WO2016061584A1

WO2016061584A1 - Production of clean hydrocarbon and nitrogen-based fuel

Info

Publication number: WO2016061584A1
Application number: PCT/US2015/056253
Authority: WO
Inventors: Kamal JAFFREY
Original assignee: Solutions Labs, Inc.
Priority date: 2014-10-17
Filing date: 2015-10-19
Publication date: 2016-04-21

Abstract

Clean hydrocarbon or nitrogen-based fuels can be produced, for example, by decarbonizing source hydrocarbons using halogen to produce elemental carbon and hydrogen halide species. The hydrogen halide species can be separated by adding energy to produce hydrogen and halogen. Additionally, fuel comprising hydrocarbons having substantially homogenous composition and a vector can be synthesized from the hydrogen and carbon. Related apparatus, systems, techniques, and compositions of matter are also described.

Description

PRODUCTION OF CLEAN HYDROCARBON AND

NITROGEN-BASED FUEL

RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 62/065,056 filed October 17, 2014, the entire contents of which is hereby expressly incorporated by reference herein.

TECHNICAL FIELD

[0002] The subject matter described herein relates to hydrocarbon and nitrogen-based fuel production. Related apparatus, systems, techniques, and compositions of matter are also described.

BACKGROUND

[0003] Fossil fuels, including coal, oil and natural gas, are currently the world's primary energy source. Formed from organic material over the course of millions of years, fossil fuels have fueled U.S. and global economic development over the past century. Yet fossil fuels are finite resources and they can also irreparably harm the environment. According to the Environmental Protection Agency, the burning of fossil fuels was responsible for 79 percent of U.S. greenhouse gas emissions in 2010. These gases insulate the planet and could lead to potentially catastrophic changes in the earth' s climate. Numerous alternate technologies such as Carbon Capture and Storage (CCS), nuclear energy and renewable energy are currently being explored as alternate energy sources, which are not harmful to our environment. [0004] In addition, many fossil fuels currently in use exhibit low energy efficiencies due to their lack of purity. For example, only about 14%-30% of the energy from the fuel one puts in a conventional automobile is used to actually move it down the road. Inefficiency in combustions of these hydrocarbon mixtures in vehicles produces many noxious side products including carbon dioxide, which is primarily responsible for the observed "greenhouse effect." The energy required to form carbon dioxide results in additional inefficiencies in the combustion process. New methods to produce cleaner hydrocarbon fossil fuels with increased energy efficiency or alternate energy fuels are in great need.

SUMMARY

[0005] Clean hydrocarbon or nitrogen-based fuels can be produced, for example, by decarbonizing source hydrocarbons using a halogen to produce elemental carbon and hydrogen halide species. For example, methane can be used as a source of hydrocarbons. In another example, coal can be used as a source of hydrocarbon. The hydrogen halide species can be separated by adding energy to produce hydrogen and halogen. Additionally, fuel comprising hydrocarbons having substantially homogenous composition and a vector can be synthesized from the hydrogen and carbon. One such fuel comprising hydrocarbons can include octane.

[0006] Clean hydrocarbon fuels can include compositions of hydrocarbons that are substantially homogenous. This can include, for example, compositions of hydrocarbons that are between 70 and 99 percent homogenous. Other percentages are possible. Dirty hydrocarbon fuels can include compositions of hydrocarbons being less than 30 percent homogenous. Other percentages are possible. [0007] In one aspect, provided is a method of producing a hydrocarbon fuel which may comprise steps of: decarbonizing a source hydrocarbon by introducing halogen to produce elemental carbon and hydrogen halide; and producing the hydrocarbon fuel by reacting the elemental carbon with hydrogen (H₂). In particular, the decarbonization may be performed in non-oxygen condition and the hydrocarbon fuel may be produced in the present of a catalyst.

[0008] Preferably, the source hydrocarbon may comprise 1 to 6 carbons.

[0009] Preferably, the halogen may be selected from the group consisting of Cl₂, Br₂, 1₂, ClBr, and mixtures thereof.

[0010] Preferably, the hydrocarbon fuel may comprise 8 to 30 carbons.

[0011] In certain embodiments, the decarbonizing may be performed in a combustion chamber. Preferably, the combustion chamber has a volume of about 1 m³ to about 10 m³. Further, during the decarbonization, an internal temperature in the combustion chamber may range from about 298 K to about 2550 K, and a pressure ranges from about 1 atm to about 20 atm.

[0012] Preferably, the catalyst may be an organometallic catalyst comprising at least one metal element selected from the group consisting of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, and Au.

[0013] Preferably, the hydrocarbon fuel is synthesized at a temperature ranging from about 300-350 °C.

[0014] The method may further comprise: decomposing the hydrogen halide by adding energy to produce the hydrogen (H₂) and reproduced halogen; and collecting the hydrogen (H₂) for synthesizing the hydrocarbon fuel. [0015] Preferably, the energy may be added by radiating UV light and a wavelength of the UV light may from about 100 nm to about 320 nm. Further, the UV light may be radiated at least for about 10 min, and at an intensity of about 50 mJ/cm².

[0016] In certain embodiments, the hydrocarbon source may be methane, the halogen may be Br₂, and a ratio between a partial pressure of the methane and a partial pressure Br₂ may be of about 1: 2-10.

[0017] In certain embodiments, the hydrocarbon fuel may be octane.

[0018] The method of claim may further comprise: liquefying the

hydrocarbon fuel.

[0019] In another aspect, provided is a hydrocarbon fuel that is manufactured by a method as described herein. Preferably, the hydrocarbon fuel obtained from the method of the present invention may comprise octane.

[0020] In another aspect, the elemental carbon may be isolated and/or purified from the hydrogen halide.

[0021] The details of one or more variations of the subject matter described herein are set forth in the accompanying drawings and the description below. Other features and advantages of the subject matter described herein will be apparent from the description and drawings, and from the claims.

Definitions

[0022] Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by a person skilled in the art to which this invention belongs. In this disclosure, "comprises," "comprising," "containing" and "having" and the like can have the meaning ascribed to them in U.S. Patent law and can mean " includes," "including," and the like; "consisting essentially of" or "consists essentially" likewise has the meaning ascribed in U.S. Patent law and the term is open-ended, allowing for the presence of more than that which is recited so long as basic or novel characteristics of that which is recited is not changed by the presence of more than that which is recited, but excludes prior art embodiments. In addition, as used herein, the following terms have the meanings ascribed to them below, unless specified otherwise. By "source hydrocarbon" is meant a carbon based material comprising hydrogen, and particularly refers to a starting material for producing desired product, i.e. hydrocarbon fuels. Exemplary hydrocarbon fuel may be hydrocarbons comprising 1 to 12 carbons, or particularly 1 -4 carbons.

[0023] By "hydrocarbon fuel" is meant a carbon based material comprising hydrogen, and particularly refers to a product or resultant from processes of the present invention. Exemplary hydrocarbon fuel may be hydrocarbons comprising 8 to 30 carbons, or particularly 8 -18 carbons, or otherwise, the hydrocarbon fuel may contain octane as major component.

[0024] By "decarbonization" is meant a reaction that dissociates or deprives carbon from hydrogen of the source hydrocarbon, particularly by reacting oxidizer with the hydrocarbons in non-oxygen condition. The oxidizer may include halogen which can make a bond (covalent bond) with hydrogen after dissociation of the carbon from the hydrogen.

[0025] By "hydrogen generation" is meant a reaction that dissociates a bond between hydrogen and halide that may be formed during decarbonization. The dissociated hydrogen may subsequently form hydrogen molecule (H₂).

[0026] By "stitching vector" is meant a chemical reagent or catalyst which serves to reduce bond dissociation energy between carbons, and/or accelerates synthesis of the hydrocarbon fuel. The stitching vector, i.e. catalyst, in the present invention may include organometallic catalyst, organic agent, or mixtures thereof.

[0027] By " liquefication vector" is meant a chemical reagent or catalyst which serves to liquefy the hydrogen fuel in standard state (at a temperature of 298 °K, at a pressure of atmospheric pressure (1 atm)).

DESCRIPTION OF DRAWINGS

[0028] FIG. 1 is a process flow diagram illustrating a process of producing a clean hydrocarbon or nitrogen-based fuel according to the current subject matter.

[0029] FIG. 2 is a system block diagram illustrating the decarbonization process of a hydrocarbon mixture (C_xH_y) to generate halogen halide species (HX) and carbon (C).

[0030] FIG. 3 is a system block illustrating the separation process of the halogen halide species 200 to hydrogen and halogen upon exposure to ultraviolet light or thermal energy.

[0031] FIG. 4 is a system block diagram illustrating the synthesis of hydrocarbon or nitrogen-based species from carbon or nitrogen with hydrogen optionally in the presence of one or more vector(s).

[0032] FIG. 5 is a system block diagram illustrating the liquefication process of hydrocarbon or nitrogen-based species optionally in the presence of energy or one or more vector(s) to generate the final hydrocarbon or nitrogen-based fuel.

[0033] FIG. 6 is a graph illustrating the energy released during

decarbonization of hydrocarbons in numerous halogen environments.

[0034] FIG. 7 is a table illustrating chemical properties of halogens, carbon, hydrogen, nitrogen and oxygen. [0035] FIG. 8 is a table illustrating the ratios of hydrogen and carbon for the preparation of hydrocarbons.

[0036] FIG. 9 is a cross-sectional diagram of another example implementation of a combustion apparatus including a combustion chamber and cyclone that performs decarbonization.

[0037] FIG. 10 is a graph illustrating the heating values in Kj/mole of various fuels based on their number of hydrogen atoms during the decarbonization process with halogens.

[0038] FIG. 11 is a graph illustrating the adiabatic Temperature in °K as a function of the number of hydrogen atoms contained in the fuel used during decarbonization with chlorine and bromine.

[0039] FIG. 12 is a graph illustrating the adiabatic Temperature in °K as a function of the number of hydrogen atoms contained in the fuel used during decarbonization with fluorine.

[0040] FIG 13 is a process flow diagram illustrating an example method of producing clean hydrocarbons.

[0041] FIG. 14 is a diagram of a compact UV reactor.

[0042] FIG. 15 is a diagram of energy according to a wavelength in the UV light.

[0043] FIG. 16 is a diagram of energy according to a frequency in the UV light.

[0044] Like reference symbols in the various drawings indicate like elements. DETAILED DESCRIPTION

[0045] The current subject matter describes production of clean hydrocarbon or nitrogen-based fuels. Clean hydrocarbon or nitrogen-based fuels can be produced, for example, by decarbonizing source hydrocarbons using halogen to produce elemental carbon and hydrogen halide species. For example, methane and/or natural gas can be used as a source of hydrocarbons. Preferably, the source hydrogen may include 1-18 carbons, 1-10 carbons or particularly 1-4 carbons. In another example, coal can be used as a solid source of hydrocarbons.

[0046] The hydrogen halide species can be separated by adding energy to produce hydrogen and halogen. Additionally, fuel comprising hydrocarbons having substantially homogenous composition and a vector can be synthesized from the hydrogen and carbon. Fuels generated comprising hydrocarbons can include octane and/or methane.

[0047] FIG. 1 is a process flow diagram illustrating a process 100 of producing a clean hydrocarbon or nitrogen-based fuel according to the current subject matter. At 110, hydrogen and carbon from hydrocarbons can be separated by combustion of the hydrocarbons in a halogen environment. In particular, the halogen environment does not contain any oxygen or nitrogen gas. This can be performed, for example, by introducing the hydrocarbons and halogen into a combustion chamber. The non-oxygen combustion can produce at least carbon and hydrogen halide species. The halide species may exist in gas, liquid or in solid states, and preferably halogen gas or halogen vapor may be introduced in the combustion chamber. The produced carbon may be elemental carbon and/or active carbon. For example, methane and/ or natural gas can be used as a hydrocarbon. In another example, coal can be used as a hydrocarbon.

[0048] At 120, hydrogen can be extracted from the hydrogen halide species produced at 110. For example, the hydrogen halide species produced in a combustion chamber can be directed to a reaction chamber. Energy can be applied to break the hydrogen halide species bond to form hydrogen and halogen. The energy can be applied by, for example, exposing the hydrogen halide species to ultraviolet light or thermal heating of the hydrogen halide species.

[0049] At 130, carbon and/or nitrogen in combination with hydrogen can react to afford a hydrocarbon and/or nitrogen-based fuel. The carbon introduced at 130 can be the carbon produced at 110 during decarbonization and the hydrogen introduced at 130 can be the hydrogen produced at 120 during separation. In some

implementations, carbon and/or hydrogen can be acquired through other means. A stitching vector can also be included to modify characteristics for example, low freezing points; controlled boiling points, viscosity, stable vapor pressure, controlled formation of pollutant species and the like, of the generated hydrocarbon and/or nitrogen-based species to produce a hydrocarbon or nitrogen-based fuel. Control of the addition of the reagents and subsequent product removal can aid in the production of a homogenous hydrocarbon or nitrogen-based fuel. For example, clean octane and/or methane can be produced as the hydrocarbon fuel.

[0050] At 140, the fuel produced by synthesis at 130 can be liquefied. Any bi- products produced by the fuel production process can also be removed at 140.

Addition of one or more liquefication vectors to the generated hydrocarbon or nitrogen-based species can produce a fuel, which can be a liquid and easy to handle and transport. Furthermore, all the vector(s) can compete in the subsequent combustion process with carbon dioxide (C0₂) and mono nitrogen oxide species (NO_x) formation. The vector(s) can be water based or nitrogen based. Example vector(s) can include any solvent or combinations thereof.

DEC ARB ONIZ ATION

[0051] FIG. 2 is a system block diagram illustrating a system 200 for decarbonizing hydrocarbons. The system can include a combustion chamber 210 and can be used, for example, during the fuel production process to decarbonize at 110 in FIG. 1.

[0052] Combustion of the starting hydrocarbon mixture (e.g., methane, natural gas, or coal) can be carried out in a halogen environment at standard temperature and pressure, or in order to facilitate the decarbonizing, the temperature and the pressure in the chamber may be elevated. However, without wishing to be bound to the theory, the internal temperature for decarbonization may be of about 298 K to 2550 K, and the internal pressure may be of about 1 atm to about 20 atm. The source of the starting hydrocarbon mixture 220 can be crude oil, processed crude oil (e.g., at an oil refinery), or any other organic material as a carbon source such as coal, natural gas, plants, etc. In one example, the source of hydrocarbons can include methane.

Methane is the simplest alkane with the chemical formula CH₄ (one atom of carbon and four atoms of hydrogen). The relative abundance of methane makes it an abundant starting material for decarbonization although capture and storing it may pose challenges due to its gaseous state found in nature. In its natural state methane is found both below and under the sea floor as methane hydrate deposits and it often finds its way to the surface and in the earth's atmosphere where it is known as atmospheric methane. Methane is also the major component found in natural gas, a naturally occurring gas mixture (about 95%) comprising addition to small quantities of nitrogen, oxygen, carbon dioxide and sulfur compounds. Natural gas can therefore also be used as a starting hydrocarbon source. Currently, natural gas is used as a primary household energy source for cooking, heating and the like as well as industrial uses such as generation of electricity and polymer synthesis.

[0053] In another example, the source of hydrocarbons can include coal. Coal is a solid fossil fuel and formed when dead plant matter is converted into peat, which in turn is converted to lignite, then sub-bituminous coal, after that butuminous coal, and lastly anthracite. Coal is a mixture of compounds composed of between 50-100% carbon, by mass, with the rest being hydrogen, nitrogen, oxygen, and trace amounts of sulfur. Coal is one of the largest sources of energy for the generation of electricity worldwide, as well as one of the largest worldwide anthropogenic sources of carbon dioxide. Coal is also being used for the production of coke and as a source of various compounds used in synthesizing dyes, solvents, and drugs. The search for alternative energy sources has periodically revived interest in the conversion of coal into liquid fuels.

[0054] In another example, the source of hydrocarbons is from a distillation column at an oil refinery. In another example, the source of starting hydrocarbon mixture from the distillation column may be selected from any fraction of the distillates within the column, although distillates with minor impurities are preferred as the starting hydrocarbon mixture. In some example implementations, clean (e.g., few impurities and/or homogenous) starting hydrocarbon mixture leads to more of an efficient decarbonization reaction, which is described in equation (1).

[0056] X₂ in equation 1 can be a halogen gas and can be selected from chlorine, bromine, iodine and fluorine, or a combination of any of the foregoing. In some implementations, methane (CH₄) and/or natural gas is the clean starting hydrocarbon C_xH_y in equation 1. In some implementations, the hydrocarbon mixture C_xH_y in equation 1 is coal.

[0057] This reaction can take place in a combustion chamber 210 with the initial conditions at standard temperature and pressure (e.g., 298 °K (24.58 °C) and atmospheric pressure (1 atm)). In other implementations, the reaction can take place in a pressurized and/or pre-heated reaction chamber. The temperature range of the decarbonization reaction is between about 298 °K and the adiabatic flame temperature (Tp) of the combustion process (e.g., T₂98<T<Tp). The pressure range of the decarbonization process is between about 1 atm and the pressure present when the adiabatic flame temperature is reached (e.g., 1 atm<P<PTF). However, without wishing to be bound to the theory, the pressure may range preferably from about 1 atm to about 20 atm.

[0058] The vapor pressure of the halogen gas 230 at 298 °K can determine the amount of halogen gas available for the starting hydrocarbon mixture 220 to react. Iodine and chlorine have a low vapor pressure range of only 10²-10³ Nm^"2 whereas bromine is slightly higher (10⁴-10⁵ Nm^"2) compared to fluorine (>10⁶ Nm^"2) at 298 °K. The selection of the halogen gas depends on the reactivity of its vapor pressure during the decarbonization process. Furthermore, the source of the halogen can be a factor in selecting an appropriate halogen. Bromine and chlorine gas can easily be generated from brine solutions such as sodium bromide and sodium chloride, which are relatively inexpensive, environmentally friendly, and easily accessible starting materials. In some example implementations, a halogen with a high vapor pressure is used relative to other halogens having a low vapor pressure at a given temperature.

[0059] In certain examples, when methane and bromine are to be reacted in the reaction chamber, the partial pressure of methane and the partial pressure (vapor pressure) bromine gas may be maintained at a ratio at least of about 1:2, however, in order f facilitate the decarbonization, the ratio may be controlled, for example, to be of about 1: about 2-10.

[0060] The halogen-hydrocarbon combustion reaction is exothermic and it is generally a function of the hydrocarbon chain length. The calculations shown in FIG. 6 illustrate the amount of energy released (ΔΗ) upon reaction of various halogens and hydrocarbons of various lengths to form hydrogen halide species 260. As depicted in FIG. 6, the formation of hydrogen bromide, hydrogen chloride, and hydrogen fluoride are exothermic, and the amount of energy released is dependent on the hydrocarbon chain length. In contrast, the formation of hydrogen iodide is endothermic, and becomes increasingly endothermic as the hydrocarbon chain length increases. In some implementations, a halogen that forms an exothermic reaction with the hydrocarbon chain can be used, since exothermic reactions release energy and generally do not require input of additional energy, which can be more economic and efficient. In some implementations, methane can be used as the hydrocarbon in the halogen-hydrocarbon combustion reaction. As depicted in FIG. 6, the formation of hydrogen bromide, hydrogen chloride, and hydrogen fluoride is exothermic, while the formation of hydrogen iodide is endothermic when methane is used (e.g., the length of the carbon chain is 1). Table 1 lists the energy 250 released of methane in different halogen environments. In some implementations, natural gas is used as the hydrocarbon in the halogen-hydrocarbon combustion reaction. [0061] Table 1. Energy released during halogen-hydrocarbon combustion reaction.

[0062] Table 1 shows that the use of chlorine releases the most amount of energy 250. In some implementations, coal is used as the hydrocarbon in the halogen- hydrocarbon combustion reaction to produce energy 250. The energy 250 released during the exothermic reaction can be captured and used in subsequent steps of this process, or can be used as an additional energy source for the refinery.

[0063] The energy or heat (Q) 250 released during the halogen-hydrocarbon combustion reaction can be calculated using the general equation (2):

[0064] ΔΗ =∑(Bond Energy) reactants -∑(Bond Energy) products or

ΔΗ =∑aAHf (products) -∑bAHf (reactants)

Q=mc ΔΤ (2)

[0065] Exemplary bond energies for chemical bonds that can be used to calculate energy or heat released in reactions are demonstrated in the following Table 2.

[0066] Where Δ ¾ is the standard heat of formation, a, b, and m are the number of moles of the compound, c is the heat capacity of the compound and ΔΤ represents the difference in temperature generated during the reaction. In equation (1) the energy 250 released, also called the heat of combustion, is equal to the change in enthalpy (ΔΗ) of the reaction system (3).

[0067] Q= ΔΗ (3) [0068] To model the reaction, it can be useful to use an adiabatic system at constant pressure. In such a system, the energy released can be determined via equation (4).

[0069] ΔΗ =m_(x)c_p(ave.) ΔΤ (4)

[0070] Where ni_(X) is a known amount of fuel in moles; c_P(ave.) is the average amount of heat capacity of all products in the combustion chamber and ΔΤ is the temperature difference of the starting temperature T;=298 °K and the final temperature TF, which is also called the adiabatic flame temperature:

[0071] AH=m_(x)c_p(ave.) (T_F-T_;) (5),

[0072] ΔΗ/ m_(x)c_p(ave.) =(T_F-T0 (6),

[0073] [ΔΗ/ m_(x)c_p(ave.)]+ T_;=T_F (7)

[0074] For example, Table 3 shows the heat capacity values of methane and all the halogens, which can be used in the halogen-combustion reaction with methane.

[0075] Table 3. Heat Capacity values of reagents in halogen-combustion reaction

[0076] Equation (7) can further be modified: [0077] [LHV/m_(x)c_p(ave.)]+ T_;=T_F (8)

[0078] LHV defines the lower heating value, which is determined by subtracting the heat of vaporization of the water vapor from the higher heating value of a given fuel. If there are multiple hydrocarbon species in the reaction chamber, equation (8) can be expressed as follows:

[0079] [LHV_ave./(∑mc_{p(ave )}]+ T_i=T_F (9)

[0080] Where LHV_ave is the average lower heating value of the fuel (e.g., No. 2 fuel oil), and m is the number of moles of reactants (hydrocarbons and halogens). The higher heating value is the amount of energy released during the combustion of a specified amount of given fuel. Therefore the adiabatic temperature is a function of the amount of halogen gas used in the combustion chamber as the LHV and heat capacity values are known and tabulated. For example, the LHV for methane is 802.32 kJ/mol (Table 3). Using equation 9, the adiabatic temperature T_f for a decarbonization process using methane and a select halogen in any given amount can be determined, with the heat capacity values of halogen and methane provided in Table 2 together with the LHV tabulated in Table 3. Analogous values can be obtained for natural gas, which consists of 95% methane. Analogous calculations can also be carried for coal, which has a LHV of 24.429 MJ/Kg. Table 4 shows a list of lower heating (LHV) values of various fuels, wherein kJ/mol stands for

kilojoules/mole, MJ/kg is megajoule/kilogram, MJ/m³ is megajoule/cubic meter, Btu/lb is British thermal unit/ pound and Btu/ft³ is British thermal unit/cubic feet. Table 4. Lower Heating Value (LHV) Of Various Common Fuels

Molecular H/C

Fuel Phase kJ/mol MJ/kg MJ/m³ Btu/lb Btu/ft³

Weight Ratio

Hydrogen gas 2.016 241.83 119.96 10.79 51,596 274

Methane gas 16.043 4.0 802.32 50.01 35.80 21,511 909

Ethane gas 30.069 3.0 1,427.84 47.49 63.70 20,424 1,618

Propane gas 44.096 2.7 2,044.00 46.35 91.19 19,937 2,317

Butane gas 58.122 2.5 2,658.45 45.74 118.61 19,673 3,013

Ethanol liquid 46.0684 2.5 1,241.66 26.95 11,593

Gasoline liquid 110 2.0 4,675.00 42.50 18,280

Kerosene liquid 178 2.1 7,519.05 42.24 18,169

Diesel oil liquid 225 2.1 9,395.99 41.76 17,961

Coal solid 1.0 24.429 10,507

Wood (dry) solid 1.6 20.09 8,639

Peat (dry) solid 20.65 8,883

— The gas temperature and pressure for the values of MJ/m³ are 0 °C and 101.325 kPa.

— The gas temperature and pressure for the values of Btu/ft³ are 60 °F and 14.696 psi.

— LPG is marketed as propane or butanes or a mixture of propane and butanes.

— Natural gas, after removal of impurities and natural gas liquids (NGL), is essentially pure methane [0081] The higher heating value (HHV) is a function of the number of hydrogen atoms present in the fuel used in the decarbonization process (FIG.10). As the number of hydrogen atoms in the fuel increase the heating value becomes more exothermic. The rate of increase in the heating value of a given fuel is also dependent on the halogen used during the decarbonization process. Chlorine, bromine, and fluorine are exothermic, whereas iodine exhibits an endothermic heating value. In some implementations, methane is used as the fuel in the decarbonization process and the HHV values of methane with any given halogen are shown in Figure 10.

[0082] When methane is used as a fuel in the decarbonization process the highest HHV are obtained in a fluorine and chlorine environment. Analogous results are obtained when natural gas is used as a fuel in the decarbonization process.

[0083] The adiabatic flame temperature is the temperature that results from a complete combustion process if theoretically no energy is lost to the outside environment. In this case the adiabatic flame temperature is a function of the type of fuel being used (e.g., each fuel has a defined LHV value) and the amount and type of halogen gas being used at 298 °K (T;). Calculations using eq. (8) have shown adiabatic temperatures in a range of 2000 to 3800 °F. The adiabatic flame temperature is also a function of the number of hydrogen atoms present in the fuel used during the decarbonization process as well as the halogen used during the decarbonization process. When a fuel is used during the decarbonization process with chlorine or bromine the adiabatic temperature is within the range of about 2000 to 2550 °K, whereas when fluorine is used the adiabatic temperature increases significantly as the number of hydrogen atoms increase in a given fuel (FIG. 12). Therefore, halogens such as chlorine or bromine would be preferred during the decarbonization process because of the stability of the adiabatic temperature as halogen atoms increase within a given fuel, which facilitates the control of the temperature released during this process. For some implementations, the adiabatic temperature during the decarbonization process of methane and/or natural gas is about 2000 or 2550 °K in a chlorine or bromine environment respectively.

[0084] The combustion of the starting hydrocarbon mixture 220, e.g., methane and/or natural gas, can be initiated using an electrical spark or pilot light in the presence of a halogenated gas 230 to initiate decarbonization and the release of heat 250. The electrical spark or pilot light can provide the energy needed to overcome the activation energy of the reaction. In some implementations, the activation energy of methane and/or natural gas would be the energy required to break C-H bonds in the methane molecule, which is about 413 Kj/mole. During the decarbonization process hydrocarbons such as methane, natural gas or coal can be broken down into hydrogen halide 260 and carbon 240, e.g. amorphous. While the hydrogen halide 260 can be gaseous, carbon 240 can accumulate at the bottom of the combustion chamber, where it can be collected using a cyclone. The collected carbon 240 can be used as a reagent in the synthesis of synthetic hydrocarbon fuel or various other industrial applications. Carbon can also be sold as a commodity. The heat of combustion 250 generated can be used in subsequent steps of the process of FIG. 1 , which may require energy, or it can be used for other applications such as electrical power generation, and the like.

[0085] FIG. 9 is a cross-sectional diagram of another example implementation of a combustion apparatus 900 including a combustion chamber 910 and cyclone 920 that performs decarbonization. Starting hydrocarbon 220, (e.g., methane, natural gas, coal, and the like), and halogen 230 can feed into the combustion apparatus 900 through a feed port 930 located towards the top of the combustion apparatus and/or arranged such that the starting hydrocarbon 220 (e.g., methane, natural gas, coal, and the like), and halogen 230 can feed into the combustion chamber 910. The starting hydrocarbon 220 (e.g., methane, natural gas, coal, and the like), and halogen 230 can, as described in more detail above, combust to form carbon 240 and halogen halide 260. The carbon 240, having a higher molecular weight than halogen halide 260, can separate from the halogen halide 260 by falling into cyclone 920 and subsequently exit the combustion apparatus 900 at a bottom exit port 960. The halogen halide 260 can be forced (e.g., under pressure) out of the combustion chamber 910 through a top exit port 950.

[0086] In some implementations, the separation of the formed hydrogen halide gas 260 from the remaining hydrocarbon mixture 220, halogen gas 230, and carbon 240 can be based on the molecular weight and physical state of these individual components at 298 °K. Carbon 240 can be a solid (and/or can be amorphous) and can be collected at the bottom of the reaction chamber 310 using a cyclone, whereas hydrogen halide gas 260 and halogen gas 230 are both gaseous and therefore mixed. The two gases can be separated based on their electromagnetic properties shown in the table of FIG. 7. As these two gases pass through a magnetic field separation of the gases occurs and the halogen gas 230 can be recycled and used in another decarbonization process in combustion chamber 210. In an example implementation, the hydrogen halide gas 260 can be removed from decarbonization system 200 (e.g., a combustion chamber 210) and passed through a magnetic field to separate from the halogen gas 230. The strength of the magnetic field can be based on the

electromagnetic properties of gases being separated. HYDROGEN GENERATION

[0087] FIG. 3 is a system block diagram illustrating a hydrogen generation system 300 for performing hydrogen generation, for example, at 120 in FIG. l. The hydrogen generation system 300 includes a reaction chamber 310. In some example implementations, the reaction chamber 310 can be combined with the combustion chamber 210. In the reaction chamber 310 the hydrogen halide gas 260 can be exposed to ultraviolet light, which carries energy of 397.32 kJ/mole. This energy can be derived from eq. 10:

AE= hv x Av (10)

[0088] Where h is defined as Max-Planck's Constant (6.626xl0^~34 J/s), v is the frequency of the ultra violet light source (e.g., l.OOxlO¹⁵ Hz), Av is Avogadro's number (6.02 x 10²³) and ΔΕ is the energy, which can be used to split the halogen halide bond. For implementations using only ultraviolet light to break bonds, the bond enthalpy, which is the energy required to break a bond therefore cannot exceed 397 kJ/mole for a hydrogen halide bond. Table 5 lists bond enthalpies of various halogen halide bonds.

[0089] Table 5. Bond Enthalpies of various hydrogen halide bonds.

[0090] Table 6 lists energy of UV light at various lengths, which is also presented in FIGS. 15-16. Type of

UV

light λ (nm) E (kJ)

100 1196.66

110 1087.87

120 997.21

130 920.50

140 854.75

150 797.77

160 747.91

170 703.92

180 664.81

UV-C 190 629.82

200 598.33

210 569.84

220 543.93

230 520.29

240 498.61

250 478.66

260 460.25

270 443.21

280 427.38

290 412.64

300 398.89

UV-B

310 386.02

320 373.95

330 362.62

340 351.96

350 341.90

360 332.40

UV-A

370 323.42

380 314.91

390 306.83

400 299.16

[0091] The two hydrogen halide bonds that can be split using ultraviolet light is an H-I bond or an H-Br bond because their bond enthalpies are less than 397.32 kJ/mole. The remaining halogen halide bonds such as H-Cl and H-F may require more energy to be split than can be supplied by the ultraviolet light source. The choice of the halogen used in reaction chamber 310 can be based on the energy 250 released when forming the halogen halide bond of 260, as was shown in FIG. 6 and the energy required to split the halogen halide bond as is required in system 300. In addition, one may consider whether the halogen is abundant, inexpensive, and/or environmentally friendly. Alternatively, a thermal process can be used to break the hydrogen halide bond of 260 by using the energy 250 generated in system 200 during the decarbonization step. The chemical reaction for splitting the halogen halide bond can be shown in the reaction equation below:

[0092] Accordingly, when the H-Br is split or dissociated, as shown in Table 6 and FIGS. 15-16, the UV light may have a suitable wavelength ranging from about 100 to about 320 nm, from about 200 to about 320 nm, or particular from about 290 to about 320 nm. Further, without wishing to be bound to the theory, the UV light may be radiated at least for about 10 min, and at an intensity of about 50 mJ/cm².

[0093] ^{2 HX} *~ ^H2 fe) ^{+ X2} fe) (11)

[0094] The hydrogen gas 340 can be used as a fuel source by itself in various stationary, transportation, and heating applications. For example, hydrogen can be used as a fuel in power engines in vehicles, boats, aircraft, spacecraft, run various electrical devices, fuel cell and battery applications or can be used in the synthesis of carbon-based or nitrogen-based synthetic fuels. The halogen 330 can be returned to the decarbonization chamber 210 and used during decarbonization of system 100.

[0095] In some example implementations, the halogen 330 formed in eq. (11) is a liquid at room temperature. The phase difference between hydrogen (gas) 340 and halogen (liquid) 330 can be advantageous as it will be easier to separate the two species. For example, bromine is a liquid at standard temperature and pressure. In this case, however, without wishing to be bound to the theory, the UV light may be radiated at least for about 10 min, and at an intensity of about 50 mJ/cm²

[0096] Alternatively, hydrogen 340 and halogen 330 can be separated based on the magnetic properties of each element. As these two gases pass through a magnetic field separation occurs and the halogen gas 330 can be recycled and used in another decarbonization process in combustion chamber 210, whereas hydrogen gas 340 can be used in the next step of the process. The strength of the magnetic field is based on the electromagnetic properties of gases being separated.

FUEL SYNTHESIS

[0097] FIG. 4 is a system block diagram illustrating a system 400 for performing fuel synthesis also called "stitching" such as at 130 in FIG. 1. The fuel synthesis system 400 can include hydrogen 340 and carbon 240 to generate one select species of hydrocarbon 440 (C_xH_y), e.g., octane (C₈H₁₈) or methane (CH₄)(eq. 12)

[0098] ^{Y ¾ + X C Cx¾y} (12)

[0099] Wherein Y and X define the amounts of hydrogen and carbon respectively. The ratio of starting materials hydrogen 340 and carbon 240, along with the environmental temperature and pressure, determines the number of hydrogen and carbon atoms present in the species of the hydrocarbon 440 being generated. In the table of FIG. 8 a list of hydrocarbons and their corresponding carbon and hydrogen content and C/H ratios is shown. In some implementations, the synthesis of octane

(C₈H₁₈) requires starting materials with a C/H ratio of 0.44. In other implementations, the synthesis of methane (CH₄) required starting materials with a C/H ratio of 0.25.

The gram quantities of starting materials 340 and 240 are based on the amount of hydrocarbon 440, (e.g., octane and/or methane, and the like), desired and its corresponding C/H ratio. Preferably, higher C/H ration is preferred, such that hydrocarbon 440 may be saturated and straight hydrocarbons. Table 4 shows a list of hydrocarbon fuels and their corresponding heat of formation (Δ¾) and heat of combustion (Δ¾), which indicate that most hydrocarbon fuels are generated in an exothermic fashion. In some implementations, the heat of formation (Δ¾) and heat of combustion (Δ¾) for octane is also exothermic with values of -252.1kJ/mol and - 5.53 MJ/mol respectively. Octane is a hydrocarbon and an alkane with the chemical formula CsHis and is a component of gasoline (petrol). As a low molecular weight hydrocarbon octane is volatile and flammable.

[00100] Methane compared to other hydrocarbon fuels when combusted produces less carbon dioxide for each unit of heat released. At about 891 kJ/mol, methane's heat of combustion is lower than any other hydrocarbon but the ratio of the heat of combustion (891 kJ/mol) to the molecular mass (16.0 g/mol, of which 12.0 g/mol is carbon) shows that methane, being the simplest hydrocarbon, produces more heat per mass unit (55.7 kJ/g) than other complex hydrocarbons.

[00101] Table 7. Heat of formation (Δ¾) and heat of combustion (Δ¾) of hydrocarbon fuels.

[00102] But to initially overcome the energy of activation to initiate the hydrocarbon formation process heat 430 may be applied to the stitching reaction chamber 410. Once the reaction has been initiated no further energy input may be required to propagate hydrocarbon fuel formation. In some implementations, the initial energy input for the stitching process to synthesize octane and/or methane is at least about the C-H bond energy of 413 Kj/mol. The range in temperature in the stitching reaction chamber is about 10-40 bars and the temperature can range from about 300-350 °C. The starting materials hydrogen gas 340 and solid carbon 240 can be introduced into the stitching reaction chamber in a controlled continuous fashion at a predetermined or predefined rate, where product formation occurs and can be immediately removed from the site of reaction. For example, if the hydrocarbon 440 (e.g., octane and the like), being produced is a liquid then starting materials hydrogen 340 and carbon 240 are added into the stitching reaction chamber at a predetermined rate, where product formation occurs as a droplet of about between lxlO^"9 m to about lxl 0^"8 m in diameter, which is continuously removed from the stitching reaction chamber 410 via gravity. Preferably the size of the droplet is about lxlO^"9 m to about 500x 10^~9 m in diameter. In some examples, the size of the droplet can range from 500xl0^"9 m to about lxlO^"8 m in diameter. In some implementations, the stitching reaction chamber 410 can include one or more micro-environments for producing hydrocarbon 440 as droplets.

[00103] For example, in some implementations, synthesizing hydrocarbons, (e.g., octane and/or methane, and the like), can be performed by providing hydrogen, a vector, and carbon into a micro-environment, for example, having a volume of microscale dimensions. The hydrogen and carbon can be provided in a predetermined ratio selected based on a target hydrocarbon composition. Pressure and temperature of the micro-environment can be controlled to predetermined levels. The predetermined levels can be based on the target hydrocarbon composition. Once the reaction has occurred, a hydrocarbon droplet formed from the provided hydrogen, the provided vector, and the provided carbon can be removed from the micro- environment. In some implementations, octane, a colorless liquid, is generated as said hydrocarbon droplet. In some implementations, methane is generated as said hydrocarbon droplet.

[00104] In some example implementations, production of a nitrogen- based fuel may also be carried out using elemental hydrogen 340 and nitrogen 240. For example, hydrogen and nitrogen can produce nitrogen-based fuel hydrazine (N₂H₄) (eq.13).

[00105] ² ¾ ^{+ N2 N2¾} (13)

[00106] Both starting materials are gaseous and the formation of the nitrogen-based fuel species 440 can be controlled by the rate of addition of each gas into the stitching reaction chamber 410. An analogous set-up of the stitching reaction chamber 410 can be used to generate nitrogen-based species 440 as in hydrocarbon 440 production.

[00107] The generated carbon-based or nitrogen-based fuel 440 can contain single, double and triple atom bonds within the hydrocarbon or nitrogen-based fuel.

[00108] A stitching vector 420 may be applied during the process of hydrocarbon or nitrogen-based fuel production. This stitching vector 420 can be used to catalyze the formation of the desired fuel 440, e.g., octane, at 298 °K and atmospheric pressure (1 atm.). Further, during the synthesis or formation of the fuel, the stitching vector may increase hydrogen concentration, for example, by forming saturated hydrocarbons, to thereby increase the energy value of the hydrocarbon fuel by increasing. Preferably, the stitching vector may be an organometallic catalyst comprising at least one metal element selected from the group consisting of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, and Au. The stitching vector 420 can be water based or nitrogen based solvents. In case of the nitrogen-based fuels 440, the stitching vector 420 can be part of the nitrogen-based fuel 440. After the hydrocarbon or nitrogen-based fuel 440 has been produced it will further be modified in a liquefication process.

LIQUEFYING FUEL

[00109] FIG. 5 is a system block diagram illustrating a fuel liquefying system 500 for liquefying fuel such as at 140 in FIG.l. The fuel liquefying system 500 can include the hydrocarbon or nitrogen-based fuel 440 generated and at least one liquefication vector 530 in the liquefier 510. The hydrocarbon, e.g., octane or methane, or nitrogen-based fuel 440 is approximately three times more efficient compared to conventional fuels. In some example implementations, in order to accommodate current combustion systems the hydrocarbon, e.g., octane or methane, or nitrogen-based fuel 440 generated can be mixed with one or more liquefication vector(s) 530 to a final hydrocarbon or nitrogen-based fuel content of about 30%. The liquefication vector 530 can be mixed with the highly efficient hydrocarbon or nitrogen-based fuel 440 generated but also to liquefy 440 so it is in liquid form at 298 °K at atmospheric pressure (1 atm). The liquefication vector 530 can be non-toxic to the environment and can prevent carbon dioxide and NO_x formation during fuel combustion. The liquefication vector 530 may be water based or nitrogen based solvents. In case of the nitrogen-based fuels 540, the liquefication vector 530 can be part of the nitrogen-based fuel 540. The liquefication vector 530 can be varying depending on the use of fuel 540 in subsequent combustion systems. Once the liquefication vector(s) 530 has been mixed with the hydrocarbon, e.g., octane or methane, or nitrogen-based fuel 440 it is ready for use in combustion systems.

OTHER ASPECTS

[00110] An example of a variation in the process shown in FIG. 1 is the modification of decarbonization 110 and hydrogen generation 120 to produce hydrogen gas 230 and elemental carbon 240. FIG.13 illustrates a process flow diagram showing a process 1300 to produce hydrogen 230 and carbon 240 and exemplifies a variation of the process shown in FIG. 1.

[00111] At 1310, chloromethane (CH₃CI) is generated by halogenation of a starting hydrocarbon source such as methane and/or natural gas. This can be performed, for example, by introducing the hydrocarbon, e.g., methane and/or natural gas, and a mixed halogen, e.g. bromochloride (BrCl), into a halogenation chamber. The halogenation can produce at least chloromethane and hydrogen bromide according to eq. (14).

BrCl

[00112] ^CH4 *~ ^CH3^{C1 + HBr} (14)

[00113] Chlorination of methane is preferred over bromination of methane because the heat of formation (ΔΗ/298, kJ/mol) of chloromethane (339 kJ/mol) is higher than bromomethane (284 kJ/mol) making chloromethane the more stable product formed in this process.

[00114] At 1320, dehalogenation of monochloromethane occurs when exposed to an ultraviolet light source to afford methane radical as shown in eq. (15).

[00115] ^{2 C}¾^{CI 2 C}¾^{' +} <¾ (15) [00116] This generated methane radical species can return to 1310 and be exposed to bromochloride to generate a monochloro methane radical species ('CH₂C1) eq. (16) this time, which in turn can be exposed again to an ultraviolet light source to produce carbon species (e.g.,CH₃, CH₂, CH, C) of various oxidation states. A series of halogenation-dehalogentation cycles (eq.17-21) can be employed using various chlorocarbon species, e.g., CH₃CI, CH₂C1, CHC1 as starting materials to generate elemental carbon as the final product.

BrCl

CH₃ CH₂C1 + HBr

[00117] (16)

2 CH₂C1 CH₂ + C1₂

[00118] (17)

BrCl

[00119] ^C¾ " ^{CHC1 + HBr}(18)

BrCl .

[00121] ^{CH CC1 + HBr} (20)

[00122] ^{2 CC1 C + Cl2} (21)

[00123] As mentioned previously, for implementations using only ultraviolet light to break bonds, the bond enthalpy, which is the energy required to break a bond cannot exceed 397 kJ/mole, which is the amount of energy carried by ultraviolet light. For example, in 1320 the energy required to break a C-Cl bond of a bond enthalpy of 330 kJ/mole as shown in eq. 15, 17, 19 and 21 to finally obtain elemental carbon can be provided by an ultraviolet light source.

[00124] At 1330, the hydrobromic acid produced in 1320 is converted to hydrogen and bromine upon exposure, for example, of an ultraviolet light source. Again, the energy supplied by an ultraviolet light source is 397.32 kJ/mole, which is enough energy to break the H-Br bond of a bond enthalpy of 366 kJ/mol (Table 5)(eq. 22)

[00125] ^HBr *~ ^H2 ^{+ Br2} (22)

[00126] Accordingly, as shown in Table 6 and FIGS. 15-16, the UV light may have a suitable wavelength ranging from about 100 to about 320 nm, from about 200 to about 320 nm, or particular from about 290 to about 320 nm.

[00127] Separation of the products can be accomplished based on their physical properties. Hydrogen is a gas, whereas bromine is a liquid at standard temperature and pressure.

[00128] At 1340, the chlorine produced from 1320 and the bromine produced from 1330 are combined to produce the mixed halogen species, bromochloride, which is subsequently used in 1310. The exposure of these two halogen species occur in the presence of an ultraviolet light source, which provides enough energy to split Br-Br bonds (193.9 Kj/mol) and Cl-Cl bonds (242.6 Kj/mol) and allow formation of Br-Cl bonds (218 Kj/mol) to form the mixed halogen species.

[00129] At 1350, the hydrogen produced from 1330 and the carbon produced from 1320 can be combined to generate hydrocarbon species as previously described in Fig. 4 using a stitching reaction chamber analogous to 410 to carry out fuel synthesis as shown in 130 of FIG. 1.

[00130] Alternate process 1300 allows for the recycling of halogen sources such as bromine and chlorine, which can be expensive when used on large scale. Process 1300 also does not require the separation of gases based on their electromagnetic properties such as the process described in FIG. 1. This separation technique can be challenging and expensive, particularly in the separation of hydrogen and chlorine gas. [00131] The process illustrated in FIG. 13 requires several chemical transformations using an ultraviolet light source. In some implementations, a compact UV reactor can be employed, which is able to use only one ultraviolet light source to execute multiple chemical transformations simultaneously and/or in parallel. FIG. 14, for example, illustrates such a schematic of a compact UV reactor for use in the processes of 1320, 1330, and/or 1340.

EXAMPLE

Producing a clean hydrocarbon fuel from methane (CH4)

(1) Decarbonization 110

[00132] As shown in FIG. 9, a reaction chamber 900 having a volume of 1 m³ may be provided for decarbonization (110, FIG. 1)

[00133] Methane 220 may be supplied via inlet and halogen gas 230 may be supplied via inlet as shown in FIG. 9. For example, the halogen gas may be a vaporized bromine gas (Br₂). A partial pressure of methane and a partial pressure bromine gas may be maintained at a ratio at least of about 1:2, however, in order f facilitate the decarbonization, the ratio may be controlled, for example, to be of about 1: about 2-10.

[00134] After reaction gases are injected, the reaction chamber may be heated to provide thermal energy, until an internal temperature thereof reaches to a temperature at least of about 400K, of about 500 K, 600 K, 700 K, 800 K, 900 K, 1000K, HOOK, 1200K, 1300K, 1400K, 1500K, 1600K, 1700 K, 1800 K, 1900K, 2000K, 2100K, 2200K, or 2300 K. The reaction chamber may have an internal pressure of about 1 to 20 atm during the decarbonization. The decarbonization may be performed for about 10 minutes to about 20 hours, to completely dissociating carbons and hydrogens and obtain elemental carbon. The obtained elemental carbon 240 may be formed in microparticles and in active carbon.

(2) Hydrogen Generation (120, FIG. 1)

[00135] From the decarbonization, hydrogen halide (HBr) 260 in FIG. 9 may be collected. The hydrogen halide HBr may be decomposed upon radiation of UV light having a wavelength of about 290-330 nm at least for about 10 minutes. To facilitate the reaction, the temperature may be maintained in a range of about 300 K to about 1000 K, while the pressure may be maintained in a range of about 0.1 atm to about 10 atm, preferably, reduced to about 0.1 atm. Thereafter, hydrogen gas 340 may be further collected to be used for synthesis of hydrocarbon fuels.

(3) Fuel Synthesis (130, FIG. 1)

[00136] The elemental carbon microparticles 240 may be placed in a reactor having a volume of 1 m³, and hydrogen gas may be supplied until the internal pressure of the chamber reaches, for example to about 10-40 bars or 7 to 20 bars, and the temperature can range from about 300-350 °C.

[00137] The synthesis reaction may be conducted in the present of a catalyst, for example, organometallic catalyst comprising at least one transition metal. The synthesis reaction may be performed at a temperature ranging from about 300- 350 °C, however, the temperature may be increased higher upon the reaction rate based on the catalyst. The synthesis of the hydrocarbon fuel may be performed at least for about 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours. [00138] The obtained hydrocarbon fuel including substantially homogeneous octane may be confirmed by using suitable mass analysis methods, for example, with GC/mass analysis by checking peak traces, but the detection methods may not be limited thereto.

[00139] Although a few variations have been described in detail above, other modifications are possible. For example, the implementations described above can be directed to various combinations and sub combinations of the disclosed features and/or combinations and sub combinations of several further features disclosed above. In addition, the logic flows depicted in the accompanying figures and described herein do not require the particular order shown, or sequential order, to achieve desirable results. Other embodiments may be within the scope of the following claims.

Claims

WHAT IS CLAIMED IS:

1. A method of producing a hydrocarbon fuel, comprising steps of:

decarbonizing a source hydrocarbon by introducing halogen to produce elemental carbon and hydrogen halide; and

producing the hydrocarbon fuel by reacting the elemental carbon with hydrogen (H₂),

wherein the decarbonization is performed in non-oxygen condition, wherein the hydrocarbon fuel is produced in the present of a catalyst.

2. The method of claim 1, wherein the source hydrocarbon comprises 1 to 6 carbons.

3. The method of claim 1, wherein the halogen is selected from the group consisting of Cl₂, Br₂, 1₂, ClBr, and mixtures thereof.

4. The method of claim 1, wherein the hydrocarbon fuel comprises 8 to 30 carbons.

5. The method of claim 1, wherein the step of decarbonizing is performed in a combustion chamber.

6. The method of claim 5, wherein the combustion chamber has a volume of about 1 m³ to about 10 m³.

7. The method of claim 5, wherein during the decarbonization, an internal temperature in the combustion chamber ranges from about 298 K to about 2550 K, and a pressure ranges from about 1 atm to about 20 atm.

8. The method of claim 1, wherein the catalyst is an organometallic catalyst comprising at least one metal element selected from the group consisting of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, and Au.

9. The method of claim 1, wherein the hydrocarbon fuel is synthesized at a temperature ranging from about 300-350 °C.

10. The method of claim 1, further comprising:

decomposing the hydrogen halide by adding energy to produce the hydrogen (H₂) and reproduced halogen; and collecting the hydrogen (H₂) for synthesizing the hydrocarbon fuel.

11. The method of claim 10, wherein the energy is added by radiating UV light.

12. The method of claim 11, wherein a wavelength of the UV light ranges from about 100 nm to about 320 nm.

13. The method of claim 12, wherein the UV light is radiated at least for about 10 min, and at an intensity of about 50 mJ/cm².

14. The method of claim 1, wherein the source hydrocarbon is methane.

15. The method of claim 14, wherein the halogen is Br₂.

16. The method of claim 15, wherein a ratio between a partial pressure of the methane and a partial pressure Br₂ is of about 1: 2-10.

17. The method of claim 1, wherein the hydrocarbon fuel is octane.

18. The method of claim 1, further comprising: liquefying the hydrocarbon fuel.

19. A hydrocarbon fuel that is manufactured by a method of claim 1.

20. The hydrocarbon fuel of claim 18, comprising octane.