CN103764804A - Production of organic materials using an oxidative hydrothermal dissolution method - Google Patents

Abstract

The present invention discloses a method for producing organic materials such as petroleum materials and aromatic acids, phenols and aliphatic polycarboxylic acids using an oxidative hydrothermal erosion (OHO) process. The OHD process includes contacting an organic solid with an oxidizing agent in a reactor containing superheated water to form at least one solubilized organic solute. The reaction breaks down the macromolecular structure of the organic solid into lower molecular weight fragments. These lower molecular weight fragments are soluble in water. These water-soluble fragments are known as dissolved organic solids, solubilized organics, or solubilized organic solutes. The solubilized fragments can then be used as raw materials for various chemical processes or as liquid fuels. If the solubilized fragment is a dissolved carbohydrate such as a low molecular weight sugar or an oxidized low molecular weight sugar, the dissolved carbohydrate can be fermented to produce alcohol or used in other processes to produce a variety of other products.

Description

Production of Organic Materials Using Oxidative Hydrothermal Dissolution

technical field

The present invention relates to methods of producing organic materials, and in particular petroleum materials and organic compounds such as aromatic acids, phenols and aliphatic polycarboxylic acids, using the oxidative hydrothermal dissolution (OHD) process.

Background technique

Most of the raw materials used in the chemical industry for the production of polymers and other uses are usually derived from petroleum. The price and availability of these raw materials is strongly influenced by the available oil supply, which has generally declined over the past decade or so due to a dramatic increase in world production capacity and increased world demand. Since the global oil supply is a non-renewable resource, the future availability of oil and the future availability of raw materials derived from oil are not expected to improve.

As recoverable reserves of conventional oil become increasingly scarce, there is increased interest in the extraction of heavy oil resources such as tar sands (also known as oil sands and/or tar sands). According to some estimates, the vast amount of petroleum in place stored in the known tar sands may be higher than and at least the same order of magnitude of all remaining conventional world petroleum reserves. However, extraction of these resources is difficult and suffers from many adverse environmental consequences.

Oxidative hydrothermal dissolution (OHD) technology is an environmentally friendly technology that uses an oxidative bond-cleavage process to decompose macromolecular organic materials, resulting in the formation of organic compounds such as low molecular weight aromatic and aliphatic acids, phenols and other products. This application describes the use of OHD technology to decompose macromolecular and heterogeneous materials such as tar sands, coal, lignined biomass, and kerogen to produce specific products that are currently being used or in the chemical industry Might work, just like other products.

Summary of the invention

In one embodiment, the process of solubilizing an organic solid contained in a composite material comprising an organic solid and an inorganic matrix may comprise contacting the composite material with an oxidizing agent in superheated water to form an aqueous solution comprising at least one solubilized organic solute. mixture.

In some embodiments, the process may also include comminuting the composite material and combining the comminuted composite material with water to form a slurry, and then contacting the composite material with the oxidizing agent in the superheated water.

In some embodiments, the oxidizing agent is molecular oxygen ( _O2 ), wherein molecular oxygen is provided by any known method of supplying, generating, or separating molecular oxygen from any known mixture in any form. Non-limiting examples of methods of obtaining a source of molecular oxygen include: in situ decomposition of hydrogen peroxide; fractional distillation of liquefied air; electrolysis of water; transfer from a stored source of oxygen; membrane separation by air, and any combination thereof.

In some embodiments, the composite material can be selected from the group consisting of coal, tar sands, carbonaceous shale, biomass, and any mixtures thereof.

In some embodiments, the composite material may be contacted with an oxidant in superheated water within a reactor, wherein the composite material, oxidant, and superheated water are maintained in a non-gaseous phase to inhibit headspace formation within the reactor.

In some embodiments, the process may also include chilling the aqueous mixture to a temperature of about 20°C.

Additional objects, advantages and novel features will be set forth in the following description, or will become apparent to those skilled in the art upon examination of the drawings and the following detailed description.

Brief description of the drawings

The following figures illustrate various aspects of a process for producing organic materials using an oxidative hydrothermal dissolution process.

Fig. 1 is the schematic diagram of oxidation hydrothermal dissolution (OHD) process;

Figure 2 is a schematic diagram of a semi-continuous microreactor system for testing and evaluating the OHD process;

Figure 3 is a schematic diagram of a continuous microreactor system for testing and evaluating the OHD process;

Figure 4 is a graph comparing carbon remaining after processing tar sands using three carbon removal methods;

Figure 5 is a photograph of a tar sands sample before and after processing using the three carbon removal methods;

Figure 6 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using the OHD method and solvent extraction of the OHD liquor using methylene chloride;

Figure 7 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using the OHD method and solvent extraction of the OHD liquor using ethyl acetate;

Figure 8 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using the OHD method and evaporative stripping of water from the OHD liquor;

Figure 9 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using dichloromethane solvent extraction;

Figure 10 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using pyrolysis;

Figure 11 is a total ion chromatogram showing the product distribution observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 12 is a multiple ion chromatogram showing the distribution of predominantly aliphatic products observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 13 is a multiple ion chromatogram showing the distribution of benzoic acid and monomethoxybenzoic acid observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 14 is a single ion chromatogram showing the distribution of phthalic acid observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 15 is a multiple ion chromatogram showing the distribution of thiophene carboxylates and thiophene dicarboxylates observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 16 is a single ion chromatogram showing the distribution of dimethoxybenzenes and dimethoxybenzoic acid observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 17 is a single ion chromatogram showing the distribution of benzenetricarboxylic acids observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 18 is a single ion chromatogram showing the distribution of dimethoxyphthalic acid observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 19 is a multiple ion chromatogram showing the distribution of monomethoxyphthalic acid and unidentified analogues observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 20 is a single ion chromatogram showing the distribution of pyromellitic acid observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 21 is a multiple ion chromatogram showing the distribution of trimethoxybenzene and furandicarboxylic acid observed for Py-GC-MS analysis of organic products recovered from Illinois coal using the OHD method;

Figure 22 is a total ion chromatogram showing the product distribution observed for Py-GC-MS analysis of organic products recovered from softwood (conifer) lignin using the OHD method;

Figure 23 is a total ion chromatogram showing the product distribution observed for Py-GC-MS analysis of organic products recovered from bamboo using the OHD method;

Figure 24 is a total ion chromatogram showing the product distribution observed for Py-GC-MS analysis of organic products recovered from carbonaceous shale using the OHD method;

Figure 25 is a total ion chromatogram showing the product distribution observed for Py-GC-MS analysis of organic products recovered from bagasse using the OHD method;

Figure 26 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using the OHD method and evaporative stripping of water from the OHD liquor;

Figure 27 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using the OHD method and solvent extraction of the OHD liquor using ethyl acetate;

Figure 28 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using pyrolysis;

Figure 29 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using the OHD method and evaporative stripping of water from the OHD liquor;

Figure 30 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using the OHD method and solvent extraction of the OHD liquor using ethyl acetate; and

Figure 31 is a graph summarizing the results of GC-MS analysis of organic products recovered from tar sands using pyrolysis.

Corresponding reference characters indicate corresponding elements in the various drawings. Headings used in the figures should not be construed as limiting the scope of the claims.

Detailed ways

The present invention generally relates to methods of producing water-soluble products from organic solids using the oxidative hydrothermal dissolution (OHD) process. Certain aspects of the OHD method are described in detail in PCT Application No. PCT/US10/23886 (hereby incorporated herein in its entirety).

As used herein, the term "biomass" may include, but is not limited to, materials containing cellulose, hemicellulose, lignin, protein, and carbohydrates such as starch and sugars, trees, shrubs, and grasses, corn and corn hulls, municipal solids Garbage (including materials associated with waste typically discarded by occupants of residential dwelling units, commercial establishments, and industry), starch-rich (including starch, sugar, or protein) biomass such as corn, grains, fruits and vegetables, tree branches , shrubs, rattan, energy crops, forest plants, fruits, flowers, grains, grasses, herbs, leaves, bark, needles, logs, roots, saplings, short-term rotation woody crops, dwarf trees, switchgrass, trees, vegetables , vines, hardwoods and softwoods, organic waste materials such as forestry wood waste, virgin biomass and/or non-virgin biomass, including agricultural biomass, commercial organics, construction and debris, generated from agricultural processes (including farming and forestry activities) Chips, paper, cardboard, wood chips, sawdust and plastics.

As used herein, the term "aqueous mixture" shall mean a homogeneous mixture of one or more substances (solutes) molecularly dispersed in a sufficient amount of dissolution medium (solvent).

As used herein, the term "composite" shall mean a combination of two or more constituent materials of distinct physical or chemical properties that remain separate and distinct in the final structure. For example, a composite material may comprise an organic solid and an inorganic matrix.

oxidative hydrothermal dissolution

The OHD process involves contacting an organic solid with an oxidizing agent in a reactor containing superheated water to form at least one solubilized organic solute. The reaction breaks down the macromolecular structure of an otherwise water-insoluble organic solid into lower molecular weight fragments. These lower molecular weight fragments are soluble in water. These water-soluble fragments are known as dissolved organic solids, solubilized organics, or solubilized organic solutes. The solubilized fragments can then be used as raw materials for a variety of chemical processes or as liquid fuels. In one aspect, if the solubilized fragment is a dissolved carbohydrate such as a low molecular weight sugar or an oxidized low molecular weight sugar, the dissolved carbohydrate can be fermented to produce alcohol or used in other processes to produce other products.

Non-limiting examples of organic solids suitable for processing using the OHD process include coal, tar sands, lignite, kerogen, biomass, and solid organic waste. Biomass as defined herein refers to biological material derived from living organisms and includes, for example, plant-based materials such as wood, grasses and grains. For example, solid organic waste can be waste plastic. Coal, for example, has a complex, high molecular weight macromolecular structure consisting of many cross-linked aromatic and aliphatic substructures. Coal is believed to be insoluble in water, primarily because of a certain degree of cross-linking between the different parts of the structure. Breaking down the cross-linked structural elements in organic solids breaks down the structure into substructural units. For example, the OHD process can be used to convert coal into new products with improved physical properties. In addition, the OHD method can be used to convert biomass into soluble organic matter. For example, biomass comprising cellulose, hemicellulose, and/or lignin can be converted to dissolved or oxidized low molecular weight sugars, among other products.

The oxidizing agent can be any oxidizing agent capable of oxidizing organic solids, including but not limited to molecular oxygen ( _O2 ). The use of molecular oxygen as the oxidizing agent eliminates the need for the use of exotic oxidizing agents such as permanganates, chromate oxides, or organic peroxides which may be environmentally harmful or expensive. Molecular oxygen may be provided by any known method of supplying, generating, or separating molecular oxygen from any known mixture in any form. Non-limiting examples of methods of obtaining a source of molecular oxygen include: in situ decomposition of hydrogen peroxide, fractional distillation of liquefied air, electrolysis of water, transfer from a stored oxygen source, membrane separation by air, and any combination thereof. Non-limiting examples of suitable stored oxygen sources include pressurized oxygen tanks. Adding an oxidizing agent to the superheated water increases the conversion and overall percent conversion of organic solids to solubilized products.

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

The pressure in the reactor can be specified to be sufficient to maintain the water in the liquid state (no loss of water to the gas phase). The pressure may, in one embodiment, range from about 100 kPa (kiloPascals) to about 22 MPa (megaPascals). 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" are used interchangeably throughout the specification.

Without being bound by any particular theory, it is believed that the oxidation reaction is a surface reaction of the oxidant with the surface of the organic solid. Therefore, maintaining a sufficiently high surface area to volume ratio of organic solids can increase the reaction rate. Organic solids may have a small particle size to provide a greater surface area per unit volume for the reaction. However, the organic solids can be of any size that does not impede the reaction. The reaction can be initiated at the surface of the organic solid and the surface etched away until the solid dissolves or until the reaction is terminated.

The OHD method can also include adding other components to the reaction including, but not limited to, pH adjusters, catalysts, additional solvents, and any combination thereof. These additives are expected to promote the formation of specific desired products or minimize the formation of undesired products.

The process may optionally further include chilling the solubilized organic solute. One advantage of including chilling the solubilized organic solute may be to prevent further oxidation of the solubilized organic solute. The solubilized organic solute can be chilled to room temperature or about 20°C. However, further processing such as distillation, evaporation, or further reaction of dissolved organics may not require cooling, whereas chilling may not be desirable.

FIG. 1 is a schematic diagram of an OHD process 100 . Organic solids may be added to reactor 200 . Reactor 200 may be an upflow reactor with no gaseous headspace to increase the efficiency of the OHD process. Superheated water may be introduced into reactor 200 through port 102 until equilibrium is reached. An oxidizing agent such as molecular oxygen may be introduced into reactor 200 through port 104 . Molecular oxygen can be provided directly from a storage tank, separated from ambient air, or molecular oxygen can be generated by a chemical process, such as thermal decomposition of hydrogen peroxide, before being added to reactor 200 . Port 106 can be used to introduce any other components added to the reaction, including but not limited to pH adjusters, catalysts or organic solvents. Solubilized organic solutes obtained by organic solids exit reactor 200 at port 108 and may optionally enter chiller 300 . The cooled effluent from port 110 can be monitored for the presence of solubilized organic solutes, or can be collected for further processing or analysis. Non-limiting examples of analytical techniques suitable for the cooled effluent include photodiode array detection (PDA), GC-MS, and any combination thereof. The OHD process can be performed as a batch, semi-continuous or continuous process.

The raw product (OHD liquor) derived from the processing of organic matter using the OHD method may be an aqueous solution of dissolved organic products. In some aspects, depending on the particular organic matter being processed and the OHD process conditions, the OHD liquor can be a clear solution free of suspended colloidal solids. In other aspects, the OHD fluid can contain suspended particles. Non-limiting examples of suspended particles include inorganic particles such as inorganic matrices, unreacted organic solids, and any combination thereof. For example, if the OHD process conditions do not result in complete conversion of the organic solids to solubilized organic solids, the OHD liquor may contain suspended particles of unreacted organic solids; in this instance, the OHD process may include too low an oxidant concentration and/or Reaction time too short.

Without being bound by any particular theory, the formation of OHD liquid products is not the result of simple hydrolysis. Based on previous observations (not shown here), lysate production is directly related to _O2 delivery, and the response of the reactor to oxidant delivery is rapid.

The OHD method can be applied to a wide variety of organic materials including, but not limited to, coal, carbonaceous shales, organic-rich carbonate rocks, tar sands, lignocellulose and other biomass as described above, lignite, Bituminous coal, anthracite and charcoal. Complete conversion of organic materials to soluble products can be readily achieved using the OHD method, although reaction rates can vary widely.

The reaction rate can depend on particle size, reaction temperature, oxidant loading and flow rate/contact time, as well as different choices of organic materials used as initial substrates. Typically, the reaction completely dissolves bituminous coal particles ranging in size from about 60 mesh to 20 mesh within minutes. In general, lower materials react faster than higher materials (possibly due to the more condensate nature of higher materials), and coalogens react in the following structural order (fastest to slowest): exinite > vitrinite > inertite.

The OHD method may occur through oxidative cleavage of unstable structures, leading to disruption of the overall macromolecular structure. As low molecular weight products are produced, they dissolve in the reaction medium (water), which serves as an excellent solvent for most organic compounds under hydrothermal conditions. Dissolved organics are separated from residual solids, thereby exposing new substrate surfaces for subsequent reaction with additional oxidizing agents. Rapid removal of water and separation or quenching of the resulting organic solutes will prevent excessive oxidation of dissolved organic compounds in the OHD liquid product.

For most of the original solid organics, about 70% to 100% of the initial carbon was recovered as solubilized products under optimal reaction conditions. Trace amounts of liquid products (CO and CO ₂ ) may also be formed. Usually, no gaseous N or S oxides are produced. Inorganic N and S remained in the aqueous phase as sulfate and nitrate, respectively. The organic S remains at least partially in the OHD liquid product as soluble organosulfur compounds.

Characterization of the solubilized product indicated that the OHD liquid product generally consisted of a moderately complex mixture of low molecular weight organics. For bituminous coal, these products consist primarily of (i) C1 to about C20 aliphatic carboxylic acids and diacids; and (ii) monoaromatic carboxylic acids, polyacids and phenols, including methoxylated analogs. In many cases, acetic acid is the single most abundant product obtained and can comprise up to about 5% of the original product, depending on the initial feedstock processed using the OHD process. In one embodiment, one or more particular organic compounds may be isolated or purified from the OHD liquid product using any known refining method, such as fractional distillation or the like.

OHD products derived from biomass tend to be mixtures of simpler organic compounds than OHD products derived from coal. Non-limiting examples of biomass-derived OHD products 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 ketone, aldehyde and carboxyl derivatives of any of the low molecular weight sugars described above. Without being bound by any particular theory, cellulose, hemicellulose, and other macromolecular carbohydrates can be broken down by the OHD process via hydrolysis and oxidative cleavage to produce these sugars. In other aspects, other specific mixtures of organic compounds contained in OHD liquid products derived from various organic materials are shown in the Examples below.

Oxidation hydrothermal dissolution device

An embodiment of a semi-continuous flow OHD device is schematically shown in FIG. 2 . Organic solids can be fed into reactor 6, and then superheated water and oxidizing agent can be introduced into reactor 6 via pumps 1 and 2. If the oxidant is derived from hydrogen peroxide, the hydrogen peroxide can be decomposed in heater 3, and the resulting molecular oxygen and superheated water can enter the reactor through ports 4 and 5, respectively. Additional components or water can be introduced into reactor 6 through port 7 . The reaction between the organic solids and the oxidizing agent occurs in reactor 6 and produces solubilized organic solute which exits reactor 6 and optionally enters chiller 8 . Effluent can be collected in container 9 and data can be collected by detector 10 .

An embodiment of a continuous flow OHD device is schematically shown in FIG. 3 . Organic solids such as coal, tar sands, or carbonaceous shale (where the inorganic components of the shale may include minerals including, but not limited to, silicates or carbonates) can be used as feedstock to the OHD unit. The feedstock may be comminuted in mill 302 and then combined with water in slurry generator 304 to form a slurry. Mill 302 and slurry generator 304 may be combined into a single operation by a process such as wet milling. The slurry may then be pumped to reactor 306 by slurry pump 308 . Preheater 320 may be used to heat the slurry prior to entering reactor 306 . An oxidizing agent such as molecular oxygen and superheated water may be introduced into reactor 306 by pump 310 . If the molecular oxygen is derived from hydrogen peroxide, the hydrogen peroxide can be decomposed in heater 312 and the molecular oxygen and superheated water then enter reactor 306 . A reaction between the organic solid and the oxidizing agent can occur in reactor 306 and produce a solubilized organic solute. The solubilized organic solute may exit reactor 306 and may optionally enter chiller 314 . Back pressure may be controlled by back pressure regulator 316 . Effluent may be collected in container 318 . Wiring and control details are omitted but are implicit in the design of the reactor system. The system can be operated continuously and the temperature and flow rate of the reactants can be automatically controlled by computer 322 or other data processing means.

III. EXTRACTION OF PETROLEUM MATERIALS FROM TAR SANDS OR OIL SHALE USING THE OHD METHOD

In other embodiments, the OHD process described above can be used to recover petroleum material from tar sands or oil shale. The particular apparatus, operating system and reactants used in this embodiment to recover petroleum material may vary depending on the nature and region of the mine where tar sands or oil shale occurs and the desired petroleum material to be extracted.

Large tar sands occur in several regions, but the two main known deposits are the Athabasca oil sands in Alberta, Canada, and the Orinoco oil sands (Venezuela). Between them, Canadian and Venezuelan mines hold about 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. m ³ ). These oil sands deposits can comprise up to two-thirds of the total remaining global recoverable petroleum resources. In addition to recovering petroleum material from tar sands, the OHD method can also be used in the context of environmental remediation, including but not limited to cleaning up oil sands from oil spills from tankers or other ocean-going vessels, oil production facilities, or oil refining facilities.

Specific examples of recovery of petroleum products using the OHD process are described in the Examples provided below.

III. Production of Aromatic Acids, Phenols and Aliphatic Acids Using the OHD Process

The OHD process described above can be used to produce feedstocks and other organic compounds useful in the chemical industry, including but not limited to aromatic acids, phenols, and aliphatic acids. The particular apparatus, operating systems, and reactants used to produce feedstocks and other organic compounds may vary depending on the particular organic solid material producing the feed to the OHD apparatus and the desired organic compound product to be produced using the OHD process. Non-limiting examples of organic matter suitable for use as OHD process feedstock in this embodiment include coal, organic-rich carbonate rocks, tar sands, lignocellulosic biomass, lignite, bituminous coal, anthracite, charcoal, and oil parent rock. As used herein, "kerogen" refers to a mixture of organic compounds that make up part of the organic matter in sedimentary rocks, including but not limited to oil shale.

Table 1 is a list of non-limiting examples of organic compounds that can be produced using the OHD method described above.

Table 1: Organic compounds produced using the OHD method

Note: R1=H or OH or OCH3, R2=H or OH or OCH3, R3=H or CH3, and n is an integer between 1 and about 30 or more.

To generate large-scale value, organic compounds from the OHD process can be recovered in high yields. The yield of OHD processing can be measured by evaluating the removal of organics from the inorganic matrix, especially in those cases where OHD processes are used to process tar sands. For OHD feedstocks that contain a large amount of inorganic phase, such as tar sands or carbonaceous shale, the yield from OHD processing can be either as residual carbon remaining in the inorganic phase after OHD processing or as a result of high temperature ashing or incineration after OHD processing. Measured by overall mass loss. Lower amounts of residual carbon in the inorganic matrix may be desirable, as this indicates that most or all bituminous material has been removed from the inorganic matrix, resulting in a "cleaner" sand or other inorganic matrix that can be returned to the environment . Additionally, it is possible to recover more of the bitumen product for refining into organic compounds.

Another method of assessing the yield of organic compounds after OHD processing may include measuring the amount of carbon contained in the aqueous phase or OHD liquor resulting from the processing of organic matter in the OHD process reactor. Yield can be quantified as % of initial carbon contained in organic matter recovered as solution product in aqueous phase or OHD liquor. The high yield of carbon in the lysates may be desirable, as this indicates that the aqueous phase contains a large proportion of raw bituminous material that can be recovered and refined into organic compounds. Carbon that is not recovered and not retained in the inorganic residue may be lost as a product of its state. Typically, in OHD, the gaseous products may include CO and some _CO2 . CO can be recovered as a useful by-product, but usually trace amounts of the gas are desired.

Specific examples of useful feedstocks and other organic compounds produced by decomposition of organic matter such as coal, lignocellulosic biomass, and kerogen using the OHD process are provided in the Examples below.

Example

Example 1: OHD Processing of the Canadian Athabasca Oil Sands

A tar sands sample of the Athabasca oil sands was processed using the OHD method described above. For comparative purposes, and to assess the relative efficiency of OHD in separating and recovering organic material from inorganic matrices, raw sand was compared with that produced by hydrothermal extraction (to roughly mimic current extraction techniques), organic solvent laboratory complete extraction, and OHD. products were compared. Soluble and insoluble products were recovered after processing by various methods and analyzed. The carbon content and high-temperature ashing yield of insoluble products were analyzed to determine the organic pitch removal efficiency. Soluble products were recovered and analyzed to investigate the properties of the organic material recovered by various methods.

Table 2 summarizes the analysis of insoluble products from various processing methods. Figure 4 is a bar graph summarizing the percentage of carbon remaining in tar sand samples after treatment by various methods to remove bituminous material from the inorganic sand matrix. These data indicate that about 86% of the carbon originally present in the tar sands was recovered by OHD processing, compared to 23% removed by superheated water alone, and completely laboratory by organic solvent ( _{CH2Cl2 ).} Extraction removed 69%.

Table 2: Analysis of insoluble products

Figure 5 is a series of photographs of a tar sand sample before and after being treated by various methods to remove bituminous material from the inorganic sand matrix sample. The residue derived from OHD processing is free flowing clean sand.

To evaluate the properties of products obtained from this type of feedstock by OHD, bituminous product from the Athabasca tar sands was recovered and analyzed using pyrolysis injection and tetramethylammonium hydroxide in situ methylation Chl was analyzed by GC-MS analysis. These data were compared with those from raw tar sands where the organic matter was simply distilled by flash pyrolysis.

The organic products were recovered from raw OHD liquor from tar sands processing by three techniques and the results of GC-MS analysis of the organic products were compared: (i) evaporative stripping (where water is removed from the product by distillation ); (ii) ethyl acetate solvent extraction; and (iii) dichloromethane (CH ₂ Cl ₂ ) solvent extraction. GC-MS analysis is summarized in Figures 6-10.

The raw tar sands data shown in Figure 10 is typical for this analysis of heavy oil and bitumen. The three OHD products shown in Figures 6-8 indicate that the carbon content of the OHD liquor samples is comparable regardless of the extraction method. Additionally, the carbon content of all OHD liquor samples (Figs. 6-8) was consistent with the distillate from the original tar sands shown in Fig. 9, except that the OHD product contained a discrete series of carboxylic and diacids that Much less is in the product from the distillate from the original tar sands. This is expected to be due to the oxidative nature of the OHD process, which does not significantly affect the usefulness of the resulting "oil".

Example 2: OHD Processing of the Canadian Athabasca Oil Sands

A tar sands sample of the Athabasca oil sands was processed using the OHD method described above. Soluble products were recovered and analyzed using methods similar to those described in Example 1.

The results of the GC-MS analysis of the recovered organic products are summarized in Figures 26-28. Gas chromatography-mass spectrometry analysis of pristine tar sands is presented in Figure 28 as volatiles generated by flash evaporation (i.e., Py-GC-MS) and OHD separated by removal of water by evaporation (Figure 26) and ethyl acetate extraction of OHD liquor. The content of the extracted oil (Figure 27) is given.

Example 3: OHD Processing of Sunnyside, Utah Oil Sands

A sample of tar sands from the Sunnyside oil sands in Utah was processed using the OHD method described above. Soluble products were recovered and analyzed using methods similar to those described in Example 1.

The results of the GC-MS analysis of the recovered organic products are summarized in Figures 29-31. Gas chromatography-mass spectrometry analysis of pristine tar sands is presented in Figure 31 as volatiles generated by flash evaporation (i.e., Py-GC-MS) and by removal of water by evaporation (Figure 29) and extraction of OHD liquor by ethyl acetate (Figure 30). The oil content obtained from the separated OHD is given.

Example 4: Organic Compounds Produced by OHD Processing of Illinois Coal

A sample of Illinois coal was processed using the OHD method described above. Soluble products were recovered and analyzed using methods similar to those described in Example 1. A total ion chromatogram summarizing the results of the GC-MS analysis of the OHD liquor derived from the Illinois coal is provided in FIG. 11 . Pyrolyze the OHD liquid at a temperature of about 480° for 10 seconds. Tetramethylammonium hydroxide was added to the OHD solution for in situ derivatization of acidic oxygen-containing functional groups (phenol + carboxylate). A key listing specific compounds associated with specific peaks is shown in Table 3.

Table 3: Specific Organic Compounds of OHD Liquor from Illinois Coal

ID compound Detailed chromatogram number A 1,4-butenedioic acid 12 B 1,4-Succinic acid 12 C 2-methylsuccinic acid 12 D. benzoic acid 13 E. Thiophene-2-carboxylic acid 15 f Thiophene-3-carboxylic acid 15 G 1,5-Glutaric acid 12 h 1,2-Dimethoxybenzene 16 I 1,4-Dimethoxybenzene 16 J 1,3-Dimethoxybenzene 16 K 1,6-Hexanedioic acid 12 L Furan-3,4-dicarboxylic acid twenty one m 1,2,3-Trimethoxybenzene twenty one N 2-methoxybenzoic acid 13 o 1,7-pimelic acid 12 P 3-methoxybenzoic acid 13 Q Furan-2,5-dicarboxylic acid twenty one R 1,2,4-Trimethoxybenzene twenty one S 4-methoxybenzoic acid 13 T 1,2,3-propanetricarboxylic acid 12 u 1,3,5-Trimethoxybenzene twenty one V 1,2-phthalic acid 14 W Thiophene-2,3-dicarboxylic acid 15 x 1,4-phthalic acid 14 Y 1,3-phthalic acid 14 Z Thiophene-2,5-dicarboxylic acid 15 AAA 3,5-Dimethoxybenzoic acid 16 BB 3,4-Dimethoxybenzoic acid 16 CC Methoxyphthalic acid (isomer not determined) 19 CC Methoxyphthalic acid (isomer not determined) 19 DD 3,4,5-Trimethoxybenzoic acid none EE C14 fatty acid (methyl ester) 12 CC Methoxyphthalic acid (isomer not determined) 19 CC Methoxyphthalic acid (isomer not determined) 19

FF 1,3-Benzodioxole-5,6-dicarboxylic acid none GG 1,2,3-Benzenetricarboxylic acid 17 HH 1,2,4-Benzenetricarboxylic acid 17 II Dimethoxyphthalic acid (isomer not determined) 18 II Dimethoxyphthalic acid (isomer not determined) 18 JJ 1,3,5-Benzenetricarboxylic acid 17 II Dimethoxyphthalic acid (isomer not determined) 18 KK C16 fatty acid (methyl ester) 12 LL Unknown (analogue of X?) 19 LL Unknown (analogue of X?) 19 LL Unknown (analogue of X?) 19 MM Pyrellitic acid (isomer not determined) 20 NN C18 fatty acid (methyl ester) 12 MM Pyrellitic acid (isomer not determined) 20 MM Pyrellitic acid (isomer not determined) 20 OO unknown none

Figures 12-21 are single and multiple ion chromatograms extracted from the total ion chromatogram of Figure 11 showing the observed distribution of products of specific structural families. Figure 12 is a multi-ion chromatogram (m/z = 74+85+87+127) showing the distribution of major aliphatic products. Figure 13 is a multi-ion chromatogram (m/z=105+135) showing the distribution of benzoic acid and monomethoxybenzoic acid. Figure 14 is a single ion chromatogram (m/z=163) showing the distribution of phthalic acid. Figure 15 is a multiple ion chromatogram (m/z=111+200) showing the distribution of thiophene carboxylates and dicarboxylates. Figure 16 is a single ion chromatogram (m/z=138) showing the distribution of dimethoxybenzenes and dimethoxybenzoic acid. Figure 17 is a single ion chromatogram (m/z=221) showing the distribution of trimellitic acid. Figure 18 is a single ion chromatogram (m/z=223) showing the distribution of dimethoxyphthalic acid. Figure 19 is a multiple ion chromatogram (m/z = 193+251) showing the distribution of monomethoxyphthalic acid and unidentified analogues. Figure 20 is a single ion chromatogram (m/z=279) showing the distribution of pyromellitic acid. Figure 21 is a multi-ion chromatogram (m/z=168+184) showing the distribution of trimethoxybenzenes and furandicarboxylic acid.

Example 5: Organic compounds produced by OHD processing of lignin

Samples of softwood (coniferous) lignin were processed using the OHD method described above. A second sample of lignin-rich grass (bamboo) was also processed using the OHD method described above. Soluble products were recovered and analyzed using methods similar to those described in Example 1. A total ion chromatogram summarizing the results of the GC-MS analysis of OHD liquors derived from coniferous lignins is provided in Figure 22. A total ion chromatogram summarizing the results of the GC-MS analysis of OHD liquors derived from bamboo lignin is provided in FIG. 23 .

Example 6: Organic Compounds Produced by OHD Processing of Carbonaceous Shale

Samples of carbonaceous shale were processed using the OHD method described above. Soluble products were recovered and analyzed using methods similar to those described in Example 1. A total ion chromatogram summarizing the results of the GC-MS analysis of OHD fluids derived from carbonaceous shale is provided in FIG. 24 . Tetramethylammonium hydroxide was added to the OHD solution for in situ derivatization of acidic oxygen-containing functional groups (phenol + carboxylate). A key listing specific compounds associated with specific peaks is shown in Table 4.

Table 4: Specific organic compounds of OHD fluids from carbonaceous shale

D. compound 1 Methyl valerate 2 Methyl hexenoate 3 Methyl caproate 4 Methoxybenzene 5 Methyl heptanoate 6 Methyl heptenoate 7 Methyl 4-oxopentanoate 8 Methyl Succinate (Dimethyl Succinate) 9 methyl octanoate 10 methyl benzoate 11 phenol 12 2-methoxyphenol (guaiacol) 13 Methyl 5-oxohexanoate 14 1,2-Dimethoxybenzene + dimethyl glutarate 15 1,4-Dimethoxybenzene 16 Methyl nonanoate 17 Methyl 2-Hydroxybenzoate 18 Dimethyl adipate+methyl 6-oxoheptanoate 19 methyl caprate

D. compound 20 unknown twenty one 4-Methoxybenzaldehyde twenty two Methyl 3-methoxybenzoate twenty three Dimethyl pimelate twenty four Methyl 7-oxooctanoate 25 Methyl 2-methoxybenzoate 26 Methyl 4-methoxybenzoate 27 4-Methoxyacetophenone 28 Dimethyl suberate 29 Methyl 8-oxononanoate 30 Dimethyl 1,3-phthalate 31 Dimethyl azelate 32 Methyl 9-oxodecanoate 33 Methyl 3-Hydroxybenzoate 34 Methyl 3,4-dimethoxybenzoate 35 Dimethyl sebacate 36 Methyl 10-oxoundecanoate 37 2-Hydroxy-1,4-phthalic acid dimethyl ester 38 Methyl 4-Hydroxybenzoate 39 unknown dicarboxylic acid 40 Dimethyl undecanedioate 41 unknown 42 Unknown oxygenated terpenoids 43 Methyl palmitate+Dimethyl dodecanedioate 44 Dimethyl tridecanedioate 45 Trimethyl 1,3,5-benzenetricarboxylate 46 methyl octadecanoate 47 Butyl stearate

Example 7: Organic compounds produced by OHD processing of bagasse

Samples of bagasse were processed using the OHD method described above. Soluble products were recovered and analyzed using methods similar to those described in Example 1. A total ion chromatogram summarizing the results of the GC-MS analysis of bagasse-derived OHD liquors is provided in Figure 25. Tetramethylammonium hydroxide was added to the OHD solution for in situ derivatization of acidic oxygen-containing functional groups (phenol + carboxylate). A key listing specific compounds associated with specific peaks is shown in Table 5.

Table 5: Specific organic compounds in OHD liquor from bagasse

ID compound 1 glycolic acid 2 Methoxyacetic acid 3 Methoxybenzene 4 Methyl furancarboxylate (isomer unknown) 5 unknown 6 Succinic acid 7 benzoic acid 8 glutaric acid 9 1,4-Dimethoxybenzene 10 Phenylacetic acid 11 2-Hydroxybenzoic acid + unknown 12 Adipic acid 13 4-Methoxybenzaldehyde 14 Pimelic acid+3-methoxybenzoic acid 15 unknown 16 4-methoxybenzoic acid 17 suberic acid 18 Terephthalic acid 19 Azelaic acid 20 3,4-Dimethoxybenzaldehyde twenty one 3,4-Dimethoxybenzoic acid twenty two tetradecanoic acid twenty three C15 carboxylic acid (unknown isomer) twenty four 3,4,5-Trimethoxybenzoic acid 25 palmitic acid 26 Octadenoic acid (unknown double bond isomer) 27 octadecanoic acid 28 eicosanic acid 29 unknown fatty acid

From the foregoing it should be appreciated that while particular embodiments have been shown and described, it will be apparent to those skilled in the art that various modifications may be made thereto without departing from the spirit and scope of the invention. Such changes and modifications are within the scope and teaching of the invention as defined in the appended claims of the present invention.

Claims (20)

CLAIMS 1. A process (100) for solubilizing organic solids contained in a composite material comprising organic solids and an inorganic matrix, said process (100) comprising: The composite material is contacted with an oxidizing agent in superheated water to form an aqueous mixture comprising at least one solubilized organic solute. 2. The process (100) according to claim 1, wherein the oxidizing agent is molecular oxygen ( _O2 ). 3. The process (100) of claim 2, wherein the molecular oxygen is provided by any method selected from the group consisting of: In situ decomposition of hydrogen peroxide; Fractional distillation of liquefied air; electrolysis of water; diverted from a stored oxygen source; Membrane separation by air; and any combination of them. 4. The process (100) of claim 3, wherein the molecular oxygen is provided by in situ decomposition of hydrogen peroxide. 5. The process (100) of claim 1, wherein the composite material is contacted with the oxidizing agent in superheated water at a temperature in the range of about 100°C to about 374°C. 6. The process (100) of claim 5, wherein the composite material is contacted with the oxidizing agent in superheated water at a temperature in the range of about 200°C to about 350°C. 7. The process (100) of claim 1, wherein the composite material is contacted with an oxidizing agent in superheated water at a pressure ranging from about 100 kPa to about 22 MPa. 8. The process (100) of claim 7, wherein the composite material is contacted with the oxidizing agent in superheated water at a pressure in the range of about 1.5 MPa to about 17 MPa. 9. The process (100) of claim 8, wherein the composite material is contacted with the oxidizing agent in superheated water at a pressure in the range of about 12 MPa to about 16 MPa. 10. The process (100) of claim 1, wherein the composite material is selected from the group consisting of coal, tar sands, carbonaceous shale, biomass, and any mixture thereof. 11. The process (100) of claim 10, wherein the composite material is biomass, and wherein the at least one solubilized organic solute comprises at least one of low molecular weight sugars, oxidized low molecular weight sugars, and combinations thereof any combination. 12. The process (100) of claim 1, wherein the composite material is contacted within a reactor (200) with an oxidant in superheated water, wherein the composite material, oxidant and superheated water are maintained in a non-gaseous phase to The formation of headspace within the reactor (200) is inhibited. 13. The process (100) of claim 1, further comprising chilling the aqueous mixture to a temperature of about 20°C. 14. The process (100) of claim 1, wherein the aqueous mixture has a pH in the range of about 1 to about 5. 15. The process (100) of claim 1, wherein said aqueous mixture comprises at least 50% of said organic solids derived from said composite material. 16. The process (100) of claim 15, wherein said aqueous mixture comprises at least 90% of said organic solids derived from said composite material. 17. The process (100) of claim 16, wherein said aqueous mixture comprises at least 95% of said organic solids derived from said composite material. 18. The process (100) of claim 1, further comprising: crushing the composite material; and The pulverized composite material is contacted with water to form a slurry, and then the composite material is contacted with an oxidizing agent in superheated water. 19. The process (100) of claim 18, wherein the comminuted composite material has a particle size in the range of about 60 mesh to about 20 mesh. 20. The solubilized organic solute of the process (100) according to any one of the preceding claims.

Images