WO2011026192A1 - Hydrocarbon extraction - Google Patents

Abstract

A process for extracting a fuel product from a carbonaceous material. The process comprises contacting the carbonaceous material with a metal and/or a metal ion containing compound in the presence of water under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product.

Description

HYDROCARBON EXTRACTION

This patent application claims priority from Australian Provisional Patent Application No.

2009904285 titled "Alkaline Hydrocarbon Extraction" and filed 4 September 2009, the entire contents of which are hereby incorporated by reference.

FIELD

Disclosed herein are processes for upgrading and/or recovering hydrocarbons from carbonaceous material. Also disclosed herein are processes for generating hydrogen gas from carbonaceous material. Also disclosed herein are processes for generating alcohols from carbonaceous material.

BACKGROUND

Dwindling oil reserves and soaring oil prices have increased commercial interest in alternative fuels. Carbonaceous materials such as coal, oil sands and oil shale, are found in high abundance. These carbonaceous materials (sometimes referred to as unconventional oil) can be converted to hydrocarbon products that can be processed to form many petroleum products such as petrol and diesel, thereby offering an alternative fuel source to traditional oil and oil products.

Oil shale is a sedimentary rock that contains significant amounts of kerogen (a solid mixture of organic chemical compounds) from which hydrocarbon products can be extracted. Oil sands (also known as tar sands or bituminous sands) are a naturally occurring mixture of sand or clay, water and a dense or viscous form of petroleum known as bitumen, which is considered a major source of unconventional oil. Oil sand deposits are found in numerous locations throughout the world, for example, Canada, the United States of America, Venezuela, Albania, Romania, Malagasy and Russia. The largest deposit is in the northeast of the Province of Alberta, Canada. The hydrocarbon content of oil sands is variable, averaging 12 wt.% of the oil sand deposit, but ranging from 0 to 18 wt.%. Water tends to range between 3 to 6 wt.% of the deposit, increasing as the hydrocarbon content decreases. The mineral content (ie sand, silica and/or clay) constitutes the balance.

Hydrocarbon products can be recovered from oil sand deposits using a steam-assisted gravity drainage (SAGD) method, which employs two horizontal well bores, one above the other, within the lower portion of an oil sand formation. These horizontal well bores may be around 2 kilometres in length, although longer bores have previously been described. SAGD employs externally applied heat supplied as steam from the surface to the upper well bore, which permeates the raw oil sand deposit, which reduces the viscosity of the entrained hydrocarbon and accordingly mobilises the hydrocarbon products within a water emulsion. The well is "shut in" for a period of time to allow thermal transfer from the steam to permeate the oil sands, and the steam flooding and shutting in may be repeated several times. The period of time from initial steam flooding to first recovery of thermally mobilised hydrocarbon product from the lower well bore is often many weeks or months, and may sometimes be longer than a year. Gravity assists the hydrocarbons to mobilise to the lower well bore, and the mobilised hydrocarbons are recovered by intersecting vertical well bores.

Advantageously, in the SAGD method, much of the sand, silica and/or clay impurities within the oil sands remain behind in the geological formation and are not recovered to surface.

However, a number of disadvantages exist with this method. While the viscosity of the hydrocarbon within the oil sands is temporarily improved by thermal transfer from steam (for example, at temperatures of 200 to 250 deg C), upon cooling the viscosity of the released hydrocarbon product may be higher than before steam mobilisation. This is due to "retrograde reactions", whereby bonds in the hydrocarbon are cleaved at high temperatures, and the cleaved hydrocarbon bonds rejoin in the absence of hydrogen. Additionally, retrograde reactions result in hydrocarbon products that resist further cleavage for upgrading or hydrogen transfer. Further, up to six barrels of water are applied to the geological formation for every barrel of oil recovered, and the energy requirement to convert this water to steam is high. The time requirement to recovery of oil is also high.

SAGD processes have also been carried out under alkaline and/or oxidising conditions. For example, US Patent No. 6,576, 145 describes a process for separating hydrocarbons from a mixture of hydrocarbons and a mineral substrate by heating the mixture and then treating it with aqueous hydrogen peroxide. In WO 2005/123608 there is described a process for recovering hydrocarbons from mixtures of hydrocarbons and a mineral substrate by treating an aqueous slurry containing the mixture with hydrogen peroxide and an alkali material. Both of these methods result in treatment of the mixture under oxidising conditions.

Alternatively, an above ground method termed a "hot water" process for extracting hydrocarbon from a carbonaceous substance such as oil sands is known, as described, for example, in US Patent Nos. 3,496,093; 3,502,566; 3,526,585; 3,502,565; 3,502,575; 3,951,800; 3,951,779; 3,509,641 and 3,751,358. First, a conditioning step is conducted wherein the oil sand is mixed with water and heated to about 80°C to 95°C with open steam to form a pulp of 70-85 wt.% solids at a pH maintained in the range of about 8.0-8.5 by addition of reagent such as sodium hydroxide. Under these conditions, hydrocarbon is stripped from the individual sand grains and mixed into the pulp in the form of discrete droplets of a particle size on the same order as that of the sand grains. Next, the conditioned pulp is diluted further so that settling can take place. The bulk of the sand-sized particles (greater than 325 mesh screen) rapidly settle and are withdrawn as sand tailings. Most of the hydrocarbon floats (settles upward) to form a coherent mass known as bitumen froth, which is recovered by skimming the settling vessel. An aqueous middlings layer containing some mineral and hydrocarbon is formed between these layers, from which additional hydrocarbon can be recovered. The recovered hydrocarbon products can be combined, diluted with naphtha (a liquid hydrocarbon mixture) and centrifuged to remove more water and residual mineral. The naphtha is then distilled for further processing. "Tailings" (ie the generally worthless materials left over from the process) can be collected throughout the process and generally will contain water (both naturally occurring water and added water), hydrocarbon and mineral and dissolved chemicals. However, this process is not efficient as a certain percentage of hydrocarbons cannot easily be separated from the oil sand, and are disposed of in the tailings portion. Furthermore, tailings are discharged and contained in tailings ponds and the finer clay particles in the tailings take years to settle. Ideally, the process will result in the production of tailings that contain less particulate matter, or in which the fine clays settle quicker.

The present applicant has realised that the application of a metal or metal ion compound to a carbonaceous material in the presence of moisture (either residual moisture in the carbonaceous material or added moisture) induces a rapid exothermic reaction that advantageously upgrades the carbonaceous material.

SUMMARY

In a first aspect, the present invention provides a process for extracting a fuel product from a carbonaceous material comprising contacting the carbonaceous material with a metal and/or a metal ion containing compound in the presence of water under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product.

In a second aspect, the present invention provides a process for upgrading a carbonaceous material comprising contacting the carbonaceous material with a metal and/or a metal ion containing compound in the presence of water under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product.

In some embodiments, the first and second aspects of the present invention further comprise contacting the carbonaceous material with an oxidising agent.

In some embodiments, the oxidising agent is a nitrate salt. In some embodiments, the nitrate salt is sodium nitrate.

In some embodiments, the oxidising agent is hydrogen peroxide.

In some embodiments, the first and second aspects of the present invention further comprise contacting the carbonaceous material with an alkaline agent.

In some embodiments, the alkaline agent is sodium hydroxide. In some embodiments, the metal and/or metal ion containing compound is aluminium. In some other embodiments, the metal and/or metal ion containing compound is iron. The metal may be metal particles. The metal particles may be selected from the group consisting of filings, shards and powder.

The fuel product may be a hydrocarbon product. Thus, in a third aspect, the present invention provides a process for extracting a hydrocarbon product from a carbonaceous material comprising contacting the carbonaceous material with: a metal and/or a metal ion containing compound; water; optionally an alkaline agent; and optionally an oxidising agent; under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product.

Alternatively or in addition, the fuel product may be hydrogen gas. Thus, in a fourth aspect, the present invention provides a process for extracting hydrogen gas from a carbonaceous material comprising contacting the carbonaceous material with: a metal and/or a metal ion containing compound; water; optionally an alkaline agent; and optionally an oxidising agent; under conditions suitable for initiating an exothermic reaction and providing the hydrogen gas.

Alternatively or in addition, the fuel product may be an alcohol product. Thus, in a fifth aspect, the present invention provides a process for extracting an alcohol from a carbonaceous material comprising contacting the carbonaceous material with: a metal and/or a metal ion containing compound; water; optionally an alkaline agent; and optionally an oxidising agent; under conditions suitable for initiating an exothermic reaction and providing the alcohol product.

In some embodiments, the process comprises applying sodium hydroxide, sodium nitrate, and aluminium shards to the carbonaceous material and then adding hydrogen peroxide.

In some embodiments, the process further comprises applying aluminium powder to the

carbonaceous material.

In some embodiments, the process further comprises applying water to the carbonaceous material.

In some embodiments, the oxidising agent, the alkaline agent and the metal and/or a metal ion containing compound are admixed and applied to the carbonaceous material as an admixture. The oxidising agent, the alkaline agent and the metal and/or a metal ion containing compound may be applied to the carbonaceous material as a solids mixture and water may then be added.

Alternatively, or in addition, the oxidising agent, the alkaline agent and the metal and/or a metal ion containing compound may be admixed with water such that the admixture is applied to the carbonaceous material as a fluid. Alternatively, some of the admixture such as the alkaline agent or the oxidising agent may be applied dry or in an aqueous fluid and the remainder of the mixture such as the aluminium may be applied in a non water fluid such as a mineral oil.

In an embodiment, the admixture may comprise sodium hydroxide at a (w/w) concentration range of 2% to 50%, sodium nitrate at a (w/w) concentration range of 2% to 50%, and metal particles and/or metal ion containing compounds at a (w/w) concentration range of 0.1% to 20%.

In some embodiments, the admixture is a fluid comprising water at a (w/w) concentration of 25% to 50%; hydrogen peroxide at a (w/w) concentration of 25% to 50%; sodium hydroxide at a (w/w) concentration of 10% to 20%»; sodium nitrate at a (w/w) concentration of 10% to 20% and aluminium particles at a (w/w) concentration of 1 to 5%.

The carbonaceous material may be in situ or ex situ when the agent(s) and metal and/or metal ion containing compound are applied.

In some embodiments, the agent(s) and metal and/or metal ion containing compound are applied to an in situ formation to release the fuel product from carbonaceous material, and the fuel product is recovered to the surface. The agent(s) and metal and/or metal ion containing compound may be applied to an in situ formation as an at least partial substitute for steam in a SAGD operation. In some alternative embodiments, the agent(s) and metal and/or metal ion containing compound is applied to the carbonaceous material ex situ during above ground extraction of hydrocarbon to release the fuel product from the carbonaceous material.

The carbonaceous material may be coal, oil sand, oil shale or carbonate rock. In some embodiments, the carbonaceous material has previously been processed to extract hydrocarbon.

The processes described herein may result in the production of gases including, but not limited to, hydrogen gas, carbon dioxide and/or carbon monoxide. The present invention may further comprise a step of upgrading the product gas mixture. This, in a sixth aspect, the present invention provides a process for extracting a fuel product from a carbonaceous material comprising: contacting the carbonaceous material with a metal and/or a metal ion containing compound in the presence of water under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product and a product gas mixture; and contacting the product gas mixture with a metal catalyst under conditions to convert at least some of any carbon dioxide or carbon monoxide in the product gas mixture to methane to produce an upgraded product gas mixture.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS/FIGURES

Figure 1 shows a flow diagram illustrating a process of the sixth aspect of the invention.

Figure 2 shows a photomicrograph of water solution decanted from reaction of oil sands described in Example 3.3.

Figure 3 shows a photomicrograph of water solution decanted from reaction of oil sands described in Example 3.4.

Figure 4 is a plot of time v temperature for treatment of a bitumen sample described in

Example 4.1.

Figure 5 is a plot of time v temperature for treatment of a bitumen sample described in

Example 4.2.

Figure 6 is a plot of time v pressure for treatment of a bitumen sample described in Example

4.3.

Figure 7 is a plot of time v pressure for treatment of an oil sand sample described in Example

4.4. Figure 8 is a plot of time v temperature for treatment of an oil sand sample described in

Example 4.5.

Figure 9 shows a photograph of the reactor contents from the process described in Example

4.5.

DETAILED DESCRD7TION

The present invention arises from the discovery that contact of carbonaceous materials, such as oil shale or tar sands, with metal and/or metal ion containing compounds in the presence of water and an oxidant results in an exothermic reaction that can be used for the beneficiation, upgrading and/or retorting of the carbonaceous material. Further, the present applicant has also discovered that this beneficiation process can be further enhanced in the presence, of another oxidising agent, such as hydrogen peroxide, and/or an alkaline agent, such as sodium hydroxide. The present applicant has realised that it is possible to improve extraction, recovery and/or upgrading of hydrocarbon products from carbonaceous material by applying to the carbonaceous material a metal and/or metal ion containing compound and, optionally, an alkaline agent and/or an oxidising agent. This initiates an exothermic reaction, and may additionally hydrogenate the hydrocarbon products. The present applicant has also realised that the process may also facilitate extraction and recovery of hydrogen gas and alcohols from carbonaceous material. Further, additional hydrogen gas may be generated due to a reaction between water (already present or added to the carbonaceous material) and the metal and/or metal ion containing compound. The present invention advantageously provides a simple, cost-effective and practical method of extraction, recovery and/or upgrading of fuel products from carbonaceous material that has already been recovered to surface and/or provides a method for extraction, recovery and/or upgrading of fuel products from in situ carbonaceous material.

Various terms that will be used throughout the specification have meanings that will be well understood by a skilled addressee. However, for ease of reference, some of these terms will now be explained.

The term "fuel product" as used herein means a substance, or- a mixture of substances, that can be consumed to produce energy. Hydrocarbon products, hydrogen gas, alcohols, and mixtures containing them are examples of fuel products.

The term "hydrocarbon" as used herein means an organic compound consisting of hydrogen and carbon. Hydrocarbons may be alkyl and/or aryl compounds. The term hydrocarbon may refer to a single compound or a mixture of two or more compounds. The term "hydrocarbon product" as used herein means the hydrocarbons released from a carbonaceous material that are suitable for use as a fuel, either directly or following an appropriate treatment, conversion or upgrade using methods well known to those persons skilled in the art. Examples of hydrocarbons contemplated herein include (but are not limited to) bitumen, keragen, asphaltenes, paraffins, alkanes, aromatics, olefins, naphthalenses, and xylenes. The hydrocarbon products may be liquid or be varying degrees of semisolid, and also comprise solid or particulate matter, including oil-soluble solids. The hydrocarbon products of present invention may also be referred to as "oil", "coal oil", "unconventional oil", "crude oil" or "crude oil substitute" by persons skilled in the art.

The term "carbonaceous material" as used herein means a solid, semi-solid or bitumous organic compound such as coal, including lignite (also known as brown coal), sub-bituminous coal, bituminous coal, anthracite and graphite, as well as oil shale oil sands (also known as tar sands), heavy or bituminous oil deposits, coal finings, oil sand (tar sand) finings, carbonate rock (from which carbonate oil, an extremely viscous bitumen/oil, can be obtained), waste materials such as municipal waste and sewerage sludge, contaminated soils, tailings, muds, slurries, colloids etc. from previous extraction processes, kerogen containing substances, and other related substances, and combinations thereof. The carbonaceous material may be a raw, naturally occurring material, or alternatively, may have already undergone at least some processing.

The term "fluid" as used herein means any state of matter which can flow with relative ease and tends to assume the shape of its container. Fluids may be solutions, suspensions, emulsions, etc. For example, a fluid may be a solution having solid particles suspended therein.

The term "in situ" as used herein is intended to limit the carbonaceous material as being in its original location, that is, within a geological deposit of carbonaceous material found naturally in the ground. A person skilled in the art would understand that an in situ deposit of carbonaceous material frequently comprises various forms of carbonaceous materials including oil shale, oil sands (tar sands), heavy or bituminous oil deposits, carbonate rock, lignite (also known as brown coal), sub- bituminous coal, bituminous coal through to anthracite and graphite and combinations thereof.

The term "hydrogenation reaction", or alternatively "hydrogenation" or "hydrogenate" is intended to refer to a chemical reaction wherein a solid, semi-solid or bituminous carbonaceous material is reduced to a less solid or liquid form by the addition of hydrogen to the hydrocarbons contained therein. The hydrogenation reaction may be characterised by substantially simultaneous reduction and hydrogenation of the hydrocarbons within the carbonaceous material, wherein chemical bonds between two atoms in a molecule (eg double bonds between two carbon atoms in a molecule of a carbonaceous material) are generally reduced by a reaction that binds hydrogen atom(s), such that the two carbon molecules previously double bonded together remain joined by a single bond and one or both are now bonded to a hydrogen (or other) atom. Alternatively, the bonds between two carbon atoms may be completely cleaved such that the molecule is separated into two distinct molecules at that point, with the cleaved bonds reforming with hydrogen (or other) atoms. The binding of a hydrogen atom to a carbon atom at a cleaved or reduced bond is also referred to as "capping".

Carbonaceous material tends to change to a more liquid state as it is hydrogenated.

The term "extracting" is to be understood as describing a process in which at least some of the hydrocarbons contained within the carbonaceous material become less viscous, whether it be by hydrogenation or be thermally induced, such that it is becomes possible to separate the hydrocarbon product from much of the surrounding mineral content.

The term "upgrade", "upgrades", "upgrading" and the like is intended to refer to both conversion of a carbonaceous material to a desired hydrocarbon that has an improved quality, such as improved flowability, reduced viscosity, reduced density, reduced molecular weight, or reduced impurities (eg sulphur, nitrogen or metal concentration); but also includes the extraction of a desired hydrocarbon (such as oil, oil precursors) from a carbonaceous material.

Thus, in a first aspect, the present invention provides a process for extracting a fuel product from a carbonaceous material comprising contacting the carbonaceous material with a metal and/or a metal ion containing compound in the presence of water under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product.

The metal and/or metal ion containing compound may compf ise any suitable metal, for example, an alkali metal (that is, lithium, sodium, potassium, rubidium, caesium and francium), an alkaline earth metal (that is, beryllium, magnesium, calcium, strontium, barium or radium) or other metals such as aluminium, iron or zinc, or any alloy or combination thereof. In some embodiments, the metal may be a silica or silicon containing compound.

In some embodiments, the metal is one that reacts with water either at ambient temperature or at elevated temperature to produce hydrogen. These metals include alkali metals (as defined above), zinc, aluminium, magnesium, and calcium. In some specific embodiments, the metal is aluminium. In some other embodiments, the metal and/or metal ion containing compound is from the iron family and is in a form that contains a proportion of iron so that upon reaction with all or any of the other components the iron substance releases hydrogen gas. The metal ion containing compound may include hydrides, hydroxides, carbonates, oxides of an ion of one of the above metals, as well as other metal ion containing compounds or combinations thereof.

The metal and/or metal ion containing compound may be soluble such that it can be dissolved within a fluid, or alternatively, may be in the form of particles comprising the metal or metal ion containing compound. For example, the particles may be small pieces, filings, powder or shards of the metal or metal ion containing compound. Filings or shards of metal or alloy may be particularly suitable metal particles due to the relative ease with which they can be transported, and also due to their relatively high surface area. In some embodiments, there may be more than one form of metal or metal ion containing compound, for example, aluminium shards and aluminium powder.

The metal and/or metal ion containing compound may be applied to the carbonaceous material in the form of a solid or a fluid, such as a solution or suspension. .

In some embodiments, the process further comprises applying an oxidising agent to the

carbonaceous material. Many oxidising agents are known to a person skilled in the art and may be used for this purpose. Suitable oxidising agents include, but are not limited to: nitrate salts, such as sodium nitrate and potassium nitrate; hydrogen peroxide; hypochlorite; perchlorate; etc. Without wishing to be bound by theory, it is thought that the oxidising agent may react with the carbonaceous material to produce hydroxyl radicals which, in turn, activate the aluminium by removing the oxide layer as described in more detail below. It is expected that once the oxidising agent has been depleted, the aluminium continues to react with water to produce heat and hydrogen gas. Thus, we expect that the oxidising agent is required for an initiation phase of the reaction but the reaction can be sustained in a continuation phase after the oxidising agent has been depleted.

In some embodiments, the process further comprises applying an alkaline agent to the carbonaceous material. The alkaline agent may be any suitable alkaline substance known to those skilled in the art. For example, a person skilled in the art would understand that the alkaline agent can facilitate the adjustment of a fluid to be alkaline using any method known to those skilled in the art. For example, the pH of the fluid may be adjusted using a base. Suitable bases include, but are not limited to, hydroxides, perborates, percarbonates, carbonates, bicarbonates, coal ash, calcium oxide, and lime. In some embodiments, the pH of the fluid is above pH 8. The fluid may be strongly alkaline, for example, above pH 10, or even pH 1 1. The alkalinity of the fluid may enhance bond cleavage in hydrocarbons and may also serve to activate metals in their various forms such that they are more reactive. For example, the alkaline agent may activate aluminium particles by removing the oxide layer from the surface of the particles to expose fresh aluminium metal.

Without wishing to be bound by theory, it is thought that the aluminium (or other metal) used in the reaction is coated with an oxide layer and, therefore, is relatively inert until it is activated. The aluminium may in some embodiments be activated by contact with the oxidising agent (eg sodium nitrate or hydrogen peroxide) and/or the alkaline agent (eg sodium hydroxide) during the reaction with the carbonaceous material. These agents may activate the aluminium by removing or eroding the oxide layer to expose a fresh aluminium surface. Alternatively, a fresh aluminium surface may be exposed by mechanical means, such as abrasion. The aluminium may then react with water in the fluid and/or in the carbonaceous material and/or the surrounding geological formation to produce heat and hydrogen gas. It is thought that the metallic aluminium will continue to react in this way until the aluminium is depleted. Also, many underground carbonaceous material deposits contain some water and that water is saline, with salinity levels of 1500ppm to 20000ppm salt being reasonably common. It is though that the salinity of these waters also acts to inhibit or prevent the accumulation of a passivating oxide layer on the surface of the metal particles, thus enabling the metal to continue reacting with water.

Preferably, the process is carried out in the presence of a nitrate salt, such as sodium nitrate or potassium nitrate. Without wishing to be bound by theory, it is thought that sodium nitrate may act as a phase change agent, in addition to its role as an oxidising agent. Specifically, it is thought that in the presence of sodium nitrate, some carbonaceous materials resist phase change after they have been heated. Sodium nitrate is known to store large amounts of energy and is commonly used as a heat exchange material in solar power plants. It is known that bitumen cracks at about 330°C and using the processes described herein, reaction temperatures in the order of 370 to 380°C are achieved. Typically, when bitumen is heated to above cracking temperature the viscosity is reduced and then when it is cooled to below cracking temperature the. viscosity increases again. However, in the presence of sodium nitrate the bitumen may remain in a "liquid" phase for a longer period of time after cooling than when sodium nitrate is not present.

The metal and/or metal ion containing compound, the alkaline agent and/or the oxidising agent may each be applied to the carbonaceous material separately, sequentially or simultaneously. In some embodiments, the metal and/or metal ion containing compound, the alkaline agent and/or the oxidising agent are applied to the carbonaceous material simultaneously.

The metal and/or metal ion containing compound, the alkaline agent and/or the oxidising agent may be applied to the carbonaceous material in the form of a solids mixture. Alternatively, the metal and/or metal ion containing compound, the alkaline agent and/or the oxidising agent may be applied to the carbonaceous material in the form of a fluid. Unless otherwise noted, the following description will refer to the use of an alkaline, oxidising fluid admixed with the metal and/or a metal ion containing compound for ease of description.

In some embodiments, the fluid may contain metal particles at a (w/w) concentration range of 0.1% to 10%. For example, the fluid may contain aluminium particles at a (w/w) concentration of 1 to 5%.

In some other embodiments, the amount of metal particles may exceed the amount that can be included in the fluid. For example, additional metal particles (over and above those contained in the fluid) may be applied to the carbonaceous material. Alternatively, the fluid may be delivered to the carbonaceous material via a pipe that contains an activating metal. In this way, a reaction between the fluid and metal may be initiated in the pipe and the fluid \n which the reaction is taking place is then applied to the carbonaceous material. This may be useful in a SAGD process. For example, the horizontal tubing of the upper well of a SAGD well pair may be constructed of metallic aluminium.

In some embodiments, the fluid comprises water at a (w/w) concentration range of 20% to 90%, hydrogen peroxide at a (w/w) concentration range of 5% to 50%, sodium hydroxide at a (w/w) concentration range of 2% to 50%, sodium nitrate at a concentration range of 1% to 30% and metal particles at a (w/w) concentration range of 0.1% to 10%.

In some embodiments, the fluid comprises water at a (w/w) concentration of 25% to 50%; hydrogen peroxide at a (w/w) concentration of 25% to 50%; sodium hydroxide at a (w/w) concentration of 10%) to 20%; sodium nitrate at a (w/w) concentration of 10% to 20% and aluminium at a (w/w) concentration of 1 to 5%.

The rate of reaction of the alkaline, oxidising fluid with the metal and/or metal ion containing compound and with the carbonaceous material can be controlled by varying the components of the fluid, for example, by using a more diluted or stronger concentration of one or more of the reagents, or by replacing a reagent with a different stronger or weaker reagent. For example, hydrogen peroxide could be substituted for a less active or more active oxidising agent; sodium hydroxide could be substituted for a less active or more active base; and/or sodium nitrate could be substituted for another nitrate.

The applicant has found that when the carbonaceous material comes into contact with the alkaline, oxidising fluid containing metal particles and/or metal ion containing compounds the reaction produces not only a hydrocarbon product but also recoverable amounts of hydrogen gas and alcohols. The recovered hydrogen gas and alcohols can advantageously be used in subsequent reactions and/or processes, as described in more detail later.

It is thought that the metal or metal ions may advantageously assist in driving hydrogenation of the carbonaceous material. As is understood by a person skilled in the art, hydrogenation of the carbonaceous material produces material having a lower viscosity which is able to flow more easily and this assists in the extraction, upgrading or recovery process. Additionally, it is possible that chemical/electrical charge effects are generated during the reactions and these provide improved separation of hydrocarbon products from raw or entrained carbonaceous material.

Advantageously, the applicant has found that when the process of the present invention is used on oil sands, the recovered water contains low levels of fine tailing solids. Using traditional oil sand surface separation processes, recovered tailings typically comprise about 77%) (w/w) suspended solids. After approximately three years of settling, this changes to about 40% (w/w) suspended solids. The intractable mature fine tailings pollute the water and may take thousands of years to settle out if ever. For every barrel of bitumen currently produced from oil sands using traditional SAGD processes, up to four barrels of fresh water are consumed because the fine colloidal solids cannot be separated from the water. The water is held in tailings ponds and some 10% of the total surface area of mineable oil sands can be taken up with tailings ponds. In contrast, we have shown that water recovered after processing oil sands using the processes of the present invention contain about 0.8% suspended solids in the initial fine tailings. This is a marked improvement on existing processes and is commercially significant.

Without intending to be bound by theory, the applicant proposes that a combination of the metal and/or metal ion containing compound with water and the alkaline agent and/or the oxidising agent leads to electrostatic interactions which act upon colloidal particles and break them apart to allow for improved extraction of hydrocarbons from the particles. Following this, it is possible that the fine clay particles are then able to coagulate to form larger particles more effectively than if they are coated with hydrocarbon, with the result that the larger particles settle more readily and, therefore, the tailings contain less particulate matter.

Without intending to be bound by theory, the applicant also proposes that liquid clathrates may form during reaction between the metal or metal ions, the hydrogen peroxide, the water, and the hydrocarbon material. Mao and Mao (Mao W. L. and Mao H., PNAS 2004 101 (3) 708-710) have previously shown that hydrogen clathrate hydrates can be formed at elevated pressures, whilst U.S. Patent 4,321 ,127 describes the formation of liquid clathrates in coal using an aluminium alkyl compound with an alkali nitrate carbonate, sulphate, azide or the like. Clathrate ices form from water and non-stoichiometric amounts of small non-polar molecules (hence usually gaseous) under moderate pressure (typically of a few MPa) and at cold temperatures (typically close to 0°C, but increased pressure raises the melting point). Thus, the applicant proposes that at the temperatures and pressures created during reaction of the carbonaceous material with water, hydrogen peroxide, sodium hydroxide, aluminium and, possibly, sodium nitrate, liquid water clathrates may be formed. An advantage of the formation of liquid water clathrates is that they may "hold" the hydrocarbon material inside the clathrate "cage", thereby effectively solubilising the hydrocarbon in an aqueous environment. In this solubilised form, it may be easier for the hydrocarbon material to move through the aqueous environment and, ultimately, to the surface in an in situ reaction. This may result in the effective yield of hydrocarbon being greater than if the liquid clathrates were not formed. Once at the surface, the liquid clathrates containing hydrocarbon material may then decompose to form water and release the hydrocarbon material.

The processes described herein may be suitable for applications wherein the carbonaceous material is coal, oil, oil sands, bitumen, coal, oil shales, carbonate rock and kerogen containing substances. Indeed, the processes may be particularly useful in extracting a fuel product from "lower quality" carbonaceous materials such as oil sands, oil shale and carbonate rock, which may require a vigorous and exothermic reaction in order for extraction of the fuel product to be more efficient. As such, the process may be particularly useful in extracting a fuel product from oil sand or oil shale.

The applicant has additionally realised that the process can be applied to above ground or in situ carbonaceous material to permit the more efficient extraction/upgrading of hydrocarbon from carbonaceous materials. The exothermic reaction, when applied in situ to a carbonaceous material, may advantageously heat the formation with reduced requirement to apply heated substances from the surface. Further, the process may advantageously extract further hydrocarbon product from tailings that have already undergone processing to remove hydrocarbon. Furthermore, the process can be applied to carbonaceous material above ground or in situ to permit extraction of hydrogen gas and/or alcohols from carbonaceous materials.

In some embodiments, the alkaline, oxidising fluid and metal and/or metal ion containing compound can be used in place of steam in a SAGD process for extracting hydrocarbon from a carbonaceous material such as an oil sand. That is, the fluid may be applied to an in situ formation as an at least partial substitute for steam in a steam-assisted gravity drainage operation. This may result in in situ generation of suitably high temperatures due to the exothermic nature of the reactions to provide thermal mobilisation of the hydrocarbon product within the oil sand, possibly via the formation of liquid clathrates as described previously. Additionally, hydrogen release from the reaction (for example as a result of contact of the alkali metal or aluminium with water and/or oxidation of metal particles and/or metal ion containing compounds with the oxidising agent) in an alkaline reaction may result in "capping" of cleaved bonds in the thermally activated hydrocarbon, thereby providing upgrading of the viscosity of the hydrocarbon product and limiting or reducing any retrograde recombination of thermally cleaved bonds which may otherwise negatively affect overall viscosity. This may similarly result in an improvement in the American Petroleum Institute (API) gravity measure of the hydrocarbon product, which is a measure of how heavy or light a petroleum liquid is compared to water. Advantageously, the alkaline, oxidising fluid and metal and/or metal ion containing compound may be applied to the carbonaceous material at ambient temperature, rather than in a heated or super-heated form, as the exothermic nature of the reaction can act to heat the carbonaceous material. Also, the amount of heat generated in the reaction is expected to produce steam in situ. Alternatively, the process may provide a means to reduce the amount of above-ground heating required in a SAGD process. Additionally, the process may advantageously have lower water requirements than a standard SAGD operation. Additionally, a portion of the produced hydrogen gas may be recovered and recycled to promote further thermal mobilisation of the hydrocarbon component of the oil sands and possibly further capping of the hydrocarbons. A proportion of the recovered/recycled hydrogen gas may be used as a fuel to heat to a higher temperature the remaining proportion of recycled hydrogen gas. A proportion of the recovered hydrogen gas may also be used as a fuel to create heated water or steam for use in thermal recovery of hydrocarbon in the same or another SAGD type recovery operation.

The process may provide a means to reduce the long periods of time between first applying steam and recovering the hydrocarbon product during SAGD processes, resulting in shorter times to recovery of hydrocarbon products from the oil sands.

Whilst not wanting to be bound by this theory, it is thought that when the alkaline, oxidising fluid and metal and/or metal ion containing compound is used in a SAGD application, approximately the same level of sand, silica and clay impurities would precipitate into the hydrocarbon product; but that the separation of the hydrocarbon product from the sand, silica and/or clay mineral content of the carbonaceous material such as oil sand is enhanced in the present case due to "ionic separation" of the hydrocarbon product from the mineral components as described earlier. Much of the mineral impurities in oil sands may be bound to the hydrocarbon via ionic forces, and it is realised by the applicant that these ionic forces may be neutralised by the chemo-electric/ ion cation interactions occurring during the reaction, thereby resulting in improved separation of the mineral content from the hydrocarbon product.

The processes described herein may also result in release of gases such as oxygen (from the peroxide). The gaseous oxygen may further drive additional oxidation reactions with surrounding carbonaceous material to produce carbon dioxide and/or carbon monoxide. The released gases may also serve to permeate and transfer heat through the in situ carbonaceous material, potentially improving the viscosity of the hydrocarbon product.

The liberated hydrogen gas may also assist with hydrogenation of the carbonaceous material. Indeed, the alumina that is formed from the oxidation of aluminium metal may act as a hydrogenation catalyst.

Alternatively or in addition, the liberated hydrogen gas can be used in practical applications involving hydrocarbon recovery or upgrading as it can reduce the energy input requirements and or hydrogen input requirements for either recovery or upgrading of hydrocarbons. Any liberated hydrogen could be stored for later use as a supply for any hydrogen powered machinery such as a power station. Notably, the hydrogen gas is liberated during the reaction and may therefore ameliorate the expense of building a hydrogen plant. The liberated hydrogen gas may also improve the viscosity of the hydrocarbon product.

Alternatively or in addition, the liberated hydrogen gas may be reacted with any carbon dioxide produced in the presence of a suitable catalyst in a Sabatier process to produce methane and water, thus sequestering or transforming any carbon dioxide emissions. Alternatively, the liberated hydrogen may be reacted with any carbon monoxide produced to produce syngas. From the foregoing description and the following examples, it will be clear that the processes described herein typically result in the production of gases including carbon dioxide, carbon monoxide and hydrogen in addition to the hydrocarbon products produced. As such, the gas mixture that is produced is similar in composition to syngas. "Syngas" is a gas mixture that contains predominantly carbon monoxide and hydrogen. The amounts of carbon monoxide and hydrogen in the mixture may vary from mixture to mixture and syngas typically also contains other gases in relatively minor amounts.

A process according to an embodiment of the invention is shown in Figure 1. The present invention provides a process 10 for extracting a fuel product 102 from a carbonaceous material 104. The process 10 comprises contacting the carbonaceous material 104 with a metal and/or a metal ion containing compound 106 in the presence of water 108 under conditions suitable for initiating an exothermic reaction. These conditions include contacting the carbonaceous material 104 with an oxidising agent 1 10 and an alkaline agent 1 12. This provides a hydrocarbon product 1 14 and a product gas mixture comprising hydrogen gas 1 16 and carbon dioxide 1 18 and/or carbon monoxide 120. The product gas mixture is then contacted with a metal catalyst 122 under conditions to convert at least some of any carbon dioxide 1 18 or carbon monoxide 120 in the product gas mixture to methane 124 to produce an upgraded product gas mixture.

The metal catalyst 122 may be selected from the group consisting of ruthenium; ruthenium compounds; nickel; nickel compounds; copper; copper compounds; platinum; platinum compounds; rhodium; rhodium compounds; silver; silver compounds; cobalt; cobalt compounds; tungsten; and tungsten compounds. Optionally, the metal catalyst may be supported on a support material.

Suitable support materials include alumina, silica, titanium dioxide, foams, etc. In some embodiments, the catalyst is nickel oxide. In some embodiments, the catalyst if ruthenium. In some embodiments, the metal catalyst comprises 0.1% to 1.0% ruthenium on alumina. In some embodiments, the metal catalyst comprises 0.2 % ruthenium on alumina. In some embodiments, the metal catalyst comprises 0.3 % ruthenium on alumina. In some embodiments, the metal catalyst comprises 0.4 % ruthenium on alumina. In some embodiments, the metal catalyst comprises 0.5 % ruthenium on alumina. In some embodiments, the metal catalyst comprises 0.6 % ruthenium on alumina. In some embodiments, the metal catalyst comprises 0.7 % ruthenium on alumina. In some embodiments, the metal catalyst comprises 0.8 % ruthenium on alumina. In some embodiments, the metal catalyst comprises 0.9 % ruthenium on alumina.

The product gas mixture upgrading process may be carried out at a temperature of about 150°C to about 600°C.

The product gas mixture upgrading process may be carried out in a reactor 126. In some embodiments, the reactor comprises a tube containing the metal catalyst 122. The product gas mixture to be upgraded may be introduced into an inlet end of the reactor tube such that it contacts the catalyst therein. Once in contact with the catalyst in the reactor tube, the gas mixture undergoes a rapid exothermic reaction and consumes at least some of the carbon dioxide in the gas mixture. The upgraded product gas mixture is then discharged from an outlet end of the reactor tube. Reactor tubes of this type are known in the art and are commonly referred to as "Sabatier reactors".

The reaction within the reactor tube is highly exothermic and, therefore, a heat exchanger may be located in or adjacent the reactor tube so as to capture the generated heat 128. The heat generated may be utilised in the production of steam for use in a UCG process.

The products of the process are methane 124, which may optionally be converted to one or more usable hydrocarbon compounds, and water which may be used for any suitable purpose, or may be recycled for use in a UCG process. Optionally, the methane 124 and water 130 in the upgraded product gas mixture may be separated. Processes and apparatus for separating methane and water are known in the art, and include condensation. Thus, the upgraded product gas mixture gas that exits the reactor tube may be fed into a condenser 132 comprising a pipe with outlets on the bottom to collect water. Natural convection on the surface of the pipe may be enough to carry out the necessary heat exchange. The amount of heat exchange surface necessary is determined by the amount of fuel to be produced and the time given to produce_^the fuel.

The Sabatier reaction takes place according to the formula:

C0₂+4H₂ <→ CH₄+2H₂0 Δ -27 Kcal/mole

The reaction typically takes place at elevated temperatures in the presence of the catalyst. Typically, the reaction takes place at a maximum temperature of about 300° C, although the catalyst selection can reduce the process conditions closer to ambient. United States patent 4,847,231 describes the use of catalysts, i.e. ruthenium, to produce gas phase methane from hydrogen and carbon dioxide, for example.

Hydrogen gas is required to reduce the carbon dioxide and/or carbon monoxide in the Sabatier reaction. Hydrogen is typically produced in relatively large amounts in the processes described herein and, therefore, the hydrogen concentration in the product gas mixture may be sufficient for the subsequent methanation reaction.

The product gas mixture produced using the processes described herein may in itself be a fuel which is potentially more efficient than direct combustion of the original fuel. However, the product gas mixture will typically have a low calorific value as a fuel (eg, 50% of the calorific value of natural gas). Furthermore, the product gas mixture may contain varying amounts of carbon dioxide which is typically vented to the atmosphere. The gases produced in the reaction may be employed to induce fractures in the geological deposit. Fracturing of the geological deposit is a technique used as a means of enhancing recovery by exposing a larger surface area. Thus, it may be possible to exceed the fracture pressure of a geological deposit using gases generated in the process of the present invention.

Advantageously, the heat generated by in situ exothermic reactions may be at least partially recoverable at the surface by any means familiar to those skilled in the art, and may be applied to suitable uses including as a heat source for the generation of steam.

In another embodiment, the process of the present invention may be used to enhance a standard "hot water" above ground extraction of hydrocarbon from a carbonaceous material such as oil sand, by substituting the alkaline water fluid used in the first step of the process with the alkaline, oxidising fluid and metal and/or metal ion containing compound. That is, the alkaline, oxidising fluid and metal and/or metal ion containing compound may be applied to the carbonaceous material during above ground extraction of hydrocarbon to more efficiently release hydrocarbon product from carbonaceous material. Subsequent application of water will further drive exothermic reactions reducing the metal component to hydrogen and alumina or an oxide of whatever metal is used and may result in a reduction of the overall quantity of water used in the conventional method. This may result in enhanced separation of the hydrocarbon product and the mineral component of the carbonaceous material, leading to cleaner tailings that may reduce environmental impact.

Further, the processes of the present invention may be used to extract further hydrocarbon product from tailings derived from the hot water (or other above ground hydrocarbon extraction methods) in order to more efficiently utilise the carbonaceous material and optimise the amount of hydrocarbon that is extracted. Accordingly, the carbonaceous material used in the present invention may previously been processed to extract hydrocarbon.

Advantageously, the processes of the present invention can be incorporated into existing extraction methods and may provide a means to elevate temperatures of the extraction methods with little or no energy required, as a consequence of the exothermic nature of the reactions.

The invention is hereinafter described by reference to the following non-limiting example. EXAMPLES

Example 1: Reaction of sub-bitumous coal with alkali metal or calcium oxide

A borehole is completed into a sub-surface coal, shale or tar sand deposit and is equipped with an oilfield jet pump. The jet pump unit fluid reservoir is charged with diesel fuel or a suitable oil carrier fluid which is entrained with sodium. The diesel fuel or oil could alternatively be entrained with any alkali metal, calcium oxide or combinations thereof.

The entrained oil is sprayed/delivered under pressure directly to the coal, shale or tar sand deposit in situ. On contact with the coal, the entrained alkali metal or calcium oxide reacts with the water contained within the geological structure of the deposit and with the water commonly found within such deposits. The reaction is rapid and exothermic and generates a significant amount of heat. The amount of heat generated is controlled by altering the proportions of the entrained alkali metal or calcium oxide. The heat that is generated by reaction of the alkali metal or calcium oxide with water in situ is sufficient to cause a reduction of the coal, shale or tar sand deposit to liquid and/or gas products by a process commonly referred to as retorting. The liquid and/or gas products produced include oil, hydrogen gas, methane gas, and steam.

The products, along with the carrier fluid are continuously transported back to surface via the annulus of the wellbore. At surface, the products are separated by conventional means and the carrier fluid is recycled back to the jet pump fluid reservoir where it is recharged with further alkali metal or calcium oxide for re-use in a continuous cycle.

The process may be run in a continuous mode or may be run intermittently to provide greater residence time for the reactions of the retorting process.

The oil, hydrogen gas and methane gas produced may be recovered for sale or use. For example, hydrogen gas is also a valuable product and can be recovered for sale or use using known methods. If calcium oxide is present in the carrier fluid it may be used to entrap carbon dioxide in the well. Many oil or gas wells contain a significant amount of carbon dioxide in the well products and such entrapment of carbon dioxide into carbonates within the well bore provides a significant commercial advantage for the well producer as carbon dioxide that is produced from oil or gas wells typically has to be stripped out of the well products prior to sale or shipping and this is a significant cost to the producer of the well. The carbonates produced from the contact of calcium oxide, water and carbon dioxide can be recovered at surface from the well typically by a solids filter or any other means.

Optionally, the hot products and carrier fluid that are returned to the surface can be passed through a heat exchanger or directly to power above ground machines, such as an electrical generator.

The process could be used to recover an oil well or a gas well that has ceased to flow because it has watered up. In this example, the heat generated by reaction of the alkali metal or calcium oxide with water acts to lift the head of water in the well bore and may also vaporise the water, thereby reducing the weight of head pressure in the well and allowing the well to flow. The hydrogen gas generated also acts to lighten the static head of pressure on the well so allowing it to flow. The process described in this example may also be used to assist or enable the production of coal seam methane (CSM). Typically, CSM is brought to surface from its subsurface location by wellbores. Typically, the wells are fractured to increase the quantity of micro fractures within the coal formation (often referred to as cleating) around the wellbore and to connect these micro fractures around the wellbore with larger fractures already existing within the coal formation so providing greater connectivity between the wellbore and underground fracture systems in the coal.

The desorption of volatile components of coal as methane gas can be enhanced and accelerated by the addition of heat. Using the process described herein, additional heat can be generated in situ in the coal seam to provide greater mobilisation of the coal volatiles into methane gas for collection from a wellbore. The heat generated by the exothermic reaction of water and the alkali metal or calcium oxide is able to travel or disperse along the fracture systems within the coal formation as is the carrier fluid itself, to provide a general elevation of temperature within the coal seam not necessarily restricted to the wellbores into which the carrier solution was pumped.

Example 2: Reaction of oil sand tailing or sub-bitumous coal with hydrogen peroxide, sodium hydroxide, sodium nitrate, and aluminium particle containing fluid

The present applicant has previously demonstrated that carbonaceous material such as coal can be liquefied to produce liquid hydrocarbon using an ambient temperature solution containing hydrogen peroxide (for example, 30% or 50% hydrogen peroxide), in a reaction that is advantageously exothermic, as described in International Patent Application PCT/AU2009/000958, filed by the present applicant . However, the present applicant has discovered that the liquefaction reaction is sub-optimal when the carbonaceous material is of low quality, for example, tailing of oil sands following extraction of bitumen using standard methods. Accordingly, the present applicant has realised that the reaction required further optimisation for optimal recovery of hydrocarbons from low quality carbonaceous material.

Materials and Methods

Tests were conducted on 25 gm of two different types of carbonaceous material: (1) oil sands obtained from Canadian oil sand fields in the Athabasca region; and (2) a sub-bitumous coal from South Australia.

The carbonaceous material samples were reacted with 15 ml of a fluid consisting of 35% water; 35% hydrogen peroxide; 14% sodium hydroxide; 14% sodium nitrate; and 2% metallic aluminium.

Control of the rate of reaction was investigated by reacting trie samples with the above fluid after it had been diluted in water. Specifically, a reaction that was commenced as described above was diluted by the addition of 5 ml of water. Additionally, the reaction was tested with by varying the quantity of the fluid to the amount of carbonaceous material. Specifically, 7.5 ml of the above (undiluted) fluid was added to 25 gm of the carbonaceous material.

Results and Discussion

The fluid demonstrated remarkably higher reaction rates compared to earlier experiments in which the ability of 30% or 50% hydrogen peroxide (only) to react with carbonaceous material was investigated, as described in International Patent Application PCT/AU2009/000958, filed by the present applicant. Contact of the fluid with both the coal sample and the oil sand tailings sample produced a rapid and vigorous exothermic reaction, during which evolution of gases and liquid hydrocarbons occurred. The reaction of the fluid with the coal sample resulted in an almost immediate commencement of production of heat, frothing, and evolution of gases and liquid hydrocarbon, which compared to a delay of several minutes for a hydrogen peroxide only solution. A similar reaction commenced approximately 30 seconds after the fluid was added to the oil sand, whereas the reaction with hydrogen peroxide solution only resulted in little discemable activity after 15 minutes. Accordingly, the fluid is rapidly able to initiate a vigorous exothermic reaction when added to carbonaceous materials.

The rate of reaction was controllable by diluting the fluid with additional proportions of water. Specifically, the rate of reaction was slightly slower when the fluid was diluted. However, when half the volume of the fluid was reacted with the samples, no discemable change in the vigour of the reaction was noted, although time until completion of the reaction was observed, indicating that the reaction rate was lower.

The viscosity of the hydrocarbon product extracted from the oil sand at ambient conditions was improved over that of the liquid component derived from standard oil sands recovery processes and from SAGD recovery. Specifically, hydrocarbons obtained from these processes have a treacle-like consistency at 30°C, whereas the hydrocarbons derived from the oil sand using the above method flowed freely at approximately 20°C. This possible indicates that hydrogenation of the hydrocarbon product has occurred, and/or less retrograde reactions have occurred compared to existing recovery methods.

These results show that the method of the present invention may provide a more efficient means of extracting hydrocarbon product from oil sands than the currently used standard methods.

A large proportion of sand/silica from the oil sands was precipitated out during the reaction. This indicates that the method of the present invention is able to separate the hydrocarbon content from the entrained sand/silica/clay of the oil sand than the current standard methods. Accordingly, the present method may result in enhanced recovery and separation of hydrocarbon over the existing process.

Example 3: Reaction of oil sand or lignite with sodium hydroxide, sodium nitrate, and metallic aluminium shards, and optionally hydrogen peroxide and/or aluminium powder

Materials and Methods

Extractions were conducted on three different types of carbonaceous material: (1) Canadian Oil Sands; (2) Angelsea Coal; and (3) Lock Coal.

Raw Anglesea coal sample was obtained from the Anglesea Coal Deposit, located near Anglesea, Victoria, Australia. The Anglesea coal is a low-rank lignite coal. The raw coal sample was obtained from the deposit from a horizontal working coal face at approximately the middle of the seam. Five individual coal samples of approximately 3-4kg each were collected and stored in sealed plastic bags within 5L sealed plastic buckets. Due to the presence of large lumps, the Anglesea coal was coned, quartered and a sub-sample crushed with a mortar and pestle.such that the particle size was less than 5mm.

Raw Lock coal was obtained from coal deposits known as the Lock Coal Deposit, located near the town of Lock, in the Polda Basin of central western Eyre Peninsula, South Australia, Australia. The Lock coal is a low-grade sub-bituminous coal of Late Jurassic age. Raw Lock coal samples were obtained from Centrex Resources Ltd, Adelaide, Australia. The raw Lock coal had a particle size of less than 5 mm, and was analysed as obtained.

The raw oil sands were obtained from a major Canadian oil sands production company and were sourced from the Fort McMurray region.

The carbonaceous material was mixed with a dry mixture comprising 49% (w/w) granulated sodium hydroxide, 49% sodium nitrate, and 2% metallic aluminium shards (1-2 mm shards) (referred to as "W10" or "W10 catalyst" herein). In some runs, hydrogen peroxide, water, and/or aluminium powder were included in the reactions in the quantities described in Table 1. Hydrogen peroxide was added in a drop-wise manner (for example, at approximately 1 ml per second), unless otherwise stated.

Table 1 Extraction conditions

Run No. Vessel³ Carbonaceous Material W10^b Al H₂0₂ H₂0₂ Water

(gm) (gm) Powder (%) (ml) (ml)

(gm) Oil sands Coal

Run 1 NF 22.5^d 5.8 50% 30

Run 2 NF 28^d 6 50% 30

Run 3 NF 34.7^d 50% 30

Run 4 NF 23.3^d 7.4 30

Run 5 NF 22.00^e 5.85 50% 30

Test 17° OB 15.00 5.00 3.00 25% 60 40

Run J OB 21.60^e 6.10 50% 30

Run GE 21.30⁶ 5.80 50% 30

Run L GE 10.94^e 3.00 1.47 50% 15 15

Run M GE 10.94^e 3.30 3.03 50% 15 15

Run N GE 1 1.10^e 3.20 2.98 50% 15 30

Run 0 OB 15.40 5.00 3.00 50% 30 30

³ Vessel was an open bowl (OB) or gas equipment (GE) or narrow neck flask (NF) ^b "W10" comprises (w/w) 49% NaOH, 49% NaN0_3, 2% metallic aluminium shards ^c In Test 17, W10 and hydrogen peroxide was added to the oil sands, which resulted in a vigorous reaction, and then water was added ^d Lock deposit sub-bituminous coal ^e Anglesea Lignite

As indicated in Table 1, the reactions were either conducted in an open Pyrex bowl of approximately 2 L capacity, a narrow necked flask or in gas equipment. The gas equipment consisted of a conical flask with a stoppered top including an injection port for the delivery of hydrogen peroxide and a second port for the addition of water. All gases were piped from the flask to a liquids trap, and from there to a gas volume meter, from which total gases were collected in Leider bags for sample collection for gas chromatography (GC) analysis. Reactions involving coal samples were considered complete when they subsided. Reactions involving oil sands were considered complete when no further reaction signs were observed after the addition of water (following the initial reactions). Observations were made during the reaction, and in some runs, resulting gas, liquids, and/or solid residue samples were taken for testing at the completion of the reaction.

Analysis of Solid Residues

The liquids were centrifuged at 1,000 rpm for 5 minutes and the separation was visually very distinct between sands and liquids. The centrifuged sands were weighed and heated to 110°C and re- weighed to reveal a dry weight that was only 60% of the wet weight.

Analysis of Liquid Residues

The liquid product was evolved in an aerated foam of considerable volume. The foam was collected and vacuum extracted through a filter to collapse the foam bubbles and collect the liquid product. An aliquot of the recovered liquid was extracted by syringe for analysis using the GC machine.

Results

The dry reagents could be applied to the coal sample, in any order without any noticeable reaction occurring.

The dry reagents, when added to the oil sand sample elicited a reaction prior to the addition of liquid ingredients (eg hydrogen peroxide), evidenced by slight fuming of gases and by the elevation of temperature above ambient level. The maximum elevation of temperature observed when the dry ingredients were added to the oil sands was 140°C, in the absence of any other agitation. Hydrogen peroxide solution was then added drop-wise to the oil sands and reactions proceeded vigorously with considerable internal agitation of the reactants and considerable discharge of gases and steam.

Water was added to the samples (where stated) after the vigour of the initial reactions had subsided. The reactions then resumed at a diminished rate.

In Run 1, 22.5 gm of sub-bituminous coal was reacted with 5.8 gm of W10 followed by a slow addition of 30 ml of a solution of 50% hydrogen peroxide (in water). This produced a mild reaction resulting in a brownish froth which collapsed into a liquid containing many bubbles. No gas chromatography (GC) was taken of the resulting liquid.

In Run 2, 28 gm of sub-bituminous coal was reacted with 6 gm of W10 followed by a more rapid addition of 30 ml of a solution of 50% hydrogen peroxide (in water). This produced a faster and more vigorous reaction resulting in a brownish froth which collapsed into a liquid containing many bubbles. Gas chromatography indicated a collection of volatile hydrocarbons in the light to medium boiling point range. The profile of the medium boiling range hydrocarbon was typical of diesel, indicating that a mixture of W10 and hydrogen peroxide is able to upgrade coal.

In Run 3, 34.7 gm of sub-bituminous coal was reacted with 30 ml 50% hydrogen peroxide solution in water (rapidly added) in the absence of W10. In comparison with Run 2, this produced a slower reaction resulting in a darker brownish froth which collapsed into a liquid containing less bubbles. Gas chromatography indicated an increase in the lighter hydrocarbon fraction compared to Run 2.

In Run 4, 23.3 gm of sub-bituminous coal was reacted with 7.4 gm of W10 followed by a rapid addition of 30 ml of water (in the absence of 50% hydrogen peroxide solution). This resulted in an increase of temperature in the coal (to approximately 50°C) but no further reaction. No GC analysis was undertaken of this sample.

In Run 5, 22 gm of Anglesea Lignite was reacted with 5.85 gm of W10 followed by the rapid addition of 30 ml of 50% hydrogen peroxide in water. This produced a fast and vigorous reaction resulting in a brownish froth which collapsed into a liquid containing many bubbles. GC analysis of this liquid indicated the presence of hydrocarbons in the medium boiling range.

Example 4: Reaction of oil sand or bitumen with sodium hydroxide, sodium nitrate, and metallic aluminium shards, and optionally hydrogen peroxide and/or aluminium powder

Example 4.1

The objective of this example was to determine if aluminum powder reacts with SAGD (steam assisted gravity drainage) bitumen from an UTF (Underground Test Facility) at elevated temperatures.

A mixture of aluminum (1 g) and bitumen (50 g) was slowly heated. At temperatures above 120°C small bubbles appeared on the top of the bitumen. This indicated that aluminum reacts with bitumen at elevated temperatures.

Example 4.2

The objective of this example was to determine if sodium nitrate (NaNC^) powder reacts with UTF bitumen at elevated temperatures.

A mixture NaN0₃ and bitumen was slowly heated. Up to a temperature of 200°C no activity was observed. This indicated that NaNOj does not react with bitumen.

Example 4.3 The objective of this example was to duplicate the bench-scale experiment referred to in Example 3.2.

A mixture of 50 g oil sand, 10 g W-10, and 6 g aluminum powder was placed in a beaker. About 60 mL H₂O₂ was added to the oil sand mixture. After the initial reaction was complete, about 60 mL water was added slowly. The total mixture was placed in a centrifuge vial and centrifuged at 2400 rpm for 20 min.

Addition of H₂0₂ resulted in a vigorous reaction. Addition of water resulted in further reaction. A small layer of black oil was observed at the top of the water. The liquid portion was decanted and centrifuged again at 2400 rpm for 20 min. A small amount of solids settled at the bottom; otherwise the liquid looked free of solids. The liquid was checked under microscope at lOx magnification. Only few small particles were observed (Figure 1). Thus, the decanted water contained very little solids.

Example 4.4

The objective of this example was to repeat test 3.3 with larger amounts of the reactants.

Oil sand (150 g) was mixed with 32 g W-10 catalyst and 18 g aluminum power. Slowly, 200 mL of H₂O₂ was poured into the beaker. After the initial reaction was complete, 200 mL of water was added. Again, a vigorous reaction was observed. The sand colour was much lighter than the original sand indicating bitumen was extracted from the oil sands. The liquid from the beaker was centrifuged at 2400 rpm for about 20 min. Small amounts of .solids settled at the bottom. The water phase was clean (Figure 2).

Example 4.5

The objective of this example was to determine if aluminum powder and water react with oil sand.

A mixture of 30 g oil sand and 10 g aluminum powder was placed in a beaker; 20 mL water was added to the mixture. No reaction was observed, indicating that aluminum powder and water does not react.

Example 4.6

The objective of this example was to determine if sodium nitrate with aluminum is sufficient to initiate the reaction. A mixture of 30 g oil sand, 6 g aluminum, and 6 g sodium nitrate was placed in a beaker; 20 mL water was added. No reaction was observed, thus indicating that hydrogen peroxide or NaOH is needed for the reaction.

Example 4.7

The objective of this example was to determine the activity of caustic water (decanted from Example 3.4).

A mixture of 30 g oil sand, 6 g aluminum, and 6 g sodium nitrate was placed in a large beaker; 20 mL caustic water was added to the mixture. A vigorous exothermic reaction started. The temperature of the mixture increased to 1 17°C. After about 5 min, addition of 20 mL water resulted in an exothermic reaction and the temperature increased to about 1 14°C. As the mixture cooled, 30 mL water was added in three 10-mL steps. At each step, exothermic reaction was observed. Further additions of water (10 mL and 20 mL in two steps) resulted in no further reaction. The successive additions of water to the solution lowered the pH and diluted the caustic water, slowing the reaction. This indicates that the spent alkaline water is able to be recycled.

Example 4.8

The objective of this example was to repeat Example 3.7 without caustic water and using W-10 catalyst and ¾(¾.

A mixture of 32 g W10 catalyst, 18 g aluminum powder, and 300 g oil sand was placed in a large beaker; 200 mL H₂O₂ was added slowly. An exothermic reaction was observed. In addition to H₂O₂, 200 mL water was added slowly (as described in Example 3.7). A similar observation was made as for Example 3.7. A hydrogen detector confirmed hydrogen production.

Example 5: Reaction of oil sand or bitumen with sodium hydroxide, sodium nitrate, and metallic aluminium shards, and optionally hydrogen peroxide and/or aluminium powder

Materials and methods

A 300cm³ autoclave reactor was used for the program. The reactor was charged with weighed amounts of bitumen, oil sand, W-10 catalyst, or other reactants (as required for each run). The reactor was sealed and pressure-tested for leaks. The H₂O₂ or NaOH/NaNC>3 solution was transferred into the reactor. The temperature of the reactor contents, reactor skin temperature, and reactor pressure were monitored for 4 h. The reactor was allowed to cool to room temperature. Vapors (gas phase) from the reactor were slowly transferred to a gas sample bag through a condenser. The reactor contents were collected and weighed. Gas volume was determined and analyzed for refinery gas. The volumetric yields of gases were calculated on a nitrogen-free basis. This gas analysis was used to calculate the mass of the gas and the overall material balance.

Example 5.1: Determining if H₂0₂ decomposes in the presence of NaOH and provides initial heat of reaction for bitumen upgrading

The reactor was charged with 55.34 g bitumen and 9.86 g NaOH. The temperature of the reactants (liquid inside the reactor) was maintained at about 60°C so the bitumen would be fluid. As soon as H2O2 was introduced into the reactor, the temperature of the contents increased to about 190°C and the pressure increased to about 425 psig. Reactor pressure and temperature then started decreasing due to heat absorption by the reactor (Figure 3).

Table 1 shows the mass balance.

Over 99% of the gas was oxygen. The molecular weight of the gas was calculated to be 32.03 using nitrogen-free gas analysis. A balance of 91.5wt% was achieved.

This example showed that in the presence of NaOH and bitumen, H₂0₂ spontaneously decomposes exothermically into water and oxygen gas. Example 5.2: Determining the reactivity of a simulated W-10 catalyst

The reactor was charged with 50.04 g bitumen, 9.86 g NaOH, 10.02 g KN0₃, and 1.99 g aluminum powder (bitumen and simulated RRL catalyst W-10). The temperature of the reactants (liquid inside the reactor) was maintained at about 60°C so the bitumen would be fluid. As soon as H2O2 was introduced the temperature of the reactor contents increased to about 295°C (not enough for bitumen conversion) and the pressure increased to about 350 psig. The reactor pressure and temperature then started decreasing due to heat absorption by the reactor (Figure 4).

The gas sample on a nitrogen-free basis contained about 29wt% hydrogen, about 25wt% oxygen, about 7wt% carbon monoxide, and about 26wt% carbon dioxide. The molecular weight was calculated to be 26.32 on a nitrogen-free basis. It seems that, in the initial stages of the reaction, produced oxygen reacted with bitumen to produce CO and CO2. A mass balance of 94.3wt% was achieved.

In the first experiment conducted in Example 4.1 only oxygen was produced; however, in this experiment produced oxygen reacted with bitumen to produce combustion gases.

Example 5.3: Determining the reactivity of W-10 catalyst with H2O2

The reactor was charged with 22 g W-10 catalyst and 2.01 g aluminum powder. The temperature was maintained at about 60°C, as in Example 4.2. Hydrogen peroxide was pumped at rate of 2 mL/min using a Quizix pump. As soon as H2O2 was introduced into the reactor, the pressure started increasing slowly to about 150 psig. It kept on increasing even after the flow of H2O2 was terminated, indicating a secondary reaction (Figure 5).

The gas sample on a nitrogen-free basis contained about 29wt% hydrogen and about 71wt% oxygen, indicating two reactions: one from the decomposition of H2O2 producing oxygen and a second from aluminum reacting with water producing hydrogen. The molecular weight of the gas was calculated to be 23.6 on a nitrogen-free basis. A mass balance of 92.0wt% was achieved.

This examples shows that hydrogen peroxide decomposes in the presence of W-10 catalyst to produce hydrogen and water and aluminum reacts with produced water to produce hydrogen gas.

Example 5.4: Processing of whole oil sand using W-10 catalyst, aluminum powder, H₂0₂, and water

The reactor was charged with 100 g oil sand, 19.9 g W-10 catalyst, and 1 1.95 g aluminum powder. About 32 g H₂0₂ was delivered to the reactor using a Quizix pump (10 g/min for about 3 min). As soon as the H₂0₂ was introduced, the temperature of the reactor contents and the pressure increased. After waiting for about 7 min, 50 g water was delivered to the reactor. The temperature and pressure increased again (Figure 6).

The gas sample on a nitrogen-free basis contained about 96wt% hydrogen, about 2wt% oxygen, and small amounts of hydrocarbon gases. The molecular weight of the gas was calculated to be 2.87 on a nitrogen-free basis. A mass balance of 84.43wt% was achieved. A loss of 15.5% may be due to errors while transferring gas phase from the reactor to the gas bag. There was no liquid phase in the reactor. The material collected from the reactor was wet sand. A small sample (only about 3 mg) was collected from the top of the stirrer. The simulated distillation of this material is shown in Figure Jl

Water (10.54 g) was collected from the condenser.

Example 5.5: Processing of whole oil sand using W-10 catalyst, aluminum powder, H₂0₂, and water

This example is a repeat of Example 4.4 using larger amounts of water. The reactor was charged with 50.8 g oil sand, 10 g W-10 catalyst, and 6.01 g aluminum powder. About 34.7 g H₂0₂ was delivered to the reactor using a Quizix pump (10 g min for about 3 min). As soon as the H₂0₂ was introduced into the reactor the temperature of the contents and the pressure increased. After waiting for about 7 min, 188 g water was delivered to the reactor. The temperature and pressure increased again. There were two distinct peaks, the first due to hydrogen peroxide decomposition and the second probably due to aluminum reacting with water to produce hydrogen. The skin temperature of the reactor also increased in similar steps, absorbing heat generated from the reactions (Figure 7).

The gas sample on a nitrogen-free basis contained about 78wt% hydrogen, about 2wt% oxygen, and small amounts of hydrocarbon gases. The molecular weight of the gas was calculated to be 2.87 on a nitrogen-free basis. A mass balance of 85wt% was achieved.

All reactor contents were transferred to a graduated cylinder. There were three layers: solids at the bottom, dark liquid, and a small black ring at the top (Figure 8). About 47 g liquid sample (dark liquid layer) was subjected to centrifugation for 20 min at 2400 rpm. 0.35 g of the solids settled at the bottom of the centrifuge vial. The remaining liquid seemed to be free of solids. A small sample (only 3 mg) was collected from the top ring.

The results indicate that the application of W 10, a dry mixture comprising an alkaline substance (sodium hydroxide), sodium nitrate and aluminium shards in the presence of hydrogen peroxide and water is able to extract or convert carbonaceous material of different ranks into a hydrocarbon which predominantly comprises hydrocarbons in the middle boiling point range (ie the "diesel" fraction) without the need to apply external sources of heat or pressure. Further, the indications are that no or negligible amounts of carbon dioxide were released. This process may provide a means for upgrading (or adding value) to carbonaceous material such as coal in commercial applications that utilises substantially lower energy inputs than conventional processes in addition to much simplified capital equipment and processes than conventional processes.

Similarly, oil sands may likewise be extracted and/or separated using the above process utilising substantially lower energy inputs and superior results compared to conventional processes.

Throughout this specification the word "comprise", or variations such as "comprises" or

"comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

All publications mentioned in this specification are herein incorporated by reference. Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is solely for the purpose of providing a context for the present invention. It is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed in Australia or elsewhere before the priority date of each claim of this application.

It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive.

Claims

1. A process for extracting a fuel product from a carbonaceous material comprising contacting the carbonaceous material with a metal and/or a metal ion containing compound in the presence of water under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product.

2. A process for upgrading a carbonaceous material comprising contacting the carbonaceous material with a metal and/or a metal ion containing compound in the presence of water under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product.

3. The process according to either claim 1 or claim 2 wherein the metal and/or metal ion containing compound is formed from a metal selected from the group consisting of an alkali metal, an alkaline earth metal, aluminium, iron and zinc.

4. The process according to claim 3 wherein the metal is aluminium.

5. The process according to any one of claims 1 to 4 further comprising applying an oxidising agent to the carbonaceous material.

6. The process according to claim 5 wherein the oxidising agent is sodium nitrate.

7. The process according to claim 5 wherein the oxidising agent is hydrogen peroxide.

8. The process according to any one of claims 1 to 7 further comprising applying an alkaline agent to the carbonaceous material.

9. A process according to claim 8 wherein the alkaline agent is sodium hydroxide.

10. A process for extracting a hydrocarbon product from a carbonaceous material comprising contacting the carbonaceous material with:

- a metal and/or a metal ion containing compound;

- water;

- optionally an alkaline agent; and

- optionally an oxidising agent; under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product.

1 1. A process for extracting hydrogen gas from a carbonaceous material comprising contacting the carbonaceous material with:

- a metal and/or a metal ion containing compound;

- water;

- optionally an alkaline agent; and

- optionally an oxidising agent; under conditions suitable for initiating an exothermic reaction and providing the hydrogen gas.

12. A process for extracting an alcohol from a carbonaceous material comprising contacting the carbonaceous material with:

- a metal and/or a metal ion containing compound;

- water;

- optionally an alkaline agent; and

- optionally an oxidising agent; under conditions suitable for initiating an exothermic reaction and providing the alcohol product.

13. The process according to any one of claims 10 to 12 further comprising applying an oxidising agent to the carbonaceous material.

14. The process according to claim 13 wherein the oxidising agent is sodium nitrate.

15. The process according to claim 13 wherein the oxidising agent is hydrogen peroxide.

16. The process according to any one of claims 10 to 15 wherein the metal and/or metal ion containing compound is formed from a metal selected from the group consisting of an alkali metal, an alkaline earth metal, aluminium, iron and zinc.

17. The process according to claim 16 wherein the metal is aluminium.

18. The process according to any one of claims 10 to 17 further comprising applying an alkaline agent to the carbonaceous material.

19. The process according to claim 18 wherein the alkaline agent is sodium hydroxide.

20. The process according to any one of claims 10 to 19 further comprising applying aluminium powder to the carbonaceous material.

21. The process according to any one of claims 10 to 20 further comprising applying water to the carbonaceous material.

22. The process according to any one of claims 1 to 21 wherein the carbonaceous material is in situ when the agent(s) and metal and/or metal ion containing compound are applied.

23. The process according to any one of claims 1 to 21 wherein the carbonaceous material is ex situ when the agent(s) and metal and/or metal ion containing compound are applied.

24. The process according to any one of claims 1 to 23 wherein the carbonaceous material is selected from the group consisting of: coal, oil sand, oil shale, and carbonate rock.

25. A process for extracting a fuel product from a carbonaceous material comprising:

- contacting the carbonaceous material with a metal and/or a metal ion containing compound in the presence of water under conditions suitable for initiating an exothermic reaction and providing the hydrocarbon product and a product gas mixture; and

- contacting the product gas mixture with a metal catalyst under conditions to convert at least some of any carbon dioxide or carbon monoxide in the product gas mixture to methane to produce an upgraded product gas mixture.

26. A process substantially as hereinbefore described.