METHOD TO PRODUCE OIL AND FUEL

专利摘要:
method for producing biofuel the invention refers generally to the field of fuel production. more specifically, the invention relates to the production of biofuel from high temperature processing of organic matter based on oil.
公开号:BR112013016484B1
申请号:R112013016484-0
申请日:2011-12-15
公开日:2020-09-29
发明作者:Thomas Maschmeyer
申请人:Licella Pty Limited；Licella Fibre Fuels Pty Ltd；Ignite Resources Pty Ltd；
IPC主号:

专利说明:

Cross-Reference Incorporation
[0001] This application claims priority of Australian Provisional Patent Application number 2011900020 filed on January 5, 2011, the content of which is incorporated herein by reference in its entirety. Technical Field
[0002] The invention refers generally to the field of fuel production. More specifically, the invention relates to the production of fuel from high temperature processing of oil-based organic matter. Background of the Invention
[0003] The conversion of solid, low-energy-density lignocellulosic biomass to liquid, high-energy-density oils, which are stable, storable, pumpable and which can be co-processed at nearby conventional refineries for conventional refinery products (ie , "drop-in" fuel products) is a primary objective that underpins sustainable fuel production.
[0004] Existing approaches to the so-called "first generation" fuel production generally use plant seeds, leaving the rest of the plant unusable. In addition to causing waste, the fuels generated by these processes are called oxygenated compounds (for example, ethanol and methyl esters of fatty acids), which have an energy density significantly lower than that of fossil diesel or gasoline.
[0005] Pyrolysis (heating biomass to very high temperatures in an atmosphere with low atmospheric oxygen content) is an alternative approach used to convert biomass into liquid oils. However, liquid oils produced by pyrolysis generally have a very high oxygen content, resulting in low energy density and increased instability ("gumming up"), making them difficult to be processed commercially. Although pyrolysis can be done after gasification and the gases used in the synthesis of diesel by Fischer-Tropsch to process pyrolysis oils in liquid drop-in fuels, the capital costs involved in doing so are significant, which prevented widespread implementation so far.
[0006] Significant progress has been made in hydrothermal modernization of pyrolysis oils (with and without catalysts) to produce more stable oil derivatives with low oxygen content. However, these processes still suffer from difficulties that significantly impact on commercial / large-scale operation, including, for example, restrictions on the proportion of raw material in reaction sludge, sub-optimal heat transfer, and product separation. Summary of the Invention
[0007] In light of the disadvantage (s) associated with current methodologies including those described above, there is a
[0008] need for improved processes for fuel production.
[0009] A number of existing methods use aqueous solvents (for example, water and / or aqueous alcohols) at high temperature and pressure for the production of oils from organic matter. It has been unexpectedly determined that the addition of oil in these solvents (for example, combining oil and / or water and / or aqueous alcohol) provides a means of increasing the efficiency of oil production.
[00010] In a first aspect, the invention provides a method for the production of fuels, the method comprising: producing a sludge comprising organic raw material, water and oil; treating the sludge in a reactor at a temperature between about 200 ° C and about 450 ° C and a pressure between about 18 MPa (180 bar) and about 35 MPa (350 bar); and cooling the sludge and releasing said pressure, thereby providing a product comprising said fuel.
[00011] In an embodiment of the first aspect, the sludge comprises between about 20% and about 60% by weight of said oil.
[00012] In an embodiment of the first aspect, the sludge comprises between about 20% and about 40% by weight of said organic matter.
[00013] In an embodiment of the first aspect, the sludge further comprises an aqueous alcohol.
[00014] In an embodiment of the first aspect, the aqueous alcohol is ethanol or methanol.
[00015] In an embodiment of the first aspect, the sludge comprises a weight percentage of said alcohol of between about 5% by weight and about 40% by weight, between about 5% by weight and about 30% by weight , between about 5% by weight and about 25% by weight, between about 5% by weight and about 20% by weight, between about 5% by weight and about 15 'by weight, or between about 5% by weight and about 10% by weight.
[00016] In an embodiment of the first aspect, organic matter is lignocellulosic material.
[00017] In an embodiment of the first aspect, organic matter is lignite.
[00018] In an embodiment of the first aspect, said treatment comprises heating and pressurizing the sludge in at least one container or chamber of said reactor apparatus.
[00019] In an embodiment of the first aspect, said treatment comprises generating subcritical or supercritical vapor independently of the sludge and contacting the sludge with the subcritical or supercritical vapor in at least one container or chamber of said reactor apparatus.
[00020] In an embodiment of the first aspect, the sludge is at room temperature and pressure or close to the environments before said contact with subcritical or supercritical steam.
[00021] In an embodiment of the first aspect, said treatment comprises: heating the sludge to a temperature selected from the group consisting of at least about 100 ° C, at least about 150 ° C, at least about 200 ° C, at least about 250 ° C, at least about 300 ° C, at least about 350 ° C, between about 200 ° C and about 250 ° C, between about 200 ° C and about 400 ° C, between about 250 ° C and about 400 ° C, and between about 250 ° C and 350 ° C; generate subcritical or supercritical steam regardless of the sludge; and contacting the sludge with subcritical or supercritical vapor in at least one container or chamber of said reactor apparatus. The sludge can be pressurized before and / or after said contact.
[00022] In a second aspect, the invention provides a method for producing a fuel, the method comprising treating organic matter with an oil-based solvent comprising less than about 50% by weight of water at a temperature between about 200 ° C and about 450 ° C, and a pressure of between about 18 MPa (180 bar) and about 35 Mpa (350 bar).
[00023] In a third aspect, the invention provides a method for producing a fuel, the method comprising treating organic matter with an oil-based solvent comprising less than about 50% by weight of water at a temperature between about 200 ° C and about 400 ° C, and a pressure of between about 10 MPa (100 bar) and about 30 Mpa (300 bar).
[00024] In a fourth aspect, the invention provides a method for producing a fuel, the method comprising treating organic matter with an oil-based solvent comprising less than about 50% by weight of water at a temperature between about 200 ° C and about 400 ° C, and said pressure is between about 5 MPa (50 bar) and about 30 Mpa (300 bar).
[00025] In an embodiment of the second, third and fourth aspects, said treatment comprises heating and pressurizing the sludge comprising said organic matter in at least one container or chamber of a reactor apparatus.
[00026] In an embodiment of the second, third and fourth aspects, said treatment consists of contacting a sludge comprising said organic matter with subcritical or supercritical steam.
[00027] In an embodiment of the second, third and fourth aspects, the sludge is at or near ambient temperatures and pressure before said contact with subcritical or supercritical steam.
[00028] In an embodiment of the second, third and fourth aspects, said treatment comprises: heating a sludge comprising said organic matter to a temperature selected from the group consisting of at least about 100 ° C, at least about 150 ° C, at least about 200 ° C, at least about 250 ° C, at least about 300 ° C, at least about 350 ° C, between about 200 ° C and about 250 ° C, between about 200 ° C and about 400 ° C, between about 250 ° C and about 400 ° C, and between about 250 ° C and about 350 ° C; generate subcritical or supercritical steam regardless of the sludge; and contacting the sludge with subcritical or supercritical vapor, in at least one container or chamber of said reactor apparatus. The sludge can be pressurized before and / or after said contact.
[00029] In an embodiment of the first, second, third and fourth aspects, the temperature is between about 300 ° C and about 380 ° C and the pressure is between about 20 MPa (200 bar) and about 30 MPa ( 300 bar).
[00030] In an embodiment of the first, second, third and fourth aspects, the treatment comprises the use of at least one additional catalyst.
[00031] In an embodiment of the first, second, third and fourth aspects, the at least one additional catalyst is a basic additional catalyst.
[00032] In an embodiment of the first, second, third and fourth aspects, the additional basic catalyst is an alkali metal hydroxide catalyst or a transition metal hydroxide catalyst.
[00033] In an embodiment of the first, second, third and fourth aspects, the additional basic catalyst is sodium hydroxide or potassium hydroxide.
[00034] In an embodiment of the first, second, third and fourth aspects, the treatment is carried out under continuous flow conditions.
[00035] In an embodiment of the first, second, third and fourth aspects, the treatment comprises the use of at least one additional catalyst that improves the incorporation of hydrogen in said organic matter.
[00036] In an embodiment of the first, second, third and fourth aspects, the catalyst that improves hydrogen incorporation is selected from the group consisting of alkali metal catalysts, transition metal catalysts, acid catalysts reactive carboxylic, transition metal catalysts including their hydrides, sulfide catalysts, noble metal catalysts including their hydrides, gas-water displacement catalysts, and combinations thereof.
[00037] In an embodiment of the first, second, third and fourth aspects, the catalyst is the sodium formate.
[00038] In an embodiment of the first, second, third and fourth aspects, the catalyst is a low-valence iron species including its hydrides, homogeneous zero-valence iron species, and heterogeneous zero-valence iron species.
[00039] In an embodiment of the first, second, third and fourth aspects, the treatment comprises the use of at least one additional catalyst that improves the removal of oxygen from said organic matter.
[00040] In an embodiment of the first, second, third and fourth aspects, the catalyst that improves the removal of oxygen from said organic matter is selected from the group consisting of alkali metal catalysts, metal catalysts transition catalysts, reactive carboxylic acid catalysts, transition metal catalysts including their hydrides, sulfide catalysts, noble metal catalysts including their hydrides, gas-water displacement catalysts, and combinations thereof.
[00041] In an embodiment of the first, second, third and fourth aspects, the organic matter is fossilized organic matter that has a carbon content of at least 50%, and said solvent is an oil comprising less than 50% by weight of Water.
[00042] In an embodiment of the first, second, third and fourth aspects, organic matter is fossilized organic matter that has a carbon content of at least 60%, and said solvent is an oil comprising less than 50% by weight of Water.
[00043] In an embodiment of the first, second, third and fourth aspects, the organic matter is lignite, the temperature is between about 330 ° C and about 350 ° C and the pressure is between about 16 MPa (160 bar) and about 25 MPa (250 bar).
[00044] In an embodiment of the first, second, third and fourth aspects, the organic matter is lignocellulosic biomass, the temperature is between about 330 ° C and about 350 ° C and the pressure is between about 16 MPa (160 bar) and about 25 MPa (250 bar).
[00045] In an embodiment of the first, second, third and fourth aspects, the treatment is for a period of time of at least about 5 minutes.
[00046] In an embodiment of the first, second, third and fourth aspects, the treatment lasts between 5 minutes and 25 minutes.
[00047] In an embodiment of the first, second, third and fourth aspects, the treatment lasts between 5 minutes and 60 minutes.
[00048] In an embodiment of the first, second, third and fourth aspects, the treatment lasts between 10 minutes and 20 minutes.
[00049] In an embodiment of the first, second, third and fourth aspects, the treatment lasts a period of about 15 minutes.
[00050] In an embodiment of the first, second, third and fourth aspects, the fuel comprises an oil component having a calorific value of more than 35 MJ / kg.
[00051] In an embodiment of the first, second, third and fourth aspects, the fuel comprises an oil component having a calorific value of more than 37 MJ / kg.
[00052] In an embodiment of the first, second, third and fourth aspects, the fuel comprises an oil component having a calorific value of more than 40 MJ / kg.
[00053] In an embodiment of the first, second, third and fourth aspects, the organic matter is in the form of a sludge comprising at least 30% by weight of said organic matter.
[00054] In an embodiment of the first, second, third and fourth aspects, the organic matter is in the form of a sludge, comprising at least 40% by weight of said organic matter.
[00055] In an embodiment of the second, third and fourth aspects, the solvent comprises at least about 30% by weight of oil.
[00056] In an embodiment of the second, third and fourth aspects, the solvent comprises at least about 40% by weight of oil.
[00057] In an embodiment of the second, third and fourth aspects, the solvent comprises at least about 50% by weight of oil.
[00058] In an embodiment of the second, third and fourth aspects, the solvent comprises at least about 60% by weight of oil.
[00059] In an embodiment of the second, third and fourth aspects, the solvent comprises at least about 70% by weight of oil.
[00060] In an embodiment of the first, second, third and fourth aspects, the oil is selected from the group consisting of paraffinic oil, diesel, crude oil, synthetic oil, tar oil, shale oil, kerosene oil, mineral oil, white mineral oil, and aromatic oil.
[00061] In an embodiment of the first, second, third and fourth aspects, the oil is recycled from the fuel.
[00062] In an embodiment of the second, third and fourth aspects, said treatment provides a fuel product comprising a first oil phase comprising: oil from said oil-based solvent and oil derived from said organic matter, an aqueous phase comprising dissolved organic compounds; and a solid phase comprising a calorific coal.
[00063] In an embodiment of the second, third and fourth aspects, said treatment additionally provides a gas phase.
[00064] In an embodiment of the fourth aspect, said cooling and release provides a fuel product comprising a first oil phase comprising: oil from said oil-based solvent and oil derived from said organic matter, a phase aqueous comprising dissolved organic compounds; and a solid phase comprising a calorific coal.
[00065] In an embodiment of the first aspect, said release additionally provides a gas phase.
[00066] In an embodiment of the first, second, third and fourth aspects, said fuel product further comprises a second oil phase comprising oil which is more polar than the oil of said first oil phase.
[00067] In a fifth aspect, the invention provides a fuel produced by the method of the first, second or third aspects.
[00068] In an embodiment of the first, second, third, fourth and fifth aspects, fuel is an oil. Brief Description of Drawings
[00069] A preferred embodiment of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which:
[00070] Figure 1 is a schematic flowchart illustrating an apparatus for converting organic matter into diesel according to an embodiment of the invention. Box numbers 1-12 correspond to chains 1-12 shown in Table 1 below (left column) that provides exemplary characteristics of the chain composition.Table 1: Characteristics of the composition of an exemplary chain using a particular biomass raw material .

[00071] Recycle ratios can be adjusted, shown here Mud oil: biomass i Conversion selectivity (all on dry basis): Supported in water (Humic, etc.) 6% in weight Oil yield (including usable fraction supported by water) (16B) 44% by weight Gas yield 50% by weight
[00072] To start a plant with 20% by weight of moisture in the feed biomass: 200,000 dry (0% humidity) tons per year, equivalent to 250,000 wet tons per year Residence time: 8 min Flow rate / hour: 31 , 6 tons / h Assume all densities equal to 1 Reactor volume: | 8.4 mJ Oil (16B) per hour: 11 tons / h Tube i.d. 24 inches Reactor length: 28.8 m Definitions
[00073] As used in this application, the singular form "one", "one" and "o" includes plural references unless the context clearly dictates otherwise. For example, the term "catalyst" also includes a plurality of catalysts.
[00074] As used herein, the term "comprising" means "including". Variations of the word "comprising", such as "understand" and "understand", have correspondingly varied meanings. Thus, for example, a material "comprising" oil may consist exclusively of oil or may include other additional substances.
[00075] As used herein, the terms "organic matter" and "organic materials" have the same meaning and include any material comprising carbon, including both fossilized and non-fossilized materials. Non-limiting examples of organic matter include lignocellulosic biomass, and materials containing hydrocarbons (for example, lignite, peat and shale oil).
[00076] As used herein, the term "fuel" refers to a material containing energy derived from the processing of organic matter. Non-limiting examples of fuels include oils, coal products (also known as improved pulverized coal injection (PCI) equivalent products), gaseous products, diesel, and alcohols (for example, ethanol and butanol).
[00077] As used herein, the term "oil" will be understood to cover oil products derived from the processing of fossilized organic material (for example, coals such as lignite), non-fossilized organic material (for example, lignocellulosic), or mixtures thereof.
[00078] As used herein, the terms "lignocellulosic matter" and "lignocellulosic biomass" are used interchangeably and have the same meaning. The terms cover any substance comprising lignin, cellulose and hemicellulose.
[00079] As used herein, the term "aqueous solvent" refers to a solvent that comprises at least one percent water based on the total weight of the solvent. An "aqueous solvent" can therefore comprise between one percent water and one hundred percent water based on the total weight of the solvent.
[00080] As used herein, the term "aqueous alcohol" refers to a solvent that comprises at least one percent alcohol based on the total weight of the solvent.
[00081] As used herein, the term "aqueous ethanol" refers to a solvent that comprises at least one percent ethanol based on the total weight of the solvent.
[00082] As used herein, the term "aqueous methanol" refers to a solvent that comprises at least one percent methanol based on the total weight of the solvent.
[00083] As used herein, the term "oil-based solvent" refers to a solvent comprising any suitable oil, non-limiting examples of which include paraffinic oil, diesel, petroleum, synthetic oils, coal oil, petroleum oil shale / kerogen, aromatic oils (i.e., single or multiple ring components or mixtures thereof), extractable ethers, extractable hexanes and any mixture of any of the above components.
[00084] As used herein, a "supercritical" substance (for example, a supercritical solvent) refers to a substance that is heated above its critical temperature and pressurized above its critical pressure (that is, a substance at a temperature and pressure above the temperature and pressure of its critical point).
[00085] As used herein, a "subcritical" substance (for example, a subcritical solvent) refers to a substance, at a temperature and / or pressure below the critical point of the substance. Thus, a substance can be "subcritical" at a temperature below its critical point and a pressure above its critical point, at a temperature above its critical point and a pressure below its critical point, or at a temperature and pressure below its critical point.
[00086] As used herein, an "additional catalyst" is a catalyst that is complementary to catalytic compounds intrinsically present in the organic matter treated according to the methods of the invention, catalytic compounds intrinsically present in an oil-based solvent used according to with the methods of the invention, and / or catalytic compounds intrinsically present in the walls of the reactor apparatus used to carry out the methods of the invention.
[00087] As used herein, the term "intrinsic catalyst" will be understood to be a catalyst that is naturally present in a particular reaction component such as, for example, any one or more of organic raw material, an aqueous solvent, and / or the walls of the receptacles of a reactor apparatus.
[00088] It will be understood that the use of the term "about" used here refers to a recited numerical value (for example, a temperature or pressure) includes the recited numerical value and numerical values within plus or minus ten percent of the value recited.
[00089] It will be understood that the use of the term "between", when referring here to a range of numerical values encompasses the numerical values at each end of the range. For example, a temperature range between 10 ° C and 15 ° C is included from temperatures 10 ° C and 15 ° C.
[00090] Any description of a prior art document here, or an indication derived here or based on the same document, is not an admission that the derived document or indication is part of the general common knowledge of the relevant technique.
[00091] For the purposes of description, all documents cited herein are incorporated by reference in their entirety, unless otherwise indicated. Detailed Description of the Invention
[00092] Current methods for producing oil from organic matter suffer from a number of disadvantages.
[00093] In addition to the generally high oxygen content and poor stability of most oils, the need to carry out depolymerization reactions at high temperature and pressure requires a reactor device (for example, continuous flow reactors, batch reactors and the like) ) introducing additional difficulties.
[00094] For example, water is generally used as the main depolymerization agent in hydrothermal liquefaction processes (for example, hydrothermal enhancement (HTU) and hydrothermal catalytic reactor technology (Cat-HTR)). The use of water limits the concentration of organic matter (for example, lignocellulosic biomass) that can be used in the raw material in mud in a reactor due to swelling. In addition, high energy levels are required to heat the water to the reaction temperature (and keep it there), resulting in carbonization inside the reactor vessel walls. Although the use of a suitable co-solvent such as ethanol provides a potential means to reduce carbonization, it also significantly increases the overall cost of the process. Ballistic heating is another method that can be used to minimize carbonization. This process involves the rapid convergence of two distinct currents (a stream of mud and a stream of sub / supercritical water) in a ballistic heating chamber. However, the cost of the supercritical boiler used in ballistics heating and the associated water de-ionization stage have a significantly adverse effect on cost efficiency.
[00095] Another disadvantage of oil production, by hydrothermal liquefaction of organic matter is that the product typically comprises several layers of oil with different chemical properties. Separating the different layers can be difficult and requires additional resources.
[00096] The present invention relates to the unexpected discovery that at least one of the aforementioned disadvantages can be alleviated by incorporating oil in solvents used in hydrothermal liquefaction processes. Without limitation to a particular mechanism of action, it is postulated that the reactive depolymerization agent (water) in these processes depolymerizes the organic raw material (for example, lignocellulosic biomass, peat, lignite and the like) by reaction with its bonds containing oxygen in a reaction commonly referred to as hydrolysis. Water is also the processing liquid that carries the raw material through the reactor assembly. Using the methods of the present invention, at least a portion of this processing liquid is changed to an oil, such as, for example, a non-reactive oil or a reactive oil (for example, multi-ring aromatics that can be reversibly hydrogenated ) that can effect hydrogen transfer, or a mixture of both. Although it is anticipated that the initial processing liquid ("start-up") may contain oil (s) (for example, paraffinic oil) and / or water from external sources, in operation in a permanent regime it is possible to execute the process using recycled oil and / or process water as a processing medium (as shown in Figure 1).
[00097] Therefore, certain aspects of the present invention relate to methods for the production of fuels by treating organic matter with oil-based solvents at elevated temperature and pressure. Additional aspects of the present invention relate to fuel products generated by the methods described herein.
[00098] The methods of the present invention are demonstrated to provide several notable advantages. For example, the proportion of raw material used in the mud can be much higher while the swelling of the raw material is prevented in the low temperature zone, where it is pressurized. This in turn allows for an increase in throughput and a significant reduction in the size of the reactor. Second, heat transfer to the oil is easier, reducing the energy required for the sludge. This in turn reduces carbonization and facilitates the use of smaller heat exchangers.
[00099] In addition, the liquefaction product is located in the oil layer and can be easily separated by centrifugation, eliminating the need to evaporate large amounts of water. The oil phase can also remove intermediate species from the water phase, influencing equilibriums, making it possible to adjust the reaction in order to produce more oil / more deoxygenated oils.
[000100] In general, the methods of the present invention facilitate the use of a much smaller plant in terms of heat exchangers, reactor size and / or product separation train (thus providing substantial cost savings in CapEx and / or OpEx). Organic matter
[000101] The present invention provides methods for converting organic matter into fuel. As used herein, "organic matter" (also referred to herein as "organic material") comprises any matter comprising carbon, including both fossilized and non-fossilized forms of matter comprising carbon.
[000102] There is no limitation as to the particular type of organic matter used in the methods of the invention, although it is contemplated that certain forms of organic matter (for example, fossilized organic matter), may be more suitable than others.
[000103] The organic matter used in the methods of the invention may comprise naturally occurring organic matter (for example, lignocellulosic biomass or fossil fuel materials, including lignite, shale oil, peat and the like) and / or synthetic organic materials (eg example, synthetic rubbers, plastics, nylons and the like). The organic matter used in the methods of the invention can comprise fossilized organic material (for example, lignite) and / or non-fossilized organic material (for example lignocellulosic material). In the event that more than one type (ie a mixture) of organic matter is used, there is no special limitation in relation to the proportion of the various components of the organic matter.
[000104] In some preferred embodiments, the organic matter used in the methods of the invention comprises fossilized organic matter. "Fossilized organic matter" ", as contemplated herein, includes any organic material that has been subjected to geothermal pressure and temperature for a period of time sufficient to remove water and concentrate carbon to significant levels.
[000105] For example, fossilized organic material can comprise more than about 10%, 20%, 30%, 40%, 503, 60%, 10%, 715%, 803%, 85%, 903 or 95% by weight of carbon. Preferably, the fossilized organic material may comprise more than about 50% by weight of carbon, more than about 60% by weight of carbon, or more than about 70% by weight of carbon. Non-limiting examples of such materials include coal (for example, anthracite coal such as meta-anthracite, anthracite and semianthracite; bituminous coal; sub-bituminous coal, lignite (ie brown coal), coking coal, coal tar, derivatives coal tar, coal, coke (for example, high temperature coke, foundry coke, low and medium temperature coke, pitch coke, petroleum coke, coke oven coke, coke powder, coke gas, brown coal coke, semi-coke), peat (for example, ground peat, turf turf), kerogen, bituminous sands, bituminous shale, tar shale, asphalt, asphaltene, natural bitumen, bituminous sand, or any combination of these.
[000106] In other preferred embodiments, the organic material used in the methods of the invention comprises lignocellulosic material. As used herein, "lignocellulosic material" refers to any substance comprising lignin, cellulose and hemicellulose.
[000107] For example, lignocellulosic material can be a woody plant or one of its components. Examples of suitable woody plants include, but are not limited to, pine (Pinus radiata, for example), birch, eucalyptus, bamboo, beech, pine, fir, cedar, poplar, willow and poplar. Woody plants can be woody plants cut into coppice (for example, willow and poplar cut into coppice).
[000108] Additionally or alternatively, the lignocellulosic material can be a fibrous plant or one of its components. Non-limiting examples of fibrous plants (or their components) include grasses (eg grasses), grass clippings, flax, corncob, corn straw, cane, bamboo, bagasse, hemp, sisal, jute, cannibas, flax, straw, wheat straw, banana, cotton plant, quenafe, rice husk, and coconut hair.
[000109] Additionally or alternatively, lignocellulosic material can be derived from an agricultural source. Non-limiting examples of lignocellulosic material from agricultural sources include agricultural crops, residues of agricultural crops, and residues from grain processing facilities (eg, wheat / oat hulls, corn fines, etc.). lignocellulosic from agricultural sources may include hardwood, softwood, wooden stems, softwood stems, nutshells, twigs, shrubs, walking sticks, corn, corn husks, corn husks, energy crops, forests, fruits, flowers, grains, grasses, herbaceous crops, "wheat straw, forage grass, salix, cane bagasse, cottonseed hair, leaves, bark, needles, trunks, roots, seedlings, short-rotation woody crops, shrubs, forage grasses, trees, vines, cattle manure and pig waste.
[000110] Additionally or alternatively, the lignocellulosic material can be derived from commercial or virgin forests (for example, trees, seedlings, forest or wood processing residues, pieces of wood such as branches, leaves, barks, trunks, roots, sheets and products derived from the processing of such materials, waste or by-product flows of wood products, sawmill and paper mill waste and cut waste, sawdust, and particle board).
[000111] Additionally or alternatively, lignocellulosic material can be derived from industrial products and by-products. Non-limiting examples include related wood materials and wood waste and industrial products (eg, cellulose, paper (eg, newspaper), papermaking sludge, cardboard, fabrics and cloths, dextran and rayon).
[000112] It will be understood that the organic material used in the methods of the invention can comprise a mixture of two or more different types of lignocellulosic material, including any combination of the specific examples provided above.
[000113] The relative proportion of lignin, hemicellulose and cellulose in a given sample will depend on the specific nature of the lignocellulosic material.
[000114] By way of example only, the proportion of hemicellulose in a woody or fibrous plant used in the methods of the invention can be comprised between about 15% and about 40%, the proportion of cellulose can be comprised between about 30% and about 60%, and the proportion of lignin can be between about 5% and about 40%. Preferably, the proportion of hemicellulose in the woody or fibrous plant can be between about 23% and about 32%, the proportion of cellulose can be between about 38% and about 50%, and the proportion of lignin can be between about 15% and about 25%.
[000115] In some embodiments, the lignocellulosic material used in the methods of the invention can comprise between about 2% and about 35% lignin, between about 15% and about 45 °; cellulose, and between about 10% and about 35% hemicellulose.
[000116] In other embodiments, the lignocellulosic material used in the methods of the invention can comprise between about 20% and about 35% lignin, between about 20% and about 45%; cellulose, and between about 20% and about 35% hemicellulose.
[000117] In some embodiments, the lignocellulosic material may comprise more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% lignin.
[000118] In some embodiments, the lignocellulosic material may comprise more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% cellulose.
[000119] In some embodiments, the lignocellulosic material may comprise more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% hemicellulose.
[000120] The person skilled in the art will recognize that the methods described herein are not limited by the relative proportions of lignin, hemicellulose and cellulose in a given source of lignocellulosic material.
[000121] In certain embodiments of the invention, a mixture of organic material comprising lignite (lignite) and lignocellulosic material can be used in the methods of the invention. The lignocellulosic material of the mixture can, for example, comprise woody plant material and / or fibrous plant material. The proportion of lignite in the mixture can be greater than about 20%, 40%, 60% or 80%. Alternatively, the proportion of lignocellulosic matter in the mixture can be greater than about 20%, 40%, 60% or 80%.
[000122] In some preferred embodiments, the organic matter used in the methods of the invention comprises polymeric materials containing carbon, non-limiting examples of which include rubbers (for example, tires), plastics and polyamides (for example nylon).
[000123] Non-limiting examples of suitable rubbers include natural and synthetic rubbers, such as polyurethanes, styrene rubbers, neoprenes, polybutadiene, fluorine rubber, butyl rubbers, silicone rubbers, plantation rubbers, acrylate rubber, thiokols and rubbers nitrile.
[000124] Non-limiting examples of suitable plastic materials include PVC, polyethylene, polystyrene, terephthalate, polyethylene and polypropylene.
[000125] The organic matter used in the methods of the invention can comprise carbon-containing waste such as sewage, manure, household or industrial waste materials. Pre-treatment of organic matter
[000126] The organic matter used in the methods of the invention can optionally be pre-treated before the conversion of the matter into fuel.
[000127] It will be recognized that there is no strict requirement to perform a pre-treatment step when using the methods of the invention. For example, pretreatment of organic matter may not be necessary if it is obtained in the form of a liquid or in particulate form. However, it is contemplated that in many cases the pre-treatment of organic matter can be advantageous to reinforce the result of the fuel production methods described here.
[000128] In general, pre-treatment can be used to break the physical and / or chemical structure of organic matter, making it more accessible for various reagents used in the methods of the invention (for example, oil-based solvents, catalysts and the like) and / or other parameters of the reaction (eg heat and pressure). In certain embodiments, pre-treatment of organic matter can be carried out with the aim of increasing solubility, increasing porosity and / or reducing the crystallinity of sugar components (for example, cellulose). The pre-treatment of organic matter can be carried out using an apparatus such as, for example, an extruder, a pressurized container, or a batch reactor.
[000129] The pretreatment of organic matter may comprise physical methods, non-limiting examples of which include crushing, chopping, shredding, grinding (e.g. vibratory grinding), compression / expansion, agitation and / or pulse treatment electric field (PEF).
[000130] In addition or alternatively, the pre-treatment of organic matter may comprise physico-chemical methods, non-limiting examples of which include pyrolysis, steam explosion, fiber explosion by ammonia (AFEX), percolation with ammonia recycling ( ARP), and / or explosion with carbon dioxide. Pretreatment with a steam explosion can also involve agitation of organic matter.
[000131] In addition or alternatively, the pre-treatment of organic matter may comprise chemical methods, non-limiting examples of which include ozonolysis, acid hydrolysis (e.g., acid hydrolysis diluted using H2SO4, and / or HC1), alkaline hydrolysis (for example, diluted alkaline hydrolysis using sodium, potassium, calcium and / or ammonium hydroxides), oxidative delignification (ie, biodegradation of lignite catalyzed by the enzyme peroxidase in the presence of H202), and / or the solvation method organic (ie using a mixture of organic solvents with inorganic acid catalysts such as H2SO4, and / or HCl to break lignin-hemicellulose bonds).
[000132] In addition or alternatively, the pre-treatment of organic matter may comprise biological methods, non-limiting examples of which include the addition of microorganisms (for example, rot fungi) capable of degrading / decomposing various components of organic matter.
[000133] In some embodiments, the organic material used in the methods of the invention is the lignocellulosic material subjected to an optional pre-treatment step in which hemicellulose is extracted. Consequently, most hemicellulose (or even all hemicellulose) can be extracted from lignocellulosic material and the remaining material (predominantly containing cellulose and lignin) used to produce a fuel by the methods of the invention. However, it will be understood that this pre-treatment is optional and there is no requirement to separate hemicellulose from the lignocellulosic material when carrying out the methods of the invention. Suitable methods for separating hemicellulose from lignocellulosic material are described, for example, in document PCT with publication number W0 / 2010/034055, the entire content of which is incorporated herein by reference.
[000134] For example, hemicellulose can be extracted from lignocellulosic material by treating a sludge comprising lignocellulosic material (for example, 5% to 15% w / v solids concentration) to treatment with an aqueous solution of mild acid (for example, pH 6.5-6.9) at a temperature between about 100 ° C and about 250 ° C, a reaction pressure between about 2 and about 50 atmospheres, for about 5 about 20 minutes. The solubilized hemicellulose component can be separated from the remaining solid matter (containing predominantly cellulose and lignin), using any suitable means (for example, by using an appropriately sized filter). The remaining solid material can be used directly in the methods of the invention, or alternatively mixed with one or more other forms of organic matter (for example, lignite) for use in the methods of the invention. Mud characteristics
[000135] The organic material used according to the methods of the present invention is preferably treated in the form of a sludge. The sludge can be generated, for example, by generating a particulate form of organic matter (for example, by means of physical methods, such as those mentioned above and / or by other means) and mixing with a suitable liquid (for example , an aqueous solvent and / or an oil). Oil component
[000136] In some preferred embodiments of the invention, the sludge comprises organic matter mixed with an oil-based solvent. The oil can be any suitable oil, non-limiting examples of which include paraffinic oil, diesel, petroleum, synthetic oils, coal oil, shale oil / kerogen oil, aromatic oils (i.e., single or multiple ring components or their mixtures), extractable ethers, extractable hexanes and any mixture of any of the above components. The oil can be incorporated into the mud mixture at any point before the target reaction temperature and / or pressure is reached. For example, oil can be added to the sludge in a sludge mixing tank as shown in Figure 1. In addition or alternatively, the oil can be added to the sludge en route to a reactor and / or during heating / pressurizing the sludge.
[000137] In particularly preferred embodiments, the oil is an oil recycled from the process product. For example, some of the oil produced can be removed as a side chain and recycled in the mud.
[000138] There is no particular limitation on the proportion of oil in a sludge comprising the organic matter treated in "accordance with the methods of the present invention. For example, the sludge may comprise more than about 2% by weight of oil, more than about 5% by weight of oil, more than about 107 by weight of oil, or more than about 20, 30, 40, 50, 60 or 70% by weight of oil. can comprise less than about 98% by weight of oil, less oil than about 95% by weight, less than about 90% by weight of oil, or less than about 80, 70, 60, 50 , 40 or 30% by weight of oil.
[000139] In some preferred embodiments, the sludge comprises between about 40% by weight and about 50% by weight of oil. In other preferred embodiments, the sludge comprises about 45% by weight of oil.
[000140] In other preferred embodiments, the sludge comprises a 0.5-1 2-1 oil based raw material. The oil can be paraffinic oil. Organic matter component
[000141] In certain embodiments of the invention, the concentration of solid material in the mud can be less than about 85% by weight, less than about 75% by weight, or less than about 50% by weight. Alternatively, the concentration of solid matter may be more than about 10% by weight, more than about 20% by weight, more than about 30% by weight, more than about 40% by weight, more than than about 50% by weight, or more than about 60% by weight. In some preferred embodiments, the sludge comprises between about 35% by weight and about 45% by weight of oil. In other preferred embodiments, the sludge comprises about 40% by weight of oil or 39.5% by weight of oil.
[000142] The optimum particle size of solid components and the optimum concentration of solids in the mud may depend on factors such as, for example, the heat transfer capacity of the organic matter used (that is, the rate at which heat can transferred into and through individual particles), the desired rheological properties of the sludge and / or the sludge's compatibility with the component (s) of a given apparatus within which the methods of the invention can be carried out (for example , reactor tubes). The optimum particle size and / or concentration of solid suspended components used for the methods of the invention can be readily determined by one skilled in the art using conventional techniques. For example, a series of sludge can be generated, each sample in the series comprising different particle sizes and / or different concentrations of the solid components compared to the other samples. Each slurry can then be treated in accordance with the methods of the invention under a set of conserved reaction conditions. The particle size and / or Optimal concentration of the solid components can then be determined by analyzing and comparing the products generated from each slurry using state of the art standard techniques.
[000143] In certain embodiments of the invention, the particle size of solid components in the mud can be between about 10 microns and about 10,000 microns. For example, the particle size can be more than about 50, 100, 500, 750, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000 or 9000 microns. Alternatively, the particle size can be less than about 50, 100, 500, 750, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000 or 9000 microns. In some embodiments, the particle size is between about 10 microns and about 50 microns, between about 10 microns and about 100 microns, between about 10 microns and about 200 microns, between about 10 microns and about 500 microns, between about 10 microns and about 750 microns, or between about 10 microns and about 1000 microns. In other embodiments, the particle size is between about 100 microns and about 1000 microns, between about 100 microns and about 750 microns, between about 100 microns and about 500 microns, or between about 100 microns and about 250 microns. Water component
[000144] In certain embodiments of the invention, the water concentration in the sludge can be above about 80% by weight, above about 85% by weight, or above about 90% by weight. Thus, the water concentration can be greater than about 75% by weight, above about 70% by weight, above about 60% by weight, above about 50% by weight, above about 40 % by weight, or above about 30% by weight. In some embodiments, the water concentration is between about 90% by weight and about 95% by weight.
[000145] In some preferred embodiments, the sludge comprises between about 10% by weight and about 30% by weight of water. In other preferred embodiments, the sludge comprises about 20e by weight of oil or about 15% by weight of water.
[000146] In particularly preferred embodiments, water is recycled from the product of the process. For example, a portion of water present after completion of the reaction can be removed as a side stream and recycled into the suspension. Aqueous alcohol component
[000147] In certain embodiments of the invention, the sludge may contain one or more of different aqueous alcohols. However, it should be noted that the inclusion of alcohols is optional and not a requirement. For example, it may be convenient or preferable to use an aqueous alcohol solution as a solvent, when the organic material used in the methods consists of, or comprises, a significant amount of lignocellulosic material and / or other materials, such as plastics and rubber, due to strong chemical bonds in these types of organic matter.
[000148] Suitable alcohols can contain between one and about ten carbon atoms. Non-limiting examples of suitable alcohols include methanol, ethanol, isopropyl alcohol, isobutyl alcohol, pentyl alcohol, isohexanol and hexanol.
[000149] The sludge may comprise more than about 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30r by weight, 35% by weight, 40% by weight , 45% by weight of alcohol or 50% by weight of aqueous alcohol.
[000150] In certain embodiments, the solvent comprises a mixture of two or more aqueous alcohols. Preferably, the alcohol is ethanol, methanol or a mixture thereof. Catalysts
[000151] According to the methods of the invention, organic matter can be treated with a solvent containing the oil under conditions of increased temperature and pressure to produce a fuel product. The treatment can be improved by the use of one or more additional catalysts. Although some catalysts may be an intrinsic component of organic matter (for example, mineral salts), solvent (for example, hydronium / water ions hydroxide, compounds in oil), and / or vessel walls of a reactor in which the organic matter can be treated (for example, transition / noble metals), the invention contemplates the use of additional catalyst (s) to increase the production of fuels from organic material.
[000152] Therefore, certain embodiments of the invention relate to the production of fuels from organic matter, by treatment with a solvent containing oil under conditions of increased temperature and pressure, in the presence of at least one additional catalyst. By "additional catalyst" it is understood that the catalyst is complementary to the catalytic compounds intrinsically present in the organic matter, solvent containing oil and / or walls of a reactor apparatus.
[000153] For example, an embodiment of the invention in which a raw material is treated with an oil-based solvent (only), under conditions of increased temperature and pressure in a reactor, would not be considered to use an "additional catalyst" .
[000154] In contrast, an embodiment of the invention, in which a raw material is treated with an oil-based solvent, in the presence of an additional base catalyst (eg sodium hydroxide), under conditions of increased temperature and pressure in a reactor, it would be considered to use an "additional catalyst."
[000155] Although the use of additional catalyst (s) may be advantageous in certain circumstances, the person skilled in the art will recognize that the methods of the invention can be performed without using them.
[000156] An additional catalyst as contemplated herein, can be any catalyst that improves the formation of fuel from organic matter, using the methods of the invention, non-limiting examples of which include basic catalysts, acid catalysts, metal hydroxide catalysts alkali, transition metal hydroxide catalysts, alkali metal formate catalysts, transition metal formate catalysts, reactive carboxylic acid catalysts, transition metal catalysts, sulfide catalysts, noble metal catalysts, gas displacement catalysts -water, and their combinations. Suitable catalysts are described, for example, in Australia's provisional patent application number 2010901473 entitled "Methods for the production of biofuels", the entire content of which is incorporated herein by reference.
[000157] The optimum amount of an additional catalyst used in the methods of the invention may depend on a variety of factors, including, for example, the type of organic matter being treated, the volume of organic matter being treated, the solvent used, the temperature and specific pressure used during the reaction, the type of catalyst and the desired properties of the fuel product. Following the methods of the invention, the optimum amount of an additional catalyst to be used can be determined by one skilled in the art without inventive effort.
[000158] In certain embodiments, an additional catalyst or combination of additional catalysts can be used in an amount between about 0.1% and about 10% w / v of catalysts, between about 0.1% and about 7 , 5% w / v catalysts, between about 0.1% and about 5% w / v catalysts, between about 0.1% and about 2.5% w / v catalysts, between about 0.1% and about 1% w / v catalysts, or between about 0.1% and about 0.5% w / v catalysts (relative to the solvent).
[000159] In general, catalysts can be used to create or assist in the formation and / or maintenance of a reducing environment favoring the conversion of organic matter into fuel. The reducing environment can favor the hydrolysis of organic matter, direct the substitution of oxygen with hydrogen, and / or stabilize the fuel formed.
[000160] Treatment under subcritical conditions (as opposed to supercritical conditions) can be advantageous in that less energy is required to perform the methods and the components of the reaction can be better preserved during treatment. When using subcritical conditions, it is contemplated that the additional use of one or more catalysts can be particularly beneficial for increasing fuel efficiency and / or quality. In addition, the cost benefits of reducing energy input (ie maintaining sub-critical conditions instead of super-critical conditions) and solvent preservation can significantly outweigh the additional cost incurred by additionally including one or more of the catalysts described herein.
[000161] It is contemplated that, under conditions of high temperature and pressure, the water molecules in the solvent can dissociate into acidic (hydronium) and basic (hydroxide) ions, facilitating the hydrolysis of the solid matter under treatment (that is, transformation solid to liquid). In certain embodiments, the temperature and pressure at which the reaction is carried out can be high enough for the desired levels of hydrolysis to occur, without the use of additional catalysts. In other cases, the temperature and pressure at which the reaction is carried out may not be high enough for desired levels of hydrolysis to occur without the additional addition of catalysts.
[000162] Additional catalysts can be hydrolysis catalysts. In certain embodiments, hydrolysis catalysts can be basic catalysts. Any suitable basic catalyst can be used.
[000163] Non-limiting examples of basic catalysts suitable for hydrolysis include alkali metal salts, transition metal salts, organic bases and mixtures thereof.
[000164] Alkali metal salts or transition metal salts can comprise any / any inorganic anion (s), non-limiting examples of which include sulfate, sulfite, sulfide, disulfide, phosphate, aluminate, nitrate, nitrite, silicate, hydroxide, methoxide, ethoxide, alkoxide, carbonate and oxide.
[000165] Preferred alkali metal or transition metal salts are sodium, potassium, iron, calcium and barium salts, and may comprise one or more anions selected from phosphate, aluminate, silicate, hydroxide, methoxide, ethoxide , carbonate, sulfate, sulfide, disulfide and oxide.
[000166] Non-limiting examples of suitable organic bases include ammonia, basic and polar amino acids (e.g., lysine, histidine, arginine), benzathine, benzimidazole, betaine, cinchonidine, cinchonine, diethylamine, diisopropylethylamine, ethanolamine, ethylenediamine, imidazole, methylamine, N-methylguanidine, N-methylmorpholine, N-methylpiperidine, phosphazene bases, picoline, piperazine, procaine, pyridine, quinidine, quinoline, trialkylamine, tributylamine, triethylamine, trimethylamine and mixtures thereof.
[000167] In certain embodiments, hydrolysis catalysts can be acid catalysts although it is recognized that acid catalysts can generally be slower to catalyze the hydrolysis of organic matter than basic catalysts. Any suitable acid catalyst can be used.
[000168] Non-limiting examples of acid catalysts suitable for hydrolysis include liquid mineral acids, organic acids, and mixtures thereof. Liquid mineral acids and organic acids can comprise any / any inorganic anion (s), non-limiting examples of which include aluminate, sulfate, sulfite, sulfide, phosphate, phosphite, nitrate, nitrite, silicate, hydroxide and alkoxide (under supercritical or quasi-supercritical conditions), and carbonate and carboxy group anions.
[000169] Non-limiting examples of suitable organic acids include acetic acid, butyric acid, caprylic acid, citric acid, formic acid, glycolic acid, 3-hydroxypropionic acid, lactic acid, oxalic acid, propionic acid, succinic acid, uric acid, and their mixtures.
[000170] In certain embodiments, the hydrolysis acid catalyst (s) can be present in minerals of organic matter and / or derivatives of the in situ formation of carboxylic and / or phenolic acids during the treatment process.
[000171] In certain embodiments of the invention, a mixture of one or more acid hydrolysis catalysts and one or more basic hydrolysis catalysts can be used to increase the hydrolysis of the solid matter under treatment.
[000172] The methods of the invention can use catalysts for the hydrolysis of organic matter (as discussed in the previous paragraphs). Additionally or alternatively, the processes can use catalysts that increase and / or accelerate the removal of oxygen (directly or indirectly) from compounds of the organic matter under treatment. Removing oxygen can provide a number of beneficial effects, such as, for example, increasing the energy content and stability of the fuel produced.
[000173] An acid catalyst can be used to increase oxygen removal, for example, by dehydrating (eliminating) water. Thus, in certain embodiments, an acid catalyst can be used to improve hydrolysis, and to increase the removal of oxygen from the organic matter under treatment.
[000174] Any suitable acid catalyst can be used to increase oxygen removal. Non-limiting examples of acid catalysts suitable for oxygen removal include liquid mineral acids, organic acids, and mixtures thereof. Mineral acids and liquid organic acids can comprise any / any inorganic anion (s), non-limiting examples of which include aluminate, sulfate, sulfite, sulfide, phosphate, phosphite, nitrate, nitrite, silicate, hydroxide and alkoxide (under supercritical or quasi-supercritical conditions), carbonate anions and the carboxy group.
[000175] Non-limiting examples of suitable organic acids include acetic acid, butyric acid, caprylic acid, citric acid, formic acid, glycolic acid, 3-hydroxypropionic acid, lactic acid, oxalic acid, propionic acid, succinic acid, uric acid, and their mixtures.
[000176] In certain embodiments aluminosilicates, including hydrated forms (for example zeolites), can be used during the treatment of organic materials to aid in the dehydration (elimination) of water.
[000177] Additionally or alternatively, oxygen removal can be increased by thermal means involving decarbonylation of, for example, aldehydes (giving R3C-H and CO gas) and decarboxylation of carboxylic acids in the material under treatment (giving R3C-H and gas CO2). The speed of these reactions can be improved by the addition of acid catalysts and / or transition metals (noble). Any suitable transition or noble metal can be used, including those supported on solid acids. Non-limiting examples include Pt / Al2O3 / SiO2, Pd / Al2O3 / SiO2, Ni / Al2O3 / SiO2, and mixtures thereof.
[000178] Additionally, or alternatively, a combined acid and hydrogenation catalyst can be used to increase the removal of oxygen, for example, by hydrodeoxygenation (ie, the elimination of water (via the acid component) and the saturation of double bonds ( through metal components)). Any suitable acid and combined hydrogenation catalyst can be used, including those supported on solid acids. Non-limiting examples include Pt / Al2O3 / SiO2, Pd / Al2O3 / SiO2, Ni / Al2O3 / SiO2, Ni0 / Mo03, CO0 / MO03, NIO / O2, zeolites loaded with noble metals (eg ZSM-S5, Beta-ITQO 2), and their mixtures.
[000179] The methods of the invention can use catalysts that increase the hydrolysis of organic matter under treatment and / or catalysts that improve the removal of oxygen from organic matter compounds (as discussed in the previous paragraphs). Additionally or alternatively, the methods can use catalysts that increase the hydrogen concentration (either directly or indirectly) in compounds of the organic matter under treatment. The concentration of hydrogen can provide a number of advantageous effects, such as, for example, increasing the energy content and stability of the fuel produced.
[000180] A hydrogenation catalyst by transfer can be used to increase the concentration of hydrogen in compounds of organic matter under treatment, for example, by hydrogenation by transfer, or by in situ generation of hydrogen.
[000181] Any suitable transfer hydrogenation catalyst can be used to increase the hydrogen concentration. Non-limiting examples of suitable transfer hydrogenation catalysts include alkali metal hydroxides (eg sodium hydroxide), transition metal hydroxides, alkali metal formats (eg sodium format), transition metal formats, acids reactive carboxylics, noble or transition metals, and mixtures thereof.
[000182] In certain embodiments, an additional sodium hydroxide catalyst is used in the reaction mixture at a concentration between about 0.1 M and about 0.5 M.
[000183] In other embodiments, catalysts of low-valence iron species (including their hydrides) are used in the reaction mixture, including homogeneous and heterogeneous zero iron species.
[000184] The alkali or shaped metal hydroxide can comprise any suitable alkali metal. Preferred alkali metals include sodium, potassium and mixtures thereof. The hydroxide or transition metal format can comprise any suitable transition metal, preferred examples including Fe and Ru. The reactive carboxylic acid can be any suitable carboxylic acid, preferred examples include formic acid, acetic acid, and mixtures thereof. The transition or noble metal can be any suitable transition or noble metal, preferred examples including platinum, palladium, nickel, ruthenium, rhodium and mixtures thereof.
[000185] Additionally, or alternatively, a transition metal catalyst can be used to increase the concentration of hydrogen in organic matter under treatment, for example, by hydrogenation with H2. Non-limiting examples of transition metal catalysts suitable for hydrogenation with H2 include zero-valence metals (eg, iron, platinum, palladium and nickel), transition metal sulphides (eg, iron sulphide (FeS, FezSy) , and their mixtures.
[000186] Additionally, or alternatively, a gas-water displacement catalyst can be used to increase the concentration of hydrogen in organic matter under treatment (ie, through a gas-water displacement reaction). Any suitable gas-water displacement catalyst (WGS) can be used, including, for example, transition metal oxides, transition metals and mixtures thereof (for example, magnetite, finely divided platinum, copper and nickel-based WGS catalysts) ).
[000187] Additionally or alternatively, the concentration of hydrogen in organic matter under treatment can be facilitated by gasification in situ (ie, thermal catalysis). In situ gasification can be increased by adding transition metals. Any suitable transition metal can be used, including, for example, those supported on solid acids (for example Pt / Al2O3 / SiO2, Pd / Al2O3 / SiO2,, Ni / Al2O3 / SiO2, and mixtures thereof), and sulfides transition metals (eg FexSy, FeS / Al203, FeS / SiO2, FeS / Al2O3 / SiO2, and mixtures thereof). Table 2 below provides a summary of the various exemplary catalysts that can be employed in the methods of the invention and the corresponding reactions that they can catalyze.Table 2: Summary of the catalysts and corresponding reactions.





[000188] Catalysts for use in the methods of the invention can be produced using chemical methods known in the art and / or purchased from commercial sources.
[000189] It will be understood that there is no particular limitation on the time that the additional catalyst (s) can be applied when performing the methods of the invention. For example, the catalyst (S) can be added to the organic matter, solvent, or a mixture of it (for example, a sludge) before heating / pressurizing until it reaches the reaction temperature and pressure during heating / pressurizing until the reaction temperature and pressure is reached, and / or after the reaction temperature and pressure is reached. The catalyst addition time may depend on the reactivity of the raw material used. For example, highly reactive raw materials can benefit from the addition of nearby catalyst or at the target reaction temperature and pressure, while less reactive raw materials may have a larger window for the catalyst addition process (ie. catalysts can be added before reaching the target reaction temperature and pressure). Reaction conditions
[000190] According to the methods of the invention, organic matter can be treated with an oil-based solvent under conditions of elevated temperature and pressure for the production of fuels.
[000191] The specific conditions of temperature and pressure used when practicing the methods of the invention may depend on several factors, including, for example, the type of oil-based solvent used, the type of organic matter under treatment, the physical form of the organic matter under treatment, the relative proportions of the components of the reaction mixture (for example, the proportion of water, oil, organic matter and any other additional component (s), such as, for example, catalyst (s) ) and / or alcohols), the types of catalysts used (if present), the retention time, and / or the type of apparatus on which the methods are carried out. These and other factors can be varied in order to optimize a given set of conditions in order to maximize throughput and / or reduce processing time. In preferred embodiments, all or substantially all of the organic material used as a raw material is converted into fuel.
[000192] The desired reaction conditions can be obtained, for example, by conducting the reaction in a suitable device (for example, a sub / supercritical reactor device) capable of maintaining high temperature and high pressure. Temperature and Pressure
[000193] According to the methods of the present invention, a reaction mixture is supplied and treated at a target temperature and pressure for a fixed period of time ("retention time"), facilitating the conversion of organic matter into oil. The temperature and / or pressure required to drive the conversion of organic material into diesel using the methods of the present invention will depend on a number of factors, including the type of organic matter under treatment and the relative proportions of the components of the reaction mixture being treated (eg , the proportion of water, oil, organic matter and any / any other additional component (s), such as, for example, catalyst (s) and / or alcohol (s). such as described here (see the subsection above entitled "Catalysts") can be used to increase the efficiency of reactions which can, in turn, reduce the temperature and / or pressure necessary to conduct the conversion of organic matter into fuel using a given oil-based solvent. Based on the description of the invention provided here the versed recipient can easily determine the reaction temperature and the appropriate pressure for a given mixture of re action. For example, the optimal reaction temperature and / or pressure for a given raw material sludge can be easily determined by the specialized recipient by preparing and executing a series of reactions that differ only by the temperature and / or pressure used and analysis of the efficiency and / or quality of the fuel produced.
[000194] The person skilled in the art will also recognize that the pressure used is a function of the sludge components and the pressure drop, induced by the sludge, and strongly dependent on any particular reactor design (for example, pipe diameter and / or length, etc.).
[000195] In certain embodiments, the treatment of organic matter for the production of fuels using the methods of the invention can be conducted at a temperature (s) between about 150 ° C and about 550 ° C and pressure (s) between about 1 Mpa (10 bar) and about 40 MPa (400 bar). Preferably, the reaction mixture is maintained at a temperature (s) between about 150 ° C and about 500 ° C and pressure (s) between about 8 Mpa (80 bar) and about 35 MPa (350 bar). More preferably, the reaction mixture is maintained at a temperature (s) between about 180 ° C and about 400 ° C and pressure (s) between about 10 Mpa (100 bar) and about 33 MPa (330 bar). Even more preferably, the reaction mixture is maintained at a temperature (s) between about 200 ° C and about 380 ° C and pressure (s) between about 12 MPa (120 bar) and about 25 Mpa (250 bar) .
[000196] In particularly preferred embodiments, the reaction mixture is maintained at a temperature (s) between about 200 ° C and about 400 ° C and pressure (s) between about 10 MPa (100 bar) and about 30 MPa (300 bar).
[000197] In other particularly preferred embodiments, the reaction mixture is maintained at a temperature (s) between about 250 ° C and about 380 ° C and pressure (s) between about 5 Mpa (50 bar) and about 30 MPa (300 bar).
[000198] In other particularly preferred embodiments, the reaction mixture is maintained at a temperature (s) between about 320 ° C and about 360 ° C and pressure (s) between about 15 Mpa (150 bar) and about 25 MPa (250 bar). In other particularly preferred embodiments, the reaction mixture is maintained at a temperature (s) between about 330 ° C and about 350 ° C and pressure (s) between about 23 Mpa (23 bar) and about 25 MPa (250 Pub). In another particularly preferred embodiment, the reaction mixture is maintained at a temperature (s) of about 340 ° C and a pressure (s) of about 24 MPa (240 bar).
[000199] In certain embodiments, the reaction mixture is maintained at a temperature (s) greater than about 180 ° C and a pressure (s) above about 15 MPa (150 bar). In other embodiments, the reaction mixture is maintained at a temperature (s) above about 200 ° C and a pressure (s) above about 18 Mpa (180 bar). In additional embodiments, the reaction mixture is maintained at a temperature (s) greater than about 250 ° C and a pressure (6es) above about 20 MPa (200 bar). In other embodiments, the treatment is carried out at a temperature (s) higher than about 300 ° C pressure (s) above about 25 MPa (250 bar). In other embodiments, the reaction mixture is maintained at a temperature (s) above about 350 ° C and a pressure (s) above about 30 MPa (300 bar).
[000200] It should be understood that, in certain embodiments, an oil-based solvent used in the methods of the invention can be heated and pressurized beyond its critical temperature and / or beyond its critical pressure (that is, beyond the "critical point" of the solvent). In this way, the solvent can be a "supercritical" solvent if heated and pressurized beyond the "critical point" of the solvent.
[000201] In certain embodiments, an oil-based solvent used in the methods of the invention can be heated and pressurized to levels below its critical temperature and pressure (i.e., below the "critical point" of the solvent). In this way, the solvent can be a "subcritical" solvent if its maximum temperature and / or its maximum pressure is lower than its "critical point". Preferably, the 'subcritical' solvent is heated and / or pressurized to levels that approach the "critical point" of the solvent (for example, between about 10 ° C to about 50 ° C below the critical temperature and / or. about 1.01 MPpa (10 atmospheres) to about 2.07 MPa (50 atmospheres) below its critical pressure).
[000202] In some embodiments, an oil-based solvent used in the methods of the invention can be heated and pressurized to levels both above and below its critical temperature and pressure (i.e. it is heated and / or pressurized both above and below the "point" of the solvent at different times). In this way, the solvent can oscillate between "subcritical" and "supercritical" states during the execution of the methods. Retention time
[000203] The specific period of time during which the conversion of organic matter can be achieved when reaching the target temperature and pressure (ie "retention time") can depend on several factors, including, for example, the type of oil-based solvent used, the percentage of alcohol (if present) in the solvent, the type of organic matter being treated, the physical form of the organic matter being treated, the type of catalyst (s) (if present) in the mixture and their various concentrations, and / or the type of apparatus on which the methods are performed. These and other factors can be varied in order to optimize a particular method in order to maximize throughput and / or reduce processing time. Preferably, the retention time is sufficient to convert all or substantially all of the organic material used as a raw material into fuel.
[000204] In certain embodiments, the retention time is less than about 60 minutes, 45 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes or less than about 5 minutes. In certain embodiments, the retention time is more than about 60 minutes, 45 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes or more than about 5 minutes. In other embodiments, the retention time is between about 1 minute and about 60 minutes. In additional embodiments, the retention time is between about 5 minutes and about 45 minutes, between about 5 minutes and about 35 minutes, between about 10 minutes and about 35 minutes, or between about 15 minutes and about 30 minutes. In other embodiments, the retention time is between about 20 minutes and about 30 minutes.
[000205] Those skilled in the art will recognize that various catalysts as described herein (see the subsection entitled "Catalysts" below) can be used to increase the effectiveness of the treatment, which in turn can reduce the retention time required to convert the organic matter in fuel. Likewise, the required retention time will be influenced by the proportions of the various components in the reaction mixture (for example, water, oil, alcohol, catalyst (s), etc.).
[000206] The optimal retention time for a given set of reaction conditions as described here can be easily determined by the person skilled in the art by preparing and executing a series of reactions that differ only by the retention time, and by analyzing the yield and / or quality of the fuel produced. Heating / cooling, pressurization / depressurization
[000207] A reaction mixture (for example, in the form of a sludge) comprising organic matter, oil-based solvent and, optionally, one or more catalysts, as defined herein can be brought to a temperature and pressure (or that is, the temperature / pressure maintained during the "retention time") over a given period of time.
[000208] Reaction mixtures that do not contain a significant proportion of oil may need a very fast initial conversion to generate some solvent in situ. However, the incorporation of oil into the reaction mixture as described herein allows the oil to act as a solvent thus alleviating the requirement for rapid heating / pressurization.
[000209] In continuous flow systems, the pressure will generally change from atmospheric pressure to the target pressure during the time it takes to get through the pump (ie closed for instantaneous), whereas in a batch system it will reflect the time it takes to heat the above mixture.
[000210] In some embodiments, the reaction mixture can be brought to a target temperature and / or pressure in a period of time between about 30 seconds and about 30 minutes.
[000211] In some embodiments, the reaction mixture can be brought to a target temperature and / or pressure in a period of time less than about 15 minutes, less than about 10 minutes, less than about 5 minutes , or less than about 2 minutes.
[000212] In certain embodiments, the reaction mixture can be brought to a target pressure substantially instantly and brought to a target temperature in less than about 20 minutes, less than about 10 minutes, or less than about 5 minutes. In other embodiments, the reaction mixture can be brought to a target pressure substantially instantly and brought to a target temperature in less than about two minutes. In other embodiments, the reaction mixture can be brought to a target pressure substantially instantly and brought to a target temperature between about 1 and about 2 minutes.
[000213] Additionally, or alternatively, after the completion of the retention period, the reaction mixture can be cooled to between about 150 ° C and about 200 ° C, between about 160 ° C and about 200 ° C, preferably between about 170 ° C and about 190 ° C, and more preferably about 180 ° C, in a period of time less than about 10 minutes, preferably less than about 7 minutes, more preferably less than about 6 minutes, preferably between about 4 and about 6 minutes, and more preferably about 5 minutes. After the initial cooling period, the temperature can still be reduced to room temperature, with concomitant depressurization by rapid release in an aqueous and cold medium (for example, cooling water).
[000214] The heating / cooling and pressurization / depressurization processes can be facilitated by carrying out the methods of the invention, in a continuous flow system (see the section entitled "Continuous Flow" below). Continuous flow
[000215] The production of fuels from organic matter using the methods of the invention can be assisted by carrying out the methods under continuous flow conditions.
[000216] Although the methods of the invention do not need to be carried out under continuous flow conditions, doing so can provide several advantageous effects. For example, continuous flow can facilitate accelerated implementation and / or removal of heat and / or pressure applied to the mud. This can help achieve the desired rates of mass and heat transfer, heating / cooling and / or pressurization / depressurization. The continuous flow can also allow the retention time to be strictly controlled. Without limitation to a particular mechanism of action, it is postulated that the increased heating / cooling and / or pressurization / depressurization speed, facilitated by continuous flow conditions, together with the ability to strictly regulate the retention time, helps in preventing occurrence of undesirable reactions (for example, polymerization) when the sludge heats / pressurizes and / or cools / depressurizes. It is also believed that the continuous flow improves reactions responsible for the conversion of organic matter into fuel due to the generation of agitation and shear forces that are believed to help emulsification, which can be an important mechanism involved in the transport and "storage" of oils generated away from the reactive surfaces of the raw material, as well as providing the surface area of the interface for the so-called "water catalysis".
[000217] Therefore, in preferred embodiments, the methods of the present invention are carried out under continuous flow conditions. As used herein, the term "continuous flow" refers to a process in which organic matter mixed with an oil-based solvent in the form of a sludge (with or without additional catalysts) is subjected to: (A) heating and pressurization at a target temperature and pressure, (B) treating the target temperature and pressure for a defined period of time (ie, the "holding time"), and (C) cooling and depressurizing, while the slurry is kept under a continuous moving current along the length (or partial length) of a given surface. It will be understood that "continuous flow" conditions, as contemplated herein, are defined by a starting point of heating and pressurization (i.e., (a) above) and by an end point of cooling and depressurization (i.e., (c ) above).
[000218] Continuous flow conditions, as contemplated herein, do not imply any particular limitation with respect to the speed of the mud flow, as long as it is maintained in a continuous movement current.
[000219] Preferably, the minimum flow rate (independent of volume) of the sludge over a given surface exceeds the speed of sedimentation of solid matter within the sludge (i.e., the terminal velocity at which a suspended particle having a density larger than the areas around the solution (by gravity) moves towards the bottom of the mud stream).
[000220] For example, the minimum flow rate of the sludge can be above about 0.01 cm / s, above about 0.05 cm / s, preferably above about 0.5 cm / s, and more preferably above about 1.5 cm / s. The higher flow rate can be influenced by factors such as volumetric flow rate and / or retention time. This, in turn, can be influenced by the components of a particular reactor used to maintain continuous flow conditions.
[000221] The continuous flow conditions can be facilitated, for example, by carrying out the methods of the invention, in a suitable reactor. A suitable reactor apparatus will generally comprise heating / cooling, pressurizing / depressurizing components and reaction components in which a continuous flow of sludge is maintained.
[000222] The use of an adequate flow rate (under continuous flow conditions) can be advantageous in preventing scale formation along the length of a particular surface on which the mud moves (for example, the walls of the reactor) and / or generating an effective mixing regime for efficient heat transfer within the sludge. Fuel products
[000223] The methods of the invention can be used for the production of fuels from organic matter. The nature of the fuel product may depend on a variety of factors, including, for example, the organic raw material, and / or conditions / reagents used in the reaction methods.
[000224] In certain embodiments, the fuel product may comprise one or more of the oil, coal oil (for example, carbon coal with bound oils), light soluble oil, gaseous products (for example methane, hydrogen, carbon monoxide and / or carbon dioxide), alcohol (for example, ethanol, methanol and the like), and diesel.
[000225] In certain embodiments, a fuel can be produced from fossil organic matter, such as, for example, lignite (white coal), shale oil or peat. The fuel can comprise the solid, liquid and gaseous phases. The solid phase can comprise a high-carbon coal (enhanced PCI equivalent coal). The liquid phase can comprise oils. The gaseous product may comprise methane, hydrogen, carbon monoxide and / or carbon dioxide.
[000226] In other embodiments, a fuel can be produced from organic material, comprising lignocellulosic material. The fuel may comprise a liquid phase that comprises oil.
[000227] Fuels (for example, oils) produced according to the methods of the invention may comprise a number of advantageous characteristics, non-limiting examples of which include reduced oxygen content, increased hydrogen content, increased energy content and increased stability. In addition, oils produced by the methods of the invention may comprise a single oil phase containing the liquefaction product. The product can be separated from the oil phase using, for example, centrifugation, eliminating the need to evaporate large amounts of water.
[000228] An oil product (also referred to herein as an "oil" product) produced according to the methods of the invention may comprise an energy content greater than about dθ 25 MJ / kg, greater than about 30 MJ / kg, more preferably greater than about 32 MJ / kg, more preferably greater than about 35 MJ / kg, even more preferably greater than about 37 MJ / kg, 38 MJ / kg, or 39 MyJ / kg, and more preferably greater at about 41 MJ / kg. The oil product may comprise less than about 15% by weight (dry base) of oxygen, preferably less than about 10% by weight (dry base) of oxygen, more preferably less than about 8% by weight. weight (dry basis) of oxygen and even more preferably less than about 7% by weight (dry basis) of oxygen, and preferably less than about 5% by weight (dry basis) of oxygen. The oil product may comprise more than about 6% by weight (dry basis) of hydrogen, preferably more than about 7% by weight (dry basis) of hydrogen, more preferably more than about 8% by weight. weight (dry basis) of hydrogen, and even more preferably greater than about 9% by weight (dry basis) of hydrogen. The hydrogen: carbon molar ratio of an oil of the invention can be less than about 1.5, less than about 1.4, less than about 1.3, or less than about 1.2.
[000229] An oil produced according to the methods of the invention can comprise, for example, any one or more of the following classes of compounds: phenols, aromatic and aliphatic acids, ketones, aldehydes, alcohols, hydrocarbons, esters, ethers, furans, furfurals, terpenes, polycyclics, oligo- and polymers from each of the categories mentioned above, plant sterols, modified plant sterols, asphaltenes, pre-asphaltenes, and waxes.
[000230] A coal or coal oil product produced according to the methods of the invention may comprise an energy content greater than about 20 MJ / kg, preferably greater than about 25 MJ / kg, more preferably greater than about 30 MJ / kg, and even more preferably greater than about 31 MJ / kg, 32 MJ / kg, 33 MJ / kg, or 34 MJ / kg. The coal or coal oil product may comprise less than about 20% by weight (dry basis) of oxygen, preferably less than about 15% by weight (dry basis) of oxygen, more preferably less than about 10% by weight (dry basis) of oxygen and even more preferably less than about 9% by weight (dry basis) of oxygen. The coal or coal oil product may comprise more than about 2% by weight (dry basis) of hydrogen, preferably more than about 3% by weight (dry basis) of hydrogen, more preferably more than about 4% by weight (dry basis) of hydrogen, and even more preferably more than about 5% by weight (dry basis) of hydrogen. The hydrogen: carbon molar ratio of a coal product or coal oil of the invention can be less than about 1.0, less than about 0.9, less than about 0.8, less than about 0, 7, or less than about 0.6.
[000231] A coal oil product produced according to the methods of the invention can comprise, for example, any one or more of the following classes of compounds: phenols, aromatic and aliphatic acids, ketones, aldehydes, alcohols, hydrocarbons, esters, ethers, furans, furfurals, terpenes, polycyclics, oligo- and polymers of each of the classes mentioned above, asphaltenes, pre-asphaltenes, and waxes.
[000232] A coal product (enhanced PCI equivalent coal) produced in accordance with the methods of the invention can comprise, for example, a mixture of amorphous carbon and graphite with partially oxygenated end groups, giving rise to carboxy- and alkoxy groups of surface, as well as carbonyl and esters.
[000233] Fuels produced according to the methods of the invention can be cleaned and / or separated into individual components using conventional techniques known in the art.
[000234] For example, the solid and liquid phases of the fuel product (for example, from the conversion of coal) can be filtered through a pressure filter press, or rotary vacuum drum filter, in a first stage of separation of solids and liquids. The solid product obtained may include a high carbon coal with bound oils. In certain embodiments, the oil can be separated from the coal, for example, by means of thermal distillation or by solvent extraction. The liquid product obtained may contain a low percentage of light oils, which can be concentrated and recovered through an evaporator.
[000235] The fuel produced according to the methods of the invention can be used in any number of applications. For example, fuels can be mixed with other fuels, including, for example, ethanol, diesel oil and the like. Additionally or alternatively, fuels can be transformed into combustible products. Additionally or alternatively, fuels can be used directly, for example, as petroleum products and the like.
[000236] It will be appreciated by persons skilled in the art that numerous variations and / or modifications can be made to the invention as shown in the specific embodiments, without departing from the spirit or scope of the invention as widely described. The present embodiments should therefore be considered in all respects as illustrative and not restrictive. Examples
[000237] The invention will now be described with reference to specific examples, which are not to be construed in any way as being limiting. Example 1: exemplary conversion of organic matter to a synthetic crude oil and / or lignite to a synthetic crude oil and processed coal product. (i) Mud Preparation
[000238] Pre-ground raw material (biomass containing 20% by weight of water, lignite containing 45-50% by weight of water) was mixed with paraffinic oil in a stirred mud formation tank with a raw material ratio press for paraffinic oil of 0.5-1.2: 1.
[000239] In the present case, paraffinic oil was used only in the starting phase and was progressively replaced by synthetic crude oils produced from the system described below.
[000240] In the case of lignocellulosic biomass, when only water was used as the mobile phase, preferred concentrations of pumpable sludge were about 20% solids, dry base (due to the increase in the volume of biomass in the water). The replacement of oil by at least part of the water in the mobile phase was used to increase the concentration of the pumpable sludge to approximately 40% solids (on a dry basis). This approximately halved both the size of the reactor and the heat required to achieve the desired reaction temperatures, due to the oil's thermal capacity of approximately 50% lower.
[000241] In the case of lignite, when water was used as the mobile phase, the concentration of water in the mud on a dry basis was in the order of 30%. Replacing the oil with at least part of the water in the mobile phase allowed for some increase in the concentration of pumpable sludge and benefited the overall heat balance (as above). (ii) Heating and pressurization
[000242] A high pressure pump was fed from the muddy tank to supply the sludge to the heating section with pressure ranges as shown in Table 3 below. The heating of the sludge can be carried out in several ways, for example, by a counter or co-current heat exchanger system and / or by immersing the heating section in a hot fluidized bed. Alternatively, the sludge can be heated in a ballistic manner by the intersection of the sludge in the heating section with a stream of oil or heated water, for example, in the range of 4000-720 degrees Celsius (see, for example, the PCT patent application number PCT / AU2011 / 000802, entitled "Ballistic heating process", all the content of which is incorporated by reference). In all cases, the target temperature of the mud was in the range of 250-350 degrees Celsius (centigrade) when entering the reactor. In certain cases, one or more catalysts were incorporated into the sludge before entering the reactor. (iii) Conversion reaction
[000243] The sludge was introduced into the reactor (which may have a vertical or horizontal orientation) under continuous flow conditions with the oil / biomass and / or oil / lignite being maintained at constant temperature and pressure within the ranges as shown in Table 3 below.
[000244] The residence time at the reaction temperature was maintained in the range of 10-25 min, depending on the raw material and the applied catalyst (s). As the reaction is slightly endothermic (3-5 MJ / kg of product), only a small amount of heat was required.
[000245] This experimental observation means that there is little restriction on the diameter of the reactor tube, since it does not need to be substantially heated; the thermal mass and coating of the reactor was sufficient. Another positive factor was the scaling of the system and keeping the reactor length to a minimum. Table 3: Non-limiting examples of process variables.
(iv) Refrigeration and Pressure Drop
[000246] At the end of the residence time, the product stream first passed through a heat exchanger with an outlet temperature in the range between 50-180 degrees Celsius (stage at which the reaction rates decrease substantially), this latter configuration temperature being dependent on raw material. This was followed by a
[000247] subsequent stage of pressure drop to atmospheric pressure. The pressure drop system was used to generate the back pressure in the reactor and heating system, allowing a continuous flow reaction to be achieved at a constant pressure and steady state temperature. A suitable pressure drop system is described, for example, in the International Patent Application (PCT) PCT / AU2010 / 001175, entitled "An assembly for reducing slurry pressure in a slurry processing system", all the content of which is incorporated herein by reference. (v) Results
[000248] It was observed that the substitution of water with heavy paraffinic oil provided a final oil phase that has only a single phase, instead of the expected / usual two layers of Oil (one being partially oxygenated oil (approximately 10-12 % by weight of oxygen) and the other being immiscible paraffin oil). This was observed to occur at a reaction temperature of 340 degrees Celsius, a residence time of 15 minutes and a pressure of 24 MPa (240 bar) in an oil / biomass sludge.
[000249] The partially oxygenated oil is not very soluble in paraffinic oil, since they are chemically different in nature. In contrast, the oil produced under the reaction conditions mentioned above is miscible with paraffinic oil and is, therefore, a much more chemically similar product (that is, less oxygenated and less polar).
[000250] It was also experimentally observed that the biomass sludge with oil, by keeping all things the same - but decreasing the temperature by 30 degrees Celsius, two phases of oil were observed. In addition, when the temperature was raised by 30 degrees Celsius, two layers of oil were also observed with solids present which were subsequently identified as very high melting polymeric biomass oils.
[000251] For these reasons, it is evident that at around 340 degrees centigrade and a residence time of 15 minutes, almost optimal conditions are reached for the production of oil with low oxygen. The pressure used is a function of the sludge components and the pressure drop, induced by the sludge, strongly dependent on any particular reactor design. In the current example, a pressure of 24 MPa (240 bar) was found to be optimal. However, the reaction itself is not very sensitive to pressure while water is predominantly present in its liquid form.
[000252] Furthermore, as these oils are very soluble in the oil phase, chemical balances are altered in comparison with the case when using water as a processing liquid. This is expected to lead to a more complete and improved conversion from lignite to oil as well.
[000253] When water was used as the mobile phase, the energy needed to heat the water to a reaction temperature in the heating system caused carbonization inside the heated tube wall - when both lignocellulosic biomass and lignite were processed using conventional heating (instead of ballistic). Carbonization inside the heated tube wall was not observed when the oil is used as the mobile phase. So far, the only way to avoid this carbonization when the biomass is processed with water as the mobile phase has been to add a co-solvent such as ethanol (very expensive) or to use ballistic heating. Ballistic heating requires that two currents converge quickly in a ballistic heating chamber; one stream being the stream of biomass sludge and unheated water and the second stream being a phase of supercritically heated water such that the final temperature of the combined streams is at the reaction temperature as they enter the reactor. The cost of the supercritical heater required with its inherent water deionization stage had a major negative impact on the plant's CAPEX, which is overcome by the current approach. Example 2: conversion of lignite from synthetic crude oil and from heated coal.
[000254] This example demonstrates the conversion of organic matter, in this case, lignite, to give a synthetic crude oil and a calorific coal. In this example, an aqueous solution of alcohol (ethanol) was included in the reaction. The reaction was carried out in a single pass through the reactor, with the emphasis on the use of a mineral oil as a mudding agent to promote the formation of oil-soluble compounds in the reaction. This is achieved by shifting the chemical balance towards oil-soluble products by capturing them from the water phase to the oil phase. Alcohol is present to assist in the formation of, for example, esters and ethers that are soluble in oil. The reaction also exemplifies the benefits of heat transfer by using a muddy medium with a substantial oil component and a substantial reduced water component.
[000255] The pre-ground water-lignite slurry (70% water) was still muddy with ethanol and white mineral oil in the slurry lignite / water: ethanol: mineral oil ratio of 5: 1: 4 by mass. The additional catalyst was sodium hydroxide at a concentration of 0.1 molar based on the total amount of water present. Reaction conditions were 24 Mpa (240 bar) pressure, 340 ° C and 25 minutes residence time. The heating of the sludge to the reaction temperature was carried out by mixing with supercritical steam in a "ballistic heating" as described above and, for example, in the PCT patent application number PCT / AU2011 / 000802, entitled "Ballistic heating process" ( all content of which is incorporated by reference). The following intrinsic catalysts were also present due to the contact between the sludge and the metal wall of the reactor: metallic iron, chromium, nickel, molybdenum, manganese, and the oxides, hydroxides, acetates, carbonates and hydrogen carbonates of these metals.
[000256] The reaction products after lowering the cooling pressure to room temperature and pressure were an oil phase containing the original mineral oil and a new oil derived from lignite (synthetic crude oil), an aqueous phase containing organic compounds dissolved, and a solid phase consisting of a calorific coal. A gaseous phase (producing gas) was also collected in the pressure lowering stage. Those skilled in the art will recognize that in case of repeated separation and cycle of part of the oily phase (mineral oil + synthetic crude oil) with new raw material, the mineral oil phase will eventually be almost completely replaced by synthetic crude oil, derived from lignite. Example 3: Conversion of Radiata pine wood flour to synthetic crude oil.
[000257] This example demonstrates the conversion of organic matter, in this case, pine radiata, to a synthetic crude oil. The reaction was carried out in a single pass through the reactor, with the emphasis on the use of a mineral oil as a mudding agent to promote the formation of oil-soluble compounds in the reaction. This was achieved by shifting the chemical balance towards oil-soluble products, capturing them from the aqueous phase to the oil phase. The reaction also exemplifies the benefits of heat transfer when using a muddy medium with a substantial oil component and a substantial reduced water component.
[000258] Radiata pine wood flour containing water was muddy with white mineral oil in the proportions: wood: water: mineral oil 2:17:17 by mass, where the wood mass is on an oven dried basis. The additional catalyst was sodium hydroxide at a concentration of 0.1 molar based on the total amount of water present. The reaction conditions were 24 MPa (240 bar) pressure, 340 ° C and 25 minutes residence time. The heating of the sludge to the reaction temperature was carried out by mixing with supercritical steam in a "ballistic heating" as described above and, for example, in PCT patent application number PCT / AU2011 / 000802, entitled "Ballistic heating process" (all the content of which is incorporated by reference here). The following intrinsic catalysts were also present due to the contact between the sludge and the metal wall of the reactor: metallic iron, chromium, nickel, molybdenum, manganese and the oxides, hydroxides, acetates, carbonates and hydrogen carbonates of these metals.
[000259] The products of the reaction after lowering the pressure and cooling to room temperature and pressure were an oil phase, less dense than the aqueous phase, containing both the original mineral oil and the new oil derived from wood (Crude oil synthetic I), a second, denser oil phase containing more polar derived wood oil (synthetic crude oil II), and an aqueous phase containing the dissolved organic compounds. A gaseous phase (producing gas) was also collected in the pressure lowering stage. Those skilled in the art will recognize that in case of repeated separation and cycle of a part of the light oil phase (mineral oil + synthetic crude oil I) with new raw material, the mineral oil phase will eventually be almost completely replaced by synthetic crude oil I, derived from wood.

权利要求:
Claims (23)
[0001]
1. Method for producing oil characterized by the fact that it comprises: producing a sludge comprising organic raw material, water and oil; treat the sludge in a reactor at a temperature between 200 ° C and 450 ° C and a pressure between 180 bar and 350 bar; and cooling the slurry and releasing said pressure, thereby providing a product comprising said oil, wherein the sludge comprises between 20% and 60% by weight of said oil.
[0002]
2. Method according to claim 1, characterized by the fact that the sludge comprises less than 40% by weight of said oil.
[0003]
3. Method according to claim 1 or 2, characterized by the fact that the sludge comprises between 20% and 40% by weight of said organic matter.
[0004]
Method according to any one of claims 1 to 3, characterized in that the sludge additionally comprises an aqueous alcohol selected from ethanol and / or methanol.
[0005]
5. Method, according to claim 4, characterized by the fact that the sludge comprises a percentage by weight of said alcohol of: between 5% by weight and 40% by weight, between 5% by weight and 30% by weight, between 5% by weight and 25% by weight, between 5% by weight and 20% by weight, between 5% by weight and 15% by weight, between 5% by weight and 10% by weight.
[0006]
Method according to any one of claims 1 to 5, characterized in that the organic raw material is lignocellulosic material, lignite or a combination thereof.
[0007]
Method according to any one of claims 1 to 6, characterized in that said treatment comprises contacting the sludge with a subcritical or supercritical vapor in a chamber of said reactor apparatus.
[0008]
Method according to any one of claims 1 to 7, characterized in that said treatment comprises contacting the slurry with a subcritical or supercritical vapor in a chamber of said reactor apparatus in which said slurry is at temperature and pressure environments or quasi-environments before said contact with subcritical or supercritical vapor.
[0009]
9. Method for producing fuel characterized by the fact that it comprises treating organic matter with an oil-based solvent comprising less than 50% by weight of water at a temperature between 200 ° C and 400 ° C, and a pressure between 100 bar and 300 bar.
[0010]
Method according to any one of claims 1 to 9, characterized in that said treatment comprises the use of at least one additional catalyst.
[0011]
Method according to claim 10, characterized in that at least one additional said catalyst is an additional basic catalyst, an alkali metal hydroxide catalyst, a transition metal hydroxide catalyst, sodium hydroxide or hydroxide of potassium.
[0012]
12. Method according to any one of claims 1 to 11, characterized in that said treatment is carried out under continuous flow conditions.
[0013]
13. Method according to any one of claims 1 to 12, characterized in that said treatment comprises the use of at least one additional catalyst that improves the incorporation of hydrogen in said organic matter.
[0014]
14. Method according to any one of claims 1 to 13, characterized by the fact that said treatment comprises the use of at least one of: (i) an additional catalyst that improves the removal of oxygen from said organic matter, or a low-valence iron species including its hydrides; (ii) homogeneous zero valence iron species, and heterogeneous zero valence iron species.
[0015]
15. Method according to claims 13 or 14, characterized in that (i) said catalyst which improves hydrogen incorporation is selected from the group consisting of alkali metal catalysts, transition, reactive carboxylic acid catalysts, transition metal catalysts including their hydrides, sulfide catalysts, noble metal catalysts including their hydrides, gas-water displacement catalysts, sodium formate and combinations thereof; (ii) said catalyst that improves oxygen removal from organic matter is selected from the group consisting of alkali metal format catalysts, transition metal shape catalysts, reactive carboxylic acid catalysts, transition metal catalysts including their hydrides , sulfide catalysts, noble metal catalysts including their hydrides, gas-water displacement catalysts, and combinations thereof.
[0016]
16. Method according to any one of claims 1 to 15, characterized in that said organic matter is fossilized organic matter having a carbon content of at least 50%, and said solvent is an oil comprising less than 50% by weight of water.
[0017]
17. Method according to any one of claims 1 to 16, characterized in that (I) said temperature is between 250 ° C and 350 ° C, and said pressure is between 100 bar and 300 bar; or (II) said temperature is between 320 ° C and 360 ° C, and said pressure is between 150 bar and 250 bar.
[0018]
18. Method according to any one of claims 1 to 17, characterized in that said treatment is for a period of time of at least 5 minutes, for a period of time between 5 minutes and 25 minutes, or for a time period of 15 minutes.
[0019]
19. Method according to any one of claims 1 to 18, characterized in that said organic matter is in the form of sludge comprising at least 30% by weight of said organic matter, or comprising at least 40% by weight of the said organic matter.
[0020]
20. Method according to claim 19, characterized in that the sludge comprises between 20% by weight and 60% by weight of oil.
[0021]
21. Method according to claim 19 or claim 20, characterized in that the sludge comprises an oil raw material ratio of 0.5-1.2: 1.
[0022]
22. Method according to any one of claims 1 to 21, characterized in that the oil is selected from the group consisting of paraffinic oil, diesel, crude oil, synthetic oil, tar oil, shale oil, kerosene oil, mineral oil, white mineral oil, and aromatic oil.
[0023]
23. Method according to any one of claims 1 to 22, characterized in that it comprises recycling said oil from the fuel for use in treating the additional raw material by said method.

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法律状态:
2018-03-20| B25C| Requirement related to requested transfer of rights|Owner name: LICELLA PTY LTD. (AU) , IGNITE ENERGY RESSOURCES LIMITED (AU) Free format text: A FIM DE ATENDER A TRANSFERENCIA, REQUERIDA ATRAVES DA PETICAO NO 860150161804 DE 28/07/2015, E NECESSARIO APRESENTAR DOCUMENTACAO QUE EVIDENCIE A TRANSFERENCIA REQUERIDA. Owner name: LICELLA PTY LTD. (AU) , IGNITE ENERGY RESSOURCES L |

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2018-05-29| B25C| Requirement related to requested transfer of rights|Owner name: LICELLA PTY LTD. (AU) , IGNITE ENERGY RESSOURCES LIMITED (AU) Free format text: A FIM DE ATENDER A TRANSFERENCIA, REQUERIDA ATRAVES DAS PETICOES NO 860150161804 DE 28/07/2015 E 860150192594 DE 28/08/2015, E NECESSARIO ESCLARECER A DIVERGENCIA ENTRE O QUE E SOLICITADO (TRANSFERENCIA DE UM DOS TITULARES PARA A CESSIONARIA) E O QUE E APRESENTADO NO DOCUMENTO DE CESSAO (TRANSFERENCIA DOS DOIS TITULARES PARA A CESSIONARIA). Owner name: LICELLA PTY LTD. (AU) , IGNITE ENERGY RESSOURCES L |

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2018-07-24| B25A| Requested transfer of rights approved|Owner name: IGNITE RESOURCES PTY LTD (AU) |

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2018-09-11| B25A| Requested transfer of rights approved|Owner name: IGNITE RESOURCES PTY LTD (AU) ; LICELLA PTY LTD E |

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2018-09-25| B25G| Requested change of headquarter approved|Owner name: IGNITE RESOURCES PTY LTD (AU) ; LICELLA PTY LTD E LICELLA FIBRE FUELS PTY LTD (AU) Owner name: IGNITE RESOURCES PTY LTD (AU) ; LICELLA PTY LTD E |

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2018-11-21| B25K| Entry of change of name and/or headquarter and transfer of application, patent and certificate of addition of invention: republication|Owner name: IGNITE RESOURCES PTY LTD (AU) ; LICELLA PTY LTD (A Free format text: RETIFICADO O DESPACHO 25.1 PUBICADO NA RPI 2488 DE 11/09/2018 SOB O ITEM (71). |

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2018-11-27| B25M| Limitations in changing the proprietorship|Owner name: IGNITE RESOURCES PTY LTD (AU) ; LICELLA PTY LTD (AU) ; LICELLA FIBRE FUELS PTY LTD (AU) Free format text: ANOTACAO DE LIMITACAO OU ONUSFICA ANOTADO, DE ACORDO COM O ART. 59, II, DA LPI, O ONUS DE SEGURANCA DE PROPRIEDADELICENCIADA PARAOCONTRATODE?JOINTVENTURE?, PROTOCOLADONAPETICAO870170035815 DE29/05/2017, ENTRE A CONCEDENTE ?LICELLA FIBRE FUELS PTY LTD? E A AVALIZADA ?CANFORPULP LTD. (CA)?, SENDO ?LICELLA PTY LIMITED?, ?IGNITE RESOURCES PTY LTD?, ?IGNITEENERGYRESOURCESLTD.? E?IGNITEENERGYRESOURCESENGINEERINGPTY.LIMITED?, AS LICENCIANTES. Owner name: IGNITE RESOURCES PTY LTD (AU) ; LICELLA PTY LTD (A Free format text: ANOTACAO DE LIMITACAO OU ONUSFICA ANOTADO, DE ACORDO COM O ART. 59, II, DA LPI, O ONUS DE SEGURANCA DE PROPRIEDADELICENCIADA PARAOCONTRATODE?JOINTVENTURE?, PROTOCOLADONAPETICAO870170035815 DE29/05/2017, ENTRE A CONCEDENTE ?LICELLA FIBRE FUELS PTY LTD? E A AVALIZADA ?CANFORPULP LTD. (CA)?, SENDO ?LICELLA PTY LIMITED?, ?IGNITE RESOURCES PTY LTD?, ?IGNITEENERGYRESOURCESLTD.? E?IGNITEENERGYRESOURCESENGINEERINGPTY.LIMITED?, AS LICENCIANTES. |

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2018-12-18| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-02-26| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-11-12| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-06-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-09-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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AU2011900020A|AU2011900020A0|2011-01-05|Processing of organic matter|

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AU2011900020|2011-01-05|

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PCT/AU2011/001624|WO2012092644A1|2011-01-05|2011-12-15|Processing of organic matter|

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