Utilization of low carbon intensity syngas for production of methanol

Abstract

A method may contact unprocessed syngas with a methanol forming catalyst. A method may produce the methanol composition, wherein. A method may a molar ratio of hydrogen and carbon monoxide in the unprocessed syngas is in a range of from about 2.6:1 to about 1.8:1.

Description

UTILIZATION OF LOW CARBON INTENSITY SYNGAS FOR PRODUCTION OF METHANOLCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63 / 635,185 entitled “UTILIZATION OF LOW CARBON INTENSITY SYNGAS FOR PRODUCTION OF METHANOL,” filed April 17, 2024, the disclosure of which is incorporated herein in its entirety by reference.BACKGROUND

[0002] Syngas, or synthesis gas, is a fuel gas mixture primarily including hydrogen, carbon monoxide, and often smaller amounts of carbon dioxide. The name comes from its use as an intermediate in creating synthetic natural gas (SNG) and for synthesizing products such as aviation fuel, diesel, base oils, naphtha, acetyls, ammonia or methanol.SUMMARY

[0003] In some aspects, the techniques described herein relate to a method of forming a methanol composition, the method including: contacting unprocessed syngas with a methanol forming catalyst; and producing the methanol composition, wherein a molar ratio of hydrogen and carbon monoxide in the unprocessed syngas is in a range of from about 2.6: 1 to about 1.8: 1.

[0004] In some aspects, the techniques described herein relate to a method of forming a methanol composition, the method including: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

[0005] In some aspects, the techniques described herein relate to a method of forming a methanol composition, the method including: contacting syngas with a methanol forming catalyst; and producing a methanol composition, wherein a total amount of greenhouse gas emissions to produce themethanol composition at least 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0006] In some aspects, the techniques described herein relate to a method of forming a methanol composition, the method including: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0007] In some aspects, the techniques described herein relate to a method of forming a methanol composition, the method including: producing syngas in a range of molar ration of hydrogen to carbon monoxide of about 1 : 1 to 1.8: 1; separating out the excess carbon monoxide to correct the ratio from 1.8: 1 to about 2.6: 1 : contacting the syngas with a methanol forming catalyst; and producing the methanol composition, wherein a total amount of energy required to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

[0008] In some aspects, the techniques described herein relate to a method of forming a methanol composition, the method including: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein greater than about 10 wt% of the methanol composition is from a non-hydrocarbon source.

[0009] In some aspects, the techniques described herein relate to a method of forming a methanol composition, the method including: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein the energy yield of the final methanol composition is greater than 58% of the total energy put into the method.BRIEF DESCRIPTION OF THE FIGURES

[0010] The drawings illustrate generally, by way of example, but not by way of limitation, various aspects of the present disclosure.DETAILED DESCRIPTION

[0011] Reference will now be made in detail to certain aspects of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0012] Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

[0013] In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section.

[0014] In the methods described herein, the acts may be carried out in any order without departing from the principles of the disclosure, except when a temporal or operational sequence is explicitly recited. Furthermore, specifiedacts may be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y may be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0015] The term “about” as used herein may allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range and includes the exact stated value or range. The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of’ as used herein may mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that about 0 wt% to about 5 wt% of the composition is the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than or equal to about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.

[0016] Described herein is a method of forming a methanol composition from a stream of unprocessed syngas.

[0017] The input composition to the methanol composition synthesis process of hydrogen and carbon dioxide can be called a syngas. Syngas, or synthesis gas, is a gas mixture primarily of hydrogen, carbon monoxide, and possibly some carbon dioxide. Syngas may be a product of coal gasification and has been used for electricity generation. Syngas is combustible and may also be used as a fuel for internal combustion engines.

[0018] Syngas may be produced from many sources, including natural gas, coal, biomass, or virtually any hydrocarbon feedstock, by reaction with steam (e.g., steam reforming), carbon dioxide (e.g., dry reforming) or oxygen (e.g., partial oxidation). Syngas may be an intermediate resource for production of hydrogen, ammonia, methanol, and synthetic hydrocarbon fuels.

[0019] The syngas production method can include a steam reforming process or a dry reforming process for forming syngas. Steam reforming or steam methane reforming (SMR) is a method for producing syngas (hydrogen and carbon monoxide) by reaction of hydrocarbons with water. Commonly natural gas is the feedstock. The steam reforming reaction may be represented as shown below:H2O + CH4^ 3H2 + CO

[0020] The reaction is strongly endothermic (AHSR = 206 kJ / mol). Hydrogen produced by steam reforming is termed “grey hydrogen” when the waste carbon monoxide is released to the atmosphere and “blue hydrogen” when the carbon monoxide is (mostly) captured and stored geologically. Zero carbon “green” hydrogen is produced by thermochemical water splitting, using solar thermal, low- or zero-carbon electricity or waste heat, or electrolysis, using lower zero-carbon electricity. Zero carbon emissions “turquoise” hydrogen is produced by one-step methane pyrolysis of natural gas.

[0021] Steam reforming of natural gas produces most of the world’s hydrogen. Hydrogen is used in the industrial synthesis of ammonia and other chemicals. The method according to the instant disclosure includes treating a catalyst (alternatively a catalytic alloy, a catalyst, a solid-solution catalyst, or a solid-solution catalyst) and method for producing syngas using the catalyst with a C1-C4 hydrocarbon such as methane and steam to produce carbon monoxide and hydrogen (syngas). The molar ratio of the steam to hydrocarbon content is in a range of from about 2: 1 to about 1 : 1, about 1 :5 to about 1 : 1, or about 1 :2 to about 1 : 1. In some examples the molar ratio of the steam to hydrocarbon content does not exceed 2.5: 1.

[0022] In some examples, the hydrocarbon reactant is a hydrocarbon with a GREET carbon score of less than 40 gCCE eq / MJ, less than 35 gCCE eq / MJ, less than 30 gCCE eq / MJ, less than 25 gCCh eq / MJ, less than 20 gCCE eq / MJ, less than 15 gCCE eq / MJ, or less than 10 gCCE eq / MJ. The GREET carbon score is derived from the GREET model, developed by Argonne National Laboratory, which evaluates the environmental impacts of various technologies,fuels, products, and energy systems throughout their life cycles. This model calculates key metrics such as total energy consumption, fossil fuel energy use, greenhouse gas emissions, air pollutant emissions, and water consumption. Specifically, the GREET carbon score measures the carbon intensity of a given technology or fuel, indicating the amount of greenhouse gases emitted per unit of energy produced or consumed. This score is essential for assessing and comparing the environmental impact of different energy sources and technologies, aiding in research, development, and regulatory decision-making.

[0023] In some aspects of the present disclosure, no carbon dioxide is purposefully introduced to the catalyst. That is the catalyst is only introduced to carbon dioxide present in the ambient atmosphere, no additional carbon dioxide is put in contact with the catalyst. Not adding carbon dioxide makes the process more environmentally friendly for at least two reasons. First, less carbon dioxide is required for use so the use of greenhouse gases is reduced. Second, without purposefully adding carbon dioxide there is less and in some cases no leftover carbon dioxide following the reaction. In some alternative examples, carbon dioxide that is harvested from a source (e.g., an industrial steam) is used as an input to prevent emission of the carbon dioxide.

[0024] The catalyst that is used for the production of syngas is a catalytic alloy catalyst. A catalytic alloy catalyst includes components that coexist as a new solid, or lattice that includes a degree of crystallinity while also including at least some amorphous character. As a non-limiting example, the amorphous portion of the catalyst may be in range of from about 0.5 wt% to about 10 wt% of the catalyst, about 2 wt% to about 7 wt%, about 3 wt% to about 5 wt%, less than, equal to, or greater than about 0.5 wt%, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or about 10 wt%. The mixing may be accomplished by combining the two solids when they have been melted into liquids at high temperatures and then cooling the resulting product to form the new solid or by depositing vapors of the starting materials onto substrates to form thin films. As with liquids, solids have different degrees of mutual solubility, depending on their chemical properties and crystalline structure, which determine how their atoms fit together in the mixed crystal lattice. The mixed lattice may besubstitutional, in which the atoms of one starting crystal replace those of the other, or interstitial, in which the atoms occupy positions normally vary in the lattice. The substances may be soluble over a partial or even complete range of relative concentrations, producing a crystal whose properties vary continuously over the range.

[0025] The reactants that form the catalytic alloy catalyst may be chosen from reactants that are capable of forming a catalytic alloy catalyst such as at least two reactants having atomic radii that are within about 15% of each other; substantially the same crystal structure; substantially the same electronegativity; substantially similar valency; or a combination thereof. The reactants may generally be chosen from metal oxides and metal oxide precursors. In some specific examples, the catalyst may include a substantially nonporous metal oxide substrate and a particulate nickel species dispersed about the metal oxide substrate and at least partially embedded therein. Examples of metal oxides for the substrate may include magnesium oxide (MgO), nickel oxide (NiO), iron oxide (FeO), cobalt oxide (CoO), manganese oxide (MnO), or a mixture thereof. The mixture may include any combination or sub-combination of the metal oxides. For example, the mixture may be a binary mixture, tertiary mixture, quaternary mixture, or the like. In any mixture, the concentration of each of the metal oxides may be substantially the same, alternatively, the concentration of at least one metal oxide may be different from the concentration of at least one different metal oxide.

[0026] The nonporous nature of the catalyst may be understood to refer to a “surface porosity” meaning that the catalyst may be free of pores that extend from the surface of the catalyst towards the interior of the catalyst. The nonporous nature of the catalyst may further be characterized by a lack of “internal porosity” meaning that the catalyst may be free of pores that extend through at least a portion of the catalyst. In some examples, the nonporous nature of the catalyst may refer to both the surface porosity and the internal porosity. Surface porosity, internal porosity, or both may be characterized by having a minimal number of pores or by individual pores, which may be present, having a small major dimension. A “major dimension” refers to the largest of thelength, width, or thickness of an object. For example, any surface pores or through pores may have a width of less than 50 nm, less than 40 nm, less than 30 nm, less than 20 nm, less than 10 nm, in a range of from about 10 nm to about 50 nm, about 10 nm to about 30 nm, or about 10 nm to about 15 nm. According to various aspects, a pore may account for less than about 20% of the total surface area of the catalyst, less than about 10% of the total surface area of the catalyst, less than about 5% of the total surface area of the catalyst, less than about 1% of the total surface area of the catalyst, or 0% of the total surface area of the catalyst. For example, a pore volume of the catalyst may be less than about 0.5 cm3 / g, less than 0.3 cm3 / g, less than 0.1 cm3 / g, or 0 cm3 / g.

[0027] The nonporous nature of the catalyst may help to prevent “coking” of the catalyst. Coking is one of several mechanisms that may be responsible for deactivation of a catalyst used for reformation of carbon dioxide. Coking refers to the deposition of coke (a hard, strong, porous material of high carbon content) on the catalyst. If the catalyst has porosity, the coke may penetrate the pores and prevent reactants from interacting with active sites on the catalyst. However, the instant catalyst may be nonporous and has a somewhat smooth-glassy surface, thus preventing or reducing coke from being deposited in any pores or on the surface of the catalyst.

[0028] Conventional catalyst design principles counsel against designing the catalyst to have such a low porosity. This is because it is thought that increasing porosity allows for a greater surface area to distribute actives on and, therefore, produce more product. However, the inventors have surprisingly and unexpectedly found that the instant catalyst may be capable of providing a very high yield of syngas despite having a comparatively smaller active surface area (e.g., exposed nickel species) than a comparative catalyst having a higher degree of porosity. Although the instant catalyst does not have an increased surface area resulting from porosity, in some examples the surface area of the catalyst may be increased by including a series of surface structures such as grooves, undulations, or peak-and-valleys on the surface of the catalyst. Unlike pores, which may be characterized as penetrating the surface of the catalyst, the surface structures do not penetrate the surface of the catalyst. For example, a bottom orlowest portion of the surface structure is still characterized as the surface of the catalyst.

[0029] The metal oxide substrate may be generally a continuous structure. The metal oxide substrate gives the catalyst its overall structure. The overall structure of the catalyst may be substantially spherical, substantially cylindrical, substantially flat, or it may have an undulating profile. The catalyst may be solid. Alternatively, the catalyst may have at least one through pore. For example, the catalyst may have a “wagon wheel” structure in which the catalyst is circular with a number of through pores extending from a first end of the catalyst to a second end of the catalyst. The catalyst may have any number of through pores, for example the catalyst may have a single through pore or a plurality of through pores. Including the through pores may have the benefit of increasing the surface area of the catalyst (relative to a corresponding catalyst that is free of a through pore or has fewer through pores), thus potentially allowing for more syngas production. In some examples, it is possible for the catalyst to include a number of indentations that penetrate partially through the thickness of the catalyst this may be helpful to increase the surface area as well. The through pore(s) may extend substantially along a largest dimension of the catalyst or a smaller dimension. A largest dimension of the catalyst may be in a range of about 20 pm to about 26 mm, about 1 mm to about 10 mm, in a range of about 4 mm to about 6 mm, or less than, equal to, or greater than about 20 pm, 100 pm, 200 pm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, or about 20 mm. The largest dimension may refer to a length, width, or diameter of the catalyst.

[0030] The particulate nickel species of the catalyst may include elemental nickel, nickel oxide, or a mixture thereof. In total, the particulate nickel species may be about 0.2 wt% to about 30 wt% of the catalyst, about 14 wt% to about 25 wt% of the catalyst, or less than, equal to, or greater than about 0.2 wt% of the catalyst, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or about 30 wt% of the catalyst. The particulate nickel species may be homogeneously distributed about the metal oxide substrate. In most examples, the particulate nickel species includes nickel oxide as opposed to elemental nickel.

[0031] At least a portion of the particulate nickel species may be exposed on a surface of the metal oxide substrate. The portion of the particulate nickel species that may be exposed on the surface of the metal oxide substrate is available to be contacted directly with the reactants and catalyze the reaction to produce syngas. The exposed portion of the particulate nickel species is bound to the metal oxide substrate. Thus, the exposed portion of the particulate nickel species may be free of unbound or free nickel or nickel oxide.

[0032] The nickel of the particulate nickel species that is exposed on a surface of the metal oxide substrate may be primarily nickel oxide as opposed to elemental nickel. For example, the nickel of the particulate nickel species that is exposed on a surface of the metal oxide substrate may be from about 80 wt% to about 100 wt% nickel oxide, about 95 wt% to about 100 wt% nickel oxide, less than, equal to, or greater than about 80 wt%, 85, 90, 95, or 100 wt% nickel oxide. In total, the amount of the particulate nickel species exposed on a surface of the metal oxide substrate may be in a range of from about 10 wt% to about 30 wt% of the particulate nickel species, about 14 wt% to about 18 wt% of the particulate nickel species, less than, equal to, or greater than about 10 wt%, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt%. The exposed particulate nickel species may account for about 10% to about 90% of the total surface area of the catalyst, about 20% to about 80% of the total surface area of the catalyst, about 30% to about 70% of the total surface area of the catalyst, about 40% to about 60% of the total surface area of the catalyst, less than, equal to, or greater than about 10% of the total surface area of the catalyst, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 ,75, 80, 85, or about 90% of the total surface area of the catalyst. As an example, a catalytic surface area may range from about 0.05 m2 / g to about 0.5 m2 / g. The pore volume of the catalyst may range from about 0.0005 cm3 / g to about 0.05 cm3 / g.

[0033] As described herein, the particulate nickel species may be generally free of unbound or free elemental nickel. However, to mitigate the risk of free elemental nickel being present, the catalyst may include potassium ions distributed in or at the surface of the catalyst. Where present, the potassium ions range from about 0.2 wt% to about 5 wt% of the catalyst, about 1 wt% to about 2 wt% of the catalyst, less than, equal to, or greater than about 0.2 wt% of the catalyst, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or about 5 wt% of the catalyst. The potassium ions may be supplied as potassium nitrate, potassium acetate, potassium carbonate, or a mixture thereof. In various aspects, the catalyst is free of free elemental nickel. However, if free elemental nickel is present, it is expected to be less than about 2 wt% free elemental nickel in the particulate nickel species, less than about 0.5 wt% free elemental nickel in the particulate nickel species, or free of free elemental nickel in the particulate nickel species.

[0034] In use, the catalyst may be contacted with a feed stream including methane and steam to produce carbon monoxide and hydrogen (syngas). To help increase the coverage of the catalyst, the steam and / or another gas (e.g., an inert gas such as argon) may be contacted with the catalyst continuously or intermediately at any suitable rate such as a slow trickle.

[0035] The catalyst may be able to produce syngas from a wide array of steam and hydrocarbon sources. For example, the steam and hydrocarbon source may be a feed stream of industrial waste (e.g., a power plant exhaust source, fermentation byproduct or primary product gas, landfill methane reclamation, bio-digestor methane production, steel furnace exhaust gas, ammonia byproducts, methanol tailgas, flare gas, or the like) an air captured carbon source, or a mixture thereof. In some examples, the feed stream may be captured and supplied to the catalyst. In some other examples, the source of the feed stream may be directly coupled (e.g., co-located) with an apparatus for the production of syngas, such that the feed stream is directly put into contact with the catalyst. Thus, a producer of an environmentally unfriendly gas may recoup environmental, economic, and / or social benefits from an off gas use. In general, pollutants such as sulfur do not negatively impact the performance of the catalyst.

[0036] Before the catalyst is contacted with the feed stream, the catalyst may be activated. Activating the catalyst may include contacting the catalyst with a mixture of hydrogen gas and nitrogen gas for a time in a range of from about 0.1 hour to about 6 hours, about 2 hours to about 5 hours, less than, equal to, or greater than about 0.11 hour, 0.5, 1, 2, 3, 4, 5, or 6 hours. Activation may occur at a temperature in a range of from about 400 °C to about 600 °C, about 450 °C to about 500 °C, less than, equal to, or greater than about 400 °C, 410, 420, 430, 440, 450, 500, 550, or about 600 °C. A ratio of hydrogen gas to nitrogen gas used to activate the catalyst may be in a range of from about 90: 10 to about 70:30 or about 85: 15 to about 75:25.

[0037] The carbon monoxide and hydrogen of the syngas may be produced in a molar ratio of about 3 : 1, 2: 1, 1 : 1, 1 :2, or about 1 :3. These ratios exclude the presence of any other gas present besides carbon monoxide and hydrogen. In the reaction at least 70 wt% of the steam and hydrocarbon that contacts the catalyst are converted to carbon monoxide and hydrogen per turn, at least 90 wt% of the steam and hydrocarbon that interact with the catalyst are converted to carbon monoxide and hydrogen per turn, about 70 wt% to about 99 wt%, about 90 wt% to about 99 wt%, or about 95 wt% to about 98 wt%. Thus, the catalyst of the instant disclosure may be capable of producing commercially viable yields of syngas. In addition to the yield, the kinetics of the catalyst are very fast. For example, the catalyst may have a gas hourly space velocity of about 1000 to about 20000, about 3000 to about 5000, less than, equal to, or greater than about 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, 11000, 11500, 12000, 12500, 13000, 13500, 14000, 14500, 15000, 15500, 16000, 16500, 17000, 17500, 18000, 18500, 19000, 19500, or about 20000. As understood a “turn” refers to a contacting event of the steam and methane with the catalyst to form syngas.

[0038] The kinetics and yield of the reaction may be impacted by the pressure at which the steam and hydrocarbon are contacted with the catalyst. For example, steam and hydrocarbon may be contacted with the catalyst at a pressure in a range of from about 25 KPa to about 3500 KPa, about 30 KPa toabout 2100 KPa, less than equal to or greater than about 25 KPa, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1500, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, or about 3500 KPa.

[0039] The kinetics and yield of the reaction may also be impacted by the flow rate of the feed stream. In some examples the flow rate of the feed stream may be measured in terms of a gas hourly space velocity (GHSV) that may be in a range of from about 500 h'1to about 11000 h'1about 1000 h'1to about 10000 h’1, less than, equal to, or greater than about 500 h’1, 1000, 1500, 2000, 25000, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, or 11000 h’1.

[0040] Additionally, the kinetics and yield of the reaction may be impacted by the temperature at which the reaction is performed. In some examples, the reaction may be performed at a temperature in a range of from about 530 °C to about 2000 °C, about 276 °C to about 1371 °C, about 815 °C to about 1093 °C, less than, equal to, or greater than about 530 °C, 540, 550, 560,570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720,730, 740, 750, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900,910, 920, 930, 940, 950, 960, 970, 980, 990, 1000, 1010, 1020, 1030, 1040,1050, 1060, 1070, 1080, 1090, 1100, 1110, 1120, 1130, 1140, 1150, 1160, 1170,1180, 1190, 1200, 1210, 1220, 1230, 1240, 1250, 1260, 1270, 1280, 1290, 1300,1310, 1320, 1330, 1340, 1350, 1360, 1370, 1380, 1390, 1400, 1410, 1420, 1430,1440, 1450, 1460, 1470, 1480, 1490, 1500, 1510, 1520, 1530, 1540, 1550, 1560,1570, 1580, 1590, 1600, 1610, 1620, 1630, 1640, 1650, 1660, 1670, 1680, 1690,1700, 1710, 1720, 1730, 1740, 1750, 1780, 1790, 1800, 1810, 1820, 1830, 1840,1850, 1860, 1870, 1880, 1890, 1900, 1910, 1920, 1930, 1940, 1950, 1960, 1970,1980, 1990, or about 2000 °C. In some examples, the temperature will be provided from the feed stream. Additionally, or in other examples the catalyst may be located in a vessel, which may be heated to a certain temperature to achieve the desired reaction temperature. The ability to run the reaction at these high temperatures allows for faster production of syngas and is made possible bythe catalyst being sintered and therefore able to be exposed to high temperatures without substantially decomposing.

[0041] Importantly, and contrary to conventional catalysts for the production of syngas, the instantly disclosed catalyst may be substantially free of coking during performance of the method. For example, the catalyst may be free of coking for a period of time of at least 1 week, at least one month, at least 6 months, at least 1 year, at least 2, years or at least 3 years. By “free of coking” it is meant that the catalyst may continuously catalyze the syngas production reaction without about 20% to about 100% loss of catalytic activity, about 40% to about 80% loss of catalytic activity, less than, equal to, or greater than about 30% loss of catalytic activity, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 100% loss of catalytic activity.

[0042] Although the catalyst of the instant disclosure shows good anticoking properties, the catalyst may be steam treated, if desired, to remove any amount of coke that may be present. The steam delivered is in addition to any steam used as a reactant. To steam treat the catalyst, the flow of the feed stream is cut off, and steam at a temperature in a range of from about 150 °C to about 1000 °C, about 200 °C to about 260 °C, or less than, equal to, or greater than about 150 °C, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300,305, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450,460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610,620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770,780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930,940, 950, 960, 970, 980, 990, or about 1000 °C, is fed to the catalyst. Steam may be fed to the catalyst for a suitable amount of time, such as an amount of time in a range of from about 0.2 hours to about 20 hours, about 2 hours to about 15 hours, less than, equal to, or greater than about 0.2 hours, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 hours. The performance of the catalyst may be continually monitored and if the performance drops below a certain threshold the syngas production may be stopped and the catalyst may besteam treated to remove any coke that may be present. Importantly, if the catalyst is treated with steam, the catalyst may be reused to produce syngas.

[0043] The catalysts described herein may be formed according to any suitable method. An example of a suitable method may include mixing a nickel solution into a metal oxide powder to form a mixed powder.

[0044] Alternatively, the mixed powder may be formed by coprecipitation of a nickel solution and a single metal or multiple metals solution selected from the group of cobalt, iron, manganese and magnesium. The nickel solution may include nickel(II) nitrate hexahydrate, nickel(II)di-acetate, nickel(II)carbonate, or a combination thereof. In some examples, nickel(II) nitrate hexahydrate may be particularly suited for the method. The metal oxide powder may include any of the metal oxides described herein. In some examples, magnesium oxide may be particularly well suited to form a catalytic alloy catalyst along with nickel(II) hexahydrate. In some examples, it was found that controlling the dso of the metal oxides present helped to form the catalytic alloy catalyst. For example, suitable dso values for the metal oxide may be in a range of from about 2 pm to about 120 pm, about 5 pm to about 100 pm, less than, equal to, or greater than about 2 pm, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, or about 120 pm. The nickel solution and the metal oxide are readily soluble in each other, which facilitates even mixing.

[0045] After the mixed powder is formed, the mixed powder may be dried. The mixed powder may be air dried or heated. Following drying, the mixed powder becomes a dried paste. The dried paste may be then crushed to form a dried powder. Crushing may be accomplished using ball-milling, granulation, or a combination thereof. Crushing may occur for a range of time of about 0.5 hours to about 5 hours, about 2 hours to about 4 hours, less than, equal to, or greater than about 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours. However, if the mixed powder is spray dried, there is no need for crushing.

[0046] The dried powder may then be calcined. Calcining the dried powder converts the nickel solution to nickel oxide. Calcining may occur at a temperature in a range of from about 400 °C to about 2000 °C, about 500 °C toabout 1500 °C, about 950 °C to about 1050 °C, less than, equal to, or greater than about 400 °C, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, or about 2000 °C. A temperature of 950 °C to about 1050 °C has been found to be particularly effective. Calcining may occur for a time in a range of from about 0.5 hours to about 12 hours, about 1 hour to about 3 hours, less than, equal to, or greater than about 0.5 hours, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or 12 hours.

[0047] The catalyst has been described as a solid. However, it is also possible and within the scope of the instant disclosure for the material of the catalyst to be a coating present on a substrate that is substantially inert to methane, carbon dioxide, carbon monoxide, and hydrogen. Examples of such a substrate include a silica or a ceramic. The substrate may take on any suitable shape such as a sphere, a rod, a latticed structure, a porous structure, or the like. The average thickness of the coating may be in a range of from about 0.1 mm to about 2.5 mm, about 0.15 mm to about 2 mm, less than, equal to, or greater than about 0.1 mm, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or about 2.5 mm. The substrate may be coated with the catalyst to any suitable degree. For example, about 30% to about 100% of the total surface area of the substrate may be coated with the catalyst, about 40% to about 90% of the total surface area of the substrate may be coated with the catalyst, about 50% to about 80% of the total surface area of the substrate may be coated with the catalyst, less than, equal to, or greater than about 30% of the total surface area of the substrate, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 100% of the total surface area of the substrate. Manufacturing the catalyst coated substrate may largely follow the protocols describe herein above with the additionally step of applying the mixed powder to the substrate material and drying the mixed powder thereon ahead of calcining the dried powder to form the catalyst coating on the substrate.

[0048] To produce syngas at a commercially desirable level, the catalyst may be incorporated into an assembly. In some examples, the catalyst may beretrofit into an existing assembly. For example, the catalyst may be located within a reaction vessel. According to various examples, a reaction vessel may include a tube. The tube may be configured to have a generally cylindrical profile with an inlet and an outlet. Without being so limited, the inlet may be located proximate to or at the bottom of the tube and the outlet may be located proximate to or at the top of the tube. The tube may be formed from a metal such as a nickel alloy and the catalyst may be distributed about the tube.

[0049] The reaction vessel may take on other shapes and configurations as well. For example, in some cases a heat source such as a furnace may be placed in thermal communication with the reaction vessel. The reaction vessel may include a feedback loop to direct any carbon dioxide produced by the heat source to the reaction vessel to participate in the instantly described method for producing syngas. Routing carbon dioxide back to the reaction vessel may significantly reduce the carbon dioxide emissions of a plant using the instantly disclosed method. In some examples, the carbon dioxide emissions may be nonexistent.

[0050] The catalyst may be fixed within the reaction vessel. For example, the catalyst may be adhered to an inner surface of the reaction vessel. As another example, a retention device may be located within the reaction vessel and the catalyst may be retained by the retention device. The reaction assembly may include any plural number of catalysts. The optimum number of catalysts in the reaction assembly may be determined with a loading test. This may involve checking for void space in the and packing density in the assembly to optimize the amount of catalysts. The composition (e.g., chemical composition) or physical characteristics (e.g., catalyst size) of the individual catalysts may be the same or different. The distribution of the catalysts may be an even distribution (e.g., an equal amount of catalysts across the reaction vessel) or an uneven distribution (e.g., a gradient of amounts of catalysts or a large or small concentration of catalysts at a first location relative to a second location). An even distribution of the catalysts may be helpful to increase the possibility that as much feed gas as possible may contact the catalysts. If the catalysts are only placed at one location, for example, there may be a risk that some feed gas maygo past the catalysts without reacting, thereby decreasing the yield of syngas relative to the amount of feed gas supplied.

[0051] The metal of the reaction vessel may be a metal showing high thermal resistivity as well as inertness to the feed gas and syngas. The high thermal resistivity may be helpful to maintain the integrity of the reaction vessel when exposed to the potentially high temperatures of the feed gas, the source of heat required to bring conditions inside the reaction vessel to a temperature suitable for conducting the reaction, as described herein, or both.

[0052] The molar ratio of hydrogen and carbon monoxide produced is in a range of from about 4: 1 to about 1 :4, about 3 : 1 to about 1 :3, about 2: 1 to about 1 :2, about 2.6: to about 1.8: 1, about 2.2: 1, or about 1 : 1. The molar ratio may be constant during the production or it may be varied depending on the amount of reactants, rate of delivery of the reactants, or other factors.

[0053] According to various aspects, the syngas produced is not subjected to any post-production processing to refine it. Thus, the syngas is properly characterized as unprocessed syngas. In some examples, less than 4 wt% methane, less than 2 wt% methane, or 0 wt% methane is left over following the production of unprocessed syngas.

[0054] Examples of post-production processing may include a gas-water shift to convert carbon monoxide to hydrogen and change or tailor the aforementioned molar ratio of hydrogen to carbon monoxide. Alternatively, post-production processing may include use of a Vacuum Pressure Swing Adsorber (VPSA) or Pressure Swing Adsorber (PSA), a cryogenic separation process, membrane unit separation process, or a combination thereof to get to a purer version of the gas or change the ratio of gas for a downstream process.

[0055] A unique and advantageous aspect of the disclosed catalyst is that it has a very high conversion efficiency of any carbon dioxide reactant (e.g., atmospheric carbon dioxide) that may be present to form unprocessed syngas.Moreover, owing to the extreme efficiency of the catalyst, it is possible to greatly reduce the amount of energy used to generate steam, for example less than about 50% of the energy used to generate steam for a corresponding catalyst. To the extent that there is any leftover carbon dioxide or heat, theexcess may be routed to another process or reused to generate more unprocessed syngas.

[0056] Additionally, very little hydrocarbon is left over following the production of unprocessed syngas. For example, less than about 2 wt% hydrocarbon is left following the production of unprocessed syngas or even no hydrocarbon is leftover.

[0057] The hydrocarbon used as a reactant may be obtained from many different sources such as a renewable natural gas, a landfill emission, an oil well emission, a coal mine emission, or a mixture thereof.

[0058] The produced syngas can be used as a feedstock for methanol synthesis. Methanol synthesis from syngas involves the catalytic conversion of hydrogen (JL) and carbon monoxide (CO) into methanol (CHsOH). The primary reactions involved in methanol synthesis are highly exothermic, meaning they release a significant amount of heat. The synthesis process can occur in fixed- bed reactors at high pressures ranging, for example, from 600 to 1,700 psig and temperatures between 200 to 315°C..

[0059] Examples of suitable catalysts for methanol synthesis are mixtures of copper (Cu), zinc oxide (ZnO), magnesium, and alumina (AI2O3). Copper acts as the active site for the reaction, while zinc oxide and alumina provide structural support and enhance the catalyst's stability. Other catalysts that may be suitable for methanol synthesis include carbon, nitrogen, and platinum. In some examples, a platinum-based catalyst can be suspended in sulfuric acid to facilitate the reaction and can be easily filtered and reused. In further examples, rhodium and its ligand catalysts are suitable as potential candidates for low-temperature methanol synthesis, offering good catalytic performance.

[0060] The produced methanol composition can range from about 80 wt% to about 100 wt% methanol, about 95 wt% to about 100 wt% methanol, less than, equal to, or greater than about 80 wt%, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or about 100 wt% methanol. If any carbon dioxide is present in the methanol composition it can be recirculated as a feedstock for syngas production.

[0061] The carbon present in the methanol composition may be in a range of from about 40 wt% to about 100 wt% carbon produced from the unprocessed syngas of the instant disclosure, about 50 wt% to about 100 wt%, about 70 wt% to about 100 wt%, less than, equal to, or greater than about 40 wt%, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or about 100 wt%.

[0062] In some examples, a high degree of the carbon produced by the instantly described methods of making unprocessed syngas may be originated from a source of carbon dioxide emissions. For example, about 40 wt% to about 80 wt% of the carbon produced may be from a source of carbon dioxide emission (e.g., a co-product or by-product), or about 70 wt% to about 80 wt% of the carbon produced may be from a source of carbon dioxide emission, less than, equal to, or greater than about 40 wt%, 45, 50, 55, 60, 65, 70, 75, or about 80 wt%.

[0063] In some additional examples an even higher amount of the carbon produced in manufacturing unprocessed syngas may be obtained. For example, if any carbon dioxide used to make unprocessed syngas is combined with a biogas for the source of methane, it is possible for about 90 wt% to about 100 wt% of carbon to be produced from greenhouse gas emissions and or renewable sources, 95 wt% to about 100 wt%, less than, equal to, or greater than about 90 wt%, 91, 92, 93, 94, 95, 96, 97, 98, 99, or about 100 wt%.

[0064] Additionally, if the unprocessed syngas may be produced by a method that consumes greenhouse gases, such as carbon dioxide and methane, a product formed from the unprocessed syngas may have a low carbon score, may be carbon neutral, or have a carbon negative score. The carbon score may be determined by quantifying the amount of greenhouse gas that is removed from the atmosphere while making the product. For example, a carbon neutral product refers to a product that has a manufacturing process resulting in the net effect not adding greenhouse gases to the atmosphere. As a further example, a carbonnegative product refers to a product that has a manufacturing process that results in a net effect of removing greenhouse gases from the atmosphere.

[0065] In some further examples the unprocessed syngas process described herein may be useful to economically produce blue hydrogen. Blue hydrogen is understood to refer to hydrogen formed when a natural gas is split into hydrogen and carbon dioxide and where the carbon dioxide is captured and not released to the atmosphere. Conventional blue hydrogen production may be environmentally and / or economically undesirable because of the carbon dioxide that is formed owing to the emission of the carbon dioxide to the atmosphere or the requirements of storing the carbon dioxide so that it is not emitted into the atmosphere. However, using the unprocessed syngas production method described herein, carbon dioxide produced to form blue hydrogen may be fed into the unprocessed syngas production method as a feedstock to react with methane to form unprocessed syngas.

[0066] Because the carbon obtained as part of the unprocessed syngas can come from an environmentally sustainable source for the aforementioned reasons, it is possible to achieve several environmental benefits in the methanol composition, according to the methods disclosed herein. For example, a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol composition, less than about 34 MMBtu / Tonne of methanol composition, less than about 33 MMBtu / Tonne of methanol composition, less than about 32 MMBtu / Tonne of methanol composition, less than about 31 MMBtu / Tonne of methanol composition, less than about 30 MMBtu / Tonne of methanol composition, less than about 29 MMBtu / Tonne of methanol composition, less than about 28 MMBtu / Tonne of methanol composition, less than about 27 MMBtu / Tonne of methanol composition, less than about 26 MMBtu / Tonne of methanol composition, less than about 25 MMBtu / Tonne of methanol composition, less than about 24 MMBtu / Tonne of methanol composition, less than about 23 MMBtu / Tonne of methanol composition, or less.

[0067] In some examples, a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower, at least 30% lower, atleast 35% lower, at least 40% lower, at least 45% lower, at least 50% lower, at least 55% lower, at least 60% lower, at least 65% lower, at least 70% lower, at least 75% lower, at least 80% lower, at least 85% lower, at least 90% lower, at least 95% lower, at least 97% lower than a corresponding method using a unprocessed syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0068] According to various examples, greater than about 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or 100 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source. The non-hydrocarbon source can include a carbon from carbon dioxide. In some examples, all or some of the carbon dioxide can be a biogenic carbon from reformed carbon dioxide. Biogenic carbon from reformed carbon dioxide generally refers to carbon that originates from biological sources and is subsequently transformed through processes that capture and convert carbon dioxide . Biogenic carbon is part of the natural carbon cycle, where carbon is absorbed by plants during photosynthesis and stored in biomass. When this biomass decomposes or is combusted, the stored carbon is released back into the atmosphere as carbon dioxide. However, this carbon dioxide can be captured and reformed into useful products, such as biofuels or other biogenic materials.

[0069] Environmental benefits of the instant disclosure can be further obtained by utilizing heat that is recovered from unprocessed syngas production to operate a carbon dioxide recovery unit and / or to create enough power to run the process without the need for grid power.

[0070] In some further examples, a plant or device associated with producing the instantly disclosed unprocessed syngas may be co-located with a plant or device for making any product that uses or may use unprocessed syngas as an at least partially feedstock. That is unprocessed syngas produced may be directly fed into a process for making a product.

[0071] In a further example, the methanol composition can be used a as a fuel for an engine such as an engine to drive a propeller for a maritime vessel. Methanol is a viable alternative fuel for maritime vessels due to itsenvironmental and operational benefits. As a liquid at ambient temperatures, methanol is easier to store and transport compared to gaseous fuels like hydrogen or ammonia. When used as a marine fuel, methanol significantly reduces emissions of sulfur oxides (SOx), nitrogen oxides (NOx), and particulate matter, contributing to improved air quality and compliance with stringent environmental regulations. The combustion of methanol produces fewer greenhouse gases compared to conventional marine fuels, making it a more sustainable option. An example of an advantage of methanol is its compatibility with existing marine engines, which can be retrofitted to use methanol with relatively minor modifications. This makes the transition to methanol more cost- effective and less disruptive compared to other alternative fuels that may require entirely new engine designs. Additionally, methanol has a high energy density among alternative fuels, providing sufficient power for long voyages.Exemplary Aspects

[0072] The following exemplary aspects are provided, the numbering of which is not to be construed as designating levels of importance:

[0073] Aspect 1 provides a method of forming a methanol composition, the method comprising: contacting unprocessed syngas with a methanol forming catalyst; and producing the methanol composition, wherein a molar ratio of hydrogen and carbon monoxide in the unprocessed syngas is in a range of from about 2.6: 1 to about 1.8: 1.

[0074] Aspect 2 provides the method of Aspect 1, wherein the molar ratio of hydrogen and carbon monoxide in the unprocessed syngas is about 2.2: 1.

[0075] Aspect 3 provides the method of any of Aspects 1 or 2, wherein the unprocessed syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

[0076] Aspect 4 provides the method of Aspect 3, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

[0077] Aspect 5 provides the method of any of Aspects 3 or 4, wherein the hydrocarbon is a C1-C4 hydrocarbon.

[0078] Aspect 6 provides the method of any of Aspects 3-5, wherein the hydrocarbon comprises methane.

[0079] Aspect 7 provides the method of any of Aspects 3-6, wherein the hydrocarbon is a low-carbon footprint hydrocarbon with a GREET carbon score of less than 40 g / MJ.

[0080] Aspect 8 provides the method of any of Aspects 3-7, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

[0081] Aspect 9 provides the method of any of Aspects 3-8, wherein the metal oxide substrate comprises MgO.

[0082] Aspect 10 provides the method of any of Aspects 3-9, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

[0083] Aspect 11 provides the method of any of Aspects 3-10, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

[0084] Aspect 12 provides the method of any of Aspects 3-11, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

[0085] Aspect 13 provides the method of any of Aspects 3-12, wherein the nickel species comprises less than 1 wt% elemental nickel.

[0086] Aspect 14 provides the method of any of Aspects 3-13, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

[0087] Aspect 15 provides the method of any of Aspects 1-14, wherein methanol comprises at least 80 wt% of the produced methanol composition.

[0088] Aspect 16 provides the method of any of Aspects 1-15, wherein methanol comprises at least 99 wt% of the produced methanol composition.

[0089] Aspect 17 provides the method of any of Aspects 1-16, wherein any carbon dioxide is present in or produced with the methanol composition and is recirculated as feedstock for syngas production.

[0090] Aspect 18 provides the method of any of Aspects 1-17, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

[0091] Aspect 19 provides the method of any of Aspects 1-18, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

[0092] Aspect 20 provides the method of any of Aspects 1-19, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

[0093] Aspect 21 provides the method of any of Aspects 1-20, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngas feedstock that is not an unprocessed syngas having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0094] Aspect 22 provides the method of any of Aspects 1-21, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 97% lower than a corresponding method using a syngas feedstock that is not an unprocessed syngas having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0095] Aspect 23 provides the method of any of Aspects 1-22, wherein heat recovered from the syngas reactor is used to operate a carbon dioxide recovery unit.

[0096] Aspect 24 provides the method of any of Aspects 1-23, wherein heat recovered from the syngas reactor is used to create enough power to run the process without the need for grid power.

[0097] Aspect 25 provides the method of any of Aspects 1-24, wherein the unprocessed syngas is not exposed to a water-gas shift process, a vacuum pressure swing adsorption process, a pressure swing adsorption process, a cryogenic separation process, membrane unit separation process, or a combination thereof prior to being exposed to the methanol forming catalyst.

[0098] Aspect 26 provides the method of any of Aspects 1-25, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0099] Aspect 27 provides the method of any of Aspects 1-26, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0100] Aspect 28 provides the method of any of Aspects 1-27, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is carbon from carbon dioxide.

[0101] Aspect 29 provides the method of any of Aspects 1-28, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is biogenic carbon from reformed carbon dioxide.

[0102] Aspect 30 provides the method of any of Aspects 1-29, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0103] Aspect 31 provides the method of any of Aspects 1-30, wherein about 100 wt% of the carbon content in the methanol composition is from a non- hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0104] Aspect 32 provides the method of any of Aspects 1-31, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

[0105] Aspect 33 provides a method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

[0106] Aspect 34 provides the method of Aspect 33, wherein a molar ratio of hydrogen and carbon monoxide in the syngas is in a range of from about 2.6: 1 to about 1.8: 1.

[0107] Aspect 35 provides the method of any of Aspects 33 or 34, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

[0108] Aspect 36 provides the method of any of Aspects 33-35, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

[0109] Aspect 37 provides the method of Aspect 36, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

[0110] Aspect 38 provides the method of any of Aspects 36 or 37, wherein the hydrocarbon is a C1-C4 hydrocarbon.

[0111] Aspect 39 provides the method of any of Aspects 36-38, wherein the hydrocarbon comprises methane.

[0112] Aspect 40 provides the method of any of Aspects 36-39, wherein the hydrocarbon is a low-carbon score hydrocarbon.

[0113] Aspect 41 provides the method of any of Aspects 36-40, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

[0114] Aspect 42 provides the method of any of Aspects 36-41, wherein the metal oxide substrate comprises MgO.

[0115] Aspect 43 provides the method of any of Aspects 36-42, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

[0116] Aspect 44 provides the method of any of Aspects 36-43, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

[0117] Aspect 45 provides the method of any of Aspects 36-44, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

[0118] Aspect 46 provides the method of any of Aspects 36-45, wherein the nickel species comprises less than 1 wt% elemental nickel.

[0119] Aspect 47 provides the method of any of Aspects 36-46, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

[0120] Aspect 48 provides the method of any of Aspects 33-47, wherein methanol comprises at least 90 wt% of the produced methanol composition.

[0121] Aspect 49 provides the method of any of Aspects 33-48, wherein methanol comprises at least 99 wt% of the produced methanol composition.

[0122] Aspect 50 provides the method of any of Aspects 33-49, wherein any carbon dioxide with the methanol composition is recirculated as feedstock for syngas production.

[0123] Aspect 51 provides the method of any of Aspects 33-50, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

[0124] Aspect 52 provides the method of any of Aspects 33-51, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

[0125] Aspect 53 provides the method of any of Aspects 33-52, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0126] Aspect 54 provides the method of any of Aspects 33-53, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 95% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0127] Aspect 55 provides the method of any of Aspects 33-54, wherein heat recovered from the syngas reactor is used to power a carbon dioxide recovery unit.

[0128] Aspect 56 provides the method of any of Aspect 33-55, wherein the syngas is not exposed to a water-gas shift process, a vacuum pressure swing adsorption process, a pressure swing adsorption process, a cryogenic separationprocess, membrane unit separation process, or a combination thereof prior to being exposed to the methanol forming catalyst.

[0129] Aspect 57 provides the method of any of Aspects 33-56, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0130] Aspect 58 provides the method of any of Aspects 33-57, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0131] Aspect 59 provides the method of any of Aspects 33-58, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is carbon from carbon dioxide.

[0132] Aspect 60 provides the method of any of Aspects 33-59, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is biogenic carbon from reformed carbon dioxide.

[0133] Aspect 61 provides the method of any of Aspects 33-60, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0134] Aspect 62 provides the method of any of Aspects 33-61, wherein about 100 wt% of the carbon content in the methanol composition is from a non- hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0135] Aspect 63 provides the method of any of Aspects 33-62, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

[0136] Aspect 64 provides a method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; and producing a methanol composition, wherein a total amount of greenhouse gas emissions to produce the methanol composition at least 25% lower than a corresponding method using asyngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0137] Aspect 65 provides the method of Aspect 64, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

[0138] Aspect 66 provides the method of any of Aspects 64 or 65, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

[0139] Aspect 67 provides the method of Aspect 66, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

[0140] Aspect 68 provides the method of any of Aspects 66 or 67, wherein the hydrocarbon is a C1-C4 hydrocarbon.

[0141] Aspect 69 provides the method of any of Aspects 66-68, wherein the hydrocarbon comprises methane.

[0142] Aspect 70 provides the method of any of Aspects 66-69, wherein the hydrocarbon is a low-carbon score hydrocarbon.

[0143] Aspect 71 provides the method of any of Aspects 66-70, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

[0144] Aspect 72 provides the method of any of Aspects 66-71, wherein the metal oxide substrate comprises MgO.

[0145] Aspect 73 provides the method of any of Aspects 66-72, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

[0146] Aspect 74 provides the method of any of Aspects 66-73, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

[0147] Aspect 75 provides the method of any of Aspects 66-74, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

[0148] Aspect 76 provides the method of any of Aspects 66-75, wherein the nickel species comprises less than 1 wt% elemental nickel.

[0149] Aspect 77 provides the method of any of Aspects 66-76, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

[0150] Aspect 78 provides the method of any of Aspects 64-77, wherein methanol comprises at least 90 wt% of the methanol composition.

[0151] Aspect 79 provides the method of any of Aspects 64-78, wherein methanol comprises at least 97 wt% of the methanol composition.

[0152] Aspect 80 provides the method of any of Aspects 64-79, wherein any carbon dioxide produced with the methanol composition is circulated for syngas production.

[0153] Aspect 81 provides the method of any of Aspects 64-80, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

[0154] Aspect 82 provides the method of any of Aspects 64-81, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

[0155] Aspect 83 provides the method of any of Aspects 64-82, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

[0156] Aspect 84 provides the method of any of Aspects 64-83, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0157] Aspect 85 provides the method of any of Aspects 64-84, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 97% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0158] Aspect 86 provides the method of any of Aspects 64-85, wherein heat recovered from the reaction to produce methanol composition is used to power a carbon dioxide recovery unit.

[0159] Aspect 87 provides the method of any of Aspect 64-86, wherein the syngas is not exposed to a water-gas shift process, a vacuum pressure swing adsorption process, a pressure swing adsorption process, a cryogenic separation process, membrane unit separation process, or a combination thereof prior to being exposed to the methanol forming catalyst.

[0160] Aspect 88 provides the method of any of Aspects 64-87, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0161] Aspect 89 provides the method of any of Aspects 64-88, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0162] Aspect 90 provides the method of any of Aspects 64-89, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is carbon from carbon dioxide.

[0163] Aspect 91 provides the method of any of Aspects 64-90, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is biogenic carbon from reformed carbon dioxide.

[0164] Aspect 92 provides the method of any of Aspects 64-91, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0165] Aspect 93 provides the method of any of Aspects 64-92, wherein about 100 wt% of the carbon content in the methanol composition is from a non- hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0166] Aspect 94 provides the method of any of Aspects 64-93, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

[0167] Aspect 95 provides a method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; andproducing the methanol composition, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0168] Aspect 96 provides the method of Aspect 95, wherein a molar ratio of hydrogen and carbon monoxide in the syngas is in a range of from about 2.6: 1 to about 1.8: 1.

[0169] Aspect 97 provides the method of Aspect 95, wherein greater than about 30% wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0170] Aspect 98 provides the method of any of Aspects 95 or 97, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

[0171] Aspect 99 provides the method of any of Aspects 95-98, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

[0172] Aspect 100 provides the method of Aspect 99, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

[0173] Aspect 101 provides the method of any of Aspects 99 or 100, wherein the hydrocarbon is a C1-C4 hydrocarbon.

[0174] Aspect 102 provides the method of any of Aspects 99-101, wherein the hydrocarbon comprises methane.

[0175] Aspect 103 provides the method of any of Aspects 99-102, wherein the hydrocarbon is a low-carbon score hydrocarbon.

[0176] Aspect 104 provides the method of any of Aspects 99-103, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or mixture comprising any two or more of the foregoing.

[0177] Aspect 105 provides the method of any of Aspects 99-104, wherein the metal oxide substrate comprises MgO.

[0178] Aspect 106 provides the method of any of Aspects 99-105, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

[0179] Aspect 107 provides the method of any of Aspects 99-106, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

[0180] Aspect 108 provides the method of any of Aspects 99-107, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

[0181] Aspect 109 provides the method of any of Aspects 99-108, wherein the nickel species comprises less than 1 wt% elemental nickel.

[0182] Aspect 110 provides the method of any of Aspects 99-109, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

[0183] Aspect 111 provides the method of any of Aspects 95-110, wherein methanol comprises at least 80 wt% of the produced methanol composition.

[0184] Aspect 112 provides the method of any of Aspects 95-111, wherein methanol comprises at least 99 wt% of the produced methanol composition.

[0185] Aspect 113 provides the method of any of Aspects 95-112, wherein any carbon dioxide is present in or produced with the methanol composition and is recirculated as feedstock for syngas production.

[0186] Aspect 114 provides the method of any of Aspects 95-113, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

[0187] Aspect 115 provides the method of any of Aspects 95-114, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

[0188] Aspect 116 provides the method of any of Aspects 95-115, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

[0189] Aspect 117 provides the method of any of Aspects 95-116, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngasfeedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0190] Aspect 118 provides the method of any of Aspects 95-117, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 95% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0191] Aspect 119 provides the method of any of Aspects 95-118, wherein heat recovered from the reaction to produce methanol composition is used to power a carbon dioxide recovery unit.

[0192] Aspect 120 provides the method of any of Aspect 95-119, wherein the syngas is not exposed to a water-gas shift process, a vacuum pressure swing adsorption process, a pressure swing adsorption process, a cryogenic separation process, membrane unit separation process, or a combination thereof prior to being exposed to the methanol forming catalyst.

[0193] Aspect 121 provides the method of any of Aspects 95-120, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0194] Aspect 122 provides the method of any of Aspects 95-121, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is carbon from carbon dioxide.

[0195] Aspect 123 provides the method of any of Aspects 95-122, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is biogenic carbon from reformed carbon dioxide.

[0196] Aspect 124 provides the method of any of Aspects 95-123, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0197] Aspect 125 provides the method of any of Aspects 95-124, wherein about 100 wt% of the carbon content in the methanol composition isfrom a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0198] Aspect 126 provides the method of any of Aspects 95-125, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

[0199] Aspect 127 provides a method of forming a methanol composition, the method comprising: producing syngas in a range of molar ration of hydrogen to carbon monoxide of about 1 : 1 to 1.8: 1; separating out the excess carbon monoxide to correct the ratio from 1.8: 1 to about 2.6: 1 : contacting the syngas with a methanol forming catalyst; and producing the methanol composition, wherein a total amount of energy required to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

[0200] Aspect 128 provides the method of Aspect 127, wherein a total amount of energy to produce the methanol composition is less than about 25 MMBtu / T onne of Methanol .

[0201] Aspect 129 provides the method of any of Aspects 127 or 128, wherein a total amount of energy to produce the methanol composition is less than about 22 MMBtu / Tonne of Methanol.

[0202] Aspect 130 provides the method of any of Aspects 127-129, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

[0203] Aspect 131 provides the method of any of Aspects 127-130, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

[0204] Aspect 132 provides the method of Aspect 131, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

[0205] Aspect 133 provides the method of any of Aspects 131 or 132, wherein the hydrocarbon is a C1-C4 hydrocarbon.

[0206] Aspect 134 provides the method of any of Aspects 131-133, wherein the hydrocarbon comprises methane.

[0207] Aspect 135 provides the method of any of Aspects 131-134, wherein the hydrocarbon is a low-carbon score hydrocarbon.

[0208] Aspect 136 provides the method of any of Aspects 131-135, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

[0209] Aspect 137 provides the method of any of Aspects 131-136, wherein the metal oxide substrate comprises MgO.

[0210] Aspect 138 provides the method of any of Aspects 131-137, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

[0211] Aspect 139 provides the method of any of Aspects 131-138, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

[0212] Aspect 140 provides the method of any of Aspects 131-139, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

[0213] Aspect 141 provides the method of any of Aspects 131-140, wherein the nickel species comprises less than 1 wt% elemental nickel.

[0214] Aspect 142 provides the method of any of Aspects 131-141, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

[0215] Aspect 143 provides the method of any of Aspects 127-142, wherein methanol comprises at least 80 wt% of the produced methanol composition.

[0216] Aspect 144 provides the method of any of Aspects 127-143, wherein methanol comprises at least 99 wt% of the produced methanol composition.

[0217] Aspect 145 provides the method of any of Aspects 127-144, wherein any carbon dioxide is present in or produced with the methanol composition and is recirculated as feedstock for syngas production.

[0218] Aspect 146 provides the method of any of Aspects 127-145, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

[0219] Aspect 147 provides the method of any of Aspects 127-146, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

[0220] Aspect 148 provides the method of any of Aspects 127-147, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0221] Aspect 149 provides the method of any of Aspects 127-148, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 97% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0222] Aspect 150 provides the method of any of Aspects 127-149, wherein heat recovered from the syngas reactor is used to power a carbon dioxide recovery unit.

[0223] Aspect 151 provides the method of any of Aspect 127-150, wherein the syngas is exposed to further processing to produce a 2.2: 1 molar ratio of hydrogen and carbon monoxide.

[0224] Aspect 152 provides the method of any of Aspects 127-151, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0225] Aspect 153 provides the method of any of Aspects 127-152, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0226] Aspect 154 provides the method of any of Aspects 127-153, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is carbon from carbon dioxide.

[0227] Aspect 155 provides the method of any of Aspects 127-154, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is biogenic carbon from reformed carbon dioxide.

[0228] Aspect 156 provides the method of any of Aspects 127-155, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0229] Aspect 157 provides the method of any of Aspects 127-156, wherein about 100 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

[0230] Aspect 158 provides the method of any of Aspects 127-157, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

[0231] Aspect 159 provides a method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein greater than about 10 wt% of the methanol composition is from a non-hydrocarbon source.

[0232] Aspect 160 provides the method of Aspect 159, wherein a molar ratio of hydrogen and carbon monoxide in the syngas is in a range of from about 2.6: 1 to about 1.8: 1.

[0233] Aspect 161 provides the method of any of Aspects 159 or 160, wherein greater than about 30% wt% of the methanol composition is from a non- hydrocarbon source.

[0234] Aspect 162 provides the method of any of Aspects 159-161, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

[0235] Aspect 163 provides the method of any of Aspects 159-162, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

[0236] Aspect 164 provides the method of Aspect 163, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

[0237] Aspect 165 provides the method of any of Aspects 163 or 164, wherein the hydrocarbon is a C1-C4 hydrocarbon.

[0238] Aspect 166 provides the method of any of Aspects 163-165, wherein the hydrocarbon comprises methane.

[0239] Aspect 167 provides the method of any of Aspects 163-166, wherein the hydrocarbon is a low-carbon score hydrocarbon.

[0240] Aspect 168 provides the method of any of Aspects 163-167, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

[0241] Aspect 169 provides the method of any of Aspects 163-168, wherein the metal oxide substrate comprises MgO.

[0242] Aspect 170 provides the method of any of Aspects 163-169, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

[0243] Aspect 171 provides the method of any of Aspects 163-170, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

[0244] Aspect 172 provides the method of any of Aspects 163-171, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

[0245] Aspect 173 provides the method of any of Aspects 163-172, wherein the nickel species comprises less than 1 wt% elemental nickel.

[0246] Aspect 174 provides the method of any of Aspects 163-173, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

[0247] Aspect 175 provides the method of any of Aspects 159-174, wherein methanol comprises at least 80 wt% of the produced methanol composition.

[0248] Aspect 176 provides the method of any of Aspects 159-175, wherein methanol comprises at least 99 wt% of the methanol composition.

[0249] Aspect 177 provides the method of any of Aspects 159-176, wherein any carbon dioxide is present in or produced with the methanol composition and is recirculated as feedstock for syngas production.

[0250] Aspect 178 provides the method of any of Aspects 159-177, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

[0251] Aspect 179 provides the method of any of Aspects 159-178, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

[0252] Aspect 180 provides the method of any of Aspects 159-179, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

[0253] Aspect 181 provides the method of any of Aspects 159-180, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0254] Aspect 182 provides the method of any of Aspects 159-181, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 97% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

[0255] Aspect 183 provides the method of any of Aspects 159-182, wherein heat recovered from the reaction to produce methanol composition is used to power a carbon dioxide recovery unit.

[0256] Aspect 184 provides the method of any of Aspect 159-183, wherein the syngas is not exposed to a water-gas shift procedure, a vacuumpressure swing adsorber procedure, a pressure swing adsorber procedure, a cryogenic separator, membrane unit, or a combination thereof prior to being exposed to the methanol forming catalyst.

[0257] Aspect 185 provides the method of any of Aspects 159-184, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

[0258] Aspect 186 provides the method of any of Aspects 159-185, wherein the methanol composition is a fuel for a maritime vessel.

[0259] Aspect 187 provides a maritime vessel comprising the methanol composition of any of Aspects 1-186, disposed in a fuel tank in communication to an engine.

[0260] Aspect 188 provides a method of powering a maritime vessel, the method comprising: combusting methanol produced according to any of Aspects 1-186; and using energy from the combustion to rotate a propeller operably connected to an engine of the maritime vessel.

[0261] Aspect 189 provides the method of Aspect 188, wherein the methanol composition is a fuel for a maritime vessel.

[0262] Aspect 190 provides a method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein the energy yield of the final methanol composition is greater than 58% of the total energy put into the method.

[0263] Aspect 191 provides the method of Aspect 190, wherein the energy yield of the final methanol composition is greater than 65% of the total energy put into the method.

[0264] Aspect 192 provides the method of Aspect 190, wherein the energy yield of the final methanol composition is greater than 70% of the total energy put into the method.

[0265] The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the aspects of the present disclosure. Thus, it should be understood that although the present disclosure has been specifically disclosed by specific aspects and optional features, modification and variation of the concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of aspects of the present disclosure.

Claims

CLAIMSWhat is claimed is:

1. A method of forming a methanol composition, the method comprising: contacting unprocessed syngas with a methanol forming catalyst; and producing the methanol composition, wherein a molar ratio of hydrogen and carbon monoxide in the unprocessed syngas is in a range of from about 2.6: 1 to about 1.8: 1.

2. The method of claim 1, wherein the molar ratio of hydrogen and carbon monoxide in the unprocessed syngas is about 2.2: 1.

3. The method of any of claims 1 or 2, wherein the unprocessed syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

4. The method of claim 3, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

5. The method of any of claims 3 or 4, wherein the hydrocarbon is a C1-C4 hydrocarbon.

6. The method of any of claims 3-5, wherein the hydrocarbon comprises methane.

7. The method of any of claims 3-6, wherein the hydrocarbon is a low- carbon footprint hydrocarbon with a GREET carbon score of less than 40 g / MJ.

8. The method of any of claims 3-7, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

9. The method of any of claims 3-8, wherein the metal oxide substrate comprises MgO.

10. The method of any of claims 3-9, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

11. The method of any of claims 3-10, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

12. The method of any of claims 3-11, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

13. The method of any of claims 3-12, wherein the nickel species comprises less than 1 wt% elemental nickel.

14. The method of any of claims 3-13, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

15. The method of any of claims 1-14, wherein methanol comprises at least 80 wt% of the produced methanol composition.

16. The method of any of claims 1-15, wherein methanol comprises at least 99 wt% of the produced methanol composition.

17. The method of any of claims 1-16, wherein any carbon dioxide is present in or produced with the methanol composition and is recirculated as feedstock for syngas production.

18. The method of any of claims 1-17, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

19. The method of any of claims 1-18, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

20. The method of any of claims 1-19, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

21. The method of any of claims 1-20, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngas feedstock that is not an unprocessed syngas having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

22. The method of any of claims 1-21, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 97% lower than a corresponding method using a syngas feedstock that is not an unprocessed syngas having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

23. The method of any of claims 1-22, wherein heat recovered from the syngas reactor is used to operate a carbon dioxide recovery unit.

24. The method of any of claims 1-23, wherein heat recovered from the syngas reactor is used to create enough power to run the process without the need for grid power.

25. The method of any of claims 1-24, wherein the unprocessed syngas is not exposed to a water-gas shift process, a vacuum pressure swing adsorption process, a pressure swing adsorption process, a cryogenic separation process, membrane unit separation process, or a combination thereof prior to being exposed to the methanol forming catalyst.

26. The method of any of claims 1-25, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

27. The method of any of claims 1-26, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

28. The method of any of claims 1-27, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is carbon from carbon dioxide.

29. The method of any of claims 1-28, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is biogenic carbon from reformed carbon dioxide.

30. The method of any of claims 1-29, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

31. The method of any of claims 1-30, wherein about 100 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

32. The method of any of claims 1-31, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

33. A method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

34. The method of claim 33, wherein a molar ratio of hydrogen and carbon monoxide in the syngas is in a range of from about 2.6: 1 to about 1.8: 1.

35. The method of any of claims 33 or 34, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

36. The method of any of claims 33-35, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

37. The method of claim 36, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

38. The method of any of claims 36 or 37, wherein the hydrocarbon is a Cl- C4 hydrocarbon.

39. The method of any of claims 36-38, wherein the hydrocarbon comprises methane.

40. The method of any of claims 36-39, wherein the hydrocarbon is a low- carbon score hydrocarbon.

41. The method of any of claims 36-40, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

42. The method of any of claims 36-41, wherein the metal oxide substrate comprises MgO.

43. The method of any of claims 36-42, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

44. The method of any of claims 36-43, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

45. The method of any of claims 36-44, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

46. The method of any of claims 36-45, wherein the nickel species comprises less than 1 wt% elemental nickel.

47. The method of any of claims 36-46, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

48. The method of any of claims 33-47, wherein methanol comprises at least 90 wt% of the produced methanol composition.

49. The method of any of claims 33-48, wherein methanol comprises at least 99 wt% of the produced methanol composition.

50. The method of any of claims 33-49, wherein any carbon dioxide with the methanol composition is recirculated as feedstock for syngas production.

51. The method of any of claims 33-50, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

52. The method of any of claims 33-51, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

53. The method of any of claims 33-52, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

54. The method of any of claims 33-53, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 95% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

55. The method of any of claims 33-54, wherein heat recovered from the syngas reactor is used to power a carbon dioxide recovery unit.

56. The method of any of claim 33-55, wherein the syngas is not exposed to a water-gas shift process, a vacuum pressure swing adsorption process, a pressure swing adsorption process, a cryogenic separation process, membrane unit separation process, or a combination thereof prior to being exposed to the methanol forming catalyst.

57. The method of any of claims 33-56, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

58. The method of any of claims 33-57, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

59. The method of any of claims 33-58, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is carbon from carbon dioxide.

60. The method of any of claims 33-59, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is biogenic carbon from reformed carbon dioxide.

61. The method of any of claims 33-60, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

62. The method of any of claims 33-61, wherein about 100 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

63. The method of any of claims 33-62, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

64. A method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; and producing a methanol composition, whereina total amount of greenhouse gas emissions to produce the methanol composition at least 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

65. The method of claim 64, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

66. The method of any of claims 64 or 65, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

67. The method of claim 66, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

68. The method of any of claims 66 or 67, wherein the hydrocarbon is a Cl- C4 hydrocarbon.

69. The method of any of claims 66-68, wherein the hydrocarbon comprises methane.

70. The method of any of claims 66-69, wherein the hydrocarbon is a low- carbon score hydrocarbon.

71. The method of any of claims 66-70, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

72. The method of any of claims 66-71, wherein the metal oxide substrate comprises MgO.

73. The method of any of claims 66-72, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

74. The method of any of claims 66-73, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

75. The method of any of claims 66-74, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

76. The method of any of claims 66-75, wherein the nickel species comprises less than 1 wt% elemental nickel.

77. The method of any of claims 66-76, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

78. The method of any of claims 64-77, wherein methanol comprises at least 90 wt% of the methanol composition.

79. The method of any of claims 64-78, wherein methanol comprises at least 97 wt% of the methanol composition.

80. The method of any of claims 64-79, wherein any carbon dioxide produced with the methanol composition is circulated for syngas production.

81. The method of any of claims 64-80, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

82. The method of any of claims 64-81, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

83. The method of any of claims 64-82, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

84. The method of any of claims 64-83, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

85. The method of any of claims 64-84, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 97% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

86. The method of any of claims 64-85, wherein heat recovered from the reaction to produce methanol composition is used to power a carbon dioxide recovery unit.

87. The method of any of claim 64-86, wherein the syngas is not exposed to a water-gas shift process, a vacuum pressure swing adsorption process, a pressure swing adsorption process, a cryogenic separation process, membrane unit separation process, or a combination thereof prior to being exposed to the methanol forming catalyst.

88. The method of any of claims 64-87, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

89. The method of any of claims 64-88, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

90. The method of any of claims 64-89, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is carbon from carbon dioxide.

91. The method of any of claims 64-90, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is biogenic carbon from reformed carbon dioxide.

92. The method of any of claims 64-91, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

93. The method of any of claims 64-92, wherein about 100 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

94. The method of any of claims 64-93, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

95. A method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

96. The method of claim 95, wherein a molar ratio of hydrogen and carbon monoxide in the syngas is in a range of from about 2.6: 1 to about 1.8: 1.

97. The method of claim 95, wherein greater than about 30% wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

98. The method of any of claims 95 or 97, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

99. The method of any of claims 95-98, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

100. The method of claim 99, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

101. The method of any of claims 99 or 100, wherein the hydrocarbon is a Cl- C4 hydrocarbon.

102. The method of any of claims 99-101, wherein the hydrocarbon comprises methane.

103. The method of any of claims 99-102, wherein the hydrocarbon is a low- carbon score hydrocarbon.

104. The method of any of claims 99-103, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or mixture comprising any two or more of the foregoing.

105. The method of any of claims 99-104, wherein the metal oxide substrate comprises MgO.

106. The method of any of claims 99-105, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

107. The method of any of claims 99-106, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

108. The method of any of claims 99-107, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

109. The method of any of claims 99-108, wherein the nickel species comprises less than 1 wt% elemental nickel.

110. The method of any of claims 99-109, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

111. The method of any of claims 95-110, wherein methanol comprises at least 80 wt% of the produced methanol composition.

112. The method of any of claims 95-111, wherein methanol comprises at least 99 wt% of the produced methanol composition.

113. The method of any of claims 95-112, wherein any carbon dioxide is present in or produced with the methanol composition and is recirculated as feedstock for syngas production.

114. The method of any of claims 95-113, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

115. The method of any of claims 95-114, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

116. The method of any of claims 95-115, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

117. The method of any of claims 95-116, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

118. The method of any of claims 95-117, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 95% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

119. The method of any of claims 95-118, wherein heat recovered from the reaction to produce methanol composition is used to power a carbon dioxide recovery unit.

120. The method of any of claim 95-119, wherein the syngas is not exposed to a water-gas shift process, a vacuum pressure swing adsorption process, a pressure swing adsorption process, a cryogenic separation process, membrane unit separation process, or a combination thereof prior to being exposed to the methanol forming catalyst.

121. The method of any of claims 95-120, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source.

122. The method of any of claims 95-121, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is carbon from carbon dioxide.

123. The method of any of claims 95-122, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source and is biogenic carbon from reformed carbon dioxide.

124. The method of any of claims 95-123, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

125. The method of any of claims 95-124, wherein about 100 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

126. The method of any of claims 95-125, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

127. A method of forming a methanol composition, the method comprising: producing syngas in a range of molar ration of hydrogen to carbon monoxide of about 1 : 1 to 1.8: 1; separating out the excess carbon monoxide to correct the ratio from 1.8: 1 to about 2.6: 1 : contacting the syngas with a methanol forming catalyst; and producing the methanol composition, wherein a total amount of energy required to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

128. The method of claim 127, wherein a total amount of energy to produce the methanol composition is less than about 25 MMBtu / Tonne of Methanol.

129. The method of any of claims 127 or 128, wherein a total amount of energy to produce the methanol composition is less than about 22 MMBtu / T onne of Methanol .

130. The method of any of claims 127-129, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

131. The method of any of claims 127-130, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

132. The method of claim 131, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

133. The method of any of claims 131 or 132, wherein the hydrocarbon is a C1-C4 hydrocarbon.

134. The method of any of claims 131-133, wherein the hydrocarbon comprises methane.

135. The method of any of claims 131-134, wherein the hydrocarbon is a low- carbon score hydrocarbon.

136. The method of any of claims 131-135, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

137. The method of any of claims 131-136, wherein the metal oxide substrate comprises MgO.

138. The method of any of claims 131-137, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

139. The method of any of claims 131-138, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

140. The method of any of claims 131-139, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

141. The method of any of claims 131-140, wherein the nickel species comprises less than 1 wt% elemental nickel.

142. The method of any of claims 131-141, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

143. The method of any of claims 127-142, wherein methanol comprises at least 80 wt% of the produced methanol composition.

144. The method of any of claims 127-143, wherein methanol comprises at least 99 wt% of the produced methanol composition.

145. The method of any of claims 127-144, wherein any carbon dioxide is present in or produced with the methanol composition and is recirculated as feedstock for syngas production.

146. The method of any of claims 127-145, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

147. The method of any of claims 127-146, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

148. The method of any of claims 127-147, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

149. The method of any of claims 127-148, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 97% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

150. The method of any of claims 127-149, wherein heat recovered from the syngas reactor is used to power a carbon dioxide recovery unit.

151. The method of any of claim 127-150, wherein the syngas is exposed to further processing to produce a 2.2: 1 molar ratio of hydrogen and carbon monoxide.

152. The method of any of claims 127-151, wherein greater than about 10 wt% of the carbon content in the methanol composition is from a nonhydrocarbon source.

153. The method of any of claims 127-152, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a nonhydrocarbon source.

154. The method of any of claims 127-153, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a non- hydrocarbon source and is carbon from carbon dioxide.

155. The method of any of claims 127-154, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a nonhydrocarbon source and is biogenic carbon from reformed carbon dioxide.

156. The method of any of claims 127-155, wherein greater than about 50 wt% of the carbon content in the methanol composition is from a nonhydrocarbon source or renewable hydrocarbon source or a combination thereof.

157. The method of any of claims 127-156, wherein about 100 wt% of the carbon content in the methanol composition is from a non-hydrocarbon source or renewable hydrocarbon source or a combination thereof.

158. The method of any of claims 127-157, wherein about 100 wt% of the carbon content in the methanol composition is from a renewable hydrocarbon source and biogenic carbon from reformed carbon dioxide.

159. A method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein greater than about 10 wt% of the methanol composition is from a nonhydrocarbon source.

160. The method of claim 159, wherein a molar ratio of hydrogen and carbon monoxide in the syngas is in a range of from about 2.6: 1 to about 1.8: 1.

161. The method of any of claims 159 or 160, wherein greater than about 30% wt% of the methanol composition is from a non-hydrocarbon source.

162. The method of any of claims 159-161, wherein the molar ratio of hydrogen and carbon monoxide in the syngas is about 2.2: 1.

163. The method of any of claims 159-162, wherein the syngas is produced by exposing a mixture comprising one or more of steam, hydrocarbon, and carbon dioxide to a metal oxide substrate comprising a nickel species, wherein an exposed surface of the catalyst particle comprises at least some of the nickel species and the exposed surface is substantially nonporous.

164. The method of claim 163, wherein a pore volume of the catalyst particle is less than 0.1 cm3 / g.

165. The method of any of claims 163 or 164, wherein the hydrocarbon is a C1-C4 hydrocarbon.

166. The method of any of claims 163-165, wherein the hydrocarbon comprises methane.

167. The method of any of claims 163-166, wherein the hydrocarbon is a low- carbon score hydrocarbon.

168. The method of any of claims 163-167, wherein the metal oxide substrate comprises NiO, CoO, FeO, MnO, MgO, or a mixture comprising any two or more of the foregoing.

169. The method of any of claims 163-168, wherein the metal oxide substrate comprises MgO.

170. The method of any of claims 163-169, wherein the nickel species is 0.2 wt% to 30 wt% of the catalyst particle.

171. The method of any of claims 163-170, wherein the nickel species is 12 wt% to 18 wt% of the catalyst particle.

172. The method of any of claims 163-171, wherein the nickel species is homogeneously distributed in the metal oxide substrate.

173. The method of any of claims 163-172, wherein the nickel species comprises less than 1 wt% elemental nickel.

174. The method of any of claims 163-173, wherein the catalyst particle does not contain free elemental nickel, free nickel oxide, or any mixture thereof in the nickel species.

175. The method of any of claims 159-174, wherein methanol comprises at least 80 wt% of the produced methanol composition.

176. The method of any of claims 159-175, wherein methanol comprises at least 99 wt% of the methanol composition.

177. The method of any of claims 159-176, wherein any carbon dioxide is present in or produced with the methanol composition and is recirculated as feedstock for syngas production.

178. The method of any of claims 159-177, wherein the methanol forming catalyst comprises copper, zinc oxide, alumina and magnesium, or a mixture comprising any two or more of the foregoing.

179. The method of any of claims 159-178, wherein a total amount of energy to produce the methanol composition is less than about 33 MMBtu / Tonne of methanol.

180. The method of any of claims 159-179, wherein a total amount of energy to produce the methanol composition is less than about 30 MMBtu / Tonne of methanol.

181. The method of any of claims 159-180, wherein a total amount of greenhouse gas emissions to produce the methanol composition is at least 25% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

182. The method of any of claims 159-181, wherein a total amount of greenhouse gas emissions to produce the methanol composition is 97% lower than a corresponding method using a syngas feedstock having a molar ratio of hydrogen and carbon monoxide in a range of from about 2.6: 1 to about 1.8: 1.

183. The method of any of claims 159-182, wherein heat recovered from the reaction to produce methanol composition is used to power a carbon dioxide recovery unit.

184. The method of any of claim 159-183, wherein the syngas is not exposed to a water-gas shift procedure, a vacuum pressure swing adsorber procedure, a pressure swing adsorber procedure, a cryogenic separator, membrane unit, or a combination thereof prior to being exposed to the methanol forming catalyst.

185. The method of any of claims 159-184, wherein greater than about 30 wt% of the carbon content in the methanol composition is from a nonhydrocarbon source.

186. The method of any of claims 159-185, wherein the methanol composition is a fuel for a maritime vessel.

187. A maritime vessel comprising the methanol composition of any of claims 1-186, disposed in a fuel tank in communication to an engine.

188. A method of powering a maritime vessel, the method comprising: combusting methanol produced according to any of claims 1-186; and using energy from the combustion to rotate a propeller operably connected to an engine of the maritime vessel.

189. The method of claim 188, wherein the methanol composition is a fuel for a maritime vessel.

190. A method of forming a methanol composition, the method comprising: contacting syngas with a methanol forming catalyst; and producing the methanol composition, wherein the energy yield of the final methanol composition is greater than 58% of the total energy put into the method.

191. The method of claim 190, wherein the energy yield of the final methanol composition is greater than 65% of the total energy put into the method.

192. The method of claim 190, wherein the energy yield of the final methanol composition is greater than 70% of the total energy put into the method.

193. The method of claim 190, wherein the energy yield of the final methanol composition is greater than 74% of the total energy put into the method.