BIOFUEL PRODUCTION METHODS

专利摘要:
methods for biofuel production. The present invention generally relates to methods for producing biofuels from organic matter, methods comprising treating organic matter with an aqueous solvent and at least one additional catalyst under heat and pressure conditions. The present invention also relates to biofuel products obtainable by the methods.
公开号:BR112012026256B1
申请号:R112012026256-4
申请日:2011-04-07
公开日:2019-07-09
发明作者:Thomas Maschmeyer；Leonard James Humphreys
申请人:Ignite Resources Pty Ltd；Licella Pty Ltd；
IPC主号:

专利说明:

Invention Patent Description Report For: METHODS
FOR PRODUCTION OF BIOFUEL.
TECHNICAL FIELD
The present invention generally relates to the field of biofuel production. More specifically, the invention relates to methods for the production of
biofuels from the matter organic. The invention also refers to products biofuel obtainable by the methods. BACKGROUND OF THE INVENTION Global demand for energy to be continued growing
while conventional oil reserves (for example, natural gas liquids, and gas, oil) are declining. A spike in oil production imposed by declining oil reserves raises the possibility of a global energy crisis, especially if demand for energy continues to grow as predicted. Therefore, there is an increasing focus on the exploitation of previously unconventional fuel resources (for example, heavy oil, asphalt sands, oil shale) and other non-fossil energy sources (for example, lignocellulosic materials).
A significant amount of research in the field of alternative energy production has focused on the generation of biofuels from lignocellulosic material. This technology raises the possibility of a shift to an abundant and renewable food supply for energy production, as an alternative to depleting reserves of crude hydrocarbon-based materials. The enrichment of low energy density fossil fuels (eg lignite, peat and oil shale) in high energy fuel products also represents a certain attractive alternative to the relative abundance of these resources.
Although most techniques have considerable potential for producing fuels from lignocellulosic material or other unconventional materials, they are unprofitable and / or fail to provide fuel products of adequate quality to be commercially viable. For example, current processes for the production of biofuels from lignocellulosic material generally require the separation of the substrate for several different components through a series of complex and long steps, and in many cases, require the use of expensive and hydrolytic enzymes. fermentation microorganisms. In addition to these drawbacks, currently available processes are unable to use a significant proportion of the substrate material that is not converted into fuel and goes to waste. In addition, fuels produced by current processes typically comprise a significantly higher oxygen content than conventional fuels.
relatively
Because of this, its energy density is poor and its stability makes processing difficult (eg storage, mixing with conventional fuels, upgrading)
There is a need for improved methods of producing biofuels from organic matter that avoid one or more of the above disadvantages.
SUMMARY
THE INVENTION
In a first aspect, the invention provides a method for producing a biofuel, the method comprising treating organic matter with an aqueous solvent and at least one additional catalyst, at a temperature between about 250 ° C and about 400 ° C , and a pressure between about 100 bar and about 300 bar.
In a second aspect, the invention provides a method for producing a biofuel, the method comprising:
providing a reaction mixture comprising organic matter and an aqueous solvent, and;
treating said reaction mixture at a temperature between about 250 ° C and about 400 ° C, and a pressure between about 100 bar and about 300 bar in a reaction vessel;
wherein said reaction mixture comprises at least one additional catalyst that originates independently of other components of the reaction mixture and said reaction vessel.
In an embodiment of the first and second aspects, the additional catalyst is not present, or substantially is not present, in any one or more of the organic matter, the aqueous solvent, or a reactor vessel wall.
In another embodiment of the first and second aspects, the additional catalyst is also present in any one or more of the organic matter, the aqueous solvent, or a reactor vessel wall.
In an embodiment of the first and second aspects, the additional catalyst is an additional base catalyst.
In an embodiment of the first and second aspects, the additional base catalyst is an alkali metal hydroxide catalyst or a transition metal hydroxide catalyst.
In an embodiment of the first and second aspects, additional base catalyst is sodium hydroxide or potassium hydroxide.
In a modality of the first second aspects, biofuel is an oily product.
In a modality of the first second aspects, biofuel is a bio-oil.
In one of the first second aspects, bio-oil is derived from the processing of fossilized organic material (for example, coals, such as lignite).
In a modality of the first and second aspects, bio-oil is derived from non-fossilized organic material (for example, lignocellulosic material).
In another embodiment of the first and second aspects, the organic matter and aqueous solvent are treated in the form of a slurry.
In another modality of the first and second aspects, the treatment is carried out under continuous flow conditions.
In another embodiment of the first and second aspects, the slurry is subjected to:
(a) heating and pressurizing to a target temperature and pressure, (b) treating to target temperatures and pressures for a defined period of time (for example, the retention time), and (c) cooling and depressurizing,
under conditions continuous flow. In another modality of the first and second aspects, the speed minimum flow (volume independent) of the paste fluid under the said continuous flow conditions is greater
than the sedimentation rate of the solid matter inside the slurry.
In another modality of the first and second aspects, the speed minimum flow (volume independent) of the paste fluid under the said continuous flow conditions is above
0.01 cm / s.
In another modality of the first and second aspects, the speed minimum flow (volume independent) of the paste fluid under the said continuous flow conditions is above
0.05 cm / s.
In another modality of the first and second aspects, the speed minimum flow (volume independent) of the paste fluid under the said continuous flow conditions is above of about 0, 5 cm / s. In another modality of the first and second aspects, the speed minimum flow (volume independent) of the paste
fluid under said continuous flow conditions is above about 1.5 cm / s.
In an additional embodiment of the first and second aspects, the treatment comprises the use of at least one additional catalyst that improves the incorporation of hydrogen in the organic matter.
In an embodiment of the first and second aspects, the additional catalyst that improves the incorporation of hydrogen in organic matter is selected from the group consisting of alkali metal formate catalysts, transition metal formate catalysts, reactive carboxylic acid catalysts , transition metal catalysts, sulfide catalysts, noble metal catalysts, gas to water conversion catalysts, and combinations thereof.
In an embodiment of the first and second aspects, the additional catalyst that improves the incorporation of hydrogen into organic matter is sodium formate.
In an additional embodiment of the first and second aspects, the treatment comprises the use of at least one additional catalyst that further increases the removal of oxygen from organic matter.
In an additional embodiment of the first and second aspects, the additional catalyst originates independently of other reaction mixture components and said reaction vessel.
In an embodiment of the first and second aspects, the additional catalyst that improves the removal of oxygen from organic matter is selected from the group consisting of acid catalysts, transition metal catalysts, noble metal catalysts, transition, solid acid catalysts, and mixtures thereof.
In a first and second aspect, organic matter is fossilized organic matter with a carbon content of at least 50%, and the aqueous solvent is water.
In another embodiment of the first and second aspects, organic matter is fossilized organic matter with a carbon content of at least 60%, and the aqueous solvent is water.
In another embodiment of the first and second aspects, the temperature is between about 320 ° C and about 360 ° C, and the pressure is between about 200 bar and about 250 bar.
In another embodiment of the first and second aspects, the fossilized organic matter is lignite, the temperature is between about 340 ° C and about 360 ° C, and the pressure is between about 200 bar and about 240 bar.
In one embodiment of the first and second aspects, biofuel comprises one or more of an oily component, a carbonaceous residue component and a gaseous component comprising methane, hydrogen, carbon monoxide and carbon dioxide.
In a first and second aspect, organic matter is lignocellulosic material, and the aqueous solvent comprises alcohol.
In a modality of the first and second aspects, the lignocellulosic material comprises more than about 10% of each of lignin, cellulose, and hemicellulose.
In another embodiment of the first and second aspects, the temperature is between about 270 ° C and about 360 ° C, the pressure is between about 170 bar and about 250 bar, and the solvent comprises between about 5% and 4 0% alcohol by weight.
In a first and second aspect, organic matter is lignocellulosic material, the temperature is between about 300 ° C and about 340 ° C, the pressure is between about 200 bar and about 240 bar, and the solvent comprises between about 10% and about 30% by weight of alcohol.
In one of the first and second aspects, alcohol is ethanol.
In another modality of the first and second aspects, the treatment is for a period of time between about 20 minutes and about 30 minutes.
In another embodiment of the first and second aspects, the method comprises the step of heating organic matter and aqueous solvent to said temperature for a period of time less than about 2 minutes, before said treatment.
In another embodiment of the first and second aspects, the method comprises the step of heating and pressurizing the organic matter and aqueous solvent for said temperature and pressure for a period of time less than about 2 minutes, before said treatment.
In another modality of the first and second aspects:
(i) additional catalyst, (ii) additional catalyst that improves the incorporation of hydrogen into organic matter; and / or (iii) additional catalyst that improves the removal of oxygen from the organic matter, is added to the organic matter after said heating and pressurization.
In another modality of the first and second aspects:
(i) additional catalyst, (ii) additional catalyst that improves the incorporation of hydrogen into organic matter; and / or (iii) additional catalyst that improves the removal of oxygen from the organic matter, is added to the organic matter after said heating and pressurization and before said treatment.
In another embodiment of the first and second aspects, the organic matter is lignite, and the (i) additional catalyst, (ii) additional catalyst that improves the incorporation of hydrogen into the organic matter; and / or (iii) additional catalyst that improves the removal of oxygen from organic matter, is added to the organic matter when said temperature is greater than about 340 ° C and said pressure is greater than about 230 bar .
In another embodiment of the first and second aspects, organic matter is lignocellulosic material, and (i) additional catalyst, (ii) additional catalyst that improves the incorporation of hydrogen into organic matter; and / or (iii) additional catalyst that improves the removal of oxygen from organic matter, is added to the organic matter when said temperature is greater than about 310 ° C and said pressure is greater than about 180 bar .
In another modality of the first and second aspects, the method comprises the steps of:
(i) cooling the organic matter to a temperature between about 160 ° C and about 200 ° C in a period of time less than about 30 seconds after said treatment; and (ii) depressurize and cool organic matter to room temperature by releasing it through a pressure stabilization device.
In another embodiment of the first and second aspects, the pressure stabilization device is wrapped in water at room temperature.
In a modality of the first and second aspects, biofuel comprises an oil component that has a calorific value of more than 35 MJ / kg.
In one embodiment of the first and second aspects, biofuel comprises an oil component that has more than about 8% by weight of hydrogen db and less than about 10% by weight of oxygen db.
In a modality of the first and second aspects, biofuel comprises a component of carbonaceous waste having a calorific value of more than 30 MJ / kg.
In a third aspect, the invention provides a biofuel produced by the method of the first or second aspect.
In amodality of third aspect, O biofuel is a product oily. In amodality of third aspect, O biofuel is a bio-oil. In a modality of third aspect, the bio-oil is
derived from the processing of fossilized organic material (for example, coals, such as lignite).
In a third aspect, bio-oil is derived from non-fossilized organic material (for example, lignocellulosic material).
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which:
Figure 1 is a graph showing the percentage by weight of oxygen in the lignocellulosic biomass derived from the concentration of sodium versus oil (moles per liter) (reaction conditions: residence time of 25 minutes, 320-350 ° C, 240 bar).
Figure 2 is a graph showing the simulated distillation of typical Lignite-derived Coal Oil for ASTM D7169.
Figures 3a-31 provide proton NMR and quantitative 13C NMR spectra for A-F fractions, as shown in Table 6 (first proton NMR). A sample code A (Figures 3A-3B); sample code B (Figures 3C-3D); sample code C (Figures 3E-3F); sample code D (Figures 3G-3H); sample code E (Figures 3I-3J); sample code F (Figures 3K-3L).
Figure 4 shows a 1H NMR spectrum of typical bio-oil derived from Radiata Pine from number 4 of the Food Stock Sample in Table 2B.
Figure 5 shows the normalized intensity (GPC) as a function of the molecular weight for typical bio-oil products from Radiata Pine.
Figure 6 shows partial Gas Chromatography Mass Spectrometry (GCMS) analyzes of water-based bio-oil derived from lignocellulosic material, showing the identification of more abundant components.
Figure 7 shows partial Gas Chromatography Mass Spectrometry (GCMS) analyzes of oil collected from the water phase associated with lignite slurry processing. The most abundant compound is catechol (1,2-benzenediol).
DEFINITIONS
As used herein, the singular forms one, one and o / a include plural references unless the context clearly indicates otherwise. For example, the term a catalyst also includes a plurality of catalysts.
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 lignin and cellulose may consist exclusively of lignin and cellulose or may include other additional substances.
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 the organic matter feed stock, an aqueous solvent, and / or container walls of a reactor apparatus.
As used herein, the term additional catalyst will be understood to mean a catalyst, which is supplied in addition to catalysts that are intrinsically present in other components of a given reaction (for example, intrinsic catalysts present in organic matter, aqueous solvent and / or walls of a reactor).
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 biomass, lignocellulosic material, and hydrocarbon-containing materials (for example, lignite, oil shale and peat).
As used herein, the term biofuel refers to a material containing energy derived from the processing of organic matter. Non-limiting examples of biofuels include oily products (ie bio-oils), carbonaceous waste products (otherwise known) such as equivalent pulverized coal injection products (PCI)), gaseous products, biodiesel, and alcohols (for example, ethanol and butanol).
As used herein, the term bio-oil will be understood to cover oily products derived from the processing of fossilized organic matter (eg, coals, such as lignite), non-fossilized organic material (eg, lignocellulosic matter), or mixtures of the same.
As used herein, the terms lignocellulosic matter and lignocellulosic biomass are used interchangeably and have the same meaning. The terms cover any substance that comprises lignin, cellulose, and hemicellulose.
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.
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.
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.
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 critical point).
It should be understood that the use of the term about here in reference 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 recited value.
It should be understood that the use of the term between here when referring to a range of numerical values encompasses the numerical values at each end point of the range. For example, a temperature range between 10 ° C and 15 ° C is inclusive of temperatures of 10 ° C and 15 ° C.
Any description of a prior art document here, or a statement here derived from or based on the same document, is not an admission that the derived document or instruction is a part of the common general knowledge of the relevant technique.
For the purposes of description, all documents referred to herein are incorporated by reference in their entirety, unless otherwise indicated.
DETAILED DESCRIPTION OF THE INVENTION
Current techniques for biofuel production suffer from a number of deficiencies. Most involve a series of complex reaction stages that often require the addition of expensive reagents (for example, hydrolytic enzymes). In addition, many are unable to efficiently use / convert a significant proportion of raw input material. More significantly, biofuels generated by current techniques generally have a significantly increased oxygen content compared to conventional fuels, which reduces their energy value and stability. Thus, these biofuels are difficult to store and / or process for downstream applications (eg mixing with conventional fuels, upgrading).
In light of these and other limitations, few biofuel production techniques currently available provide a commercially available alternative providing a commercially viable alternative to using conventional fuels.
Certain aspects of the present invention provide methods for the production of biofuels from organic matter. In contrast to existing techniques, the biofuel production methods described here comprise a single stage in which the organic substrate material is converted into a biofuel. No separation of the substrate material into different components is required before carrying out the methods of the invention. In addition, the methods do not require the use of hydrolytic enzymes or microorganisms that ferment sugars. Instead, the substrate material mixed with the aqueous solvent is subjected to a single treatment stage under conditions of increased temperature and pressure and, optionally in the presence of specific catalysts for the production of a biofuel product. Without being limited to a particular mode of action, it is postulated that the inclusion of catalysts helps to maintain a reducing environment by conducting a series of reactions, in which the substrate material is decomposed and modified by the reduction of oxygen and incorporation of hydrogen.
Certain aspects of the invention relate to biofuels produced by the methods of the present invention. Biofuels are characterized by low oxygen content, high energy density and / or increased stability compared to those produced by currently available methods
Accordingly, the biofuels of the invention are more suitable for storage and / or mixing with conventional fuels (e.g., diesel), and more easily transformed into higher quality fuel products (if necessary).
ORGANIC MATTER
The present invention provides methods for converting organic matter into biofuel. 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.
Without existing 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 may be more appropriate than others.
The organic matter used in the methods of the invention can be naturally occurring organic materials (for example, lignocellulosic biomass or fossil fuel materials including lignite, oil shale, peat and the like) or synthetic organic materials (for example, synthetic rubbers, plastics, nylon) and the like).
The organic matter used in the methods of the invention can be fossilized organic matter (e.g., lignite), non-fossilized organic matter (e.g., lignocellulosic matter), or a mixture thereof.
It should be understood that the organic material may comprise mixtures of two or more different types of naturally occurring organic materials, two or more different types of synthetic organic materials, or a mixture of naturally occurring and synthetic organic materials. There is no limitation regarding the particular proportion of the different components within the mixture.
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. For example, fossilized organic material can comprise more than about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90% or 95% in carbon weight. 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 coals (for example, anthracitic coal, such as metaanthracite, anthracite and semianthracite; bituminous coals; sub-bituminous coals; lignite (ie lignite), coking coal, coal tar, derivatives of coal tar, carbonaceous residue), coke (for example, high coke temperature, foundry coke, medium and low coke temperature, rosin coke, petroleum coke, coke oven coke, coal powder, coke gas , lignite coke, semi-coke), peat (for example, ground peat, sod peat), kerogen, tar sands, oil shale, shale tar, asphalt, asphalt, natural bitumen, asphalt sands, or any combination thereof.
In other preferred embodiments, the organic matter used in the methods of the invention comprises lignocellulosic material. As used herein, lignocellulosic material refers to any substance that comprises lignin, cellulose and hemicellulose.
For example, lignocellulosic material can be a woody plant or component thereof. Examples of suitable woody plants include, but are not limited to, pine (for example, Pinus radiata), birch, eucalyptus, bamboo, beech, spruce, fir, cedar, poplar, willow and poplar. Woody plants can be renewed into woody plants (eg, renewed willow, renewed poplar).
Additionally or alternatively, the lignocellulosic material can be a fibrous plant or a component thereof. Non-limiting examples of fibrous plants (or components thereof) include grasses (for example, switchgrass), grass clippings, flax, corncobs, corn straw, cane, bamboo, bagasse, hemp, sisal, jute, cannibas , hemp, straw, wheat straw, pineapple, cotton plant, kenaf, rice husk, and coconut hair.
Additionally or alternatively, the lignocellulosic material can be derived from an agricultural source. Non-limiting examples of lignocellulosic material from agricultural sources include agricultural crops, agricultural crop residues, and grain processing facility residues (eg, wheat / oat hulls, fine corn, etc.). In general, lignocellulosic material from agricultural sources can include hardwoods, softwoods, hardwood trunks, softwood trunks, nutshells, twigs, shrubs, canes, corn, corn straw, corn cob, energy crops , forests, fruits, flowers, grains, grasses, herbaceous plants, wheat straw, switchgrass, salix, cane bagasse, cotton seed hair, leaves, bark, needles, trunks, roots, seedlings, short rotation woody crops, shrubs, grasses, trees, vines, cattle manure, and pig waste.
In addition or alternatively, lignocellulosic material can be derived from commercial or virgin forests (for example, trees, young plants, forestry or wood processing residues, scrap wood, such as branches, leaves, bark, trunks, roots, leaves and products derived from the processing of such materials, residues or by-product product wood flows, sawmill and paper mill waste and chips, sawdust, and boar particles).
Additionally or alternatively, industrial products and by-products can be used as a source of lignocellulosic material. Non-limiting examples include materials related to wood and wood residues and industrial products (eg pulp, papermaking mud (eg newspaper), cardboard, textiles and fabrics, dextran, and artificial silk).
It should 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.
The relative proportion of lignin, hemicellulose and
cellulose and a certain sample will depend gives nature of matter lignocellulosic. THE title of example only, the proportion in
hemicellulose in a woody or fibrous plant used in the methods of the invention can be between about 15% and about 40%, the proportion of cellulose can be 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%.
In some embodiments, the lignocellulosic material used in the methods of the invention may comprise between about 2% and about 35% lignin, between about 15% and about 45% cellulose, and between about 10% and about 35 % of hemicellulose.
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 % of hemicellulose.
In some embodiments, lignocellulosic material may comprise more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% lignin.
In some embodiments, lignocellulosic material may comprise more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% cellulose.
In some embodiments, lignocellulosic material may comprise more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% hemicellulose.
The person skilled in the art will recognize that the methods described here are not limited by the relative proportions of lignin, hemicellulose and cellulose in a given source of lignocellulosic material.
The organic matter used in the methods of the invention can comprise a mixture of a fossilized organic matter and non-fossilized organic matter (e.g., lignocellulosic matter). Non-limiting examples of suitable fossilized and non-fossilized organic matter that can be included in the mixture are presented in the paragraphs above. It should be understood that no limitations exist in relation to the relative proportion of fossilized and non-fossilized organic matter in the mixture.
In certain embodiments of the invention, the mixture comprises lignite (lignite) and lignocellulosic material. 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 matter i
lignocellulosic mixture may be greater than about
20%, 40%, 60% or 80%.
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).
Non-limiting examples of suitable rubbers include natural and synthetic rubbers, such as polyurethanes, styrene rubbers, neoprenes, polybutadiene, fluoroborches, butyl rubbers, silicone rubbers, plantation rubber, acrylate rubbers, thiokols, and nitrile rubbers. .
Non-limiting examples of suitable plastics include PVC, polyethylene, polystyrene, terthalate, polyethylene and polypropylene.
The organic matter used in the methods of the invention can comprise carbon-containing waste, such as sewage, manure, or industrial or domestic waste materials.
PRE-TREATMENT OF ORGANIC MATTER
The organic matter used in the methods of the invention can optionally be pre-treated before carrying out the conversion of the matter to biofuel.
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, whether it is obtained in the form of a liquid or in a particulate form. However, it is contemplated that in many cases, pretreatment of organic matter can be advantageous in improving the result of the biofuel production methods described here.
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, aqueous solvents, catalysts) and / or other parameters of the reaction (eg heat and pressure). In certain modalities, pretreatment 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). Pre-treatment of organic matter can be carried out using an apparatus such as, for example, an extruder, a pressurized container, or batch reactor.
Pretreatment of organic matter may comprise physical methods, non-limiting examples of which include grinding, chipping, grinding, grinding (eg, vibrating ball mill), compression / expansion, agitation, and / or electric pulse field treatment (PEF).
In addition or alternatively, the pre-treatment of organic matter may comprise physico-chemical methods, non-limiting examples of which include pyrolysis, vapor explosion, ammonia fiber explosion (AFEX), ammonia recycling percolation (ARP), and / or explosion of carbon dioxide. For example, the steam explosion consists of exposing organic matter to high pressure steam in a contained environment before the resulting product is explosively discharged to atmospheric pressure. Pre-treatment with steam explosion can additionally include agitation of the organic matter.
In addition or alternatively, the pretreatment of organic matter may comprise chemical methods, non-limiting examples of which include ozonolysis, acid hydrolysis (eg, diluted acid hydrolysis using H2SO4 and / or HCl), alkaline hydrolysis (eg, diluted alkaline hydrolysis using sodium, potassium, calcium and / or ammonium hydroxides), oxidative delignification (ie, biodegradation of lignin catalyzed by the enzyme peroxidase in the presence of H2O2), and / or the organosolvation method (that is, use of an mixture of organic solvent with inorganic acid catalysts, such as H2SO4 and / or HC1 to break the lignin-hemicellulose bonds).
In addition or alternatively, the pre-treatment of organic matter may comprise biological methods, non-limiting examples of which include the addition of microorganisms (eg putrefaction fungi) capable of
to degrade / decompose various components of matter organic. In modalities preferred, the matter organic used in the methods of the invention is provided in the form
of a fluid paste. The slurry can be generated, for example, by generating a particulate form of organic matter (for example, by physical methods, such as those mentioned above and / or by other means) and mixing with a suitable liquid (for example, an aqueous solvent).
ideal particle size of the solid components and the ideal concentration of solids in the slurry may depend on factors such as, for example, the heat transfer capacity of the organic matter used (ie the rate at which heat can be transferred to within and through individual particles), the desired rheological properties of the slurry and / or the compatibility of the slurry with components of a given apparatus within which the methods of the invention can be carried out (for example, reactor tubes). The ideal particle size and / or concentration of solid components in a slurry used for the methods of the invention can be readily determined by one skilled in the art using standard techniques. For example, a series of slurries can be generated, each sample in the series comprising different particle sizes and / or different concentrations of solid components compared to the other samples. Each slurry can then be treated according to the methods of the invention under a conserved set of reaction conditions. The ideal particle size and / or concentration of solid components can then be determined by analyzing and comparing the products generated from each slurry using standard techniques in the field.
In certain embodiments of the invention, the particle size of solid components in the slurry 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.
In certain embodiments of the invention, the concentration of solid matter in the slurry may be above about 50% w / v. Alternatively, the concentration of solid matter can be less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, or less than about 5% w / v. In some embodiments, the concentration of solid matter is between about 2% and about 30%, between about 2% and about 20%, between about 2% and about 10%, between about 5% and about 10%, between about 5% and about 20%, or between about 1% and about 10% w / v.
In some embodiments, the organic material used in the methods of the invention is the lignocellulosic material submitted to an optional pre-treatment step in which the hemicellulose is extracted. Therefore, most hemicellulose (or, in fact, all hemicellulose) can be extracted from lignocellulosic material and the remaining material (containing predominantly cellulose and lignin) used to produce a biofuel by the methods of the invention. However, it should be understood that this pretreatment is optional and there is no need to separate hemicellulose from the lignocellulosic material when carrying out the methods of the invention. Suitable methods for separating hemicelluloses from lignocellulosic material are described, for example, in PCT publication number WO / 2010/034055, the entire content of which is incorporated by reference.
For example, hemicellulose can be extracted from lignocellulosic material by treating a slurry comprising lignocellulosic material (for example, 5% to 15% w / v solid concentration) for treatment with a mild aqueous acid ( for example, pH 6.56.9) at a temperature between about 100 ° C and about 250 ° C, a reaction pressure between about 2 and about 50 atmospheres, for between about 5 and about 20 minutes . The solubilized hemicellulose component can be separated from the rest of the solid matter (containing predominantly cellulose and lignin), using any suitable means (for example, by using an appropriately sized filter). The remainder of the solid matter 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.
BIOFUEL PRODUCTION
The methods of the invention provide a means of generating a biofuel from organic matter. In general, the methods require treatment of the organic matter with an aqueous solvent under conditions of increased temperature and pressure and, optionally in the presence of catalysts that maintain a reducing environment.
PUTATIVE REACTION MECHANISMS
Without limitation to the particular mechanistic description, it is believed that the organic matter used in the methods of the invention is decomposed (i.e., liquid to solid transformation) mainly by base and / or acid catalyzed hydrolysis. Hydrolysis reactions can be mediated by aqueous cations (hydronium) and anions (hydroxide) dissociated from water molecules under increased temperature and pressure. The hydrolysis of the organic substrate can also be increased by including additional acid and / or base catalysts for the mixture of organic matter and aqueous solvent. Exemplary reactions that may be involved in the hydrolysis of the material include the conversion of glycosidic bonds and / or ether of organic matter into alcohols, and the conversion of esters of organic matter to carboxylic acids and alcohols.
In certain embodiments, aqueous solvents used in the methods of the invention are aqueous alcohols. It is postulated that under increased temperature and pressure alcohols present in the solvent they can decompose the solid organic matter by alcoholization. Additional functions of alcohols (if present) in the aqueous solvent may include swelling of the organic matter to induce greater reaction capacity, and / or the removal of hydrolyzed species from the surface of the matter to expose the fresh surface that can further hydrolyze ( thus increasing income globally). Alcohols in the aqueous solvent can also function as radical modifiers by reducing the occurrence and / or severity of undesirable radical side reactions (for example, polymerizations).
It is also postulated that the conversion of organic matter into biofuel by the methods of the invention involves the removal of oxygen from the matter. Again, without being linked to particular mechanistic pathways, it is believed that the inclusion of specific catalysts in the mixture of aqueous solvent and organic matter under treatment and / or thermal catalysis of the matter facilitates the elimination reactions (dehydration) (ie, elimination of water to provide double bonds), decarboxylation reactions (ie, removal of the carboxyl group from compounds with organic matter such as carbon dioxide), and / or decarbonylation reactions (ie, removal of carbon monoxide at from aldehydes), each of which can assist in removing oxygen from the compounds present in the organic matter under treatment.
In addition, the hydrogenation of organic matter compounds is also a postulated mechanism that contributes to the conversion of organic matter to biofuel. Hydrogenation can be facilitated by specific catalysts added to the mixture of aqueous solvent and organic matter under treatment. Without limiting the particular mechanisms, catalysts are proposed to improve:
(i) hydrogenation by transferring aldehydes, ketones and / or aromatic or unsaturated systems in organic matter compounds to produce alcohols (from which oxygen can then be removed by dehydration, that is, the elimination of water) and portions saturated and / or;
(ii) direct hydrogenation of aldehydes, ketones and / or aromatic or unsaturated systems to produce alcohols (which can then be eliminated by removing oxygen) and saturated portions.
Hydrogenation and subsequent dehydration can occur in a cascade reaction system (referred to as hydrodeoxygenation).
It is believed that the hydrogen in the system can be made available by gasifying the organic matter (and alcohols in the aqueous solvent, if present), obtaining a mixture of hydrogen, carbon monoxide and water, the latter two can then be subjected to the reaction of conversion of gas into water to form molecular hydrogen and carbon dioxide. In addition, the carbon monoxide resulting from gasification is thought to interact with specific catalysts (for example, sodium hydroxide or potassium hydroxide), which can be added to the mixture of aqueous solvent and organic matter under treatment to form a formate (eg example, sodium formate or potassium formate). The formate thus formed can function as a hydrogen transfer agent to facilitate the hydrogenation of compounds in organic material. Other hydrogen transfer agents that can be generated through the decomposition of organic matter are low molecular weight acids, especially formic, acetic and oxalic acid.
In general and again, without limitation to particular modes of action, it is thought that the partial gasification of reactive species in the presence of the catalysts described here triggers a cascade of interrelated reactions that culminate in the generation of biofuels with high energy and stability.
In general, the stability (and high energy content) of biofuels produced by the methods of the invention is thought to arise, at least in part, from relatively low oxygen and high hydrogen content which reduces the degree of unsaturation (a point starting point for unwanted polymerization leading to 'resin' of the material). In addition, it is considered that unsaturated or aromatic bonds present in the product may be less likely to be activated by neighboring oxygen groups, further reducing the potential for repolymerization.
Aqueous Solvents
The solvents used according to the methods of the invention can be aqueous solvents. The specific nature of the aqueous solvent used will depend on the form of organic matter used.
In certain embodiments, the solvent may be water. For example, it may be appropriate or preferable to use water as the solvent, when the organic matter used in the methods consists of, or comprises a significant amount of, fossilized organic matter (e.g., lignite, peat and the like).
It will be recognized that water can also be used as the solvent when other types of organic matter are treated using the methods of the invention, although in the case of some organic materials (e.g., lignocellulosic matter), the results can be sub-ideal.
In other embodiments, the aqueous solvent is an aqueous alcohol. For example, it may be appropriate or preferable to use an aqueous alcohol as the solvent, when the organic matter used in the methods consists of, or comprises a significant amount of lignocellulosic material and / or other materials such as rubber and plastics, due to the strong chemical bonds in these types of organic matter.
Suitable alcohols can comprise between one and about ten carbon atoms. Non-limiting examples of suitable alcohols include methanol, ethanol, isopropyl alcohol, isobutyl alcohol, pentyl alcohol, hexanol and isohexanol.
In certain embodiments, the solvent comprises a mixture of two or more aqueous alcohols.
Preferably, the alcohol is ethanol, methanol, or a mixture thereof.
The aqueous alcohol will generally comprise at least one percent alcohol based on the total weight of the solvent. In certain embodiments, aqueous alcohol comprises more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% by weight of alcohol. In other embodiments, aqueous alcohol comprises less than about 5%, 10%, 15%, 20%, 25%,
30%, 35%, 40%, 45% or 50% by weight of alcohol.
Preferably, the aqueous alcohol comprises between about 1% and about 50% by weight of alcohol, between about 5% and about 50% by weight of alcohol, between about 5% and about 40% by weight of alcohol , between about 5% and about 30%
by weight of alcohol, among about 5% and about 20% by weight of alcohol, between about 5% and about in 10% in Weight in alcohol, in between fence in 10% and fence in 50% in Weight in alcohol, in between fence in 20% and fence in 50% in Weight in alcohol, in between fence in 25% and fence in 50% in Weight in alcohol, or between fence 30% and about 50% in Weight in
alcohol.
In certain embodiments, the aqueous alcohol can act as an alkylating agent. Without limiting the particular mechanisms, the transfer of an alkyl group from aqueous alcohol to one or more components of organic matter is designed to facilitate the solvation and / or chemical stabilization of organic matter.
In preferred embodiments, an aqueous solvent used in the methods of the invention is aqueous methanol or aqueous ethanol.
In particularly preferred embodiments, the alcohol is aqueous ethanol. Preferably, aqueous ethanol comprises between about 5% and about 30% by weight of ethanol, more preferably between about 10% and about 25% by weight of ethanol, and even more preferably between about 15% and about 25% by weight of ethanol.
Temperature and Pressure
According to the methods of the invention, organic matter can be treated with an aqueous solvent, under conditions of increased temperature and pressure for the production of biofuel.
The specific temperature and pressure conditions used when practicing the methods of the invention may depend on a number of different factors, including, for example, the type of aqueous solvent used, the percentage of alcohol (if present), in the aqueous solvent, type of organic matter under treatment, the physical form of the organic matter under treatment, the types of catalysts used (if present) and their various concentrations, the retention time, and / or the type of apparatus on which the methods are performed. 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 feed stock is converted into biofuel.
Desired reaction conditions can be achieved, for example, by conducting the reaction from an appropriate apparatus (for example, a sub / supercritical reactor apparatus) capable of maintaining increased temperature and increased pressure.
In certain embodiments, an aqueous solvent used in the methods of the invention can be heated and pressurized beyond its critical temperature and / or beyond its critical pressure (i.e., beyond the critical point of the solvent). Therefore, the aqueous solvent can be a 'supercritical' aqueous solvent if heated and pressurized beyond the solvent's 'critical point'.
In certain embodiments, an aqueous solvent used in the methods of the invention can be heated and pressurized to the level below its critical temperature and pressure (i.e., below the critical point of the solvent). Therefore, the aqueous solvent can be a subcritical aqueous solvent, if the maximum temperature and / or maximum pressure is less than its 'critical point'. Preferably, the subcritical aqueous solvent is heated and / or pressurized to levels approaching the 'critical point' of the solvent (for example, between about 10 ° C to about 50 ° C below the critical temperature and / or between about 10 atmospheres at about 50 atmospheres below its critical pressure).
In some embodiments, an aqueous 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., heated and / or pressurized, both above and below the 'critical point' of the solvent at different times). Therefore, the aqueous solvent can oscillate between subcritical and supercritical states when carrying out the methods.
In some embodiments, an aqueous solvent used in the methods of the invention can be heated to a level above its critical temperature, but pressurized to a level below its critical pressure. In other embodiments, an aqueous solvent used in the methods of the invention can be heated to a level below its critical temperature, but pressurized to a level above its critical pressure.
Those skilled in the critical temperature and critical pressure technique of a given aqueous solvent will depend, at least in part, on the percentage of water in the solvent. For example, if an aqueous solvent comprises a certain percentage of water in combination with a certain percentage of a second component that has a lower critical point than water (for example, an alcohol), the solvent's critical point will generally be more lower than pure water.
Conversely, if an aqueous solvent comprises a certain percentage of water in combination with a certain percentage of a second component that has a high water critical point, the solvent's critical point will generally be greater than that of pure water.
In cases where an aqueous solvent comprises two core components (for example, water and an alcohol), an approximately linear relationship may exist between the percentage of alcohol present in the solvent and the critical temperature and pressure of the solvent, the end points being defined one end of the pure water critical point and the other end of the pure alcohol critical point. For example, if the water critical point is defined as 374 ° C and 221 atm and the ethanol critical point is defined as 240 ° C and 60 atm, the critical point of a 25% aqueous ethanol solution may be approximately 340 ° C / 180 atm, the critical point of a 50% aqueous ethanol solution can be approximately 307 ° C / 140 atm, and the critical point of a 75% aqueous ethanol solution can be approximately 273 ° C / 100 atm.
In cases where an aqueous solvent comprises more than two core components (for example, water and two different types of alcohol), calculations of a similar nature can be used to determine the critical point of the solvent when the proportions of the various alcohols in the solvent are varied.
Therefore, it should be understood that when a temperature and / or pressure (or a range of temperatures and / or pressures) is provided here, in relation to a given aqueous solvent comprising two or more core components, in specified proportions ( for example, a 10% w / v aqueous alcohol), the corresponding values and ranges of temperature and / or pressure can be easily derived when the relative proportions of the core components are varied.
It will also be understood that the critical point of a given aqueous solvent will be influenced by additional factors, such as the chemical state of the organic material under treatment. For example, the critical point of a given aqueous solvent is likely to change over the course of a given reaction as the feed stock material becomes solvated.
In certain embodiments, the treatment of organic matter for the production of biofuels using the methods of the invention can be carried out at temperatures between about 200 ° C and about 450 ° C and pressures between about 50 bar and about 350 bar. In other modalities, the treatment can be carried out at temperatures between about 250 ° C and about 400 ° C and pressures between about 100 bar and about 300 bar. In additional modalities, the treatment can be carried out at temperatures between about 275 ° C and about 375 ° C and pressures between about 150 bar and about 275 bar. In some preferred embodiments, the treatment can be carried out at temperatures between about 300 ° C and about 375 ° C and pressures between about 175 bar and about 275 bar. In other preferred embodiments, the treatment can be carried out at temperatures between about 330 ° C and about 360 ° C and pressures between about 200 bar and about 250 bar. In still other preferred embodiments, the treatment can be carried out at temperatures between about 340 ° C and about 360 ° C and pressures between about 200 bar and about 250 bar.
The person skilled in the art will understand that a generally inverse relationship may exist between the temperature and / or pressure required to convert the organic material into biofuel, using the methods of the invention, and the proportion of additional components (for example, alcohol) , combined with water in the aqueous solvent. For example, the use of an aqueous solvent that substantially comprises water (i.e., in the absence of additional components, such as alcohol) may require increased temperature and / or pressure to drive the conversion of organic matter into biofuel compared to a solvent aqueous which comprises a more proportion. significant alcohol (which may require ^{temperatures:} comparatively smaller and / or pressure to drive the conversion). It would therefore be immediately apparent to the person skilled in the art to increase the proportion of, for example, alcohol (for example, ethanol and / or methanol), in an aqueous solvent allowing a corresponding reduction in the temperature and / or pressure required to obtain a efficient conversion of organic matter into biofuel, using the methods of the invention. On the other hand, it would be readily apparent that decreasing the proportion of, for example, alcohol (for example, ethanol and / or methanol) in an aqueous solvent may require a corresponding increase in the temperature and / or pressure necessary to obtain a conversion efficiency of organic matter to biofuel using the methods of the invention.
It will also be recognized that several catalysts as described here (see subsection below entitled Catalysts) can be used to increase the efficiency of the treatment which can, in turn, reduce the temperature and / or pressure needed to drive the conversion of organic matter to biofuel using a certain aqueous solvent.
Retention time
The specific period of time in which the conversion of organic matter can be achieved, upon reaching a target temperature and pressure (ie the retention time) can depend on a number of different factors, including, for example, the type of solvent aqueous used, the percentage of alcohol (if present), in the aqueous solvent, the type of organic matter under treatment, the physical form of the organic matter under treatment, the types of catalysts (if present) in the mixture and the various concentrations, and / or the type of apparatus on which the methods are performed. These and other factors can, in order to optimize a given method, be varied 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 into biofuel.
In certain modalities, that about 60 minutes, as a stock of food, the retention time is less than minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes or 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 5 minutes. In other embodiments, the retention time is between about 1 minute and about 60 minutes. In additional modalities, 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 additional embodiments, the retention time is between about 20 minutes and about 30 minutes.
Those skilled in the art will recognize that various catalysts, as described herein (see subsection below entitled Catalysts) can be used to increase the effectiveness of the treatment, which in turn can reduce the retention time required to convert organic matter into biofuel. Likewise, the required retention time may, in some cases, be shorter when the temperature and / or pressure are increased, and / or the proportion of additional components (e.g., alcohol), in the aqueous solvent is increased.
ideal 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 analyzing the yield and / or quality of biofuel produced. Heating / Cooling, Pressurization / Depressurization
A reaction mixture (for example, in the form of a slurry), comprising organic matter, aqueous solvent and, optionally, one or more catalysts, as defined herein, can be carried out at a target temperature and pressure (ie, the temperature / pressure maintained during the retention time) in a period of time between about 30 seconds and about 30 minutes. In some embodiments, the reaction mixture can be carried out at a target temperature and pressure in less than about 5 minutes or less than about 2 minutes. Preferably, the reaction mixture is carried out at a target temperature and pressure in less than about 2 minutes.
In certain embodiments, the reaction mixture can be carried out at a substantially instantaneous target pressure and carried out at a target temperature in less than 5 minutes. In other embodiments, the reaction mixture can be carried out at a substantially instantaneous target pressure and carried out at a target temperature in less than about two minutes. In other embodiments, the reaction mixture can be carried out at a substantially instantaneous target pressure and carried out at a target temperature between about 1 and about 2 minutes.
Additionally or alternatively, after the end of the retention period of the reaction mixture, it 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 shorter period of time about 10 minutes, preferably minutes, more preferably minutes, preferably between less than smaller less about
of what fence in of what fence in in 4 and fence in
minutes, and more preferably about 5 minutes.
After the initial cooling period, the temperature can still be reduced to room temperature with the concomitant depressurization by rapid release in a cold aqueous medium (for example, chilled water).
The heating / depressurization and cooling / depressurization processes can be facilitated by carrying out the methods of the invention, in a system of
continuous flow (will see section below entitled Flow Continuous). Catalysts According with methods gives invention, The matter organic can be treated with one solvent aqueous under
increased temperature and pressure conditions to produce a biofuel product. In certain embodiments, the organic matter can be treated with a subcritical aqueous solvent. In other embodiments, the organic matter can be treated with a subcritical aqueous solvent. In both cases, treatment can be increased by using one or more additional catalysts. Although some catalysts may be an intrinsic component of organic matter (for example, minerals), aqueous solvent (for example, hydronium ions / water hydroxide under sub / supercritical conditions), and / or the vessel walls of a reactor in the which organic matter can be treated (for example, transition / noble metals), the invention contemplates the use of additional catalysts to improve biofuel production from organic material.
(i) Additional catalysts
Certain embodiments of the invention relate to the production of biofuel from organic matter by treatment with an aqueous solvent under conditions of increased temperature and pressure in the presence of at least one additional catalyst. By additional catalyst it will be understood that the catalyst is complementary (i.e., separated) to the catalytic compounds intrinsically present in other components of the reaction, such as organic matter, aqueous solvent and / or walls of a reactor apparatus. In other words, an additional catalyst, as contemplated herein, can be considered as an extrinsic catalyst in the sense that it is provided for the reaction as a component of the individual reaction.
For example, an embodiment of the invention in which lignite feed stock is treated with aqueous water (only) under conditions of increased temperature and pressure in a reactor apparatus that would not be considered to use an additional catalyst.
In contrast, a modality of the invention in which lignite feed stock is treated with aqueous water in the presence of a supplementary base catalyst (eg sodium hydroxide) under conditions of increased temperature and pressure in a reactor that would be considered for use an additional catalyst.
An additional catalyst as contemplated herein can be any catalyst that improves the formation of biofuel from organic matter using the methods of the invention, non-limiting examples of which include base catalysts, acid catalysts, alkali metal hydroxide catalysts, transition metal hydroxide catalysts, alkali metal formate catalysts, transition metal formate catalysts, reactive carboxylic acid catalysts, transition metal catalysts, sulphide catalysts, noble metal catalysts, gas conversion catalysts in water, and combinations thereof.
The methods of the invention can be carried out using additional catalysts in combination with an intrinsic catalyst.
The ideal amount of an additional catalyst used in the methods of the present invention can depend on a variety of different factors including, for example, the type of organic matter under treatment, the volume of organic matter under treatment, the aqueous solvent used, the specific temperature and pressure used during the reaction, the type of catalyst and the desired properties of the biofuel product. Following the methods of the invention, the ideal amount of an additional catalyst to be used can be determined by one skilled in the art of the invention.
In certain embodiments, an additional catalyst or combination of additional catalysts can be used in an amount of between about 0.1% and about 10% w / v of catalysts, between about 0.1% and about 7.5 % w / v of catalysts, between about 0.1% and about 5% w / v of catalysts, between about 0.1% and about 2.5% w / v of catalysts, between about from 0.1% and about 1% w / v of catalysts, or between about 0.1% and about 0.5% w / v of catalysts (relative to the aqueous solvent).
In certain embodiments, an additional catalyst used alkaline in the reaction process can be a metal and / or alkaline earth salt (for example, potassium, calcium and / or sodium salts). For example, it has been shown here that alkali metal hydroxides and carbonates can be effective in reducing the oxygen content in the bio-oil product in which all conditions except the additional catalyst concentration are constant. In one embodiment, the concentration of the ideal catalyst (in the reaction itself) of an alkali metal hydroxide and / or alkali metal carbonate catalyst, under a given set of reaction conditions substantially otherwise may be in the range of about from 0.1 Molar to about 1 Molar. In preferred embodiments, the concentration can be from about 0.1 Molar to about 0.3 Molar. Preferably, the concentration of alkali metal hydroxide and / or alkali metal carbonate catalyst used provides a product with a low oxygen content (for example, less than about 11% w / w; between about 6% and about 11% w / w).
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 biofuel. The reducing environment can favor the hydrolysis of organic matter, trigger the replacement of oxygen with hydrogen, and / or stabilize the biofuel formed.
Treatment with a subcritical aqueous solvent (as opposed to the supercritical aqueous solvent) can be advantageous in that less energy is required to perform the methods and the solvent can be better preserved during treatment. When a subcritical aqueous solvent is used, it is contemplated that the additional use of one or more catalysts can be particularly beneficial for increasing the yield and / or quality of the biofuel. In addition, the reduced input energy cost benefits (i.e., to maintain subcritical rather than supercritical conditions) higher preservation when including one or the solvent can significantly be additional cost incurred by, in addition to more of the catalysts described herein.
It is contemplated that, under conditions of increased temperature and water molecules under pressure in the aqueous solvent, it can dissociate into acidic (hydronium) and basic ions (hydroxide) to facilitate hydrolysis of the solid matter under treatment (that is, solid to liquid transformation) ). In certain embodiments, the temperature and pressure at which the reaction is carried out may be high enough for the desired levels of hydrolysis to occur without the use of additional catalysts. In addition or alternatively, the specific organic material used may be relatively easy to hydrolyze (and additional catalysts are therefore not needed).
For example, sufficient hydrolysis of fossilized organic matter, such as lignite, can be achieved using subcritical water without further addition of the catalysts described herein. However, the inclusion of such catalysts can be used as a means to increase the yield and / or quality of biofuel produced.
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 further addition of catalysts. In addition or alternatively, the specific organic material used can be difficult to hydrolyze, due to its specific chemical structure (for example, lignocellulosic material).
Therefore, hydrolysis catalysts can be added to improve (i.e., increase and / or accelerate) the hydrolysis of the solid matter under treatment (i.e., hydrolysis catalysts).
In certain embodiments, hydrolysis catalysts can be base catalysts. Any suitable base catalyst can be used.
Non-limiting examples of base catalysts suitable for hydrolysis include alkali metal salts, transition metal salts, organic bases, and mixtures thereof.
Alkali metal salts or transition metal salts can comprise any inorganic anions,
examples non-limiting of which include sulphate, sulfite, sulfide, disulfide, phosphate, aluminate, nitrate, nitrite, silicate, hydroxide, methoxide, ethoxide, alkoxide, carbonate and oxide. Alkali metal salts or
preferred transition metal salts are sodium salts,
potassium, iron, calcium and barium, and may comprise one or
more anions selected from phosphate, aluminate, silicate, hydroxide, methoxide, ethoxide, carbonate, sulfate, sulfide, disulfide and oxide.
Non-limiting examples of suitable bases include ammonia, basic amino acids (e.g., organic and polar benzathin, benzimidazole, betaine, cinchonidine, cinchonine, diethylamine, diisopropylethylamine, ethanolamine, ethylenediamine, methylmorpholine, imidazole, methyl amine, N-methylguanidine, N -methylpiperidine, phosphazene bases, picoline, piperazine, procaine, pyridine, quinidine, quinoline, trialkylamine, tributylamine, triethyl amine, trimethylamine and mixtures thereof.
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 base catalysts. Any suitable acid catalyst can be used.
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 inorganic anions, non-limiting examples of which include aluminate, sulfate, sulfite, sulfide, phosphate, phosphite, nitrate, nitrite, silicate, hydroxide and alkoxide (under supercritical and close to supercritical conditions), and anions of carbonate and carboxy group.
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 mixtures thereof.
In certain embodiments, acid catalysts for hydrolysis may be present in the minerals of organic matter and / or derived from the in situ formation of carboxylic and / or phenolic acids during the treatment process.
In certain embodiments of the invention, a mixture of one or more acid hydrolysis catalysts and one or more base hydrolysis catalysts can be used to increase the hydrolysis of the solid matter under treatment.
The methods of the invention can employ catalysts for the hydrolysis of organic matter (as discussed in the previous paragraphs). Additionally or alternatively, the methods can use catalysts that increase and / or accelerate the removal of oxygen (directly or indirectly) from compounds in the organic matter under treatment. The removal of oxygen can provide a number of advantageous effects, such as, for example, increasing the energy content and stability of the biofuel produced.
An acid catalyst can be used to increase oxygen removal, for example, by dehydrating (eliminating) water. Therefore, in certain embodiments, an acid catalyst can be used to improve hydrolysis, and to increase the removal of oxygen from organic matter under treatment.
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. Liquid mineral acids and organic acids can comprise any inorganic anions, non-limiting examples of which include aluminate, sulfate, sulfite, sulfide, phosphate, phosphite, nitrate, nitrite, silicate, hydroxide and alkoxide (under supercritical or near supercritical conditions) , anions of carbonate and carboxy group.
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 mixtures thereof.
In certain aluminum-silicate modalities including hydrated forms (for example, zeolites) they can be used during the treatment of organic matter to aid in the dehydration (elimination) of water.
Additionally or alternatively, oxygen removal can be increased by thermal means involving decarbonylation of, for example, aldehydes (providing R3C-H and CO gas) and decarboxylation of carboxylic acids in the material under treatment (providing R3C-H and CO gas ₂ ) · The speed of these reactions can be improved by adding acid and / or transition (noble) metal catalysts. Any suitable transition or noble metal can be used including those that are supported on solid acids. Non-limiting examples include Pt / Al ₂ O ₃ / SiO2, Pd / Al ₂ O ₃ / SiO2, NÍ / AI2O3 / SiO2, and mixtures thereof.
In addition or alternatively, a combined acid and a hydrogenation catalyst can be used to increase oxygen removal, for example, by hydrodeoxygenation (ie, elimination of water (via the acid component) and saturation of double bonds (via the metal)). Any suitable combined acid and hydrogenation catalyst can be used, including those supported on solid acids. Non-limiting examples include Pt / Al ₂ O3 / SiO2, Pd / A12O ₃ / SiO ₂ , Ni / Al ₂ O ₃ / SiO ₂ , N1O / M0O3, C0O / M0O3, NiO / WO ₂ , zeolites loaded with noble metals ( for example, ZSM-5, Beta, ITQ-2), and mixtures thereof.
The methods of the invention can employ catalysts that increase the hydrolysis of organic matter under treatment, and / or catalysts that increase 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 the organic matter compounds 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 biofuel produced.
A transfer hydrogenation catalyst can be used to increase the hydrogen concentration in organic matter compounds under treatment, for example, by transfer hydrogenation or hydrogen generation in situ.
Any suitable transfer hydrogenation catalyst can be used for the hydrogen concentration. Non-limiting examples of suitable transfer hydrogenation catalysts include alkali metal hydroxides (eg sodium hydroxide), transition metal hydroxides, alkali metal forms (eg sodium formate), transition metal forms , reactive carboxylic acids, noble or transition metals, and mixtures thereof.
The alkali metal hydroxide or formate can comprise any suitable alkali metal. Preferred alkali metals include sodium, potassium and mixtures thereof. The transition metal hydroxide or formate 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 noble or transition metal can be any suitable noble or transition metal, preferred examples include platinum, palladium, nickel, ruthenium, rhodium, and mixtures thereof.
Additionally or alternatively, a transition metal catalyst can be used to increase the concentration of hydrogen in the organic matter under treatment, for example, by hydrogenation with H ₂ . Non-limiting examples of transition metal catalysts suitable for hydrogenation with H ₂ include zero valiant metals (eg platinum, palladium, and nickel), transition metal sulphides (eg, iron sulphide (FeS, Fe _x S _y ), and mixtures thereof.
In addition or alternatively, a gas-to-water catalyst can be used to increase the concentration of hydrogen in the organic matter under treatment (that is, through a gas-to-water reaction). Any suitable gas to water conversion catalyst (WGS) can be used including, for example, transition metals, transition metal oxides and mixtures thereof (for example, magnetite,
platinum, finely divided copper and nickel based WGS catalysts).
Additionally or alternatively, the concentration of hydrogen in the 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 / A ^ CL / SiCL,
Pd / Al ₂ O3 / SiO2, Ni / AI2O3 / SiO2, and mixtures thereof, and transition metal sulphides (for example, Fe _x S _y , FeS / Al ₂ O3, FeS / SiO ₂ , FeS / A12O3 / SiO ₂ , and mixtures thereof).
Table 1 below provides a summary of the various exemplary catalysts that can be used in the methods of the invention and their corresponding reactions that can catalyze.
Table 1: Summary of the catalyst and corresponding reactions
Kind ofReaction Familycatalyst Member ofFamilycatalyst Specific Examples Preferred Catalysts / Comments Hydrolysis Base catalysts Sub / supercritical water hydroxide ion in watersub / supercritical All metal salts oftransition andalkali, both cations and anions can contribute. All include anions M = any transition metal or alkaliA = anions,including: aluminate, sulfate, sulfite, phosphate M = Na, K, Fe, Ca, BaA = aluminate, phosphate, silicate, hydroxide, methoxide, ethoxide
common inorganic sulfide, phosphite nitrate, nitrite silicate hydroxide alkoxide carbonate oxide carbonate sulfate sulfide disulfide (FeS2) oxide Any organic base Ammonia, pyridine, etc.Hydrolysis Acid catalysts (moreslow) Sub / supercritical water hydronium ion in sub / supercritical water Any liquid mineral or organic acid HA, whereA = anions,including: aluminate, sulfate, sulfite, sulfide phosphate, phosphite, phosphite nitrate, nitrite silicate hydroxide alkoxide carbonate carbonoxy group Acids can form from the formation of acids in situcarboxylic, phenolic and the presence of minerals Dehydration (elimination) Acid catalysts Sub / supercritical water hydronium lon in sub / supercritical water Any liquid mineral or organic acid HA, whereA = anions,including: aluminate, sulfate, sulfite, sulfide phosphate, phosphite nitrate, nitrite silicate, hydroxide alkoxide carbonate carbon group Acids can form from the formation of acids in situcarboxylic, phenolic and the presence of minerals.Zeolites or aluminosilicates in general can be added Transfer hydrogenation or generation in situ H2 Transfer hydrogenation catalysts All thehydroxides ofmetals oftransition andalkaline andformiatesAll acids M = any transition metal or alkaliA = hydroxide formate M = Na, KA = formate ofhydroxide
reactive carboxylicsAcetic Acid All noble and transition metals All noble and transition metals M = Pd, Pd, Ni, Ru, Rh Decarboxylation Widely thermal Metal acid and cations(noble) oftransition were related to assist the process All noble metals andtransition supported insolid acids Pd / AI ₂ O ₃ / SiO ₂ Ni / AI ₂ O ₃ / SiO ₂ Decarboxylation Widely thermal How todecarboxylation How to decarboxylation How to decarboxylation In-situ gasification Widely thermalMetals oftransition Supported transition metals PVAI ₂ O3 / SiO ₂ Pd / AI ₂ O ₃ / SiO ₂ Ni / AI ₂ O ₃ / SiO ₂ sulfides Fe _x S _and FeS / AI ₂ O ₃ FeS / SiO ₂ FeS / AI ₂ O ₃ / SiO ₂ Conversion of gas to water WGS Catalysts Standard WGS catalysts As per literature As per literature Direct hydrogenation with H2 Transition metals in Zero valiant metalsPt, P, Ni as valiant zero SulfidesFeSj FexSy Hydrogenation Combined acid and hydrogenation catalyst Metals oftransition and solid acid M = transition metalA = acidic solid Pt / AbOs / SiOa Pd / AI ₂ O ₃ / SiO ₂ Ni / AI ₂ O ₃ / SiO ₂ NiO / MoO ₃ CoO / MoO ₃ NíO / WO ₂ Zeolites loaded with noble metals, for example, ZSM-5, Beta, ITQ-2
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.
It will be understood that no particular limitation exists regarding the time that the additional catalyst can be applied when carrying out the methods of the invention. For example, catalysts can be added to organic matter, aqueous solvent, or a mixture of them (for example, a slurry), before heating / pressurizing to reaction temperature and target pressure, during heating / pressurizing to temperature of target reaction and pressure, and / or after the reaction temperature and pressure are reached. The timing of adding the catalyst may depend on the reactivity of the feed stock used. For example, highly reactive feed stocks can benefit from adding catalyst to or near the target reaction and pressure temperature, while less reactive feed stocks can have a window into the larger process for adding catalyst (ie , catalysts can be added before reaching the target pressure and reaction temperature).
(ii) Intrinsic catalysts
Certain embodiments of the invention relate to the production of biofuel from organic matter by treatment with an aqueous solvent under conditions of increased temperature and pressure, in the presence of at least one additional catalyst. As noted above, an additional catalyst will be understood to indicate that the catalyst is fed to complement catalysts intrinsically present in other reaction components.
Additionally or alternatively, the production of biofuel from organic matter according to the methods of the invention can be increased by the presence of intrinsic catalysts that are naturally present in a particular reaction component, such as, for example, any one or more of feed stock of organic matter, aqueous solvent, and / or vessel walls of a reactor in which organic matter can be treated.
Accordingly, the methods of the invention can be performed using additional catalysts in combination with intrinsic catalysts, or intrinsic catalysts alone.
The ideal amount of an intrinsic catalyst used in the methods of the invention can depend on a variety of different factors, including, for example, the type of organic matter under treatment, the volume of organic matter under treatment, the aqueous solvent used, the specific temperature and pressure employed
during the reaction, the type of catalyst and the desired properties of the biofuel product.
In certain embodiments, an intrinsic catalyst or combination of intrinsic and additional catalysts can be used in an amount of 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 aqueous solvent).
In certain embodiments, an intrinsic catalyst used in the reaction process can be an alkali and / or alkaline earth metal salt (for example, potassium, calcium and / or sodium salts). For example, alkali metal hydroxides and carbonates can be effective in reducing the oxygen content in the bio-oil product. In one embodiment, the concentration of the ideal catalyst (in the reaction itself) of an alkali metal hydroxide and / or alkali metal carbonate catalyst, under a given set of otherwise substantially constant reaction conditions can be in the range of about 0.1 Molar to about 1 Molar. In preferred modalities, the concentration
it can be about 0.1 Molar to about 0.3 Molar. Preferably, the concentration of alkali metal hydroxide and / or catalyzed alkali metal carbonate used provides a product with a low oxygen content (for example, less than about 11% w / w; between about 6% and about 11% (w / w) ·
One or more different types of catalysts may be present in the organic matter used as the feed stock for the reaction. Non-limiting examples of these catalysts include mineral and / or alkali and / or alkaline earth metal salts. In certain modalities, potassium and / or calcium salt present in the supply of organic matter can provide catalytic activity in the reaction.
For example, lignocellulosic biomass can comprise a variable amount of ash (for example, between 0.1% to about 50% ash) and, in turn, the ash can contain various amounts of alkaline salts (for example, potassium salts and / or calcium salts) (see, for example, Stanislav et al., An Overview of the Chemical Composition of Biomass, Fuel 89 (2010), 913-933). For example, ash can comprise between about 0.2% to about 64% potassium (as potassium oxide) and / or between about 1% to about 83% calcium (as calcium oxide). Alkaline salts present in the feed stock, such as, for example, the potassium and calcium salts can be catalysts for a series of reactions under the reaction conditions of the present invention, including the reactions described in Table 1 above.
Additionally or alternatively, an aqueous solvent used in the methods of the invention can provide catalysts intrinsic to the reaction. Non-limiting examples of these catalysts include hydronium ions and / or water hydroxide.
In addition or alternatively, intrinsic catalysts can be provided by the vessel walls of a reactor in which organic matter can be treated. Non-limiting examples of materials commonly used for reactor construction (ie, including reactor vessel walls) are iron alloys with other metals, including chromium, nickel, manganese, vanadium, molybdenum, titanium and silicon. Non-limiting examples of suitable steel grades are 310, 316, and 625 alloy.
In certain embodiments, intrinsic catalysts that can be supplied by the vessel walls of a reactor are transition / noble metals.
Non-limiting examples of intrinsic catalysts can be provided by the vessel walls of a reactor including iron metal, iron hydroxides, iron oxides, iron carbonates, iron hydrogen carbonates, iron acetates; nickel metal, nickel hydroxides, nickel oxides, nickel carbonates, nickel hydrogen carbonates; chromium metal, chromium hydroxides, chromium oxides, chromium carbonates, chromium hydrogen carbonates; manganese metal, manganese metal hydroxides, manganese metal oxides, manganese metal carbonates, and / or manganese metal hydrogen carbonates. Hydroxides may be present due to the reaction of metals with additional alkaline catalysts and water. Oxides may be present due to the reaction of metals with oxygen-containing compounds and as passivation layers. Hydrogen carbonates and carbonates may be present due to the reactions of metals, metal oxides and / or metal hydroxides with the carbon dioxide generated in situ by decarboxylation reactions. Metal acetates may be present due to reactions of metals, metal oxides, metal hydroxides, metal hydrogen carbonates and metal carbonates with acetic acid generated in-situ by hydrolysis of organic matter.
Metals or metal compounds associated with surfaces made of steel and similar materials can catalyze diverse reactions, including but not limited to, one or more of the reactions described in Table 1 above. For example, catalysts can catalyze hydrothermal reactions such as, for example, decarboxylation reactions (see, for example, Maiella and Brill, Spectroscopy of Hydrothermal Reactions. 10. Evidence of Wall Effects in Decarboxylation Kinetics of 1.00 m HCO2X (X = H , Na) at 280-330 ° C and 275 bar, J. Phys. Chem. A (1998), 102, 5886-5891) and hydrogen transfer reactions (see, for example, Onwudili and Williams, Hydrothermal reactions of sodium formate and sodium acetate as model intermediate products of the sodium hydroxide-promoted hydrothermal gasification of biomass, GreenChem., (2010), 12, 2214-2224).
(iii) Recycling catalysts
The catalysts according to the invention can be recycled for use in subsequent reactions for converting the feed stock from organic matter into biofuel. The recycled catalysts can be additional catalysts and / or intrinsic catalysts as described herein.
As a non-limiting example only, intrinsic catalysts (for example, alkaline salts, such as potassium and calcium salts) can be transferred to the aqueous liquid phase during the reaction. As the significant concentrations of such catalysts (for example, alkaline potassium and calcium salts) may be present in the feed stocks of organic matter processed according to the methods of the invention, in certain embodiments of the aqueous phases containing dissolved catalysts (for example , potassium and / or calcium salts) can be recycled.
Therefore, in certain embodiments, the intrinsic catalysts of various reaction components (for example, from any one or more of the organic matter feed stock, the aqueous solvent, and / or the vessel walls of a reactor apparatus) can be renewed in situ to alleviate or reduce the need to supply additional catalysts in subsequent rounds of feed stock conversion. This can be particularly advantageous in embodiments of the invention, related to prolonged operation at scales at or greater than the scale of the pilot plant.
In general, it is contemplated that the recycling of intrinsic catalysts present in reaction components, such as supplying organic matter (for example, alkaline salts), may allow a situation in which additional catalysts are needed during the start-up operation only.
In preferred embodiments, an intrinsic catalyst recycled in the reaction process is an alkali and / or alkaline earth metal salt (for example, potassium, calcium and / or sodium salts).
Examples of reaction conditions
In certain embodiments, the organic matter treated using the methods of the invention is (or comprises) a fossilized organic matter (see section above entitled Organic matter). For example, the treated organic matter can be lignite.
Conversion of fossilized organic matter into biofuel can be carried out, for example, using an aqueous solvent at temperatures between about 200 ° C and about 400 ° C and pressures between about 150 bar and about 350 bar; preferably at temperatures between about 250 ° C and about 375 ° C and pressures between about 175 bar and about 300 bar; more preferably at temperatures between about 300 ° C and about 375 ° C and pressures between about 200 bar and about 250 bar; more preferably at temperatures between about 320 ° C and about 360 ° C and pressures between about 200 bar and about 250 bar; and even more preferably, at temperatures between about
340 ° C and about 360 ° C and pressures between about 200 bar and about 240 bar.
Preferably, the aqueous solvent is water, or an aqueous alcohol (for example, aqueous ethanol or methanol) comprising between about 1% and about 5% w / v of alcohol, an aqueous alcohol (for example, aqueous ethanol or methanol) comprising between about 1% and about 10% w / v alcohol, between about 5% and about 15% w / v alcohol, or between about 5% and about 20% w / v alcohol.
Preferably, the retention time is between about 15 minutes and about 45 minutes, more preferably between about 15 minutes and about 40 minutes, and even more preferably between about 20 minutes and about 30 minutes.
Conversion of fossilized organic matter to biofuel can be improved by adding one or more catalysts (see subsection above entitled Catalysts). For example, conversion can be increased by adding a transfer hydrogenation catalyst (eg formic acid, sodium formate, and / or sodium hydroxide (under a reducing atmosphere)) or a direct hydrogenation catalyst (eg , Ni, Pt, Pd on silica or carbon (under a reducing atmosphere)).
Therefore, in some embodiments, a biofuel can be produced from organic matter that comprises fossilized organic matter (eg lignite) using water as a solvent, at temperatures between 300 ° C and 375 ° C and pressures between about 200 bar and about 250 bar, and a retention time of more than about 15 minutes. Optionally, the conversion can be increased by adding one or more catalysts, as described herein. The catalyst may comprise one or more transfer hydrogenation catalysts (for example, sodium formate, sodium hydroxide (under a reducing atmosphere), formic acid and / or formate).
In certain embodiments, the reaction comprises an alkali metal hydroxide and / or alkali metal carbonate catalyst (e.g., sodium hydroxide, and / or sodium carbonate) in the range of about 0.1 Molar to about 1 Molar (in reaction). In preferred embodiments, the concentration can be from about 0.1 Molar to about 0.3 Molar. In certain embodiments, the organic matter treated using the methods of the present invention is (or comprises) lignocellulosic material (see section above entitled Organic matter). For example, the treated organic matter can be pine radiata.
Conversion of lignocellulosic material to biofuel can be carried out, for example, using an aqueous solvent at temperatures between about 200 ° C and about 400 ° C and pressures between about 150 bar and about 350 bar; preferably at temperatures between about 250 ° C and about 375 ° C and pressures between about 150 bar and about 250 bar; more preferably at temperatures between about 270 ° C and about 360 ° C and pressures between about 170 bar and about 250 bar; and more preferably at temperatures between about 300 ° C and about 340 ° C and pressures between about 200 bar and about 240 bar.
Preferably, the aqueous solvent is selected from an aqueous alcohol (for example, aqueous ethanol or aqueous methanol) comprising between about 1% and about 50% w / v of alcohol, between about 1% and about 40% w / v alcohol, between about 5% and about 50% w / v alcohol, between about 5% and about 35% w / v alcohol, between about 5% and about 30% w / v alcohol, between about 10% and about 30% w / v alcohol, between about 15% and about 25% w / v alcohol, or between about 18 % and about 22% w / v of alcohol.
Conversion of lignocellulosic matter to biofuel can be improved by adding one or more catalysts (see subsection above entitled Catalysts). For example, the conversion can be enhanced by the addition of a transfer hydrogenation catalyst (for example, formic acid, sodium formate and / or sodium hydroxide).
In certain embodiments, the reaction comprises an alkali metal hydroxide and / or alkali metal carbonate catalyst (e.g., sodium hydroxide, and / or sodium carbonate) in the range of about 0.1 Molar to about 1 Molar (in reaction). In preferred embodiments, the concentration can be from about 0.1 Molar to about 0.3 Molar.
Therefore, in some embodiments, a biofuel can be produced from organic matter comprising lignocellulosic matter using between about 5% and about 50% w / v of aqueous alcohol (for example, aqueous methanol ethanol) to temperatures between 250 ° C and 400 ° C and pressures between about 150 bar and about 250 bar, and a retention time of more than about 15 minutes. Optionally, the conversion can be increased by adding one or more catalysts, as described herein. The catalyst may comprise one or more transfer hydrogenation catalysts (for example, formic acid, formate and / or sodium hydroxide).
Continuous flow
The production of biofuel from organic matter, using the methods of the invention can be assisted by carrying out the methods under continuous flow conditions.
Although the methods of the invention need not be performed under continuous flow conditions, this can provide a number of advantageous effects. For example, continuous flow can facilitate accelerated implementation and / or removal of heat and / or pressure applied to the slurry. This can help achieve the desired rates of mass and heat transfer, heating / cooling and / or pressurization / depressurization. Continuous flow can also allow the retention time to be well controlled. Without limitation, for a particular mode of action, it is postulated that the increased speed of heating / cooling and / or pressurization / depressurization facilitated by continuous flow conditions together with the ability to firmly regulate the retention time helps to prevent the occurrence of undesirable side reactions (eg polymerization) as the slurry heats / pressurizes and / or cools / depressurizes. Continuous flow is also believed to improve the reactions responsible for the conversion of organic matter to biofuel due to the generation of mixing and shear forces that aid in emulsification which can be an important mechanism involved in the transport and storage of the generated oils away from the reactive surfaces of the feed stock.
Therefore, in preferred embodiments, the methods of the invention are carried out under continuous flow conditions. As used here, the term continuous flow refers to a process in which organic matter mixed with the aqueous solvent in the form of a slurry (with or without additional catalysts) is subjected to:
(d) heating and pressurizing to a target temperature and pressure, (e) treating at target temperatures and pressures for a defined period of time (ie, the retention time), and (f) cooling and depressurizing, while the slurry is fluid. it is maintained in a continuous movement current along the length (or partial length) of a given surface. It will be understood that the continuous flow conditions as contemplated herein are defined by a starting point of heating and pressurization (that is, (a) above) and by an end point of cooling and depressurization (that is, (c) above).
Continuous flow conditions, as contemplated herein, do not imply a particular limitation with respect to the flow rate of the supplied slurry which is maintained in a continuous motion current.
Preferably, the minimum flow rate (independent volume) of the slurry over a given surface exceeds the sedimentation rate of solid matter within the slurry (i.e., the terminal velocity at which a suspended particle having a greater density than than those surrounding the aqueous solution movements (by gravity) to the bottom of the slurry stream).
For example, the minimum flow rate of the slurry 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 device used to maintain continuous flow conditions.
Continuous flow conditions can be facilitated, for example, by carrying out the methods of the invention in an appropriate reactor. A suitable reactor apparatus will generally comprise heating / cooling, pressurization / depressurization and the components of the reaction in which a continuous flow of slurry is maintained.
Ά using an adequate flow rate (under continuous flow conditions) can be advantageous in preventing scale formation along the length of a particular surface that the slurry moves along (for example, vessel walls of a reactor) and / or generates an effective mixing regime for efficient heat transfer in and within the slurry.
Biofuel products
The methods of the invention can be used for the production of biofuel from organic matter. The nature of the biofuel product may depend on a variety of different factors, including, for example, the feed stock of organic material, and / or reaction conditions / reagents used in the methods.
In certain embodiments, the biofuel product may comprise one or more of bio-oil, coal oil (for example, carbon from carbonaceous residue with bound oils), soluble clear oil, gaseous products (for example, methane, hydrogen, carbon monoxide carbon and / or carbon dioxide), alcohol (for example, ethanol, methanol, and the like), and biodiesel.
In certain embodiments, a biofuel can be produced from fossilized organic matter, such as, for example, lignite (lignite), peat or oil shale. Biofuel can comprise solid, liquid and gas phases. The solid phase can comprise a high carbon carbonaceous residue (upgraded to PCI equivalent coal). The liquid phase can comprise bio-oils. The gaseous product may comprise methane, hydrogen, carbon monoxide and / or carbon dioxide.
In other modalities, a biofuel can be produced from organic material that comprises lignocellulosic material. The biofuel can comprise a liquid phase that comprises bio-oil.
Biofuels produced according to the methods of the invention can comprise a number of advantageous features, non-limiting examples of which include the reduced oxygen content, the increased hydrogen content, the increased energy content and an increased stability.
A bio-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 25 MJ / kg, preferably greater than about 30 MJ / kg, more preferably greater than about 32 MJ / kg, even more preferably greater than about 35 MJ / kg, and even more preferably greater than about 37 MJ / kg, 38 MJ / kg, or 39 MJ / kg. The bio-oil product may comprise less than about 15% by weight of oxygen db, preferably less than about 10% by weight of oxygen db, more preferably less than about 8% by weight of oxygen db and even more preferably less than about 7% by weight of db oxygen. The bio-oil product may comprise more than about 6% by weight of hydrogen db, preferably greater than about 7% by weight of hydrogen db, more preferably greater than about 8% by weight of hydrogen db, and even more preferably greater than about 9% by weight of db hydrogen. The molar ratio of hydrogen: carbon of a bio-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.
A bio-oil produced according to the methods of the invention may comprise, for example, any one or more of the following classes of compounds: phenols, aromatic and aliphatic acids, ketones, aldehydes, hydrocarbons, furfural, terpene, polycyclic ethers esters alcohols , oligo- and polymers of each of the aforementioned classes, plant sterols, modified plant sterols, asphaltenes, pre-asphaltenes, and waxes.
A carbonaceous residue or carbonaceous oil residue 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, or 32 MJ / kg. The carbonaceous residue or carbonated oil residue product may comprise less than about 20% by weight of db oxygen, preferably less than about 15% by weight of oxygen db, more preferably less than about 10% by weight oxygen db and even more preferably less than about 9% by weight of oxygen db. The carbonaceous residue or carbonaceous oil residue product may comprise more than about 2% by weight of hydrogen db, preferably greater than about 3% by weight of hydrogen db, more preferably greater than about 4% by weight of hydrogen db, and even more preferably greater than about 5% by weight of hydrogen db. The molar ratio of hydrogen: carbon of a carbonaceous residue or carbonaceous oil residue product 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.
A carbonaceous oil residue 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, hydrocarbons, alcohols, esters, ethers, furans, furfural, terpenes, polycyclics, oligo- and polymers of each of the aforementioned classes, asphaltenes, pre-asphaltenes, and waxes.
A carbonaceous residue product (upgraded as PCI equivalent coal) produced according to the methods of the invention can comprise, for example, a mixture of amorphous and graphitic carbon with partially oxygenated end groups, giving rise to surface alkoxy and carboxy groups, as well like carbonyl and esters.
Biofuels produced according to the methods of the invention can be cleaned and / or separated into individual components using standard techniques known in the art.
For example, the solid and liquid phases of the biofuel product (for example, from the conversion of coal) can be filtered through a pressure filter press, or rotary vacuum drum filter in a first solid separation stage and liquid. The solid product obtained may include a high carbon of carbonaceous residue with bound oils. In certain embodiments, the oil can be separated from the carbonaceous residue, for example, by means of thermal distillation or by solvent extraction. The liquid product obtained can contain a low percentage of clear oils, which can be concentrated and recovered through an evaporator.
A bio-oil product (for example, from the conversion of lignocellulosic material) can be recovered by decantation or by density separation. Water-soluble light oils can be concentrated and recovered by means of an evaporator. Bio-oils produced according to the methods of the invention can be polished or distilled to remove any remaining water, or in preparation for further processing.
Biofuel produced according to the methods of the invention can be used in any number of applications. For example, biofuels can be mixed with other fuels, including, for example, ethanol, diesel, and the like.
In addition or alternatively, biofuels can be transformed into larger fuel products.
In addition or alternatively, biofuels can be used directly, for example, as petroleum products and the like.
It will be appreciated by those 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 modalities are, therefore, considered in all aspects as illustrative and not restrictive.
Examples
The invention will now be described with reference to specific examples, which should not be construed as limiting in any way.
Example 1: Conversion of organic matter into biofuel (i) Appliances
The apparatus consisted, in part, of an elongated continuous flow reactor assembly, with a high surface area, constructed of 310 stainless steel. Because of the high degree of interaction of the materials that react with the reactor wall under continuous flow conditions. , that is, turbulence with a small radius (21.4 mm maximum and 4.25 mm minimum inches) and significant length (84 meters total), the following intrinsic catalysts were present in each of the different reactions described (that is, regardless of whether additional catalysts are included): iron metal, iron hydroxides, iron oxides, iron carbonates, iron hydrogen carbonates, iron acetates; nickel metal, nickel hydroxides, nickel oxides, nickel carbonates, nickel hydrogen carbonates; chromium metal, chromium hydroxides, chromium oxides, chromium carbonates, chromium hydrogen carbonates; manganese metal, manganese metal hydroxides, manganese metal oxides, manganese metal carbonates, manganese metal hydrogen carbonates. Hydroxides were present due to the reaction of the metals with additional water and alkali catalysts. Oxides were present due to the reaction of metals with oxygen-containing compounds and as passivation layers. Hydrogen carbonates and carbonates were present due to the reactions of metals, metal oxides
I and metal hydroxides with carbon dioxide generated in situ by decarboxylation reactions. Metal acetates were present due to the reactions of metals, metal oxides, metal hydroxides, metal hydrogen carbonates and metal carbonates with acetic acid generated by means of hydrolysis of organic matter.
(ii) Preparation of slurry
Feed stock was molded to a micron level suitable for pumping. The grinding process was wet or dry, depending on the nature of the feed stock (ie, lignite or lignocellulosic biomass). The soil feed stock was passed through a screening system to remove any remaining large particles or foreign objects. The feed stock was then slurried with water in feed tanks and kept ready for processing. In certain cases, ethanol (20% by weight) was added to the slurry (lignocellulosic biomass feed stock numbers 1-4: see Table 2B).
Stages (ii) - (iv) below were carried out under continuous flow conditions.
(iii) Heating and Pressurization
The slurry from the feed stock was obtained from the feed tanks and brought to the target reaction pressure (see Tables 2A and 2B), using a two-stage pumping system. The first stage used a low pressure pump to supply the slurry to a second high pressure pump stage. The high pressure pump was used to bring the slurry to the desired reaction pressure (subsecond interval). The slurry was then passed through five stages of the concentric tube heating system. Each heating stage has process process control and the slurry was taken to 1-2 minutes thereafter (individual sample numbers to adjust heating rates. The reaction temperature over a period of (approximately 6-7 ° C / sec), catalysts were added when lignite feed stock 4, 6, 7, 8, 9, and 10 were applied - see
Table 2A; lignocellulosic feed stock sample numbers 2, 3, and 4 - see Table 2B), and the mixture was pushed into the reactor.
A summary of the feed stocks used and the parameters that were treated under is provided in Tables 2A and 2B below. The cellulose / lignin fractions of radiata pine (feed stock sample numbers 1 and 2 in Table 2B) where generated by the extraction of hemicellulose from lignocellulosic starting material (Radiata pine), using methods described in the PCT publication number WO / 2010/034055, all the content of which is incorporated herein by reference.
Table 2A: Lignite feed stock and conditions
Sample number of feed stock Feed stock type Slurry solids (% by weight) Temp. (° C) Pressure (bar) Retention (min) Additions 1. Lignite 22.00 350 240 20 none 2. Lignite 11.50 350 240 20 none 3. Lignite 8.00 250 220 25 none 4. Lignite 9.10 350 220 25 1.3% by weight of HCOONa 5. Lignite 11.50 350 240 25 none 6. Lignite 12.73 350 240 25 0.2M NaOH 7. Lignite 12.00 350 220 25 1.5% by weight ofHCOONa 8. Lignite / lignocellulosic biomass (Banna Grass) 11.00 350 220 25 4g / L ofNaOH; 10% of Banna Grass 9. Lignite 10 340 230 25 0.35L / h NaOH, CO, 23.8 g / min 10. Lignite 16.00 330 240 5 0.1M NaOH 11. Lignite 5 260 240 20 none 12. Lignite 15.0 350 240 25 none 13. Lignite 20.0 340 240 25 none 14. Lignite 22.0 350 240 25 1% by weight of solid iron oxide, 0.03M NaOH 15. Scarlet lignitis 16.0 350 240 25 1% Fe ₂ O3 / 0.33M NaOH / 10% sucrose 16. Lignite and lignocellulosic biomass 26.5 340 240 25 0.5% ofoxideiron, 6% Bannagrass, 20%lignite 17. Lignite 25.0 350 240 25 none 18. Lignite 25.0 350 240 25 0.07M NaOH 19. Lignite 25.0 350 240 25 0.03M ofNaOH
20. Lignite 25.0 350 240 13 none 21. Lignite 25.0 350 240 13 0.015M NaOH 22. Lignite 25.0 280 240 13 none 23. Lignite 22.0 350 240 25 2% by weight of iron pyrites
Table 2B: Lignocellulosic biomass feed stock and conditions
Food stock sample number of of3 Feed stock type Slurry solids (% by weight) Temp. (° C) Pressure (bar) Residence (min) Additions 1. Lignin / fractioncellulose (RadiataPine) extracted hemi 8.00 330 180 10 20% by weight of ethanol 2. Lignin / cellulose fraction (Radiata Pine) hemi extracted 8.00 320 180 30 20% by weight of ethanol; 1M sodium hydroxide 3. Lignocellulosic material (Banna Grass) / Lignite 12.00 350 220 25 20% by weight of ethanol; 4 g / L sodium hydroxide;10% by weight of banna grass (dry basis) 4. Lignocellulosic material (Radiata Pine) 10.00 320 190 30 20% inweight ofethanol; 0.2M sodium hydroxide 5. Angioperm 10.00 320 200 3.0 20% by weight of ethanol 6. Lignocellulosic material (Radiata Pine) 10.00 320 240 25.0 20% ofethanol;0.07M sodium hydroxide 7. Lignocellulosic matter 10.00 320 240 25.0 20% ofethanol;
(Radiata Pine) 0.13M sodium hydroxide 8. Lignocellulosic material (Radiata Pine) 10.00 350 240 25.00 20% ofethanol;0.13M sodium hydroxide 9. Lignocellulosic material (Radiata Pine) 10.00 350 240 25.0 16.6% methanol;0.13M sodium hydroxide 10. Lignocellulosic material (Radiata Pine) 10.00 350 240 25.00 20% ofethanol;0.13M sodium hydroxide 11. Lignocellulosic material (Radiata Pine) 10.00 350 240 25.00 20% ofethanol;0.13M sodium hydroxide 12. Lignocellulosic material (Radiata Pine) 10.00 350 240 12.5 20% ethanol 13. Lignocellulosic material (Radiata Pine) 10.00 350 240 12.5 none 14. Lignocellulosic material (Radiata Pine) 10.00 350 240 12.5 0.03M NaOH 15. Lignocellulosic material (Radiata Pine) 10.00 350 240 12.5 20% ofethanol;0.03M sodium hydroxide 16. Lignocellulosic material (Radiata Pine) 10.00 350 240 12.5 20% ofethanol;0.02M sodium carbonate 17. Lignocellulosic material (Radiata Pine) 10.00 350 240 25 none 18. Lignocellulosic material (Radiata Pine) 10.00 350 240 25.0 none 19. Lignocellulosic matter 10.00 350 240 25.0 0.13M NaOH
(Radiata Pine)20. Lignocellulosic material (Radiata Pine) 10.00 350 240 25.0 0.13M NaOH
(iv) Conversion reaction
The reactor used is designed to keep the slurry in a laminar flow regime for a specific residence time (ie retention time). The reactor consists of a series of multiple tubular reaction vessels that can be coupled or uncoupled to adjust the total residence time. The residence time used depended on the time it took for sufficient conversion of the feed stock to occur, and in some cases varies, depending on the nature of the feed stock, the nature of the aqueous solvent used, and / or the presence / absence additional catalysts in the slurry (see Tables 2Ά and 2B). The reactor used has external trace heating, so that precise control of the temperature profile can be achieved.
(v) Cooling and pressure drop
Once sufficiently reacted, the slurry left the reactor and was passed through a concentric tube cooling module. The cooling module was used as a heat exchanger to reduce the
100 process temperature at levels suitable for the pressure drop system, and to provide an opportunity for heat recovery to improve overall thermal efficiency.
The slurry was cooled to about 180 ° C over a period of about 5 to 30 seconds (preferably 25 seconds), the cooling rate was optimized to minimize solid formation and precipitation. The slurry was passed through a pressure drop system that reduced the pressure to atmospheric levels and directed the product into a collection tank. The pressure drop system is comprised of a combination of fixed, selectable orifice, parallel paths, and also a variable orifice control valve. The collection tank uses a water jacket to cool the slurry to room temperature. Therefore, the pressure drop system and water jacket of the collection tank facilitated an almost instantaneous depressurization at ambient pressure and a rapid decrease in temperature from about 180 ° C at room temperature.
(vi) Biofuel processing The biofuel product was then processed for separation and refining. During the supply of lignite feed, the biofuel product was
101 filtered through a pressure filter press, or rotary vacuum drum filter to facilitate the first stage of separation of solids and liquids. The solid product includes a high carbonaceous carbon residue with bound oils. The oil was separated from the carbonaceous residue, either by thermal distillation or solvent extraction. The liquid product contains a low percentage of light oils, which have been concentrated and recovered through an evaporator.
During lignocellulosic biomass feed stock (or cellulose / lignin fraction feed stock), the product may be all oil (that is, without the presence of solid), depending on the processing conditions and the nature of the stock of lignin. feeding (ash content, etc.). Most did. recovered by decantation or density separation. There was also a small percentage of clear water-soluble oils that were concentrated and recovered through an evaporator. Product oils can also be polished or distilled to remove any remaining water, or in preparation for further processing.
Example 2: Analyzes of the biofuel product
102
Analyzes of the biofuel product were performed using standard techniques as per the brief descriptions below:
Analysis of Coal / Carbonaceous Residue:
Close analyzes including percentage of moisture, ash yield, volatile matter and fixed carbon were performed according to Australian Standard Methods AS2434.1, 2 and 8.
Latest analyzes, including carbon, hydrogen and nitrogen and total sulfur were carried out according to Australian Standard Methods AS1038.6.4 and AS1038.6.3.2.
The calorific value was determined according to the Australian Standard Method AS1038.5.
Ash analyzes were performed according to the Australian Standard Method AS1038.14.
Determination of ash melting temperatures under an oxidation atmosphere was performed according to the Australian Standard Method AS1038.15.
Oil analysis:
Latest analyzes, including carbon, hydrogen and nitrogen were carried out according to the Australian Standard Method AS1038.6.4.
Total sulfur analyzes were performed according to the United States Environmental Protection Agency
103 (USEPA) 5050, followed by inductively coupled plasma atomic emission spectroscopy (ICPAES).
calorific value was performed according to the Australian Standard Method AS1038.5.
Determination of total moisture in oils was carried out according to Active Standard ATSM D6304.
Table 3 below provides details on the properties of raw feed stock materials used in the biofuel generation process. Tables 4a, 4b 10 and 5 below provide details on the properties of biofuels produced according to the process.
Table 3: Analysis of characteristics of food stock
Feed stock GCV (MJ / kg db) Carbon (wt% db) Hydrogen (% indb weight) Nitrogen (wt% db) Sulfur (% by weight of db) Gray (% by weight dedb) Oxygen (% by weight of db) Molar Ratio H / C Lignite Feed Stock Sample Numbers 1 & 2 25.6 66.3 4.4 0.6 0.2 3.1 25.4 0.8 3 & 4 25.4 67.1 4.2 0.7 0.2 2.4 25.4 0.7 11, 24.1 62.2 5.4 0.6 3.8 12.9 15.1 1.0 5.6.7 & 8 25.5 65.5 4.6 0.7 0.3 2.2 26.8 0.8 9 & 10 24.7 63.4 4.4 0.5 0.3 3.6 27.8 0.8 Sample numbers ofstock offeeding of lignocellulosic material 1.2.3 & 4 17.8 48.0 5.6 0.1 0.0 0.5 45.7 1.4
104
Table 3 (continued): Analysis of characteristics of food supply
Feed stock GCV (MJ / kg db) Carbon (% indb weight) Hydrogen Nitrogen Sulfur Oxygen (% indb weight) Molar Ratio H / C (% db weight) in from (% db weight) in from (% db weight) in from Lignite Feed Stock Sample Numbers 12 25.64 66.30 4.35 0.63 0.23 25.39 0.78 13a 17 & 23 24.70 63.40 4.40 0.48 0.33 27.79 0.83 18 to 22 26.00 64.30 4.90 0.79 0.70 23.31 0.91 Lignocellulosic feed stock sample numbers 5 19.40 46.40 6.20 3.48 0.30 37.52 1.59 6 to 20 17.81 48.00 5.61 0.13 0.02 45.74 1.39
Table 4a: Lignite-derived coal oil product analyzes
No. oflignite feed stock Product analyzedDistilled oil GCV (MJ / kg db) Carbon (wt% db) Hydrogen (% indb weight) Nitrogen (wt% db) Sulfur (% by weight of db) Gray (% by weight of db) Oxygen (% by weight of db) 1 Coal oil Note: wet analysis56.43 9.50 0.65 0.20 0.082 Coal oil - 37.2 78.64 8.16 1.00 12.2Distilled half distilled 39.1 - -0.3 3 Coal oil - 30.3 82.7 8.4 0.4 0.2 0.3 7.9 4 Coal oil 43% 38.4 84.3 9.1 0.4 0.2 0.1 6.0 5 Coal oil 23% 39.3 83.2 9.1 0.2 0.1 0.1 7.4Coal oil 23% - 82.8 9.6 7.6 6 Coal oil 28% 37.0 80.4 8.8 0.3 0.1 0.1 10.2Oil 28% - 83.9 9.4 - - - 6.7
105
coal 7 Coal oil 32% 38.7 82.5 9.0 0.3 0.1 0.1 8.0Coal oil 32% - 82.8 9.2 - - - 8.0 8 Coal oil 23% 38.7 83.5 9.7 0.3 0.26.4 9 Coal oil 23% 37.5 79.8 8.1 0.4 0.28.5 10 Coal oil 16% 38.5 82.2 8.8 0.3 0.2 - 8.6 11 Coal oil 19% 39.2 79.9 8.8 0.2 0.2 - 7.1
Table 4a (continued): Analyzes of coal oil product derived from lignite
Sample No. Sample Oil yield indication GCV (MJ / kg db) Carbon (wt% db) Hydrogen (% indb weight) Nitrogen (wt% db) Sulfur (% by weight of db) Gray (% by weight of db) Oxygen (% by weight of db) Molar Ratio H / C 12 Coal oil 14-30% - 13 Coal oil 14-30% 39.23 83.06 9.20 0.21 0.16 - 7.37 1.32 14 Coal oil 14-30% 38.63 82.67 9.20 0.23 0.16 - 7.75 1.33 15 Coal oil 14-30% 39.32 82.75 9.10 0.27 0.17 - 7.71 1.31 16 Coal oil 14-30% 36.63 81.77 9.00 0.19 0.18 0.01 8.86 1.31 17 Coal oil 14-30% 38.33 83.47 8.90 0.28 0.17 0.02 7.16 1.27 18 Coal oil 14-30% 39.42 82.95 9.29 0.26 0.33 0.10 7.06 1.34 19 Coal oil 14-30% 39.64 84.73 9.08 0.30 0.33 0.10 5.45 1.28 20 Coal oil 14-30% 39.34 83.28 9.20 0.24 0.38 0.10 6.80 1.32 21 Coal oil 14-30% 39.36 84.14 9.29 0.29 0.35 0.10 5.83 1.32 22 Coal oil 14-30% 39.33 82.77 9.00 0.37 0.39 0.10 7.37 1.30 23 Coal oil 14-30%
106
Φ I -------- 1 φ Λ
Φ Η
I — I ο CL
Φ -Ρ Η β • Η
Φ Ό
W Φ Ό
Φ> • Η ρ φ
Ό
Ο Ό
Φ Ν -Η ι — I
Φ Φ Ρ Φ
Ο Ό
Φ
Ν Η
Ρ
Φ> Γ — 1 φ α
CV analysis and latest RelationshipMolar H / C 1 0.54 I I 0.64 I I 0.54 I b * LO o 0.57 I 0.60 I 0.61 I 0.71 I 0.67 I 0.59 | Oxygen (% by weight ofdb) 1 13.6 I | 13.3 I oo I 13.9 I 8.8 I 9.0 I CO 16.7 I 16.2 I 8.9 | Sulfur (% by weight ofdb) | 0.31 I I 0.18 I the o I 0.18 I I 0.23 I | 0.18 I I 0.20 | L 0.22 I I 0.28 I I 2.59 | Nitrogen (% by weight ofdb) I 0.891 06'0 | I 0.89 | I 0.75 | I 0.75 | I 0.74 | 1The bo CO CO o I 0.83 | I 0.79 | Hydrogen (% by weight ofdb) Z9'e | 8f'fr | I 3.80 | I 3.70 | 3.80 | O 4.10 | I 4.40 | OV * I 3.47 I Carbon (% by weight ofdb) I 78.9 | oo I 84.5 | OO b-. B- the CO 81.0 | 79.9 | 79.1 | 73.4 | 69.9 | GCV (MJ / kgdb) | 30.62 | I 31.12 I | 33.30 | | 30.20 ι 31.80 | 32.30 | 31.40 | I 31.6 | I 28.90 | I 27.52 | Close analyzes Fixed C. (% by weightdb) V I 6'99 I I 76.9 | b- CO 71.6 | 69.9 | 69.5 | I 68.9 I 62.0 | I 55.6 | Volatiles (% by weight db) I 26.2 | CO b- CM I 20.5 | I 29.3 | I 22.1 I I fsz I I 26.6 | I 26.9 | I 32.8 I the CO Ash (% by weightdb) The b *.CM I 3.30 | 2.60 | I 3.701 l 6.30 I I 5.00 | I 3.80 | The CM I 5.20 | I 14.3 Humidity (% by weight ofair) I 4.60 | I 2.20 I O o'T— I 2.60 | I 1.80 I O I 0.80 | I 1,001 I 3.80 I I 6.00 IProduct analyzed I pci the CL I PCI the CL I pci I I pci I the CL I PCI ω CL I PCINo. oflignite feed stock CX1 COLO CO B- OO σ> O
LD
107
Table 4b (continued): Analysis of equivalent injection product (carbonaceous residue)
I — I
The CL
O P • H c
-H <—I
The b w is b>> -H (D b
B is N • r4 <—I'm 4-> ok
The b is N H
O> Γ — 1 are you>
OK
O
The b
Constituents of Ash S O- Ui, - „C4 E φ> 2 ^ Φ CLT3 bs. the o | 90’0 I I 0.03 I z-x O<2 _ c- (Λ .—>c E J2N Φ Q-XJ δ o V S o o 8 _<J5 E Φ -QOQ Φ Q_ Ό 0.14 bo LO OCD Q o c ° -C / J φ o. = O [0.23 0.56 O Mn3O4 (% by weightdb) I 0.12 | 10.19 | ! 0.09 I LO ~the g _or g2 E φ xaO. 2 / Φ O.X3 The Q> I 0.40 | co θ ' the oθ ' co OE Φ SCO 2-, Φ CL T5 I 20.50 | I 17.30 I l 18.40 | l 10.90 | | 10.20 II 13.70 | 12.90 0.68 | o oooo oo cn <O £ φ X5 O φ Ο-Ό [22.60 | | 25.60 | 16.90 | OIO 3.506.50 | The CN b- 11.70 | 23.30 I the oAnd oSZ 2— Φ CLT3 I 0.90 | LO LOO | 13.00 | the b- ~ | 28.10 |I 12.10 | I 09’9j I 12.50 | | 0.39 | O o°> S2 E Φ λ2 2— φ Q.-O I 15.60 | 5 θ ' OCO The coconut I 11.60 |Hmõi Γ 15.601 | 10.20 | The CNCN o ° _ÇN g2 E φ -a X 2 ^ φ Ο.Ό | 99‘0 | pooO b * r *. O [0.40 Π CN o0.55 I 0.23 Ί ρτι, 7οη '80'0 I CN OQ gÇ E φ xa1— 2-- Φ CL Ό I 0.64 | | 20.00 I l 0.39 I COCD 0.21I 0.26] CN CO θ ' [0.53] LO CNO Fe2O3 (% by weightdb) | 12.80 | The coconut I 18.50 | | 52.00 | f 34.30 II 42.10 | | 45.40 | I 31.90 | | 18.50 | 8thgS E φ xa <2— · φ CL-o | 7.70 1 | 5.80 j The OD The co OcoThe mCN The coconut** I 7.20 ^; | The coCD Si02 (wt% db) 1 17.70 I | 16.80 | 111.10 | I 6.60 I 14.90 |I 6.80 | 16.40 1 I 13.40 | 19.50 | Product analyzed ω o. the CL ω CL I pci I I pci I I lOd I the CL 1 lOd I the CL ω CL No. oflignite feed stock CN COLO co B- oo O O
108
Table 4b (continued): Product analysis (carbonaceous residue) equivalent of upgraded pulverized coal injection derived from lignite (PCI)
No. oflignite feed stock Product analyzed Ash melting temperature AFT-Ox DT(0 AFT-Ox ST(Ç) AFT-Ox HT(Ç) AFT-Ox FT(Ç) 2 PCI 3 PCI 4 PCI 5 PCI 6 PCI 7 PCI 8 PCI 9 PCI 10 PCI > 1550 > 1550 > 1550 > 1550 11 PCI
109
Η
Ο CM α> Ρ • Η α σ> Η φ
Ό w Φ
Ό <0> Η
Μ φ
Ό
Ο Ό
Φ Ν
-Η ι — I
Φ
Φ
4->
Φ
Ο Ό
Φ Ν
Ή
Μ
Φ> r — I
Φ
Λ
Ο <Φ>
Μ Φ
Ο
Φ τ>
CV analysis and latest RelationshipMolar H / C sCO 1 0.64 I 1 0.66 I o CO o I 0.62 1 0.64 I I 0.61 I I 0.66 I I 0.69 I | 99‘0 | 1 0.87 IOxygen (% by weight ofdb) oo co 1 13.3 | cm σ> co Poo 1 10.2 J ‘G’ 6 Il 12.2 | CM 1 16.5 |Sulfur (% by weight ofdb) i 0.28 | bCM o 1 0.27 | 0.26 | 0.26 | 0.49 | 0.50 | I 0.34 I1 0.46 | I 0.69 |Nitrogen (% by weight ofdb) 109'0 I b * CO θ bCO θ ' 1 tz‘o 1 1 0.85 | I 0.95 | I 0.90 | I 0.89 | CO CO CD T “σ>GOHydrogen (% by weight ofdb) 1 3.90 | I 4.10] 1 oz> | 1 5.00 1 1 3.90 | O l 4.00 | W I the CO [5.10 ICarbon (% by weight ofdb) COCO b- I 76.41 1 75.8 | 1 74.6 | 1 s> z | I 76.5 | I 9’ZZ I I 76.2 | I6’9Z I OOLO b- I 69.9 |GCV (MJ / kgdb) Γ 29.9 | CO 1 29.8 | 1 30.2 1 1 29.6 | I 30.2 | I 30.8 | Γ 30.2 | ro CM 1 30.0 ι ,0 28.0 |Close analyzes Fixed C. (% by weight db) The b- CO 1 67.9] 1 65.9 | 1 54.2 1 1 65.8 | I 65.4 I OO b- CO 632Ί I 63.01 poo [49.61Volatiles (% by weight db) oo CM h * CM xt b- CM CO o 1 26.9 | I 26.8 I COThe I 29.0 I 1 30.5 bσ> CM 1 . 43.6 IGray (% by weight db) 1 4.90 | Oun 1 08’9 | 1 5.50 | The CM I 7.80 | the CO I 7.301 1 6.50 | the CM 1 6.90 |Humidity (% by weight ofair) 1 2.00 | Ox— The bo 1 7.00 | 1 oz‘t Π I 0.40 | I 0.60 | I 0.90 | 1 0.90 1 The CNV | 36.40 Product analyzed Q Q. 6th CL 6th CL 1 ldl ω CL the CL α CL the CL O0- LPÇi! the CL 1PCISample No. CM COLO CO br— COThe CM CM CM CM | 23
110
Table 4b (continued): Analysis of product (carbonaceous residue) equivalent to injection o -P -H
C CP -H <L>
ω <0> -H
5-1 (D 75
O (0 N
-H i — I ro O -P rú
O
Π5 N -H
P
Φ> rp
Ch o «T5> M
H5 O (D
Ash constituents | V2O5 (% by weightdb) ZnO (% by weightdb) BaO (% by weightdb) SrO(% by weightdb) Mn3O4 (% by weightdb) P2O5 (% by weightdb) 1 0.23 | to* COCD O 1hθ ' 1 0.05 | I 0.10 | CD OT "CD I 0.05 | SO3 (% by weightdb) 1 8.20 | the MCO LO CJ> I 6.30 | 1 3.90 | 1 14.20 | I 12.40 | [8.00 | | 18.00 | I 13.30 | CaO (% by weightdb) 8.90 | I 7.80 | r * r-T I 6.80 | 1 5.60 | I 18.50 | I 16.30 | CO xF | 25.90 | I 24.40 I Na2O (% by weightdb) 1 2.20 | O2.30 | 1 1.80 | Γ 0.60 | CO _W Γ 1.60 | I 0.50 | The CM MgO (% by weightdb) | 12.10 | | 10.90 | O I 8.60 | I 6.60 | I 7.101 I 9.10 I 9.80 I 8.20 O O oo K20 (% by weightdb) I 0.58 | LO o I 0.66 | I 0.491 | 06’0 | I 0.381 I 0.41 I 0.40 I 0.30 I 0.24 ΊΊ02 (% by weightdb) 0.68 | 0.78 | 0.50 | The 1 ^ -. O I 0.63 | I 0.441 I 0.56 | 99'0 | I 0.43 CO o Fe2O3 (% by weightdb) I 37.90 | | 38.70 | I 47.2 | | 45.50 1 | 46.90 | | 29.90 | | 29.00 | | 28.00 | I 24.50 | I 24.00 | A12O3 (% by weightdb) I 9.40 I I 9.401 CO <o I 8.30 1 I 8.60 | I 7.30 I 8.20 I 9.00 I 6.90 I 7.30 SiO2 (wt% db) I 18.70 I I 18.50 I O> I 19.00 I I 26,101 I 23.00 | CO | 28.80 I 17.00 I 23.00 Sample No. CM it's theLO CDCO σ> The CM CM CM CM | 23
111
Table 4b (continued): Product analysis (carbonaceous residue) equivalent of upgraded pulverized coal injection derived from lignite (PCI)
Ash Melting Temperature Sample No. AFT-Ox DT (C) AFT-Ox ST (C) AFT-Ox HT (C) AFT-Ox FT (C) 12 13 14 15 1,410 1,430 1,460 1,480 16 17 18 1,180 1,190 1,190 1,200 19 1,030 1,050 1,060 1,170 20 1,290 1,300 1,310 1,320 21 1,160 1,200 1,210 1,210 22 23
112
Table 5: Analyzes of bio-oil products derived from lignocellulosic material
Distilled oil | Molar Ratio H / C O CO OI 1.28 I s 3 I 1.09 I CO o O cm CO- ΙΟ - 1 1.08 I C0 O <0 O I am! | Oxygen(% by weight of db) | 18.04 | and the coo00 I 8.82 | | 14.00 | I 14.30 | | 11.99 I 12.67 | 1 13.95 | I 12.45 I I 20.65 | I 23.19 | 1 19.42 | I 23.72 | 19.80 I 18.13 I I 18.39 | 1 οε'οΠ | 10.09 | Gray (% by weight dedb)O I 10.39 | The b- I 1.02 | The I ^ o O I 0.30 | Ο ο Ο χ— θ ' Ο θ ' Γ0.20 | 1 1.20 | I 0.30] Frex (% by weight ofdb)O" c © o * O Hi o r ^. the o ! 0.03 | I 0.04 I I 0.03] I 0.03 | I 0.04 | b * O θ ' I 0.03 | I 0.03 | I 0.02 Ί 10.02 | I 0.02 1 the o Nitrogen(% by weight ofdb)I 0.4 I 05 o 10th ” o l · · »co I 0.18 I bo “ I 0.20 | COO I 0.18 | O ο I 0.09 | I 0.08 Π 10.10 Ί ο 'Μο O 1 0.06 1 I 0.08 I Hydrogen(% by weight ofdb) I 6.39 | C000 C0 10th o> CO Tf b-T I 6.77 | CO oo <x> I 7.20 η I 7.02 I 05 05 co r < I 6.99 | I 6.69 I Γ 6.88 | 6.69 | 05 co “ 05 r *. shit * [6.58 Π O> b- I 7.19 | Carbon(% by weight dedb) I 74.71 | I 82.2 | 82.6 1 1 81.0 | I 69.25 | ,98 78.98 | I 78.64 | I 78.87 | I 79.09 | I 77.95 Π I 78.91 | Γ71.84 | ,9069.90 | I 73.50 I I 69.37 | 1 73.08 1 I 74.94 | Γ74.92 I | 33't8 I Γ82.33 I > <8 = ^10 cp 1 36.6 1 05c $ COCO | 38.86 | | 35.93 I I 34.93 I I 34.86 | I 34.16] I 34.74 | I 31.56 I I 30.49 I I 31.97 I ί 30.37 | dog | 32.20 | Γ33.14] 1 35.15 | .5035.50 1BE CO>> s® © * · CO o> +| + 98% | | 25-40% | | 25-40% | | 25-40% | | 25-40% | o * »O 'T10 C | | 25-40% | 25-40% | 25-40% Ο10 ΟΙ | 25-40% I 25-40% | 25-40% | 25-40% 1 25-40% | 25-40% | 25-40% Product analyzed bio-oil I bio-oil bio-oil bio-oil bio-oil Π | bio-oil | bio-oil | bio-oil | bio-oil | bio-oil | | bio-oil Bio-oil | bio-oil ¹ I bio-oil Γ bio-oil 1 bio-oil | bio-oil Γ bio-oil | bio-oil Γ bio-oil No. of lignocellulosic feed stockHI CO •P· L0 CO l · - CO O> OCM CO10 CO B- CO 05 Γ 20
113
Table 5 (continued): Analysis of bio-oil product derived from matter
Gray Constituents | V2O5 (% by weightdb) ZnO (% by weight db) BaO (% by weightdb) SrO (% by weightdb) Mn3O4 (% by weightdb) P2O5 (% by weightdb) 1 34.60 1 I 8.10 | I 13.10 | SO3 (% by weightdb) CO I 3.50 | The co CaO (% by weightdb) 40.60 | | 20.80 | | 28.00 | Na2O (% by weightdb) 1 0.60 | | 34.50 | I 2.20 | MgO (% by weightdb) 5.00 | 5.30 | 9.90 | K20 (% by weightdb) 1 0.36 | I 0.56 | O o Ti02(% by weightdb) 1 0.36 | I 0.21 I 0.49 Fe2O3 (% by weightdb) 7.40 | CO I 14.50 | AI2O3 (% by weightdb)1 1.70 I I 8.40 | I 12.10 | SiO2 (% by weightdb) 6.20 I I 9.60 | I 15.30 I Sample No. LO COCO σ> OCM COLO COOO| 20
114
Effect of alkali metal hydroxides and carbonates on oxygen content:
Figure 1 shows the effectiveness of alkali metal hydroxides and carbonates in reducing the oxygen content of the bio-oil product in which all conditions, except the additional catalyst concentration are constant. The ideal catalyst concentration of sodium hydroxide or sodium carbonate, under the conditions stated in the range of approximately 0.1 Molar to 1 Molar, as this provides a product with a low oxygen content (8-10% w / w p), without using unnecessarily high catalyst concentrations.
Additional characterization of Lignite-derived Coal Oil:
As shown in Table 6 below and in Figure 2, the simulated distillation of coal oil derived from typical lignite (Table 2a - feed stock sample No. 20) illustrates the product's similarity to crude oil. 99% of the oil is recovered from the GC column used for the simulated distillation at 620 ° C, which indicates that the product does not have a significant amount of low volatility residues.
Table 6: Percentage of mass recovery at different temperatures
115
Report number / COQ numbers
322196
Method properties UnitsD7169 Initial boiling point ° C 123.01% mass recovered @ ° C 157.55% of recovered mass @ ° C 218.510% of recovered mass @ ° C 252.520% of recovered mass @ 0C 294.030% of recovered mass @ ° C 332.540% of recovered mass @ ° C 387.050% of recovered mass @ ° C 428.060% of recovered mass @ ° C 459.570% of recovered mass @ ° C 484.580% mass recovered @ OC 508.090% of recovered mass @ ° C 537.595% of recovered mass (ô) ° C 560.599% of recovered mass @ ° c 620.5Final boiling point ° c 676.5% of Rec @ 360 ° C % of mass 35.2 D7169 % deRec @ 370 ° C % of mass 37.0 % of Rec @ 555 ° C % of mass 94.0
The characteristics of lignite coal oil were also investigated by quantitative 1H and 13C NMR spectroscopy. The product oil was distilled at different boiling ranges for this test, and the NMR spectra of the fractions were recorded. The fractions in this example are designated as follows.
Table 7: Designation of fractions for NMR
Sample code Approx. boiling range / C Approx. abundance% by weight THE 60-300, mainly 250-300 17 B 300-340 C 17 ç 160-200 to approximately 1-10 mbar 9 D 200-250 at approximately 1-10 mbar 24
116
AND 250-300 at approximately 1-10 mbar 15 F Up to 620 18
Proton NMR and quantitative 13C NMR spectra are shown for each fraction referred to in Table 7 as
Figures 3A-3L (first proton
NMR). A sample code A (Figures
3A-3B);
sample code
B (Figures 3C-3D) sample code
C (Figures
3E-3F);
sample code (Figures
3G-3H);
sample code
E (Figures 3I-3J) sample code
F (Figures 3K-3L).
The 1H NMR spectra have been integrated into three regions of chemical shifts that have been loosely designated as follows:
Aromatic
9.5 to about 6.2 ppm
Olefins
6.2 to about 3.5 ppm
Aliphatics below 3.5 ppm
In practice, olefinic protons can deviate up to 7.1 ppm or more, depending on substitution patterns, so it is likely to be overlap between olefinic and aromatic protons.
During 1H NMR, the integration is approximately proportional to the number of protons present in a particular chemical shift region. The integrations were used to designate the percentage of protons present Aromatic, Olefin and Aliphatic in the fractions.
117
Table 8: Oil characteristics derived from lignite
Fraction ID Approx. BP / ° C range Appearance Abundance of proton type /% "Aromatic" "Olefin "Aliphatic" THE 150-300 Mobile oil 14 6 81 B 300-340 Mobile oil 12 4 84 Ç 160-200 @ 0 (mbar) Wax oil 13 3 84 D 200-250 @ 0 (mbar) Wax 12 3 85 AND 250-300 @ 0 (mbar) wax 10 2 87 F > 300 @ 0(mbar) Betumen type 13 2 85
The 1H NMR spectra show a wide variety of chemical environments for the protons in the fractions, as expected. By far, the most abundant environment in all fractions is close to 1.4 ppm, typical of a methylene proton (-CH2-) in a linear alkyl chain. This suggests an abundance of linear hydrocarbon chains, which is an indication of a high quality bio-oil, 10 relatively easy to update a dropin fuel, such as diesel or gasoline.
The 13C spectra suggest that the ratio of (aromatic and olefinic): aliphatic carbon environments is approximately 1: 1, in most fractions, with the exception of fraction E, where it is more like 2: 3. Fraction A contained a significant abundance of carbonyl environments.
118
Overall, the combination of data
1Η and 13C suggests that all coal oil may be a mixture of substituted mono-, dithriaromatic straight-chain hydrocarbons, with most of the remaining oxygen associated with the aromatic compounds. Again, this suggests a high quality bio-oil, relatively easy to upgrade by hydrotreating / hydrocracking to a drop-in fuel, such as diesel, jet fuel or gasoline. The abundance of carbons connected to a heteroatom, such as oxygen decreases with the increase of the boiling point, this is confirmed by elementary analyzes (Table
9, below).
This suggests that most of the oxygen may be present in aromatic single ring structures, for example, phenols, and this suggests relatively mild hydrotreatment conditions that they can be. effective in removing remaining oxygen from coal oil
Table 9: Elementary analyzes of oil fractions derived from lignite
Fraction Carbon Hydrogen Nitrogen % of Sulfur 0 bydifference% by weight as rec'd % by weight as rec'd % by weight as rec'd % by weight as rec'd % by weight as rec'd THE 80.7 9.1 0.29 0.30 9.61 B 83.3 9.1 0.32 0.30 6.98 Ç 84.6 9.0 0.27 0.34 5.79
119
D 84.7 9.2 0.39 0.29 5.42 AND 86.1 9.4 0.36 0.22 3.92 F 92 8.0 0.26 0.27 0.00
Additional Characterization of Bio-Oil Derived from Lignocellulosic Material (Radiata Pine):
The 1H NMR spectrum of a typical Bio-Oil sample is shown in Figure 4. The spectrum is shown in wide peaks, the proportion of protons (aromatic plus olefinic): aliphatic is approximately 1: 4, which is similar to proportions found in the coal oil fractions. There are some proton environments close to 4 ppm, suggestive of methoxy protons - (- OCH3). These are generally less prominent in the coal oil fractions.
By far, the most abundant environment in all fractions is close to 1.4 ppm, typical of a methylene proton (-CH2-) in a linear alkyl chain. This suggests an abundance of linear hydrocarbon chains, which is an indication of a high quality bio-oil, relatively easy to upgrade to a dropin fuel, such as diesel or gasoline.
Figure 5 shows a series of molecular weight distributions determined by gel permeation chromatography for typical bio-oils prepared from pine radiata. The molecular weight distribution varies according to the
120 processing conditions; Longer residence times tend to produce broader molecular weight distributions.
The peaks in molecular weight distributions are about 200-300 Daltons, which suggests a substantial amount of material in the diesel-like molecular weight range (Cetane has a molecular weight of 226 Daltons). Again, this suggests a high quality bio-oil.
Characterization of Water Soluble Organic Materials
Despite the relatively low abundance, organic molecules contained in the water phase associated with the production of bio-oil are of interest as chemical feed stocks. Water-soluble compounds can be collected by, for example, liquid-liquid extraction (LLE) with appropriate solvents (for example, ethers, ketones, acetates, toluene), or by evaporation of water, or a combination of these steps.
Table 10 shows the typical elementary analyzes of bio-oils collected from the water phase for lignite and feed stocks of lignocellulosic material (radiata pine).
Table 10: Caloric value and elemental composition of bio oils collected from the water phases.
121
Feed stock type GCV (MJ / kg db) Carbon (wt% db) Hydrogen Nitrogen Sulfur Gray (% by weight of db) Oxygen (% by weight of db) Molar Ratio H / C (% db weight) in from (% db weight) in from (% feet db) in the of Radiata Pinus 31.27 65.87 7.66 0.04 0.01 - 26.42 1.38 Radiata Pinus 32.09 67.05 7.80 0.48 0.10 - 24.58 1.39 Radiata Pinus 31.67 69.80 7.61 0.07 0.03 - 22.49 1.30 Lignite 28.48 67.88 6.76 0.01 0.09 - 25.26 1.19
Gas Chromatography Mass Spectrometry (GCMS) analyzes show that oils obtained from water phases of processed lignocellulosic material, such as pine radiata slurries contain valuable chemical feed stocks used in industry. Non-limiting examples Phenol, 2-methoxy- (Guaiacol);
and intermediates, including food and perfume, such compounds are Phenol;
Phenol, 4-ethyl-2-methoxy- (410 ethylguaiacol); Phenol, 2-methoxy-4-propyl- (dihydroeugenol);
Vanillin; Phenol, 2-methoxy-4- (1-propenyl) - (isoeugenol);
Eugenol.
Figure 6 shows a partial GCMS analysis of a typical sample. Peak information corresponding to Figure 15 6 is shown below.
ICT Peak Report # Peak Weather R. Time I. Weather F. Area % Area Weight Name 1 4,110 4,083 4,158 1892961 1.10 1048103 2-heptene, (E) - 2 5.551 5.525 5,600 4845322 2.82 3361465 2-cyclopenten-1-one,2-methyl- 3 6,176 6.150 6.208 1836161 1.07 1328869 2-cyclopenten-1-one,2,3-dimethyl- 4 6,925 6,900 6,958 5118173 2.98 4399064 phenol
122
5 7.174 7.117 7.217 2212872 1.29 1363247 2-cyclopenten-1-one,2,3-dimethyl- 6 7,999 7,975 8.042 4111643 2.39 3678258 phenol, 3-methyl- 7 8.264 8.208 8.308 5505584 3.20 2978128 phenol, 3-methyl- 8 8,472 8,442 8.517 24317667 14.15 20429867 phenol, 2-methoxy- 9 9,167 9,142 9,200 2169182 1.26 1291213 phenol, 2,5-dimethyl- 10 9,367 9,342 9,417 2291667 1.33 1407891 phenol, 3-ethyl- 11 9,699 9,667 9,750 26143596 15.22 23765767 2.3-dimethylhydroquinone 12 10,367 10,325 10.408 6205053 3.61 5239459 1,2-benzenediol, 4-methyl- 13 10.603 10,492 10,625 11674941 6.80 9207746 phenol, 4-ethyl-2-methoxy- 14 10,649 10,625 10,692 9139019 5.32 8685435 1,2-benzenediol, 4-methyl- 15 11,158 11,133 11,175 5024156 2.92 4774011 1,4-benzenediol, 2-methyl- 16 11,270 11,175 11,292 2962108 1.72 1531083 2.5-dimethylhydroquinone 17 11,457 11,342 11,492 6551464 3.81 4601891 phenol, 2-methoxy-4-propyl- 18 11,547 11,492 11,600 8491644 4.94 5946841 4-ethylcatechol 19 11,757 11,742 11,817 2958977 1.72 1869419 vanillin 20 11,915 11,875 11,950 2381124 1.39 1213818 1,3-benzenediol, 4-ethyl- 21 12.108 12,000 12,133 2438145 1.42 719577 phenol, 4-ethyl-2-methoxy- 22 12,200 12,133 12,225 1762113 1.03 706135 phenol, 2-methoxy-4- (1propenyl) -, Z 23 12,281 12,233 12,300 1752692 1.02 1284826 phenol, 2-methoxy-4-propyl- 24 12,366 12,300 12,383 6740063 3.92 5519653 1,3-benzenediol, 4propyl- 25 12.403 12,383 12,442 2804791 1.63 2064444 phenol, 2-methoxy-4- (1propenyl) -, E 26 12,525 12,442 12,542 1818747 1.06 1125844 Ethanone, 1- (4-hydroxy3-methoxy 27 12,710 12,667 12,742 2391608 1.39 1887661 1,2-dimethoxy-4-npropylbenzene 28 12,902 12,875 12,933 2804803 1.63 2228508 5methoxycarbonylpyridine2-carboxy 29 13,154 13,125 13,183 10441687 6.08 8068955 Benzoic acid, 2,3dimethyl- 30 13,832 13.808 13,858 3020188 1.76 2467624 Eugenol
Bio-oils collected from the water phase generated when lignite slurries are processed, are generally richer in catechols and phenols and contain 5 poorer methoxy substituted compounds. These materials are valuable food stocks for
123 chemical industry. Figure 7 shows a partial GCMS analysis of a given oil. Peak information corresponding to Figure 7 is shown below.
ICT Peak Report # Peak Weather R. Time I. Weather F. Area % Area Weight Name 1 3,599 3,583 3,658 1470437 4.16 1189280 2-hexanol, 2-methyl- 2 4,749 4,733 4.817 2767299 7.83 3347650 phenol 3 5.159 5.142 5.183 516144 1.46 713147 Phenol, 3-methyl- 4 5.259 5.183 5.308 1600549 4.53 1552532 Phenol, 3-methyl- 5 5.325 5.308 5.375 1642620 4.65 2096663 phenol, 2-methoxy- 6 5.644 5.617 5.683 858510 2.43 614175 phenol, 2,3-dimethyl- 7 5,748 5.683 5,892 9552121 27.04 9352902 1,2-benzenodiol 8 5,674 5,892 6.025 2548485 7.21 1635189 1,2-benzenediol, 4-methyl- 9 6.067 6.025 6,133 4619295 13.07 3752632 1,2-benzenediol, 4-methyl- 10 6.268 6.208 6.292 2364042 6.69 891727 2-methoxy-6-methylphenol 11 6.325 6.292 6.383 2903853 8.22 536646 1,4-benzenediol, 2-methyl- 12 6.477 6.458 6.517 891055 2.52 481187 1,4-benzenediol, 2,6dimethyl- 13 6.533 6.517 6.575 1382085 3.91 874823 Methanol, (4-carboxymethoxy) benzoyl
Incorporation by Reference
This application claims priority from Australian Provisional Patent Application number 2010901473 filed on April 7. 2010, the complete content of which is incorporated by reference.

权利要求:
Claims (11)
[1]
1. Method for producing a biofuel characterized by the fact that it comprises:
treat organic matter with an aqueous solvent and at least one additional catalyst that increases the formation of biofuel from said organic matter selected from the group consisting of: an acid catalyst, a gas-to-water catalyst, a sulfide catalyst and a base catalyst which is an alkali metal salt or a transition metal salt, and an alkali metal hydroxide catalyst which increases the incorporation of hydrogen in said organic matter, in which the organic matter and the aqueous solvent are supplied in the in the form of a slurry, and said treatment is under continuous flow conditions with a flow rate independent of the minimum volume of the slurry greater than the sedimentation rate of the solid matter within the slurry, wherein said treatment comprises:
heating and pressurizing to a target temperature of between 250 ° C and 400 ° C, and up to a pressure between 100 bar and 300 bar to produce the biofuel, treatment at a target temperature and pressure for a defined period of time, and to cool and depressurize the slurry;
Petition 870190008472, of 01/25/2019, p. 14/17 and wherein, at least one additional catalyst is added to the organic matter after heating to said temperature and after pressurizing to said pressure, the biofuel is a bio-oil, and the organic matter is coal or lignocellulosic matter.
[2]
2. Method, according to claim 1, characterized by the fact that said treatment comprises the use of at least one additional catalyst that improves the incorporation of hydrogen for said organic matter, selected from the group consisting of sodium hydroxide, potassium hydroxide, transition metal hydroxide catalysts, alkali metal formate catalysts such as sodium formate, transition metal formate catalysts, reactive carboxylic acid catalysts, noble metal catalysts, and combinations thereof.
[3]
3. Method according to claim 1, characterized in that the transition metal salt catalyst comprises one or more anions selected from phosphate, aluminate, silicate, hydroxide, methoxide, ethoxide, carbonate, sulfate, sulfide, disulfide and oxide.
Petition 870190008472, of 01/25/2019, p. 15/17
[4]
Method according to claim 1, characterized in that said alkali metal salt catalyst is a carbonate or a sulfide.
[5]
5. Method according to claim 1 or 2,
5 characterized by the fact that said organic matter is fossilized organic matter having a carbon content of at least 50%, such as at least 60%, and said aqueous solvent is water.
[6]
6. Method according to claim 5,
10 characterized by the fact that:
(i) said temperature is between 320 ° C and 360 ° C, and said pressure is between 200 bar and 250 bar, or (ii) said temperature is between 340 ° C and 360 ° C, and said pressure is between 200 bar and 240 bar.
15
[7]
Method according to any one of claims 1, 2, 5 or 6, characterized in that said biofuel comprises one or more of an oily component, a carbonaceous component and a gaseous component comprising methane, hydrogen, monoxide 20 carbon and carbon dioxide.
[8]
Method according to any one of claims 1 to 2 or 5 to 7, characterized in that said organic matter is lignocellulosic material, and said aqueous solvent comprises alcohol, wherein the
Petition 870190008472, of 01/25/2019, p. 16/17 said temperature is between 300 ° C and 340 ° C, and said pressure is between 200 bar and 240 bar, and said solvent comprises between 10% and 30% by weight of alcohol.
[9]
9. Method, according to any of the
5 claims 1 to 2 or 5 to 8, characterized by the fact that said method comprises the steps of:
(i) cool the organic matter to a temperature between 160 ° C and 200 ° C in a period of time less than 30 seconds after said treatment; and
[10]
(Ii) depressurize and cool organic matter to room temperature by releasing it through a pressure stabilization device.
10. Method according to any one of claims 1 to 2 or 5 to 9, characterized by the fact that
[11]
15 that said biofuel comprises an oil component that has more than 8% by weight db of hydrogen and less than 10% by weight db of oxygen.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112012026256B1|2019-07-09|BIOFUEL PRODUCTION METHODS

---

US9481833B2|2016-11-01|Processing of organic matter

---

US10751690B2|2020-08-25|Biorefining method

---

US10450701B2|2019-10-22|Pulping liquors and uses thereof

---

US10100258B2|2018-10-16|Ballistic heating process

---

RU2575707C2|2016-02-20|Methods of producing biofuel

同族专利:

---

公开号 | 公开日

---

MX351457B|2017-10-16|

---

MX2012011589A|2013-02-26|

---

CN102947421A|2013-02-27|

---

RS56465B1|2018-01-31|

---

CN102947421B|2015-02-25|

---

CA2795563C|2017-03-21|

---

NO2556132T3|2018-01-06|

---

AU2011238428B2|2013-04-04|

---

CA2795563A1|2011-10-13|

---

KR101933726B1|2018-12-28|

---

UY33318A|2011-10-31|

---

PT2556132T|2017-11-15|

---

PL2556132T3|2018-01-31|

---

ES2641863T3|2017-11-14|

---

US9944858B2|2018-04-17|

---

BR112012026256A2|2016-07-12|

---

MY161205A|2017-04-14|

---

EP2556132A4|2014-03-12|

---

AR081449A1|2012-09-05|

---

US20130192123A1|2013-08-01|

---

NZ603011A|2015-07-31|

---

WO2011123897A1|2011-10-13|

---

AU2011238428A1|2012-11-08|

---

SG184477A1|2012-11-29|

---

BR112012026256B8|2021-08-03|

---

EP3275974A1|2018-01-31|

---

EP2556132B1|2017-08-09|

---

EP2556132A1|2013-02-13|

---

KR20130079389A|2013-07-10|

---

RU2012147243A|2014-05-20|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3864096A|1973-01-04|1975-02-04|Universal Oil Prod Co|Process for converting cellulose|

---

US4266083A|1979-06-08|1981-05-05|The Rust Engineering Company|Biomass liquefaction process|

---

US4396786A|1980-10-27|1983-08-02|Johnson Matthey Public Limited Company|Method for producing fuel oil from cellulosic materials|

---

US4451351A|1980-11-17|1984-05-29|Pentanyl Technologies, Inc.|Method of liquefaction of carbonaceous materials|

---

JPH0336872B2|1984-11-09|1991-06-03|Kogyo Gijutsuin|

---

GB8511587D0|1985-05-08|1985-06-12|Shell Int Research|Producing hydrocarbon-containing liquids|

---

US4846963A|1986-04-18|1989-07-11|Knudson Curtis L|Ionic liquefaction process|

---

JP3354438B2|1996-06-04|2002-12-09|株式会社荏原製作所|Method for treating aqueous medium containing organic matter and hydrothermal reactor|

---

EP1184443A1|2000-09-04|2002-03-06|Biofuel B.V.|Process for the production of liquid fuels from biomass|

---

CN1257252C|2004-07-30|2006-05-24|神华集团有限责任公司|Method for directly liquefying coal|

---

KR101397634B1|2005-04-29|2014-05-22|에스씨에프 테크놀로지스 에이/에스|Method and apparatus for converting organic material|

---

US7964761B2|2005-05-02|2011-06-21|University Of Utah Research Foundation|Processes for catalytic conversion of lignin to liquid bio-fuels and novel bio-fuels|

---

CN1952043A|2005-10-20|2007-04-25|北京化工大学|Method for biomass catalyzing and liquefying for producing bio-fuel|

---

MY154790A|2007-03-08|2015-07-31|Virent Inc|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons|

---

EP1862527B1|2006-05-30|2011-01-19|Environmental Consulting Catalysts & Processes for a Sustainable Development|A process for the production of light hydrocarbons from natural bitumen or heavy oils|

---

CN100554377C|2007-02-13|2009-10-28|中国矿业大学|The method and apparatus of a kind of biomass liquefied oil under mild condition modification, upgrading|

---

WO2008098358A1|2007-02-18|2008-08-21|David Rendina|Liquid fuel feedstock production process|

---

WO2009002566A1|2007-06-26|2008-12-31|The Board Of Trustees Of The Leland Stanford Junior University|Integrated dry gasification fuel cell system for conversion of solid carbonaceous fuels|

---

CN101348726B|2007-07-19|2012-06-27|汉能科技有限公司|Coal direct liquefaction method|

---

JP4957661B2|2007-07-25|2012-06-20|トヨタ自動車株式会社|Method for producing liquefied fuel oil from biomass|

---

CN101333448B|2008-07-09|2012-05-09|煤炭科学研究总院|Direct liquefaction process of coal by replacing circling solvent with petroleum or petroleum refining byproduct|

---

CA2941318A1|2008-07-16|2010-01-21|Renmatix, Inc.|Method of extraction of furfural and glucose from biomass using one or more supercritical fluids|

---

CN102209787A|2008-09-11|2011-10-05|水流生态有限公司|Transformation of biomass|

---

WO2010034055A1|2008-09-23|2010-04-01|Licella Pty Ltd|Fractionation of lignocellulosic matter|

---

EP2340293B1|2008-10-01|2018-07-18|Licella Pty Limited|Bio-oil production method|

---

US9303226B2|2009-12-31|2016-04-05|Shell Oil Company|Direct aqueous phase reforming of bio-based feedstocks|US20120016167A1|2010-07-15|2012-01-19|Exxonmobil Research And Engineering Company|Hydroprocessing of biocomponent feeds with low pressure hydrogen-containing streams|

---

BR112013016484B1|2011-01-05|2020-09-29|Licella Pty Limited|METHOD TO PRODUCE OIL AND FUEL|

---

RU2014101358A|2011-06-17|2015-07-27|БИОКЕМТЕКС С.п.А.|METHOD FOR TRANSFORMING LIGNIN|

---

WO2012177138A1|2011-06-23|2012-12-27|Universiteit Utrecht Holding B.V.|Process for the liquid-phase reforming of lignin to aromatic chemicals and hydrogen|

---

EP2800798A4|2012-01-04|2015-10-07|Univ Maine Sys Board Trustees|Formate-assisted pyrolysis|

---

ES2412241B1|2012-03-22|2014-01-28|Eduardo Pérez Lebeña|Lignocellulosic biomass liquefaction method and installation to perform said method|

---

BR112015014153A2|2012-12-18|2017-07-11|Univ Hokkaido Nat Univ Corp|plant biomass hydrolysis method|

---

WO2014097801A1|2012-12-18|2014-06-26|昭和電工株式会社|Plant-biomass hydrolysis method|

---

US9085735B2|2013-01-02|2015-07-21|American Fuel Producers, LLC|Methods for producing synthetic fuel|

---

US10427132B2|2013-06-11|2019-10-01|Licella Pty Ltd|Biorefining method|

---

CN103484141B|2013-09-05|2015-03-18|北京林业大学|Method for preparing bio-oil through online deoxygenation and hydrogenation of biomass thermal cracking liquification|

---

WO2015080660A1|2013-11-27|2015-06-04|Kat2Biz Ab|Depolymerisation of lignin in biomass|

---

CN103614168B|2013-12-09|2016-01-20|华东理工大学|The processing method of liquid fuel is prepared in a kind of mud liquefaction|

---

US20150247095A1|2014-01-30|2015-09-03|Kior, Inc.|Method of biomass conversion using a multifunctional catalyst system|

---

KR101558735B1|2014-02-13|2015-10-08|포항공과대학교 산학협력단|Inorganic nanoparticle deposited catalyst for hydrogenation and manufacturing method of the same, and hydrogenation for biomass derived hydrocarbon compounds|

---

US20200040273A1|2014-06-06|2020-02-06|Glommen Technology As|Wood processing method|

---

WO2016004473A1|2014-07-07|2016-01-14|Commonwealth Scientific And Industrial Research Organisation|Processes for producing industrial products from plant lipids|

---

WO2016048233A1|2014-09-24|2016-03-31|Power 8 Energy Pte Ltd|Method for producing liquid crude palm-coal oil|

---

WO2016058098A1|2014-10-15|2016-04-21|Canfor Pulp Ltd|Integrated kraft pulp mill and thermochemical conversion system|

---

AU2016275550B2|2015-06-11|2021-12-02|Ignite Energy Resources Limited|Upgrading residues, heavy oils and plastics|

---

EP3307950A4|2015-06-11|2019-04-17|Tyton Biosciences, LLC|Process and system for producing pulp, energy, and bioderivatives from plant-based and recycled materials|

---

RU2019109455A3|2016-09-02|2021-06-17|

---

WO2017219151A1|2016-06-24|2017-12-28|The University Of Western Ontario|Hydrothermal liquefaction of lignocellulosic biomass to bio-oils with controlled molecular weights|

---

CN108085082A|2016-11-21|2018-05-29|江苏宇之源新能源科技有限公司|A kind of improved new energy fuel formula|

---

US10392565B2|2017-12-14|2019-08-27|Savannah River Nuclear Solutions, Llc|Conversion of biomass by efficient base-catalyzed decarboxylation reaction|

---

CN107987896A|2017-12-19|2018-05-04|练仕菊|bio-fuel and preparation method thereof|

---

AU2019206607A1|2018-01-12|2020-07-16|Circ, LLC|Methods for recycling cotton and polyester fibers from waste textiles|

---

US11021659B2|2018-02-26|2021-06-01|Saudi Arabia Oil Company|Additives for supercritical water process to upgrade heavy oil|

---

CN111218307A|2018-11-25|2020-06-02|中国科学院大连化学物理研究所|Method for converting material containing polycarbonate compound into cyclic hydrocarbon in aviation kerosene|

---

CN112058216A|2020-09-04|2020-12-11|山东大学|Modified silicon-based adsorption material and low-temperature in-situ degradation method of organic pollutants|

法律状态:
2017-11-21| B25G| Requested change of headquarter approved|Owner name: LICELLA PTY LTD (AU) |

---

2017-12-12| B25A| Requested transfer of rights approved|Owner name: IGNITE RESOURCES PTY LTD, LICELLA FIBRE FUELS PTY LTD (AU) , LICELLA PTY LTD (AU) Owner name: IGNITE RESOURCES PTY LTD, LICELLA FIBRE FUELS PTY |

---

2018-05-29| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

---

2018-10-30| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

---

2018-11-27| B25M| Limitations in changing the proprietorship|Owner name: IGNITE RESOURCES PTY LTD, LICELLA FIBRE FUELS PTY LTD (AU) ; LICELLA 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?, PROTOCOLADONAPETICAO870170035893 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, LICELLA FIBRE FUELS PTY 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?, PROTOCOLADONAPETICAO870170035893 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. |

---

2019-04-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2019-07-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/04/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/04/2011, OBSERVADAS AS CONDICOES LEGAIS |

---

2021-08-03| B16C| Correction of notification of the grant|Free format text: REF. RPI 2531 DE 09/07/2019 QUANTO AO TITULAR. |

优先权:

---

申请号 | 申请日 | 专利标题

---

AU2010901473|2010-04-07|

---

AU2010901473A|AU2010901473A0|2010-04-07|Methods for biofuel production|

---

PCT/AU2011/000404|WO2011123897A1|2010-04-07|2011-04-07|Methods for biofuel production|

---