embodiments disclosed above are illustrative only, as the present disclosure may be modified and practiced in various but equivalent ways, obvious to those skilled in the art, having effect from the ideas within the scope of the present invention. In addition, no limitation is intended to the details of construction or design shown within the scope of the present invention other than those described in the formula.

- 19 042919 of the invention below. Therefore, it is obvious that the specific illustrative embodiments disclosed above may be changed or modified, and all such variations are considered to be within the scope and spirit of the present disclosure. Alternative embodiments that result from combining, integrating and/or eliminating features of the embodiments are also within the scope of the disclosure. While compositions and methods are described in broader terms having, including, containing, or including a variety of components or steps, compositions and methods may also consist essentially of, or consist of, various components and steps. The use of the term optional with respect to any element of a claim means that the element is required or, alternatively, the element is not required, both alternatives being within the scope of the claim.

The numbers and intervals disclosed above may vary by some amount. Whenever a numeric range with a lower limit and an upper limit is disclosed, any number and any included interval falling within the range are specifically disclosed. In particular, each range of values (in the form of from about a to about b, or equivalently from about a to b, or equivalently from about a-b) disclosed in the present invention, should be understood as reciting each number and interval covered by the broader range of values. Also, the terms in the claims have their accessible, ordinary meaning, unless the patentee expressly and understandably defines them otherwise. In addition, singular expressions used in the claims are defined within the scope of the present invention to mean one or more of the elements they introduce. If there is any conflict as to the applicability of a word or term in this specification and one or more patent or other documents, definitions shall be adopted that are consistent with the present specification.

Embodiments of the present invention disclosed herein include:

A: a process for producing acetic acid, which includes: (a) reacting, by means of a partial catalytic oxidation (CRO) reaction, a mixture of CRO reagents in a CRO reactor to produce hydrogen-depleted synthesis gas; where the mixture of reagents FRO contains hydrocarbons, O ₂ and optionally carbon dioxide (CO ₂ ) and/or water vapor; where the hydrocarbons contain no less than about 3 mol.% With ₂₊ alkanes; where the FRO reactor contains the FRO catalyst; where depleted in hydrogen synthesis gas contains hydrogen, carbon monoxide (CO), CO ₂ and unreacted hydrocarbons; and wherein the hydrogen-depleted synthesis gas is characterized by a molar ratio of hydrogen to carbon monoxide (H2/CO) of about 0.7 to about 1.3; (b) feeding at least a portion of the hydrogen-depleted synthesis gas and dimethyl ether (DME) to a DME carbonylation unit to produce methyl acetate and hydrogen-rich synthesis gas; where the hydrogen-rich synthesis gas contains hydrogen, CO, CO2 and unreacted hydrocarbons, and where the hydrogen-rich synthesis gas has an H2/CO molar ratio of from about 1.8 to about 2.2; and (c) feeding at least a portion of methyl acetate and water to a methyl acetate hydrolysis reaction zone to produce acetic acid and a methanol stream;

B: a process for producing acetic acid, comprising: (a) reacting, by means of an FRO reaction, a mixture of FRO reactants in an FRO reactor to produce H ₂ depleted synthesis gas; where the mixture of reagents FRO contains hydrocarbons, O ₂ and optionally CO ₂ ; where the hydrocarbons contain no less than about 5 mol.% With ₂₊ alkanes; where the FRO reactor contains the FRO catalyst; where the FRO reactor differs in FRO pressure; where depleted H ₂ synthesis gas contains H ₂ , CO, CO ₂ and unreacted hydrocarbons; and wherein the H2 depleted synthesis gas has an H2/CO molar ratio of about 0.8 to about 1.3; (b) optionally compressing at least a portion of the H ₂ depleted synthesis gas to form compressed synthesis gas; (c) feeding at least a portion of the H2 depleted syngas and/or compressed syngas and DME to a DME carbonylation unit to produce methyl acetate and H2 rich syngas; where the DME carbonylation unit is characterized by the DME carbonylation pressure; where the pressure of depleted H2 synthesis gas and/or compressed synthesis gas is approximately equal to the carbonylation pressure of DME; wherein the H ₂ -rich synthesis gas contains H ₂ , CO, CO ₂ and unreacted hydrocarbons, and wherein the H ₂ -rich synthesis gas has an H ₂ /CO molar ratio of from about 1.4 to about 2.2; (d) feeding at least a portion of methyl acetate and water to a methyl acetate hydrolysis reaction zone to produce acetic acid and a first methanol stream; (e) feeding at least a portion of the H ₂ -rich synthesis gas to the methanol synthesis unit to produce a second methanol stream and a purge gas stream, where the purge gas stream contains H ₂ , CO, CO ₂ and unreacted hydrocarbons; (f) feeding at least a portion of the first methanol stream and/or at least a portion of the second methanol stream to a DME synthesis reaction zone to produce a DME stream, wherein the conventional reactor comprises both a methyl acetate hydrolysis reaction zone and a synthesis reaction zone DME; and (g) feeding at least a portion of the DME stream to the DME carbonylation unit in step (c);

C: a process for producing dimethyl ether (DME) comprising: (a) reacting, via a partial catalytic oxidation (CPO) reaction, a mixture of CRO reactants in a CRO reactor to produce hydrogen-depleted synthesis gas; where the mixture of reagents FRO contains hydrocarbons, O 2 and optionally CO ₂ and/or water vapor; where hydrocarbons contain no less than about 3

- 20 042919 mol.% C ₂₊ alkanes; where the FRO reactor contains the FRO catalyst; where the FRO reactor differs in FRO pressure; where the hydrogen-depleted synthesis gas contains hydrogen, CO, CO2 and unreacted hydrocarbons; and wherein the hydrogen-depleted synthesis gas is characterized by a molar ratio of hydrogen to CO (H2/CO) of about 0.8 to about 1.3; (b) feeding at least a portion of the hydrogen-depleted synthesis gas to a DME reactor to produce an effluent from the DME reactor; where the DME reactor is different pressure in the DME reactor; where the pressure in the FPO reaction and the pressure in the DME reactor are the same or different; where the effluent from the DME reactor contains DME, methanol, water, and CO ₂ ; (c) separating at least a portion of the DME reactor effluent into a DME stream, a methanol stream, a water stream, and a CO2 stream; (d) optionally recycling at least a portion of the methanol stream to the DME reactor, and (e) optionally recycling at least a portion of the CO2 stream to the FRO reactor.

Each of embodiments A, B, and C of the present invention may have one or more of the following additional elements.

Element 1 where hydrocarbons contain methane, natural gas, natural gas liquids, liquefied petroleum gas (LPG), petroleum gas, associated gas, enriched gas, paraffins, shale gas, shale fluids, fluid catalytic cracking (FCC) gas, gases working installations, gases from objects between installations, residual gases, fuel gas from the fuel gas manifold, or combinations thereof.

Element 2, where C ₂₊ alkanes contain ethane, propane, butanes, or combinations thereof.

Element 3, where the FRO reactor is characterized by at least one FRO operating parameter selected from the group consisting of the temperature of the mixture of FRO reagents, from about 100 to about 500°C; an FRO pressure of from about 20 barg to about 80 barg; a contact time in the FRO reaction of from about 0.001 milliseconds (ms) to about 5 seconds (s); molar ratio of carbon to oxygen (C/O) in the CPO reactant mixture from about 0.5:1 to about 3:1, where the C/O molar ratio refers to the total number of moles (C) in hydrocarbons in the reactant mixture divided by on the total number of moles of O ₂ in the mixture of reagents; molar ratio of water vapor to carbon (S/C) in the CPO reactant mixture less than about 0.6:1, where the molar S/C ratio refers to the total number of moles of water (H ₂ O) in the reactant mixture divided by the total number of moles carbon (C) in hydrocarbons in the reactant mixture; molar ratio of CO ₂ to carbon (CO ₂ /C) in the CRO reagent mixture not less than about 0.5:1, where the CO 2 /C molar ratio refers to the total number of moles of CO 2 in the reactant mixture divided by the total number of moles of carbon (C) in hydrocarbons in a mixture of reactants; and their combinations.

Element 4 in which the step of introducing at least a portion of the H2 _- depleted synthesis gas into the hydrogen recovery unit to reduce the amount of H2 in the H2-depleted synthesis gas is eliminated.

Element 5, where the FRO reactor is characterized by FRO pressure; where the DME carbonylation unit is characterized by the DME carbonylation pressure; and where the pressure in the CRO reaction is approximately equal to the carbonylation pressure of DME.

Element 6, where the FRO reactor is characterized by FRO pressure; where the DME carbonylation plant is characterized by the DME carbonylation pressure; where at least part of the depleted H ₂ synthesis gas is compressed in the compressor to obtain a compressed synthesis gas; where the compressed synthesis gas differs in pressure, which is approximately equal to the carbonylation pressure of DME; and wherein at least a portion of the compressed synthesis gas is fed to the DME carbonylation unit in step (b).

Element 7, where the size of the compressor is smaller than the size of the compressor used to compress the lean H ₂ synthesis gas according to another similar method, in which (i) an H2 regeneration unit is used to produce lean H 2 synthesis gas and/or (ii) lean H 2 is obtained synthesis gas from hydrocarbons containing less than about 3 mol.% With ₂₊ alkanes.

Element 8 further including feeding at least a portion of the H ₂ -rich synthesis gas to the methanol synthesis unit to produce another methanol stream and a purge gas stream, where the purge gas stream contains H ₂ , CO, CO ₂ and unreacted hydrocarbons, and wherein at least a portion of the purge gas stream is optionally used as a fuel.

Element 9 further comprising: (1) feeding at least a portion of a methanol stream and/or at least a portion of another methanol stream to a DME synthesis reaction zone to produce a DME stream; and (2) feeding at least a portion of the DME stream to the DME carbonylation unit in step (b).

Element 10, wherein the conventional reactor contains both a methyl acetate hydrolysis reaction zone and a DME synthesis reaction zone.

Element 11, where the amount of acetic acid produced is greater than the amount of acetic acid produced by another similar process in which (i) an H2 recovery plant is used to produce H2-depleted synthesis gas and/or (ii) an H2-depleted synthesis gas is produced from hydrocarbons, containing less than about 3 mol.% WITH ₂₊ alkanes.

Element 12, where the FRO reactor is characterized by at least one FRO operating parameter, you

- 21 042919 brane from the group consisting of the temperature of the mixture of CPO reagents, from about 100°C to about 500°C; an FRO pressure of from about 25 barg to about 80 barg; a contact time in the FRO reaction of from about 0.001 milliseconds (ms) to about 5 seconds (s); molar C/O ratio in the CPO reactant mixture of from about 0.5:1 to about 2:1, where the C/O molar ratio refers to the total number of moles (C) in the hydrocarbons in the reactant mixture divided by the total moles of O ₂ in a mixture of reagents; an S/C molar ratio in the CRO reactant mixture of less than about 0.25:1, where the S/C molar ratio refers to the total moles of water in the reactant mixture divided by the total moles of carbon (C) in hydrocarbons in the reactant mixture; a CO2/C molar ratio in the CPO reactant mixture not less than about 0.5:1, where the CO2/C molar ratio refers to the total moles of CO2 in the reactant mixture divided by the total moles of carbon (C) in the hydrocarbons in the mixture reagents; and their combinations.

Element 13 further comprising: (1) optionally compressing at least a portion of the H ₂ depleted synthesis gas to form compressed synthesis gas, wherein the pressure of the compressed synthesis gas is approximately equal to the pressure in the DME reactor; and (2) feeding at least a portion of the compressed synthesis gas to the DME reactor in step (b).

Element 14, where the amount of DME obtained exceeds the amount of DME obtained by another similar method in which (i) an H ₂ recovery unit is used to produce H ₂ -lean synthesis gas and/or (ii) an H _{2 -lean} synthesis gas is obtained from hydrocarbons containing less than about 3 mol.% With ₂₊ alkanes.

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

Numerous other modifications, equivalents, and alternatives will become apparent to those skilled in the art once they fully appreciate the above disclosure. The authors mean that the following claims are interpreted to cover all such modifications, equivalents, alternatives, where applicable. Accordingly, the scope of the present invention is not limited to the description set forth above, but is limited only by the claims that follow, the scope of which includes all equivalents of the subject matter of the claims. Each claim is included in the description as an embodiment of the present invention. Thus, the claims are a further description and addition to the detailed description of the present invention. Disclosures of all patents, patent applications and publications cited herein are incorporated herein by reference.

Claims (25)

1. A method for producing acetic acid, including: (a) reacting, via a catalytic partial oxidation (CPO) reaction, a mixture of CPO reactants in a CPO reactor to produce a hydrogen-depleted synthesis gas; where the mixture of reagents FRO contains hydrocarbons and oxygen; where hydrocarbons contain not less than 3 mol.% With ₂₊ alkanes; where the FRO reactor contains the FRO catalyst; where depleted in hydrogen synthesis gas contains hydrogen, carbon monoxide, carbon dioxide and unreacted hydrocarbons; and wherein the hydrogen-depleted synthesis gas is characterized by a molar ratio of hydrogen to carbon monoxide (H2/CO) of 0.7 to 1.3; (b) feeding at least a portion of the hydrogen-depleted synthesis gas and dimethyl ether (DME) to a DME carbonylation unit to produce methyl acetate and hydrogen-rich synthesis gas; wherein the hydrogen-rich synthesis gas contains hydrogen, carbon monoxide, carbon dioxide, and unreacted hydrocarbons, and wherein the hydrogen-rich synthesis gas has an H2/CO molar ratio of 1.4 to 2.2; and (c) feeding at least a portion of methyl acetate and water to a methyl acetate hydrolysis reaction zone to produce acetic acid and a methanol stream. 2. The method of claim 1, wherein the hydrocarbons comprise methane, natural gas, natural gas liquids, liquefied petroleum gas (LPG), petroleum gas, associated gas, enriched gas, paraffins, shale gas, shale fluids, fluid catalytic cracking gas (FCC), work plant gases, gases from sites between installations, residual gases, fuel gas from the fuel gas header, or combinations thereof. 3. The method according to any one of claims 1 to 2, wherein the C ₂₊ alkanes contain ethane, propane, butanes, or combinations thereof. 4. The method according to any one of claims 1 to 3, where the FRO reactor is characterized by at least one working steam - 22 042919 CRO meter selected from the group consisting of the temperature of the mixture of CRO reagents, equal to from 100 to 500°C; SRO pressure equal to from 20 bar overpressure to 80 bar overpressure; a contact time in the FRO reaction of 0.001 milliseconds (ms) to 5 seconds (s); the molar ratio of carbon to oxygen (C/O) in the CPO reactant mixture from 0.5:1 to 3:1, where the molar C/O ratio refers to the total number of moles (C) in hydrocarbons in the reactant mixture divided by the total the number of moles of oxygen (O ₂ ) in the mixture of reagents; molar ratio of water vapor to carbon (S/C) in the CPO reagent mixture, less than 0.6:1, where the molar ratio S/C refers to the total number of moles of water (H ₂ O) in the reagent mixture divided by the total number of moles of carbon (C) in hydrocarbons in a mixture of reactants; the molar ratio of CO2 to carbon (CO2/C) in the CPO reactant mixture not less than 0.5:1, where the CO2/C molar ratio refers to the total number of moles of _CO2 in the reactant mixture divided by the total number of moles of carbon ( C) in hydrocarbons in a mixture of reagents; and their combinations. 5. A method according to any one of claims 1 to 4, wherein the step of introducing at least a portion of the hydrogen-depleted synthesis gas into the hydrogen recovery unit to reduce the amount of hydrogen in the hydrogen-depleted synthesis gas is omitted. 6. The method according to any one of claims 1 to 5, where the FRO reactor is characterized by FRO pressure; where the DME carbonylation unit is characterized by the DME carbonylation pressure; and where the pressure in the CRO reaction is equal to the carbonylation pressure of DME. 7. The method according to any one of claims 1 to 6, where the FRO reactor is characterized by FRO pressure; where the DME carbonylation unit is characterized by the DME carbonylation pressure; wherein at least a portion of the hydrogen-depleted synthesis gas is compressed in a compressor to form compressed synthesis gas; where the compressed synthesis gas differs in pressure, which is equal to the carbonylation pressure of DME; and wherein at least a portion of the compressed synthesis gas is fed to the DME carbonylation unit in step (b). 8. The method of claim 7, wherein the compressor is smaller than the compressor used to compress the hydrogen-depleted synthesis gas according to another similar method, wherein (i) a hydrogen recovery unit is used to produce hydrogen-depleted synthesis gas and/or (ii ) get depleted in hydrogen synthesis gas from hydrocarbons containing less than 3 mol.% WITH ₂₊ alkanes. 9. The method according to any one of claims 1 to 8, further comprising feeding at least a portion of the hydrogen-rich synthesis gas to the methanol synthesis unit to produce another methanol stream and a purge gas stream, where the purge gas stream contains hydrogen, monoxide carbon, carbon dioxide and unreacted hydrocarbons, and wherein at least a portion of the purge gas stream is optionally used as a fuel. 10. The method of claim 9, further comprising: (1) feeding at least a portion of a methanol stream and/or at least a portion of another methanol stream to a DME synthesis reaction zone to produce a DME stream; and (2) feeding at least a portion of the DME stream to the DME carbonylation unit in step (b). 11. The method of claim 10 wherein the conventional reactor comprises both a methyl acetate hydrolysis reaction zone and a DME synthesis reaction zone. 12. A process according to any one of claims 1 to 11, wherein the amount of acetic acid produced is greater than the amount of acetic acid produced by another similar method, wherein (i) a hydrogen recovery unit is used to produce hydrogen-depleted synthesis gas and/or (ii ) get depleted in hydrogen synthesis gas from hydrocarbons containing less than 3 mol.% With ₂₊ alkanes. 13. The method according to claim 1, where the mixture of CPO reagents contains hydrocarbons, oxygen and optionally carbon dioxide and/or steam. 14. A method for producing acetic acid, including: (a) reacting, via a catalytic partial oxidation (CPO) reaction, a mixture of CPO reactants in a CPO reactor to produce a hydrogen-depleted synthesis gas; where the mixture of reagents FRO contains hydrocarbons and oxygen; and where the hydrocarbons contain not less than 5 mol.% With ₂₊ alkanes; where the FRO reactor contains the FRO catalyst; where the FRO reactor differs in FRO pressure; where depleted in hydrogen synthesis gas contains hydrogen, carbon monoxide, carbon dioxide and unreacted hydrocarbons; and wherein the hydrogen-depleted synthesis gas is characterized by a molar ratio of hydrogen to carbon monoxide (H2/CO) of 0.8 to 1.3; (c) feeding at least a portion of the hydrogen-depleted synthesis gas and/or compressed synthesis gas and dimethyl ether (DME) to a DME carbonylation unit to produce methyl acetate and hydrogen-rich synthesis gas; where the DME carbonylation unit is characterized by the DME carbonylation pressure; where the pressure of the hydrogen-depleted synthesis gas and/or compressed synthesis gas is equal to the carbonylation pressure of DME; wherein the hydrogen-rich synthesis gas contains hydrogen, carbon monoxide, carbon dioxide, and unreacted hydrocarbons, and wherein the hydrogen-rich synthesis gas has an H2/CO molar ratio of 1.4 to 2.2; (d) feeding at least a portion of methyl acetate and water to a methyl acetate hydrolysis reaction zone to produce acetic acid and a first methanol stream; (e) feeding at least a portion of the hydrogen-rich synthesis gas to the methane synthesis unit - 23 042919 nola to obtain a second methanol stream and a purge gas stream, where the purge gas stream contains hydrogen, carbon monoxide, carbon dioxide and unreacted hydrocarbons; (f) feeding at least a portion of the first methanol stream and/or at least a portion of the second methanol stream to a DME synthesis reaction zone to produce a DME stream, wherein the conventional reactor comprises both a methyl acetate hydrolysis reaction zone and a synthesis reaction zone DME; and (g) feeding at least a portion of the DME stream to the DME carbonylation unit in step (c). 15. The method according to claim 14, where the FRO reactor is characterized by at least one FRO operating parameter selected from the group consisting of the temperature of the mixture of FRO reagents, equal to from 100 to 500°C; SRO pressure equal to from 25 bar overpressure to 80 bar overpressure; a contact time in the FRO reaction of 0.001 milliseconds (ms) to 5 seconds (s); molar ratio of carbon to oxygen (C/O) in the mixture of CRO reagents, equal to from about 0.5:1 to 2:1, where the molar ratio C/O refers to the total number of moles (C) in hydrocarbons in the mixture of reagents, divided by the total number of moles of oxygen (O ₂ ) in the mixture of reagents; molar ratio of water vapor to carbon (S/C) in the CPO reagent mixture, less than 0.25:1, where the molar ratio S/C refers to the total number of moles of water (H ₂ O) in the reagent mixture divided by the total number of moles of carbon (C) in hydrocarbons in a mixture of reactants; molar ratio of CO ₂ to carbon (CO 2 /C) in the mixture of CPO reagents not less than 0.5: 1, where the molar ratio of CO ₂ /C refers to the total number of moles of CO ₂ in the mixture of reagents divided by the total number of moles of carbon ( C) in hydrocarbons in a mixture of reagents; and their combinations. 16. The method of claim 14, wherein the CPO reactant mixture contains hydrocarbons, oxygen, and optionally carbon dioxide and/or steam. 17. The method of claim 14, further comprising (b) optionally compressing at least a portion of the hydrogen-depleted synthesis gas to form compressed synthesis gas. 18. A method for producing dimethyl ether (DME), including: (a) reacting, via a catalytic partial oxidation (CPO) reaction, a mixture of CPO reactants in a CPO reactor to produce a hydrogen-depleted synthesis gas; where the mixture of reagents FRO contains hydrocarbons and oxygen; where the hydrocarbons contain not less than 3 mol.% With ₂₊ alkanes; where the FRO reactor contains the FRO catalyst; where the FRO reactor differs in FRO pressure; where depleted in hydrogen synthesis gas contains hydrogen, carbon monoxide, carbon dioxide and unreacted hydrocarbons; and wherein the hydrogen-depleted synthesis gas is characterized by a molar ratio of hydrogen to carbon monoxide (H2/CO) of 0.8 to 1.3; (b) feeding at least a portion of the hydrogen-depleted synthesis gas to a dimethyl ether (DME) reactor to produce an effluent from the DME reactor; where the reactor for producing DME differs in pressure in the reactor for producing DME; where the pressure of the CPO reaction and the pressure in the reactor to obtain DME are the same or different; where the output stream from the reactor to obtain DME contains DME, methanol, water and carbon dioxide; (c) separating at least a portion of the DME reactor effluent into a DME stream, a methanol stream, a water stream, and a carbon dioxide stream. 19. The method of claim 18 wherein the hydrocarbons comprise methane, natural gas, natural gas liquids, liquefied petroleum gas (LPG), petroleum gas, associated gas, enriched gas, paraffins, shale gas, shale fluids, fluid catalytic cracking gas (FCC), plant gases, gases from sites between installations, residual gases, fuel gas from the fuel gas header, or combinations thereof, and where C ₂₊ alkanes contain ethane, propane, butanes, or combinations thereof. 20. The method according to any one of claims 18-19, where the FRO reactor is characterized by at least one FRO operating parameter selected from the group consisting of a temperature of the mixture of CRO reagents equal to from 100 to 500°C; SRO pressure equal to 20 bar overpressure to 80 bar overpressure; a contact time in the FRO reaction of 0.001 milliseconds (ms) to 5 seconds (s); the molar ratio of carbon to oxygen (C/O) in the CPO reactant mixture from 0.5:1 to 3:1, where the molar C/O ratio refers to the total number of moles (C) in hydrocarbons in the reactant mixture divided by the total the number of moles of oxygen (O ₂ ) in the mixture of reagents; the molar ratio of water vapor to carbon (S/C) in the CRO reactant mixture is less than 0.6:1, where the molar S/C ratio refers to the total moles of water (H ₂ O) in the reactant mixture divided by the total moles of carbon ( C) in hydrocarbons in a mixture of reagents; molar ratio of CO ₂ to carbon (CO ₂ /C) in the mixture of CRO reagents equal to at least 0.5: 1, where the molar ratio of CO 2 / C refers to the total number of moles of CO ₂ in the mixture of reagents divided by the total number of moles of carbon ( C) in hydrocarbons in a mixture of reagents; and their combinations. 21. The method according to any one of claims 18 to 20, wherein the step of introducing at least a portion of the hydrogen-depleted synthesis gas into the hydrogen recovery unit to reduce the amount of hydrogen in the hydrogen-depleted synthesis gas is omitted. 22. The method according to any one of claims 18-21, further comprising: (1) optionally compressing at least a portion of the hydrogen-depleted synthesis gas to obtain compressed synthesis gas, where the pressure of the compressed synthesis gas is equal to the pressure in the reactor for receiving DME; and (2) feeding at least a portion of the compressed synthesis gas to the DME reactor in step (b). 23. The method according to any one of claims 18-22, where the amount of DME obtained exceeds the amount of DME, - 24 042919 obtained by another similar method, in which (i) using a hydrogen recovery unit to obtain hydrogen-depleted synthesis gas and/or (ii) obtaining hydrogen-depleted synthesis gas from hydrocarbons containing less than 3 mol.% C ₂ alkanes . 24. The method of claim 18, wherein the CPO reactant mixture contains hydrocarbons, oxygen, and optionally carbon dioxide and/or steam. 25. The process of claim 18, further comprising (d) optionally recycling at least a portion of the methanol stream to the DME reactor, and (e) optionally recycling at least a portion of the carbon dioxide stream to the FRO reactor.