EA044982B1 - ELECTRIC DISCHARGE IN A MIXTURE OF METHANE AND HYDROGEN IMMEDIED IN LIQUID HYDROCARBONS - Google Patents

Description

Cross reference to related application

This application claims priority to U.S. Provisional Patent Application No.

62/660725 entitled SUBMERGED METHANE AND HYDROGEN MIXTURE DISCHARGE IN

LIQUID HYDROCARBONS, filed April 20, 2018, and incorporated herein by reference in its entirety.

Field of technology

The present technology generally refers to a highly efficient gas spark discharge electrical circuit used to economically convert heavy liquid hydrocarbons into lighter products.

State of the art

The oil and gas industry is divided into three chronologically operating sectors: exploration and production, transportation and storage, and refining. The first sector includes the exploration and production sector. It involves searching for, producing and extracting crude oil and/or natural gas from underground or subsea deposits. It also covers the process of drilling and operating wells to extract and bring crude oil and crude gas to the surface. Exploration involves conducting geological and geophysical surveys, searching for potential underground or subsea crude oil and natural gas deposits, obtaining leases and drilling permits, and the entire drilling process.

The intermediate sector involves the transportation of crude oil or petroleum products, typically by pipeline, oil tankers, barges, trucks or rail. The final destination is oil refineries, which then begin the third stage of refining. The second sector also includes the storage of these products as well as any wholesale marketing activities. The second stage may also include elements necessary for its operation due to its intermediate position. For example, the second sector may include natural gas processing plants that purify raw natural gas and also remove and produce elemental sulfur and liquefied natural gas (LNG) as end products.

Recently, due to rising crude oil prices, declining medium and light crude oil reserves and the abundance of unconventional crude oils, the development of heavy crude oil and bitumen reserves has become significantly more favored. However, both when extracting heavy crude oil and bitumen and when transporting it to refineries, there are many challenges that must be overcome. Transporting heavy crude oil via pipeline is difficult due to its high density and viscosity (>1000 cP) and low mobility at reservoir temperatures. In addition, contaminants such as asphaltene deposits, heavy metals, sulfur and brine or salt make it difficult to transport and purify using conventional petroleum refining methods [1]. The presence of mineral solution or salt in heavy oil leads to pipeline corrosion. In some cases, this can lead to the formation of an emulsion, such as an oil-water mixture, which makes transportation difficult [2]. Due to the high molecular weight and high viscosity of heavy oil, high pressure drops along the pipeline are expected, making it expensive and energy intensive. In addition, asphaltene deposits are deposited on the walls of pipelines, reducing the cross-sectional area available for oil flow.

Therefore, additional processes must be performed to solve these problems and transport heavy oil. These include:

reducing viscosity, for example by preheating heavy crude oil and bitumen and then heating the pipeline, mixing and diluting with light hydrocarbons or solvent. The viscosity of the mixed mixture is determined by the added diluent and the degree of dilution. Dilution of heavy oil requires two pipelines, one for oil and one for diluents, which further increases costs;

emulsification to form an oil-in-water emulsion;

drag/friction reduction (e.g., pipeline lubrication using annular flow, anti-turbulence additive), and partial in-situ upgrading of heavy crude oil to produce synthetic crude oil with improved viscosity, API gravity, and minimal content asphaltenes, sulfur and heavy metals [3].

Partial oil upgrading involves converting only a portion of the vacuum distillation residues and producing synthetic crude oil (SCO) containing 5-25% of the residue. These processes can be developed at half the cost of full upgrading, but are not mass produced due to lack of technology, stability issues and CLO economics. However, in countries like Canada, due to huge reserves of heavy crude oil, partial upgrading becomes a viable option. The downstream sector is the latest stage in the oil and gas industry. It includes the refining of crude oil and the processing and purification of raw natural gas. Marketing and distribution of products derived from crude oil and natural gas are also part of this sector. Products supplied to general consumers include

- 1 044982 gasoline, kerosene, jet fuel, diesel fuel, heating oil, petroleum fuel, lubricants, paraffins, asphalt, natural gas and liquefied petroleum gas (LPG), as well as hundreds of petrochemical products.

In the standard petroleum refining process, crude oil is desalted and passed through atmospheric distillation, which separates it into fractions based on their boiling point range. The cutoff temperature of atmospheric residue (AR) is approximately 350-360°C [4]. Fractions below these boiling points are evaporated and separated, while the atmospheric distillation residue, containing longer carbon chains, requires further distillation under reduced pressure and high temperature. Therefore, a vacuum distillation process is required, which is important for further upgrading of crude oil and recovery of petroleum products. The cut-off temperature of the vacuum residue (VR) is approximately 565°C [5].

However, despite the AO and BO treatments, refineries that process heavy oil will still have a significant fraction of the incoming oil as residue (eg Lloydminster oil residue is approximately 50% at 460°C). Therefore, several more processes are required to crack heavy oil. Several crude oil cracking technologies are currently known. Of these, thermal cracking is considered the most efficient and is widely used to convert heavy, high molecular weight hydrocarbons into lighter, low molecular weight fractions.

The most commonly used cracking technologies are hydrocracking, fluid catalytic cracking and delayed coker. Although all of these cracking processes have certain common advantages, they also have significant disadvantages. General advantages include the ability to produce a variety of fuels, from light aviation kerosene to heavy fuel oil in large quantities.

However, a significant drawback of the currently used methods for synthesizing light fuels from crude oil is the high financial costs associated with the implementation of the technology. These methods are characterized by high capital and operating costs. Additionally, due to economies of scale, the entire thermal process is only most efficient at high volume to surface area. The minimum efficient scale for a full-cycle refinery is estimated to be approximately 200 thousand barrels per day (MBD) of crude oil. In particular, the existing technology is implemented at high temperatures and pressures of the working environment and therefore requires special materials for the manufacture of chemical reactors and other special equipment. For example, reactors are usually made of special grades of alloy steel. Another factor adding to the enormous costs of these processes is hydrogen embrittlement of the metal and H ₂ quality control. Hydrogen embrittlement is a process in which hydride-forming metals such as titanium, vanadium, zirconium, tantalum and niobium become brittle and fracture due to the introduction and subsequent diffusion of hydrogen into the metal. Operating conditions for a single stage hydrocracker are 348-427°C (660-800°F) with an increase of approximately 0.05-0.1°C (0.1-0.2°F) per day to compensate for loss of activity catalyst and pressure ranging from 8724 to 13790 kPa (1200-2000 psi). The fuel coker operates at 487-500°C (910-930°F) with a typical pressure of 103.4 kPa (15 psi). For a fluid catalytic cracking unit, a reactor and a regenerator are considered to be the main components of a fluid catalytic cracking unit. The reactor is at a temperature of approximately 535°C and a pressure of approximately 172.4 kPa (25 psi), while the catalyst regenerator operates at a temperature of approximately 715°C (1320°F) and a pressure of approximately 241.3 kPa (35 psi) [7]. Maintaining such working conditions is very expensive.

The capital costs of a reformer such as a hydrocracker are also very high. It is estimated that a hydrocracker requires 5 times the capital cost of atmospheric distillation. For example, if a 100,000 barrels per day crude oil distillation unit costs approximately $90 million, then a complexity index 5 hydrocracker unit of the same capacity would require $450 million in crude oil refining costs [8].

In addition, catalysts used in fluid catalytic cracking (FCC) processes are very sensitive to various impurities in crude oil. In particular, the presence of sulfur in crude oil leads to rapid decomposition of the catalyst with loss of catalytic properties. Thus, pre-treatment (desulfurization) of raw materials is necessary, which increases the share of costs. Moreover, nickel, vanadium, iron, copper and other contaminants present in FCC feedstocks all have a negative impact on the activity and performance of the catalyst. Nickel and vanadium are especially problematic. Additionally, removing a portion of the circulating catalyst as spent catalyst and replacing it with fresh catalyst to maintain the desired activity level for FCC technology increases the operating costs of the process.

Plasma-chemical methods use various types of electrical discharges to create

- 2 044982 plasma. Such methods for cracking and reforming oil are described in various patents and publications. For example, US Patent Application Publication No. 2005/0121366 discloses a method and apparatus for reforming petroleum by passing an electrical discharge directly through a liquid. The disadvantage of this method is the short service life of the electrodes and the associated high probability of spark ignition failure between these electrodes. Due to the high electrical resistance of oil, the distance between the electrodes must be very small. For example, the distance may be on the order of approximately 1 mm. However, the interelectrode distance increases rapidly due to electrode erosion, resulting in system failure and/or failure. In addition, the use of such small gaps between electrodes allows only a very small volume of feed material to be processed at any given time.

US Pat. No. 5,626,726 describes a petroleum cracking process that uses a heterogeneous mixture of liquid hydrocarbon materials with various gases, such as arc plasma treatment. This method has the same disadvantages associated with the small discharge gap described above, and requires special equipment for mixing gas and liquid, as well as the resulting heterogeneous suspension. Heating the mixture with a continuous arc discharge leads to significant energy losses, increased carbon formation and low efficiency.

Russian patent No. 2452763 describes a method in which a spark discharge is carried out in water, and the impact of the discharge is transmitted to a heterogeneous mixture of gas and liquid hydrocarbon or oil through a membrane. This increases the discharge gap between the electrodes, which increases the service life of the electrode, but reduces the effectiveness of the spark discharge on hydrocarbon or oil. This happens because most of the direct contact of the plasma discharge with the hydrocarbon medium is excluded. In addition, the already complex design using a high voltage pulse generator is further complicated by the use of a device for preparing a heterogeneous mixture and a device for separating the treated medium from the water in which the spark discharge was created.

U.S. Patent Application Publication No. 2010/0108492 and U.S. Patent No. 7,931,785 describe processes that have high efficiency in converting heavy oil into light hydrocarbon fractions. In these methods, a heterogeneous oil-gas environment is exposed to an electron beam and a non-self-sustaining electrical discharge. However, the practical use of the proposed method is problematic, since in addition to a complex system for preparing a heterogeneous mixture, an electron accelerator with a device for outputting the electron beam from the accelerator vacuum chamber into a high-pressure gas-liquid mixture is required. An electron accelerator is a complex technical device that significantly increases both capital and operating costs. In addition, any use of a beam of fast electrons is accompanied by bremsstrahlung X-ray radiation. Thus, the entire device requires appropriate biological containment, which further increases the cost.

Plasma-chemical reactors can be added to oil refinery equipment as an upgrading technology for all types of raw materials. The introduction of such reactors into the oil refining process, rather than in the heavy oil field, offers a simple and step-by-step development plan compared to implementing it in the field. This is mainly due to the fact that the oil that must pass through these reactors in refineries has already undergone many pre-treatments such as dehydration, desalting and atmospheric distillation. Therefore, the whole process as a whole will be much simpler compared to its implementation in the field. The refinery can provide mains voltage and carrier gases without additional requirements for their inclusion in the upgrading process. In addition, these reactors would not have to meet the stringent pipeline requirements for viscosity, density, olefin content and oil stability required in the field.

In the future, for the oil refinery, the production of the required distillates will increase, and the load on the coker and hydrocracking unit will decrease, which will eliminate bottlenecks in the process chain.

Disclosure of the Invention

In one aspect, a method is provided for cracking liquid hydrocarbon materials into a light hydrocarbon fraction using a spark discharge, the method comprising passing the liquid hydrocarbon material through an electric discharge chamber and into an interelectrode gap within the electric discharge chamber, in which the interelectrode gap is formed between a negative electrode having a first end and a second end. , and a positive electrode having a first end and a second end, while in the electric discharge chamber the first end of the negative electrode is spaced from the first end of the positive electrode by a distance that determines the interelectrode gap. The method further includes injecting a carrier gas containing hydrogen (H ₂ ) and methane into the liquid hydrocarbon material as it enters the interelectrode gap to form a gas-liquid hydrocarbon mixture; and exposing the gas-liquid mixture to a current between the electrodes at a voltage sufficient to cause a spark discharge. The second end of the negative electrode and the second end of the positive electrode are connected to the capacitor; and the capacitor is charged to a voltage equal to or greater than the breakdown voltage of the carrier gas. In some embodiments, the carrier gas consists of hydrogen (H2) and methane. In some embodiments, the carrier gas contains from 15% v/v. up to 30% v/v hydrogen. In some embodiments, the spark discharge is a pulsed spark discharge.

In some embodiments, the method further includes recovering light hydrocarbon fractions resulting from the action of a pulsed spark discharge on a gas-liquid hydrocarbon mixture.

In some embodiments, the light hydrocarbon fractions have a viscosity of less than 100 centipoise (cP). In some embodiments, the light hydrocarbon fractions have an API gravity greater than 30.

In some embodiments, the average ratio of hydrogen atoms to carbon atoms in the light hydrocarbon fractions is in the range of 2 to 2.5.

In some embodiments, the concentration of hydrogen and/or methane in the carrier gas varies over time during the period of injection of the carrier gas into the liquid hydrocarbons. In some embodiments, the carrier gas introduced into the liquid hydrocarbons is recycled from the gas-liquid hydrocarbon mixture.

In another aspect, a plant is provided for converting liquid hydrocarbon material into a light hydrocarbon fraction, the plant including an electrical discharge chamber comprising a negative electrode having a first end and a second end, and a positive electrode having a first end and a second end, the first end of the negative electrode spaced from the first end of the positive electrode by a distance that defines the interelectrode gap, and wherein the second end of the negative electrode and the second end of the positive electrode are connected to the capacitor. The apparatus also includes a carrier gas inlet for supplying a carrier gas containing hydrogen and methane to the liquid hydrocarbon material. The apparatus also includes an inlet port for introducing liquid hydrocarbon material into the discharge chamber. The installation also includes an outlet designed to remove the light hydrocarbon fraction from the spark discharge chamber. In some embodiments, the carrier gas contains from 15% v/v. up to 30% v/v hydrogen.

Brief description of drawings

Fig. 1: Photograph of an oil processing reactor that is used to treat oil with a pulsed electrical discharge according to possible embodiments of the invention.

Fig. 2: Schematic representation of a reactor with electrical circuitry that is used to process various types of oil in a continuous flow mode according to possible embodiments of the invention.

Fig. 3: Photograph of a sample of oil processed by the method and installation of the present invention, with various mixtures of hydrogen and methane as carrier gas according to possible embodiments of the invention.

Fig. 4: Photograph of the top electrode, which is used for treating oil with hydrogen and methane, described herein, according to possible embodiments of the invention.

Fig. 5: GC-MS plot showing peak intensity versus time for hexadecane treated with hydrogen and argon according to possible embodiments of the invention.

Detailed description

Among the advantages and improvements that have been disclosed, other objects and advantages of this invention may become apparent from the following description taken with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it should be understood that the disclosed embodiments of the invention are illustrative only and may be embodied in various forms. Moreover, each of the examples given in connection with various embodiments of the invention is intended to be illustrative and not limiting. Any changes and further modifications to the features of the invention illustrated herein, and any additional applications of the principles illustrated herein that would normally occur to one skilled in the art and knowledgeable about this disclosure, should be considered within the scope of this application.

Throughout the specification and claims, the following terms have the meanings expressly applied herein unless the context clearly dictates otherwise. The phrases in one aspect, in some aspects, and the like used herein do not necessarily refer to the same embodiment(s), although they may. In addition, the phrases in another aspect and in certain other aspects used herein do not necessarily refer to another aspect (embodiment of the invention), although they may. Thus, as described below, various aspects (embodiments) of the invention can be easily combined without departing from the scope or spirit of the invention.

Additionally, as used herein, the term or includes the conjunction or and is equivalent to

- 4 044982 term and/or, unless the context clearly dictates otherwise. The term based is non-exclusive and allows for the use of additional factors not described unless the context clearly dictates otherwise. Furthermore, throughout the specification, the use of the singular includes references to the plural. The meaning of the preposition in includes in and on. As used herein, the term is approximately obvious to those skilled in the art and varies to some extent depending on the context of its use. If some uses of a term are not clear to those skilled in the art, given the context in which it is used, it will approximately mean up to plus or minus 10% of a specific value.

The use of the singular in the context of the described elements (especially in the context of claims) is intended to cover both the singular and plural unless otherwise indicated or clearly inconsistent with the context. The statement of ranges of values herein is simply intended to serve as a shorthand way of individually referring to each individual value falling within the range unless otherwise indicated, and each individual value is included in the description as if separately set forth herein. All methods described herein may be performed in any suitable order unless otherwise indicated or clearly contrary to context. The use of any and all examples, or exemplary language (eg, such as) given herein is intended merely to better illuminate embodiments of the invention, and is not intended to limit the scope of the claims unless otherwise indicated. No language in the description should be construed as indicating any element not stated to be material.

As used herein, the term liquid hydrocarbon material refers to hydrocarbon compounds and mixtures thereof that are liquid under atmospheric conditions. Liquid hydrocarbon materials may optionally have solid particles suspended therein. Liquid hydrocarbon materials may contain other conventional additives, including, but not limited to, flow improvers, antistatic agents, antioxidants, wax anti-deposition agents, corrosion inhibitors, ashless detergents, anti-knock agents, ignition improvers, degassers, odorants, drag reducers piping, lubricants, cetane improvers, spark enhancers, valve seat protectors, synthetic or mineral oil based carrier fluids and defoamers. Typical liquid hydrocarbon materials include, but are not limited to, petroleum; petroleum products such as crude oil, gasoline, kerosene and fuel oil; straight and branched chain paraffinic hydrocarbons; cycloparaffin hydrocarbons; monoolefin hydrocarbons; diolefin hydrocarbons; alkene hydrocarbons; and aromatic hydrocarbons such as benzene, toluene and xylene.

As used herein, the term cracking refers to a process that breaks down long-chain or heavy-weight hydrocarbons into lighter-weight, shorter-chain hydrocarbons by breaking the carbon-carbon bonds in the original long-chain hydrocarbons.

As used herein, the terms discharge, spark discharge, electrical discharge and similar terms refer to an instantaneous electrical discharge between two electrodes occurring when an electric field creates an ionized electrically conductive channel through a normally insulating medium that contains a gas.

In the context of this document, the term Target Energy Input refers to the energy input during a process when the process is profitable, for example, 200 kJ/kg. In some embodiments, the energy input for the method or apparatus described herein is approximately 1000 kJ/kg.

This technology relates to the field of converting liquids containing heavy hydrocarbon molecules into light liquid and/or gaseous fractions. The present technology can also be used to crack liquid heavy oil into a light hydrocarbon fraction by using a stream of carrier gas that is injected into the liquid heavy oil to form a mixture, followed by ionization of the mixture by electrical discharge. This technology can be effectively applied to achieve efficient conversion of heavy oil to light hydrocarbons while minimizing the formation of unwanted solids.

Electrical discharges within gas bubbles immersed in oil can be used to change the chemical structure of crude oil or other hydrocarbons. Depending on the characteristics of the gas and the properties of the discharge, the value of the hydrocarbon can be increased or decreased. Electrical parameters alone, such as low energy and short high voltage pulses, are sometimes insufficient to provide a cost-effective discharge process. Control of the gas mixture can significantly affect the characteristics of the electrical discharge and the plasma-chemical process as a whole. For example, it has been shown that as the API gravity increases and the viscosity of heavy crude oil decreases, gas discharge in methane is economically beneficial. The discharge will generate reactive species that can react with liquid hydrocarbons, effectively increasing the overall hydrogen to carbon ratio of the molecules. However, discharges in methane can lead to the formation of nano- and microparticles of carbon, which is generally undesirable. The addition of hydrogen during submerged spark discharge helps reduce the formation of particulate matter in the reaction zone. However, excess hydrogen in the gas mixture reduces the solids reduction effect and may adversely affect the properties of hydrocarbons. Careful selection of the gas mixture provides the most advantageous effects in combination with a narrow range of gas flow and electrical discharge characteristics. This electrical discharge hydrogenation process is applicable to crude oil and other petroleum intermediates, as well as other hydrocarbons.

The considered discharge in a gas mixture immersed in hydrocarbons can be used in an installation for upgrading crude oil. A discharge in a gas mixture immersed in a light hydrocarbon will produce lighter hydrocarbon compounds and fewer solids. The resulting substances can be used as a diluent for local mixing with raw materials and to reduce the viscosity of the mixture.

The benefits of discharging in this submerged gas mixture are the production of lighter substances since the diluent is produced on site and mixed directly with the crude oil, eliminating the need to pump the diluent separately into the pipeline. Second, discharge in a gas mixture minimizes the formation of particulate matter or produces no particulate matter at all. Blended crude oil better suits the requirements of transportation pipelines. This design typically helps reduce or eliminate the need for external diluent and improve the quality of the diluent produced. This special control of the gas mixture allows for efficient operation over a wider range of electrical discharge characteristics and oil properties in the process.

Various embodiments of the present invention utilize a discharge in a mixture of methane and hydrogen immersed in liquid hydrocarbons. Discharge in methane, which is in the gas phase, is relatively well studied and produces long-chain molecules and particulates. According to observations, a discharge in a mixture of methane and hydrogen should produce fewer solid particles. However, this mechanism is thought to rely on providing sufficient hydrogen radicals to improve the selectivity of the reaction. Embodiments of the invention combine the mechanism of interaction of methane and hydrogen with short pulses immersed in a heavy hydrocarbon material. In various embodiments of the invention, the products may vary significantly with different carrier gases; for example, hexadecane treated with argon may produce large amounts of reactive species that can be identified by GC-MS (Gas Chromatography Mass Spectrometry), whereas hexadecane treated with hydrogen or methane under similar conditions may produce significantly fewer reactive species.

The gas discharge unit in question may be integrated into a continuous crude oil flow system such that the crude oil can be processed as it passes through the discharge chamber. It may be located next to a production well in an oil field in front of a transport pipeline. Upgraded oil will be transported or shipped if it meets pipeline specifications. Gas mixtures will be produced from associated gases, and recirculation will occur from the reactor. The use of a mixture of methane and hydrogen in the submerged discharge gap limits the formation of solids when hydrogen is added to the gas mixture. There is also a decrease in the viscosity of the products.

Way

In one aspect, a method is provided for cracking liquid hydrocarbon materials into light hydrocarbon fractions using a spark discharge, the method comprising passing the liquid hydrocarbon material through an electric discharge chamber and into an interelectrode gap within the electric discharge chamber, in which the interelectrode gap is formed between a negative electrode having a first end and a second end , and a positive electrode having a first end and a second end, while in the electric discharge chamber the first end of the negative electrode is spaced from the first end of the positive electrode by a distance that determines the interelectrode gap; injecting a carrier gas into the liquid hydrocarbon material as it enters the interelectrode gap to form a gas-liquid hydrocarbon mixture; and exposing the gas-liquid mixture to a current between the electrodes at a voltage sufficient to cause a spark discharge; wherein the second end of the negative electrode and the second end of the positive electrode are connected to the capacitor. In some embodiments, the capacitor is charged to a voltage equal to or greater than the breakdown voltage of the carrier gas. In some embodiments, the liquid hydrocarbon material includes crude oil. In some embodiments, the liquid hydrocarbon material includes, but is not limited to, paraffins, aromatics, naphthenes, cycloalkanes, alkenes, dienes, and alkynes. A liquid hydrocarbon material can be characterized by the total number of carbon atoms (C) and/or the number of single (C-C), double (C=C) or triple (C=C) bonds between carbon atoms.

A variety of hydrocarbon gases can be used to produce plasma. The use of methane or natural gas is advantageous not only in terms of the energy required to break the bonds, but also because of its relative low cost. Using methane breaks bonds

CH to form a hydrogen radical and a methyl radical, each of which can combine with larger hydrocarbon radicals in the chain termination step.

Non-hydrogen containing gases such as nitrogen, helium, neon, argon and xenon can be used with hydrogen donor gases in the discharge gap. They can change the distribution of electrical potential and vibrational temperature of molecules in the plasma, allowing free radicals to interact with each other to terminate the chain rather than with the hydrogen atom from the hydrogen donor. In various embodiments of the invention, the type of products and the selectivity of the product can be changed through the use of non-hydrogen gas. Water and ammonia can also serve as hydrogen donors in the process, as long as they do not contain the elements nitrogen N and oxygen O, which may be incompatible with the existing refining system. Although there is a possibility that they could be used as hydrogen donor gases with another system that also uses pulsed electrical discharge technology.

In some _embodiments , the carrier gas comprises one or more of the following: _hydrocarbon , natural gas, ammonia, water, nitrogen (N2), helium, argon, neon, krypton, and xenon. In some embodiments, the carrier gas includes a hydrogen bond donor gas. In some embodiments, the carrier gas contains from 0.1% v/v. up to 5% v/v inert gas. In some embodiments, the carrier gas contains from 0.2% v/v. up to 3% v/v inert gas. In some embodiments, the carrier gas contains from 0.5% v/v. up to 2% v/v inert gas. In some embodiments, the carrier gas contains from 0.75% v/v. up to 1.5% v/v inert gas. In some embodiments, the carrier gas contains from 0.9% v/v. up to 1.1% v/v inert gas.

In some embodiments, the carrier gas contains hydrogen (H2) and methane ( _CH4 ). In some embodiments, the molar ratio of hydrogen (H2) to methane is in the range of 1:99 to 99:1. In some embodiments, the molar ratio of hydrogen to methane is in the range of 5:95 to 95:5. In some embodiments, the molar ratio of hydrogen to methane is in the range of 10:90 to 50:50. In some embodiments, the molar ratio of hydrogen to methane is in the range of 15:85 to 40:60. In some embodiments, the molar ratio of hydrogen to methane is in the range of 20:80 to 35:65. In some embodiments, the molar ratio of hydrogen to methane is in the range of 25:75 to 30:70. In some embodiments, the carrier gas contains from 5 to 40% v/v. H2. In some embodiments, the carrier gas contains from 10 to 35% v/v. N ₂ . In some embodiments, the carrier gas contains from 15 to 30% v/v. N ₂ . In some embodiments, the carrier gas contains from 20 to 25% v/v. H2.

In some embodiments, the molar ratio of hydrogen to methane in the injected carrier gas varies over time. In some embodiments, the hydrogen and methane in the injected gas are premixed. In some embodiments, hydrogen and methane are injected separately. In some embodiments, the injected hydrogen and methane are injected separately, and the rates at which they are injected are independent and do not necessarily vary over time. In some embodiments, the injected carrier gas is recycled from the gas-liquid hydrocarbon mixture.

In some embodiments, the carrier gas is injected into the liquid hydrocarbon material at a rate of from 0.005 L/min to 0.15 L/min. In some embodiments, the carrier gas is injected into the liquid hydrocarbon material at a rate of from 0.01 L/min to 0.1 L/min. In some embodiments, the carrier gas is injected into the liquid hydrocarbon material at a rate of from 0.012 L/min to 0.075 L/min. In some embodiments, methane is injected at a rate of 0.01 L/min to 0.07 L/min. In some embodiments, methane is injected at a rate of 0.014 L/min to 0.06 L/min. In some embodiments, methane is injected at a rate of 0.019 L/min to 0.05 L/min. In some embodiments, methane is injected at a rate of 0.02 L/min to 0.04 L/min. In some embodiments, hydrogen (H ₂ ) is injected at a rate of 0.02 L/min to 0.07 L/min. In some embodiments, hydrogen (H ₂ ) is injected at a rate of 0.03 L/min to 0.05 L/min. In some embodiments, hydrogen (H2) is injected at a rate of 0.04 L/min to 0.045 L/min. In some embodiments, the spark discharge is a pulsed spark discharge with a pulse frequency. In some embodiments, the pulse frequency is in the range of 100-200 Hz. In some embodiments, the pulse frequency is in the range of 15-20 Hz. In some embodiments, the pulse frequency is in the range of 10-15 Hz. In some embodiments, the pulse frequency is in the range of 5-10 Hz. In some embodiments, the pulse frequency is in the range of 1-5 Hz. In some embodiments of the invention, the spark discharge is continuous. In various embodiments of the invention, pulse frequency may be associated with process scaling.

In some embodiments, the method further includes analyzing the liquid hydrocarbon after the spark discharge. In some embodiments, the method further includes analyzing light hydrocarbon fractions. In some embodiments, the assay is a colorimetric assay. In some embodiments, the analysis method is gas chromatography (GC)/mass spectrometry (MS) (GCMS or GC-MS). In some embodiments, gas chromatography with flame ionization detector (GC-FID) is the analysis method. In some embodiments, the method further includes collecting light hydrocarbon fractions. In some embodiments, light hydrocarbon fractions are collected by distillation.

With reference to FIG. 5, one example involves a discharge in hexadecane with hydrogen and argon. Argon as a carrier gas can significantly alter products by creating more reactive species that are able to react strongly in the GC column and then be identified by MS. These reactive species may be hydrocarbon acids or radicals, which may not be identified by the GC-MS system. Methane or hydrogen as a carrier gas may produce less reactive species. This method may also include analysis of selectivity and quality of products. In some embodiments, the method includes the analysis of cyclic or branched hydrocarbon products. In some embodiments, the analysis further includes a product selectivity analysis.

In some embodiments, the light hydrocarbon fractions have a viscosity of 0.5 to 100 cP. In some embodiments, the light hydrocarbon fractions have a viscosity of 0.5 to 10 cP. In some embodiments, the light hydrocarbon fractions have an API gravity of 25 to 60. In some embodiments, the light hydrocarbon fractions have an API gravity of 40 to 60.

In some embodiments, the light hydrocarbon fractions have a molecular weight of from 60 g/mol to 320 g/mol. In some embodiments, the liquid hydrocarbon material includes a weight from 1 g to 5 g. In some embodiments, the liquid hydrocarbon material includes a weight from 5 g to 10 g. In some embodiments, the liquid hydrocarbon material includes a weight from 10 g to 15 g In some embodiments, the liquid hydrocarbon material includes a mass of from 15 g to 25 g. In some embodiments, the liquid hydrocarbon material includes a mass of from 25 g to 35 g. In some embodiments, the liquid hydrocarbon material includes a mass greater than 35 g. In some embodiments, the liquid hydrocarbon material includes a mass greater than 100 g. In some embodiments, the liquid hydrocarbon material includes a mass greater than 1 kg. In some embodiments, the liquid hydrocarbon material includes a mass greater than 100 kg. In some embodiments, the liquid hydrocarbon material includes a mass greater than 1000 kg. In some embodiments, the liquid hydrocarbon material includes a mass greater than 10,000 kg. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in the light hydrocarbon fraction is in the range of 2.01 to 2.05. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.05 to 2.1. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.1 to 2.2. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.2 to 2.3. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.3 to 2.4. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.4 to 2.5. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.5 to 2.6. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.6 to 2.7. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.7 to 2.8. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.8 to 2.9. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.9 to 3.0. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in the light hydrocarbons is in the range of 3.0 to 3.1. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.1 to 3.2. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.2 to 3.3. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.3 to 3.4. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.4 to 3.5. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.5 to 3.6. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.6 to 3.7. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.7 to 3.8. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.8 to 3.9. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.9 to 4.0.

In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 285 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 271 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 257 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 243 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 229 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 215 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 201 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 187 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 173 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 159 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 145 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 131 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 117 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 103 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 89 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 75 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 61 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 47 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 33 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 19 g/mol.

In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a boiling point at atmospheric pressure of less than 175°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 152°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 127°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 99°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 37°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 2°C. In some embodiments, fresh liquid hydrocarbon is continuously passed through the electrical discharge chamber. In some embodiments, the liquid hydrocarbon material is recycled to pass through the same electrical discharge chamber again. In some embodiments, the interelectrode spacing ranges from about 1 mm to 100 mm. In some embodiments, the electrode spacing distance is from 3 mm to 20 mm. In some embodiments, the electrode spacing distance is from 6 mm to 15 mm. In some embodiments, the electrode spacing distance is less than 10 mm. In some embodiments, the electrode gap distance is less than 5 mm. In some embodiments, the electrode gap distance is less than 1 mm. In some embodiments, the capacitor is charged to a voltage of between 10 kV and 100 kV. In some embodiments, the invention

- 9 044982 teniya the capacitor is charged to a voltage from 20 kV to 80 kV. In some embodiments, the capacitor is charged to a voltage of between 30 kV and 50 kV. In some embodiments, the carrier gas breakdown voltage is between 10 kV and 100 kV. In some embodiments, the carrier gas breakdown voltage is between 10 kV and 40 kV. Without being limited by theory, in any of the disclosed methods or embodiments of the invention, liquid hydrocarbon materials with a high carbon content are broken down into molecules having a lower carbon content to form light hydrocarbon fractions that are lighter (in terms of both molecular weight and and boiling points) on average than the heavy liquid hydrocarbon materials in the feedstock. Again, without being limited by theory, it is believed that the breakdown of heavy molecules occurs through the rupture of C-C bonds. For these molecules, the energy required to break a C-C bond is approximately 261.9 kJ/mol. This amount of energy is significantly lower than that required to break a C-H bond (364.5 kJ/mol). Since the process must occur continuously, the various steps or stages of the process may occur simultaneously or sequentially, such that liquid hydrocarbon material is continuously fed into the electrical discharge chamber as finished light hydrocarbon fractions exit the chamber.

In some embodiments, the method includes creating a spark discharge plasma in a gas stream in an interelectrode discharge gap. The breakdown voltage of the carrier gas will be less than the breakdown voltage of the liquid; accordingly, a gas jet can be used at the same voltage level to create a longer discharge gap. Increasing the interelectrode discharge gap while simultaneously reducing the corrosive effect of the process on the electrodes increases the area of direct contact between the plasma discharge and the liquid hydrocarbon material. Without wishing to be bound by any particular theory, it is believed that when the spark discharge plasma contacts liquid hydrocarbon material in the interelectrode discharge gap, the liquid hydrocarbon material rapidly heats up and evaporates to form steam. Thus, the molecules of the liquid hydrocarbon material are mixed with the molecules of the carrier gas and the plasma particles formed in them. Plasma electrons collide with hydrocarbon molecules, thus breaking them into smaller molecules that have one unsaturated bond and are practically free radicals, that is, they are fragments of molecules with a free bond. Free radicals also arise from the direct interaction of rapidly moving electrons with the liquid walls formed around the plasma channel between the electrodes. Various carrier gases known in the art can be used in the methods and apparatus of the present technology. Typical carrier gases include, but are not limited to, helium, neon, argon, xenon, and hydrogen (H ₂ ), among other gases. In some embodiments, the carrier gas is a hydrogen-containing gas, such as, but not limited to, water, steam, pure hydrogen, methane, natural gas, or other hydrocarbon gases. Mixtures of two or more such hydrogen-containing gases can be used in any of the described embodiments of the invention. In addition, non-hydrogen containing gases such as helium, neon, argon and xenon can be used either as gas diluents for any of the hydrogen containing gases, or they can be used with liquid hydrocarbon materials, thereby allowing free radicals to terminate with each other instead of terminating with a hydrogen atom from the carrier gas. To select a suitable carrier gas in terms of the energy required to form one free hydrogen atom, it is necessary to compare the dissociation energies of different carrier gases or hydrogen-containing gases.

For example, to break the bond between hydrogen atoms in an H2 molecule, approximately 432 kJ/mol will be required. For water vapor, the energy required to release a hydrogen atom is approximately 495 kJ/mol, while the energy required to remove a hydrogen atom from a hydrocarbon molecule such as methane requires approximately 364.5 kJ/mol.

In some embodiments, the carrier gas is methane. The use of methane or natural gas is advantageous not only in terms of the energy required to break the bonds, but also because of its relatively low cost. The use of methane ensures that C-H bonds are broken to form a hydrogen radical and a methyl radical, each of which can combine with larger hydrocarbon radicals in the chain termination step. In some embodiments, the carrier gas is methane or a mixture of methane and an inert gas such as helium, argon, neon or xenon.

In some embodiments of the invention, spark discharges can be created in either a continuous mode or a pulsed mode. In some embodiments, the continuous discharge is an arc discharge or a glow discharge. However, the use of this type of discharge for cracking heavy hydrocarbons may be limited by the fact that heating the gas mixture by continuously passing current may lead to an undesirable increase in temperature inside the electric discharge chamber. This increase in temperature can lead to increased coking and soot formation. In addition, when using a continuous discharge, the products of the hydrocarbon fraction are constantly exposed to the discharge until they leave the plasma. In contrast, the use of pulsed discharge, especially pulsed spark discharge,

- 10 044982 may be desirable for the purpose of producing a light hydrocarbon fraction from heavy oil fractions, since the interval between pulses allows the formation of free radicals to stop and allows time for the resulting light hydrocarbon to leave the plasma.

Installation

In another aspect, a plant is provided for converting liquid hydrocarbon material into a light hydrocarbon fraction, the plant including a spark chamber including a negative electrode having a first end and a second end, and a positive electrode having a first end and a second end. The first end of the negative electrode is spaced from the first end of the positive electrode by a distance that defines the interelectrode gap. The second end of the negative electrode is connected to a capacitor. The apparatus includes a carrier gas inlet for supplying carrier gas to the liquid hydrocarbon material. The installation also includes an inlet port for introducing liquid hydrocarbon material into the spark discharge chamber and an outlet port for removing the light hydrocarbon fraction from the spark discharge chamber. In some embodiments, the carrier gas contains hydrogen and/or methane. In some _embodiments , the carrier gas comprises one or more of the following: _hydrocarbon , natural gas, ammonia, water, nitrogen (N2), helium, argon, neon, krypton, and xenon. In some embodiments, the carrier gas includes a hydrogen bond donor gas. In some embodiments, the carrier gas contains from 0.1% v/v. up to 5% v/v inert gas. In some embodiments, the carrier gas contains from 0.2% v/v. up to 3% v/v inert gas. In some embodiments, the carrier gas contains from 0.5% v/v. up to 2% v/v inert gas. In some embodiments, the carrier gas contains from 0.75% v/v. up to 1.5% v/v inert gas. In some embodiments, the carrier gas contains from 0.9% v/v. up to 1.1% v/v inert gas.

In some embodiments, the carrier gas contains hydrogen (H2) and methane ( _CH4 ). In some embodiments, the molar ratio of hydrogen to methane is in the range of 1:99 to 99:1. In some embodiments, the molar ratio of hydrogen to methane is in the range of 5:95 to 95:5. In some embodiments, the molar ratio of hydrogen to methane is in the range of 10:90 to 50:50. In some embodiments, the molar ratio of hydrogen to methane is in the range of 15:85 to 40:60. In some embodiments, the molar ratio of hydrogen to methane is in the range of 20:80 to 35:65. In some embodiments, the molar ratio of hydrogen to methane is in the range of 25:75 to 30:70. In some embodiments, the carrier gas contains from 5 to 40% v/v. H2. In some embodiments, the carrier gas contains from 10 to 35% v/v. H2. In some embodiments, the carrier gas contains from 15 to 30% v/v. H2. In some embodiments, the carrier gas contains from 20 to 25% v/v. H2. In some embodiments, the light hydrocarbon fractions have a viscosity of 0.5 to 100 cP. In some embodiments, the light hydrocarbon fractions have a viscosity of 0.5 to 10 cP.

In some embodiments, the light hydrocarbon fractions have an API gravity of 25 to 60. In some embodiments, the light hydrocarbon fractions have an API gravity of 40 to 60.

In some embodiments, the light hydrocarbons have a molecular weight of from 60 g/mol to 320 g/mol.

In some embodiments, the average ratio of hydrogen atoms to carbon atoms in the light hydrocarbon fraction is in the range of 2.01 to 2.05. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.05 to 2.1. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.1 to 2.2. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.2 to 2.3. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.3 to 2.4. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.4 to 2.5. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.5 to 2.6. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.6 to 2.7. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.7 to 2.8. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.8 to 2.9. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 2.9 to 3.0. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons

- 11 044982 is in the range from 3.0 to 3.1. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.1 to 3.2. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.2 to 3.3. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.3 to 3.4. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.4 to 3.5. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.5 to 3.6. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.6 to 3.7. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.7 to 3.8. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.8 to 3.9. In some embodiments, the average ratio of hydrogen atoms to carbon atoms in light hydrocarbons is in the range of 3.9 to 4.0.

In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 285 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 271 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 257 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 243 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 229 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 215 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 201 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 187 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 173 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 159 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 145 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 131 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 117 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 103 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 89 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 75 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 61 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 47 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 33 g/mol. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a molecular weight of less than 19 g/mol.

In some embodiments, the light hydrocarbon fractions contain hydrocarbons with a boiling point at atmospheric pressure of less than 175°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 152°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 127°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 99°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 37°C. In some embodiments, the light hydrocarbon fractions contain hydrocarbons with an atmospheric boiling point of less than 2°C.

In some embodiments, the electrical discharge chamber may also include a gas jet device configured to introduce a carrier gas proximal to the discharge gap to allow mixing of the liquid hydrocarbon material with the carrier gas. The carrier gas may be introduced into the liquid hydrocarbon material during, or immediately before, injection into the discharge gap. The second end of the negative electrode and the second end of the positive electrode are connected to the capacitor. In some embodiments, a power source is provided configured to generate a spark discharge in the interelectrode discharge gap.

- 12 044982

In an electric discharge chamber, a spark discharge is created in the interelectrode charging gap when a voltage (V) equal to or greater than the breakdown voltage ( _Vb ) of the interelectrode gap is applied to the electrodes. The spark discharge is initiated by free electrons, which can appear on the positive electrode by field emission or other electron emission processes. Free electrons are accelerated in an electric field extending across the gap, and when the gas in the gap is ionized, a plasma spark discharge channel is created. After creating a spark discharge channel, a discharge current flows through the plasma. The voltage inside the plasma channel ( _Vd ) is lower than the breakdown voltage ( _Vb ).

In some embodiments, an arc discharge is created when the power supply is sufficient to continuously flow current in the discharge path. Plasma heating takes place in a spark discharge. In some embodiments, the temperature is controlled by adjusting the discharge current. In some embodiments, the temperature is controlled by the duration of the discharge. In certain embodiments of the invention, as a result of the plasma channel created in the carrier gas, the temperature of the carrier gas reaches several thousand °C.

In some embodiments of the invention, various pulse generators are used to ignite the spark discharges. In some embodiments, a circuit may be used that discharges the precharge of the storage capacitor under load. The parameters of the pulse voltage under load are determined by the capacitance of the capacitor, as well as the parameters of the entire discharge circuit. Energy losses will depend on the characteristics of the discharge circuit, in particular, on losses in the spark gap. In some embodiments of the present technology, the spark gap is directly used as a load, that is, a plasma reactor, thereby reducing energy losses in the discharge circuit. In addition, a storage capacitor can be connected in parallel with the spark gap in a circuit with minimal inductance. Breakdown of the discharge gap occurs when the voltage on the storage capacitor reaches the breakdown voltage, and energy is supplied to the spark discharge plasma during the discharge of the capacitor. Therefore, the energy loss in this circuit is low.

In any of the above-described embodiments, the positive electrode may be in the form of a planar electrode, such as a sheet, web, or flat lead, while the negative electrode is in the form of a tube, that is, cannulated. The negative cannulated electrode is a hollow electrode through which a carrier gas can be injected into the liquid hydrocarbon material in the interelectrode space. Thus, the negative cannulated electrode can serve as a channel for carrier gas. When the negative electrode is cannulated, the passage of the hollow tube will have a radius of curvature at the tube opening. The height or length of the discharge electrode is usually measured from the base, which is its attachment point, to the top. In some embodiments, the ratio of the radius of curvature to the height or length of the cathode may be greater than about 10.

The interelectrode discharge gap, that is, the distance between two electrodes, affects the efficiency of the process. The interelectrode discharge gap is a characteristic that can be optimized based on, for example, the particular liquid hydrocarbon material supplied to the discharge chamber, the carrier gas injected, and the applied voltage and/or current.

In some embodiments, the electrode spacing distance is from about 1 mm to about 100 mm. In some embodiments, the electrode spacing distance is from 3 mm to 20 mm. In some embodiments, the electrode spacing distance is from 6 mm to 15 mm. In some embodiments, the electrode spacing distance is less than 10 mm. In some embodiments, the electrode spacing distance is less than 5 mm. In some embodiments, the electrode spacing distance is less than 1 mm. In some embodiments, the electrode spacing distance is approximately 4 mm.

In some embodiments, the capacitor is charged to a voltage of between 10 kV and 100 kV. In some embodiments, the capacitor is charged to a voltage between 20 kV and 80 kV. In some embodiments, the capacitor is charged to a voltage of between 30 kV and 50 kV. The negative electrode and the positive electrode may both protrude into the electric discharge chamber.

In some embodiments, the capacitor may be charged to a voltage equal to or greater than the breakdown voltage of the carrier gas such that a spark discharge occurs. In some embodiments, the spark discharge occurs between the positive electrode and the carrier gas near the first end of the positive electrode. In some embodiments, the spark discharge is continuous. In other embodiments of the invention, the spark discharge is pulsed. In some embodiments, the rate of spark discharge is controlled by the amount of resistance in the charging circuit

- 13 044982 storage capacitor.

In some embodiments, the spark discharge is a pulsed spark discharge with a pulse frequency. In some embodiments, the pulse frequency is in the range of 15-20 Hz. In some embodiments, the pulse frequency is in the range of 10-15 Hz. In some embodiments, the pulse frequency is in the range of 5-10 Hz. In some embodiments, the pulse frequency is in the range of 1-5 Hz. In some embodiments, the spark discharge is continuous.

In some embodiments, a power source is connected to the entire system to provide the energy required to initiate the spark discharge. In some embodiments, the power source is a DC power supply. In some embodiments, the DC power supply has an operating voltage of 15-25 kV. The power source depends on the number of discharge gaps for processing the hydrocarbon liquid, their length, pulse repetition rate, liquid flow rate through the reactor, gas flow rate through each discharge gap.

In some embodiments, the apparatus may include a reactor that uses spark gaps of approximately 3.5 mm in length, capacitors of approximately 100 picofarads with an operating voltage of approximately 18 kV and a pulse repetition rate of approximately 5 Hz. The power supply can consume 1 to 2 W, while the plasma can absorb approximately 0.97 W of power directly from the discharge. The remaining energy can be dissipated in the capacitor charging system. In some embodiments, a reservoir or piping system may connect an inlet for liquid hydrocarbon material to a source of liquid hydrocarbon material, and the reservoir or piping system may be connected to a first outlet for collecting light hydrocarbon fraction products. The light hydrocarbon fraction products can be further processed by separating the lower molecular weight components by distillation, with the higher molecular weight components returning to the inlet for possible further processing in an electrical discharge chamber. A gas recovery system may be connected to the outlet of the unit, allowing low molecular weight hydrocarbon gases and/or carrier gases to be captured, the latter being recycled for re-injection as a carrier gas and the former being collected for other uses.

The installation can be adapted to any specific processing mode of liquid hydrocarbon materials. This adaptive flexibility provides easy control over the processing of crude oils, which can vary in a wide range of compositions and impurities. Control of process conditions for cracking liquid hydrocarbon materials is possible by changing only a few operating parameters. For example, such parameters may include changes in the length of the discharge gap and/or the applied voltage (V). An increase in voltage can lead to an increase in the energy accumulated on the capacitor in proportion to the square of the voltage W=CV ² /2. The change in capacitance of the capacitor is directly proportional to the change in energy W supplied to the discharge.

Control of the pulse repetition rate can be achieved by manipulating the capacitance and resistance of the circuit. In some embodiments, the pulse rate is from about 1 to about 10 pulses per second. In other embodiments, the pulse rate is from about 2 to about 7 pulses per second. In any of the above-described embodiments, the pulse rate is from about 3 to about 5 pulses per second.

In any of the embodiments of the invention, the spark discharge can be controlled by changing the injection rate of the carrier gas or liquid hydrocarbon materials. In some embodiments, the spark discharge is controlled by controlling the time of processing of liquid hydrocarbons and hydrocarbon fraction products in the electric discharge chamber.

In some embodiments of the invention, streams or jets of carrier gas of various diameters can be formed in the interelectrode gap depending on the gas flow rate and the viscosity of the liquid hydrocarbon material or light hydrocarbon fractions. In some embodiments, the spark discharge plasma is not in direct contact with the liquid hydrocarbon material due to the large diameter gas jet if generated at a high carrier gas flow rate. In embodiments of the invention with a low flow rate of the carrier gas, the diameter of the gas jet is comparable to the diameter of the spark discharge channel. In such embodiments, there is intense interaction between the discharge plasma and the surrounding fluid. Intense interaction indicates that the contact area of the plasma channel with the liquid is maximized.

The method and apparatus described herein provide several advantages over other known methods. For example, in the currently known method,

- 14 044982 set forth in US patent No. 5626726, uses a heterogeneous mixture of liquid and gas in which an arc is created. In embodiments of the proposed technology, a gas jet propagating in a liquid is used to implement a spark discharge. Moreover, breakdown of the discharge gap in a heterogeneous mixture requires a high electric field strength, for which short discharge gaps were used in the '726 patent. Short discharge gaps and the associated long-term operation of electrical discharges lead to wear of the discharge gap electrodes with a simultaneous increase in the gap length and breakdown voltage. At a fixed operating voltage, as the length increases, the discharge in the gap decreases and eventually stops. In contrast, in the technology according to the present invention, since electrical breakdown occurs in a gas for which the electrical breakdown field is much lower than that of a liquid (eg oil), longer discharge gaps can be used for the same operating voltage. Due to the ability to use longer discharge intervals, increasing the breakdown voltage has little effect on the electrodes, so discharge ignition is stable at a fixed operating voltage.

The invention is further defined by the following embodiments:

Embodiment A. A method for cracking liquid hydrocarbon materials into a light hydrocarbon fraction using a spark discharge, the method comprising: passing the liquid hydrocarbon material through an electric discharge chamber and into an interelectrode gap within the electric discharge chamber, in which an interelectrode gap is formed between a negative electrode having a first end and a second end, and a positive electrode having a first end and a second end, wherein in the electric discharge chamber the first end of the negative electrode is spaced from the first end of the positive electrode by a distance that determines the interelectrode gap; injecting a carrier gas containing hydrogen (H2) and methane into the liquid hydrocarbon material as it enters the interelectrode gap to form a gas-liquid hydrocarbon mixture; and exposing the gas-liquid hydrocarbon mixture to a current between the electrodes at a voltage sufficient to cause a spark discharge; wherein the second end of the negative electrode and the second end of the positive electrode are connected to the capacitor; and the capacitor is charged to a voltage equal to or greater than the breakdown voltage of the carrier gas.

Embodiment B. The method of Embodiment A, wherein the carrier gas consists of hydrogen (H ₂ ) and methane. Embodiment C. The method according to Embodiment A or B, wherein the carrier gas contains from 15% v/v. up to 30% v/v hydrogen.

Embodiment D. The method of any one of Embodiments AC, wherein the spark discharge is a pulsed spark discharge.

Embodiment E. The method according to any one of Embodiments AD, further comprising recovering light hydrocarbon fractions resulting from the action of a pulsed spark discharge on a gas-liquid hydrocarbon mixture.

Embodiment F. The method of any one of Embodiments AE, wherein the light hydrocarbon fractions have a viscosity of less than 100 cP.

Embodiment G. The method of any one of Embodiments AF, wherein the light hydrocarbon fractions have an API gravity greater than 30.

Embodiment H. The method of any one of Embodiments AG, wherein the average ratio of hydrogen atoms to carbon atoms in the light hydrocarbon fractions is from 2 to 2.5.

Embodiment I. The method according to any one of Embodiments A-H, wherein the concentration of hydrogen and/or methane in the carrier gas changes over time during the period of injection of the carrier gas into the liquid hydrocarbons.

Embodiment J. The method of any one of Embodiments A-I, wherein the carrier gas introduced into the liquid hydrocarbons is recycled from the gas-liquid hydrocarbon mixture.

Embodiment K. An apparatus for converting liquid hydrocarbon material into a light hydrocarbon fraction, the apparatus comprising: a spark chamber comprising a negative electrode having a first end and a second end, and a positive electrode having a first end and a second end, wherein the first the end of the negative electrode is spaced from the first end of the positive electrode by a distance that defines the interelectrode gap, and the second end of the negative electrode and the second end of the positive electrode are connected to the capacitor; a carrier gas inlet for supplying a carrier gas containing hydrogen and methane to the liquid hydrocarbon material; an inlet port for introducing liquid hydrocarbon material into the spark chamber; and an outlet designed to remove the light hydrocarbon fraction from the spark discharge chamber.

Embodiment L. Installation according to Embodiment K, in which the carrier gas contains from 15% v/v. up to 30% v/v hydrogen.

- 15 044982

Embodiment M. A plant according to Embodiment K or L, wherein the light hydrocarbon fractions have a viscosity of less than 100 cP.

Embodiment N. Installation according to any one of the embodiments of the invention

K-M, in which light hydrocarbon fractions have an API density of more than 30.

Embodiment O. A plant according to any one of the K-N embodiments, wherein the average ratio of hydrogen atoms to carbon atoms in the light hydrocarbon fractions is from 2 to 2.5.

Embodiment P. An apparatus according to any one of the K-O embodiments, in which the capacitor is charged to a voltage equal to or greater than the breakdown voltage of the carrier gas.

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[8]Kaiser, M. J., & Gary, J. H. (2007). Study updates refinery investment cost curves. Oil and Gas Journal, 84-94. Retrieved March 25, 2018.

For purposes of the present invention, unless otherwise indicated, a singular noun means one or more.

As used herein, the term will roughly be understood by those skilled in the art and will vary to some extent depending on the context in which it is used. If the use of the term is not readily apparent to those skilled in the art, given the context in which it is used, approximately will mean up to plus or minus 10% of a specific value.

All publications, patent applications, issued patents or other documents referred to in this specification are incorporated herein by reference as if each individual publication, patent application, issued patent or other document were specifically and individually identified as incorporated by reference in their entirety. Definitions contained in the text incorporated by reference are excluded to the extent that they conflict with the definitions herein.

The embodiments of the invention illustratively described herein may be suitably practiced in the absence of any element or elements, limitation or limitations not specifically disclosed herein. Thus, for example, the terms including, containing, and the like should be read broadly and without limitation. In addition, the terms and expressions given herein have a descriptive but non-limiting meaning, that is, the use of such terms and expressions is not intended to exclude any equivalents of the specified and described characteristics or parts thereof, but implies that various modifications are possible within the stated technology . In addition, the phrase consisting substantially of should be understood to include the elements that are specifically enumerated and additional elements that do not materially affect the essential and novel characteristics of the claimed technology. The phrase consisting of excludes any unspecified element.

The present invention is not limited to the specific embodiments described in this application, which are intended to illustrate various aspects. It will be apparent to those skilled in the art that many modifications and variations may be made without departing from the spirit and scope of the invention. Functionally equivalent compositions, apparatuses and methods within the scope of this specification, in addition to those listed herein, will be apparent to those skilled in the art from the preceding description. It is intended that such modifications and variations fall within the scope of the appended claims. This specification is intended to be limited only by the terms of the appended claims together with the full scope of equivalents to which such claims are entitled. It should be understood that this description is not limited to specific methods, reagents, compound compositions or biological systems, which, of course, may vary. It should also be understood that the terminology

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Claims (10)

used herein is intended only to describe specific embodiments of the invention and is not intended to be limiting. Moreover, if features or aspects of the invention are described in terms of Markush groups, those skilled in the art will understand that the invention is also thus described in terms of any individual member or subgroup of members of the Markush group. One skilled in the art will understand that, for any and all purposes, particularly for the purpose of providing a written description, all ranges disclosed herein also include any and all possible sub-ranges, and combinations of sub-ranges. Any specified range can be easily recognized as being sufficiently descriptive to allow the same range to be broken down into at least equal halves, thirds, quarters, fifths, tenths, and the like. By way of non-limiting example, each range discussed herein can easily be broken down into a lower third, a middle third, and an upper third, and the like. It will also be understood by one skilled in the art that all linguistic expressions such as up to at least more than, less than, and the like include the number indicated and refer to ranges that can subsequently be broken down into subranges as discussed above. Finally, one skilled in the art will understand that the range includes each individual term of the range. While certain embodiments of the invention have been illustrated and described, it should be understood that changes and modifications thereto may be made by those skilled in the art without departing from the technology in its broader aspects as defined in the following claims. CLAIM 1. A method for cracking liquid hydrocarbon materials into the light hydrocarbon fraction using a spark discharge, including: the passage of liquid hydrocarbon material through the electric discharge chamber and into the interelectrode gap inside the electric discharge chamber, in which the interelectrode gap is formed between a negative electrode having a first end and a second end, and a positive electrode having a first end and a second end, while in the electric discharge chamber the first end of the negative the electrode is spaced from the first end of the positive electrode at a distance that determines the interelectrode gap; injecting a carrier gas containing hydrogen (H2) and methane into the liquid hydrocarbon material as it enters the interelectrode gap to form a gas-liquid hydrocarbon mixture, the carrier gas containing from 15% v/v. up to 30% v/v hydrogen, wherein hydrogen is added to the carrier gas to achieve efficient conversion of liquid hydrocarbon materials into light hydrocarbon fractions while reducing the formation of particulates in the reaction zone of the electric discharge chamber, but avoiding excess hydrogen so as to prevent the reduction of the reduction of particulates from being weakened; and exposing the gas-liquid hydrocarbon mixture to a current between the electrodes at a voltage sufficient to cause a spark discharge; wherein the second end of the negative electrode and the second end of the positive electrode are connected to the capacitor; and the capacitor is charged to a voltage equal to or greater than the breakdown voltage of the carrier gas. 2. The method according to claim 1, characterized in that the carrier gas consists of hydrogen (H2) and methane. 3. The method according to claim 1, characterized in that the spark discharge is a pulsed spark discharge. 4. The method according to claim 3, characterized in that it additionally includes the extraction of light hydrocarbon fractions formed as a result of the action of a pulsed spark discharge on a gas-liquid hydrocarbon mixture. 5. The method according to claim 1, characterized in that the light hydrocarbon fractions have a viscosity of less than 100 cP. 6. The method according to claim 1, characterized in that the light hydrocarbon fractions have an API density of more than 30. 7. The method according to claim 1, characterized in that the average ratio of hydrogen atoms to carbon atoms in the fractions of light hydrocarbons is from 2 to 2.5. 8. The method according to claim 1, characterized in that the concentration of hydrogen and/or methane in the carrier gas changes over time during the period of injection of the carrier gas into liquid hydrocarbons. 9. The method according to claim 1, characterized in that the carrier gas introduced into the liquid hydrocarbons is recirculated from the gas-liquid hydrocarbon mixture. 10. Installation for implementing the method according to claim 1, including: the specified electric discharge chamber containing the specified negative electrode and the specified