RU2604726C2 - Production of organic materials using oxidative hydrothermal dissolution method - Google Patents

Abstract

FIELD: ecology; technological processes.

SUBSTANCE: invention relates to environmentally friendly methods of organic substances production, such as oil substances and aromatic acids, phenols and aliphatic polycarbonate acids using hydro-thermic oxidative dissolution process (PER). Method of solid organic substance solubilizing contained in composite material containing organic solid substance and inorganic matrix includes: bringing said composite material in contact with oxidizing agent in superheated water to form aqueous mixture, containing at least one solubilized organic dissolved substance, wherein composite material is selected from group consisting of tar sand, carbonaceous oil shale and any mixture thereof.

EFFECT: disclosed is environmentally safe method of organic substances production.

16 cl, 31 dwg, 5 tbl, 7 ex

Description

[0001] This document relates to methods for producing organic materials and, in particular, to methods for producing petroleum materials and organic compounds, such as aromatic acids, phenols and aliphatic polycarboxylic acids, using the method of oxidative hydrothermal dissolution (OGR).

BACKGROUND

[0002] Most of the raw materials used in the chemical industry for the production of polymers and for other purposes are typically obtained from petroleum sources. The cost and availability of these raw materials is largely dependent on available oil reserves, which have generally declined over the past decade due to a surge in global production and growing global demand. Since global oil reserves are a non-renewable source, the availability of oil and raw materials derived from oil will not improve in the future.

[0003] As recoverable reserves of conventional oil are becoming increasingly scarce and costly to produce, there is increasing interest in recovering stocks of heavy oil such as tar sands (also known as oil sands and / or tar sands). According to some estimates, the amount of oil in known tar sands deposits may be greater than all the remaining world reserves of ordinary oil, and at least amounts to the same order as all the remaining world reserves of ordinary oil. However, extraction from these sources is difficult and entails a number of undesirable consequences for the environment.

[0004] The method of oxidative hydrothermal dissolution (OGR) is an environmentally friendly technology in which macromolecular organic materials are destroyed using an oxidative cleavage method, resulting in the formation of organic compounds such as low molecular weight aromatic and aliphatic acids, phenols and other products. This application describes methods of applying OGR technology for the destruction of macromolecular and heterogeneous materials, such as tar sands, coal, lignocellulosic biomass and kerogen, with the formation of certain products that are currently used or potentially applicable in the chemical industry, as well as other products.

SHORT DESCRIPTION

[0005] In one embodiment, the process of solubilizing an organic solid contained in a composite material containing an organic solid and an inorganic matrix may include contacting said composite material with an oxidizing agent in superheated water to form an aqueous mixture containing at least one solubilized organic solute.

[0006] In some embodiments, the process may further include spraying the composite material and mixing the atomized composite material with water to form a suspension, before bringing the composite material into contact with the oxidizing agent in superheated water.

[0007] In some embodiments, the oxidizing agent is molecular oxygen (O ₂ ), wherein molecular oxygen is delivered by any known method of delivery, production, or isolation of molecular oxygen from any known mixture in any form. Non-limiting examples of methods for providing molecular oxygen delivery include: in situ decomposition of hydrogen peroxide; fractional distillation of liquefied air; electrolysis of water; delivery from a place of storage of oxygen; membrane release from the air and any combination thereof.

[0008] In some embodiments, the composite material may be selected from the group consisting of coal, tar sand, carbonaceous shale, and any combination thereof.

[0009] In some embodiments, the composite material may be brought into contact with the oxidizing agent in superheated water in the reactor, wherein said composite material, oxidizing agent and superheated water are not held in the gaseous phase to slow the formation of free space above the liquid in the reactor.

[0010] In some embodiments, the process may further include cooling the aqueous mixture to a temperature of about 20 ° C.

[0011] Additional objects, advantages and new features are set forth further in the description below, or they will become clear to experts in this field when studying graphic materials and the following detailed description.

BRIEF DESCRIPTION OF GRAPHIC MATERIALS

[0012] The following figures illustrate various aspects of an organic material production process using an oxidative hydrothermal dissolution process.

[0013] Figure 1 is a diagram of a process of oxidative hydrothermal dissolution (OGR);

[0014] Figure 2 is a schematic representation of a semi-continuous microreactor system used to test and evaluate the OGR process;

[0015] Figure 3 is a schematic representation of a continuous microreactor system used to test and evaluate the OGR process;

[0016] Figure 4 is a comparison chart of the carbon content remaining after processing tar tar using three carbon recovery methods;

[0017] Figure 5 is a photograph of tar sand samples before and after processing using three carbon recovery methods;

[0018] Figure 6 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using an OGR method and solvent extraction of an OGR solution using methylene chloride;

[0019] Figure 7 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using the OGR method and solvent extraction of the OGR solution using ethyl acetate;

[0020] Figure 8 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using the OGR method and the evaporative removal of water from the OGR solution;

[0021] Figure 9 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using solvent extraction with methylene chloride;

[0022] Figure 10 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using pyrolysis;

[0023] Figure 11 is a general ion chromatogram illustrating the distribution of products observed by pyrolysis-GC-MS analysis of organic products recovered from Illinois coal using the OGR method;

[0024] Figure 12 is a multi-ion chromatogram illustrating the distribution of major aliphatic products observed by pyrolysis-GC-MS analysis of organic products recovered from Illinois coal using the OGR method;

[0025] Figure 13 is a multi-ion chromatogram illustrating the distribution of benzoic acid and monomethoxy benzoic acids observed by pyrolysis-GC-MS analysis of organic products extracted from Illinois coal using the OGR method;

[0026] Figure 14 is a single-ion chromatogram illustrating the distribution of benzene-dicarboxylic acids observed by pyrolysis-GC-MS analysis of organic products recovered from Illinois coal using the OGR method;

[0027] Figure 15 is a multi-ion chromatogram illustrating the distribution of thiophenecarboxylates and dicarboxylates observed by pyrolysis-GC-MS analysis of organic products recovered from Illinois coal using the OGR method;

[0028] Figure 16 is a single-ion chromatogram illustrating the distribution of dimethoxy benzenes and dimethoxy benzoic acids observed by pyrolysis-GC-MS analysis of organic products recovered from Illinois coal using the OGR method;

[0029] Figure 17 is a single-ion chromatogram illustrating the distribution of benzene-tricarboxylic acids observed by pyrolysis-GC-MS analysis of organic products recovered from Illinois coal using the OGR method;

[0030] Figure 18 is a single-ion chromatogram illustrating the distribution of dimethoxy-benzene-dicarboxylic acids observed by pyrolysis-GC-MS analysis of organic products recovered from Illinois coal using the OGR method;

[0031] Figure 19 is a multi-ion chromatogram illustrating the distribution of monomethoxy-benzene-dicarboxylic acids and undefined analogues observed by pyrolysis-GC-MS analysis of organic products extracted from Illinois coal using the OGR method;

[0032] Figure 20 is a single-ion chromatogram illustrating the distribution of benzene-tetracarboxylic acids observed by pyrolysis-GC-MS analysis of organic products recovered from Illinois coal using the OGR method;

[0033] Figure 21 is a multi-ion chromatogram illustrating the distribution of trimethoxybenzenes and furan-dicarboxylic acids observed by pyrolysis-GC-MS analysis of organic products recovered from Illinois coal using the OGR method;

[0034] Figure 22 is a general ion chromatogram illustrating the distribution of products observed by pyrolysis-GC-MS analysis of organic products extracted from softwood (lignin) wood using the OGR method;

[0035] Figure 23 is a general ion chromatogram illustrating the distribution of products observed by pyrolysis-GC-MS analysis of organic products extracted from bamboo using the OGR method;

[0036] Figure 24 is a general ion chromatogram illustrating the distribution of products observed by pyrolysis-GC-MS analysis of organic products extracted from carbonaceous shale using the OGR method;

[0037] Figure 25 is a general ion chromatogram illustrating the distribution of products observed by pyrolysis-GC-MS analysis of organic products extracted from bagasse of sugarcane using the OGR method;

[0038] Figure 26 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using the OGR method and the evaporative removal of water from the OGR solution;

[0039] Figure 27 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using an OGR method and extracting the OGR solution with a solvent using ethyl acetate;

[0040] Figure 28 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using pyrolysis;

[0041] Figure 29 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using the OGR method and the evaporative removal of water from the OGR solution;

[0042] Figure 30 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using an OGR method and extracting the OGR solution with a solvent using ethyl acetate; and

[0043] Figure 31 is a diagram summarizing the results of an GC-MS analysis of organic products recovered from tar sand using pyrolysis.

[0044] Corresponding conventions indicate corresponding elements in various projections of said drawings. The headings used in the figures should not be construed as limiting the scope of the claims.

DETAILED DESCRIPTION

[0045] The present invention relates generally to methods for producing water-soluble products from solid organic substances using an oxidative hydrothermal dissolution (OGR) process. Some aspects of the OGR method are described in detail in PCT application number PCT / US 10/23886, which is incorporated herein in its entirety.

[0046] As described herein, the term "biomass" may include, but is not limited to, materials containing cellulose, hemicellulose, lignin, protein and carbohydrates such as starches and sugars, trees, shrubs and herbs, corn and leaf wrap maize, municipal solid waste, including materials that are commonly disposed of by apartment owners, commercial establishments and industry, biomass rich in starch, including starch, sugar or protein, such as corn, crops, fruits and vegetables cabbage soup, branches, shrubs, reeds, energy crops, forest, fruits, flowers, crops, herbs, grasses, leaves, bark, needles, logs, roots, shoots, short-cycle wood crops, bushes, millet, trees , vegetables, vines, hard and soft woods, organic waste materials generated in agricultural processes, including frame construction and silvicultural activities such as silvicultural wood wastes, primary biomass and / or non-primary biomass, including agricultural biomass, industrial organic matter, debris during construction or demolition, paper, cardboard, wood waste, sawdust and plastics.

[0047] As used herein, the term "aqueous mixture" means a homogeneous mixture of one or more substances (solutes) molecularly dispersed in a sufficient amount of a solvent medium (solvent). In some embodiments, the aqueous mixture has a pH in the range of 1 to 5. In some embodiments, the aqueous mixture contains at least 50%, preferably 90%, even more preferably 95% of an organic solid from a composite material.

[0048] As used herein, the term "composite material" means a combination of two or more composite materials with different physical or chemical properties that remain isolated and separate in the final structure. For example, a composite material may contain an organic solid and an inorganic matrix.

I. Oxidative hydrothermal dissolution

[0049] The OGR process involves contacting an organic solid with an oxidizing agent in a reactor containing superheated water to form at least one solubilized organic solute. In this reaction, the macromolecular structure of the organic solid, which is otherwise insoluble in water, is destroyed to fragments with a lower molecular weight. These fragments with a lower molecular weight are soluble in water. These water soluble fragments are referred to as dissolved organic solids, solubilized organic substances, or solubilized organic solutes. The solubilized fragments can then be used as starting materials for various chemical processes or as liquid fuel. In one aspect, if the solubilized fragments are dissolved carbohydrates, such as low molecular weight sugars or oxidized low molecular weight sugars, these dissolved carbohydrates can be fermented to form alcohols or used in other processes to produce many other products.

[0050] Non-limiting examples of organic solids suitable for processing by the OGR method include coal, tar sand, lignite, kerogen, biomass, and solid organic waste. Biomass, as described herein, refers to biological material obtained from living organisms, and includes, for example, plant materials such as wood, grass, or crops. For example, solid organic waste can be plastic waste. Coal, for example, has a complex, high molecular weight structure built from a variety of cross-linked aromatic and aliphatic substructures. It is assumed that coal is insoluble in water, mainly due to the high degree of cross-linking between different parts of this structure. The rupture of the crosslinking structural elements in organic solids destroys this structure into smaller substructural units. For example, using OGR methods, coal can be converted into a new product with modified physical properties. In addition, the OGR method can be used to convert biomass to soluble organic matter. For example, biomass containing cellulose, hemicellulose and / or lignins can be converted into dissolved low molecular weight sugars or oxidized low molecular weight sugars, or other products.

[0051] The oxidizing agent may be any oxidizing agent capable of oxidizing an organic solid, including, but not limited to, molecular oxygen (O ₂ ). The use of molecular oxygen as an oxidizing agent avoids the use of exotic oxidizing agents, such as permanganates, chromate oxides or organic peroxides, which can be harmful to the environment or expensive. Molecular oxygen can be delivered by any known method of delivery, production or isolation of molecular oxygen from any known mixture in any form. Non-limiting examples of methods for providing molecular oxygen delivery include: in situ decomposition of hydrogen peroxide; fractional distillation of liquefied air; electrolysis of water; delivery from a place of storage of oxygen; membrane release from the air and any combination thereof. Non-limiting examples of suitable oxygen storage locations include pressurized oxygen cylinders. The addition of an oxidizing agent to superheated water increases the degree of conversion and the overall conversion of the organic solid to solubilized products.

[0052] The reaction medium in the OGR process may be superheated water having a temperature of from about 100 ° C to about 374 ° C. In other embodiments, superheated water may have a temperature in the range of from about 200 ° C to about 350 ° C.

[0053] The pressure in the reactor can be set so that it is sufficient to maintain water in a liquid state (without loss of water in the gas phase). In one embodiment, the pressure may range from about 100 kPa (kilopascal) to about 22 MPa (megapascal). In other embodiments, the pressure may range from about 1.5 MPa to about 17 MPa and from about 12 MPa to about 16 MPa. The terms "hydrothermal water" and "superheated water" may be used interchangeably herein.

[0054] Without being limited to any particular theory, it is contemplated that the oxidation reaction is a surface reaction between the oxidizing agent and the surface of an organic solid. Therefore, maintaining a sufficiently high ratio of surface area to volume of organic solid can increase the reaction rate. The organic solid may have small particles to provide a higher surface area per volume for the reaction. However, the organic solid can be of any size without affecting the course of the reaction. The reaction may begin on the surface of the organic solid and penetrate deeper from the surface until the solid dissolves or the reaction ceases.

[0055] The OGR process may also include adding other components to the reaction mixture, including but not limited to pH modifiers, catalysts, additional solvents, and any combination thereof. It is understood that these additives can accelerate the formation of certain predetermined products or minimize the formation of undesirable products.

[0056] The process may optionally further include cooling the solubilized organic solute. One advantage of cooling the solubilized organic solute may be to prevent further oxidation of the solubilized organic solute. The solubilized organic solid can be cooled to room temperature or to about 20 ° C. However, subsequent processing, such as distillation, evaporation or further reaction of dissolved organic substances, may not require cooling, and cooling may be undesirable.

[0057] Figure 1 is a schematic diagram of an OGR 100 process. Organic solid may be loaded into a reactor 200. The reactor 200 may be an upflow reactor without gaseous space above the liquid to increase the efficiency of the OGR method. Superheated water can be introduced into the reactor 200 through the opening 102 until equilibrium is reached. An oxidizing agent, for example molecular oxygen, can be introduced into the reactor 200 through the opening 104. Molecular oxygen can be delivered directly from the storage tank, can be extracted from ambient air, or molecular oxygen can be obtained chemically, such as thermal decomposition of hydrogen peroxide, before being added to reactor 200. Hole 106 may be used to introduce any other components added to the reaction mixture, including, but not limited to, pH modifiers, catalysis ry or organic solvents. The solubilized organic solute obtained from the organic solid exits the reactor 200 through an opening 108 and may optionally enter a cooler 300. The cooled effluent from the opening 110 may be checked for solubilized organic solute or may be collected for further processing or analysis . Non-limiting examples of suitable analysis techniques for chilled effluent include matrix photodiode detection (MFI), GC-MS, and any combination thereof. The OGR method can be carried out in a batch, semi-continuous or continuous manner.

[0058] The raw material (OGR solution) obtained by processing organic matter using OGR methods may be an aqueous solution of dissolved organic products. In some aspects, depending on the particular processed organic matter and the conditions of the OGR process, the OGR solution may be a clear solution and may not contain suspended colloidal solids. In other aspects, the OGR solution may contain suspended particles. Non-limiting examples of suspended particles include inorganic particles, such as an inorganic matrix, unreacted organic solids, and any combination thereof. For example, if the OGR process does not completely convert the organic solids to solubilized organic solids, then the OGR solution may contain suspended particles of unreacted organic solid; in this example, the OGR process may include too low an oxidizing agent concentration and / or too short a reaction time.

[0059] Without being limited to any particular theory, the formation of a product of an OGR solution is not the result of simple hydrolysis. Based on previous observations (not shown in this document), the preparation of a dissolved product is directly related to the delivery of O ₂ and the quick response of the reactor to the delivery of the oxidizing agent.

[0060] OGR methods can be used for a wide range of organic materials, including, but not limited to coal, carbonaceous shales, organic matter-rich carbonate rocks, tar sands, lignocellulosic and other biomass, as described above, lignite, bituminous coal, anthracite and charcoal. Using the OGR method, complete conversion of organic materials to soluble products can easily be achieved, although reaction rates can vary significantly.

[0061] The reaction rate may depend on the particle size, reaction temperature, oxidizer loading and flow rate / contact time, as well as a change in the choice of organic material used as the starting substrate. Typically, the reaction proceeds within a few minutes to completely dissolve the tar particles having a particle size in the range of about 60 mesh to about 20 mesh. As a rule, low-grade materials react faster than high-grade materials (presumably due to the more polycondensed nature of high-grade materials), and macerals interact in the following order of structures (from the fastest to the slowest): liptinite> vitrinite> inertinite.

[0062] The OGR method is likely due to the oxidative cleavage of mobile structures, which leads to the destruction of the macromolecular structure as a whole. As low molecular weight products form, they dissolve in the reaction medium (water), which under hydrothermal conditions acts as an excellent solvent for most organic compounds. Dissolved organic compounds are isolated from the residual solid, thus acting on the fresh surface of the substrate, for further reaction with an additional amount of oxidizing agent. The rapid removal of water and the isolation of the resulting organic solute or the extinction prevents excessive oxidation of the dissolved organic substances in the product of the OGR solution.

[0063] For most of the starting solid organic materials, under optimal reaction conditions, approximately 70% to 100% of the original carbon is released as solubilized products. Small amounts of gaseous products (CO and CO ₂ ) may also form. Gaseous oxides of N or S, as a rule, are not formed. Inorganic N and S are stored in the aqueous phase as sulfate and nitrate, respectively. Organic S is at least partially retained as soluble organosulfur compounds in the product of the OGR solution.

[0064] The characterization of the solubilized products shows that the product of the OGR solution usually consists of moderately complex mixtures of low molecular weight organic substances. For bituminous coal, it consists mainly of: (i) aliphatic carboxylic acids and dibasic acids from C1 to about C20; and (ii) mono-aromatic carboxylic acids, polyacids and phenols, including methoxylated analogues. Acetic acid is in many cases the single most common product formed, and may account for up to about 5% of the original product, depending on the feedstock processed by the OGR process. In one embodiment, one or more specific organic compounds may be isolated or purified from the product of the OGR solution by any known purification method, such as fractional distillation and others.

[0065] The OGR products obtained from biomass are simpler mixtures of organic compounds compared to the OGR products obtained from coal. Non-limiting examples of OGR products derived from biomass include mixtures of low molecular weight sugars, including glucose, fructose, galactose, sucrose, maltose, lactose, oxidized low molecular weight sugars, and any combination thereof. Non-limiting examples of oxidized low molecular weight sugars include keto, aldo, and carboxy derivatives of any of the low molecular weight sugars described above in this document. Not limited to any particular theory, cellulose, hemicellulose and other macromolecular carbohydrates can be destroyed during the OGR by hydrolysis and oxidative cleavage to form these products. Other specific mixtures of organic compounds contained in the products of the OGR solution obtained in other aspects from various organic materials are presented in the Examples below.

II. Apparatus for oxidative hydrothermal dissolution

[0066] An embodiment of a semicontinuous OGR flow apparatus is shown schematically in Figure 2. Organic solid can be charged into reactor 6, and superheated water and an oxidizing agent can be introduced into reactor 6 by pumps 1 and 2. If the oxidizing agent is obtained from hydrogen peroxide, then peroxide hydrogen can decompose in heater 3, and the resulting molecular oxygen and superheated water can enter the reactor through openings 4 and 5, respectively. Additional components or water can be introduced into the reactor 6 through the opening 7. The reaction between the organic solid and the oxidizing agent takes place in the reactor 6, resulting in the formation of a solubilized organic solute, which leaves the reactor 6 and optionally enters the cooler 8. The effluent may be collected in capacitance 9, and data is collected by detector 10.

[0067] An embodiment of a continuous OGR in-line apparatus is schematically depicted in Figure 3. As a raw material for the OGR apparatus, an organic solid such as coal, tar sand or carbonaceous shale may be used, in which the inorganic component of the shale may contain minerals, including but not limited to silicates or carbonates. Raw materials can be pulverized in a mill 302 and mixed with water to form a suspension in a suspension generator apparatus 304. The mill 302 and a suspension generator apparatus 304 can be combined in a single operation using a process such as wet grinding. Then, the suspension can be pumped into the reactor 306 using a suspension pump 308. The suspension can then be heated before entering the reactor 306 using a pre-heater 320. An oxidizing agent, such as molecular oxygen, and superheated water can be introduced into the reactor 306 by pump 310 If molecular oxygen is obtained from hydrogen peroxide, then hydrogen peroxide can decompose in the heater 312, and molecular oxygen and superheated water can then enter the reactor 306. The reaction between the organic solid and oxidizes Lemma can occur in the reactor 306, to form a solubilized organic solute. The solubilized organic solute may exit reactor 306 and may optionally enter a cooler 314. The back pressure may be controlled by a back pressure regulator 316. The effluent may be collected in a tank 318. Details of the wiring and controls are omitted, but are implied by the design of the reactor system. This system can be operated continuously, and the temperature and flow rate of the reagents can be controlled automatically by a computer 322 or other data processing device.

III. Extraction of petroleum materials from tar sands or oil shale using OGR methods

[0068] In other embodiments, the OGR methods described herein can be used to recover petroleum materials from tar sands or oil shales. The particular apparatus, operating systems, and reagents used to extract the petroleum materials in this embodiment may vary depending on the nature and location of the deposit in which tar sands or oil shale occur, as well as on the specified petroleum materials to be extracted.

[0069] Large tar sands deposits are found in several places, but the two main known reserves are the Athabasca oil sands in Alberta, Canada, and the Orinoco oil sands (Venezuela). Of these, Canadian and Venezuelan fields contain approximately 3.6 trillion barrels (570 × 10 ⁹ m ³ ) of recoverable oil, compared with 1.75 trillion barrels (280 × 10 ⁹ m ³ ) of conventional oil worldwide. These oil sand deposits may include up to two thirds of the total remaining world recoverable oil reserves. In addition to extracting petroleum materials from tar sands, OGR methods can also be used in the context of environmental restoration, including, but not limited to, cleaning oil contaminated sand from oil spills from an oil tanker or other ocean vessel, oil refinery or refinery.

[0070] Specific examples of the recovery of petroleum products using OGR methods are described in the Examples presented later in this document.

III. Obtaining aromatic acids, phenols and aliphatic acids using OGR methods

[0071] The OGR processes described hereinabove can be used to produce useful raw materials and other organic compounds for the chemical industry, including, but not limited to, aromatic acids, phenols, and aliphatic acids. The specific apparatus, operating systems and reagents used to obtain raw materials and other organic compounds may vary depending on the specific organic solid materials from which the raw materials for the OGR apparatus are produced, as well as on the desired organic products to be obtained using the OGR method . Non-limiting examples of organic materials useful as raw materials in the OGR process in this embodiment include coal, shale, organic matter-rich carbonate rocks, tar sands, lignocellulosic biomass, lignite, tar coal, anthracite, charcoal and kerogen. “Kerogen,” as used herein, refers to a mixture of organic chemical compounds that form part of the organic matter in sedimentary rocks, including, but not limited to, oil shale.

[0072] Table 1 is a list of non-limiting examples of organic compounds that can be prepared using the OGR process described hereinabove.

[0073] In order to be valuable on a large scale, organic compounds obtained by OGR processes can be recovered in high yield. The output from processing OGR can be measured by evaluating the extraction of organic substances from an inorganic matrix, especially in those cases in which tar sand is processed using the OGR method. For OGR raw materials containing a significant amount of inorganic phase, such as tar sands or carbonaceous shales, the output from OGR processing can be measured as the residual amount of carbon remaining in the inorganic phase after processing the OGR, or as the total weight loss due to high temperature ashing or burning after processing OGR. Low amounts of residual carbon remaining in the inorganic matrix may be desirable, as this indicates that most or all of the bituminous material has been recovered from the inorganic matrix to form “cleaner” sand or another inorganic matrix that can be returned to the environment. In addition, a potentially larger amount of bituminous product can be recovered for separation into organic compounds.

[0074] Another method for estimating the yield of organic compounds after processing the OGR may include measuring the amount of carbon contained in the aqueous phase or the solution of the OGR resulting from the processing of organic matter in the reactor during the OGR. The yield can be quantitatively measured as% of the starting carbon contained in the organic matter, which was recovered as a dissolved product in the aqueous phase or in the solution of the OGR. High yields of carbon in the dissolved product may be desirable, as this indicates that the aqueous phase contains a large proportion of the raw bituminous material, which can be recovered and separated into organic compounds. Carbon not recovered and not left in the inorganic residue may be lost in the form of gaseous products. Typically, in OGR processes, gaseous products may include CO with a small amount of CO ₂ . CO can be isolated as a useful by-product, but minimal gas formation is usually desirable.

[0075] Specific examples of applicable starting materials and other organic compounds obtained using the OGR method for breaking down organic matter such as coal, lignocellulosic biomass and kerogen are presented hereinbelow in the Examples.

EXAMPLES

Example 1

Processing OGR Canadian oil sands Athabasca

[0076] A sample of tar sand from the Athabasca oil sands was processed using the OGR method described hereinabove. For comparison purposes, to assess the relative effectiveness of OGR for the separation and extraction of organic materials from an inorganic matrix, raw sand was compared with products obtained by extraction with hot water (to approximate the existing extraction technologies), complete laboratory extraction with organic solvents and OGR. After processing in each way, soluble and insoluble products were isolated and analyzed. Insoluble products were analyzed for carbon content and high temperature ash yield, to determine the efficiency of the extraction of organic bitumen. Soluble products were isolated and analyzed to study the nature of the organic materials recovered in each way.

[0077] Table 2 presents the results of analyzes of insoluble products for each processing method. Figure 4 is a bar graph summarizing the percentage of carbon remaining in tar sand samples after processing in various ways to recover bituminous materials from an inorganic sand matrix. These data show that about 86% of the carbon originally present in tar sands was recovered during the processing of OGR, compared with 23% recovered only with superheated water and 69% recovered by complete laboratory extraction with an organic solvent (CH ₂ Cl ₂ ).

[0078] Figure 5 is a series of photographs of tar sand samples before and after processing in various ways to extract tar materials from inorganic sand matrix samples. The residue obtained by processing the OGR is loose, clean sand.

[0079] To assess the nature of the product obtained by OGR from this type of raw material, a tar product obtained from Athabasca tar sand was isolated and analyzed by GC-MS analysis using pyrolytic injection and in-situ methylation with tetramethylammonium hydroxide. These data were compared with data for raw tar sand, from which the organic matter was simply distilled by flash pyrolysis.

[0080] The organic product was isolated from the primary OGR solution formed by treating tar sand in three ways, and the results of GC-MS analysis of organic products were compared: (i) evaporative removal (where water was removed from the product by distillation); (ii) solvent extraction with ethyl acetate; and (iii) solvent extraction with methylene chloride (CH ₂ Cl ₂ ). GC-MS analysis data are summarized in Figures 6-10.

[0081] The data for the original tar sands shown in Figure 10 are standard for this type of analysis of heavy oil and bitumen. The three OGR products shown in Figures 6-8 show that the carbon content in the samples of the OGR solution is comparable, regardless of the extraction method. In addition, the carbon content in all samples of the OGR solution (Figures 6-8) is consistent with the distillate of the original tar sands shown in Figure 9, except that the OGR products contain separate series of carboxylic acids and dibasic acids, which are much less noticeable in the product distillates of the original tar sands. This exception is due to the oxidative nature of the OGR process and does not significantly affect the applicability of the resulting "oil".

Example 2

Processing OGR Canadian oil sands Athabasca

[0082] A sample of tar sand from the Athabasca oil sands was processed using the OGR method described hereinabove. Soluble products were isolated and analyzed using the same methods as described in Example 1.

[0083] The results of a GC-MS analysis of the extracted organic products are summarized in Figures 26-28. The analysis of gas chromatographic mass spectrometry of the source tar sand is presented in Figure 28 as the content of volatile substances formed by flash distillation (i.e. pyrolysis-GC-MS) and obtained by OGR of oils isolated by evaporative removal of water (Figure 26) and extraction of a solution of OGR ethyl acetate (Figure 27).

Example 3

OGR Processing Oil Sands Sunnyside, Utah

[0084] A sample of tar sand from the oil sands of Sunnyside, Utah, was processed using the OGR method described hereinabove. Soluble products were isolated and analyzed using the same methods as described in Example 1.

[0085] The results of a GC-MS analysis of the recovered organic products are summarized in Figures 29-31. The analysis of gas chromatographic mass spectrometry of the source tar sand is shown in Figure 31 as the content of volatile substances formed by flash distillation (i.e., pyrolysis-GC-MS) and obtained by OGR oils extracted by evaporative removal of water (Figure 29) and extraction of a solution of OGR ethyl acetate (Figure 30).

Example 4

Organic compounds obtained by processing OGR Illinois coal

[0086] A sample of Illinois coal was processed using the OGR method described hereinabove. Soluble products were isolated and analyzed using the same methods as described in Example 1. A general ion chromatogram summarizing the results of a GC-MS analysis of an OGR solution obtained from Illinois coal is shown in Figure 11. The OGR solution was pyrolyzed at a temperature of about 480 ° C. for about 10 seconds. Tetramethylammonium hydroxide was added to the OGR solution for in situ derivatization of acidic oxygen-containing functional groups (phenol + carboxylate). A basic list of specific compounds associated with specific peaks is presented in Table 3.

[0087] Figures 12-21 are single-ion and multi-ion chromatograms isolated from the general ion chromatogram of Figure 11, illustrating the observed product distributions of certain structural families. Figure 12 is a multi-ion chromatogram (m / z = 74 + 85 + 87 + 127) illustrating the distribution of major aliphatic products. Figure 13 is a multi-ion chromatogram (m / z = 105 + 135) illustrating the distribution of benzoic acid and monomethoxybenzoic acids. Figure 14 is a single-ion chromatogram (m / z = 163) illustrating the distribution of benzene-dicarboxylic acids. Figure 15 is a multi-ion chromatogram (m / z = 111 + 200) illustrating the distribution of thiophene-carboxylates and dicarboxylates. Figure 16 is a single-ion chromatogram (m / z = 138) illustrating the distribution of dimethoxy benzenes and dimethoxy benzoic acids. Figure 17 is a single ion chromatogram (m / z = 221) illustrating the distribution of benzene-tricarboxylic acids. Figure 18 is a single ion chromatogram (m / z = 223) illustrating the distribution of dimethoxy-benzene-dicarboxylic acids. Figure 19 is a multi-ion chromatogram (m / z = 193 + 251) illustrating the distribution of monomethoxy-benzene-dicarboxylic acids and undefined analogues. Figure 20 is a single-ion chromatogram (m / z = 279) illustrating the distribution of benzene-tetracarboxylic acids. Figure 21 is a multi-ion chromatogram (m / z = 168 + 184) illustrating the distribution of trimethoxy-benzenes and furan-dicarboxylic acids.

Example 5

Organic compounds obtained by OGR processing lignins

[0088] A sample of lignin from softwood was processed using the OGR method described hereinabove. A second sample of lignin-rich grass (bamboo) was also processed using the OGR method described hereinabove. Soluble products were isolated and analyzed using the same methods as described in Example 1. A total ion chromatogram summarizing the results of a GC-MS analysis of an OGR solution obtained from coniferous lignin is shown in Figure 22. A total ion chromatogram summarizing the results of a GC-MS analysis a solution of OGR obtained from bamboo lignin is shown in Figure 23.

Example 6

Organic Compounds Obtained by OGR Processing of Carbon Shale

[0089] A carbon shale sample was processed using the OGR method described hereinabove. Soluble products were isolated and analyzed using the same methods as described in Example 1. A general ion chromatogram summarizing the results of a GC-MS analysis of an OGR solution obtained from carbon shale is shown in Figure 24. Tetramethylammonium hydroxide was added to the OGR solution for in situ derivatization acid oxygen-containing functional groups (phenol + carboxylate). A basic list of specific compounds associated with specific peaks is presented in Table 4.

Example 7

Organic compounds obtained by OGR processing sugarcane bagasse

[0090] A sample of sugarcane bagasse was processed using the OGR method described hereinabove. Soluble products were isolated and analyzed using the same methods as described in Example 1. A general ion chromatogram summarizing the results of a GC-MS analysis of an OGR solution obtained from sugarcane bagasse is shown in Figure 25. In situ, tetramethylammonium hydroxide was added for in situ derivatization of acid oxygen-containing functional groups (phenol + carboxylate). A basic list of specific compounds associated with specific peaks is presented in Table 5.

[0091] From the foregoing, it should be understood that although specific embodiments have been presented and described, various modifications may be made without departing from the general idea and scope of the present invention, as those skilled in the art will understand. Such changes and modifications are included in the scope and guidance of the present invention, as indicated in the attached claims.

Claims (16)

1. A method of solubilizing an organic solid contained in a composite material containing an organic solid and an inorganic matrix, a method comprising:
bringing said composite material into contact with an oxidizing agent in superheated water to form an aqueous mixture containing at least one solubilized organic solute,
wherein the composite material is selected from the group consisting of tar sand, carbonaceous shale and any mixture thereof. 2. The method according to p. 1, characterized in that the oxidizing agent is molecular oxygen (O ₂ ). 3. The method according to p. 2, characterized in that molecular oxygen is provided by any of the methods selected from the group consisting of:
in situ decomposition of hydrogen peroxide;
fractional distillation of liquefied air;
electrolysis of water;
deliveries from a place of storage of oxygen;
membrane discharge from the air; and
any combination of them. 4. The method according to p. 3, characterized in that molecular oxygen is provided in situ by decomposition of hydrogen peroxide. 5. The method according to p. 1, characterized in that the composite material is brought into contact with the oxidizing agent in superheated water at a temperature in the range from 100 ° C to 374 ° C. 6. The method according to p. 5, characterized in that the composite material is brought into contact with the oxidizing agent in superheated water at a temperature in the range from 200 ° C to 350 ° C. 7. The method according to p. 1, characterized in that the composite material is brought into contact with the oxidizing agent in superheated water at a pressure in the range from 100 kPa to 22 MPa. 8. The method according to p. 7, characterized in that the composite material is brought into contact with the oxidizing agent in superheated water at a pressure in the range from 1.5 MPa to 17 MPa. 9. The method according to p. 8, characterized in that the composite material is brought into contact with the oxidizing agent in superheated water at a pressure in the range from 12 MPa to 16 MPa. 10. The method according to p. 1, further comprising cooling the aqueous mixture to a temperature of 20 ° C. 11. The method according to p. 1, characterized in that the aqueous mixture has a pH in the range from 1 to 5. 12. The method according to p. 1, characterized in that the aqueous mixture contains at least 50% of an organic solid from a composite material. 13. The method according to p. 12, characterized in that the aqueous mixture contains at least 90% of an organic solid from a composite material. 14. The method according to p. 13, characterized in that the aqueous mixture contains at least 95% organic solid from a composite material. 15. The method according to p. 1, further comprising:
spraying composite material; and
mixing the atomized composite material with water to form a suspension, before bringing the composite material into contact with the oxidizing agent in superheated water. 16. The method according to p. 15, characterized in that the atomized composite material has a particle size in the range from 60 mesh to 20 mesh.

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