EA043578B1 - METHOD FOR PRODUCING METHANOL FROM SYNTHESIS GAS PRODUCED BY CATALYTIC PARTIAL OXIDATION INTEGRATED WITH CRACKING - Google Patents

Description

Field of technology

The invention relates to methods for producing methanol, more specifically to methods for producing methanol from synthesis gas obtained by catalytic partial oxidation (CPO) of hydrocarbons such as methane.

State of the art

Synthetic gas (syngas) is a mixture containing carbon monoxide (CO) and hydrogen (H2), as well as small amounts of carbon dioxide (CO2), water (H2O) and unreacted methane ( _CH4 ). Synthesis gas is commonly used as an intermediate in the production of methanol and ammonia, and as an intermediate in the creation of synthetic petroleum for use as a lubricant or fuel. Syngas is typically produced by steam reforming natural gas (steam methane reforming or SMR), although other hydrocarbon sources can be used to produce syngas, such as refinery off-gases, naphtha feedstocks, heavy hydrocarbons, coal, biomass, etc. PRM is an endothermic process and requires significant energy input to promote the reaction. Traditional endothermic technologies, such as PRM, produce synthesis gas containing more _H2 than required for methanol synthesis. Typically, the PMR produces synthesis gas with an M ratio ranging from 2.6 to 2.98, where the M ratio is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ).

In the autothermal reforming (ATR) process, a portion of natural gas is burned as fuel to promote the conversion of natural gas to synthesis gas, resulting in relatively low concentrations of hydrogen and relatively high concentrations of CO2. Conventional methanol plants use combined reforming (CR) technology, which combines ATR with autothermal reforming (ATR) to reduce the amount of hydrogen present in the synthesis gas. ATP produces synthesis gas with an H2 content below that required for methanol synthesis. Typically, ATP produces synthesis gas with an M ratio ranging from 1.7 to 1.84. According to the CR technology, the volumetric flow rate of natural gas supplied to the PRM and ATP can be adjusted to achieve an M ratio of total synthesis gas from 2.0 to 2.06. In addition, the KR synthesis gas has a H2 content greater than that required for methanol synthesis. Moreover, PFP is a highly endothermic process, and the endothermic nature of PFP technology requires fuel combustion to promote syngas synthesis. Consequently, the PRM technology reduces the energy efficiency of the methanol synthesis process.

Synthesis gas can also be produced (non-commercially) by catalytic partial oxidation (CPO (CPO) or CPOk (CPOx)) of natural gas. The COC process uses partial oxidation of hydrocarbon feedstock to synthesis gas containing CO and H2. The CPO process is exothermic, eliminating the need for external heat input. However, the composition of the commonly produced synthesis gas is not suitable for methanol synthesis, for example due to the reduced H2 content. In addition, maintaining the desired catalyst activity and performance during the CPR process can be challenging due to elevated or rapidly increasing CPR temperatures leading to catalyst deactivation. The CPO reaction is exothermic and can lead to a strong increase in the temperature of the CPO catalyst bed, which, in turn, can lead to deactivation of the catalyst. Thus, there is a continuing need to develop synthesis gas production through CPR processes that control the reaction temperature and also produce synthesis gas that is acceptable for the methanol production process.

Brief description of drawings

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

Fig. 1 shows a system diagram of a methanol production method.

Fig. 2 is a diagram of another methanol production method system.

Fig. 3 is a diagram of yet another methanol production method system.

Detailed description

The present invention discloses methods for the production of synthesis gas and olefins, including (a) feeding a mixture of catalytic partial oxidation reagents (CPO (CPO) or CPO (CPOx)) into a CPO reactor; where the mixture of CPO reagents contains oxygen, first hydrocarbons and optionally water vapor; wherein at least a portion of the mixture of CPO reactants is reacted through a CPO reaction in a CPO reactor to produce a CPO reactor effluent; where the CPO reactor contains a CPO catalyst; where the effluent stream of the CPO reactor contains hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted first hydrocarbons; and wherein the CPO reactor effluent is characterized by the ratio M of the CPO reactor effluent, wherein the ratio M is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ); (b) feeding the cracker feedstock to the cracker to produce a cracker product stream, a hydrogen-rich stream, and a hydrocarbon recovery stream; wherein the cracker feedstock contains second hydrocarbons; wherein the first hydrocarbons and the second hydrocarbons are the same or different; Where

- 1 043578 the product stream of the cracking unit contains olefins; wherein the hydrogen-rich stream contains H2, methane and optionally unreacted second hydrocarbons; and wherein the hydrocarbon recovery stream contains C ₄₊ hydrocarbons; and (c) contacting at least a portion of the CPO reactor effluent with at least a portion of the hydrogen-rich stream to produce hydrogen-enriched synthesis gas, wherein the hydrogen-enriched synthesis gas is characterized by the ratio M of hydrogen-enriched synthesis gas, and where the ratio M of the hydrogen-enriched synthesis gas is greater than the ratio M of the effluent stream of the CPO reactor. In some aspects, the hydrogen-rich stream may be introduced into a hydrogen recovery unit to produce a hydrogen-rich stream and a hydrocarbon-rich stream, where the hydrogen-rich stream may be further contacted with the CPO reactor effluent to produce hydrogen-rich synthesis gas. The hydrocarbon recovery stream can be fed into the CPO reactor. The first hydrocarbons and/or the second hydrocarbons may contain methane, ethane, propane, butanes, naphtha, natural gas, liquefied natural gas, associated gas, wellhead gas, enriched gas, paraffins, shale gas, shale liquids, fluid catalytic cracking off-gas ( FCC), refinery process gases, flue gases, fuel gas from the fuel gas header, or combinations thereof; and olefins may contain ethylene. The synthesis gas can be used further in the methanol production process.

To adjust synthesis gas H2/CO molar ratios to values greater than about 1.7-1.9, the methods disclosed herein illustrate methods for increasing the _H2 /CO molar ratio and/or decreasing the hydrocarbon concentration in the synthesis gas ( for example, reducing methane leakage). In one aspect, steam cracker effluent gas, which has a hydrogen-rich composition, can be mixed with the CPO reactor effluent in any suitable proportions to produce a hydrogen-rich synthesis gas having an H ₂ /CO molar ratio of greater than about 2.0. In another aspect, steam cracker off-gas, which is hydrogen-poor, can be mixed with fresh methane or natural gas and fed into the CPR reactor along with oxygen. In such an aspect, the residual H2 present in the steam cracker off-gas can (1) increase the _H2 content of the resulting synthesis gas and/or (2) increase the reaction temperature in the CPO catalyst bed due to the combustion of _H2 , where the increased temperature increases the reaction rate of CPO, as well as selectivity for CO and H2. The rapidly rising temperature in the CPO reactor can be eliminated by cracking ethane in coils immersed in the CPO catalyst bed. The process heat produced by the CPO reaction can be further used to crack ethane in coils located outside the CPO catalyst bed.

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

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

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

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

As used in this invention, the terms inhibition, or reduction, or prevention, or elimination, or any variant of these terms include any measurable reduction or complete inhibition to achieve the desired result. As used herein, the term effective means adequate to achieve the desired, expected or intended result. As used in this invention, the terms containing (and any

- 2 043578 form of content, such as contain and contains), having (and any form of presence, such as have and has), including (and any form of inclusion, such as include and includes) or consisting of (and any form of composition, such how consist of and consists of) are inclusive and open-ended and do not exclude additional, unlisted elements or method steps.

Unless otherwise defined, technical and scientific terms used in the invention have the same meanings as commonly understood by one skilled in the art. The compounds are described in the invention using standard nomenclature. For example, any position unsubstituted by any specified group is understood to have its valence filled by a bond or hydrogen atom. A dash (-) that is not between two letters or symbols is used to show the attachment point for a substituent. For example, the -CHO group is attached through the carbon atom of the carbonyl group. As used herein, the terms Cx hydrocarbons and Cx are used interchangeably and refer to any hydrocarbon having x number of carbon atoms (C). For example, both the terms C ₄ hydrocarbons and C ₄ refer to any hydrocarbons having exactly 4 carbon atoms, such as n-butane, isobutane, cyclobutane, 1-butene, 2-butene, isobutylene, butadiene, etc., or their combinations. As used in this invention, the term C _x+ hydrocarbons refers to any hydrocarbon having equal to or greater than x number of carbon atoms (C). For example, the term C2 ₊ hydrocarbons refers to any hydrocarbons having 2 or more carbon atoms, such as ethane, ethylene, _C3 , _C4 , _C5 , etc.

In fig. 1 discloses a methanol production system 1000. The methanol production system 1000 typically includes a catalytic partial oxidation reactor (CPR or CPR) 100; methanol reactor 200; gas-liquid separator 300; distillation unit 400; first hydrogen extraction unit (H ₂ ) 500; and cracker 600. In FIG. 2 discloses a methanol production system 2000. The methanol production system 2000 typically includes a KCHO reactor 100; methanol reactor 200; gas-liquid separator 300; distillation unit 400; first extraction unit H ₂ 500; and cracker 600. In FIG. 3, a methanol production system 3000 is disclosed. The methanol production system 3000 typically includes a KCHO reactor 100; methanol reactor 200; gas-liquid separator 300; distillation unit 400; first extraction unit H ₂ 500; cracking unit 600; and a second H2 extraction assembly 700. As will be appreciated by one skilled in the art and with the benefit of this description, the components of the methanol production system shown in FIG. 1-3 may be in fluid communication with each other (as indicated by connecting lines indicating the direction of fluid flow) through any suitable conduits (eg, pipes, streams, etc.). General reference numerals refer to the common components represented in one or more figures, and the description of a particular component generally applies to the corresponding figures in which the component appears, except as specified in this invention.

In one aspect, the method disclosed in this invention may include the step of reacting by reacting a mixture of CSC reactants 10 in a CRC reactor 100 to produce a CRC reactor effluent (eg, synthesis gas); where the mixture of reagents KCHO 10 contains hydrocarbons (for example, first hydrocarbons, second hydrocarbons) and oxygen; where the KChO reactor 100 contains the KChO catalyst; and wherein the CPO reactor effluent stream (eg, synthesis gas) contains hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO2), water, and unreacted hydrocarbons (eg, unreacted first hydrocarbons, unreacted second hydrocarbons). As will be appreciated by one skilled in the art and with the benefit of this description, depending on the composition of the reactant mixture of the CPO 10, the composition of the resulting CPO reactor effluent (eg, synthesis gas) extracted from the CPO reactor 100 may vary.

For example, and in accordance with the configuration of the methanol production system 1000 in FIG. 1, the CPO reactant mixture may contain O2, first hydrocarbons, optionally at least a portion of hydrocarbon recovery stream 71 (eg, C4+ hydrocarbons), and optionally water vapor; and the effluent of the reactor 15 can be recovered from the reactor 100, where the effluent of the reactor 15 contains H ₂ , CO, CO ₂ , water and unreacted hydrocarbons (eg, first hydrocarbons and optionally C ₄₊ hydrocarbons). As another example, and in accordance with the configuration of the methanol production system 2000 in FIG. 2, the CPO reactant mixture may contain O ₂ , first hydrocarbons, at least a portion of the hydrogen-poor stream 72 (e.g., H ₂ , CH ₄ , optionally second hydrocarbons such as C ₂ - ₃ hydrocarbons), optionally at least a portion of the hydrocarbon recovery stream 71 (eg, C ₄₊ hydrocarbons) and optionally water vapor; and the synthesis gas 17 can be recovered from the CPO reactor 100, where the synthesis gas 17 contains H2, CO, CO2, water and unreacted hydrocarbons (eg, CH4, first hydrocarbons, optionally second hydrocarbons, optionally C4+ hydrocarbons). As another example, and in accordance with the configuration of the methanol production system 3000 in FIG. 3, the CPO reactant mixture may contain oxygen, first hydrocarbons, optionally at least a portion of hydrocarbon recovery stream 71 (e.g., C4+ hydrocarbons), optionally at least a portion of hydrocarbon-enriched stream 76 (e.g., methane, optionally second hydrocarbons, such as C ₂ _ ₃ hydrocarbons) and optionally water vapor; and the synthesis gas 18 can be extracted from the KCHO reactor 100, where the synthesis gas 18 contains H ₂ , CO, CO2, water and

- 3 043578 unreacted hydrocarbons (for example, first hydrocarbons, optionally methane, optionally second hydrocarbons, optionally C ₄₊ hydrocarbons).

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

CH4+I/2O2 2СО+2Н ₂ (1)

Without intending to be bound by any theory, it should be noted that side reactions may occur along with the COC reaction depicted in equation (1); and such side reactions can produce CO2 and H2O, for example through the combustion of hydrocarbons, which is an exothermic reaction. As will be appreciated by one skilled in the art and by use of this description, and without intending to be bound by any theory, the CPO reaction represented by equation (1) can produce synthesis gas with a molar ratio of hydrogen to carbon monoxide (H2/ CO), having a theoretical stoichiometric limit of 2.0. Without intending to be bound by any theory, it should be noted that the theoretical stoichiometric limit of 2.0 for the H2/CO molar ratio means that the CCO reaction represented by equation (1) produces 2 moles of H2 for every 1 mole of CO, that is, the H2/CO molar ratio (2 mol H ₂ /mol CO) is 2. As will be appreciated by one skilled in the art and from this description, the theoretical stoichiometric limit of 2.0 for the H2/CO molar ratio in the CCO reaction is practically not can be achieved because reactants (eg hydrocarbons, oxygen) as well as products (eg H2, CO) undergo side reactions under the conditions used for the CPO reaction. As will be appreciated by one skilled in the art and by this description, and without intending to be bound by any theory, in the presence of oxygen, CO and H2 can be oxidized to 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 altered by shifting the equilibrium of the water gas shift (WGS) reaction, which will be discussed in more detail later. Side reactions that may occur in the CPO reactor 100 can have a direct effect on the M ratio of the synthesis gas produced (e.g., CPO reactor effluent, synthesis gas effluent, synthesis gas 17, synthesis gas 18), where the ratio M is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ). In the absence of any side reaction (theoretically), the CPO reaction represented by equation (1) results in synthesis gas with an M ratio of 2.0. However, the presence of side reactions (in practice) reduces H2 and increases CO2, resulting in synthesis gas with an M ratio below 2.0.

Additionally, and without intending to be bound by any theory, it should be noted that the CPO reaction shown in equation (1) is an exothermic heterogeneous catalytic reaction (i.e., a moderately exothermic reaction) and it occurs in a single reactor unit such as KChO 10 reactor (as opposed to more than one reactor block, as is the case with traditional synthesis gas production processes, such as combinations of steam methane reforming (SMR) with autothermal reforming (ATR)). Although it is possible to carry out partial oxidation of hydrocarbons as a homogeneous reaction in the absence of a catalyst, the process of homogeneous partial oxidation of hydrocarbons entails excessive temperatures, long residence times, and excessive coke formation, which greatly reduces the controllability of the partial oxidation reaction and may not produce synthesis gas of the desired quality in one reactor block. In addition, without intending to be bound by any theory, it should be noted that the CPO reaction is quite resistant to chemical poisoning, and as such it allows the use of a wide range of hydrocarbon feedstocks, including some sulfur-containing hydrocarbon feedstocks; this can in some cases increase catalyst life and performance. In contrast, traditional ATP processes have more stringent requirements for raw materials, for example, in terms of the content of impurities in the feedstock (for example, ATP feedstock is subjected to desulfurization), as well as hydrocarbon composition (for example, CH ₄ enriched feedstock is predominantly used in ATP).

In one aspect, hydrocarbons (e.g., first hydrocarbons, second hydrocarbons) suitable for use in the COC reaction disclosed in this invention may include methane (CH ₄ ), ethane, propane, butanes, naphtha, natural gas, natural gas condensate, oil field gas, associated gas, enriched gas, paraffins, shale gas, shale liquids, fluid catalytic cracking (FCC) off-gas, refinery process gases, flue gases, fuel gas from a fuel gas header, etc., or combinations thereof. Hydrocarbons (eg, first hydrocarbons, second hydrocarbons) may include any suitable hydrocarbon source and may contain Q-C6 hydrocarbons as well as some heavier hydrocarbons.

In one aspect, the reactant mixture CCO 10 may comprise natural gas. Typically, natural gas consists predominantly of methane, but may also contain ethane, propane and heavier hydrocarbons (e.g. isobutane, n-butane, isopentane, n-pentane, hexanes, etc.), as well as very small amounts of nitrogen (N2 ), oxygen, CO2, sulfur compounds and/or water. Natural gas may be provided from a number of sources, including, but not limited to, gas fields, oil fields, coal fields, hydraulic fracturing fields, biomass, landfill gas, and the like, or combinations thereof. In some aspects, the KCHO 10 reagent mixture may

- 4 043578 contain CH ₄ and O2.

Natural gas may contain any suitable amount of methane. In some aspects, natural gas may contain biogas. For example, natural gas may contain from about 45 to 80 mol% methane, from about 20 to 55 mol% carbon dioxide, and less than about mol% N2.

In one aspect, natural gas may contain CH ₄ in an amount equal to or greater than about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 82, about 84, about 86, about 88 , about 90, about 91, about 92, about 93, about 94, about 95, about 96, about 97, about 98 or about 99 mol.%

In some aspects, hydrocarbons (e.g., first hydrocarbons) suitable for use in the CPO reaction disclosed in this invention may contain C1-C6 hydrocarbons, N2 (e.g., about 0.1 to 15, or about 0.5 to 11, or about 1 to 7.5, or about 1.3 to 5.5 mol.%), and CO2 (for example, about 0.1 to 2, or about 0.2 to 1 or approximately 0.3 to 0.6 mol.%). For example, hydrocarbons (e.g., first hydrocarbons) suitable for use in the CPO reaction disclosed in this invention may contain C1 hydrocarbons (about 89 to 92 mol.%), C ₂ hydrocarbons (about 2.5 to 4 mol. %); C3 hydrocarbons (about 0.5 to 1.4 mol%); C ₄ hydrocarbons (about 0.5 to 0.2 mol%); C ₅ hydrocarbons (approximately 0.06 mol%); and C6 hydrocarbons (approximately 0.02 mol%); and optionally N2 (about 0.1 to 15 mol.%), CO2 (about 0.1 to 2 mol.%), or both N2 (about 0.1 to 15 mol.%) and CO2 ( approximately 0.1 to 2 mol.%).

The oxygen used in the KCHO 10 reagent mixture may contain 100% oxygen (essentially pure O2), oxygen gas (which can be produced through a membrane separation process), industrial oxygen (which may contain some air), oxygen-enriched air, oxygen-containing gaseous compounds (for example, NO), oxygen-containing mixtures (for example, O ₂ /CO ₂ , O ₂ /H ₂ O, O ₂ /H ₂ O ₂ /H ₂ O), oxy-radical generators (for example, CH3OH, CH2O ), hydroxyl radical generators, etc., or combinations thereof.

In one aspect, the CCO reactant mixture 10 can be characterized by a carbon to oxygen (C/O) molar ratio of less than about 3:1, or less than about 2.6:1, or less than about 2.4:1, or or less than about 2.2:1, or less than about 2:1, or less than about 1.9:1, or equal to or greater than about 2:1, or equal to or greater than about 2, 2:1, or equal to or greater than about 2.4:1, or equal to or greater than about 2.6:1, or from about 0.5:1 to 3:1, or from about 0.7: 1 to 2.5:1, or about 0.9:1 to 2.2:1, or about 1:1 to 2:1, or about 1.1:1 to 1.9: 1, or about 2:1 to 3:1, or about 2.2:1 to 3:1, or about 2.4:1 to 3:1, or about 2.6: 1 to 3:1, where the C/O molar ratio refers to all moles of carbon (C) hydrocarbons in the reactant mixture divided by all moles of oxygen (O ₂ ) in the reactant mixture. For example, when the only carbon source in a mixture of CCHO 10 reagents is CH ₄ , the CH ₄ /O ₂ molar ratio is the same as the C/O molar ratio. As another example, when a mixture of reagents KCHO 10 contains other carbon sources in addition to CH ₄ , such as ethane (C ₂ H ₆ ), propane (C3H8), butanes (C ₄ H ₁₀ ), etc., the C/O molar ratio takes into account moles of carbon in each component (for example, 2 moles of C in 1 mole of C2H6, 3 moles of C in 1 mole of C3H8, 4 moles of C in 1 mole _{of C4H10 ,} etc.). As will be appreciated by one skilled in the art and by reference to this description, the C/O molar ratio in the CPO 10 reactant mixture can be adjusted along with other reactor process parameters (e.g., temperature, pressure, flow rate, etc.) to obtain synthesis gas of the desired composition (for example, synthesis gas with the desired molar ratio of H ₂ /CO; synthesis gas with the desired CO ₂ content, etc.). The C/O molar ratio in the KChO 10 reagent mixture can be adjusted to provide a reduced amount of unreacted hydrocarbons in the synthesis gas. The C/O molar ratio of the KCHO 10 reactant mixture can be adjusted based on the temperature of the KCHO effluent stream to reduce (e.g., minimize) the unreacted hydrocarbon content of the produced synthesis gas (e.g., KCHO 15 reactor effluent; synthesis gas effluent; synthesis -gas 17; synthesis gas 18). As will be appreciated by one skilled in the art and with the benefit of this description, when synthesis gas is subsequently used in a methanol production process, unreacted hydrocarbons present in the synthesis gas may undesirably accumulate in the methanol reaction loop, thereby reducing the efficiency of the process. methanol production.

In one aspect, a portion of the hydrocarbons (e.g., first hydrocarbons, second hydrocarbons) in the reactant mixture CCO 10 may undergo a thermal decomposition reaction to carbon (C) and H ₂ , for example, as represented by equation (2):

- 5 043578

CH4 -+ C+2H ₂ (2)

The decomposition reaction of hydrocarbons such as methane is enhanced at elevated temperatures and increases the H2 content in the CPO reactor effluent (eg, synthesis gas). As will be appreciated by one of ordinary skill in the art and by the use of this description, and without intending to be bound by any theory, although the percentage of hydrocarbons in the CPO 10 reactant mixture that undergoes a decomposition reaction (e.g., the decomposition reaction represented by Equation (2) )), increases with increasing C/O molar ratio in the KChO 10 reagent mixture, some hydrocarbons can undergo a decomposition reaction to carbon (C) and H ₂ even at relatively low C/O molar ratios in the KChO 10 reagent mixture (for example, the molar ratio C/O in the mixture of reagents KCHO 10 is less than approximately 2:1).

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

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

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

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

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

CSC processes, CSC reactors, CSC catalysts, and CSC catalytic bed configurations suitable for use in the present invention are described in more detail in US Provisional Patent Application No. 62/522910, filed June 21, 2017 (International Application No. PCT/1B2O18/O54475 , filed June 18, 2018) entitled Improved Reactor Designs for Heterogeneous Catalytic Reactions, and in US Provisional Patent Application No. 62/521831, filed June 19, 2017 (International Application No. PCT/Ш2018/054470, filed June 18, 2018 d.) entitled An Improved Process for Syngas Production for Petrochemical Applications, each of which is incorporated herein by reference in its entirety.

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

In some aspects, the CPO reactor 100 can be characterized by at least one CPO operating parameter selected from the group consisting of CPO reactor temperature (eg, CPO catalyst bed temperature); the temperature of the CCHO supply (for example, the temperature of the mixture of CCHO reagents); target temperature of the CCHO outlet stream; pressure of the reactor (for example, the pressure of the reactor of the reactor); contact time of the CWC (for example, contact time of the CWC reactor); molar ratio C/O in

- 6 043578 mixture of reagents KChO; the molar ratio of water vapor to carbon (P/S (S/C)) in a mixture of reagents of CPO, where the molar ratio S/C means the total number of moles of water (H2O) in the mixture of reagents divided by the total number of moles of carbon (C) of hydrocarbons in mixtures of reagents; and their combinations. As used herein, the temperature of the CPO effluent stream is the temperature of the synthesis gas (e.g., CPO reactor effluent 15, synthesis gas effluent; synthesis gas 17; synthesis gas 18) measured at the point where the synthesis gas exits KChO reactor (KChO 100 reactor), for example, the synthesis gas temperature measured at the outlet of the KChO reactor, the temperature of the outlet synthesis gas stream, the temperature of the outlet synthesis gas stream. For purposes of the present disclosure, the CSF effluent temperature (eg, the target CSF effluent temperature) is considered an operating parameter. As will be appreciated by one skilled in the art and with the help of this description, the selection of operating parameters for the CSF reactor, such as the CSF feed temperature; CCH pressure; CWC contact time; molar C/O ratio in the mixture of CCHO reagents; molar ratio P/S in the mixture of CCHO reagents; etc. determines the temperature of the outlet stream of synthesis gas (for example, the outlet stream of the KChO 15 reactor, the outlet stream of synthesis gas; synthesis gas 17; synthesis gas 18), as well as the composition of the outlet stream of synthesis gas (for example, the outlet stream of the KChO 15 reactor, the outlet stream synthesis gas; synthesis gas 17; synthesis gas 18). In addition, as one skilled in the art will appreciate and with the benefit of the present disclosure, monitoring the temperature of the CSF effluent stream can provide feedback for changes in other operating parameters (e.g., CSF feed temperature; CSF pressure; CSF contact time; C molar ratio /O in the mixture of CSC reagents; molar ratio of P/S in the mixture of CSC reagents; etc.) as necessary to ensure that the temperature of the CSC effluent stream corresponds to the target temperature of the CSC effluent stream. In addition, as will be understood by one skilled in the art and with the aid of this description, the target CSF effluent temperature is the desired CSF effluent temperature, and the CSF effluent temperature (e.g., the measured CSF effluent temperature, the actual effluent temperature) CCHO flow) may or may not coincide with the target temperature of the CCHO outlet stream. In aspects where the temperature of the CSF effluent stream differs from the target temperature of the CSF effluent stream, one or more operating parameters of the CSF (e.g., CSF supply temperature; CSF pressure; CSF contact time; C/O molar ratio of the CSF reagent mixture; P/M molar ratio C in the mixture of CSC reagents; etc.) can be adjusted (for example, changed) so that the temperature of the CSC effluent stream corresponds to (for example, is the same, coincides with) the target temperature of the CSC effluent stream. The CPO reactor 100 can be operated at any suitable operating parameters that can provide synthesis gas of the desired composition (eg, synthesis gas with a desired H2/CO molar ratio; synthesis gas with a desired CO2 content, etc.).

The CPO reactor 100 may have a CPO feed temperature of about 25 to 600, or about 25 to 500, or about 25 to 400, or about 50 to 400, or about 100 to 400°C. In aspects where the CPO reactant mixture contains water vapor, the CPO feed temperature may reach about 600, or about 575, or about 550, or about 525°C. In aspects where the CPO reactant mixture does not contain steam, the CPO feed temperature may reach about 450, or about 425, or about 400, or about 375°C. The CSF reactor 100 may be characterized by a CSF effluent temperature (e.g., a target CSF effluent temperature) equal to or greater than about 300, about 600, about 700°C, about 750, about 800, about 850, or about 300 to 1600, or approximately 600 to 1400, or approximately 600 to 1300, or approximately 700 to 1200, or approximately 750 to 1150, or approximately 800 to 1125, or, on the other hand, approximately 850 up to 1100°C.

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

The CPO reactor 100 can be operated at any suitable temperature condition that can provide synthesis gas of the desired composition (eg, synthesis gas with a desired H2CO molar ratio; synthesis gas with a desired CO2 content, etc.). The KChO 100 reactor can operate under adiabatic conditions, non-adiabatic conditions, isothermal conditions, nearly isothermal conditions, etc. As used herein, the term non-adiabatic conditions refers to process conditions in which the reactor is subjected to external heat exchange or heat transfer (e.g., the reactor is heated or the reactor is cooled), which may be direct heat exchange and/or not

- 7 043578 direct heat exchange. As will be appreciated by one skilled in the art and from this description, the terms direct heat transfer and indirect heat transfer are known to one skilled in the art. In contrast, the term adiabatic conditions refers to process conditions in which the reactor is not subject to external heat exchange (eg, the reactor is not heated or the reactor is not cooled). Typically, external heat exchange refers to an external heat exchange system (eg, cooling system, heating system) that requires energy input and/or output. As one skilled in the art will appreciate and with the benefit of this description, external heat transfer can also result from heat loss from the catalyst (or reactor) bed due to radiative heat transfer, conduction, convection heat transfer, and the like, or combinations thereof. For example, the catalyst bed may participate in heat exchange with the external environment and/or with the reactor zones upstream and/or downstream of the catalyst bed.

As used herein, the term isothermal conditions refers to process conditions (e.g., CPO operating parameters) that allow the temperature of the reactor and/or catalyst bed to be maintained substantially constant (e.g., isothermal temperature), which can be defined as a temperature that varies less than approximately ±10, approximately ±9, approximately ±8, approximately ±7, approximately ±6, approximately ±5, approximately ±4, approximately ±3, approximately ±2 or approximately ±1°C throughout the reactor and/or catalyst bed, respectively. Additionally, as used herein, the term isothermal conditions refers to process conditions (e.g., CPO operating parameters) effective to produce synthesis gas of the desired composition (e.g., desired _H2 /CO molar ratio, desired CO2 content, etc. ), where isothermal conditions include a temperature change of less than about ±10°C throughout the reactor and/or catalyst bed. The KCHO 100 reactor can be operated at any suitable operating parameters that can provide isothermal conditions.

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

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

In one aspect, the method disclosed in this invention may include conducting a CPO reaction under near isothermal conditions to produce synthesis gas, where near isothermal conditions include a temperature change of less than about ±100°C throughout the reactor and/or catalyst bed. The KCHO 100 reactor can be operated at any suitable operating parameters that can provide near isothermal conditions. Near isothermal conditions can be achieved by a number of process and catalyst variables such as temperature (e.g. heat exchange or heat transfer), pressure, gas flow rate, reactor configuration, catalyst bed configuration, catalyst bed composition, reactor cross-sectional area, gas staging , gas supply injection, gas supply composition, etc., or combinations thereof. Generally, and without intending to be bound by any theory, the terms heat transfer or heat exchange refer to thermal energy exchanged or transferred between two systems (for example, two reactors such as a CPR reactor and a cracking reactor), and the terms heat transfer or heat exchange are used interchangeable in the invention.

In some aspects, achieving a target CSF effluent temperature and/or near isothermal conditions can be achieved through heat exchange or heat transfer. Heat exchange may involve heating the reactor or cooling the reactor. In one aspect, achieving a target CSF effluent temperature and/or near isothermal conditions can be achieved by cooling the reactor. In another aspect, achieving a target CSF effluent temperature and/or near isothermal conditions can be achieved by heating the reactor. In some

- 8 043578 aspects, achieving the target temperature of the CPO outlet stream and/or near isothermal conditions can be achieved by direct heat exchange and/or indirect heat exchange. As will be appreciated by one skilled in the art and from this description, the terms direct heat transfer and indirect heat transfer are known to one skilled in the art. Heat transfer may include external heat exchange, external coolant cooling, reaction cooling, liquid nitrogen cooling, cryogenic cooling, electrical heating, electric arc heating, microwave heating, radiation heating, natural gas combustion, solar heating, infrared heating, use of a diluent in the COC reagent mixture, and etc., or combinations thereof. For example, reaction cooling can be accomplished by conducting an endothermic reaction in a cooling coil/jacket associated with the reactor (eg, located within the reactor).

In some aspects, achieving a target CSF effluent temperature and/or near isothermal conditions can be achieved by removing process heat from the CSF reactor. In other aspects, achieving a target CSF effluent temperature and/or near isothermal conditions can be achieved by introducing heat into the CSF reactor. As will be appreciated by one skilled in the art and with the help of this description, the CSF reactor may require both heating and cooling to achieve a target CSF effluent temperature and/or near isothermal conditions.

In one aspect, heat exchange or heat transfer may include introducing a cooling agent, such as a diluent, into a reactor (e.g., a KCHO 100 reactor) to reduce the temperature of the reactor and/or the temperature of the catalyst bed, while increasing the temperature of the cooling agent and/or changing the phase of the cooling agent . The cooling agent may be reactive or inert. The coolant may be in a liquid and/or vapor state. As will be appreciated by one skilled in the art and by reference to this description, the coolant may act as a flame retardant, for example by lowering the temperature within the reactor, changing the composition of the gas mixture, reducing the combustion of hydrocarbons to CO2, and the like.

In some aspects, the CPO reactant mixture 10 may further comprise a diluent, wherein the diluent helps achieve a target CPO effluent temperature and/or near isothermal conditions through heat exchange as disclosed herein. The diluent may contain water, steam, inert gases (eg, argon), nitrogen, carbon dioxide, etc., or combinations thereof. Typically, the diluent is inert to the COC reaction, for example, the diluent does not participate in the COC reaction. However, as one skilled in the art will appreciate and with the benefit of this disclosure, some diluents (e.g., water, steam, carbon dioxide, etc.) may undergo chemical reactions other than the CPO reaction within the reactor and can change the composition of the resulting synthesis gas, as will be described in more detail below in this invention; however, other diluents (for example, nitrogen (N), argon (Ar)) may not participate in reactions that change the composition of the resulting synthesis gas. As will be appreciated by one skilled in the art and with the benefit of the present disclosure, a diluent can be used to change the composition of the resulting synthesis gas. The diluent may be present in the KCHO 10 reagent mixture in any suitable amount.

In one aspect, achieving a target CPO effluent temperature and/or near isothermal conditions can be achieved by removing process heat (Q _out ) from the CPO reactor 100, for example by cooling the CPO reactor 100, for example by heating the cracking reactor and/or heating water for steam production. As one skilled in the art will appreciate and with the benefit of this description, a positive value of Q coming out (in the direction of arrow 13) means that heat is being transferred from that particular reactor, for example, that particular reactor is being cooled. For example, Qout 13 in FIG. 1-3 indicates that heat is transferred from the CPO reactor 100 (eg, the CPO reactor 100 is cooled), for example, to a cracking process and/or a steam production process, respectively. As will be understood by one skilled in the art, and with the aid of this description, a positive value of Q going in (in the direction of arrow 13') means heat transferred to a particular system/assembly/reactor, e.g., that particular system/assembly/reactor heated.

In some aspects, heat transfer may include cooling the CPO reactor 100 while simultaneously heating a cracking reactor (eg, the cracking reactor in cracker 600), where the cracking reactor may optionally produce ethylene by cracking ethane. In one aspect, the cracker feed 60 may be fed to a cracking reactor, wherein the cracker feed includes second hydrocarbons such as alkanes (eg, ethane, propane, butanes, naphtha, and the like, or combinations thereof); wherein at least a portion of the second hydrocarbons undergo an endothermic cracking reaction in a cracking reactor to form a cracking reactor product stream; and wherein the cracking reactor product stream contains olefins (eg, ethylene), hydrogen, and unreacted alkanes. In other aspects, heat transfer may include cooling the CCH reactor 100 while heating water to produce steam. In some aspects, the KCHO reactor 100 may be a water-cooled reactor. The KChO 100 reactor may have internal and/or external cooling elements

- 9 043578 you for converting water into water vapor. For example, water-to-steam pipelines can be used as internal cooling elements in a KCHO 100 reactor, where some of the process heat from the KCHO reaction heats the water inside such pipelines, thereby converting the water into steam. As another example, an external cooling jacket can be used to convert water into steam. Integration of the CPO process with cracking and/or steam production processes is described in more detail in US provisional patent applications No. 62/787620, filed January 2, 2019, entitled Catalyst Activity Management in Catalytic Partial Oxidation, and No. 62/810629, filed February 26 2019 entitled An Integrated Process for the Production of Syngas and Olfins by Catalytic Partial Oxidation and Cracking), each of which is incorporated by reference in its entirety.

In some aspects, heat transfer (e.g., heat transfer that achieves a target CPO effluent temperature and/or near isothermal conditions) eliminates heat transfer to the synthesis gas effluent (e.g., CPO 15 reactor effluent, synthesis gas effluent, synthesis gas 17; synthesis gas 18) after the effluent stream of synthesis gas (for example, the effluent stream of the KChO reactor 15, the effluent stream of synthesis gas; synthesis gas 17; synthesis gas 18) leaving the KChO reactor (for example, the KChO reactor 100). In other aspects, heat transfer (e.g., heat transfer that achieves a target CPO effluent temperature and/or near isothermal conditions) may include heat transfer with a synthesis gas effluent stream (e.g., CPO 15 reactor effluent, synthesis gas effluent, synthesis gas 17 by synthesis gas 18) after the effluent stream of synthesis gas (for example, the effluent stream of the KChO reactor 15, the effluent stream of synthesis gas; synthesis gas 17; synthesis gas 18) leaving the KChO reactor (for example, the KChO reactor 100).

The CPR reactor 100 may be characterized by a CPR pressure (e.g., reactor pressure measured at the outlet or outlet of the reactor) equal to or greater than about 1, about 10, about 20, about 25, about 30, about 35 bar(g), about 40 or about 50 bar(g), or, on the other hand, less than about 30, about 25, about 20 or about 10, or about 1 to 90, or about 1 to 70, or about from 1 to 40, or from about 1 to 30, or from about 1 to 25, or from about 1 to 20, or from about 1 to 10, or from about 20 to 90, or from about 25 to 85, or, on the other hand, from approximately 30 to 80 bar(g).

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

All operating parameters of the CFC disclosed in the invention are applicable in all embodiments disclosed in the invention, unless otherwise indicated. As one skilled in the art will appreciate and with the help of this description, each operating parameter of the CPR can be adjusted to produce a desired quality of synthesis gas, such as a synthesis gas of a desired composition (for example, a synthesis gas with a desired H ₂ molar ratio /CO, synthesis gas with the desired CO ₂ content, etc.). For example, the operating parameters of the EPC may be adjusted to provide increased H ₂ content of synthesis gas F. As another example, the operating parameters of the EPC may be adjusted to provide reduced CO ₂ content of synthesis gas F. As another example, the operating parameters The NOR can be adjusted to produce a reduced content of unreacted hydrocarbons (eg unreacted CH ₄ ) in the synthesis gas.

In one aspect, the CCO reagent mixture 10 may further comprise a diluent such as water and/or steam, CO ₂ , N 2 , argon, etc. The CPO reactor 100 can be operated under any suitable operating conditions (e.g., CPO operating parameters) that can provide the CPO reactor effluent (e.g., synthesis gas) of the desired composition (e.g., desired H2/CO molar ratio; desired CO2 content, etc.). d.); for example, the KCHO reactor 100 can be operated by introducing water and/or steam and optionally CO ₂ into the KCHO reactor 100.

When carbon is present in the reactor (for example, coke; C resulting from the reaction

- 10 043578 decomposition represented by equation (2)), the diluent water and/or steam can react with carbon and generate additional amounts of CO and H ₂ , for example, as represented by equation (3):

C+H ₂ O # CO+H ₂ (3)

As will be appreciated by one skilled in the art and with the benefit of the present description, the presence of water and/or steam in the CPO reactor 100 can reduce the amount of coke in the CPO reactor 100.

Additionally, as one skilled in the art will appreciate and with the benefit of the present disclosure, water and/or steam can be used to change the composition of the resulting synthesis gas in the CPO reactor effluent (eg, synthesis gas). Water vapor can react with methane, for example, as represented by equation (4):

CH4+H ₂ O CO+ZN ₂ (4)

In one aspect, a diluent containing water and/or steam can increase the H ₂ content of the resulting CPO reactor effluent (eg, synthesis gas). For example, in aspects where the CPO reactant mixture 10 contains the diluent water and/or steam, the resulting CPO reactor effluent (e.g., synthesis gas) may be characterized by a molar ratio of H ₂ to CO that is increased relative to the molar ratio of H ₂ to the CO of the effluent stream of the CPO reactor (for example, synthesis gas), obtained in an otherwise similar process, carried out with a mixture of reagents containing hydrocarbons and oxygen, without the diluent of water and/or water vapor. Without intending to be bound by any theory, the reforming reaction (eg, represented by equation (4)) is believed to be an endothermic reaction. The reforming reaction represented by Equation (4) can remove a portion of the process heat (eg, the heat produced by the exothermic CPO reaction represented by Equation (1)).

In the presence of water and/or steam in the reactor, KCHO 100 CO can react with water and/or steam to form CO2 and _H2 through a water gas shift (WGS) reaction, for example, as represented by equation (5):

CO + H ₂ O # CO ₂ + H ₂ (5)

Although the WGS reaction can increase the H2/CO molar ratio of the synthesis gas produced in the KChO 100 reactor, it also produces CO ₂ .

In one aspect, the CPO reactor 100 can be operated at a P/S molar ratio of the CPO 10 reactant mixture of less than about 2.4:1, about 2:1, about 1.5:1, about 1:1, about 0.8: 1, about 0.5:1, or, on the other hand, from about 0.01:1 to less than 2.4:1, or from about 0.05:1 to 2:1, or from about 0 .1:1 to 1.5:1, or about 0.15:1 to 1:1 or, on the other hand, about 0.2:1 to 0.8:1. As will be appreciated by one skilled in the art and by reference to this description, the steam that is introduced into the reactor for use as a diluent in the CPO reaction disclosed in the invention is present in significantly smaller quantities than the quantities of steam used in the processes steam reforming (eg, SMR), and as such, the synthesis gas production method disclosed in this invention can produce synthesis gas with lower amounts of H ₂ compared to the amounts of H ₂ in synthesis gas produced by SMR.

The P/S molar ratio of the CPO reactant mixture 10 can be adjusted based on the desired CPO effluent temperature (e.g., target CPO effluent temperature) to increase (e.g., maximize) the H ₂ content of the CPO reactor effluent (e.g., synthesis gas ). As will be appreciated by one skilled in the art and from this description, reaction (4), which consumes water vapor in the CPO reactor, is preferred over the water gas shift (WGS) reaction (5) in the CPO 100 reactor because reaction (4) allows the _H2 content of the CPO reactor effluent (e.g., synthesis gas) to be increased, as well as the M ratio of the CPO reactor effluent (e.g., synthesis gas), where the M ratio is a molar ratio, defined as ( H ₂ -CO ₂ )/(CO+CO ₂ ). In addition, as one skilled in the art will appreciate and from this description, reaction (4) converts water and CO into both H ₂ and CO ₂ .

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

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

- 11 043578 water and/or water vapor in the KChO 100 reactor allows the KChO 100 reactor to be operated at relatively high pressures.

As will be appreciated by one skilled in the art and with the benefit of this description, the introduction of water and/or steam into the CPO reactor 100 can result in an increase in the amount of unreacted hydrocarbons in the CPO reactor effluent (eg, synthesis gas). Additionally, as will be appreciated by one skilled in the art and with the benefit of this description, methanol production processes typically allow limited amounts of unreacted hydrocarbons in the synthesis gas.

In some aspects, the CPO reactor effluent stream (e.g., synthesis gas) may contain less than about 7.5, or less than about 5, or, alternatively, less than about 2.5 mole percent hydrocarbons (e.g., unreacted hydrocarbons). , unreacted CH4). In such aspects, the CPO reactor effluent can be produced in a CPO process that uses water and/or steam. In such aspects, the CPO reactor effluent can be used for methanol synthesis.

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

C+O ₂ CO ₂ (6)

When carbon is present in the reactor (e.g., coke; C produced by the decomposition reaction as represented by equation (2)), CO ₂ (e.g., introduced into the KCHO 100 reactor as part of the KCHO 10 reactant mixture and/or produced by the reaction represented by equation (6)) can react with C, for example, as represented by equation (7):

C+CO ₂ # 2CO (7), thereby reducing the amount of CO ₂ in the resulting CPO reactor effluent (for example, in synthesis gas). As will be appreciated by one skilled in the art and with the aid of this description, the presence of CO ₂ in the CPO 100 reactor can reduce the amount of coke in the CPO 100 reactor.

Additionally, CO2 can react with CH4 in a dry reforming reaction, for example, as represented by equation (8):

CH ₄ +CO ₂ 2CO+2H ₂ (8), thereby reducing the amount of CO ₂ in the resulting effluent stream of the CPO reactor (for example, in synthesis gas). Without intending to be bound by any theory, the dry reforming reaction (eg, represented by equation (8)) is believed to be an endothermic reaction (eg, a highly endothermic reaction). The dry reforming reaction can remove a portion of the process heat (eg, the heat produced by the exothermic CPO reaction, such as represented by equation (1)).

In one aspect, the CO2 containing diluent can increase the CO content of the resulting CPO reactor effluent (eg, synthesis gas). For example, in aspects where the CPO reactant mixture 10 contains a CO ₂ diluent, the CPO reactor effluent (e.g., synthesis gas) may be characterized by a molar ratio of H ₂ to CO that is reduced compared to the molar ratio of H 2 to CO in the reactor effluent. COC (for example, in synthesis gas) obtained in an otherwise similar process, carried out with a mixture of reagents containing hydrocarbons and oxygen, without the diluent CO ₂ . Without intending to be bound by any theory, it is believed that CO ₂ can react with coke inside the KCHO 100 reactor and generate additional CO, for example, as represented by equation (7). Additionally, and without intending to be bound by any theory, it is believed that CO ₂ may participate in the dry reforming reaction of methane, thereby generating additional amounts of 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 H ₂ , which leads to the formation of additional quantities of CO and water.

The use of CO2 in the KChO 10 reactant mixture can advantageously reduce the amount of hydrocarbons converted to CO ₂ in the KChO 100 reactor, for example, as a result of a combustion reaction. Without intending to be bound by any theory, and according to Le Chatelier's principle, the equilibrium of a dry hydrocarbon reforming reaction will shift toward consuming CO ₂ with an increase in the amount of CO ₂ in the reactant mixture, allowing more hydrocarbons to be converted into synthesis gas.

As one skilled in the art will appreciate, and with the benefit of the present disclosure, CO2-depleted synthesis gas has a higher M ratio than CO2-rich synthesis gas: the lower the CO ₂ content of the synthesis gas, the higher the M synthesis gas ratio. gas. The CO ₂ content of the synthesis gas can be adjusted, as described in more detail in co-pending US Provisional Patent Application No. 62/787574, filed January 2, 2019, entitled Hydrogen Enrichment in Syngas Produced via Catalytic Partial Oxidation); which is incorporated herein by reference in its entirety.

In one aspect, the CPO reactor effluent (e.g., synthesis gas) can be recovered from

- 12 043578 of the KChO 100 reactor, where the outlet stream of the KChO reactor (for example, synthesis gas) contains H2, CO, water,

CO2 and unreacted hydrocarbons (eg, unreacted first hydrocarbons, unreacted methane, optionally unreacted second hydrocarbons, optionally unreacted C4 ₊ hydrocarbons).

According to the configuration of the methanol production system 1000 in FIG. 1, the effluent stream of the KCHO reactor 15 may contain H2, CO, CO2, water and unreacted hydrocarbons (for example, first hydrocarbons and optionally C ₄₊ hydrocarbons). The effluent of the CPO reactor 15, as disclosed herein, may have an H ₂ /CO molar ratio of greater than about 1.6, or greater than about 1.7, or greater than about 1.8, or greater than about 1.9 or, on the other hand, greater than about 2.0. In some aspects, the effluent of the CPO reactor 15 as disclosed herein may have a H2/CO molar ratio of about 1.6 to 2.3, or about 1.7 to 2.2, or, alternatively, approximately 1.8 to 2.1. In one aspect, the effluent stream of the CPO reactor 15 can be characterized by an M ratio equal to or greater than about 1.6, or equal to or greater than about 1.7, or equal to or greater than about 1.8, or from about 1 .6 to 2.3, or approximately 1.7 to 2.2 or, on the other hand, approximately 1.8 to 2.2.

According to the configuration of the methanol production system 2000 in FIG. 2, synthesis gas 17 may contain H ₂ , CO, CO ₂ , water and unreacted hydrocarbons (eg, methane, first hydrocarbons, optionally second hydrocarbons, optionally C ₄₊ hydrocarbons). Synthesis gas 17 as described herein may have a H2/CO molar ratio of greater than about 1.7, or greater than about 1.8, or greater than about 1.9, or greater than about 2 .0 or, on the other hand, greater than about 2.1. In one aspect, the synthesis gas 17 can be characterized by an M ratio equal to or greater than about 1.7, or equal to or greater than about 2.0, or equal to or greater than about 2.1, or from about 1. 7 to 2.4, or approximately 1.8 to 2.2 or, on the other hand, approximately 1.9 to 2.1.

According to the configuration of the methanol production system 3000 in FIG. 3, synthesis gas 18 may contain H ₂ , CO, CO ₂ , water, and unreacted hydrocarbons (eg, first hydrocarbons, optionally methane, optionally second hydrocarbons, optionally C ₄₊ hydrocarbons). The synthesis gas 18 described in this invention may have a H ₂ /CO molar ratio of greater than about 1.7, or greater than about 1.8, or greater than about 1.9, or greater than about 2 .0 or, on the other hand, greater than about 2.1. In one aspect, the synthesis gas 18 can be characterized by an M ratio equal to or greater than about 1.7, or equal to or greater than about 2.0, or equal to or greater than about 2.1, or from about 1. 7 to 2.4, or approximately 1.8 to 2.2 or, on the other hand, approximately 1.9 to 2.1.

In some aspects, the CPO reactor effluent and/or synthesis gas (e.g., CPO reactor effluent 15, synthesis gas 17, synthesis gas 18) can be used in a downstream process (e.g., methanol production) without additional processing for enrichment of hydrogen (H ₂ ) reactor effluent and/or synthesis gas, respectively.

In other aspects, the CPO reactor effluent and/or synthesis gas (e.g., CPO reactor effluent 15, synthesis gas 17, synthesis gas 18) can be further processed before using the CPO reactor effluent and/or synthesis gas ( for example, KCHO reactor effluent 15, synthesis gas 17, synthesis gas 18) in a downstream process such as methanol production. The KChO reactor effluent and/or synthesis gas (for example, the KChO reactor effluent 15, synthesis gas 17, synthesis gas 18) can be processed to enrich it in H ₂ content; for example, by contacting the KCHO reactor effluent and/or synthesis gas (for example, the KCHO reactor effluent 15, synthesis gas 17, synthesis gas 18) with additional (for example, auxiliary) H ₂ (for example, with a hydrogen stream 51; hydrogen-rich stream 70; hydrogen-rich stream 75).

As will be appreciated by one skilled in the art and with the benefit of the present description, although the CPO reactor effluent and/or synthesis gas (e.g., CPO reactor effluent 15, synthesis gas 17, synthesis gas 18) can be characterized with an H ₂ /CO molar ratio greater than about 1.8, which may be acceptable for methanol synthesis, CPO reactor effluent and/or synthesis gas (e.g., CPO reactor effluent 15, synthesis gas 17, synthesis gas 18) can be processed to further increase H2 content. Additionally, as one skilled in the art will appreciate and with the help of this description, the CPO reactor effluent and/or synthesis gas (e.g., CPO reactor effluent 15, synthesis gas 17, synthesis gas 18) may be undergo minimal processing, such as recovery of unreacted hydrocarbons, diluent, water, etc., without significantly changing the H2/CO molar ratio in the CPO reactor effluent and/or synthesis gas (for example, in the CPO reactor effluent 15, synthesis 13 043578 gas 17, synthesis gas 18). For example, water can be condensed and separated from the CPO reactor effluent and/or synthesis gas (eg, CPO reactor effluent 15, synthesis gas 17, synthesis gas 18), for example, in a condenser.

In one aspect, the method described in the invention may further comprise (i) recovering at least a portion of the unreacted hydrocarbons (e.g., unreacted first hydrocarbons, optionally unreacted methane, optionally unreacted second hydrocarbons, optionally unreacted C4 ₊ hydrocarbons) from the CPO reactor effluent stream and/or synthesis gas (for example, the effluent of the KChO reactor 15, synthesis gas 17, synthesis gas 18) to obtain recovered hydrocarbons; and (ii) recycling at least a portion of the recovered hydrocarbons in the CPO reactor 100. As will be appreciated by one skilled in the art and with the benefit of this description, although fairly high conversions can be achieved in CPO processes (e.g., conversions equal to or greater than about 90%), the unreacted hydrocarbons may be recovered and recycled back to the CCH reactor 100. In some aspects, at least a portion of the recovered hydrocarbons may be used as fuel (e.g., to preheat the CCH reactant mixture; to heat the reactor cracking) and/or fed to cracking unit 600.

In one aspect, the CPO reactor effluent and/or synthesis gas (e.g., CPO reactor effluent 15, synthesis gas 17, synthesis gas 18) may have a CO2 content of less than about 7, or less than about 6, or less than about 5, or less than about 4, or less than about 3, or less than about 2, or less than about 1, or from about 0.1 to 7, or from about 0.25 to 5 or, on the other hand, from about 0.5 to 3 mol.% For example, the side reactions represented by equations (7) and/or (8) can lead to the CPO reactor effluent and/or synthesis gas (for example , the effluent of the KChO reactor 15, the synthesis gas 17, the synthesis gas 18), which has a CO2 content of approximately 0.1 to 7 mol.%

In one aspect, the CPO reactor effluent and/or synthesis gas (e.g., CPO reactor effluent 15, synthesis gas 17, synthesis gas 18) may have a hydrocarbon content of less than about 10, or less than about 7.5. or less than about 5, or less than about 4, or less than about 3, or less than about 2, or less than about 1, or less than about 0.1, or, on the other hand, less than about 0.01 mol.%

In some aspects, such as shown in FIG. 1 and 3, the process described in the invention may include the step of feeding a cracker feed 60 to a cracker 600 to produce a cracker product stream 65, a hydrogen-rich stream 70, and a hydrocarbon recovery stream 71. In other aspects, for example, as shown in fig. 2, the method described in the invention may include the step of feeding cracker feed 60 to cracker 600 to produce cracker product stream 65, hydrogen-lean stream 72, and hydrocarbon recovery stream 71.

In one aspect, cracker 600 includes a cracking reactor and a separation unit. In some aspects, such as shown in FIG. 1 and 3, cracker 60 feed may be introduced into a cracker reactor to produce a cracker reactor product stream, where at least a portion of the cracker reactor product stream may be introduced into a separation unit to produce a hydrogen-rich cracker product stream 65 stream 70 and hydrocarbon recovery stream 71. In other aspects, for example, as shown in FIG. 2, cracker feed 60 may be introduced into a cracker reactor to produce a cracker product stream, where at least a portion of the cracker reactor product stream may be introduced into a separation unit to produce a cracker product stream 65, a hydrogen-poor stream 72, and a hydrocarbon extraction 71.

Cracker unit 600 may include any suitable cracker unit configured to convert saturated hydrocarbons (eg, alkanes) to olefins. For example, cracker 600 may include any suitable cracking reactor configured to convert cracker 60 feedstock containing second hydrocarbons (eg, saturated hydrocarbons, alkanes) into a cracker reactor product stream containing olefins. Non-limiting examples of cracking units (e.g., cracking reactors) suitable for use in the present invention include a thermal cracking unit (e.g., a thermal cracking reactor), a catalytic cracking unit (e.g., a catalytic cracking reactor), a steam cracking unit (e.g., a steam cracking reactor), cracking), etc., or combinations thereof. As will be appreciated by one skilled in the art and by reference herein, thermal cracking processes, catalytic thermal processes, steam cracking processes, and the like. or combinations thereof are known to one skilled in the art.

Without intending to be bound by theory, cracking is believed to refer to an endothermic reaction that converts alkanes to olefins and hydrogen. Typically, as one skilled in the art will appreciate and by reference to this description, heat (eg, thermal energy) must be supplied to the cracking reactor to effect the cracking reaction that produces olefins. In some aspects, at least a portion of the heat that the cracking reactor uses can be provided by the CCC reactor 100, as disclosed in this invention. As will be appreciated by one skilled in the art, and with the help of this description, the process heat of the KCHO reactor 100 may not be sufficient to provide all the heat required for the cracking reactor. In one aspect, a fuel stream may be burned to provide additional heat needed for the cracking reactor.

In some aspects, the cracking reactor may include a gas cracking unit (eg, a gas cracking reactor). For example, in aspects where the feedstock of cracker 60 contains ethane and/or propane, the cracking reactor may include a gas cracker unit.

In other aspects, the cracking reactor may include a fluid cracking unit (eg, a fluid cracking reactor). For example, in aspects where the feedstock of cracker 60 contains C ₄₊ hydrocarbons, such as butanes, naphtha fractions (eg, naphtha feedstock), and the like, or combinations thereof, the cracking reactor may include a fluid cracking unit.

In one aspect, second hydrocarbons suitable for supply to a cracker as disclosed herein may include saturated hydrocarbons such as alkanes. Non-limiting examples of second hydrocarbons suitable for supply to a cracker as disclosed herein may include alkanes, ethane, propane, butanes, naphtha, and the like, or combinations thereof. In some aspects, the first hydrocarbons and the second hydrocarbons may be the same. For example, the feed naphtha can be introduced into the cracking reactor, as well as into the CPO reactor. In other aspects, the first hydrocarbons and the second hydrocarbons may be different. As another example, ethane (eg, second hydrocarbons) may be introduced into a cracking reactor, and methane (eg, first hydrocarbons) may be introduced into a COC reactor.

In some aspects, the cracker separation unit 600 may include any suitable separation unit that is configured to separate the cracking reactor product stream into a cracker product stream 65, a hydrogen-rich stream 70, and a hydrocarbon recovery stream 71. In other aspects, the cracker separation unit 65 unit 600 may include any suitable separation unit that is configured to separate the cracking reactor product stream into a cracker product stream 65, a hydrogen-lean stream 72, and a hydrocarbon recovery stream 71.

The cracking reactor product stream contains olefins (eg, ethylene, but also propene, butenes, etc.), H ₂ , methane, and unreacted secondary hydrocarbons (eg, alkanes, ethane, propane, butanes, naphtha, etc., or their combinations). For example, the separation unit of cracker 600 may employ gas-liquid separation, distillation, cryogenic distillation, extractive distillation, selective adsorption, selective absorption, and the like, or combinations thereof. The separation unit of the cracker 600 may include a gas-liquid separator, a distillation column, a cryogenic distillation column, a tray and/or packed separation column, a compressor, a heat exchanger, a cooling tower, a pressure swing adsorption (PSA) unit, etc.

The cracker separation unit 600 may include a gas-liquid separator. In one aspect, the cracking reactor product stream may be introduced into a gas-liquid separator to produce a hydrocarbon recovery stream (eg, hydrocarbon recovery stream 71) and a first gas stream. The gas-liquid separator of cracker 600 may include any suitable gas-liquid separator configured to separate the cracking reactor product stream into a liquid stream (eg, a hydrocarbon recovery stream, such as hydrocarbon recovery stream 71) and a first gas stream. For example, the gas-liquid separator of cracker 600 may include a vapor-liquid separator, a flash drum, a gas separator, a condensate collector, a compressor inlet separator, etc. The liquid stream may be recovered from the gas-liquid separator of the cracker 600 as a bottoms stream. The liquid stream recovered from the gas-liquid separator of cracker 600 may contain C4+ hydrocarbons such as butanes, butenes, butadiene, pentane, pentenes, hexanes, hexenes, benzene, toluene, xylene, and the like, or combinations thereof. The first gas stream may be recovered from the gas-liquid separator of the cracker 600 as an overhead stream. The first gas stream recovered from the gas-liquid separator of cracker 600 may contain H ₂ , methane, ethane, ethylene, propane, propylene, CO 2 , CO, and the like, or combinations thereof. As will be appreciated by one skilled in the art and with the aid of this description, the composition of the cracking reactor product stream, the composition of the liquid stream, and the composition of the first gas stream depend on a variety of factors, such as the feed composition of the cracker 60, the type of cracker, the operating cracking unit conditions, etc.

In some aspects, at least a portion of the olefins and/or aromatic hydrocarbons may be recovered from the liquid stream to produce olefins and/or aromatic hydrocarbons, respectively, and a hydrocarbon recovery stream 71. In one aspect, at least a portion 71a of the recovery stream hydrocarbons 71 may be fed to the reactor reactor 100. In one aspect, at least a portion of the hydrocarbon recovery stream 71 may be used as fuel (e.g., to preheat the mixture of reactants of the reactor; to heat the cracking reactor) and/or fed to the cracker - setting 600.

- 15 043578

In one aspect, the first gas stream may be further subjected to one or more separation steps to recover olefins (eg, the product stream of cracker 65). In one aspect, the first gas stream may be separated into a second gas stream and a product stream of cracker 65, for example, using any suitable separation method such as distillation, cryogenic distillation, extractive distillation, selective adsorption, selective absorption, and the like, or their combinations. The product stream of cracker 65 may contain olefins such as ethylene and/or propylene. In one aspect, the second gas stream may comprise H2, _CH4 , ethane, propane, CO2, CO, and the like, or combinations thereof.

In some aspects, the product stream of cracker 65 may contain olefins such as ethylene, propene, butenes, and the like, or combinations thereof. For example, the product stream of cracker 65 may contain olefins that were recovered from the first gas stream. In other aspects, the product stream of cracker 65 _{may further contain other unsaturated hydrocarbons, such as butadiene, C5_6 olefins , C6_8} aromatic hydrocarbons, etc. For example, the product stream of cracker 65 may contain olefins and other unsaturated hydrocarbons that have been recovered from the liquid stream. The product stream of cracker 65 may also be subjected to additional purification or separation processes, for example, to recover one or more components. For example, ethylene can be recovered from the product stream of cracker 65, which ethylene can be further used in the polymerization process.

In aspects where the cracking reactor includes a gas cracker, such as an ethane cracker and/or a propane cracker, the second gas stream may contain fairly large amounts of H2 (e.g., about 5 to 65, or about 15 to 60). or, alternatively, about 25 to 55 weight percent H2 based on the total weight of the second gas stream), and the second gas stream may be referred to as a hydrogen-rich stream as used herein (eg, hydrogen-rich stream 70). The hydrogen-rich stream (eg, hydrogen-rich stream 70) may contain fairly low amounts of hydrocarbons, such as methane, unreacted hydrocarbons (eg, ethane, propane), or combinations thereof. For example, a hydrogen-rich stream (e.g., hydrogen-rich stream 70) may contain from about 35 to 95, or from about 40 to 85, or alternatively from about 45 to 75 weight percent hydrocarbons (e.g., methane and optionally ethane). and/or propane) based on the total weight of the hydrogen-rich stream (eg, hydrogen-rich stream 70).

In aspects where the cracking reactor includes a fluid cracker, such as a naphtha cracker, the second gas stream may contain fairly low amounts of H2 (for example, from about 0.1 to 25, or from about 0.5 to 15 or, with on the other hand, from about 1 to 10 wt.% H ₂ based on the total weight of the second gas stream), and the second gas stream may be referred to as a hydrogen-lean stream as used herein (eg, hydrogen-lean stream 72). The hydrogen-poor stream (eg, hydrogen-poor stream 72) may contain fairly large amounts of hydrocarbons, such as methane, unreacted hydrocarbons (eg, ethane, propane), or combinations thereof. For example, a hydrogen lean stream (eg, hydrogen lean stream 72) may contain from about 75 to 99.9, or from about 85 to 99.5, or alternatively from about 85 to 99.5, or from 90 to 99 wt.% hydrocarbons (eg, methane and optionally ethane and/or propane) based on the total weight of the hydrogen-lean stream (eg, hydrogen-lean stream 72).

In one aspect, at least a portion of the hydrogen-poor stream 72 may be supplied to the CSF reactor 100. In one aspect, at least a portion of the hydrogen-lean stream 72 may be used as fuel (e.g., to preheat a mixture of CSF reactants, to heat the cracking reactor) and/or fed to the cracking unit 600.

While the present disclosure is discussed in detail in the context of a hydrogen-lean cracker recovery stream being introduced into a CPO reactor, it should be understood that any suitable hydrogen-lean stream may be introduced into a CPO reactor where such hydrogen-lean stream contains fairly low amounts of H ₂ (e.g., about 0.1 to 25, or about 0.5 to 15, or alternatively, about 1 to 10 weight percent H ₂ based on the total weight of the hydrogen-lean stream), and also quite large the amount of hydrocarbons (eg, about 75 to 99.9, or about 85 to 99.5, or about 90 to 99 weight percent hydrocarbons, based on the total weight of the hydrogen-poor stream). For example, the hydrogen-poor stream may comprise a cracker gas stream, a refinery gas stream, a fuel gas stream, fuel gas from a fuel gas header, or combinations thereof.

In one aspect, for example, as shown in FIG. 1, at least a portion 70b of the hydrogen-rich stream 70 may be introduced into a second hydrogen recovery unit 700 (e.g., a PSA unit, a membrane separation unit, a cryogenic separation unit, etc., or combinations thereof) to further replenish the H2 content. hydrogen-rich stream 70, for example, to recover H2 from hydrogen-rich stream 70.

In one aspect, for example, as shown in FIG. 1 and 3, at least part of 70c rich water

- 16 043578 a stream 70 may be introduced into the first hydrogen recovery unit 500 (eg, a PSA unit, a membrane separation unit, a cryogenic separation unit, etc., or combinations thereof) to further replenish the H2 content of the hydrogen-rich stream 70; for example, to recover H2 from the hydrogen-rich stream 70. In such an aspect, the hydrogen-rich stream 70 may be compressed before being supplied to the first hydrogen recovery unit 500. As will be appreciated by one skilled in the art, and with reference to the present description, methanol production loops operate at fairly elevated pressures (e.g., approximately 70-100 bar(g)), and how such streams (e.g., at least a portion 70c of hydrogen-rich stream 70) that are introduced into the methanol reaction loop must be compressed to satisfy pressure requirements for the methanol production loop.

In some aspects, the first hydrogen recovery assembly 500 and the second hydrogen recovery assembly 700 may be the same hydrogen recovery assembly. In other aspects, the first hydrogen extraction unit 500 and the second hydrogen extraction unit 700 may be different hydrogen extraction units.

In some aspects, at least a portion 70b of the hydrogen-rich stream 70 may be separated into a hydrogen-rich stream 75 and a hydrocarbon-rich stream 76 at a second hydrogen recovery unit 700. The hydrogen-rich stream 75 contains at least a portion of the H2 hydrogen-rich stream 70 and optionally hydrocarbons (eg, hydrocarbons that were present in the hydrogen-rich stream 70, such as methane, and optionally ethane and/or propane). The hydrocarbon-rich stream 76 contains at least a portion of the hydrocarbons (eg, methane and optionally ethane and/or propane) of the hydrogen-rich stream 70 and optionally hydrogen. In one aspect, the amount of H2 in hydrogen-rich stream 75 is greater than the amount of H2 in hydrogen-rich stream 70. In one aspect, the amount of hydrocarbons in hydrocarbon-rich stream 76 is greater than the amount of hydrocarbons in hydrogen-rich stream 70.

In one aspect, at least a portion 76a of the hydrocarbon-enriched stream 76 may be supplied to the CSF reactor 100. In one aspect, at least a portion of the hydrocarbon-enriched stream 76 may be used as a fuel (e.g., to preheat the CSF reactant mixture ; to heat the cracking reactor) and/or supplied to the cracking unit 600.

In some aspects, at least a portion 71a of the hydrocarbon recovery stream 71 and/or at least a portion of the hydrogen-rich stream 70 may be supplied to the CER reactor 100, for example, through a mixture of CRC reactants 10. The hydrocarbon recovery stream 71 and/or The hydrogen-rich stream 70 may provide additional (e.g., auxiliary) hydrocarbons to participate in the CPO reaction in the CPO reactor 100.

In other aspects, for example, as shown in FIG. 2, at least a portion 71a of the hydrocarbon recovery stream 71 and/or at least a portion of the hydrogen-poor stream 72 may be supplied to the reactor 100, for example, through a mixture of reactants of the reactor 10. The hydrocarbon recovery stream 71 and/or the hydrogen-poor stream 72 may provide additional (eg, auxiliary) hydrocarbons to participate in the CPO reaction in CPO reactor 100.

In still other aspects, for example, as shown in FIG. 3, at least a portion 71a of the hydrocarbon recovery stream 71 and/or at least a portion 76a of the hydrocarbon-enriched stream 76 may be supplied to the CER reactor 100, for example, through a mixture of CRC reagents 10. The hydrocarbon recovery stream 71 and/or enriched hydrocarbons, stream 76 may provide additional (e.g., auxiliary) hydrocarbons to participate in the CPO reaction in CPO reactor 100.

Hydrogen (H2) present in the KCHO 10 reactant mixture (e.g., hydrogen-rich stream 70, hydrogen-poor stream 72, hydrocarbon-rich stream 76) can burn in the KCHO 100 reactor in the presence of oxygen, thereby further increasing the temperature inside the KCHO 100 reactor As will be appreciated by one skilled in the art, and by reference to this description, a controlled increase in temperature within the CPR reactor (as opposed to an uncontrolled, rapidly increasing temperature) can increase the CO and H2 selectivity of the CPR process, thereby providing the resulting CPR reactor effluent. and/or synthesis gas (eg, CCHO reactor effluent 15, synthesis gas 17, synthesis gas 18) with an increased H2/CO molar ratio (eg, equal to or greater than about 2.0). Additional process heat generated in the CPO process by introducing H ₂ into the CPO reactor 100 can also be used to heat the cracking reactor, as shown in this invention. However, as will be appreciated by one skilled in the art and by reference to this description, the amount of H ₂ that can be introduced into the CPO reactor 100 is dictated (e.g., controlled) by the ability to control (e.g., the ability to regulate) the heat in the CPO reactor, to prevent uncontrollable rapidly rising temperatures.

In one aspect, the reagent mixture CCO 10 may contain H2 in an amount of less than about 20, or less than about 17.5, or less than about 15, or less than about 14, or less than about 12.5, or less than about 10 or, on the other hand, less than about 5 mol.%

In one aspect, the hydrogen-rich stream 70 may be supplied to the CPR reactor 100 in an amount effective to provide less than about 20 or, alternatively, less than about 14 mole percent H2 in the CCR reactant mixture 10.

In one aspect, the hydrogen-poor stream 72 may be supplied to the FCC reactor 100 in an amount effective to provide less than about 20 or, alternatively, less than about 14 mole percent H2 in the FCC reactant mixture 10.

In one aspect, the hydrocarbon-enriched stream 76 may be supplied to the reactor reactor 100 in an amount effective to provide less than about 20 or, alternatively, less than about 14 mole percent H2 in the reactant mixture of the reactant 10.

In aspects where a hydrocarbon recovery stream and/or a hydrogen-rich stream is introduced into the CPO reactor 100, the M ratio and/or H2/CO mole ratio of the CPO reactor 15 effluent stream may be greater than the M ratio and/or H2/CO mole ratio, respectively, synthesis gas produced in an otherwise similar process in which a mixture of CPO reactants is fed to the CPO reactor without a hydrocarbon recovery stream and/or without a hydrogen-rich stream.

In aspects where a hydrocarbon recovery stream and/or a hydrogen-poor stream is introduced into the CPO reactor 100, the M ratio and/or H2/CO molar ratio of the synthesis gas 17 may be greater than the M ratio and/or _H2 /CO molar ratio, respectively, synthesis gas produced in an otherwise similar process in which the mixture of CPO reactants is fed to the CPO reactor without the hydrocarbon recovery stream and/or without the hydrogen-poor stream.

In aspects where a hydrocarbon recovery stream and/or a hydrocarbon-enriched stream is introduced into the CPO reactor 100, the M ratio and/or H2/CO molar ratio of the synthesis gas 18 may be greater than the M ratio and/or _H2 /CO molar ratio, respectively, synthesis gas produced in an otherwise similar process in which a mixture of CPO reactants is fed to the CPO reactor without a hydrocarbon recovery stream and/or without a hydrocarbon-enriched stream.

In one aspect, at least a portion of the hydrocarbon recovery stream 71 and/or at least a portion of the hydrocarbon-lean stream 72 may be recycled to the cracking reactor, such as through cracker feed 60. In one aspect, at least a portion of the hydrocarbon recovery stream 71 and/or at least a portion of the hydrocarbon-lean stream 72 may be used as a fuel, for example, to heat a cracking reactor and/or preheat the CPO reactant mixture.

In one aspect, at least a portion of the hydrocarbon recovery stream 71 and/or at least a portion of the hydrocarbon-rich stream 76 may be recycled to the cracking reactor, for example, through cracker feed 60. In one aspect, at least a portion of the hydrocarbon recovery stream 71 and/or at least a portion of the hydrocarbon-enriched stream 76 may be used as a fuel, for example, to heat a cracking reactor and/or preheat the CPO reactant mixture.

In one aspect, at least a portion of the hydrogen-rich stream 70 can be contacted with at least a portion of the effluent stream of CPO reactor 15 to produce hydrogen-rich synthesis gas 16, for example, as shown in FIG. 1. The H2/CO molar ratio in the hydrogen-enriched synthesis gas 16 is greater than the _H2 /CO molar ratio of the effluent stream of the KChO reactor 15. The M ratio of the hydrogen-enriched synthesis gas 16 is greater than the M ratio of the effluent stream of the KChO reactor 15.

In another aspect, at least a portion of the synthesis gas 18 may be contacted with at least a portion of the hydrogen-rich stream 75 and optionally at least a portion 70a of the hydrogen-rich stream 70 to produce a hydrogen-rich synthesis gas. 19, for example, as shown in FIG. 3. The H2/CO molar ratio of hydrogen-enriched synthesis gas 19 is greater than the H2/CO molar ratio of synthesis gas 18. The M ratio of hydrogen-enriched synthesis gas 19 is greater than the M ratio of synthesis gas 18.

The hydrogen-enriched synthesis gas 16, 19 as described herein may have a H2/CO molar ratio of greater than about 1.8, or greater than about 1.9, or greater than about 2.0, or greater than about 2.1 or, on the other hand, greater than about 2.2. In one aspect, the hydrogen-enriched synthesis gas 16, 19, as described in this invention, can be characterized by an M ratio equal to or greater than about 1.8, or equal to or greater than about 2.0, or equal to or greater than about 2.1, or about 1.8 to 2.4, or about 1.9 to 2.3, or, on the other hand, about 2.0 to 2.2.

In one aspect, the hydrogen-enriched synthesis gas 16, 19 as disclosed herein may contain less than about 7 CO2, or less than about 6, or less than about 5, or less than about 4, or less than about 3, or less than about 2, or less than about 1, or from about 0.1 to 7, or from about 0.25 to 5, or, on the other hand, from about 0.5 up to 3 mol.% The amount of CO2 in the hydrogen-enriched synthesis gas 16 may be less than the amount of CO ₂ in the effluent of the KChO reactor 15. The amount of CO ₂ in the hydrogen-enriched synthesis gas 19 may be less than the amount of CO ₂ in the synthesis gas 18. How will be clear to a person skilled in the art

- 18 043578 technology, as well as using this description, the hydrogen-containing streams recovered from the cracker 600 may have a reduced CO2 content compared to the reactor effluent

COR 100. Therefore, the combination of hydrogen-containing streams extracted from the cracking unit

600, with reactor effluent 100 CPO may result in a reduced content stream

CO ₂ compared to the effluent from the KChO 100 reactor.

In one aspect, the hydrogen-enriched synthesis gas 16, 19 as disclosed herein may contain hydrocarbons in an amount of less than about 5, or less than about 4, or less than about 3, or less than about 2, or less than about 1, or less than about 0.1 or, on the other hand, less than about 0.01 mol.% The amount of hydrocarbons in the hydrogen-enriched synthesis gas 16 may be less than the amount of hydrocarbons in the effluent of the reactor 15. The amount of hydrocarbons in the hydrogen-enriched synthesis gas 19 may be less than the amount of hydrocarbons in the synthesis gas 18. As will be appreciated by one skilled in the art and with the benefit of this description, the hydrogen-containing streams recovered from the cracker 600 may have reduced hydrocarbon content compared to the effluent from the reactor 100. Therefore, combining hydrogen-containing streams recovered from the cracker 600 with the effluent from the reactor 100 can result in a stream with a reduced hydrocarbon content compared to the effluent from reactor KCHO 100.

In aspects where the synthesis gas (e.g., synthesis gas 17, 18; hydrogen-enriched synthesis gas 16, 19) has an M ratio of about 1.8 to 2.2, the synthesis gas can be further used in the production of methanol (CH ₃ OH).

In one aspect, the method for producing methanol disclosed in this invention may include introducing at least a portion of synthesis gas (e.g., synthesis gas 17, synthesis gas 18, hydrogen rich synthesis gas 16, hydrogen rich synthesis gas 19 or combinations thereof) into methanol reactor 200 to produce methanol reactor effluent 30; wherein the effluent of methanol reactor 30 contains methanol, water, H ₂ , CO, CO ₂ and hydrocarbons. The methanol reactor 200 may be any reactor suitable for the synthesis reaction of methanol from CO and H2, such as, for example, a thin trickle bed reactor, a fluidized bed reactor, a slurry reactor, a loop reactor, a cooled multi-tubular reactor, and the like. or combinations thereof.

Typically, CO and H ₂ can be converted to methanol, for example, as represented by equation (9): CO+H ₂ CH ₃ OH (9)

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

CO ₂ + ZN ₂ # CH ₃ OH + H ₂ O (10)

Without intending to be bound by any theory, it is believed that the lower the CO2 content of the synthesis gas, the less the amount of water produced in the methanol reactor 200. As will be appreciated by one skilled in the art and by the use of this description, the synthesis gas , produced using PRM, has a fairly high H ₂ content (compared to the H ₂ content of synthesis gas produced using CPR), and synthesis gas with increased H ₂ content can promote the conversion of CO ₂ to methanol, for example, as represented by equation (10), which in turn may result in increased water content in the crude methanol stream (eg, crude methanol stream 40).

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

In one aspect, the methanol production method disclosed in this invention may include the step of separating at least a portion of the effluent stream of methanol reactor 30 into a crude methanol stream 40 and a steam stream 50; wherein the crude methanol stream 40 contains methanol and water; wherein the steam stream 50 contains H ₂ , CO, CO ₂ and hydrocarbons (eg, first hydrocarbons and/or second hydrocarbons). The effluent stream of methanol reactor 30 may be separated into a crude methanol stream 40 and a vapor stream 50 in a gas-liquid separator 300, such as a vapor-liquid separator, a flash drum, a gas separator, a condensate collector, a compressor suction separator, etc.

In one aspect, the methanol production method disclosed in this invention may include the step of separating at least a portion of the crude methanol stream 40 in the distillation unit 400 into a methanol stream 45 and a water stream 46, wherein the distillation unit 400 includes one or more distillation columns . Water stream 46 contains water and residual methanol. Typically, one or more distillation columns may separate components of the crude methanol stream 40 based on their boiling points. As will be appreciated by one skilled in the art and with the benefit of the present disclosure, the higher the water content of the crude methanol stream 40, the greater the distillation

- 19 043578 columns are needed for methanol purification.

In one aspect, methanol stream 45 may contain an amount of methanol equal to or greater than about 95, or equal to or greater than about 97.5, or equal to or greater than about 99, or alternatively equal to or greater than about 99, 9 wt.% based on the total weight of the methanol stream 45.

In one aspect, the method for producing methanol disclosed in this invention may include the step of separating at least a portion of the steam stream 50 into a hydrogen stream 51 and a tail gas stream 52; wherein the hydrogen stream 51 contains at least a portion of the H ₂ steam stream 50; wherein the tail gas stream 52 contains CO, CO2 and hydrocarbons (eg, first hydrocarbons and/or second hydrocarbons). The steam stream 50 may be divided into a hydrogen stream 51 and a residual gas stream 52 in a hydrogen recovery unit 500, such as a PSA unit, a membrane separation unit, a cryogenic separation unit, or the like, or combinations thereof. In some aspects, at least a portion 70c of the hydrogen-rich stream 70 may be introduced into the first hydrogen recovery unit 500.

In one aspect, the methanol production method disclosed in this invention may include recycling at least a portion 51a of the hydrogen stream 51 to the methanol reactor 200, for example, by supplying synthesis gas to the methanol reactor 200.

In some aspects, at least a portion of the residual gas stream 52 may be removed. In other aspects, at least a portion of the tail gas stream 52 can be used as a fuel, for example, to preheat the reactant mixture of the CCC 10, heat the cracking reactor in the cracker 600, etc., or a combination thereof.

In other aspects, at least a portion 52a of the tail gas stream 52 may be supplied to the CCC reactor 100. In other aspects, at least a portion of the tail gas stream 52 may be supplied to the cracking reactor.

In one aspect, the method for producing methanol and olefins disclosed in this invention may include the steps of (a) feeding a cracker 60 feedstock to a cracker 600 to produce a cracker product stream 65, a hydrogen-rich stream 70, and a hydrocarbon recovery stream 71; wherein the cracker 60 feedstock contains second hydrocarbons; wherein the product stream of cracker 65 contains olefins; wherein the hydrogen-rich stream 70 contains H ₂ , methane and optionally unreacted second hydrocarbons; and wherein the hydrocarbon recovery stream 71 contains C ₄₊ hydrocarbons; (b) introducing at least a portion 70b of the hydrogen-rich stream 70 into a second hydrogen recovery unit 700 to produce a hydrogen-rich stream 75 and a hydrocarbon-rich stream 76; wherein the hydrogen-rich stream 75 contains at least a portion of the H2 hydrogen-rich stream 70; and wherein the hydrocarbon-rich stream 76 contains at least a portion of the hydrocarbons of the hydrogen-rich stream 70; (c) feeding a mixture of catalytic partial oxidation (CPO) reagents 10 into the CPO reactor 100; wherein the reactant mixture of the COC 10 contains oxygen, first hydrocarbons, optionally at least a portion 71a of the hydrocarbon recovery stream 71 and/or at least a portion 76a of the hydrocarbon-enriched stream 76, and optionally water vapor; wherein the first hydrocarbons and the second hydrocarbons are the same or different; wherein at least a portion of the hydrocarbons in the mixture of CPO reagents react through the CPO reaction in the CPO reactor 100 to produce synthesis gas 18; where the hydrocarbons in the mixture of CCHO reagents contain first hydrocarbons, optionally methane, optionally second hydrocarbons and optionally C ₄₊ hydrocarbons; where the KChO reactor 100 contains the KChO catalyst; wherein the synthesis gas 18 contains H ₂ , CO, CO ₂ , water and unreacted hydrocarbons, where the synthesis gas 18 is characterized by the ratio M of the synthesis gas 18, where the M ratio is a molar ratio defined as (H ₂ -CO ₂ )/ (CO+CO ₂ ); and wherein the synthesis gas 18 is characterized by the molar ratio of H2 to CO (H2/CO) of the synthesis gas 18; (d) contacting at least a portion of the synthesis gas 18 with at least a portion of the hydrogen-enriched stream 75 to produce a hydrogen-enriched synthesis gas 19; wherein the hydrogen-enriched synthesis gas 19 is characterized by the M ratio of the hydrogen-enriched synthesis gas 19, wherein the M ratio of the hydrogen-enriched synthesis gas 19 is greater than the M ratio of the synthesis gas 18; wherein the hydrogen-enriched synthesis gas 19 is characterized by the _H2 /CO molar ratio of the hydrogen-enriched synthesis gas 19, and wherein the H2/CO molar ratio of the hydrogen-enriched synthesis gas 19 is greater than the H2/CO molar ratio of the hydrogen-enriched synthesis gas 18; (e) introducing at least a portion of the hydrogen-enriched synthesis gas 19 into the methanol reactor 200 to produce a methanol reactor effluent 30; wherein the effluent stream of methanol reactor 30 contains methanol, water, H2, CO, CO2, methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (f) separating at least a portion of the effluent stream of methanol reactor 30 into a crude methanol stream 40 and a steam stream 50; wherein the crude methanol stream 40 contains methanol and water; and wherein the steam stream 50 contains H2, CO, CO2, methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (g) introducing at least a portion of the steam stream 50 into the first hydrogen recovery unit 500 to produce a hydrogen stream 51 and a residual gas stream 52, wherein the hydrogen stream 51 contains at least a portion of the H2 of the steam stream 50, and where the residual gas stream gas 52 contains CO, CO ₂ , methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (h) recycling at least a portion 51a of the hydrogen stream 51 to the methanol reactor 200; (i) optionally recycling at least a portion 52a of the tail gas stream 52 in the CPO reactor 100; (j) separating at least a portion of the crude methanol stream 40 into a methanol stream 45 and a water stream 46 in a distillation unit 400; and (k) optionally cooling 13 the reactor KCHO 100; wherein the cooling 13 of the CPO reactor 100 includes heating 13' of the cracker 600 while simultaneously cooling 13 of the CPO reactor 100 due to heat transfer between the CPO reactor 100 and the cracker 600. In such an aspect, the ratio M of the hydrogen-enriched synthesis gas 19 may be equal to or greater than about 1.8, and the H ₂ /CO molar ratio in hydrogen-enriched synthesis gas 19 may be greater than about 2.0. In such an aspect, the second hydrocarbons may comprise ethane, wherein the cracker 600 may include an ethane cracker, and wherein the olefins comprise ethylene.

In one aspect, the method disclosed in this invention may include setting up a modular system for the production of olefins and methanol, where the modular system may include a cracker (eg, cracker 600); KChO unit (for example, KChO 100 reactor); and a methanol production unit. Each unit of the modular system can be installed on a movable platform (for example, on a modular base) and can be transported and placed at the site of an oil or gas well for the production of olefins and methanol. Each unit of the modular system mounted on a movable platform can advantageously be moved to remote locations, such as a remote location with gas production wellheads (eg, natural gas and/or associated gas wellheads, etc.). Some of the gaseous hydrocarbons at a remote location can be converted into synthesis gas followed by methanol synthesis, in which case it is advantageous to transport liquid methanol (as opposed to natural gas, associated gas, etc.) from the remote location. Liquid pipelines are usually more cost effective than gas pipelines. In some aspects, the resulting olefins can be compressed, stored, transported, etc.

In an embodiment, setting up at least one modular system for processing unused tight gas at a wellbore site may include transporting each assembly of the modular system to a wellbore site, where each assembly may be transported simultaneously, sequentially, or in combination thereof relative to other assemblies. Accordingly, the size and configuration of each unit will be such as to facilitate transportation to the well site. For example, a ground service unit may be sized and configured for ground transportation (eg, to be mounted on a trailer or modular base) as a standard or oversized tractor-trailer vehicle. The offshore service unit may be sized and configured to be transported on a vessel (eg, to be placed on a barge or modular base). If necessary, each unit can be stored in the wellbore. Each node can be placed and/or positioned on the well site in a joint structural placement or arrangement (including at different elevations if necessary, for example, to accelerate gravity flow).

In one aspect, the synthesis gas and olefins production process disclosed in this invention may advantageously exhibit improvements in one or more process characteristics compared to another otherwise similar process that integrates a CPO reactor with a cracker. In the process disclosed in this invention, it may be advantageous to use hydrocarbon-rich cracker off-gas as feed to the CPO reactor, as well as hydrogen-rich cracker off-gas to increase the H ₂ content of the CPO reactor effluent. As will be appreciated by one skilled in the art and from this description, since the CPO reaction is exothermic, very little heat input in the form of combustion of fuel is required (for example, to preheat the reactants in the reaction mixture that is supplied to the synthesis production site). gas) compared to conventional steam reforming. As such, the synthesis gas production method described herein can advantageously produce less CO2 due to fuel combustion compared to steam reforming.

In addition, the method described herein can utilize process heat from the CPO reactor to heat the cracker, thereby preventing rapidly rising temperatures in the CPO reactor (eg, in the CPO catalyst bed) that lead to catalyst deactivation. As will be appreciated by one skilled in the art and with the aid of this description, operating a CPO reactor at a relatively low C/O ratio (e.g., less than about 2:1) can result in rapidly rising temperatures, and therefore heat being removed from reactor KChO can primarily ensure the operation of the reactor

CNC at relatively low C/O ratios.

In one aspect, the hydrogen-rich stream 70 may advantageously be mixed with a mixture of reactants of the CSC 10 such that the resulting mixture of reactants of the CSC 10 has an H2 content of less than about 20 mol.% or, on the other hand, less than about 14 mol.%, resulting in the ability to use hydrocarbons in the hydrogen-rich stream 70 in the CPO reaction. As will be appreciated by one skilled in the art and with the benefit of the present disclosure, a hydrogen-rich stream 70 is produced when the cracking reactor is an ethane cracker. Moreover, how will

- 21 043578 will be understood by one skilled in the art and by this description, cracking of feedstocks other than ethane results in a cracker effluent stream that has a low H2 content in the offgas, resulting in a hydrogen-poor stream (eg , hydrogen-poor stream 72). In one aspect, the hydrogen-poor stream 72 may advantageously be mixed with a mixture of CPO reactants 10, wherein the resulting mixture of CPO reactants 10 has an H2 content of less than about 20 or, alternatively, less than about 14 mole percent.

In one aspect, the cracker off-gas (eg, hydrogen-rich stream 70) has a higher H2 content than hydrogen-poor streams resulting from cracking feedstocks other than ethane, and as such, the hydrogen-rich stream 70 can be subjected to H2 separation and unreacted hydrocarbons, which can be accomplished using an existing hydrogen separation unit (eg, first H2 extraction unit 500) in the methanol loop or using a separate unit (eg, second _H2 extraction unit 700). Hydrogen (H ₂ ) recovered in hydrogen recovery units 500, 700 may preferably be recycled 51a, 75 to the inlet of the methanol loop, and unreacted hydrocarbons may be preferably recycled 52a, 76a in the CCH reactor 100. As disclosed in this invention, in aspects where the ethane cracker off-gas (e.g., hydrogen-rich stream 70) is introduced directly (e.g., without separation, without hydrogen recovery) into the CPO reactor feed (e.g., into the CPO 10 reactant mixture), the resulting CPO 10 reactant mixture may have less H2 content than about 20 or, on the other hand, less than about 14 mol.% in the combined feed to the CPO reactor.

In one aspect, the method for producing synthesis gas and olefins disclosed in this invention may advantageously include introducing at least a portion 70c of the hydrogen-rich post-compression stream 70 into the first H ₂ recovery unit 500 of the methanol loop. In such an aspect, the method for producing synthesis gas and olefins disclosed in this invention may advantageously include introducing at least a portion 52a of the residue as stream 52 from a portion of the purge stream from the first H ₂ recovery unit 500 into the CPO reactor 100 through a mixture of reagents BER 10. In such an aspect, hydrocarbons in the hydrogen-rich stream 70 will accumulate less or not in the methanol loop, thereby reducing the size of the methanol loop equipment. In such an aspect, the hydrocarbons in the hydrogen-rich stream 70 can be advantageously converted to synthesis gas in the CPO reactor 100. In such an aspect, the second H2 recovery assembly (eg, the second H2 recovery assembly 700) can be advantageously eliminated. Additional advantages of the methods for producing synthesis gas and/or methanol disclosed in this invention may be apparent to one of ordinary skill in the art upon reviewing this disclosure.

Examples.

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

Example 1.

Yields from cracking light hydrocarbon feedstocks through a conventional cracking process (eg, gas cracking process) are presented in Table.

Typical yields for light hydrocarbon feedstocks

Ethane (%) Propane(%) Butane (%) Conversion per pass 60 90 95 Yield per pass (wt.%) CO/ _CO2 / _H2S 0.20 0.2 0.4 n ₂ 3.5 1.5 1.0 dn ₄ 4.3 23.8 22.5 С2Н2 0.2 0.7 0.5 C ₂ H ₄ 47.7 36.5 34.5 C ₂ H ₆ 40.0 3.2 4.5 SzSh 0.05 0.5 0.4 SzNb 1.15 14.7 16.5 from ₃ to ₈ 0.4 10.0 0.4 from ₄ to ₆ 1.4 2.65 3.5 from ₄ to ₈ 0.15 1.15 3.2 S ₄ Nude 0.25 But. 3.4 from ₅₊ 0.7 5.1 9.2 TOTAL 100 100 100 Final ethylene yield including recycle streams 80 45.5 38.4

Additional description.

The first aspect, which is a method for producing synthesis gas and olefins, comprising (a) feeding a mixture of catalytic partial oxidation (CPO) reactants into a CPO reactor; where the mixture of CPO reagents contains oxygen, first hydrocarbons and optionally water vapor; where, by

- 22 043578 at least a portion of the mixture of CPO reactants is reacted through the CPO reaction in the CPO reactor to produce the CPO reactor effluent; where the CPO reactor contains a CPO catalyst; where the effluent stream of the CPO reactor contains hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted first hydrocarbons; and wherein the CPO reactor effluent is characterized by the ratio M of the CPO reactor effluent, wherein the ratio M is a molar ratio defined as (H2- _CO2 )/(CO+CO2); (b) feeding the cracker feedstock to the cracker to produce a cracker product stream, a hydrogen-rich stream, and a hydrocarbon recovery stream; where the cracker feedstock contains second hydrocarbons; wherein the first hydrocarbons and the second hydrocarbons are the same or different; wherein the cracker product stream contains olefins; wherein the hydrogen-rich stream contains H2, methane and optionally unreacted second hydrocarbons; and wherein the hydrocarbon recovery stream contains C ₄₊ hydrocarbons; and (c) contacting at least a portion of the CPO reactor effluent with at least a portion of the hydrogen-rich stream to produce hydrogen-rich synthesis gas; wherein the hydrogen-enriched synthesis gas is characterized by an M ratio of the hydrogen-enriched synthesis gas, and wherein the M ratio of the hydrogen-enriched synthesis gas is greater than the M ratio of the CPO reactor effluent.

The second aspect, which is a method of the first aspect, in which the first hydrocarbons and/or the second hydrocarbons comprise methane, ethane, propane, butanes, naphtha, natural gas, natural gas condensate, associated gas, wellhead gas, rich gas, paraffins, shale gas, shale fluids, fluid catalytic cracking (FCC) off-gas, refinery process gases, flue gases, fuel gas from a fuel gas header, or combinations thereof; and where the olefins contain ethylene.

The third aspect, which is a process of any of the first and second aspects, wherein the hydrogen-enriched synthesis gas contains carbon dioxide in an amount of from about 0.25 to 5 mole percent.

The fourth aspect, which is a method according to any of the first to third aspects, wherein the cracking unit includes a cracking reactor and a separation unit; and where the method further includes cooling the reactor of the CCHO; where cooling the CPO reactor includes heating the cracking reactor while simultaneously cooling the CPO reactor due to heat transfer between the CPO reactor and the cracking reactor.

The fifth aspect, which is a method according to any of the first to fourth aspects, wherein the CPO reactor is characterized by at least one CPO operating parameter selected from the group consisting of a CPO feed temperature of about 25 to 600° C.; temperature of the CCHO outlet stream is approximately from 300 to 1600°C; CCH pressure from approximately 1 to 90 bar(g); CCO contact time is approximately from 0.001 milliseconds (ms) to 5 seconds (sec); The molar ratio of carbon to oxygen (C/O) in the reactant mixture is approximately 0.5:1 to 3:1, where the molar ratio C/O means the total number of moles of carbon (C) hydrocarbons in the reactant mixture divided by the total number of moles oxygen (O ₂ ) in the mixture of reagents; the molar ratio of water vapor to carbon (W/C) in the CWC reactant mixture is from approximately 0.01:1 to less than 2.4:1, where the molar ratio P/C means the total number of moles of water (H ₂ O) in the reactant mixture , divided by the total number of moles of carbon (C) hydrocarbons in the reactant mixture; and their combinations.

The sixth aspect, which is a method according to any of the first to fifth aspects, wherein the M ratio of the hydrogen-enriched synthesis gas is equal to or greater than about 1.8.

The seventh aspect, which is a method according to any of the first to sixth aspects, wherein the hydrogen-enriched synthesis gas has a hydrogen to carbon monoxide (H2/CO) molar ratio of greater than about 2.0; and where the H2/CO molar ratio in the hydrogen-enriched synthesis gas is greater than the H2/CO molar ratio of the CPO reactor effluent.

The eighth aspect, which is a method according to any of the first to seventh aspects, further comprising (i) introducing at least a portion of the hydrogen-enriched synthesis gas into the methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent contains methanol, water, H ₂ , CO, CO ₂ , methane, first hydrocarbons, and optionally second hydrocarbons; (ii) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; and wherein the steam stream contains H ₂ , CO, CO ₂ , methane, first hydrocarbons and optionally second hydrocarbons; (iii) introducing at least a portion of the steam stream into a first hydrogen recovery unit to produce a hydrogen stream and a tail gas stream, wherein the hydrogen stream contains at least a portion of the hydrogen of the steam stream, and where the tail gas stream contains CO, CO2, methane, first hydrocarbons and optionally second hydrocarbons; (iv) recycling at least a portion of the hydrogen stream to the methanol reactor; and (v) separating at least a portion of the crude methanol stream into a methanol stream and a water stream.

The ninth aspect, which is the method of the eighth aspect, in which (1) at least a portion of the residual gas stream is purged, used as fuel, supplied to the CPO reactor

- 23 043578 at stage (a) or a combination thereof; and/or (2) at least a portion of the hydrocarbon recovery stream is recycled to the cracker, used as fuel, fed to the CPO reactor in step (a), or combinations thereof.

The tenth aspect, which is a method for producing synthesis gas and olefins, comprising (a) feeding a cracker feedstock to a cracker to produce a cracker product stream, a hydrogen-lean stream, and a hydrocarbon recovery stream; where the raw material of the cracking unit contains second hydrocarbons; wherein the cracker product stream contains olefins; wherein the hydrogen-poor stream contains H ₂ , methane and optionally unreacted second hydrocarbons; and wherein the hydrocarbon recovery stream contains C ₄₊ hydrocarbons; and (b) feeding a mixture of catalytic partial oxidation (CPO) reactants into the CPO reactor; wherein the mixture of CPO reagents contains oxygen, first hydrocarbons, at least a portion of the hydrogen-poor stream, and optionally water vapor and/or at least a portion of the hydrocarbon recovery stream; wherein the first hydrocarbons and the second hydrocarbons are the same or different; wherein at least a portion of the hydrocarbons in the mixture of CPO reagents are reacted through a CPO reaction in a CPO reactor to produce synthesis gas; where the hydrocarbons in the mixture of CCHO reagents contain first hydrocarbons, methane and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; where the CPO reactor contains a CPO catalyst; where the synthesis gas contains H ₂ , CO, CO ₂ , water and unreacted hydrocarbons; wherein the synthesis gas is characterized by a synthesis gas ratio M, wherein the M ratio is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ); and wherein the synthesis gas is characterized by a molar ratio of hydrogen to carbon monoxide (H ₂ /CO) of the synthesis gas.

The eleventh aspect, which is the method of the tenth aspect, wherein (1) the M ratio of the synthesis gas is equal to or greater than about 1.8; and/or (2) the H2/CO molar ratio of the synthesis gas is greater than about 2.0.

The twelfth aspect, which is a method according to any of the tenth and eleventh aspects, wherein the mixture of CPO reactants contains hydrogen in an amount of less than about 20 mol.%

The thirteenth aspect, which is a method according to any of the tenth to twelfth aspects, wherein the M ratio and/or H ₂ /CO molar ratio of the synthesis gas is greater than the M ratio and/or H ₂ /CO molar ratio, respectively, synthesis -gas obtained in an otherwise similar process, in which a mixture of CPO reagents is fed into the CPO reactor without a hydrogen-poor stream.

The fourteenth aspect, which is the method of any of the tenth to twelfth aspects, further comprising (i) introducing at least a portion of the synthesis gas into a methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent contains methanol, water, H2, CO, CO2, methane, first hydrocarbons and optionally second hydrocarbons and/or C4+ hydrocarbons; (ii) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; and wherein the steam stream contains H ₂ , CO, CO ₂ , methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (iii) introducing at least a portion of the steam stream into a first hydrogen recovery unit to produce a hydrogen stream and a tail gas stream, wherein the hydrogen stream contains at least a portion of the hydrogen of the steam stream, and where the tail gas stream contains CO, CO ₂ , methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (iv) recycling at least a portion of the hydrogen stream to the methanol reactor; (v) separating at least a portion of the crude methanol stream into a methanol stream and a water stream; and (vi) optionally recirculating at least a portion of the tail gas stream in the CPO reactor.

The fifteenth aspect, which is a method for producing methanol and olefins, comprising (a) feeding a cracker feedstock to a cracker to produce a cracker product stream, a hydrogen-rich stream, and a hydrocarbon recovery stream; where the raw material of the cracking unit contains second hydrocarbons; wherein the cracker product stream contains olefins; wherein the hydrogen-rich stream contains H ₂ , methane and optionally unreacted second hydrocarbons; and wherein the hydrocarbon recovery stream contains C ₄₊ hydrocarbons; (b) introducing at least a portion of the hydrogen-rich stream into a second hydrogen recovery unit to produce a hydrogen-rich stream and a hydrocarbon-rich stream; wherein the hydrogen-rich stream contains at least a portion of the H ₂ hydrogen-rich stream; and wherein the hydrocarbon-rich stream contains at least a portion of the hydrocarbons of the hydrogen-rich stream; (c) feeding a mixture of catalytic partial oxidation (CPO) reactants into the CPO reactor; wherein the mixture of CPO reagents contains oxygen, first hydrocarbons, optionally at least a portion of the hydrocarbon recovery stream and/or at least a portion of the hydrocarbon-enriched stream, and optionally water vapor; wherein the first hydrocarbons and the second hydrocarbons are the same or different; wherein at least a portion of the hydrocarbons in the CPO reactant mixture are reacted through a CPO reaction in a CPO reactor to produce synthesis gas; where the hydrocarbons in the mixture of CCHO reagents contain first hydrocarbons, optionally methane, optionally second hydrocarbons and optionally C ₄₊ hydrocarbons; Where

- 24 043578 KChO reactor contains a KChO catalyst; where the synthesis gas contains H2, CO, CO2, water and unreacted hydrocarbons; wherein the synthesis gas is characterized by a synthesis gas ratio M, wherein the M ratio is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ); and wherein the synthesis gas is characterized by the molar ratio of H2 to CO (H2/CO) of the synthesis gas; (d) contacting at least a portion of the synthesis gas with at least a portion of the hydrogen-enriched stream to produce a hydrogen-enriched synthesis gas; wherein the hydrogen-enriched synthesis gas is characterized by an M ratio of the hydrogen-enriched synthesis gas, wherein the M ratio of the hydrogen-enriched synthesis gas is greater than the M ratio of the synthesis gas; wherein the hydrogen-enriched synthesis gas is characterized by an H2/CO molar ratio of the hydrogen-enriched synthesis gas, and wherein the H2/CO molar ratio of the hydrogen-enriched synthesis gas is greater than the H2/CO molar ratio of the synthesis gas; (e) introducing at least a portion of the hydrogen-enriched synthesis gas into the methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent stream contains methanol, water, H2, CO, CO2, methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (f) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; and wherein the steam stream contains H ₂ , CO, CO 2 , methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (g) introducing at least a portion of the steam stream into a first hydrogen recovery unit to produce a hydrogen stream and a tail gas stream, wherein the hydrogen stream contains at least a portion of the H ₂ steam stream, and where the tail gas stream contains CO, CO ₂ , methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (h) recycling at least a portion of the hydrogen stream to the methanol reactor; (i) optionally recirculating at least a portion of the tail gas stream in the CPO reactor; (j) separating at least a portion of the crude methanol stream into a methanol stream and a water stream; and (j) optionally cooling the CCHO reactor; where cooling the CPO reactor includes heating the cracking unit while simultaneously cooling the CPO reactor due to heat transfer between the CPO reactor and the cracking unit.

The sixteenth aspect, which is the method of the fifteenth aspect, wherein the M ratio of the hydrogen-enriched synthesis gas is equal to or greater than about 1.8, and wherein the H2/CO molar ratio of the hydrogen-enriched synthesis gas is greater than about 2.0.

The seventeenth aspect, which is a method according to any of the fifteenth and sixteenth aspects, wherein each of the first hydrogen recovery unit and the second hydrogen recovery unit may independently include a pressure swing adsorption (PSA) unit, a membrane separation unit, a cryogenic separation unit, or combinations thereof .

The eighteenth aspect, which is the method of any one of the fifteenth to seventeenth aspects, wherein the second hydrocarbons comprise ethane; wherein the cracking unit includes an ethane cracking unit; and where the olefins contain ethylene.

The nineteenth aspect, which is a method for producing synthesis gas, including supplying a mixture of catalytic partial oxidation (CPO) reactants in a CPO reactor; wherein the mixture of CPO reagents contains oxygen, first hydrocarbons, at least a portion of the hydrogen-poor stream, and optionally water vapor; wherein the hydrogen-poor stream contains H2, methane and optionally C2-3 hydrocarbons; wherein at least a portion of the hydrocarbons in the CPO reactant mixture are reacted through a CPO reaction in a CPO reactor to produce synthesis gas; where the hydrocarbons in the mixture of CCHO reagents contain the first hydrocarbons, methane and optionally C ₂ _ ₃ hydrocarbons; where the CPO reactor contains a CPO catalyst; where the synthesis gas contains H2, CO, CO2, water and unreacted hydrocarbons; and wherein the mixture of CPO reagents contains H2 in an amount of less than about 15 mol.%

The twentieth aspect, which is a method of the nineteenth aspect, wherein the hydrogen-poor stream comprises a cracker gas stream, a refinery gas stream, a fuel gas stream, fuel gas from a fuel gas header, or combinations thereof.

For purposes of this U.S. domestic filing, all publications and patents mentioned in this specification are hereby incorporated by reference in their entirety to describe and disclose the designs and methodologies described in those publications that could be used in connection with the methods hereof. inventions. Any publications and patents discussed herein are provided solely for their disclosure prior to the filing date of this application. Nothing in this invention should be construed as an admission that inventors are not entitled to backdate such an invention by virtue of a prior invention.

Any application filed with the United States Patent and Trademark Office shall provide an abstract of that application to satisfy the requirements of 37 CFR § 1.72 and the purpose of 37 CFR § 1.72(b) to enable the United States Patent and Trademark Office and the public In general, quickly determine, based on a quick review, the nature and essence of the technical disclosure. Accordingly, the abstract of this application is not intended to be used in interpreting the scope of the claims or to limit the scope of the subject matter disclosed in this invention. Moreover, any headings that may be used in this invention are also not intended to be used for the purpose of construing the scope of the claims or for the purpose of limiting the scope of the subject matter disclosed.

-

Claims (25)

in this invention. Any use of the past tense to describe an example otherwise designated as constructive or prophetic is not intended to reflect that the constructive or prophetic example was actually brought to pass. Although preferred embodiments of the invention have been presented and described, modifications thereof may be made by one skilled in the art without deviating from the teachings of the present invention. The embodiments described in the invention are only exemplary and are not intended to be limiting. Many changes and modifications to the disclosed invention are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the above description, but is limited only by the claims below, which scope includes all equivalents of the subject matter of the claims. Each claim is included in the description as an embodiment of the present invention. Thus, the claims are intended to further describe and supplement the detailed description of the present invention. The descriptions of all patents, patent applications and publications cited in this invention are incorporated herein by reference. CLAIM 1. A method for producing synthesis gas and olefins, including: (a) feeding a mixture of catalytic partial oxidation (CPO) reactants into the CPO reactor; where the mixture of CPO reagents contains oxygen and the first hydrocarbons; wherein at least a portion of the mixture of CPO reactants is reacted through a CPO reaction in a CPO reactor to produce a CPO reactor effluent; where the CPO reactor contains a CPO catalyst; where the effluent stream of the CPO reactor contains hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted first hydrocarbons; and wherein the CPO reactor effluent is characterized by the ratio M of the CPO reactor effluent, wherein the ratio M is a molar ratio defined as (H2-CO2)/(CO+CO2); (b) feeding the cracker feedstock to the cracker to produce a cracker product stream, a hydrogen-rich stream, and a hydrocarbon recovery stream; where the cracker feedstock contains second hydrocarbons; wherein the first hydrocarbons and the second hydrocarbons are the same or different; wherein the cracker product stream contains olefins; wherein the hydrogen-rich stream contains hydrogen and methane; and wherein the hydrocarbon recovery stream contains C ₄₊ hydrocarbons; and (c) contacting at least a portion of the CPO reactor effluent with at least a portion of the hydrogen-rich stream to produce hydrogen-enriched synthesis gas, wherein the hydrogen-enriched synthesis gas is characterized by the ratio M of hydrogen-enriched synthesis gas, and where the ratio M of the hydrogen-enriched synthesis gas is greater than the ratio M of the effluent stream of the CPO reactor. 2. The method according to claim 1, in which the mixture of CPO reagents contains oxygen, first hydrocarbons and optionally water vapor. 3. The method of claim 1, wherein the hydrogen-rich stream contains hydrogen, methane, and optionally unreacted second hydrocarbons. 4. The method according to claim 1, in which the first hydrocarbons and/or second hydrocarbons contain methane, ethane, propane, butanes, naphtha, natural gas, natural gas condensate, associated gas, wellhead gas, enriched gas, paraffins, shale gas, shale liquids , fluid catalytic cracking (FCC) off-gas, refinery process gases, flue gases, fuel gas from a fuel gas header, or combinations thereof; and where the olefins contain ethylene. 5. The method of claim 1, wherein the hydrogen-enriched synthesis gas contains carbon dioxide in an amount of about 0.25 to 5 mol%. 6. The method according to claim 1, in which the cracking unit includes a cracking reactor and a separation unit; and where the method further includes cooling the reactor of the CCHO; where cooling the CPO reactor includes heating the cracking reactor while simultaneously cooling the CPO reactor due to heat transfer between the CPO reactor and the cracking reactor. 7. The method according to claim 1, in which the CPO reactor is characterized by at least one CPO operating parameter selected from the group consisting of a CPO supply temperature of approximately 25 to 600°C; temperature of the CCHO outlet stream is approximately from 300 to 1600°C; CCO pressure from approximately 1 to 90 bar(g); CCO contact time is approximately from 0.001 milliseconds (ms) to 5 seconds (s); The molar ratio of carbon to oxygen (C/O) in the reactant mixture is approximately 0.5:1 to 3:1, where the molar ratio C/O means the total number of moles of carbon (C) hydrocarbons in the reactant mixture divided by the total number of moles oxygen (O2) in the mixture of reagents; the molar ratio of water vapor to carbon (W/C) in the CWC reactant mixture is from approximately 0.01:1 to less than 2.4:1, where the molar ratio P/C means the total number of moles of water (H ₂ O) in the reactant mixture , divided by the total number of moles of carbon (C) hydrocarbons in the reactant mixture; and their combinations. 8. The method according to claim 1, in which the ratio M of the hydrogen-enriched synthesis gas is equal to or greater - 26 043578 than approximately 1.8. 9. The method of claim 1, wherein the hydrogen-enriched synthesis gas has a hydrogen to carbon monoxide (H2/CO) molar ratio of greater than about 2.0; and where the H ₂ /CO molar ratio of the hydrogen-enriched synthesis gas is greater than the H ₂ /CO molar ratio of the CPO reactor effluent. 10. The method according to claim 1, additionally including: (i) introducing at least a portion of the hydrogen-enriched synthesis gas into the methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent stream contains methanol, water, hydrogen, carbon monoxide, carbon dioxide, methane, first hydrocarbons and optionally second hydrocarbons; (ii) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; and wherein the steam stream contains hydrogen, carbon monoxide, carbon dioxide, methane, first hydrocarbons and optionally second hydrocarbons; (iii) introducing at least a portion of the steam stream into the first hydrogen recovery unit to produce a hydrogen stream and a tail gas stream, wherein the hydrogen stream contains at least a portion of the hydrogen of the steam stream, and where the tail gas stream contains carbon monoxide, dioxide carbon, methane, first hydrocarbons and optionally second hydrocarbons; (iv) recycling at least a portion of the hydrogen stream to the methanol reactor; and (v) separating at least a portion of the crude methanol stream into a methanol stream and a water stream. 11. The method according to claim 10, in which (1), at least part of the residual gas stream is purged, used as fuel, supplied to the CPO reactor in step (a) or combinations thereof; and/or (2) at least a portion of the hydrocarbon recovery stream is recycled to the cracker, used as fuel, fed to the CPO reactor in step (a), or combinations thereof. 12. A method for producing synthesis gas and olefins, including: (a) feeding the cracker feedstock to the cracker to produce a cracker product stream, a hydrogen-poor stream, and a hydrocarbon recovery stream; where the cracker feedstock contains second hydrocarbons; wherein the cracker product stream contains olefins; wherein the hydrogen-poor stream contains hydrogen and methane; and wherein the hydrocarbon recovery stream contains C ₄₊ hydrocarbons; and (b) feeding a mixture of catalytic partial oxidation (CPO) reactants into the CPO reactor; wherein the mixture of CPO reagents contains oxygen, first hydrocarbons, at least a portion of the hydrogen-poor stream, and/or at least a portion of the hydrocarbon recovery stream; wherein the first hydrocarbons and the second hydrocarbons are the same or different; wherein at least a portion of the hydrocarbons in the CPO reactant mixture are reacted through a CPO reaction in a CPO reactor to produce synthesis gas; where the hydrocarbons in the mixture of CCHO reagents contain the first hydrocarbons and methane; where the CPO reactor contains a CPO catalyst; where the synthesis gas contains hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water and unreacted hydrocarbons; wherein the synthesis gas is characterized by a synthesis gas ratio M, wherein the M ratio is a molar ratio defined as (H ₂ CO ₂ )/(CO+CO ₂ ); and wherein the synthesis gas is characterized by a molar ratio of hydrogen to carbon monoxide (H ₂ /CO) of the synthesis gas. 13. The method of claim 12, wherein the mixture of CPO reagents contains oxygen, first hydrocarbons, at least a portion of the hydrogen-poor stream, and optionally water vapor and/or at least a portion of the hydrocarbon recovery stream. 14. The method according to claim 12, in which the hydrocarbons in the mixture of CCHO reagents contain first hydrocarbons, methane and optionally second hydrocarbons and/or C4+ hydrocarbons. 15. The method of claim 12, wherein the hydrogen-poor stream contains hydrogen, methane, and optionally unreacted second hydrocarbons. 16. The method of claim 12, wherein (1) the synthesis gas M ratio is equal to or greater than about 1.8; and/or (2) the H ₂ /CO synthesis gas molar ratio is greater than about 2.0. 17. The method of claim 12, wherein the mixture of CPO reagents contains hydrogen in an amount of less than about 20 mol%. 18. The method according to claim 12, in which the M ratio and/or molar ratio H2/CO of the synthesis gas is greater than the ratio M and/or molar ratio _H2 /CO, respectively, of the synthesis gas obtained in an otherwise similar a process in which the CPO reactor is fed with a mixture of CPO reagents without a hydrogen-poor stream. 19. The method according to claim 12, additionally including: (i) introducing at least a portion of the synthesis gas into the methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent stream contains methanol, water, hydrogen, carbon monoxide, carbon dioxide, methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (ii) separating at least a portion of the methanol reactor effluent stream into a crude stream - 27 043578 methanol and steam flow; wherein the crude methanol stream contains methanol and water; and wherein the steam stream contains hydrogen, carbon monoxide, carbon dioxide, methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (iii) introducing at least a portion of the steam stream into the first hydrogen recovery unit to produce a hydrogen stream and a tail gas stream, wherein the hydrogen stream contains at least a portion of the hydrogen of the steam stream, and where the tail gas stream contains carbon monoxide, dioxide carbon, methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons; (iv) recycling at least a portion of the hydrogen stream to the methanol reactor; (v) separating at least a portion of the crude methanol stream into a methanol stream and a water stream; and (vi) optionally recycling at least a portion of the residual gas stream to the CPO reactor. 20. A method for the production of methanol and olefins, including: (a) feeding the cracker feedstock to the cracker to produce a cracker product stream, a hydrogen-rich stream, and a hydrocarbon recovery stream; where the cracker feedstock contains second hydrocarbons; wherein the cracker product stream contains olefins; where the hydrogen-rich stream contains hydrogen and methane; and wherein the hydrocarbon recovery stream contains C ₄₊ hydrocarbons; (b) introducing at least a portion of the hydrogen-rich stream into a second hydrogen recovery unit to produce a hydrogen-rich stream and a hydrocarbon-rich stream; wherein the hydrogen-rich stream contains at least a portion of the hydrogen of the hydrogen-rich stream; and wherein the hydrocarbon-rich stream contains at least a portion of the hydrocarbons of the hydrogen-rich stream; (c) feeding a mixture of catalytic partial oxidation (CPO) reactants into the CPO reactor; where the mixture of CPO reagents contains oxygen and the first hydrocarbons; wherein the first hydrocarbons and the second hydrocarbons are the same or different; wherein at least a portion of the hydrocarbons in the CPO reactant mixture are reacted through a CPO reaction in a CPO reactor to produce synthesis gas; where the hydrocarbons in the mixture of CCHO reagents contain the first hydrocarbons; where the CPO reactor contains a CPO catalyst; where the synthesis gas contains hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), water and unreacted hydrocarbons; where the synthesis gas is characterized by the ratio M of the synthesis gas, where the ratio M is a molar ratio defined as (H ₂ -CO ₂ )/(CO+CO ₂ ); and wherein the synthesis gas is characterized by a molar ratio of hydrogen to carbon monoxide (H ₂ /CO) of the synthesis gas; (d) contacting at least a portion of the synthesis gas with at least a portion of the hydrogen-enriched stream to produce a hydrogen-enriched synthesis gas; wherein the hydrogen-enriched synthesis gas is characterized by an M ratio of the hydrogen-enriched synthesis gas, wherein the M ratio of the hydrogen-enriched synthesis gas is greater than the M ratio of the synthesis gas; wherein the hydrogen-enriched synthesis gas is characterized by a H2/CO molar ratio of the hydrogen-enriched synthesis gas, and wherein the H2/CO molar ratio of the hydrogen-enriched synthesis gas is greater than the _H2 /CO molar ratio of the synthesis gas; (e) introducing at least a portion of the hydrogen-enriched synthesis gas into the methanol reactor to produce a methanol reactor effluent; wherein the methanol reactor effluent contains methanol, water, hydrogen, carbon monoxide, carbon dioxide, methane and first hydrocarbons; (f) separating at least a portion of the methanol reactor effluent stream into a crude methanol stream and a steam stream; wherein the crude methanol stream contains methanol and water; and wherein the steam stream contains hydrogen, carbon monoxide, carbon dioxide, methane and the first hydrocarbons; (g) introducing at least a portion of the steam stream into a first hydrogen recovery unit to produce a hydrogen stream and a tail gas stream, wherein the hydrogen stream contains at least a portion of the hydrogen of the steam stream, and where the tail gas stream contains carbon monoxide, dioxide carbon, methane and first hydrocarbons; (h) recycling at least a portion of the hydrogen stream to the methanol reactor; and (j) separating at least a portion of the crude methanol stream into a methanol stream and a water stream. 21. The method of claim 20, wherein the hydrogen-rich stream comprises hydrogen, methane, and optionally unreacted second hydrocarbons. 22. The method according to claim 20, in which the mixture of CPO reagents contains oxygen, first hydrocarbons, optionally contains at least a portion of the hydrocarbon recovery stream and/or at least a portion of the hydrocarbon-enriched stream, and optionally water vapor. 23. The method according to claim 20, in which the hydrocarbons in the mixture of CPO reagents contain first hydrocarbons, optionally methane, optionally second hydrocarbons and optionally C4+ hydrocarbons. 24. The process of claim 20, wherein the methanol reactor effluent comprises methanol, water, hydrogen, carbon monoxide, carbon dioxide, methane, first hydrocarbons and optionally second hydrocarbons and/or C4+ hydrocarbons. 25. The method of claim 20, wherein the steam stream contains hydrogen, carbon monoxide, carbon dioxide, methane, first hydrocarbons and optionally second hydrocarbons and/or C ₄₊ hydrocarbons. -