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    • 专利摘要:
    fractional method and rapid pyrolysis of integrated biomass methods, process, apparatus, equipment and systems are disclosed for converting biomass into fractions of biomass for chemicals, materials, raw materials and fuels using a low integrated rapid pyrolysis system. cost. The system enhances the prior art by creating stable bio-oil fractions that have unique properties that make them individually superior to conventional bio-oil. The invention allows water and low molecular weight compounds to be separated into a final added value fraction suitable for enhancement or extraction into value added chemicals, fuels and water. Initial process bio-oil fractions are chemically distinct, have low acidity and water content which reduces processing costs typically associated with improved conventional bio-oil post-production as fewer separation steps, mild processing conditions and inlets lower auxiliaries are required. biochar is stabilized so that it can be safely handled. The integrated rapid pyrolysis process includes storage, preparation, pretreatment and conversion of biomass, create and store biochar processing, and product recovery for stable bio-oil fractions.
    公开号:BR112013029457B1
    申请号:R112013029457-4
    申请日:2012-05-14
    公开日:2019-07-16
    发明作者:Cody Ellens；Jared Brown；Anthony Pollard；Dennis Banasiak
    申请人:Avello Bioenergy, Inc.；
    IPC主号:
    专利说明:

    FRACTIONATION METHOD AND QUICK PYROLYSIS OF
    INTEGRATED BIOMASS
    PRIORITY DATA
    This International Patent Application claims the priority benefit of US Patent Application 13 / 174,849, filed on July 1, 2011; Patent Application No. US 61 / 491,188, filed on May 28, 2011; and Patent Application No. US 61 / 486,304, filed on May 15, 2011; their disclosure is incorporated into this document as a reference.
    FIELD OF THE INVENTION
    The present invention relates generally to integrated process methods, apparatus, equipment and systems for converting biomass into chemical substances,
    15 pyrolysis materials. and fuels withBACKGROUND use of separations and reactions from Crude oil is a resource based in fossilused for production fuels transport, 20 heat and power, asphalt, chemical substances , stickers,
    pharmaceuticals, polymers, fibers and other products. The United States is a large importer of crude oil and is therefore dependent on foreign countries to satisfy demand.
    The nation's dependence on oil has partly accelerated the demand for reliable renewable energy technologies. Wind and solar technologies provide renewable heat and electricity as well as geothermal and tidal technologies. Lignocellulosic biomass, which is an organic material composed of lignin, cellulose and hemicelluloses and derived from a variety of wood and bio-waste raw materials, represents the only renewable carbon resource for energy, fuels, chemicals and other basic products
    2/47 biological.
    Non-food biomass is a geographically diverse and abundant domestic resource, which the United States Department of Agriculture (USDA) estimates can be produced in quantities that exceed 1 billion dry tons annually (see Perlack, RD; Stokes, BJ; et al. Biomass as feedstock for a bioenergy and bioproducts industry: The technical feasibility of a billion-ton annual supply, USDA-DOE, 2005). As noted above, the -10 biomass resources include agricultural waste such as wheat straw, mill and forestry waste, wood, energy crops such as yellow millet, miscanthus, energy cane, algae, process waste products industrial and similar. Biomass is a sustainable raw material15 for the production of fuels, chemicals, specialty products, electrical power and heat that can reduce the nation's dependence on foreign oil.
    The first generation of biofuels, including 20 biodiesel and grain ethanol, is produced from food biomass crops. These products are being scrutinized because of the perceived competition between food and fuel, liquid energy output and product incompatibility with existing infrastructure. The second generation of 25 biofuels is produced from non-food biomass using biochemical or thermochemical processing.
    Biochemical conversion is a multi-step process that first separates biomass into lignin and fermentable sugars. Sugars are converted biochemically into biofuels while lignin is passed through the unconverted process, reducing the overall biomass conversion efficiencies. Biochemical conversion of biomass requires
    3/47 of selective, complex and expensive microorganisms and enzymes that have been tested in the laboratory, but not commercially.
    The conversion of biomass is a high and robust temperature trajectory that can process 100% of 5 lignocellulosic biomass. There are three major trajectories of high temperature: gasification, pyrolysis and combustion. Biomass gasification is a thermal process that produces a gas mixture called synthesis gas or syngas, which can be burned directly to produce heat and power or improved for advanced biofuels using Fischer-Tropsch synthesis, fermentation or other breeding technologies. This type of process, however, requires facilities with massive capital to become economical and has a limited history of demonstration using 15 biomass raw materials (see Anex, R.P. Aden,
    THE.; Kazi, F.K .; Fortman, J.; Swanson, R.M .; Wright, M.M .; et al. Techno-economic comparison of biomass-to-transportation fuels via pyrolysis, gasification, and biochemical pathways. Fuel 2010, 89, S29 to S35). The direct combustion of biomass or 20 co-combustion generates sensitive heat that can be used to create electricity in existing installations, however it requires modified equipment to handle the biomass. In addition, since the heat of combustion cannot be easily stored, the heat energy must be used immediately.
    Pyrolysis is the thermal decomposition of biomass in the absence of oxygen (see Bridgwater AV. Review of fast pyrolysis of biomass and product upgrading. Biomass and Bioenergy 2011, doi: 10.1016 / j.biombioe.2011.01.048). It is the only thermochemical process that directly produces a high-performance liquid, called pyrolysis oil (or bio-oil, crude bio-oil, wood oil, pyrolenhosoic acid or various related terms). Since the liquid product can be
    4/47 stored and transported, the pyrolysis process can be separated from end use, providing increased flexibility over gasification and direct combustion that involve heat and process integration. However, conventional bio-oil 5 has poor properties that limit its application for petroleum substitute products. Poor properties include high water and oxygen content, instability, complex chemical nature and inability to mix with hydrocarbons (see Qi, Z.; Jie, C .; Tiejun, W .; Ying, X. Review of Ί0 biomass pyrolysis oil properties and upgrading research.
    Energy Conversion and Management 2007, 48, 87 to 92.). Pre-treatment of biomass, catalytic pyrolysis and post-production improvement are schemes that are being developed to change the product or improve its properties.
    Although conventional bio-oil has been subjected to combustion to generate heat and power, improved for fuels and extracted in chemicals and materials, it is not particularly suitable for any application. In addition, the high water content and acidity 20 generally make it a poor, corrosive and incompatible fuel with existing liquid fuel infrastructure. The high water and oxygen content makes it difficult and expensive to catalytically improve conventional bio-oil for transport fuels. The complex mixture of chemical substances in conventional bio-oil makes multi-stage separation and extraction processes necessary, but expensive and time-consuming in the production of chemicals and other materials.
    One of the challenges in conversion in biomass is : a 30 preparation integration and conversion in biomass with storage and improvement of product. Another challenge is adaptation and processing in different raw materials of biomass to to produce an
    5/47 consistent product quality.
    Another challenge is the incomplete conversion of biomass.
    Biochemical processing cannot overcome the resilient structure of lignin with the reduction of conversion efficiency of general biomass.
    Another challenge is to supply products compatible with biodiesel infrastructure, syngas renewable products and the existing fuel system. Ethanol, and conventional bio-oil, among others, have limited use in pipelines, engine pumps, turbines, and other equipment without
    remodeling, redesign and enhancements capital significant.Other challenge are the costs in tall captain inherent to improves for products in goal in 15 hydrocarbon. The improvement of syngas com use of synthesis in
    gas
    Fischer-Tropsch needs face cleaning units, operates at high temperatures, needs large, high pressure receptacles with unique metallurgy and involves catalysts. Hydrotreating, hydrodesoxygenation, hydrocracking of conventional bio-oil, require robust catalysts that minimize coking incrustation, are effective in the presence of water and acid and do not quickly deactivate hydrogen due to pyrolysis oil.
    for pyrolysis oil alkaline contaminants purchase or production necessary to remove oxygen and is an expensive part of the process and can increase the carbon footprint in the overall process.
    Another challenge is to recover phases of soluble water and insoluble water (for example, pyrolytic lignin oligomers and other conventional bio-oil compounds. Although both phases can be used independently and
    are improved raw materials for fuels, chemicals and
    6/47 materials versus conventional bio-oil, they must undergo an intensive, expensive and time-consuming extraction process.
    Another challenge is to produce bio-oil that is versatile and is well suited for multiple different products with properties that are particularly advantageous for each application.
    Another challenge involves the production of a stable bio-oil with low acidity, low oxygen content and low humidity that is miscible (easily mixed) with hydrocarbons.
    Bio-oil with high acidity, moisture and oxygen content does not mix with hydrocarbons, corrosive and expensive to improve. Frequently expensive temperature catalyst processes, with high pressure in multiple steps, are used to remove oxygen and reduce acidity (see Elliot,
    Neuenschwander, G.G., Battelle
    D.C., Hu, J., Hart, T.R.,
    Memorial Institute (2011)
    Palladium Catalyzed Hydrogenation of Bio-Oils and Organic Compounds, US Patent 7,956,224).
    Another challenge is to simplify the chemical composition of bio-oil so that it is compatible with existing products and infrastructure or improved more easily, efficiently and cost-effectively than conventional bio-oil.
    Another challenge involves the production of a solid, safe and stable bi-coal by-product that resists spontaneous combustion once exposed to ambient conditions. Conventional biochar also remains a danger in powder form as it is easily inhaled and ignited. In addition, because it is easily transported by air, it is difficult to handle and apply to the soil or use as a solid renewable fuel.
    What is needed in the technique are methods and devices that combine the preparation and conversion of biomass with collection
    7/47 product, improvement and storage to form an integrated rapid pyrolysis process that produces stable bio-oil fractions and safe biochar. A preferably low pressure, low cost of capital and integrated pyrolysis process will produce stable, value-added and distinct bio-oil fractions, each of which has unique properties, making them individually superior to bio-oil conventional for direct use or improvement for fuels, chemicals and materials -10 regardless of the biomass raw material.
    SUMMARY OF THE INVENTION
    The present invention addresses the needs mentioned earlier in the art by providing a unique and innovative solution to the challenges above, as will be summarized now and then further described in detail below.
    In some variations, the invention provides a method of fractionation and rapid pyrolysis of integrated biomass, the method comprising:
    (a) supplying a raw material comprising 20 biomass;
    (b) introducing the biomass prepared in a reactor, operated under conditions of rapid pyrolysis, and in the presence of a heat distributor and / or a heated gas to convert the biomass into a reaction mixture comprising condensable vapors, aerosol droplets, non-condensable gases and solid biochar;
    (c) removing at least some part of the solid biochar from the reaction mixture to produce an intermediate mixture comprising condensable vapors, aerosol droplets and non-condensable gases;
    (d) introducing the intermediate mixture into a multistage separator comprising less a heated electrochemical separator followed by at least one
    8/47 heat exchanger, in which at least one electrochemical separator and at least one heat exchanger are operated under conditions effective to collect individual liquid bio-oil fractions, including a final liquid bio-oil fraction, each derived from condensable vapors and aerosol droplets, in which the at least one heat exchanger and at least one electrochemical separator are operated with a heat exchanger wall temperature and an electrochemical separator wall temperature maintained above the water saturation temperature in the water vapor pressure determined inside the heat exchanger and the electrochemical separator, respectively, so that the water content is maximized in the final liquid bio-oil fraction;
    (e) recover and recycle at least some of the non-condensable gas from the intermediate mixture back to the reactor; and (f) recovering at least some part of the solid biochar as a cooled, stable biochar product.
    In some embodiments, the multistage separator comprises two or more electrochemical separators and / or two or more heat exchangers in series or in parallel. Each electrochemical separator can be an electrostatic precipitator, electrostatic separator, electrodynamic separator, separator based on capacitor or any other means or apparatus to employ the principles of separation by electrical forces. In preferred embodiments, each electrochemical separator is an electrostatic precipitator.
    In some embodiments, the method further comprises reducing the particle size of the biomass, drying the biomass or both of these steps. In certain embodiments, biomass comprises about 10% by weight of
    9/47 humidity or less and contains an average effective particle size of about 6 mm or less.
    biomass can be pre-treated biomass selected from the group consisting of roasted biomass, acid-treated biomass, enzyme-treated biomass, steam-treated biomass, washed biomass, modified density biomass, modified viscosity biomass and any combination of the same.
    In some embodiments, the reactor in step (b) is a -10 fluidized bed reactor whose fluidizing gas that includes at least some of the non-condensable gas recycled from step (e). In other embodiments, the reactor is an auger type reactor that comprises at least one auger to transmit the reaction mixture and the heat distributor. In modalities employing auger reactors, the intermediate can be substantially separated from part of the biochar and the reactor distributor. The biochar can be separated minus some interior of the distributor distributor by mixing heat with heat, followed by heat for step (b) and recycling feed from step (f), if desired.
    biochar for the
    In several modalities, at least bio-oil is additionally treated by one of the fractions or more techniques selected from the group consisting of heating, aging, blending, improving, refining, hydrotreating, adding an emulsifier, adding a surfactant , addition of a chemical additive and any combination thereof.
    Another variation of the invention provides a method of fractionation and rapid biomass pyrolysis, the method comprising:
    (a) supplying a raw material that comprises biomass;
    10/47 (b) introducing the biomass into a reactor, operated under conditions of rapid pyrolysis, and in the presence of a heat distributor and / or a heated gas to convert the biomass into a reaction mixture comprising condensable vapors, droplets of aerosol, non-condensable gases and solid biochar;
    (c) removing and recovering at least some part of the solid biochar from the reaction mixture to produce an intermediate mixture comprising condensable vapors, aerosol droplets and non-condensable gases; and (d) introducing the intermediate mixture into a multistage separator comprising at least one heat exchanger and at least one electrochemical separator, in which at least one heat exchanger and at least one electrochemical separator are operated under effective conditions to collect individual liquid bio-oil fractions, including a first fraction of liquid bio-oil, each derived from condensable vapors and aerosol droplets, in which at least one heat exchanger (such as a first heat exchanger) in a series) is operated with a wall temperature maintained above the water saturation temperature at the water vapor pressure determined inside the heat exchanger to minimize the water content in the first fraction of liquid bio-oil.
    In some embodiments, the multistage separator comprises two or more heat exchangers and two or more electrochemical separators collectively integrated to collect multiple liquid fractions from the intermediate mixture. The multistage separator may include a first electrochemical separator arranged before (i.e., upstream of) a first heat exchanger.
    first heat exchanger is operated, in some
    11/47 modalities, with a heat transfer fluid maintained above 100 ° C. Optionally, at least one of the heat exchangers is a multi-zone heat exchanger with multiple established temperature values.
    The method may further comprise the ionization of at least a portion of the aerosol droplets prior to the introduction of the aerosol droplets into the electrochemical separator to increase collection efficiency within the electrochemical separator.
    10 Another variation of the present invention provides onefractionation method and rapid biomass pyrolysis, beingthat the method comprises: (a) supply a raw material that comprisesbiomass; 15 (b) introduce the biomass in a reactor, operated inpyrolysis conditions fast, and in the presence of oneheat distributor or a heated gas for to convert The
    biomass in a reaction mixture comprising condensable vapors, aerosol droplets, non-condensable gases and solid biochar;
    (c) removing at least some part of the solid biochar from the reaction mixture to produce an intermediate mixture comprising condensable vapors, aerosol droplets, and non-condensable gases;
    (d) introducing the intermediate mixture into a multistage separator comprising at least one heat exchanger and at least one electrochemical separator, in which at least one heat exchanger and at least one electrochemical separator are operated under conditions effective for collecting individual liquid bio-oil fractions each derived from condensable vapors and aerosol droplets;
    (e) recover and recycle at least some part of the
    12/47 non-condensable gas from the intermediate mixture back to the reactor; and (f) recovering at least some part of the solid biochar as a cooled, stable biochar product, in which the heat contained in the solid biochar is integrated into any one or more of steps (a) to (e).
    In some embodiments, step (f) comprises using a portion of the non-condensable gas to optimize the recovery and cooling of the biochar. In some 10 embodiments, step (f) comprises introducing the biochar into a fluidized bed that is fluidized with the non-condensable gas. In these or other embodiments, step (f) comprises introducing an inert gas to subject the biochar to elutriation out of a mixture with the heat distributor.
    The method may further comprise the production of agglomerated biochar which includes one or more added binders selected from the group consisting of lignosulfonates, vegetable oils, water, integral bio-oil, 20 fractions of bio-oil, biomass, clay, bitumen, coal and any combination thereof.
    BRIEF DESCRIPTION OF THE DRAWINGS
    The advantages of the described technology can be better understood with reference to the descriptions below with the accompanying drawings. The drawings are not to scale and represent exemplary configurations that depict the general principles of technology. The dotted lines in the figures are representative of the optional process currents or currents used during startup, 30 emergency or breakdown conditions and are included as parts of the process.
    Figure 1 provides an exemplary low-cost integrated rapid pyrolysis process that includes
    13/47 biomass storage, preparation and conversion using a bubbling fluidized bed reactor, product processing and recovery to create biochar and stable bio-oil fractions, heat integration and product storage.
    Figure 2 provides an exemplary low-cost integrated rapid pyrolysis process that includes biomass storage, preparation and conversion using an auger reactor, biochar separation and heat distributor, product processing and recovery to create biochar and bio fractions -stable oil, heat integration and product storage.
    Figure 3 provides an exemplary low-cost integrated rapid pyrolysis process that includes storage, preparation and conversion of biomass using a fluidized bed reactor, product recovery, processing and liquid treatment to create direct oil product substitutions, integration of heat and product storage.
    The Figure provides analytical data on the moisture content of the bio-oil fraction and moisture distribution among the fractions produced from a pilot plant integrated rapid pyrolysis process.
    DETAILED DESCRIPTION OF THE INVENTION
    The apparatus, devices, systems and methods that include the innovative and unique general integrated process of this invention will now be described in detail with reference to various non-limiting approaches, including figures that are exemplary only.
    Unless otherwise stated, all figures that express dimensions, capabilities and so forth in the specification and in the claims should be understood as being modified in all instances.
    14/47 by the term about. Without limiting the application of the doctrine of equivalents to the scope of the claims, each numerical parameter must at least be interpreted taking into account the number of significant digits reported and 5 by applying common rounding techniques.
    The present invention can be practiced by implanting process steps in different orders than specifically presented in this document. All references to a step can include multiple steps (or -10 substeps) in the meaning of a step. Likewise, all references to steps in the plural form can also be interpreted as a single process step or several combinations of steps.
    The present invention can be practiced by implanting process units in different orders than specifically presented in this document. All references to a unit can include multiple units (or subunits) in the meaning of a unit. Likewise, all references to units in plural form 20 can also be interpreted as a single process unit or several combinations of units.
    As used in this specification and in the claims, the singular forms one (a) and the (a) include plural referents unless the context clearly indicates otherwise.
    Unless otherwise stated, all technical and scientific terms used in this individual document belong.
    contrary have the same meaning understood as common skill
    If a definition a or, otherwise by one in the technique to which this invention presented in that section is a form, inconsistent with a published definition presented in patents, patent applications and other publications that are incorporated in the
    15/47 of this document as a reference, the definition presented prevails over the definition that is incorporated in this document as a reference.
    Some variations of the present invention consist of an integrated method for the pre-treatment and conversion of biomass into fractions of liquid bio-oil, solid biochar and non-condensable gas that are collected, produced and recycled or stored in a rapid pyrolysis plant. The particular combination of stages is integral to the low-cost production of value-added products that include asphalt binders, fuels, chemicals and other renewable products.
    Biomass, for the purposes of the present invention, is any material not derived from fossil resources and comprising at least carbon, hydrogen and oxygen. Biomass includes, for example, plant and material derived from plant, vegetation, agricultural residue, wood residue, paper residue, animal residue and bird residue. The present invention can also be used for raw materials that contain carbon other than biomass, such as a fossil fuel (e.g., coal, oil, oil and oil sands) and solid urban waste. Thus, any method, apparatus or system described in this document with reference to biomass can be used alternatively with any other raw material. In addition, various mixtures can be used, such as mixtures of biomass and coal.
    The methods and systems of the invention can accommodate a wide range of raw materials of various, types, sizes and moisture content. In some approaches to the invention, the raw material from biomass may include one or more materials selected from construction wood harvest waste, white wood chips, wood chips from
    16/47 lei, tree branches, tree stumps, leaves, bark, sawdust, paper pulp out of specification, corn, wheat straw, wheat straw, rice straw, soy straw, cane bagasse sugar, yellow millet, miscanthus, commercial residue 5, grape pulp, almond shells, nutshell shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, seaweed or roasted version of any biomass materials listed above. Industrial by-products such as fiber from a wet ethanol milling process 10 or lignin from a cellulosic ethanol plant can also be raw materials. A person of ordinary skill in the art will readily appreciate that the carbon based raw material options are virtually limitless.
    Biomass storage and preparation
    With reference to Figures 1 to 3, the purpose of unit 105 is to receive, store, grind and further prepare the biomass raw material for conversion. As the received biomass is unloaded from the transport vehicle and can be stored in bulk in the case of wheat straw, yellow millet or similar biomass. Wood biomass can arrive as logs or chips and stored in piles, covered or uncovered buildings, silos, deposits, destackers or other means. Additional biomass types, such as algae, can be stored in a similar way.
    Biomass packaged or similarly prepared is fed to a chisel to provide a ground material roughly less than 15 cm in length, in some 30 approaches, before drying. Trunk biomass is fed in a horizontal grinder to produce wood chips smaller than 15 cm in length, in some approaches. The biomass in chips smaller than 8 cm in
    17/47 length does not generally require grinding before drying. Biomass particles between 1 cm and 8 cm in length and less than 2 cm in thickness are a preferred size that goes into the dryer, however other sizes can be accommodated, if appropriate.
    The cut and cut biomass is then dried. The purpose of the drying step is to provide feed material with a moisture content of less than, for example, 10% by weight (wet basis). In various process approaches, the raw materials can be dried to a moisture content of about 5%, 10%, 15%, 20%, 25% by weight or more.
    The dryer may consist of a rotating drum, drying oven, fluidized bed, roasting device, conveyor, deposit or other direct or indirect contact drying device. Biomass, bio-oil, biochar, non-condensable gas and fossil-based fuels can be subjected to combustion to provide heat to dry the biomass. Flue gas or vapor smoke can also be used to heat and dry biomass.
    The cooled flue gas can escape from the dryer into the atmosphere or is treated in a conventional manner, if necessary, with biomass removed by evaporated moisture. The dry biomass material is transported to a storage container, pile or grinder.
    At this point, it is preferable that the dry biomass is ground to a uniform size before conversion. In some approaches, dry biomass that is between 6 and 60 mm in length is shaped into a uniform size of less than 6 mm. In various approaches, dry biomass is shaped into a uniformly smaller size that is about 25 mm, 15 mm, 10 mm, 9 mm, 8 mm, 7 mm, 6 mm, 5 mm, 4 mm, 3 mm, 2 mm or 1 mm. A grinder with a preferred screen size between 3.1 to 12.7 mm can be used to prepare dry biomass. THE
    18/47 grinder can consist of a hammer crusher, knife mill, sprayer, vortex grinder or other such device.
    An additional biomass pretreatment unit 110 can be included in the process to further prepare biomass current input unit 115 (Figures 1 or 3) or unit 215 (Figure 2). In a preferred approach, this unit provides roasting of the 105 unit's biomass stream between 250 ° C and 340 ° C. In general, roasting is a chemical reaction process that involves heating the biomass slowly to temperatures between 250 ° C and 340 ° C in an inert environment. Roasting removes a portion of the hemicellulose biomass structure and residual moisture. Roasting vapors or other liquid or gaseous fuels can be used to heat the endothermic process. The reduction of hemicellulose in a pretreatment step is beneficial since this portion of the biomass can create low molecular weight compounds, including acetic acid during pyrolysis. Roasting has the added effect of producing more friable biomass, that is, brittle and easy to grind, as well as providing hydrophobic properties that can improve the biomass storage characteristics and reduce the water content in bio oil.
    In another acceptable approach, biomass can be prepared in unit 110 using acid pretreatment or washing with water to remove alkaline materials. In this variation, the biomass that leaves unit 110 would need to be dried at 10% humidity or less before entering units 115 or 215.
    The pre-treated, dried and molded biomass is transported inside the unit 105 or 110 to a bulk storage location. Bulk biomass storage
    19/47 acts as a buffer for the conversion process on units 115 or 215 if any repairs or maintenance are required upstream. In one approach, bulk storage can be one or more deposits, silos or destackers. Filters or cyclones can be used to remove particulate from the vent gas as bulk storage containers are filled. A nitrogen clearance cushion for sealed storage containers can be used to prevent moisture from being absorbed from the outside atmosphere and to minimize dust explosion or fire hazard.
    Pressure relief valves can be used to control layer pressure.
    The prepared and / or pre-treated biomass is fed to units 115 or 215 from bulk storage. In a particular approach, the material stored in deposits or silos is discharged using chains that swing around a vertical rotary axis using vanes (agitator), an unstacker or similar tank discharge device or silo. In another acceptable process approach, a destacker or moving floor is used to transport stored biomass. From bulk storage, biomass is transported by a conveyor to the conversion facility. The conveyor may consist of a pneumatic, ball, helical or other type of system. In the case of a belt or helical conveyor, a bucket elevator may be required to lift the material to a receiving area on units 115 or 215.
    Conversion of biomass thermal processing to convert the biomass prepared into condensable organic vapors, aerosol droplets, solid biochar and a mixture of non-condensable gas. THE
    20/47 biomass conversion is accomplished by maintaining specific reaction temperatures, an oxygen-deprived environment, short steam residence times in the reactor and high heat transfer rates on a plurality of control bridges. This conversion step takes place in a pyrolysis type reactor. Rapid pyrolysis is best performed under the following conditions: biomass particle size less than 3 mm in critical size, moisture content of the raw material less than 10% by weight, rapid biomass heating rate of 1000 ° C / s or greater , steam temperatures between
    450 to 500 ° C, oxygen-filled environment, steam residence time less than 2 seconds, rapid cooling and collection of pyrolysis vapors and aerosols in bio-oil.
    Rapid pyrolysis is a thermochemical process in which the raw material is rapidly heated in the absence of oxygen. The raw material decomposes or depolymerizes to generate vapors, aerosols, biochar and non-condensable pyrolysis gas. Rapid pyrolysis processes typically produce 60 to 75% by weight of liquid bio-oil, 15 to 25% by weight of solid coal and 10 to 20% by weight of non-condensable gases, depending on the raw material and operating conditions used.
    Condensable vapors include organic compounds that can be condensed by cooling the product stream 25 out of a pyrolyzer. Organic compounds contain carbohydrates (such as carboxylic acids), alcohols, esters, furans and phenolic compounds. Condensable water vapors will also be present.
    Aerosol refers to discrete amounts of 30 organic compounds present as solid particles and / or liquid droplets suspended in a gas phase. An aerosol droplet usually contains at least one compound that has a boiling point higher than the process temperature
    21/47 at that point in the process or has not undergone sufficient heat transfer to vaporize completely. Aerosol droplets can form from vapor condensation after leaving the pyrolysis reactor as the mixture 5 begins to cool. In the present context, aerosols tend to consist of carbohydrates (such as anhydrous sugars), phenolic compounds and lignin-derived oligomers that leave the reactor as liquids. Typically, the size (e.g., effective diameter) of aerosols is in the order of 1 pm 10 or less, although larger aerosol particles are possible, depending on the dynamics of the fluid surrounding the particle or droplet.
    Non-condensable gases include hydrogen, carbon monoxide, carbon dioxide, methane and another 15 light hydrocarbons created during pyrolysis. Non-condensable gases can also include inert gases injected into the pyrolysis system. Typically, non-condensable gases represent about 10% by weight to about 25% by weight of pyrolysis products.
    Biochar or coal is a solid product of biomass pyrolysis. Rapid pyrolysis conditions maximize the yield of bioliquid and minimize the yield of biochar. Both primary and secondary biochar formations occur in a rapid pyrolysis process. Primary coal or coal is formed as a direct product of biomass pyrolysis. Secondary coal is not a direct result of biomass pyrolysis, but secondary reactions that occur when pyrolysis vapors, aerosols and bio oil are converted to coal and / or non-condensable gas 30 due to high temperatures or the presence of primary coal .
    Biomass with a high lignin and ash content tends to increase primary coal yields while slow heating rates, long steam residence times and high pressures
    22/47 lead to the formation of secondary coal. Secondary coal formation must be minimized or eliminated in rapid pyrolysis as it is created at the expense of bio-oil yield.
    Any pyrolysis reactor can be used to pyrolyze the raw material. Exemplary reactor configurations include, but are not limited to, bubbling fluidized bed reactors, circulating fluidized bed reactors, auger reactors, ablative reactors, rotary cones, entrained flow reactors, vacuum moving bed reactors, transported bed reactors, fixed bed reactors and microwave assisted reactors. Preferably, the selected pyrolysis reactor has the ability to achieve rapid heat transfer to prepared biomass and provide short steam residence times.
    In some approaches to the present invention, the biomass prepared from unit 110 and / or 115 is transferred to a loading hopper, hopper or compensation tank in unit 115 and / or 215. Nitrogen or other inert gas can be used to purge the solid oxygen biomass hopper. The biomass is transferred from the loading hopper to a feeder system. The feeder is used to measure and inject feed into the reactor.
    The process heat must be supplied to the reactor to perform endothermic reactions that occur between 400 ° C and 550 ° C. The heat source can be electrical, flue gas combustion, steam smoke, solid heat distributor or other source, or any combination thereof. Although in some approaches reactions occur substantially in the absence of air and oxygen, reactor heating can be provided in part by partial combustion
    23/47 of the biomass raw material. Controlled amounts of oxygen can be fed into the reactor to regulate the reaction temperature during pyrolysis.
    In a particular approach, reactor unit 115 is a bubbling fluidized bed that contains a bed material and fluidized with a gas. Fluidizing gases are preferably preheated before entering the reactor as noted in unit 140. The flue gases leaving unit 115 can be used to preheat the fluidizing gas. In a preferred approach, the fluidizing gas entering unit 115 is recycled non-condensable gas from unit 120. In another acceptable approach, pressurized hydrogen or nitrogen from unit 145 and preheated in unit 140 can be used to fluidize the reactor during startup, operation, emergency or breakdown conditions.
    In another approach depicted in Figure 2, unit 215, the reactor includes an auger with one or more propellers. The auger reactor uses mechanical agitation to transport and mix biomass with a heat distributor to pyrolyze the biomass.
    In a preferred approach, a heat distributor is used to transfer process heat to the biomass prepared in unit 115 (fluidized bed), in unit 215 (auger reactor) or other reactors. The close contact between the heat exchanger and the biomass provides fast, accurate heat transfer. Upon contact with the heat distributor, the prepared biomass will pyrolyze, releasing vapors, aerosols, solid biochar and gaseous reaction products. The heat distributor can be inert solids such as stainless steel or steel shot, sand, silica, alumina, dolomite, olivine or limestone, to list a few. The heat distributor, in some approaches, is a
    24/47 catalyst material (for example, a metal oxide) that not only transfers heat, but confers some ability to catalyze the chemistry of pyrolysis.
    In an approach that uses a fluidized bed reactor at unit 115, the reaction product leaves the reactor and enters unit 150, where the biochar is removed and the reaction product stream continues to unit 120.
    In another approach using an auger reactor at unit 215, the reaction product stream leaves the reactor and enters unit 120 directly, while large biochar particles not entrained with the reaction product stream are separated from the heat distributor in the unit 250.
    In some approaches where an auger reactor is used, the raw material and the heat distributor are fed into one end of a reactor that contains one or more propellers. The propeller (s) mix (es) the heat distributor and the raw material and transport them through the. The speed and geometry of the propeller (s) can provide good control of the mixing behavior and residence time of the heat distributor. This mechanical mixing can eliminate the need for a fluidizing gas that dilutes products. The heat distributor can be reheated in a separate container.
    In some approaches, the pyrolysis reaction temperature is between about 300 to 600 ° C, such as about 400 to 500 ° C. Any effective reaction condition can be used to pyrolyze the raw material in the pyrolysis reactor. One skilled in the art can select a combination of temperature, pressure and residence time that produces high liquid yields from the pyrolysis process. Or the temperature, pressure and residence time can be selected to increase biochar yields, if desired.
    25/47
    In some approaches, pyrolysis can be performed in the presence of a catalyst. Exemplary catalysts include heterogeneous catalysts (such as SiO2-AI2O3, Pt / SiO2-Al 2 O 3 , WO x / ZrC> 2, SO x / ZrO 2 ), zeolites, acid catalysts, clay catalysts (for example, catalysts of clay activated or acidified clay), Al-MCM-41 mesoporous catalysts or activated alumina. In some approaches, a catalyst shows a lower temperature to be used, such as about 250 to 450 ° C.
    In some approaches, the pyrolysis reaction pressure is between about 0 to about 13789.5 kPa (2,000 psi), as well as between about 0 to about 344.7 kPa (50 psi).
    In some approaches, the residence time of the pyrolysis gas is between about 0.1 second to about 10 seconds, such as about 1 to 5 seconds.
    In some approaches, vacuum pyrolysis is used. In this method, the raw material is heated under vacuum to decrease the residence time of the gas and boiling point and / or avoid adverse chemical reactions. Fast or slow heating rates can be used. Some approaches employ a temperature of around 450 ° C and occur below atmospheric pressure (<720 mm Hg).
    Product Recovery
    The purpose of unit 120 is to collect and process only condensable vapors, liquid aerosols and non-condensable gas that leave units 115, 150 and 215. In some variations, the present invention incorporates technology described in Patent Application 2 US 12 / 551,103, entitled Bio-oil Fractionation and Condensation filed on August 31, 2009 by Brown et al., which is incorporated by reference in this document in its entirety.
    Unit 120 is particularly important,
    26/47 providing a low cost and distinct pyrolysis system for the production of value-added products, including asphalt binders, fuels, chemicals and renewable raw materials from different liquid fractions.
    In some approaches, various combinations of condensers (such as shell and tube heat exchangers) and electrochemical separators (such as pyrolysis precipitators. Electrostatic condensers) are configured to collect individual liquid products that comprise oil fractions and electrostatic precipitators are simple equipment, maintenance used commercially proven and low industrial. That same production of fractions in all types of technology can add value to applications used for bio-oil with superior properties in comparison with conventional bio-oil. The present invention additionally integrates these auxiliary unit operations with rapid pyrolysis equipment and enhances the prior art by providing a complete package for low-cost and efficient production of unique bio-oil fractions.
    This technology and the combination of equipment provides a value-added bio-oil product that is much more cost-effective than combining rapid pyrolysis 25 with Fischer-Tropsch high pressure and high temperature technology to create liquid fuels. Similarly, the invention reduces post-production improvement costs normally associated with conventional bio-oil post-production by simplifying the product (s) in chemically distinct fractions that require few separation steps, processing conditions lower auxiliary inputs.
    The presence of one or more capacitors as well
    27/47 as one or more electrochemical separators explores the different behavior and properties of vapors and aerosols leaving the pyrolysis reactor in order to collect chemically unique liquid products. Capacitors are devices that are well known in the art, but are only integrated in this process. A liquid-cooled heat exchanger can be employed. Exemplary capacitors include a Liebig capacitor, a Graham capacitor, a Dimroth capacitor and a spiral finger capacitor.
    Hull and tube heat exchangers can also be used to collect condensable steam products. Hull and tube heat exchangers can use water, a water / glycol mixture, oil, steam smoke or other fluid as a means of heat transfer. The temperature control of the heat exchanger can be provided through the use of liquid to liquid heat exchangers or forced air to liquid heat exchangers, refrigeration tanks, refrigerators, groundwater, boilers and / or other techniques.
    Although preferred approaches to the present invention use electrostatic precipitators, it should be noted that the invention is not so limited. Generally speaking, in preferred approaches, the product recovery unit 120 uses at least one electrochemical separator with the ability to separate aerosol particles using electrical forces. Electrochemical separators as intended in this document may include electrostatic precipitators, electrostatic separators, electrodynamic separators, capacitor-based separators and other means or apparatus to employ the principles of separations by electrical forces.
    Electrostatic precipitators are designed to
    28/47 collect aerosol and particulate droplets using electric field forces instead of condensation. Electrostatic precipitators work by charging particles, then collecting charged particles in an electric field. The loading takes place through two mechanisms: diffusion loading and field loading. In diffusion charging, ions in the gas jump due to Brownian motion, bombard a particle and transfer their charges to it. Field charging occurs when a particle 10 is in an electric field that contains ions.
    In the context of the present invention, electrostatic precipitators, when used, separate and collect liquid aerosols from the product stream. Electrostatic precipitators use a high voltage power supply to create a potential electrical difference between discharge electrodes and collection electrodes in order to capture polarized or charged aerosols.
    In some approaches, an electrostatic precipitator includes one or more tubes, channels or ducts through which the gas and vapors flow, acting as an electrical ground and collection surface for aerosols. A discharge electrode is suspended in the center of the pipe, acting as the high voltage electrode (for example, ± 20 to 60 kV DC). The high voltage applied to the electrode causes an electrostatic field 25 to be formed between the electrode and the grounding channel. This field projects a force on any particle (aerosol or particulate) that passes through it. As the particle passes through the field, it moves forward towards the soil wall and joins the wall. Gravity forces these aerosol-derived liquids to flow under the electrostatic precipitator to be collected. The electrostatic precipitator uses a negative or positive polarity supply.
    29/47
    In exemplary approaches, there are five subunits contained in unit 120, mainly three heat exchanger subunits and two electrostatic precipitator subunits, configured in series with a heat exchanger followed by an electrostatic precipitator, then another heat exchanger, then another electrostatic precipitator and finally one last heat exchanger. Each subunit can contain multiple electrostatic heat exchangers or precipitators in series or parallel configurations. Many other configurations are possible, including (but not limited to) those variations described in Patent Application No. 2 US 12 / 551,103.
    In one approach, the first subunit in product recovery unit 120 is a heat exchanger 15 designed to condense and collect vapors that flow in laminar conditions from unit 150 or 215. The liquid to liquid heat exchanger can operate at a constant temperature , or at a varying temperature, to collect the first liquid fraction. To prevent build-up on the walls 20 of the heat exchanger, the heat exchanger must be operated at temperatures higher than 75 ° C. The heat exchanger can be designed to operate with a refrigerant kept at 75 to 150 ° C and the ability to cool the inlet current temperature to 90 to 200 ° C, for example. In various approaches, the heat exchanger has the ability to cool the incoming current to about 90 ° C, 100 ° C, 110 ° C,
    120 ° C, 130 ° C, 140 ° C, 150 ° C or higher. In some approaches, the extent of cooling is selected to allow condensation of a particular species, or class 30 of molecules, of interest with a function of temperature, pressure and general concentrations.
    Laminar flow conditions in the first heat exchanger help prevent impact and droplet collection
    30/47 aerosol on the condenser walls. However, flow conditions can include local turbulent regions, turbulent eddies, instabilities, flow transitions and transients that separate from the true laminar flow.
    In preferential approaches, the number of
    Calculated flow Reynolds, on average and in a balanced state, provide for substantially laminar flow.
    In unity with some approaches, the second subunit in product recovery 120 is an electrostatic precipitator that operates isothermally above the water's dew point to collect at least some of the aerosol droplets present in the reaction stream, thereby producing a second net fraction. The electrostatic precipitator can be heated using electric heat, heat transfer fluid such as oil, steam smoke, gas, water / glycol mixtures or other such methods.
    In some approaches, the third subunit in the product recovery unit 120 is a second heat exchanger designed to operate at a constant temperature above the water's dew point to condense and collect a third liquid fraction. As an alternative, the heat exchanger can be designed to operate at a temperature above the dew point of another species in addition to water or a temperature selected for other reasons.
    In some approaches, the fourth subunit in the product recovery unit
    120 is a second electrostatic precipitator designed to operate in an isothermal manner to remove at least some of the aerosol droplets still present, thereby producing a fourth liquid fraction.
    In some approaches, the fifth subunit in product recovery unit 120 is a heat exchanger
    31/47 final designed to operate at a low temperature (at or below atmospheric temperature), preferably where the water vapor condenses to recover a fifth liquid fraction. This heat exchanger is preferably operated at a temperature low enough to condense the water
    remainder and low compounds Weight molecular. Preferably, each exchanger in heat has an cooling temperature selected in so that the liquids that condense into each internship no freeze in
    walls, preventing unwanted side reactions and equipment encrustation. Refrigerants and relatively warm equipment surfaces are therefore preferred. In some approaches, refrigeration temperatures and equipment surfaces can be controlled (adjusted) based on, for example, compositions of one or more liquid products, as they are responsible for side reactions that may be occurring.
    Preferably, each electrostatic precipitator has a unique operating temperature selected so that vapors do not condense at each stage and aerosol droplets are collected first. In some approaches, each electrostatic precipitator has a unique operating temperature so that vapors condense at each stage and are collected with aerosol droplets. In some approaches, temperatures at each stage are selected to be consistent with known saturation temperatures for the chemical species of interest. In some approaches, temperatures at each stage are selected in the context of the overall energy balance, either for economic reasons, or for equipment-specific reasons, for example.
    In certain approaches, there are between two and four subunits contained in unit 120, including at least one
    32/47 heat exchanger and at least one electrostatic precipitator. These subunits are configured to recover at least a liquid fraction derived from the organic pyrolysis vapors and at least a liquid fraction 5 derived from the pyrolysis aerosols (or that is formed downstream of the pyrolysis reactor).
    It would generally be preferable to start the sequence with a heat exchanger to prevent a high temperature current from entering an electrostatic precipitator. However, it is possible to start the recovery sequence with an electrostatic precipitator (or another type of electrochemical separator), particularly one adapted for higher temperatures. This configuration can allow rapid removal of primary aerosols from pyrolysis, before secondary aerosols 15 can form.
    In other approaches, there are between two and ten subunits contained in unit 120, including liquid-to-liquid heat exchangers and electrostatic precipitators. It will be recognized by a skilled person that many numbers and combinations of heat exchangers and electrostatic precipitators are possible in the present invention.
    Depending on the number of subunits in the recovery unit 120, there will be multiple liquid products, such as 25 two, three, four, five, six, seven, eight, nine, ten or more liquid products (fractions), usually with physical properties and compositions different chemicals. Chemical species that may be present in liquid products include, for example, furans, carbohydrates, acetic acid, levoglucosan, 30 syringes, guaiacols, aldehydes, ketones, phenolic compounds and water.
    In preferential approaches, the material entering unit 120 is fractionated so that water and acids are
    33/47 separated from resulting in water, liquid acidity.
    One or more compounds and organic oxygen of high molecular weight, liquid products that have lower levels than the other initial fraction products have low content and tend to contain high amounts (for example, anhydrous sugars) lignin making them material and asphalt, water extraction and acidity of carbohydrates and oligomers derived from suitable for use as chemical adhesives, thinners), as candidates for fermentable sugars and catalyst improvement for fuels. The fractions of medium have low content of water and acidity and phenolics and tend to improve furans, contain high amounts of compounds making them suitable for catalytic mode for fuels and chemicals (for example, diluents). The final fraction (s) contains (contains) high amounts of water and low molecular weight compounds that are suitable fuels; use of (eg, acetic acid) making for reform to direct hydrogen, extraction or distillation (eg, acetic acid, fluids, chemical substances, billing or drilling) and use as water replacement.
    Electrostatic products and separately to or from liquids collected by heat exchanger precipitators are pumped unit
    130 for storage, merging and transportation.
    The tubing from the collection unit to the storage area is expected to be heated (electrically or with a heat transfer fluid) or well insulated to reduce the viscosity of some liquids and prevent freezing.
    non-condensable gas from units 115 and 215 is cleaned before leaving the unit
    120. Non-condensable gas can pass through filters, a stuffed bed, washer
    34/47 liquid or similar to remove remaining vapors (including water) or fine aerosols before being reheated in units 125, 140, 240 and / or 250 and used as a fluidizing gas in units 115 and / or 125, and / or used as a fuel source in the 110, 140, 240 and / or 250 units.
    Biocarbon Separation
    The purpose of units 15.0 and 250 is to recover the biochar for processing at unit 125.
    In a particular approach in which a fluidized bed reactor is used in unit 115, the biochar is separated from the reaction product stream using one or more cyclones in unit 150. The use of cyclones is a standard method for removing solids from a gas stream. Additional filters can be used in conjunction with or in place of cyclone filters. The cyclone filters must be kept at the reactor temperature and be well insulated or heated to prevent condensation or incrustation.
    In another approach where an auger reactor is used in unit 215, the heat distributor and the biochar leave the reactor and are separated or combusted at unit 250. If the biochar is subjected to combustion at unit 250, the heat distributor it may be hot enough to be recirculated directly to unit 215. If biochar is subjected to combustion in unit 250, the ash must be separated from the heat distributor, for example, by a cyclone in the flue gas stream. In a preferred approach, the biochar is separated at unit 250, the heat distributor is reheated using process heat at unit 240 and recirculated back to unit 215.
    In another approach, the unit 250 can be a fluidized bed of biochar and heat distributor of the reactor. In this case, the fluidizing gas that could include non-gas
    35/47 condensable for purposely subjecting the biochar to the bed to be collected using a cyclone for elutriation while the heat distributor reactor leaves the bed to be reheated in unit 240.
    In a particular approach, the biochar and the ferrous heat distributor are separated in unit 250 using magnets, screens, screens, shakers, fluidized beds, piles and the like.
    In another approach, the biochar and the non-ferrous heat distributor are separated in unit 250 using screens, sieves, shakers, fluidized beds, piles and the like.
    In another approach, the biochar and the heat distributor are exposed to an oxidizing environment in the unit 250 to combust the biochar to provide heat to reheat the heat distributor.
    The biochar, once separated and recovered from unit 150 in the case of a fluidized bed reactor or 250 in the case of an auger reactor, is transported to unit 125 for further processing.
    Biochar Processing
    The purpose of unit 125 is to create a stable, storable, safe and unique biochar product. The hot biochar between 300 ° C and 600 ° C is received from unit 150 and 250 by pneumatic or mechanical transmission. When leaving unit 125, the biochar preferably has less than 60 ° C and is ready for storage in unit 135.
    Unit 125 may include cooling the biochar in a heat exchanger by transferring heat directly or indirectly to a heat transfer medium. The heat transfer medium can include water, bio-oil, non-condensing gas, flue gas, nitrogen, vapor smoke, air or other substance.
    36/47
    In a particular approach, unit 125 may be a container with a biochar bed and fluidized with non-condensable gas or nitrogen which also acts as a heat transfer medium. The bed may include an internal cooling loop to further remove heat. The recycled water from unit 120 can be used in the cooling loop. Good coal elutriation from the bed can be captured by one or more cyclones and reintroduced into the bed with a dipleg. A drop tube in the center of the freeboard can be used to remove cold biochar from the bed.
    In another approach, a conveyor is used to transport and cool the biochar from units 150 and 250. The conveyor may include a spray cooling system to directly cool the biochar with an external heat transfer medium.
    In yet another biochar it can be used: simultaneously the biochar spheres or other similar form or a cooling jacket approach, the sweetener to cool and process in pellets, granules, briquettes, air. Thus, the biochar product can be processed in a pelletizer, granulator, mixer with pin or other type of agglomerator. Binders or additives can be added to create a compact and uniform biochar. Binders can include lignosulfonates, water, bio-oil, vegetable oil, biomass, clay or other material. The binder can also act as a heat transfer medium. The conditioned biochar can be exposed to ambient conditions when sufficiently cooled. Stable, the conditioned biochar is transported to unit 135 for storage.
    Biochar Storage
    The biochar product received from unit 125 is ready to be stored in unit 135, if desired. O
    37/47 biochar can be stored in steel tanks, tanks, oil tankers, bulk bags, trailers, rail cars or other containment methods and can be stacked under ambient conditions. Inert purge gas can be used to remove oxygen from storage areas for safety. The biochar in storage is a point for transport and use beyond the biorefinery.
    Biochar can be transported in and out of unit 135 by means of the conveyor, pneumatic line 10, front end loader bucket or other method.
    Merging and Storage of Liquid Product
    The purpose of the unit 130 is to place and store fractions of liquid product in the unit 120. The tanks 15 used to store the product are sized according to the amount of liquid produced and the desired duration of storage. A liquid retention dyke can be located around the storage area to quarantine potential leaks or spills.
    Construction materials can include stainless steel, coated carbon steel, various polymers or other corrosion resistant materials or coatings.
    Liquids stored in unit 130 can be kept under a layer of inert gas to prevent oxidation, aging or other quality issues. This layer also minimizes the release of light volatility from the tanks. The tanks can be insulated and heated to reduce viscosity for pumping and to prevent freezing in cold weather. The tanks can be heated 30 electrically or using hot oil or steam coils.
    Tanks can be mechanically agitated in some approaches.
    From storage tanks, liquid fractions
    38/47 individual can be pumped into a blending unit to combine liquid fractions in specified proportions. The blending unit is equipped with measuring equipment to mix common blends. A stirred, heated and insulated mixing tank 5 can be used to store and certify that the product is mixed prior to transportation. A loading platform is required to fill drums, paths or shipping containers for transportation.
    Liquid Treatment
    The purpose of unit 350 in Figure 3 is to treat bio-oil fractions or combinations of fractions from units 130 or 120 before commercial sale. In some variations, the present invention incorporates technology described in Non-Provisional Patent Application No. 2 US 12 / 772,945, entitled Asphalt Materials Containing Bio-oil and Methods for Production Thereof, filed on May 3, 2010 by Williams et al., and Non-Provisional Patent Application No. US 13 / 149,183 and International PCT Patent Application No. 2 PCT / US11 / 38577, 20 entitled Bio-oil Formulation as an Asphalt Substitute, both filed on May 31, 2011 by Williams et al. which are incorporated by reference in this document in their entirety.
    In one approach, liquid treatment may take place in the mixing tank at unit 130. Treatment may include heating, aging, filtering, adding an emulsifier or surfactant, introducing chemical additives, adjusting the pH or acid content, or any another treatment using a device or material that modifies the product or mix before transportation.
    In another approach, liquid treatment at unit 350 may include a conversion process that improves the low water content bio-oil fractions of unit 130
    39/47 in value-added fuels, chemicals and / or other products. The hydrogen can be added to a catalyst reactor (with a catalyst based on Pt- or Ni, for example) to produce transport fuels that include green diesel, jet fuel or gasoline. A liquid product can be converted into a fuel or chemical by reacting with hydrogen gas, or with a species that contributes hydrogen. Species that can contribute hydrogen include acids, metal hydrides, water 10 in the water vapor change reaction, an alkane in a dehydrogenation reaction, and so on.
    In yet another approach, liquid treatment can yield one or more refinery raw materials that can be merged or co-financed with existing infrastructure 15. Of course, such liquid treatments can be performed at another location as well, such as a refinery or other operation. The process provides sufficient flexibility that, for commercial reasons, it may be preferable to produce and distribute liquids that can be added to existing operations 20 if the user needs to further treat the liquid first.
    In some embodiments, one or more bioderivative products produced by the present invention are used as described in Provisional Patent Application n-US 25 61 / 486,304 entitled Methods, Apparatus, and Systems for
    Incorporating Bio-Derived Materials into Oil Sands Processing, filed on May 15, 2011 or in Provisional Patent Application No. 2 US 61 / 491,188, entitled Compositions, Methods, Apparatus, and Systems for 30 Incorporating Bio-Derived Materials in Drilling and Hydraulic Fracturing, filed on May 28, 2011. These patent applications are incorporated by reference in this document in their entirety.
    40/47
    Process Heat
    Process heat for the reactor, fluidizing gas and / or heat distributor in units 115 and 215 is supplied in units 140 and 240, respectively.
    In one approach, the fluidizing gas stream for unit 115 must be preheated in unit 140 to maintain optimal reaction conditions.
    The preheating of the fluidizing gas can be carried out using a burner system supplied with 10 natural gas, propane, bio-oil, biomass, syngas or other fuel, including non-condensable gas. The combustion air entering the units 140 and 240 can be pressurized using a blower. The fluidizing gas is preheated by flue gas in a heat exchanger. The flue gas from the 15 units 140 and 240 can provide additional indirect heating for other unit operations including the reactor casing at units 115 and 215, the biomass dryer at unit 105 and the biomass pretreater at unit 110 and combustion air. Once cooled, the combustion gas is released into the atmosphere.
    Fluidizing gas can include non-condensing gas from units 120 and 220, nitrogen, hydrogen, vapor smoke, air or other fluid. A blower may be required to pressurize the fluidizing gas entering units 115 25 and 215. Once heated to 300 to 600 ° C, for example, non-condensable gas can be fed into the reactor system.
    In another approach, using an auger reactor or other type of reactor in unit 215, fluidizing gas may not be necessary. However, a heat distributor such as steel shot, catalyst, silica sand or other materials must be heated to maintain the reactor's operating conditions. The non-condensable gas of the unit 120 can be subjected to combustion in a burner system with
    41/47 other fuel such as natural gas or propane to preheat the heat distributor in unit 240 of unit 250. The hot combustion gas from the burner can transfer heat directly or indirectly to the heat distributor and the reactor.
    In another approach, the heat distributor of unit 250 is reheated using a direct or indirect heat exchanger in unit 240. Heat can be transferred to the heat distributor using 10 combustion gas, non-condensable gas, smoke of steam, direct combustion of biochar within the mixture of the heat distributor or by other means. Since the heat distributor is between 400 to 700 ° C, in some approaches, it is recirculated and fed to the auger reactor at unit 215.
    If any residual biochar remains in the heat distributor of unit 250, it may be advantageous to subject the biochar with non-condensable gas and / or other fuel and air to combustion directly so that the biochar is removed and the heat distributor is heated.
    Auxiliary Systems
    The purpose of Unit 145 is to provide auxiliary utilities for the pyrolysis process
    These systems include compressed air, fire water, drinking water, cold water, fast drinking water, integrated smoke.
    water for steam, pressurized nitrogen, electrical power, natural gas, other necessary utilities.
    Water can come from a well or be obtained from local supplies, including lakes. Compressed air is piping, ponds, rivers, or generated using a compressor.
    A cooler supplies cold water. A boiler can be used to supply steam smoke. Pressurized nitrogen can either be supplied with a nitrogen generator or purchased. THE
    42/47 power can be purchased from a nearby network or generated within the biorefinery location. Natural gas can be supplied from local pipes or wells.
    In another approach, the fractionation process and integrated rapid pyrolysis can be colocalized with an industrial processing facility in order to provide mutual benefit for each other. The colocalization of an integrated biomass rapid pyrolysis processing plant and fractionation with an outlet installation (eg cellulosic grain / ethanol plant, pulp and paper mill, sawmill, soybean crusher, power plant, sand processor oil, hydrocarbon drilling operation, etc.) can provide access to utilities and auxiliary infrastructure.
    The fractionation and rapid pyrolysis process of integrated biomass has the ability to use many different raw materials including lignocellulosic biomass and other carbon-based energy sources. In certain approaches, industrial facilities cannot completely process input raw materials into value-added outputs. Unconverted raw material is often considered a by-product. For example, wet mill corn ethanol mill fiber and cellulosic ethanol process lignin are two such by-products, among others. These by-products are often sold for much less than the primary product or used as lower-cost energy sources.
    In some approaches, colocalizing fractionation plants and rapid biomass pyrolysis integrated with existing processing facilities can create a number of synergistic advantages. A rapid biomass fractionation and pyrolysis process can convert biobased by-products into value-added products
    43/47 (specifically including asphalt, fuels, chemicals, specialized products and biobased biochar) to supplement the primary product yield stream. At the same time, fractionation plants and rapid pyrolysis 5 of integrated biomass will be able to share facilities, site licensing, logistics, management and other resources.
    In another approach, colocalizing fractionation process plants and rapid integrated biomass pyrolysis can '10 reduce a life cycle analysis of the processing facility or greenhouse gas footprint (GHG). Rapid pyrolysis products can offset the use of fossil resources in a processing facility. Reducing natural gas, coal, diesel and other fossil resources with renewable products is a way to meet renewable energy mandates, renewable portfolio standards, reduce the carbon footprint and dependence on fossil sources while improving sustainability.
    EXAMPLE
    The Example presented below is for illustrative purposes only and is not intended to limit the scope of the present invention in any way.
    Example: Rapid pyrolysis process integrated on pilot scale
    For example, the process of fractionation and rapid pyrolysis of integrated biomass was demonstrated using a pilot scale system located at BioCentury Research Farm in Boone County, Iowa. Red oak biomass was received in 30 batches in a road transport. The batch bags were unloaded from road transport and placed in storage. A biomass arrived at 8% moisture by weight and was chipped to reduce
    44/47 approximately 2.5 cm.
    The looped biomass was not additionally dried as it arrived with less than 10% moisture by weight. A biomass was milled in a hammer crusher to a decrease of 5 3.2 mm using a 3.2 mm sieve size. A biomass was not pre-treated at unit 110, instead it was transported directly to the receiving hopper at unit 115.
    A bucket elevator in unit 115 transmitted the * 10 biomass from the receiving hopper to an outbreak hopper. The outbreak hopper was purged with nitrogen to remove oxygen. A feeder below the outbreak hopper measured biomass in a bubbling fluid bed reactor.
    The 15.2 cm bubbling fluidized bed reactor was electrically heated to maintain the bed temperature close to 500 ° C. about 180 standard liters per minute of nitrogen gas fluidized the sand bed. The prepared biomass entered the reactor at about 5.5 kg / hr. Through contact with the hot sand bed, the
    biomass pirolisou, forming a chain of product in reaction in vapors, aerosols, biochar and gas no condensable. The product stream has passed across one set in filters cyclone wherein biochar was
    removed.
    Biochar was collected in sealed steel containers and allowed to cool to atmospheric temperature before transporting to sealed drums for storage.
    THE current product remaining entered into one 30 condenser in the unit 120. 0 fluid job at thecondenser was kept to 85 ° C and vapors condensed atbi fraction o-oil 1.
    Following the condenser there was a precipitator
    45/47 electrostatic maintained at 115 ° C. The electrostatic precipitator collected aerosols from the product stream that formed the bio-oil 2 fraction. The electrostatic precipitator used a high voltage power supply configured at 5 to -30 kV.
    The remaining product stream then entered a second condenser maintained at 65 ° C. Vapors from the product stream have been condensed here, forming the bio-oil fraction 3.
    -10 A second electrostatic precipitator was maintained at 65 ° C. The precipitator collected aerosols from the product stream that forms the bio-oil 4 fraction. The second electrostatic precipitator used a high voltage power supply set at -30 kV.
    A third and final condenser was set up at ° C to condense and concentrate water and low molecular weight compounds in a fraction of liquid bio-oil 5. Non-condensable gas was then passed through a packed bed filter to clean the gas.
    In this case, the non-condensable gas was not recirculated to fluidize the bed; instead, it was sent to a flame and combusted.
    Fractions of liquid bio-oil were collected and stored inside plastic containers until further processing or use.
    The yield of bio-oil, biochar and non-condensable gas fractions for this particular example are given in Table 1. The yields are the result of an experiment that lasted approximately 120 hours.
    Table 1: Yield of rapid pyrolysis process on a pilot scale (% by weight of biomass)
    46/47
    Bio-oil fraction
    2 3 4 5
    Bíocí
    15 5 2 25 moisture content of each individual fraction, as well as the moisture distribution among all fractions, is provided in Figure 4. More than 90% of the total moisture distributed among fractions is concentrated in the fraction of bio5 final liquid oil 5. Fractions 1 to 4 individually contain less than 10% by weight of moisture which is noticeably less than conventional bio-oil which typically contains 25% by weight (see Bridgwater, A V. The Production of biofuels and renewable chemicals by fast 10 pyrolysis of biomass, Int. J. Global Energy Issues 27.2 (2007).
    The bio-oil fractions in this example were used directly for a demonstration of bioasphalt and R&D for applications, including fuel oil, catalytic evolution 15 for fuels, specialty chemicals and other applications without costly processing and auxiliary equipment that would certainly be needed for bio -conventional oil.
    In the present description, reference has been made to 20 multiple approaches to the process, equipment, and systems that constitute this unique and integrated biomass fractionation and pyrolysis rapid invention. The accompanying drawings illustrate specific examples of the invention by way of illustration. These approaches are described in sufficient detail to allow those skilled in the art to practice the invention, and it should be understood that modifications to the various approaches presented can be made by an individual skilled in the art.
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    When the methods and steps described above indicate certain events that occur in a certain order, those of ordinary skill in the art will recognize that the ordering of certain steps can be modified and that such changes are in accordance with the principles of the invention.
    In addition, certain steps can be performed simultaneously in a parallel process, when possible, as well as performed sequentially.
    All publications, patents, and patent applications mentioned in this specification are incorporated herein by reference in their entirety, as if each publication, patent or patent application was specifically and individually presented in this document.
    The approaches, variations and figures described above provide an indication of the usefulness and versatility of the present invention. Other approaches that do not provide all the features and advantages presented in this document can also be used, without departing from the essence and scope of the present invention. Such modifications and variations are considered to be within the scope of the principles of the invention defined by the claims.
    权利要求:
    Claims (21)
    [1]
    1. METHOD OF FRACTIONATION AND RAPID PYROLYSIS OF INTEGRATED BIOMASS, and this method is characterized by understanding:
    (a) supplying a raw material that comprises biomass;
    (b) introducing said biomass into a reactor, operated under conditions of rapid pyrolysis, and in the presence of a heat distributor and / or a heated gas to convert said biomass into a reaction mixture comprising condensable vapors, aerosol droplets , non-condensable gases and solid biochar;
    (c) removing at least some part of said solid biochar from said reaction mixture to produce an intermediate mixture comprising condensable vapors, aerosol droplets, and non-condensable gases;
    (d) introducing said intermediate mixture into a multistage separator comprising at least one heated electrochemical separator followed by at least one heat exchanger, wherein said at least one electrochemical separator and said at least one heat exchanger are operated under effective conditions to collect individual liquid bio-oil fractions, including a fraction of final liquid bio-oil, each derived from said condensable vapors and said aerosol droplets, wherein said at least one heat exchanger and said by at least one electrochemical separator are operated with a heat exchanger wall temperature and an electrochemical separator wall temperature maintained above the water saturation temperature at the water vapor pressure determined within said at least one heat exchanger and the said at least one electrochemical separator, respectively, so that the water content
    [2]
    2/6 is maximized in the said fraction of final liquid bio-oil;
    (e) recovering and recycling at least some part of said non-condensable gas from said intermediate mixture back to said reactor; and
    (F) recovering at least some part of said solid biochar as a stable and cooled biochar product.
    2. METHOD, according to claim 1, wherein said method is characterized in that it comprises
    It is additionally the reduction of the particle size of said biomass, drying of said biomass or both of these steps.
    [3]
    3. METHOD, according to claim 1, characterized in that said biomass comprises about 10% by weight of moisture or average effective of about
    [4]
    4. METHOD, characterized in that less and contains one of 6 mm or less.
    according to said particle size biomass claim 1, pre-treated biomass selected from roasted, enzyme treated biomass, washed, biomass biomass treated with modified viscosity
    [5]
    5. METHOD, characterized in which group with acid, consists of biomass in biomass treated with steam smoke, biomass density and any modified agreement, biomass with combination thereof.
    according to claim 1, said reactor is a fluidized bed reactor whose fluidizing gas includes at least some of said non-condensable gas recycled from step (e).
    [6]
    6.
    METHOD, according to claim 1, characterized by a screw with no end in which end to transmit said reactor is a reactor of the type comprising at least one screw without said reaction mixture and said heat distributor.
    [7]
    METHOD, according to claim 6, characterized in that said intermediate mixture is
    3/6 substantially separated from at least some part of said biochar and said heat distributor within said worm reactor; said method further comprising separating said biochar from said heat distributor, recycling said heat distributor to step (b) and feeding said biochar to step (f) ·
    [8]
    Method according to claim 1, characterized in that said multi-stage separator Ί0 comprises two or more electrochemical separators and / or two or more heat exchangers in parallel.
    [9]
    9. METHOD, according to claim 1, characterized in that at least one of said bio-oil fractions is additionally treated by one or more technologies 15 selected from the group consisting of heating, aging, blending, improvement, refinement, hydrotreating , adding an emulsifier, adding a surfactant, adding a chemical additive and any combination thereof.
    20
    [10]
    10. FRACTIONATION METHOD AND QUICK PYROLYSIS OF
    BIOMASS, and said method is characterized by understanding:
    (a) supplying a raw material that comprises biomass;
    (B) introducing said biomass into a reactor, operated under conditions of rapid pyrolysis, and in the presence of a heat distributor and / or a heated gas to convert said biomass into a reaction mixture comprising condensable vapors, droplets of aerosol, non-condensable gases and 30 solid biochar;
    (c) removing and recovering at least some part of said solid biochar from said reaction mixture to produce an intermediate mixture comprising vapors
    Condensable 4/6, aerosol droplets and non-condensable gases; and (d) introducing said intermediate mixture into a multistage separator comprising at least one heat exchanger and at least one electrochemical separator, wherein said at least one heat exchanger and said at least one electrochemical separator are operated under effective conditions to collect individual liquid bio-oil fractions, including a first fraction of liquid bio-oil 10, each derived from said condensable vapors and said aerosol droplets, wherein said at least one heat exchanger is operated with a wall temperature maintained above the water saturation temperature at the water vapor pressure 15 determined within said at least one heat exchanger to minimize the water content in said first liquid bio-oil fraction.
    [11]
    11. METHOD, according to claim 10, characterized in that said multistage separator
    20 comprises two or more heat exchangers and two or more electrochemical separators collectively integrated to collect multiple liquid fractions of said intermediate mixture.
    [12]
    12. METHOD, according to claim 10,
    25 characterized in that said at least one heat exchanger is operated with a heat transfer fluid maintained above 100 ° C.
    [13]
    13. METHOD, according to claim 10, characterized in that at least one of said heat exchangers
    30 heat is a multi-zone heat exchanger with multiple established temperature values.
    [14]
    14. METHOD, according to claim 10, characterized in that said multistage separator
    5/6 comprises a first electrochemical separator before a first heat exchanger.
    [15]
    15. METHOD according to claim 10, wherein said method is characterized in that it further comprises ionizing at least a portion of said aerosol droplets prior to the introduction of the aerosol droplets in said electrochemical separator to increase the collection efficiency in the inside said electrochemical separator.
    [16]
    16. METHOD OF
    FRACTIONATION
    AND QUICK PYROLYSIS OF
    BIOMASS, and said method is characterized by understanding:
    (a) supplying a raw material that comprises biomass;
    (b) introducing said biomass into a reactor, operated under conditions of rapid pyrolysis, and in the presence of a heat distributor or a heated gas to convert said biomass into a reaction mixture comprising condensable vapors, aerosol droplets, gases non-condensable and 20 solid biochar;
    (c) removing at least some part of said solid biochar from said reaction mixture to produce an intermediate mixture comprising condensable vapors, aerosol droplets and non-condensable gases;
    (D) introducing said intermediate mixture into a multistage separator comprising at least one heat exchanger and at least one electrochemical separator, wherein said at least one heat exchanger and said at least one electrochemical separator are operated in conditions
    30 effective to collect individual liquid bio-oil fractions, each derived from said condensable vapors and said aerosol droplets;
    (e) recover and recycle at least some part of the
    6/6 said non-condensable gas from said intermediate mixture back to said reactor; and (f) recovering at least some part of said solid biochar as a stable and cooled biochar product, wherein the heat contained in said solid biochar is integrated with any one or more of steps (a) to (e).
    [17]
    17. METHOD, according to claim 16, characterized in that step (f) comprises the use of a portion of said non-condensable gas to improve the
    Recuperação0 recovery and cooling of the biochar.
    [18]
    18. METHOD according to claim 16, characterized in that step (f) comprises introducing said biochar into a fluidized bed which is fluidized with said non-condensable gas.
    15
    [19]
    19. METHOD according to claim 16, characterized in that step (f) comprises the introduction of an inert gas to subject said biochar to elutriation out of a mixture with said heat distributor.
    [20]
    20. METHOD, according to claim 16, being
    20 that said method is characterized in that it additionally comprises the production of agglomerated biochar which includes one or more added binders selected from the group consisting of lignosulfonates, vegetable oils, water, integral bio-oil, bio-oil fractions, biomass clay
    [21]
    25 bitumen, coal and any combination thereof.
    类似技术:
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    同族专利:
    公开号 | 公开日
    US8100990B2|2012-01-24|
    WO2012158651A2|2012-11-22|
    BR112013029457A2|2017-01-17|
    WO2012158651A3|2013-02-21|
    US20110258914A1|2011-10-27|
    CA2873385C|2019-07-23|
    EP2710092A4|2014-12-17|
    US8425633B2|2013-04-23|
    US20120090221A1|2012-04-19|
    AU2012256008A1|2013-12-19|
    CA2873385A1|2012-11-22|
    EP2710092A2|2014-03-26|
    AU2012256008B2|2017-05-04|
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    法律状态:
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-05-14| B09A| Decision: intention to grant|
    2019-07-16| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/05/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/05/2012, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161486304P| true| 2011-05-15|2011-05-15|
    US61/486,304|2011-05-15|
    US201161491188P| true| 2011-05-28|2011-05-28|
    US61/491,188|2011-05-28|
    US13/174,849|US8100990B2|2011-05-15|2011-07-01|Methods for integrated fast pyrolysis processing of biomass|
    US13/174,849|2011-07-01|
    PCT/US2012/037853|WO2012158651A2|2011-05-15|2012-05-14|Methods for integrated fast pyrolysis processing of biomass|
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