method to hydropyrolyze an oxygenated organic raw material

专利摘要:
METHOD FOR HYDROPYROLYZING AN OXYGENED ORGANIC RAW MATERIAL. It is a process to thermochemically transform biomass or other oxygenated raw materials into high-quality liquid hydrocarbon fuels. In particular, a catalytic hydropyrolysis reactor, which contains a deep bed of fluidized catalyst particles is used to accept the biomass particles or other oxygenated raw materials that are significantly smaller than the catalyst particles in the fluidized bed. The reactor has an insertion element or other structure disposed inside the reactor container that inhibits fluidization of the bed and, consequently, minimizes the friction of the catalyst. Inside the bed, the biomass feedstock is converted into a vapor phase product that contains hydrocarbon molecules and other process vapors, and a entrained solid charcoal product, which is separated from the vapor stream after the steam flow has been exhausted from the top of the reactor. When the product's vapor stream is cooled to room temperatures, a significant proportion of the hydrocarbons in the product's vapor stream can be recovered as a hydrophobic hydrocarbon liquid stream with (...).
公开号:BR112013026816B1
申请号:R112013026816-6
申请日:2012-03-23
公开日:2020-11-24
发明作者:Terry L. Marker；Larry G. Felix；Martin B. Linck；Michael J. Roberts
申请人:Gas Technology Institute；
IPC主号:

专利说明:

[0001] This invention relates to a process to thermochemically transform biomass or other oxygenated raw materials into high-quality liquid hydrocarbon fuels. Description of the Related Art
[0002] Oxygenated raw materials, such as solid biomass (wood, agricultural waste, paper waste, etc.) can be converted into liquid products through rapid heating in the absence of oxygen (pyrolysis). A solid charcoal product (which consists mainly of carbon, but which also contains any non-volatile and inert compounds found in the raw material) and non-condensable vapors (such as CO2 and CH4) are produced, together with condensable species such as: water , hydrocarbons and molecules that contain carbon atoms, hydrogen atoms and oxygen atoms. The proportions of the resulting products obtained depend on the rate of heating of the raw material particles, as described by Mohan, et al. (Mohan, Pittman, and Steele, "Pyrolysis of Wood / Biomass for Bio-oil: A Critical Review", in "Energy & fuels", Volume 20, pages 848 to 889, 2006). A type of biomass pyrolysis, called "rapid pyrolysis", minimizes the amount of charcoal produced and maximizes the amount of condensable liquid obtained by heating the biomass as quickly as possible. A part of charcoal is always produced, particularly since biomass always contains some non-volatile and non-reactive compounds (in general, referred to as ash). Conventional biomass pyrolysis, typically rapid pyrolysis, does not use or require hydrogen gas or catalysts and produces a dense, acidic and reactive liquid product that contains water, oils and charcoal formed during the process. Due to the fact that rapid pyrolysis is more typically carried out in an inert atmosphere, most of the oxygen present in the biomass is transported to the liquid products obtained, which increases its chemical reactivity. Rapid pyrolysis liquids also contain high levels of acids (such as acetic acid), as well as olefins and polyaromatic hydrocarbons. The chemically unstable liquids produced by conventional pyrolysis tend to thicken over time and can also react to a point where the hydrophilic and hydrophobic phases form. Dilution of pyrolysis liquids with methanol or other alcohols has been shown to reduce subsequent oil activity and viscosity, but this approach is not considered practical and economical, since large amounts of sunk alcohol would be needed to stabilize a large amount pyrolysis liquids for transport and subsequent use.
[0003] In conventional biomass pyrolysis carried out in an inert environment, the water-miscible liquid product is highly oxygenated and reactive, for example, with the total acid numbers (TAN) in the range of 100 to 200, it has low chemical stability for polymerization. tion, is incompatible with petroleum hydrocarbons due to the inherent miscibility of water and the very high oxygen content (in the order of about 40% by weight) and has a low heating value. As a result, transportation and use of this product are problematic and it is difficult to upgrade the product to a liquid fuel, due to the retrograde reactions that normally occur in conventional pyrolysis and conventional rapid pyrolysis. Enhancement technologies, as applied to conventional pyrolysis liquids, tend to produce only small amounts of high-quality deoxygenated liquid hydrocarbons that are suitable for use as transport fuels.
[0004] In addition, the separation of charcoal generated during conventional pyrolysis from the liquid pyrolysis product presents a technical challenge due to the large amounts of oxygen, olefins, acids and free radicals in the hot pyrolysis vapors that remain highly reactive and form a pitch-like material when they come into intimate contact with charcoal particles on the surface of a barrier filter, inertial separation device or electrostatic precipitator. In particular, barrier filters used to separate charcoal from hot pyrolysis vapors (before cooling and condensation of liquid pyrolysis products) can quickly detect irreversible clogging (concealment) due to reactions of charcoal and reactive vapors that occur in and within the charcoal bed on the filter surface.
[0005] In order to improve conventional pyrolysis liquids, attempts have been made to react conventional pyrolysis liquids with hydrogen, in the presence of solid catalysts, in order to remove oxygen from the liquids and produce a useful and stable hydrocarbon product. This process is called hydroconversion. However, the improvement of conventional pyrolysis liquids through hydroconversion is not commercially viable. Hydroconversion of conventional pyrolysis liquids consumes significant H2 under extreme process conditions, such as very high hydrogen pressures of 138 bar (2,000 psig) or more. High specific pressures of hydrogen are necessary for the desired reactions to proceed, but these pressures create conditions in which most of the oxygen removed from the liquid is removed through the formation of water (H20). This approach consumes large amounts of hydrogen, thus making the process economically unattractive. In addition, hydroconversion reactors often close due to accumulations of coke precursors present in pyrolysis oils from coke products that result from catalysis. Coke is a solid product, consisting mainly of carbon, and the maintenance required to eliminate it from hydroconversion reactors further reduces the economic viability of hydroconversion of conventional pyrolysis liquids.
[0006] The present state of the art also describes a different means by which oxygenated raw materials such as biomass can be converted to create useful liquid hydrocarbons, called hydropyrolysis. Hydropyrolysis can be carried out with or without the aid of a catalyst. However, lower hydrocarbon yields and lower deoxygenation tend to be a feature of non-catalytic hydropyrolytic processes. Therefore, as described in the present invention, "hydropyrolysis" will be considered to refer to a process of catalytic pyrolysis carried out in the presence of molecular hydrogen (H2). Typically, the goal of conventional hydropyrolysis processes has been to remove heteroatoms (atoms other than carbon and hydrogen) from biomass, and to maximize the yield of liquid hydrocarbons. In the previous work by Meier, et al. (Meier, Jakobi and Faix, "Catalytic Hidroliquefation of Spruce Wood", for the Journal of Wood Chemistry and Technology, Vol. 8, No. 4, pages 523 to 542, 1988), the raw material for solid biomass was processed in a reactor containing liquid, in which the solid biomass raw material was suspended. The reaction was carried out at high internal pressures of more than 138 bar (2,000 psig) with recycled slurry oil and the lowest reported oxygen content for the hydrocarbons produced was 7.6% by mass. This value was obtained when a precious metal palladium (Pd) catalyst was used. In another study by Meier and Faix (Meier and Faix, "Solvent-Free Hidroliquefation of Pine Wood and Miscanthus Stems", in Proceedings of the International Conference on Biomass for Energy and Industry, Lisbon, Portugal, 9 to 13 October 1989) , in which a slurry oil was not used, the lowest oxygen content reported in the hydrocarbon product was 9.7% oxygen by mass, and the reaction was still carried out at high internal hydrogen pressures of more than 138 bar (2,000 psig) inside a reactor heated with a NiMo catalyst.
[0007] In the hydropyrolysis studies of a single stage of cellulose and other raw materials derived from biomass, Rocha, et al. (Rocha, Luengo and Snape, "The Scope for Generating Bio-Oils with Relatively Low Oxygen Contents via Hydropyrolysis", in Organic Geochemistry, Vol. 30, pages 1527 to 1534, 1999) demonstrated that with a FeS catalyst, as partial hydrogen pressure in the hydropyrolysis reactor decreased, the oxygen content of the hydrocarbon product tended to increase. Experiments carried out at lower hydrogen pressures have typically produced hydrocarbon products with oxygen levels above 15%. In one case described by Rocha, et al., Cellulose was subjected to hydropyrolysis at a hydrogen pressure of 99 bar (1,440 psig), and the lowest oxygen content of the resulting hydrocarbon product was 11.5% by mass . Unfortunately, this approach compromises the economy, since it requires an external source of H2 and must be carried out at high reactor pressures. In addition to exhibiting a continuous external hydrogen input, such conventional hydropyrolysis processes produce excess H20 which generally represents a disposal stream. In this type of reactor, biomass hydrolysis is still not economically attractive since the oxygen content of the hydrocarbon product is still quite high after processing and the reaction conditions required by the process are too severe to be put into practice.
[0008] Finally, hydropyrolysis can be performed in a fluidized bed (typically, a shallow fluidized bed with a length-to-diameter ratio <1.5). However, the present invention relates to the means by which effective hydropyrolysis can be carried out in a single step in a deep fluidized bed of particles of an active catalyst, at partial pressures of H2 from 200 to 600 psig, so that the content oxygen content of the liquid hydrocarbon product is reduced to below 4% by mass. In addition, in the present invention, the hydropyrolysis reaction is exothermic and provides the reaction heat so that there is no need to provide external heating or circulate the regenerated hot catalyst or sand through the fluidized bed reactor as is typically necessary for the traditional pyrolysis. Fluidized beds generally include solid particles, such as particles of sand or catalyst, which are agitated and fluidized by a flow of gas, which moves upwards through the bed and leaves the bed at or near the top of the bed. reactor. The behavior of fluidized beds is known to depend at least partially on the depth (or height or length) of the bed. The depth of the bed is, in general, characterized by the L / D ratio (length / diameter), which means the ratio of the depth, height or length of the bed, divided by the diameter of the bed. The behavior of the bed will largely depend on the particle size distribution of the material from which the bed is formed. In general, fluidized beds are developed with an L / D of 1 to 2, since the beds in this range exhibit uniform fluidization, once the fluidization gas flow rate is sufficient to move the bed particles quickly, were provided. In this case, "uniform fluidization" means that, once fully fluidized, the particles in the bed are in a universal random motion. The mixing and internal heat transfer within a fully fluidized bed are both very fast, and a relatively shallow bed can often be operated in an almost isothermal manner, meaning that the temperature at any point within the bed is almost completely uniform.
[0009] Fluidized beds can be adversely affected by a phenomenon called "fluidization". Fluidization develops in beds that have an L / D ratio (length / diameter) greater than 1.5 to 2.0 and fluidized beds composed of particles larger than a few hundred microns are specifically prone to fluidization. Fluidization is a phenomenon in which a bubble of gas forms in the bed, and the diameter of the bubble expands rapidly to reach the total diameter of the bed. Then the entire bed above the bubble begins to move upwards, like a coherent body (a "bag"), with very little relative movement between the particles in the "bag". The bag can rise to various diameters of the bed before the bag's cohesion begins to break, and the particles in the bag then quickly fall back down towards the lower levels of the reactor. In general, the bubble forms at an elevation of 1.5 to 2.0 diameters of the reactor above the bottom of the bed. While the bag is increasing, a region of well-fluidized bed material can be seen in the lower parts of the bed, with an open space, containing only the fluidizing gas, which appears between the upper part of the well-fluidized region of the coherent bag , as the bag disintegrates, the bed material of the bag falls to the bed material in the lower parts of the bed, suppressing fluidization until the bubble forms again and the next bag is filled. Fluidization is, in general, cyclic or periodic and, once it begins, it can continue with regularity until it is interrupted by a change in operating conditions. Fluidization can also be affected by the properties of the material bed. Two beds of equal depth and volume density can behave very differently if the particle size distribution is different or the sphericity of the particles is changed.
[0010] Fluidization is not desired for several reasons. Most importantly, when fluidization occurs, longitudinal mixing in the bed is slowed down, and particles from the highest points in the bed move very slowly towards the bottom of the bed (and vice versa). The uniformity of the axial temperature is thus compromised, and considerable temperature gradients can be observed over the height of the bed. Fluidization also creates cyclic stresses on the walls and floor of the bed, particularly if the bed is disposed within a reactor, and the effect of cyclic loading and unloading on the reactor support structure and the concomitant effect on the process chemistry can destroy any uniformity process appearance. Vibration, or cyclic loading, of the reactor walls and the support structure, can lead to mechanical failures, and variation in the process chemistry will also make it impossible to operate with a useful level of process control. Fluidization can also significantly increase the friction of the particles that comprise the fluidized bed, due to the great amplitude the cyclic movement of the bed tends to involve the particles of the bed in more energetic collisions with other particles and with the walls of the container within which the bed is contained.
[0011] As mentioned above, the fluidization problem can be avoided, in general, simply by using a shallower bed or, in some cases, by using particles of smaller diameters. However, there are applications where a flat bed is simply not practical. If the bed has catalytic properties, which are essential for the process chemistry, then the weight of the catalyst in the fluidized bed may need to be higher than a limit in relation to the mass flow rate of vapors that pass through the bed in order to that the desired reactions take place. In the case of the present invention, the deoxygenation reactions that are required to perform effective hydropyrolysis cannot be performed in a shallow fluidized catalyst bed. If the bed is too shallow, the vapors will leave the bed before the desired effect is achieved. The mass flow rate of the fluidization gas required to fluidize a bed also depends on the diameter of the bed. In some situations, particularly in pressurized reactors, the diameter of the bed needs to be kept below a certain value, so that a gas velocity sufficient to fluidize the bed can be obtained with the available mass flow rate of the fluidization gas. The process of the present invention, as described below, preferably includes the use of a deep fluidized bed, composed of relatively large catalyst particles. Due to the fact that this bed is inherently prone to fluidization, a means of reducing fluidization has been incorporated into this invention. Fluidization is prevented or controlled through the use of an insertion element or other anti-fluidization modification of the hydropyrolysis reactor, which is disposed within the fluidized bed. The design and application of the insertion element inside the reactor or other modifications of the hydropyrolysis reactor to inhibit fluidization are important aspects of the invention. The use of the insertion element or other anti-fluidization modification of the hydropyrolysis reactor allows the fluidized bed to maintain adequate fluidization and to have the appropriate depth to carry out the appropriate hydropyrolysis reactions. The insertion element also allows the bed to be composed of relatively large catalyst particles, which are large enough to be retained in the bed while the smaller particles of solid waste (charcoal) are decanted and transported from the bed into the gas product stream. .
[0012] The behavior of a fluidized bed will depend on the flow rate of the fluidizing gas that passes through the bed. The process of the present invention, as described below, specifically involves a bubbling fluidized bed. In a bubbling fluidized bed, a fluidization gas flow rate is provided that is sufficient to vigorously stir and mix the bed, and is large enough that it opens gaps that contain almost exclusively fluidizing gas, is formed. However, the flow rate is not large enough to entrain the solid catalyst particles from which the bed is composed in the exhaust gas stream and permanently separates them from the bed. Summary of the Invention
[0013] This invention relates to a process to thermochemically transform biomass or other oxygenated raw materials into high-quality liquid hydrocarbon fuels. In particular, a catalytic hydropyrolysis reactor, which contains a deep bed (length: diameter> 1.5 ratio) of fluidized catalyst particles is used. The reactor accepts particles from a biomass or other oxygenated raw materials that are significantly smaller than the catalyst particles in the fluidized bed. Preferably, the reactor has an insertion element or other structure disposed inside the reactor container that inhibits fluidization of the bed and, consequently, minimizes the friction of the catalyst. Inside the bed, the raw material biomass is converted into a vapor-phase product containing hydrocarbon molecules and other process vapors, and a entrained solid charcoal product, which is separated from the vapor stream after the flow of steam was exhausted from the top of the reactor. When the product vapor stream is cooled to room temperatures, a significant proportion of the hydrocarbons in the product vapor stream can be recovered as a liquid stream of hydrophobic hydrocarbons, which contain less than 4% by mass of oxygen, with the properties consistent with those of gasoline, kerosene and diesel fuel. The separation of gasoline, kerosene and diesel fuel flows can also be achieved either through the selective condensation of each type of fuel, or through the distillation of the combined hydrocarbon liquid.
[0014] It is an objective of this invention to provide a process and / or an apparatus by which biomass, or other oxygenated organic raw materials, which include solid biomass, such as lignocellulosic biomass such as wood, agricultural by-products, crop residues and waste, industrial waste derivatives of these materials (for example, paper and sludge residues), animal residues (manure, offal, and sewage sludge), algae and similar uni- and multicellular aquatic biomass, residues from fish processing and mixtures of the above, etc., can be substantially converted to obtain a product flow consisting of hydrocarbons that are liquid under ambient conditions, contain less than approximately 4% by mass of oxygen and have properties, such as boiling points, heating values and aromaticities, which are consistent those of gasoline, kerosene and diesel fuel.
[0015] It is another object of this invention to provide a process and / or apparatus by which biomass, or other oxygenated organic raw materials as described above, can be substantially converted to create the liquid hydrocarbon product described above, under conditions where partial pressure of hydrogen in the process reactor of the present invention is maintained between approximately 200 psig and 600 psig
[0016] It is another objective of this invention to provide a process and / or apparatus by which the solid residues that remain after the conversion of the raw material in the process of the present invention are removed from the reactor of the present invention as entrained particles carried out in the reactor by the product vapor flow. coming out of the reactor. It is another object of this invention to provide a process and / or apparatus by which the entrained solid residues carried out in the process reactor of the present invention can be easily filtered from the product vapor streams.
[0017] It is another objective of this invention to provide a process and / or apparatus in which the exothermic deoxygenation reactions that take place in the fluidized bed hydropyrolysis reactor of the present invention generate an amount of thermal energy sufficient to heat the incoming flow of the raw material for the temperature of the fluidized bed, as well as to overcome the heat required to trigger the processes and endothermic reactions that occur in the bed during the conversion of the raw material.
[0018] It is another objective of this invention to provide a process and / or apparatus by which the conversion of any of the aforementioned raw materials can be carried out in a deep bubbling fluidized bed consisting of relatively large catalyst particles, while using the media of this invention to prevent fluidization within the bubbling fluidized bed and to minimize the friction of catalyst particles within the bubbling fluidized bed.
[0019] Preferably, the subject of the invention includes a process for the production of liquid products from biomass (or other oxygenated, solid, slurry or liquid raw material) in which the raw material is rapidly heated in a reactor vessel which contains molecular hydrogen and the deoxygenation catalyst, which produces a deoxygenated pyrolysis liquid product that has less than approximately 4 wt.% oxygen, an aqueous liquid product containing water and water-soluble species, a solid charcoal product , a product flow comprising non-condensing vapors and process heat. The product's steam stream contains species that include hydrogen, methane, ethane, propane, carbon monoxide (CO) and carbon dioxide (CO2). The hydropyrolysis process of the present invention is, in general, carried out at hydrogen partial pressures of approximately 200 psig to 600 psig, which are much less than would be required to carry out the conventional hydrotreatment or hydropyrolysis processes. The hydropyrolysis process of the present invention has shown to convert at least approximately 24% by mass of cellulosic biomass feedstock into deoxygenated liquid hydrocarbon products (see examples below).
[0020] The deoxygenated liquid hydrocarbon product produced by the hydropyrolysis process of the present invention mainly includes hydrocarbons that are liquid at room temperature and pressure; this product is hydrophobic, and not miscible with water.
[0021] The low oxygen content (generally less than 4% by mass) of the liquid hydrocarbon stream produced by the process of the present invention at low partial pressure of hydrogen is desired. The high yield of deoxygenated liquid hydrocarbons from the biomass feedstock is also desired. The ease with which solid waste (charcoal and ash) can be removed from process vapors through filtration is also desired. These characteristics derive from the high level of deoxygenation that is carried out in the hydrocarbons that leave the hydropyrolysis reactor. When highly deoxygenated gaseous hydrocarbons and charcoal encounter a barrier filter, the gaseous vapors preferably contain no high-boiling components that could be absorbed or reside in the charcoal particles and then the highly deoxygenated gaseous hydrocarbons they are effectively separated from charcoal, which would then be easily removed from the filter by the minimum levels of retropulsion. In conventional pyrolysis, charcoal particles adsorb and retain reactive pyrolysis oils. When these particles encounter a barrier filter, they aggregate and create a dense, almost impermeable layer of charcoal that resists cleaning by retropulsion.
[0022] Unlike the present invention, other processes described in the related art (pyrolysis, hydropyrolysis, conventional hydrotreating of conventional pyrolysis oils) all suffer from deficiencies that make it impossible to obtain yields and products characteristic of the hydropyrolysis process of the present invention. A detailed comparison between the experimental results obtained during the development of the hydropyrolysis process of the present invention for the performance of other conventional biomass pyrolysis, biomass hydropyrolysis and hydrotreatment processes is presented in the examples below below.
[0023] The hydropyrolysis reactor vessel of the process of the present invention preferably comprises an elongated deep bed fluidized bed reactor with a bed which preferably includes relatively large catalyst particles. In the event that a solid raw material is conducted in the hydropyrolysis reactor of the process of the present invention, the raw material is fed into said reactor in the form of particles that are substantially smaller in size than the catalyst particles in the bed , in order to maximize the thermal decomposition of the biomass, to minimize the particle friction of the catalyst, and to allow the effective separation of green carbon from the fluidized bed and the process vapor flow that leaves the fluidized bed. In addition, one or more insertion elements or other anti-fluidization modifications of the reactor can be arranged within the reactor to inhibit fluidization of the fluidized bed during the hydropyrolysis process. A specific design approach, related to the insertion elements or other anti-fluidization modifications of the hydropyrolysis reactor, is incorporated into the present invention, which makes it possible to prevent fluidization of the bed disposed within the fluidized bed reactor, even under circumstances in which fluidization would generally be expected to occur.
[0024] 1) Desvolatização, em que a matéria-prima é termicamente decomposta para produzir um produto de carvão vegetal sólido (que contém uma fração de cinzas não volátil e inerte), e produtos de decomposição que entram na fase de vapor no reator de hidropirólise; 2) Hidrodesoxigenação, em que o oxigênio é removido de uma molécula, e combinado ao hidrogênio ([3/4]) para produzir água (H20); 3) Descarbonilação, em que uma molécula de monóxido de carbono (CO) é removida da estrutura de uma molécula; 4) Deslocamento de água e gás, em que CO é reagido com H20 para produzir CO2 e H2; 5) Polimerização, em que pequenas olefinas se combinam para produzir grandes moléculas; 6) Saturação de olefina, em que o hidrogênio é adicionado a uma olefina para produzir uma parafina. In describing the present invention, the term "hydropyrolysis" is used to describe a process by which a biomass feedstock (which includes, but is not limited to, all the varieties of biomass listed in the Summary of the Invention, above) is rapidly heated and thermally decomposed, in the presence of solid catalyst particles and an atmosphere consisting largely of hydrogen gas. In addition, the term "hydropyrolysis" will be used to refer to all reactions carried out on the thermal decomposition products of the raw material within the hydropyrolysis reactor. In the present invention, hydropyrolysis involves five classes of reactions. They are: 1) Devolatization, in which the raw material is thermally decomposed to produce a solid charcoal product (which contains a non-volatile and inert fraction of ash), and decomposition products that enter the vapor phase in the hydropyrolysis reactor; 2) Hydrodesoxygenation, in which oxygen is removed from a molecule, and combined with hydrogen ([3/4]) to produce water (H20); 3) Decarbonylation, in which a molecule of carbon monoxide (CO) is removed from the structure of a molecule; 4) Displacement of water and gas, in which CO is reacted with H20 to produce CO2 and H2; 5) Polymerization, in which small olefins combine to produce large molecules; 6) Olefin saturation, in which hydrogen is added to an olefin to produce a paraffin.
[0025] In describing the present invention, the term "deoxygenation" refers to the chemical processes by which chemically bound oxygen is removed from molecules (mainly hydrocarbon molecules) and transferred to other chemical species such as water (H20), monoxide carbon (CO) or carbon dioxide (CO2). As described above, the term "hydrodeoxygenation" refers to a subset of those processes in which water is formed.
[0026] In describing the present invention, the term "hydrotreatment" refers to a range of chemical reactions in which hydrocarbon species (which may contain carbon and carbon double or triple bonds, benzene rings, chemically bonded hetero atoms and a wide variety of other functional groups) are reacted with molecular hydrogen (H2), in general, in the presence of a catalyst. Hydrotreating generally involves breaking a bond in the hydrocarbon molecule and adding hydrogen to the structure of the hydrocarbon molecule, so that heteroatoms (such as oxygen and nitrogen) are removed, the double or triple bonds of carbon and carbon are saturated and replaced by carbon and hydrogen bonds, and the ring structures are opened, resulting in linear hydrocarbon molecules. Hydrotreating also involves "hydrocracking" (or "cracking") which involves breaking long hydrocarbon chairs into shorter hydrocarbon chains, producing smaller molecules with lower boiling points.
[0027] In describing the present invention, the term "hydroconversion" is defined as a reaction carried out in the presence of hydrogen and, in general, a catalyst, which removes heteroatoms such as sulfur, nitrogen and oxygen or performs cracking at the same time as adding the hydrogen to the structure of the reagent molecule.
[0028] The catalytic hydropyrolysis process of the present invention provides a means to remove oxygen from biomass and other raw materials that contain significant amounts of carbon and chemically bonded oxygen to produce light hydrocarbon products with a large part of oxygen removed directly from liquids derived from the raw material. This is called "deoxygenation". In the reactor described in the present invention, the deoxygenation of molecules derived from the biomass raw material inherently releases a great reaction heat that provides the energy necessary to heat the cold biomass as it enters the bubbling fluid bed. However, a problem with conventional catalytic hydropyrolysis is the separation of charcoal and ash from the catalyst. Another potential problem with conventional catalytic hydropyrolysis, such as that performed in a fluidized bed, is that the rapid wear of the catalyst particles can lead to high catalyst replacement costs and, thus, be economically unviable. The reactor described in the present invention, which involves a bubbling fluidized bed hydropyrolysis system with catalyst particles that are much larger in size than decomposed raw material (reacted) waste, provides a new way to minimize friction from the catalyst, while ensuring that charcoal and ash are separated from the catalyst by being worn (reduced in size) and decanted from the bubbling bed reactor. Decantation occurs when a particle has been reduced in size to a point where it is entrained in the gas stream exiting the top of the fluidized bed, and is permanently removed from the bed. Within the fluidized catalytic hydropyrolysis reactor described in the present invention, the catalytic hydropyrolysis charcoal product of the raw material, which is highly composed of carbon, acts as a lubricant within the bubbling bed and serves to protect large particles from catalyst for auto-friction. However, the action of the bed on the charcoal and soft ash is such that the charcoal and ash are effectively worn out by the catalyst and reduced to a size where the charcoal and ash are readily decanted from the bubbling bed. The problem of removing charcoal and ash from the catalyst fluidized bed is thus addressed.
[0029] It is noted that in the present invention, it can be advantageous to process efficiency and quality for more than one type of catalyst to be disposed within the bed. In the simplest case, two physically and chemically different catalysts could be arranged within the bed. Due to the fact that the two types of catalyst can be manipulated to have different densities or sizes, the catalysts can mix within the bubbling fluidized bed, or a catalyst would tend to rise to the top of the bed (for example, be lighter, or be dimensioned to have a smaller aerodynamic diameter) so that the chemistry of this process can be carried out gradually. It is evident that in a vertically extended bubbling fluidized bed, a number of catalysts could be arranged so that some can mix while others maintain different vertical positions in the bed.
[0030] In the present invention, biomass or other solid particles of raw material are fed into the fluidized bed catalytic hydropyrolysis reactor, preferably near the bottom of the bed, and are rapidly heated and decomposed to produce solid ash, coal residues plant and vapor phase products. The ash and charcoal and vapors then travel through the bed, where process vapors (and solid particles small enough to be dragged aerodynamically) are permanently transported away from the top surface of the bed. fluidized where they leave the reactor.
[0031] 1. O leito profundo faz com que os vapores de processo fiquem em contato com as partículas de catalisador durante um período mais longo de tempo, uma vez que a trajetória assumida pelo vapor de produto através do leito profundo é muito mais longo do que seria se ele atravessasse um leito raso. 2. A taxa de fluxo de massa de gás de fluidização (que, no caso dessa invenção, compreende principalmente hidrogênio) necessária para fluidizar o leito depende do diâmetro do leito. Se um leito profundo for usado, uma grande quantidade de catalisador pode ser fluidizado por uma taxa de fluxo de massa relativamente pequena de gás de fluidização. Por exemplo, se o diâmetro de um leito de catalisador for reduzido de modo que o L/D do leito é aumentado a 1,5 a 10, ao mesmo tempo em que mantém um volume de catalisador no leito constante, a taxa de fluxo de massa de gás de fluidização necessária para obter o mesmo grau de fluidização no leito é reduzida por um fator de 3,5. Esse efeito é essencial a fim de aprimorar a viabilidade econômica do processo. 3. As obstruções, obstáculos ou constrições associadas ao elemento de inserção de rompimento de bolsa podem ser instrumentados e equipados com as características internas que permitem que eles removam ou adicionem calor ao leito. As obstruções, obstáculos ou constrições interagem diretamente com o leito nas localizações radiais que podem incluir o centro do reator. Essa abordagem permite a transferência de calor mais eficiente para ocorrer em locais específicos no leito do que seria o caso se a transferência de calor ocorresse apenas do outro lado da parede externa do reator, e melhora o controle do processo, uma vez que a temperatura local em cada ponto no leito pode ser melhor. Although the process described above could be carried out in a shallow fluidized bed (meaning that the bed has an L / D ratio (length / diameter) of 2 or less), it is preferably carried out in a deep fluidized bed ( with an L / D of approximately 10 or more). A deep fluidized bed, particularly one that comprises relatively large catalyst particles, will develop fluidization and cannot be operated without a bag-breaking insert. The insertion element consists of obstacles, obstructions or constrictions, positioned at regular intervals within the bed, and oriented or contoured in such a way that a coherent pocket of the bed material cannot form along the entire length of the bed. The use of the insertion element makes the operation of the reactor with a deep bed possible, and provides three advantages over the operation of the reactor with a shallow bed: 1. The deep bed causes the process vapors to stay in contact with the catalyst particles for a longer period of time, since the path taken by the product vapor through the deep bed is much longer than it would be if he crossed a shallow bed. 2. The mass flow rate of fluidization gas (which, in the case of this invention, mainly comprises hydrogen) required to fluidize the bed depends on the diameter of the bed. If a deep bed is used, a large amount of catalyst can be fluidized by a relatively small mass flow rate of fluidizing gas. For example, if the diameter of a catalyst bed is reduced so that the L / D of the bed is increased by 1.5 to 10, while maintaining a constant volume of catalyst in the bed, the flow rate of mass of fluidization gas required to obtain the same degree of fluidization in the bed is reduced by a factor of 3.5. This effect is essential in order to improve the economic viability of the process. 3. The obstructions, obstacles or constrictions associated with the rupture bag insertion element can be instrumented and equipped with internal characteristics that allow them to remove or add heat to the bed. Obstructions, obstacles or constrictions interact directly with the bed at radial locations that may include the center of the reactor. This approach allows for more efficient heat transfer to occur at specific locations in the bed than would be the case if the heat transfer occurred only on the other side of the outer wall of the reactor, and improves process control, since the local temperature at each point in the bed can be better.
[0032] The flow of steam from the top of the fluidized bed includes the fluidizing gas, the product vapors that were generated by thermal decomposition and hydropyrolysis of the raw material, and any solid particles (ash, charcoal, or fine catalyst solids) worn out), which are small enough to be dragged in an aerodynamic way in said steam flow. The process described by that invention specifies that the product vapor species that leave the fluidized bed need sufficiently chemically stable, so that they are substantially unable to react with other product vapor species, and with solids entrained in the flow of water. vapor, or with solid surfaces with which the vapor flow is in contact, such as a barrier filter. In practice, this means that the most unstable species produced by the initial thermal decomposition of the raw material, such as aldehydes and acids, must be substantially deoxygenated through the reaction with hydrogen in the catalytic fluidized bed. The combined flow of vapors and entrained solids can pass through an inertial separation device, such as a cyclone or virtual pendulum, an electrostatic precipitator (ESP), and / or filter elements, or some combination of the above, and not it will form a dense cake on the cyclone, on the ESP plate or on the filter surfaces, or create scale as the solid particles are filtered out of the vapor stream.
[0033] Any suitable inertial separation device, porous filter, electrostatic precipitator or other means of removing solids from the vapor stream can be used once the vapor stream (with entrained solids) has left the reactor containing the fluidized bed . If a cyclone or virtual pendulum is used for the first time to remove larger solids entrained in the vapor stream and a porous filter is then used to remove the remaining entrained fine solids in the vapor stream, most of the charcoal and ash leaving the reactor can preferably be collected from the cyclone, while most of the worn catalyst can be recovered from the filter. This is due to the fact that the catalyst is much more rigid than charcoal, and will essentially break down into very fine particles, which will pass through the cyclone to the filter. Charcoal, on the other hand, is softer and less rigid, and will be divided into a range of particle sizes by the fluidized bed milling action. Larger charcoal particles will be trapped mainly by the cyclone, and will not reach the filter. Finally, if the catalyst is arranged to remain as a metallic material, which can be magnetized, the particles composed of worn catalysts can be collected efficiently in a filter or inertia separation device that can be energized periodically with a field. magnetic to retain the magnetic particles. De-energizing the magnetic field would allow these particles to be removed and recovered en masse.
[0034] Once the entrained solid particles have been removed from the process steam stream, the vapors can be cooled to room temperature, immediately to the point where all species with boiling points below room temperature will condense to form liquids, or the flow of process vapors can be directed to a subsequent reactor or reactors for further treatment.
[0035] One approach is to send the filtered process vapors from the hydropyrolysis reactor to a second phase reactor, where the process vapors can still be hydrogenated using a hydroconversion catalyst. This approach can be used to produce a product stream that substantially contains fully deoxygenated hydrocarbon species, water vapor, a gas mixture comprising CO, CO2, and light hydrocarbon gases (C1 - C4) and even more heat from process. If this approach is used, the general process can be referred to as integrated hydropyrolysis and hydroconversion.
[0036] Also, it is observed that, while biomass is an ideal raw material for use in the hydropyrolysis process described above, the raw material sent into the fluidized bed hydropyrolysis reactor does not need to be biomass, and it does not need be composed only of solids. Any raw material that can be subjected to hydropyrolysis, under the conditions described above, and that produces products similar to those described above, can be fed into the reactor. Thus, streams of raw materials that contain polymers or plastics, or streams of raw materials that comprise solid particles suspended in a carrier liquid, or streams of raw materials that comprise a carrier gas, where solids or liquids are entrained, or the raw material flows that comprise, in whole or in part, liquids that can be deoxygenated and reacted with hydrogen to produce the deoxygenated hydrocarbons, can be subjected to hydropyrolysis using the method described in the present invention. If liquids are present in the raw material flow, those liquids must be able to evaporate and enter the vapor phase very shortly after being introduced into the fluidized bed. The set of reactions that occur in the process of the present invention is mainly the vapor phase reactions, and the liquids initially present in the raw material flow, or formed through the chemical decomposition of the raw material flow, must enter the steam in order to be processed effectively by the fluidized bed reactor of the present invention. Brief Description of Drawings
[0037] These and other objectives and characteristics of the present invention will be better understood from the following detailed description considered in conjunction with the drawings, in which: Figure 1 is a schematic flow diagram of a hydropyrolysis process for producing liquid fuels from biomass or other raw materials in accordance with an embodiment of the present invention; Figure 2A is a schematic view of a container containing an insertion element, with bag-breaking obstructions attached to an axial support in the center of the container according to an embodiment of the present invention; figure 2B is a top-down view of the insert shown in figure 2A Figure 3A is a schematic view of a container containing an insertion element, with the bag-breaking constraints attached to a support on the circumference of the container according to an embodiment of the present invention; figure 3B is a top-down view of the insertion element shown in figure 3a; and Figure 4 is a graph of the oxygen content of liquid product as a function of the partial pressure of hydrogen. Detailed Description of Preferred Modalities
[0038] A schematic diagram of the process described in the present invention is shown in figure 1. A flow of fluidizing gas 150, which essentially consists of hydrogen, but possibly also contains other gases, is fed to the bottom of a fluidized bed reactor vessel 100. The fluidization gas flow passes through a bed of catalyst particles contained within the fluidized bed reactor container, and fluidizes the bed to a point where its state is consistent with that of a bubbling fluidized bed. An insertion element 130 or other modification into the container is present and interacts with the bed 140 in such a way that fluidization is prevented. The depth of the bed, therefore, is not limited by the diameter of the container, and a deep bed, the axial dimension of which can be many times greater than the diameter of the container can therefore be used.
[0039] The mass flow rate of fluidization gas passing through the bed is determined by the size and fluidization characteristics of the catalyst particles. In the present invention, the catalyst particles are approximately spherical and are approximately 3200 microns in diameter or more, but can be smaller or larger. The density of each particle can vary from 0.5 to 2 kg per liter. Based on laboratory studies, a surface rate of gas fluidization of about 1 to 1.5 meters / second is required to achieve effective fluidization of such a bed. The surface velocity is defined as the average velocity that the fluidization gas would achieve if it passed through the empty reactor, in the absence of a fluidized bed. The diameter of the vessel is essentially regulated by the amount of fluidization gas available, and the depth of the bed is regulated by the amount of catalyst necessary to achieve the deoxygenation requirement of the raw material. There is no defined upper limit to the depth of the bed since the use of an anti-fluid insertion element or anti-fluid modifications within the reactor, as specified in the present invention, ensures that fluidization is avoided, no matter how deep the reactor bed is. The bed must be as deep as necessary to achieve the desired degree of reaction of the process vapors released by the raw material. The fluidization gas mass flow rate must not exceed the minimum necessary to achieve fluidization. If a higher fluidization gas flow rate is used, the material and equipment costs associated with the fluidization gas flow will increase, and the catalyst particles, which have been entrained to some extent, but are still useful, will be decanted the bed. This result is not desirable, so that the mass flow rate of the fluidizing gas is not increased above the minimum necessary to fluidize the bed.
[0040] The temperature distribution within the fluidized bed as described in the present invention is almost uniform due to the rapid exchange of heat between the moving particles throughout the bed. The bed temperature must be at least 343 degrees Celsius (650 degrees Fahrenheit) and need not be higher than 593 degrees Celsius (1,100 degrees Fahrenheit). The exact operating temperature of the bed depends on the composition of the raw material that is subjected to hydropyrolysis, on the characteristics of the catalyst and on the desired composition of products to be obtained.
[0041] The pressure inside the fluidized bed reactor should be such that the partial pressure of hydrogen is about 200 psig to 600 psig. The exact pressure of the fluidized bed reactor depends on the composition of the raw material that is subjected to hydropyrolysis, the choice of the catalyst and the desired composition of the products that must be obtained.
[0042] The raw material that is subjected to hydropyrolysis is fed to the bottom of the fluidized bed, close to the point where the fluidization gas enters the reactor. The raw material is introduced in such a way that it is heated very quickly from room temperature to the temperature of the fluidized bed, through interaction with the fluidized bed. The feed material is introduced into the fluidized bed in such a way that any solid residues (remaining after the raw material has been heated to the bed temperature) form distinct solid particles, which are significantly smaller in size than the catalyst particles at from which the bed is mainly composed. Then, these particles will be transported to the top of the bed and, if they are small enough, they will be dragged through the gas and vapor stream and taken out of the bed. If they are not small enough to be dragged, the particles will continue to move in the fluidized bed and will wear out until they are small enough to be dragged and transported out of the bed. In the case of biomass raw materials, the raw material is prepared and introduced as distinct particles approximately spherical up to, but not exceeding, the diameter of the catalyst particles in the bed. In the present invention, the rapid heating of the raw material causes the raw material to decompose, displacing the products in the thermal decomposition steam phase and leaving behind a solid product (referred to as charcoal), which mainly comprises carbon, but it also includes any non-volatile inorganic materials (ash) initially present in the raw material. The individual particles of solid waste remaining after decomposition generally contain charcoal and ash within a single coherent structure.
[0043] Since these solid waste particles basically consist of carbon, and are physically smoother than the catalysts that comprise the bed, they are more easily subjected to abrasion, friction or grinding. They lubricate the catalyst particles as they move within the fluidized bed, and break down into smaller particles much more quickly than the catalyst particles. This lubricating effect provides a significant benefit since the fine solids of the catalyst that are milled in sizes small enough to be entrained by the gas flow that leaves the top of the bed will leave the bed, and are no longer available to promote chemical reactions. The lubricating effect of charcoal moving around the fluidized bed serves to reduce the catalyst's friction rate, and thus reduce the need (and cost) for the necessary catalyst replacement to maintain the desired degree of chemical reactivity inside the bed.
[0044] In one embodiment of the present invention, in which the solid biomass particles comprise the raw material, the raw material undergoes a very rapid thermal decomposition into product vapors and a relatively soft solid material composed of coal and ash (charcoal being the dominant part). This residue is often referred to as charcoal. This charcoal is rapidly milled (entrained) by catalyst particles in the fluidized bed reactor, which are significantly larger than charcoal particles, until the charcoal is sufficiently reduced in size (and aerodynamic diameter), so that its terminal velocity is less than the ascending velocity of the fluidizing gas and the product vapors. At that point, the entrained charcoal is decanted and transported out of the bed, while relatively large and heavy particles of the catalyst remain behind in the bed. This effect can be promoted and accelerated if the solid particles in the biomass raw material are significantly smaller, in their larger dimension, than the fluidized bed catalyst particles. In addition, the carbon particles entrained in this embodiment of the present invention act as a microscale lubricant, and reduce the friction of the fluidized bed catalyst particles. Thus, the friction catalyst is less when the biomass is hydropyrolyzed in the reactor than it would be if only the fluidized catalyst particles were present.
[0045] The rate at which the raw material is fed into the reactor depends on the amount of catalyst and the partial pressure of hydrogen inside the reactor. The relationship between the rate of raw material that is sent to the bed and the amount of catalyst present in the bed can be quantified in terms of an hourly volume spatial velocity (VHSV). The VHSV can be calculated by dividing the volumetric flow per hour of raw material sent to the reactor by most of the volume of catalyst present in the bed, in the absence of any fluidizing gas flow. In the present invention, the hydropyrolysis reactor can be operated in a catalyst VHSV range from 1 h-1 to 45 h-1. The exact VHSV of catalyst that is appropriate for a given combination of raw materials and catalyst depends on the nature of the raw material and the catalyst, and the desired composition of the products that must be obtained. The atmosphere in the reactor must consist mainly of hydrogen (although other inert gases, such as CO2, may also be present), and the flow rate of raw material cannot be so great that products in the vapor phase of decomposing matter raw materials dilute the hydrogen atmosphere to a point where the partial pressure of hydrogen required to perform the set of desired reactions is no longer available.
[0046] The most important reactions that are carried out in the hydropyrolysis reactor as described in the present invention involve the deoxygenation of oxygenated hydrocarbon molecules. These oxygenated hydrocarbon molecules that contain oxygen are initially present in the raw material, and oxygen is often present in the form of functional groups that make chemically reactive oxygenated hydrocarbons very reactive. The hydropyrolysis reactor of the present invention eliminates these oxygen atoms from the hydrocarbon molecules with which they are associated. Inside the reactor, oxygen can be converted to either water vapor (H2O), or to vapor phase species that contain carbon monoxide (CO) carbon and carbon dioxide (CO2). If some of the oxygen from the raw material is initially removed through a reaction that forms CO (decarboxylation), and some part is initially removed in reactions that form H2O (hydrodeoxygenation), the molecules of CO and H2O can react to form CO and H2. This last reaction is referred to as a water and gas displacement reaction and, once it releases a molecule of H2, it can be useful in reducing the amount of hydrogen that is sent into the reactor in the fluidization gas stream. The relative amounts of CO, CO2 and H2O that are present in the vapors that emerge from the top of the fluidized bed inside the reactor depend on the raw material, the operating conditions and the characteristics of the catalyst. The set of reactions that occur during deoxygenation of the raw material releases significant amounts of liquid heat, since the heats of formation of CO, CO2 and H2O are high enough to overcome the amount of heat necessary for the effect of heating and endo-thermal thermal decomposition of the raw material, and the chemical decomposition of oxygenated molecules in the process vapors. The excess heat generated by deoxygenating the raw material is at least sufficient to heat the raw material that enters to the fluidized bed temperature, and provides the heat consumed by any endothermic processes, including the evaporation of liquid species. , which occurs during the hydropyrolysis of the raw material.
[0047] The gaseous products and vapors exiting the top of the fluidized bed must have certain characteristics, so that the process described in the present invention is carried out successfully. First, it must consist largely of hydrogen. Second, the small particles of solid matter (charcoal and ash, as well as the entrained catalyst) need to be dragged inside them. In steady state, the mass flow rate of entrained solids leaving the top of the fluidized bed must be equal to the rate at which the solid waste is generated by hydropyrolysis of the raw material in the fluidized bed, plus the rate at which the catalyst is being dragged to form the fine solids small enough to be decanted. Third, the vapors must contain the hydrocarbon species produced when the raw material is hydropyrolyzed. Fourth, the molecules that make up the hydrocarbon vapors must be sufficiently deoxygenated and chemically stabilized so that they do not react quickly with other hydrocarbon molecules, or with solid surfaces with which they can come into contact. Fifth, the total mass oxygen content of condensable hydrocarbons in the product vapor stream should be 4% or less. The condensable term, in this case, indicates that the species in question has boiling points of 21 degrees Celsius (70 degrees Fahrenheit) or less, at atmospheric pressure, or is highly soluble, and not subjected to rapid vaporization, when dissolved in a liquid with a boiling point below 21 degrees Celsius (70 degrees Fahrenheit).
[0048] The flow of gases and vapors from products leaving the top of the fluidized bed, therefore, contains hydrogen, water, steam, CO, CO2, and the entrained solid particles. It also contains hydropyrolysis hydrocarbon products from the raw material, namely methane, ethane, propane, butane, and a variety of other hydrocarbon molecules with boiling points at atmospheric pressure in line with those of gasoline, kerosene and diesel. . Some hydrocarbons, with oxygen in their molecular structure, and / or other heteroatoms such as nitrogen, sulfur and phosphorus, may also be present in the flow of steam that leaves the fluidized bed. Other vapors, such as H2S and ammonia, may also be present, depending on the composition of the raw material. However, the product vapors are sufficient and chemically stable that they can be effectively separated from the entrained solid particles by means of filtration, by means of inertia, or electrostatically, without binding or otherwise harming the separation devices through which they pass.
[0049] In the present invention, the product vapor stream from the top of the fluidized bed reactor 100 is kept hot enough to prevent condensation of the entire liquid product and then transported to one or more 110, 120. In a preferred embodiment, separation of inertia and filtration are used in series and occur primarily in a primary separation system 110 (for example, a cyclone or a virtual impactor), which removes the larger particles that mainly consist of in charcoal and ash. The gases and vapors are then transported to a hot filtration system 120 (for example, a porous barrier filter that may or may not be increased with a magnetic separation step), which removes any remaining entrained solid particles , and can produce a solid flow consisting mainly of fine catalyst solids from the fluidized bed. However, any other effective means by which charcoal can be removed from the flow of hot process gases and steam can be applied.
[0050] The product vapor stream can then be cooled to condense water and condensable liquid hydrocarbon product, or the product vapor stream can be directed to another reactor for further processing. If the hydropyrolysis products are cooled to condense the liquid products, and transferred to an environment where the pressure is equal to or close to the ambient pressure, and the temperature is at or near 21 degrees Celsius (70 degrees Fahrenheit) two liquid phases are recovered. One phase floats on top of the other, and that upper phase is composed of hydrophobic hydrocarbons, and contains less than about 4% by weight of oxygen. The lower phase comprises mainly water, as well as all the water-soluble species produced by the process. The hydrocarbon phase comprises mainly hydrocarbons with properties consistent with those of gasoline, kerosene and diesel.
[0051] According to one embodiment of the present invention, the raw material subjected to hydropyrolysis essentially comprises a type of biomass, such as certain species of algae, which contain a significant fraction of the lipids. When subjected to hydropyrolysis, this type of raw material will produce significant amounts of deoxygenated diesel oil, which could be produced from lipids extracted from algae. In addition, the hydropyrolysis of algae that contains a significant fraction of lipids will also give rise to additional gasoline and diesel hydrocarbons, which are produced as a result of the hi-dropyrolysis of non-lipid fractions of the algae (cell walls, etc.). This is particularly attractive because extracting lipids from algae through, for example, hexane-based solvent extraction, is expensive. It should also be noted that conventional algae biomass rapid pyrolysis would be very unattractive because the uncontrolled thermal reactions that occur during rapid pyrolysis would degrade lipids in algal raw materials. Thus, the process of the present invention is ideal for converting algae, because it can be carried out on algae raw materials that are, in general, only partially dehydrated, and still produce high quality diesel and gasoline hydrocarbons as a resultant product. .
[0052] The process of the present invention provides several distinct advantages over processes based on conventional rapid pyrolysis in that it produces a liquid hydrocarbon product that contains low or insignificant amounts of solid charcoal, very little oxygen, is chemically stable and is hydrophobic. Hot filtration of solid coal from the product vapor stream is generally not possible with rapid pyrolysis vapors, particularly when biomass is used as a raw material. However, the hot filtration of a solid charcoal is easily applied to the hydropyrolysis biomass product vapor streams according to the process of the present invention. In addition, rapid pyrolysis of biomass raw materials does not produce a stream of hydrophobic and deoxygenated liquid product, which means that the recovery of a usable liquid hydrocarbon fuel from liquids produced through rapid biomass pyrolysis has a significant technical challenge. However, recovering a usable liquid hydrocarbon fuel stream from biomass hydropyrolysis via the process of the present invention is simple as described above.
[0053] Due to the fact that liquid hydrocarbon fuels produced in the process of the present invention have an inherently low oxygen content, the flow of water-based (aqueous) liquid product produced by this process remains relatively free of dissolved hydrocarbons and, probably, contains less than 5% by weight of total dissolved organic carbon (TOC). Due to this relatively low concentration of TOC, the flow of aqueous liquid product can be handled and eliminated relatively easily. The aqueous liquid product stream will also contain a concentration of dissolved ammonia that will depend on the amount of nitrogen initially present in the raw material.
[0054] The hydropyrolysis process of the present invention produces primary streams of charcoal, water, steam, hydrogen, hydrocarbon gases, such as methane, ethane and pro-cloth and liquid hydrocarbon fuels. These can be integrated with other processes that produce biomass or fuels from related renewable materials. In addition, secondary nutrient flows can be obtained from the hydropyrolysis process of the present invention, which can be useful in promoting biomass growth. Ammonia is one of these nutrients, which can be recovered from the process of the present invention, and can be used as a fertilizer in order to promote the growth of biomass. The charcoal obtained from the process can also be used as a soil conditioner to improve the production of crops such as corn and sugarcane. Sources of biomass receptive to the production of a process integrated with the process of the present invention include, but are not limited to, algae, pine nuts, corn husks, wood, bagasse, grasses, miscant and walnut (or nut shells). The processes that produce high value nutraceutical products obtained from plants or other crops can also be integrated into the process of the present invention.
[0055] In addition, the hydropyrolysis process modality of the present invention that converts corn straw into liquid fuel for transportation can be integrated into facilities that produce ethanol from corn. The water and steam produced by hydropyrolysis of corn hybrids could find use in the production of corn ethanol, which normally requires both energy and water as inputs. Residues from corn ethanol production can also be used as food for the hydropyrolysis process.
[0056] The biomass hydropyrolysis process can also be integrated into an oil refinery. Coal from the hydropyrolysis process can be burned to produce energy in refinery furnaces, thereby reducing refinery gas emissions, since CO2 emissions from renewable sources do not count as greenhouse gas emissions. Liquid hydrocarbons from the hydropyrolysis process can go directly to the hydrotreating unit refinery for further improvement and are fully compatible. The hydrocarbon gases C1 - C3 from the hydropyrolysis unit can go to the hydrogen unit to produce the hydrogen needed for hydropyrolysis. Preferred Catalyst Features
[0057] 1. As partículas de catalisador precisam ser aproximadamente esféricas com diâmetros de partículas significativamente maiores do que o diâmetro dos resíduos sólidos de matéria-prima formados durante a hidropirólise. As densidades de partículas catalisadoras de cerca de 0,5 a 2 kg por litro são necessárias, de modo que o catalisador será retido de forma eficaz no leito, enquanto carvão vegetal e outras pequenas partículas (que possuem densidade de partículas e diâmetros aerodinâmicos menores que o catalisador) são decantados do leito. 2. As partículas de catalisador precisam fornecer uma atividade catalítica suficiente para permitir que o processo de hidropirólise da presente invenção, descrito anteriormente, prossiga em conformidade com as condições especificadas acima. 3. As partículas do catalisador devem catalisar de forma eficaz as reações de deso-xigenação do processo da presente invenção, sem catalisar as reações que formariam uma quantidade excessiva de resíduo carbonáceo sólido (coque) nas superfícies cataliticamente ativas do catalisador. 4. As partículas de catalisador precisam ser resistentes ao atrito, de modo que a quantidade de catalisador arrastado por dia, semana, mês ou ano de funcionamento seja baixa o suficiente para ser facilmente substituído, sem comprometer a viabilidade econômica do processo. In order for the hydropyrolysis to be carried out effectively in the fluidized bed reactor, as described in the process of the present invention, the catalyst preferably includes several characteristics: 1. The catalyst particles need to be approximately spherical with particle diameters significantly larger than the diameter of the solid raw material residues formed during hydropyrolysis. Catalyst particle densities of about 0.5 to 2 kg per liter are necessary, so that the catalyst will be effectively retained in the bed, while charcoal and other small particles (which have particle density and aerodynamic diameters less than the catalyst) are decanted from the bed. 2. The catalyst particles must provide sufficient catalytic activity to allow the hydropyrolysis process of the present invention, described above, to proceed in accordance with the conditions specified above. 3. The catalyst particles must effectively catalyze the deoxygenation reactions of the process of the present invention, without catalyzing the reactions that would form an excessive amount of solid carbonaceous residue (coke) on the catalytically active surfaces of the catalyst. 4. The catalyst particles must be resistant to friction, so that the amount of catalyst dragged per day, week, month or year of operation is low enough to be easily replaced, without compromising the economic viability of the process.
[0058] In general, the use of spherical catalyst particles (as opposed to other forms) will produce the lowest friction rate.
[0059] As described above, the hydropyrolysis catalyst of the present invention is disposed within a fluidized bed reactor and the catalyst bed has an L / D ratio significantly greater than 2. Fluidization of the bed, during operation, is prevented by use of an anti-fluidization insert or other anti-fluidization modification of the reactor (described in more detail below). The particle size of the catalyst is determined by the smaller size so that the solid particles in the raw material flow can be reduced, without compromising the viability or commercial viability of the process. In general, if the particles of a solid raw material, such as biomass, are reduced below approximately 2,800 microns in a commercial operation, the cost of milling and preparing the raw material can increase significantly. In order for the solid waste produced from solid particles of raw material that are about 2800 microns in diameter to easily rise through the bed and, finally, be decanted from the bed, without a concomitant loss of catalyst, a particle size 3,200 microns or more is generally specified for catalysts according to the process of the present invention. In cases where smaller particles of raw material can be applied, in practice, the size of the catalyst particles can then be reduced, as long as the catalyst particles remain large enough to be effectively retained in the fluidized bed. , while the hydropyrolysis solid residues are decanted.
[0060] The process requires an active catalyst that effectively deoxygenates and chemically stabilizes hydropyrolysis vapors, but this is not so catalytically active that it molds quickly. The fluid bed catalyst of the present invention can be any highly active deoxygenation catalyst that reduces the collective oxygen content of hydrocarbon vapors produced with more than four carbon atoms in their molecular structure (C4 + hydrocarbons) to less than 4% of oxygen. Preferably, the catalyst in the fluidized bed should satisfy the requirements mentioned above, and carry out the necessary reactions at a VHSV greater than 1h-1. A variety of catalysts can be used in the hydropyrolysis fluidized bed of the present invention, however, the catalysts, in general, in accordance with preferred embodiments of the present invention are as follows: In a preferred embodiment, the catalyst comprises spherical particles of porous aluminum or other suitable support, which have been impregnated with a catalytic material consisting of nickel and molybdenum (NiMo) or cobalt and molybdenum (Co and Mo), and were then impregnated with sulfide . Catalysts comprising NiMo or CoMo with sulfide on a porous aluminum support material have been shown to be good catalysts for hydropyrolysis and exhibit good activity in the experimental deoxygenation test. As described above, spherical catalyst particles are required in fluidized beds to minimize friction. If the catalysts are not spherical they will wear out quickly, and excess catalyst losses will occur which could threaten the economic viability of the process. In another embodiment of the process of the present invention, the catalyst comprises the spherical particles of porous aluminum or other suitable support impregnated with nickel or cobalt or iron, or other metals that can be used for hydrotreating. Any metal or combination of metals impregnated on a suitable support, which is suitable for use in hydrogen treatment, can also be used as a hydropyrolysis catalyst in the process of the present invention, as long as the resulting material exhibits sufficient catalytic activity to reduce the collective oxygen content of C4 + hydrocarbon vapors present in the hydropyrolysis product stream to less than 4% by mass, while releasing sufficient exothermic heat from the reaction to keep the fluidized bed temperature stable in the hydropyrolysis reactor. In a preferred embodiment of the present invention, the raw material comprises solid biomass particles that comprise a volume density of approximately 0.2 to 0.4 kg per liter, and the catalyst particles comprise a volume density of approximately 0, 7 to 1.2 kg per liter. The difference in the volume density of the raw material and the catalyst in this modality ensures that the solid residue (charcoal) from biomass hydropyrolysis is transported quickly through the fluidized bed and decanted. Preferred Insertion Element Features
[0061] 1. Leito inclinado. A inclinação do reator mostrou eliminar a fluidização e aumentar a mistura axial no leito fluidizado sob determinadas condições. No entanto, a distribuição radial e a velocidade do fluxo de gás aumentam em não uniformidade na medida em que o ângulo de inclinação é maior. Isso cria uma condição na qual a maior parte do gás de fluidização e vapores de processo podem passar pelo catalisador no leito, e as reações de hidro-pirólise desejadas não podem ser realizadas. 2. Leito em cano/leito cônico. Também é possível construir um reator cônico, um que é mais largo no topo do que no fundo. Essa disposição é muitas vezes referida como um leito em cano. A inclinação da parede do reator, nesse caso, pode interromper a formação e a propagação de uma bolsa até certo ponto. No entanto, é muito mais difícil fabricar um recipiente de reator que seja cônico do que fabricar um recipiente de reator com lados retos verticais. Além disso, a velocidade do gás de fluidização no reator é muito maior perto da parte inferior de um reator de cônico, onde a área da seção transversal do cone é menor, do que perto do topo. Em geral, esse efeito cria um espaço em torno da base do cone, onde não existe qualquer material do leito, uma vez que a velocidade do gás de fluidização é tão elevada que o material do leito é elevado para fora desse espaço. A alta velocidade do gás de fluidização nessa região também pode criar o atrito catalisador em excesso. As discussed above, the fluidized bed of catalyst particles of the present invention is of sufficient depth that it is prone to fluidization. In order to ensure that fluidization does not occur, an anti-fluid insertion element or other anti-fluid modifications to the reactor vessel are used. There are several strategies that can be used to decrease fluidization in fluidized beds, which do not involve the introduction of obstructions, obstacles or constrictions in the bed. However, these cannot be usefully applied in the case of the present invention. Two of these other anti-fluidization strategies are: 1. Inclined bed. The slope of the reactor has been shown to eliminate fluidization and increase axial mixing in the fluidized bed under certain conditions. However, the radial distribution and the speed of the gas flow increase in non-uniformity as the angle of inclination is greater. This creates a condition in which most of the fluidizing gas and process vapors can pass through the catalyst in the bed, and the desired hydro-pyrolysis reactions cannot be carried out. 2. Pipe bed / conical bed. It is also possible to build a conical reactor, one that is wider at the top than at the bottom. This arrangement is often referred to as a pipe bed. The slope of the reactor wall, in this case, can interrupt the formation and propagation of a bag to a certain extent. However, it is much more difficult to manufacture a reactor vessel that is tapered than to manufacture a reactor vessel with straight vertical sides. In addition, the velocity of the fluidizing gas in the reactor is much higher near the bottom of a conical reactor, where the cross-sectional area of the cone is smaller, than near the top. In general, this effect creates a space around the base of the cone, where there is no bed material, since the fluidization gas velocity is so high that the bed material is elevated out of that space. The high speed of the fluidizing gas in this region can also create excess catalyst friction.
[0062] Insertion Elements and Container Modifications that present Obstacles or Lateral Obstructions
[0063] Due to the fact that the inclined and tapered beds do not provide a practical means by which fluidization can be controlled in the hydropyrolysis process of the present invention, a different approach is used. According to a preferred embodiment of the present invention, one or more insertion elements of 130, as shown schematically in figure 1, are included and / or installed in the fluidized bed reactor 100, preventing the formation of pockets and allowing mixing fast, uniform, axial and radial in depth beds. In the present invention, this method is applied in a hydropyrolysis reactor, where exceptionally deep fluidization beds 140, composed of large particles, are used.
[0064] Figure 2 shows a reactor that has a container wall 230 that defines a fluidized bed 240 in which particles 260 of raw materials are fed along a flow of fluidizing gas 250. Process vapors 220 are shown schematic exiting fluidized bed 240. In an embodiment of the present invention, fluidization is minimized or avoided by installing side obstructions 200 installed on a central support rod, as shown in figure 2A. Obstructions 200 extend at least part of the path from the center line of the reactor to the wall of the reactor 230, on at least one side of the center line. In a preferred embodiment, the obstructions extend all the way through the reactor and, at their longest point, have a length that is equal to the diameter D of the reactor. The obstruction width, W, is such that the obstruction covers about 40% of the reactor's cross-sectional area. The obstructions 200 are installed at regular and axial intervals, H, equivalent to the length of approximately one to two diameters of the bed. The orientations (as shown in figure 2B as 1, 2, 3) of the obstructions 200 are adjusted so that the axis of each obstruction is separated by 60 degrees of rotation from the axis of the obstructions above and below it, as shown in top view in figure 2B. This arrangement ensures that a coherent bag of bed particles, which occupies the total diameter of the reactor, is not possible to form, and cannot propagate along the axis of the reactor. In order to avoid fluidization over the entire bed, the obstructions must be installed in such a way that they extend over the entire height of the fluidized bed, L, since the bed is fully fluidized. The upper part of the fluidized bed must extend to less than one reactor diameter, D, after the start of the highest obstruction.
[0065] In other embodiments of the present invention, a wide variety of obstruction geometries can be applied to stop the formation of pockets in the bed, including rectangular flaps, obstructions with triangular cross sections, diamond shaped obstructions with cross sections, oval obstructions with cross sections , grids, etc. The open areas in the obstructions, or the open cross-sectional areas of the reactor, are preferably not aligned with each other, and should overlap as little as possible when viewed from above.
[0066] Dead spots in the fluidized bed 240 may form on the upper surface of obstructions 200, if the obstructions are not developed correctly. In a neutral position, the solid particles settle on the upper surface of the obstruction, and do not move in the fluidized bed. In order to avoid this effect, the upper surface of the obstructions must be inclined, tapered, or rounded, so that the bed material cannot rest on the top surface of the obstruction.
[0067] Another approach to prevent the formation of dead spots is to use a porous insertion element or an insertion element that uses a porous upper part so that hydrogen, for example, can flow through the central support 210 and be routed to cylindrical obstructions of disruption of porous or partially porous pouches used along the length of the central support 210.
[0068] In some cases, they may be advantageous to allow for limited fluidization or cyclic expansions of fluidized bed 240 that do not fully meet the fluidization definition at the top of the bed. This may be necessary in order to more effectively grind large particles of hydropyrolysis from solid waste into smaller sizes, which can be decanted from bed 240. If this effect is desired, a part at the top of the expanded bed 240 may remain unobstructed , in which case that section of the bed will tend to form the pocket (if it extends a sufficient distance) or it may begin to oscillate up and down periodically, without presenting the coherent bed movement, which is characteristic of fluidization.
[0069] The type of obstruction 200 shown in figure 2 can be used to prevent fluidization in beds with very large length and depth (L / D) ratios, due to the fact that a pouch tends to require an unobstructed path of the axial path equal to approximately 1 to 2 bed diameters to form, and the installation of these obstructions interrupts the pouch as soon as it starts to become coherent. Since the obstructions are placed at intervals of approximately one to two diameters, D, there is no section of the fluidized bed 240 within which a coherent pocket can form.
[0070] The action of the bed 240 tends to wear the material of the obstructions 200, and can limit the life of the obstructions 200. In one embodiment, which can be used in situations where this is a concern, the insertion element can be constructed in such a way way that is easily removed and replaced.
[0071] In another embodiment, the obstructions and the central support of the insertion element can be produced to be highly resistant to abrasion, for example, by making them from a ceramic or ceramic glass material or from a ceramic-coated material. A combination of materials can also be used in which, for example, the components that are likely to be most worn are produced from an extremely rigid material, and other components such as the central support rod 210 are produced from metal.
[0072] In another embodiment, the surfaces of the insert and the walls of the container 230 can be formulated so that they are also catalytically active, and contribute to the catalytic activity necessary to complete the process chemistry in the reactor.
[0073] In another embodiment, the side obstructions 200 are equipped with means by which they can be heated or cooled, and / or are equipped with instrumentation that allows the local temperature of the fluidized bed 240 to be measured and / or regulated.
[0074] In another embodiment, the side obstructions 200 are not attached to a central support, but are associated with, or installed directly on the reactor container wall 230. If this modality is applied, the obstructions cannot be easily removed from the reactor, and replaced as part of a single coherent insertion element. However, this mode allows access to the interior of each obstruction, through the location on the wall of the container, where the obstruction is fixed. The means of heat transfer, instrumentation, or steam generation and then can be applied within each obstruction 200 through the locations where the obstructions 200 are attached to the vessel wall 230. Insertion Elements and Container Modifications featuring Constraints
[0075] Bed diameter constraints 300, such as those shown schematically in Figure 3, can have the same bag-breaking effect created by lateral obstacles or obstructions 200. According to this embodiment of the present invention, one or more insertion elements 130, as shown schematically in figure 1, are included and / or installed in the fluidized bed reactor 100, preventing the formation of pockets and allowing rapid, axial, uniform and radial mixing in deep beds. As described above, this approach is applied in a hydropyrolysis reactor, where deep fluidized beds 140 are used, abnormally, composed of large particles.
[0076] Figure 3 shows a reactor that has a container wall 330 that defines a fluidized bed 340 in which the raw material particles 360 are fed along a flow of fluidizing gas 350. The process vapors 320 are shown schematic drawing from the fluidized bed 340. In one embodiment of the present invention, fluidization is minimized or avoided by installing constraints on the cross section of the reactor 300 installed on a circumferential support, as shown in figure 3. The cross section area, A , of constriction 300 is such that the constriction covers about 40% of the reactor cross-sectional area. Constrictions 300 are installed at regular, H, axial intervals, equivalent to the length of approximately one to two diameters of the bed. The orientation of constrictions 300 is adjusted so that the centerline of the open area of each constriction is separated by 120 degrees of rotation from the centerline of the open area of the constructions above and below it, as shown in the top-down view in the figure 3B. This arrangement ensures that a coherent bag of bed particles that occupies the total diameter of the reactor does not form, and cannot extend along the axis of the reactor. In order to avoid fluidization over the entire bed, the constrictions must be installed in such a way that they extend over the entire height of the fluidized bed, L, since the bed is fully fluidized. The upper part of the fluidized bed must extend to less than one reactor diameter, D, in addition to the type of the highest constriction.
[0077] In other embodiments of the present invention, a wide variety of constriction geometries can be applied to interrupt the formation of pockets in the bed, including constrictions with multiple openings, rounded contours, irregular contours, etc. The open areas in the constraints, or the open areas of the cross section of the reactor are not blocked by the constrictions, they are preferably not aligned with each other, and should overlap as little as possible when viewed from above.
[0078] As is the case when obstructions or obstacles are installed in the bed, dead spots in the fluidized bed 340 can form on the upper surface of the constraints 300, if the constrictions are not developed correctly. In order to avoid this effect, the upper surface of the constriction should be inclined, conical or rounded, so that the bed material cannot rest on the top surface of the obstruction.
[0079] Another approach to suppress the formation of dead spots is to use a porous constriction or constriction that uses a porous upper portion so that hydrogen, for example, can flow through tubes implanted along circumferential support 310 and be routed to cylindrical obstructions. porous or partially porous bag rupture implanted along the length of the central support 310.
[0080] In some cases, it may be advantageous to allow limited fluidization, or cyclic expansions of fluidized bed 340, which do not fully meet the definition of fluidization, at the top of the bed. This may be necessary in order to more effectively grind large particles of hydropyrolysis from solid waste into smaller sizes, which can be decanted from the 340 bed. If this effect is desired, a part at the top of the expanded bed 340 may remain unobstructed, in which case, that section of the bed will tend to create the pocket (if it extends a sufficient distance) or it may begin to oscillate up and down periodically, without presenting a coherent bed movement, which it is characteristic of fluidization.
[0081] The type of constriction 300 shown in figure 3 can be used to prevent fluidization in beds with very large length and depth (L / D) ratios, since a bag tends to require an unobstructed path of the axial path equal to approximately 1 2 bed diameters to form, and the installation of these constrictions breaks the pouch as soon as it becomes coherent. Since the constrictions are placed at intervals of approximately one to two diameters, D, there is no section of the fluidized bed 340 within which a coherent pocket can form.
[0082] The action of the bed 340 will tend to abrasion the material of the constrictions 300, and can limit the useful life of the constrictions 300. In one modality, which can be used in situations where this is a concern, the insertion element can be constructed in such a way way that can be easily removed and replaced.
[0083] In another embodiment, the constraints and circumferential support of the insertion element can be made to be highly resistant to abrasion, through, for example, making them from a ceramic or ceramic glass material or a material coated with pottery. A combination of materials can also be used, in which, for example, the components likely to see the most wear are made of an extremely hard material, and other components are made of metal.
[0084] In another embodiment, the insertion element surfaces and vessel walls 330 can be formulated so that they are also catalytically active, and contribute to the catalytic activity necessary to complete the process chemistry in the reactor.
[0085] In another embodiment, constrictions are equipped with means by which they can be heated or cooled, and / or are equipped with instrumentation that allows the local temperature of the fluidized bed 340 to be measured and / or regulated.
[0086] In another embodiment, the constraints 300 are not attached to a removable bracket, but are associated with, or installed directly on, the reactor container wall 330. If this modality is applied, the constrictions cannot be easily removed from the reactor, and replaced , as part of a single coherent insertion element. However, this modality allows access to the interior of each constriction, through the location on the wall of the container where the constriction is fixed. The means of heat transfer, instrumentation and / or steam generation can then be applied within each constriction 300, through the locations where the constrictions 300 are attached to the vessel wall 330. General Information on Anti-Fluidization Obstructions and Constraints
[0087] Each type of bag bursting obstacle can be installed on a central support, which extends along the axis of the reactor, or on a circumferential support, which extends around the outside of the reactor. There is no requirement that a particular type of bag break feature be installed on a particular type of support in order for it to be effective.
[0088] The vertical cross section of a bag-breaking feature can be contoured to remove or accentuate sharp angles. The more rounded contours will be more resistant to wear, while the sharper contours can break the pockets more effectively.
[0089] In fluidized bed reactors that are coated with a molded or molten refractory material, the refractory can be molded or melted, such that the bag breaking characteristics are an integral part of the reactor lining.
[0090] Combinations of obstructions and constrictions of different shapes, or alternating obstructions (connected to a central support) and constrictions (which project into the bed from the circumference of the reactor) can provide the ideal bed movement.
[0091] Obstructions and constrictions do not need to be installed horizontally along the reactor and can be installed at some other angle of 90 degrees to the central axis of the bed.
[0092] Obstructions can be circular or rounded in cross section when viewed from the top of the reactor.
[0093] If desired, obstructions can protrude from a central support on only one side of the reactor's center line, which extends outwards, to the reactor wall. As long as obstructions of this type are properly arranged, the formation of pockets can be stopped effectively.
[0094] In general, obstructions or constrictions at each location in the reactor should create a pressure drop equal to about 10-20% of the total pressure drop that the entire fluidized bed would create if there were no obstructions or constrictions present.
[0095] Finally, the obstructions or constrictions used inside the fluidized bed can incorporate heat exchangers so that they can perform the dual function of attenuating the bag formation and managing bed temperature increases related to the exothermic nature of this invention. These heat exchangers can be used to create process steam (for example, converting water from liquid to steam) or the use of liquids to refine temperature distributions within the bed, which can be caused by the use of catalysts different activity levels that stratify and segregate in different layers within the bed by choosing the density, the aerodynamic diameter, or both. Examples Fluidized Bed Mixing Studies without Insertion Element
[0096] The experiments were carried out in order to study the fluidization in bubbling fluidized beds, consisting of relatively large, solid and spherical particles similar to the catalyst used in the hydropyrolysis process of the present invention. The bed material consisted of porous aluminum spheres, with an average diameter of 1,800 microns. The particle diameters of the bed material were within about 200 microns of average diameter. The volume density of the bed material was 0.75 kg per liter.
[0097] The fluidized beds expand as the fluidizing gas passes through them, so that they are more easily compared on an unexpanded basis. In this case, the depth of the unexpanded bed is the depth of the bed when no fluidizing gas passes through it.
[0098] Beds with an unexpanded L / D close to 6 were studied in two transparent plastic tubes. One of the tubes had an inner diameter of 3.33 centimeters, and the other had an inner diameter of 7.62 centimeters. The tube had a small grid, at its base for the distribution of fluidizing gas. The tube with the largest diameter had an inverted conical base, with a 90 degree angle included in the cone, and a central gas jet at the apex of the cone. The aluminum ball beds described above required a minimum characteristic fluidization speed (UF) of about 0.61 meters / second at 0.76 meters per second. The minimum fluidization speed, UF, is the speed at which the pressure drop across the bed stops increasing with the increase in the surface velocity of the gas through the bed, but in which no movement is observed in the bed. Once the gas flow through the bed in each clear plastic tube was lifted above Uf, the bed expanded to its volume reached about 1.5 times the undilated volume and then began to move in large amounts. Fluidization in both tubes was observed when the unexpanded L / D was 6 and large amounts of movement occurred in the bed.
[0099] Fluidization in both tubes can only be avoided if the unexpanded L / D ratio of the bed is less than 1.5. The phenomena that affect the movement of large quantities in the bed do not seem to be influenced by the diameter of the tube in which each of the tests was performed, or by the very different methods of flow distribution associated with each tube (the sprinkler grid in the case of the tube with the smaller diameter, and the jet base, in the case of the tube with the larger diameter). The bed's tendency to create a pocket, therefore, occurred when the bed of porous aluminum spheres had an unexpanded L / D greater than 1.5, and the phenomena responsible for the start and spread of fluidization were not sensitive to the diameter of the device test tube or medium used to introduce fluidized gas into the bottom of the bed. Mixing Studies of Fluidized Bed with Insertion Element
[0100] Additional studies were performed on the larger plastic tube, in order to analyze the effect on the fluidization of the introduction of lateral obstructions fixed to an insertion element. The insertion element consisted of a metal rod, located in the central line of the tube, with several obstructions and obstacles installed in it, in order to break the coherent bag of aluminum spheres.
[0101] Near the bottom of the tube, three steel washers were installed at 7.62 cm intervals. The lowest of these washers was installed at an altitude of 7.62 cm (or a diameter of the tube, D) above the bottom of the tube. The diameter of each washer was about 2.54 centimeters, which means that the washing machine clogged about 10% of the cross-sectional area of the tube. Circular obstructions (washers) increased the speed of the gas as the gas passed around the obstruction, visibly interrupting the formation and propagation of pockets in the bed. However, it was observed that during the initial tests of the bed above the last washer they exhibited a pronounced tendency to create a pocket, and the addition above that pressure level had little or no effect on fluidization. Obstacles circulate around the center line, therefore, to provide little benefit in a bed with an unexpanded depth greater than L / D = 2 (with the bed expanded, after fluidization occupying a depth with an L / D ratio approximately 3).
[0102] During this work, it was observed that the integrity of the portion was important in the development of fluidization. Inside the bag, either the entire bed has to move as a single body, or the bag starts to collapse immediately. In order to collapse the bag, and eliminate the fluidization problem, the rectangular flaps have been cut and perforated so that they can be installed on the same metal rod. The outer end of each flap has been rounded to conform to the inner wall of the tube. Three flaps were prepared with a width of 2.54 cm and a length of 3.18 cm. Each flap blocked approximately 20% of the cross-sectional area of the tube, and accessible from the central rod, to the reactor wall, which means that the fluidization gas had to accelerate as it passed through each flap, and the particles of the bed in the stock exchange have reorganized themselves to pass around this obstacle. The flaps were installed at axial intervals of 7.62 cm, with the smallest flap located 7.62 cm above the base of the tube. When a pouch of bed material began to form and encountered the obstruction created by the flaps, the obstruction created enough movement within the pouch that the pouch's cohesion was interrupted. Open gas passages formed around the flap and the particles came out of the pouch and down towards lower levels of the bed.
[0103] Two flap arrangements were examined: on one, the flaps were placed on alternate sides of the reactor with the orientation of each flap separated from the next on the 180 degree line, and on the other, they were arranged so that each flap was oriented in 120 degrees from the top and bottom flap.
[0104] A systematic effort was then made to study fluidization in the clear plastic tube, with an internal diameter of 7.62 cm, using aluminum ball beds with an unexpanded L / D of 3, and a gas velocity surface fluidization of 0.91 meters per second. A population of spheres in the bed in general with a diameter slightly less than 1700 micrometers was identified, separated by sieving, and dyed red. The rest of the bed was white. The red spheres can be mixed into the bed, and readily recovered. The movement and distribution of red spheres in the bed provided a means by which the distribution of the particles and the mixture in the bed can be observed directly, and quantified.
[0105] A protocol for analyzing the mixing rate was developed, which involved depositing a bed of red spheres on top of the white spheres in the bed, and then from a stopwatch at the same time that the flow of the fluidization gas was sent through the bed. When the red balls were visible at the bottom of the bed, the timer was stopped, and this was then referred to as the characteristic mixing time observed for the bed, under a given set of experimental conditions.
[0106] The mixing time characteristic of the bed, in the absence of any insertion element of bag rupture, was found to be: 15 seconds. Fluidization occurred.
[0107] The insertion element configurations described above (flaps separated by 180 degrees and flaps separated by 120 degrees) were then tested.
[0108] The characteristic mixing time obtained with the flaps arranged at 180 degrees was found to be: 5.3 seconds. Fluidization did not occur.
[0109] The characteristic mixing time obtained with the flaps at 120 degrees was found to be: 5.0 seconds. Fluidization did not occur.
[0110] Fluidization was not observed when an insertion element was used inside the 7.62 cm clear plastic tube. The mixing times obtained with the insertion elements were both shorter and shorter than the mixing time observed when the reactor did not have the insertion element. The 120-degree separation angle guide arrangement is particularly effective, as the gas flow that cannot find a single clear and unobstructed path to the top of the bed, and has to change its path each time it finds a tab. While some cyclic bubble formation can still be observed, the bubbles cannot occupy the entire diameter of the tube, and cannot travel the entire length of the bed. The mechanisms that caused the bed to form a pocket were thus defeated.
[0111] Finally, a deep bed with an unexpanded L / D of 5.5 was tested. When expanded, this bed had an L / D of about 7.5.
[0112] With the 120 degree flange separation insert, the deepest bed L / D = 5.5 mixed quickly and evenly. However, a portion of the expanded bed extended above the upper flap, and fluidization occurred in that upper part of the bed. This result indicates that the flaps need to be positioned at axial intervals of approximately 1 to 2 diameters of the bed, over the entire expanded depth of the bubbling fluidized bed, in order to avoid the occurrence of fluidization. If this methodology is followed, it is evident that, in the absence of other limitations, there is no upper limit for the depth of the bed; it can be accommodated as much as necessary in order to create a bed of any desired depth, and fluidization would not occur at any point in the bed.
[0113] The examples described above were carried out with the obstructions (washers, guides) located at axial intervals of a diameter of the tube. Obstructions installed at intervals that are larger or smaller will also break the pockets. An ideal arrangement and spacing of obstructions exists for any bed. Axial spacing greater than 2 diameters, however, is not likely to produce the ideal longitudinal mixture, since a coherent pocket may be able to form between the obstructions if the obstructions are too far apart. Likewise, very narrow spacing (very close obstructions) will delay the return of the bed material to the bottom of the reactor, increasing the mixing time and introducing non-uniformities in the bed's axial temperature profile.
[0114] The rectangular and upper obstructions (flaps) that were tested on the device above obstructed about 20% of the open area of the bed. These obstructions need not be rectangular; a wide variety of other shapes can be considered (triangular, oval, diamond, etc.).
[0115] Significantly, based on the tests described above that were performed with an unexpanded bed of L / D = 5.5, it appears that a bed of essentially unlimited depth could be fluidized, without fluidization, at the same time as maintains fast longitudinal mixing, if properly oriented obstructions or constrictions are placed at appropriate intervals along the bed axis. If the entire bed is placed in an isothermal environment (such as a long multi-zone oven, where each zone is kept at the same temperature), the entire bed would be essentially the same temperature. Alternatively, over a very long time, the axial variations of the deep bed (very large L / D ratio) in the bed temperature can be induced by changing the temperature of the site, around the reactor, since the exchange rate of heat along the bed axis is finite. Demonstration of Experimental Process
[0116] The following table compares the experimental results obtained during the manifestations of the process of the present invention, with the processes that represent the state of the art of pyrolysis and hydropyrolysis. As is evident from the table, the process of the present invention differs significantly from the state of the art, and uses a very low partial pressure of hydrogen to remove much more oxygen from the finished liquid hydrocarbon product. The results of two experimental demonstrations of the process of the present invention are presented. These are referred to as Case 1 and Case 2. The same raw material (wood) was used in both cases. The tests in both cases were performed at the same hydrogen partial pressure of 325 psig (23 bar absolute). The catalyst particles made up of a porous aluminum material impregnated with nickel were used in process 1 (Catalyst D). The catalyst particles made up of a porous aluminum support impregnated with a material of molybdenum and cobalt with sulfide were used in process 1 (Catalyst B). The fluidized bed in Case 1 was maintained at a slightly different temperature than in Case 2.
[0117] The additional information is presented in figure 4, which presents a graph that relates the oxygen content in liquid hydrocarbon products with the partial pressure of hydrogen used during processing. As is evident from what has been said, the processes described in the present state of the art are able to produce hydrocarbon products with low oxygen content only if the very high partial pressures of hydrogen are used during processing. The partial hydrogen pressure of 325 psig (23 bar absolute) applied during the processing of biomass, in Cases 1 and 2, would be expected to produce a liquid product containing approximately 22% by mass of oxygen. Instead, the process of the present invention, as demonstrated in Cases 1 and 2, produced significant yields of liquid hydrocarbon products with oxygen content of less than 4% by weight.
[0118] Although the aforementioned specification report for that invention has been described in relation to certain preferred embodiments of it, and many details have been presented for purposes of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional modalities and that some of the details here described can vary considerably without departing from the basic principles of the invention.

1. Mohan, Pittman, and Steele, "Pyrolysis of Wood / Biomass for Bio-oil: A Critical Review," in Energy & fuels, Volume 20, pages 848 to 889, 2006; 2. Meier, Jakobi and Faix, "Catalytic Hidroliquefation of Spruce Wood," in Journal of Wood Chemistry and Technology, Vol. 8, No. 4, pages 523 to 542, 1988; 3. Meier and Faix, "Solvent-Free Hidroliquefation of Pine Wood and Miscanthus Stems," in Proceedings of the International Conference on Biomass for Energy and Industry, Lisbon, Portugal, 9 to 13 October 1989; 4. Rocha, Luengo and Snape, "The Scope for Generating Bio-Oils with Relatively Low Oxygen Contents via Hydropyrolysis," in Organic Geochemistry, Vol. 30, pages 1527 to 1534, 1999.

权利要求:
Claims (16)
[0001]
Method to hydropyrolyze an oxygenated organic raw material (160, 260, 360) CHARACTERIZED by the fact that it comprises: a) introducing an oxygenated organic raw material (160, 260, 360) and a fluidizing gas (150, 250, 350) comprising hydrogen in a fluidized bed hydropyrolysis reactor (100) comprising a fluidized bed (140 , 240, 340) of solid particles, including catalyst, under hydropyrolysis conditions sufficient to generate product vapors (220, 320) from thermal decomposition and hydropyrolysis of the oxygenated organic raw material (160, 260, 360); wherein said hydropyrolysis conditions include a partial hydrogen pressure of 200 psig and 600 psig, a temperature of 343 ° C to 593 ° C (650 ° F to 1100 ° F) and a space velocity of the volume (VHSV) of 1 h-1 to 45 h-1; and wherein an average particle size of the catalyst is greater than an average particle size of the oxygenated organic raw material (160, 260, 360); and b) recovering from the product vapors (220, 320) a product stream containing entirely deoxygenated hydrocarbon species, where the product stream comprises less than 4% oxygen by mass; where the fluidized bed (140, 240, 340) of solid particles has a greater depth than the diameters of two reactors (D) and includes lateral inserts (200) selected from the group consisting of obstructions, obstacles, constrictions and combinations thereof, at spaced axial intervals (H) along the fluidized bed (140, 240, 340) from 1 to 2 reactor diameters (D) in such a way that fluidization does not occur within the fluidized bed hydropyrolysis reactor (100 ).
[0002]
Method according to claim 1, CHARACTERIZED by the fact that the suspended solids leave the fluidized bed hydropyrolysis reactor (100), the method further comprising separating the suspended solids from a mixture of the fluidizing gas (150 , 250, 350) and the product vapors (220, 320).
[0003]
Method, according to claim 1, CHARACTERIZED by the fact that in step (b), the product stream is recovered by condensation of the product vapors (220, 320).
[0004]
Method according to claim 1, CHARACTERIZED by the fact that the fully deoxygenated hydrocarbon species include hydrocarbons with boiling points at atmospheric pressure consistent with those of at least one among gasoline, kerosene and diesel.
[0005]
Method according to claim 1, CHARACTERIZED by the fact that hydropyrolysis conditions include a surface velocity of the fluidizing gas (150, 250, 350) sufficient to maintain a bubbling fluidized bed (140, 240, 340).
[0006]
Method, according to claim 1, CHARACTERIZED by the fact that the oxygenated organic raw material (160, 260, 360) comprises lignocellulosic biomass.
[0007]
Method according to claim 1, CHARACTERIZED by the fact that the oxygenated organic raw material (160, 260, 360) comprises solid particles of an oxygenated polymer.
[0008]
Method, according to claim 1, CHARACTERIZED by the fact that the oxygenated organic raw material (160, 260, 360) comprises algae with high-lipid totally or partially dehydrated.
[0009]
Method, according to claim 1, CHARACTERIZED by the fact that the oxygenated organic raw material (160, 260, 360) comprises organic waste material of animal origin.
[0010]
Method according to claim 1, CHARACTERIZED by the fact that the oxygenated organic raw material (160, 260, 360) comprises an oxygenated organic liquid which undergoes hydropyrolysis in the fluidized bed hydropyrolysis reactor (100).
[0011]
Method according to claim 1, CHARACTERIZED by the fact that the positions of the lateral inserts (200) are varied, so as to prevent a single open axial passage extension within the fluidized bed (140, 240, 340) for a distance more than two reactor diameters (D).
[0012]
Method, according to claim 1, CHARACTERIZED by the fact that fluidization in the fluidized bed (140, 240, 340) is prevented by the use of equipment for incorporating lateral inserts (200) centrally over the interior of the hydropyrolysis reactor fluidized bed (100).
[0013]
Method, according to claim 1, CHARACTERIZED by the fact that the upper surfaces of the side inserts (200) are at least one among rounded, peaked and inclined, in order to prevent the coming solid particles from settling on the upper surfaces.
[0014]
Method according to claim 1, CHARACTERIZED by the fact that the upper surfaces of the side inserts (200) are porous to allow the passage of product vapors (220, 320), in order to prevent the solid materials that are coming deposit on the upper surfaces.
[0015]
Method according to claim 1, CHARACTERIZED by the fact that the upper surfaces of the side inserts (200) comprise an abrasion resistant sintered glass ceramic material.
[0016]
Method according to claim 1, CHARACTERIZED by the fact that the surfaces of the lateral inserts (200) are catalytically active and facilitate hydropyrolysis.

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法律状态:
2018-12-18| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-01-22| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2019-07-02| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2020-09-01| B09A| Decision: intention to grant|

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2020-11-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/089,010|2011-04-18|

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US13/089,010|US8841495B2|2011-04-18|2011-04-18|Bubbling bed catalytic hydropyrolysis process utilizing larger catalyst particles and smaller biomass particles featuring an anti-slugging reactor|

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PCT/US2012/030386|WO2012145123A1|2011-04-18|2012-03-23|Bubbling bed catalytic hydropyrolysis process utilizing larger catalyst particles and smaller biomass particles featuring an anti-slugging reactor|

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