process to produce hydrocarbon fuels from biomass and fuel hydrocarbon

专利摘要:
PRODUCTION OF FRACTIONAL AND ENHANCED FUELS FROM BIOMASS Multi-stage biomass processing to produce at least two separate fungible fuel streams, one dominated by liquids in the gasoline boiling range and the other by liquids in the boiling point range of diesel. Processing involves hydrotreating the biomass to produce a hydrotreating product including a deoxygenated hydrocarbon product from materials in the gasoline and diesel boiling range, followed by separation of each of the materials in the gasoline and diesel boiling range from the hydrotreating product and each other's.
公开号:BR112015007671B1
申请号:R112015007671-8
申请日:2013-10-01
公开日:2020-10-27
发明作者:Terry L. Marker；Larry G. Felix；Michael J. Roberts；Martin B. Linck
申请人:Gas Technology Institute；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED REQUESTS
[OO1] This claim claims the priority benefit of U.S. Serial Order No. 13 / 644,984, filed on October 4, 2012, the disclosure of which is hereby incorporated by reference in its entirety. BACKGROUND OF THE INVENTION Field of the Invention
[002] This invention relates to an integrated process to thermochemically transform biomass directly into fractionated and improved liquid fuels, particularly hydrocarbon fuels, such as materials in the boiling range of gasoline and diesel, for example . Description of the Related Art
[003] Conventional biomass pyrolysis, typically rapid pyrolysis, does not use or require H2 or catalysts and produces a reactive, acidic, dense liquid product that contains water, oils, and animal coal formed during the process. In typical pyrolysis processing, animal charcoal and ash are intercombined or intermixed. Therefore, from now on references to animal charcoal should be understood as referring to a material that includes or may include animal charcoal and intercombined or intermixed ash. Because rapid pyrolysis is most typically carried out in an inert atmosphere, much of the oxygen present in biomass is transported in the oils produced in pyrolysis, which increases its chemical reactivity. The unstable liquids produced by conventional pyrolysis tend to thicken over time and can also react to a point where hydrophilic and hydrophobic phases form. Dilution of pyrolysis liquids with methanol or other alcohols has been shown to reduce the activity and viscosity of oils, but this method is not considered to be practical or economically viable, because large amounts of sunk alcohol would be needed to stabilize and transport large amounts of pyrolysis.
[004] In conventional pyrolysis carried out in an inert environment, the liquid water-miscible acid product is highly oxygenated and reactive. Conventional pyrolysis oils are characterized by total acid numbers (TAN) in the range 100 to 200, low chemical stability for polymerization, incompatibility with petroleum hydrocarbons due to miscibility in water, very high oxygen content, in the order about 40% by weight, and a low heating value. As a result, stabilization, transport, and use of liquids derived from pyrolysis are problematic and it is difficult to upgrade this product to a liquid fuel due to the backward reactions that typically occur in conventional pyrolysis and conventional rapid pyrolysis. In addition, the separation of animal charcoal generated by conventional pyrolysis from the liquid pyrolysis product presents a significant technical challenge due to the large amounts of oxygen and free radicals in the pyrolysis vapors that remain highly reactive in a vapor state and form a material similar to tar when they come into intimate contact with animal charcoal particles on the surface of a barrier filter. Consequently, filters used to separate the charcoal from the hot pyrolysis vapors tend to bind quickly due to the reactions of charcoal and unstable oils that occur on and within the layer of the separated charcoal on the filter surface.
[005] The improvement of pyrolysis oils produced by conventional rapid pyrolysis by means of hydroconversion consumes large amounts of H2 and the extreme process conditions make it uneconomical. Also, the reactions in such processing are inherently out of balance in that, due to the necessary high pressures, more water is formed than the process requires while more H2 is consumed than is produced by the process. This leads, in part, to a need for an external H2 source. In a balanced process, all the hydrogen required by the process is produced by the process and the water produced by the process is largely consumed. In addition, when upgrading conventional pyrolysis oil, hydroconversion reactors often plug due to coke precursors present in pyrolysis oils or the coke produced as a result of the catalytic hydroconversion process.
[006] In general, hydropyrolysis is a catalytic pyrolysis process carried out in the presence of molecular hydrogen. Hydropyrolysis may be an inappropriate name in which it can be taken to be an aqueous process. However, for those skilled in the art, the context of the process provides sufficient clarity to avoid such a misconception. Typically, the goal of conventional hydropyrolysis processes was to maximize the net yield in a single step. However, in a known case, a second stage reaction was added, the goal of which was to maximize the hydrocarbon yield while keeping oxygen removal high. However, even this method compromises the economy, because excessive internal pressures are needed together with an external source of H2.
[007] Because of such inefficiencies, significant interest remains in the economical production of hydrocarbon fuels from biomass, particularly materials in the boiling range of gasoline and diesel. SUMMARY OF THE INVENTION
[008] The present invention provides a new and compact integrated process for the direct production of fractionated liquid fuels, particularly improved or high quality hydrocarbon fuels, from biomass. This process distinguishes itself from other biomass-to-fuel processes due to its level of integration, economics of the process as established by independent techno-economic and life cycle analyzes, wide range of raw materials, and quality of the finished product .
[009] According to one aspect, a process to directly produce fractionated and enhanced hydrocarbon fuels from biomass is provided in which the biomass is hydrotreated under hydrotreatment reaction conditions to produce a hydrotreated product that includes a substantially or completely deoxygenated hydrocarbon product including materials in the boiling range of gasoline and diesel. Hydrotreatment processing involves hydropyrolyzing the biomass in a reactor, preferably a bubbling fluid bed reactor, containing molecular hydrogen and a hydrogen deoxygenation and addition catalyst under hydropyrolysis reaction conditions to produce a substantially hydrocarbon hydropyrolysis product. completely deoxygenated comprising animal charcoal and vapors. As with pyrolysis and rapid pyrolysis, in hydropyrolysis, animal charcoal and ash are typically intercombined or intermixed. Therefore, hereinafter references to animal coal produced in hydropyrolysis should be understood as generally referring to a material that includes or may include both animal coal and intermixed or intercombined ash. Deoxygenated hydrocarbons are non-reactive even when adsorbed to animal charcoal and thus animal charcoal can be easily separated from gasoline vapors and in the boiling range of diesel by conventional barrier filtration, or through other forms of gas-particle separation as known to those skilled in the art. Subsequently, all or at least a substantial portion of the animal charcoal is separated from the deoxygenated hydrocarbon hydropyrolysis product to produce a charcoal and particle-free hydropyrolysis product. The hydrotreated product is then processed to separate and enhance each of the gasoline fractions and within the boiling point range of the hydrotreated product and one another.
[010] According to other specific and particular embodiments, suitable processing for the direct production of fractionated and enhanced hydrocarbon fuels from biomass may include one or more of the following aspects: a replacement port for introduce the fresh, used, or revitalized catalyst into the reactor and located at a convenient point along the reactor length, usually, but not necessarily at the bottom of the reactor; at least one of the materials in the boiling range of separate gasoline and diesel is further chemically and / or catalytically enhanced; the fraction in the boiling point range of the separate gasoline is catalytically improved in catalytic gasoline improvement conditions to form an improved gasoline product; the fraction in the separated diesel boiling point range is treated to produce an ultra low sulfur diesel product; treatment of the fraction in the separate diesel boiling point range to produce an ultra low sulfur diesel product involves treating the fraction in the separate diesel boiling point range in a diesel content drip bed reactor ultra-low sulfur; where treatment by means of a diesel drip bed reactor with ultra low sulfur content produces a product stream that mainly includes ultra low sulfur diesel and some residual gasoline, the process additionally involves separating at least a portion of the residual gasoline diesel with ultra-low sulfur content; the hydrotreating product additionally includes gaseous and aqueous fractions that are separated from it; the gasoline boiling point fraction and the gas fraction are simultaneously separated from the hydrotreating product and are subjected to catalytic gasoline enhancement under catalytic gasoline enhancement conditions to form a catalytic gasoline enhancement product including catalytically enhanced gasoline and a gaseous fraction, with the process still further involving separating the gaseous product from catalytically improved gasoline; separating hydrogen from the catalytic gasoline enhancement product before separating other gaseous components from it; separating the gaseous product from catalytically enhanced gasoline involves processing said catalytic gasoline enhancement product via an effective sorbent bed to absorb catalytically enhanced gasoline; separating the gaseous product from catalytically enhanced gasoline involves processing the catalytic gasoline enhancement product via a hydrocarbon absorber to produce a stream of gaseous effluent and a stream rich in gasoline; hydrotreating also includes hydroconverting the hydropyrolysis product free of animal charcoal and particle in a hydroconversion reactor using a hydroconversion catalyst under hydroconversion reaction conditions to produce the deoxygenated hydrocarbon product including fractions in the ebu point range - gasoline and diesel lesson; at least a portion of the fraction in the separate diesel boiling point range is added to the animal and particle-free hydropyrolysis product; and at least a portion of the separate fraction in the diesel boiling range is recirculated to the hydropyrolysis reactor.
[011] A process to directly produce fractionated and enhanced hydrocarbon fuels from biomass according to another aspect involves hydropyrolyzing the biomass in a reactor vessel containing mole-molecular hydrogen and a deoxygenation and hydrogen addition catalyst. Such hydropyrolysis produces a hydropyrolysis product including a hydropyrolysis gas comprising CO2, CO and C1-C3 gases, a partially deoxygenated hydropyrolysis liquid, water and animal charcoal. As the catalyst inside the reactor is suppressed by friction or deactivation, provision is made to add a replacement current of fresh, used, or revitalized catalyst located at a convenient point along the length of the reactor, usually, but not necessarily in the bottom of the reactor. All or at least a substantial portion of the charcoal is subsequently removed from at least the partially deoxygenated hydropyrolysis liquid to form a partially deoxygenated hydropyrolysis liquid substantially free of animal charcoal and particle. The partially deoxygenated hydropyrolysis liquid substantially free of animal charcoal and particle is hydroconverted into a hydroconversion reactor vessel using a hydroconversion catalyst in the presence of the hydropyrolysis gas to produce a deoxygenated and hydrogenated hydrocarbon liquid including fractions in the dot range. boiling gasoline and diesel, a gas mixture comprising CO, CO2, light hydrocarbon gases (C1-C3) and water. At least a portion of the gas mixture is steam reformed using water produced in at least one of the hydropyrolysis and hydroconversion steps to produce reformed molecular hydrogen. At least a portion of the reformed molecular hydrogen is subsequently introduced into the reactor vessel. Each of the fractions in the gasoline and diesel boiling point range is separated from the deoxygenated hydrocarbon liquid and one from the other.
[012] As used here, the term “biomass” refers to biological material derived from living or dead organisms and includes lignocellulosic materials, such as wood, residues from forest and agricultural land, aquatic materials such as algae, plants aquatic, seaweed, and animal by-products and waste, such as offal, fats, and sewage sludge, or any combination of these or other forms of biomass. In one aspect, this invention relates to a multi-stage hydropyrolysis process for the direct production of a variety of high quality liquid fuels, particularly enhanced hydrocarbon fuels, from biomass.
[013] As used herein, references to the separation or removal of "substantially all" of a specifically identified material or component and references corresponding to a "substantially free" product or chain of a specifically identified material or component are to be understood to generally correspond removing at least 95 percent, preferably at least 99% of the specifically identified material or component such that less than 5%, preferably less than 1% of such specifically identified material or component remains. Those skilled in the art and guided by the teachings provided herein will assess which references to the separation or removal of "substantially all" a specifically identified material or component and correspondingly a "substantially free" product or chain of a specifically identified material or component, at least at least some particular embodiments, refer to such a product or chain as having no more than trace or residual amounts of the specifically identified material or component.
[014] Likewise, as used here, references to the separation or fractionation of products in the boiling point range of "gasoline" and "diesel" from a partially deoxygenated hydropyrolysis liquid substantially free of animal coal and particle do not refer the production of two simple fractions of the hydrocarbon liquids produced in this process that are not subsequently modified by practices familiar to those skilled in this technique in finished gasoline and diesel fuels. Thus, following the method shown here, those skilled in the art will realize that other fractions can be isolated and finished in, for example, kerosene and jet fuel.
[015] In addition, as used here the terms “ULSD” and “diesel with ultra-low sulfur content” are used to describe diesel fuel with substantially decreased sulfur content. As of 2006 and 2007, almost all of the petroleum-based diesel fuel available in Europe and North America is of a ULSD type. As used here and currently in the United States, the permissible sulfur content for ULSD is 15 ppmw.
[016] Other objectives and advantages will be evident to those skilled in the art from the following detailed description taken in combination with the claims and attached drawings. BRIEF DESCRIPTION OF THE DRAWINGS
[017] These and other objectives and characteristics of this invention will be better understood from the following detailed description taken in combination with the drawings in which:
[018] FIG. 1 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to an embodiment of the invention and involving partial distillation of hydrocarbons;
[019] FIG. 2 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, in which materials in the boiling range of diesel are added to a hydropyrolysis product feed. substantially free of animal coal and particle to the hydroconversion reactor;
[020] FIG. 3 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, in which materials in the boiling range of the diesel are recirculated to the hydropyrolysis reactor;
[021] FIG. 4 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, in which materials in the boiling range of gasoline and diesel are still chemically and / or catalytically improved;
[022] FIG. 5 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, where materials in the boiling range of gasoline and diesel are still chemically and / or catalytically enhanced by another process;
[023] FIG. 6 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, in which effective hydropyrolysis and hydroconversion are carried out in a single reactor so that a separate hydroconversion reactor it is not necessary and a legitimate ultra low sulfur (ULSD) diesel product is produced;
[024] FIG. 7 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, in which effective hydropyrolysis and hydroconversion are carried out in a single reactor so that a separate hydroconversion reactor it is not necessary and enhanced H2 extraction is used;
[025] FIG. 8 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, in which effective hydropyrolysis and hydroconversion are carried out in a single reactor so that a separate hydroconversion reactor it is not necessary and solid sorbent beds are used; and
[026] FIG. 9 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, in which effective hydropyrolysis and hydroconversion are carried out in a single reactor so that a separate hydroconversion reactor it is not necessary and adsorption of gasoline is used. DETAILED DESCRIPTION OF PRESENTLY PREFERRED EMBODIMENTS
[027] FIGS. 1 to 9 show several preferred embodiments of the subject invention.
[028] FIG. 1 shows a schematic flow diagram, illustrating a process of the present invention in one of its simplest forms. Unless otherwise specifically noted, it should be understood that in this and the following schematic process described flow diagrams, similar currents and component parts, including currents and component parts not specifically evoked in subsequent diagrams, are generally numbered using the same last two numeric digits but with the first numeric digit varying depending on the particular figure.
[029] The process shown in FIG. 1 is generally designated by reference numeral 110 and is a process for producing hydrocarbon fuels from biomass according to an embodiment of this invention. As more fully described below, the process shown in FIG. 1 involves modifications to the process, shown and / or described in one or more of the following US Patent Applications Serial No. 12 / 419,535, filed on April 7, 2009; Serial N2 12 / 685,352, filed on January 11, 2010; Serial N2 13 / 089.010, filed on April 18, 2011; and Serial N2 13 / 196.645, deposited on August 2, 2011, as well as to take into account the partial distillation of product hydrocarbons. Disclosures for each of these prior applications are hereby incorporated by reference here and made a part thereof, including but not limited to any portions of these applications that specifically appear below.
[030] Process 110 shown in FIG. 1 is a compact, balanced, integrated, multi-stage process for thermochemically thermoforming biomass to produce or form a liquid gasoline product and a liquid die-sel product suitable for use as a transport fuel without the need for heating the externally supplied process, H2, CH4, or water. In fact, water is a product of the process so that an excess of water beyond that necessary for the process is produced. Thus, FIG. 1 shows that a stream of water produced by the process is purified and the stream of purified water is directed to a packaged steam reformer-PSA / MSS unit 170, described more fully below, while unnecessary process water is discarded. As will be assessed by a person skilled in the art and guided by the teachings provided here, a greater amount of purified water or drinking water must be required, such additional water can be obtained from the discarded water stream by appropriate treatment.
[031] An important aspect of the invention is that the thermal energy required in the process is provided by the reaction heat of the deoxygenation reaction, which is exothermic, occurring in both the first and second stages, 116 and 134. Another key aspect of The invention is that the biomass feed does not need to be severely dry and, in fact, adding water to the feed or as a separate feed can be advantageous for the process because it enhances the formation of H2 in situ through a reaction of water-gas replacement.
[032] The first stage or reaction stage of this process employs a pressurized reactor vessel, catalytically enhanced to create a partially or substantially deoxygenated hydro-pyrolysis liquid product and animal charcoal. In this first step of process 110, biomass (such as through a stream 112) and molecular hydrogen (such as through a stream 114) are introduced into a reactor vessel 116 containing a deoxygenation catalyst and a vessel in which the biomass undergoes hydropyrolysis and hydroconversion, to produce an output stream 120 comprising a liquid hydropyrolysis product at least partially deoxygenated, pyrolysis vapors (gases C1-C3), H2O, CO, CO2, H2, and animal carcass . The reactor vessel 116 is provided with a replacement port 118, located in a convenient location along the length of the reactor, usually, but not necessarily at the bottom of the reactor providing a place where fresh, used, or revitalized catalyst can be added to the reactor to replace the catalyst that has been frayed or eluted from the reactor.
[033] While any reactor vessel suitable for hydropyrolysis and hydroconversion can be used, a preferred reactor vessel employs a fluidized bed reactor. The hydropyrolysis step employs rapid heating (greater than about 550 ° C / min) of the biomass feed such that the residence time of the pyrolysed vapors in the reactor vessel is less than about 5 minutes. In contrast to this, the residence time of the charcoal is relatively long because it is not removed through the bottom of the reactor vessel and thus must be reduced in particle size until the particles are small enough to allow they are carried out with the vapors that come out near the top of the reactor vessel.
[034] The biomass feed used in the process of the invention may be in the form of loose biomass particles having a majority of particles preferably smaller than about 3 mm in size or in the form of a biomass / slurry . However, it will be appreciated by those skilled in the art that the biomass feed can be pre-treated or otherwise processed in a manner such that larger particle sizes can be accommodated. Suitable means of introducing the biomass feed into the reactor vessel include, but are not limited to, a propeller current, fast (greater than about 5 m / s) of carrier gas, such as inert gases and H2, positive displacement, impellers, or turbine pumps.
[035] Hydropyrolysis is typically performed in the reactor vessel at a temperature in the range of about 425 ° C to about 550 ° C. and a gauge pressure in the range of about 0.69 Mpa (100 psig) at about 5.5 Mpa (800 psig). The heating rate of the biomass is preferably greater than about 5500 ° C./min. The mass hourly space velocity (WHSV) in gm of biomass / gm of catalyst / h for this step is typically in the range of about 0.2 to about 10. In conventional hydropyrolysis processes, the objective is to maximize yield of the liquid product, which requires operation at substantially higher pressures, for example, 14 MPa (2000 psig). This is because decarboxylation is favored at lower pressures whereas hydrodeoxygenation is favored at higher operating pressures. Keeping the manometric pressures in the process of this invention in the range of 0.69 to 5.5 Mpa (100 to 800 psig), most preferably around 3.4 Mpa (500 psig), the decarboxylation and dehydrodeoxygenation are balanced, but the yield of the liquid product is reduced. At higher pressures, hydrodeoxygenation is favored and the reactions become unbalanced.
[036] As previously indicated, in the hydropyrolysis step of the invention, the solid biomass feed is rapidly heated, preferably in a hot fluidized bed, resulting in yields of the liquid product comparable to and possibly better than yields obtained with rapid conventional pyrolysis. -nal. However, the hydropyrolysis vapors resulting from the invention are typically in the presence of a catalyst and a high partial pressure of H2 within the fluidized bed, which provides hydrogenation activity and also some deoxygenation activity, depending on the activity of the material catalytically. active in the fluidized bed. Hydrogenation activity is very desirable to prevent reactive olefins from polymerizing, thereby reducing the formation of unstable free radicals. Similarly, deoxygenation activity is important so that the heat of the hydropyrolysis reaction is provided by the exothermic deoxygenation reaction, thereby obviating the need for external heating. An advantage of hydropyrolysis as shown by this invention over existing pyrolytic processes is that hydropyrolysis as shown by this invention prevents retrograde reactions from pyrolysis, which are usually performed in an inert atmosphere, most certainly in the absence of H2 and usually in the absence of a catalyst, thus promoting the undesirable formation of polynuclear aromatics, free radicals and olefinic compounds that are not present in the original biomass.
[037] The first stage hydropyrolysis step of this invention operates at a warmer temperature than is typical of a conventional hydroconversion process, as a result of which the biomass is rapidly devolatilized. Thus, this step requires an active catalyst to stabilize hydropyrolysis vapors, but not so active that it quickly cokes. Catalyst particle sizes are preferably greater than about 100 µm. Although any deoxygenation catalyst suitable for use in the temperature range of this process can be used in the hydropyrolysis step, catalysts according to preferred embodiments of this invention are as follows:
[038] Glass-ceramic catalysts - Glass-ceramic catalysts are extremely strong and resistant to friction and can be prepared as thermally impregnated (ie sustained) or as bulk catalysts. When used as a sulphide NiMo, Ni / NiO, or Co-based vitroceramic catalyst, the resulting catalyst is a friction-resistant version of a readily available but flexible Co-based NiMo, Ni / NiO catalyst, conventional. Glass-sulphide NiMo, Ni / NiO, or Co-based catalysts are particularly suitable for use in a hot fluidized bed because these materials can provide the catalytic effect of a conventional sustained catalyst, but in a much more robust form, friction resistant. In addition, due to the resistance to friction of the catalyst, the biomass and animal charcoal are simultaneously ground into smaller particles as the hydropyrolysis reactions proceed inside the reaction vessel. Thus, the charcoal that is basically recovered is substantially free of catalyst catalyst contaminants due to the extremely high strength and resistance to friction of the catalyst. The catalyst friction rate will typically be less than about 2% by weight per hour, preferably less than 1% by weight per hour as determined in a standard high speed jet cup friction test. .
[039] Nickel phosphide catalyst - Ni Phosphide catalysts do not require sulfur to function and therefore will only be as active in a sulfur-free environment as in an environment containing H2S, COS and other sulfur-containing compounds. Therefore, this catalyst will only be as active for biomass that has little or no sulfur present as with sulfur-containing biomass (eg, corn crop residues). This catalyst can be impregnated with carbon as a separate catalyst or impregnated directly into the biomass raw material by itself.
[040] Bauxite - Bauxite is an extremely inexpensive material and can therefore be used as a disposable catalyst. Bauxite can also be impregnated with other materials such as Ni, Mo, or it can also be sulphidized.
[041] Small size spray dried silica-alumina catalyst impregnated with NiMo or C0M0 and sulphide to form a hydroconversion catalyst - commercially available NiMo or C0M0 catalysts are normally supplied as 3, 2 to 1.6 mm (1/8 to 1/16 inch) for use in fixed or confined solid beds. In the present case, NiMo is impregnated in a spray dried silica-alumina catalyst and used in a fluidized bed. This catalyst exhibits higher strength than a conventional NiMo or C0M0 catalyst and would be an appropriate size for use in a fluid bed.
[042] Because the catalytically enhanced hydropyrolysis process is exothermic, process 110 includes means, for example, a heat exchanger 122 (which, depending on the needs of the process may be optional), to remove excess heat from reactor 116.
[043] Output process stream 120 is treated to remove animal charcoal and particles from it. In the past, removal of charcoal has been a major barrier in conventional rapid pyrolysis because charcoal tends to cover filters and react with oxygenated pyrolysis vapors to form viscous coatings that can bind to hot process filters. Animal charcoal can be removed according to the process of the invention by filtration of the vapor stream, or via filtration from a bed-washing step with confined solid. Retropulsation can be used to remove the charcoal from the filters, as long as the hydrogen used in the process of this invention sufficiently reduces the reactivity of the pyrolysis vapors to allow for effective retropulsing. Electrostatic precipitation, inertial separation, magnetic separation, or a combination of these technologies can also be used to remove charcoal and ash particles from the hot vapor stream prior to cooling and condensation of the liquid product.
[044] Because of their resistance to friction, glass-ceramic catalysts are typically more easily separated from animal charcoal by inertial separation energy technologies that use impact, interception, and / or diffusion processes sometimes combined with electrostatic precipitation to separate, concentrate , and collect the animal charcoal in a secondary stream for recovery. An additional virtue of these materials is that because they are receptive to magnetic separation (in a reduced state, Fe and Ni being attracted to a permanent or electrically induced magnetic field), magnetic techniques as well as combinations of magnetic, inertial, and electrostatic media can be used to separate animal charcoal from these catalysts which are not possible with softer materials.
[045] According to an embodiment of the invention, hot gas filtration can be used to remove animal charcoal and particles. In this case, because hydrogen stabilized free radicals and saturated olefins, the dust cake trapped in the filters was found to be more easily separated from the filter element than the charcoal removed in the hot filtration of aerosols produced in conventional rapid pyrolysis. In accordance with another embodiment of this invention, the charcoal is removed by bubbling the gas of the first stage product through a recirculating liquid. The recirculated liquid used is the high boiling portion of the finished oil from this process and is thus a fully saturated (hydrogenated) oil, stabilized having a boiling point typically above 350 ° C. Fine animal charcoal or catalyst of the first type - reaction stage are captured in this liquid. A portion of the liquid can be filtered to remove the fines and a portion can be recirculated back to the first stage hydropyrolysis reactor. An advantage of using a recirculating liquid is that it provides a way to reduce the temperature of the process vapors loaded with animal charcoal from the first reaction stage to the desired temperature for the hydroconversion step of the second reaction stage while removing the fine particles of animal charcoal and catalyst. Another advantage of using liquid filtration is that the use of hot gas filtration with its resulting, well-documented filter cleaning problems is completely avoided.
[046] In accordance with an embodiment of this invention, NiMo or CoMo catalysts of large size, positioned in a bed with confined solid, are used for removal of animal charcoal to further provide simultaneous deoxygenation with the removal of fine particles . Particles of this catalyst should be large, preferably about 3.2 to 1.6 mm (1/8 to 1/16 inch) in size, thereby making them easily separable from the fine animal transported from the first reaction stage, which is typically less than 200 mesh (about 70 micrometers).
[047] As shown, the outlet process stream 120 is passed to and through an optional char separator 124, a barrier filter 126 (such as to remove catalyst fines) and a process heat exchanger 130 that can be used to produce process steam. The product stream free of animal charcoal and particle 132 passes from the heat exchanger 130 to a second reaction stage that employs a hydroconversion reactor vessel 134 in which a hydroconversion step is performed to complete the deoxygenation and hydrogenation of the hydrocarbon product. received from the hydropyrolysis reactor 116.
[048] In the hydroconversion reactor vessel 134, the hydroconversion step of the second reaction stage is preferably performed at a lower temperature (250 to 450 ° C) than the hydropyrolysis step of the first reaction stage for increase the life of the catalyst and at substantially the same gauge pressure (100 to 800 psig) as the hydropyrolysis step of the first reaction stage. The mass hourly space velocity (WHSV) for this step is in the range of about 0.2 to about 3. The catalyst used in this step is preferably protected from Na, K, Ca, P, and other metals present in the biomass that can poison the catalyst, which will tend to increase the life of the catalyst. This catalyst must also be protected from olefins and free radicals by the catalytic improvement carried out in the first reaction stage. Catalysts typically selected for this step are high activity hydroconversion catalysts, for example, sulfated NiMo and sulfated CoMo catalysts. In this reaction stage, the catalyst is used to catalyze a water-gas substitution reaction of CO + H2O to prepare CO2 + H2, thereby allowing the in situ production of hydrogen in the vessel of the second stage reactor 134, which, for This in turn reduces the hydrogen needed for hydroconversion. Both NiMo and CoMo catalysts catalyze the water-gas substitution reaction. The objective in this second reaction stage is to once again balance deoxygenation reactions. This balancing is carried out using relatively low hydrogen manometric pressures (100 to 800 psig) together with the correct choice of catalyst. In conventional pyrolysis oil hydro-deoxygenation processes, partial manometric pressures of hydrogen in the range of about 14 Mpa (2000 psig) to about 21 MPa (3000 psig) are typically used. This is because the processes are intended to convert pyrolysis oils, which are extremely unstable and difficult to process at lower H2 partial pressures.
[049] The completely deoxygenated product passes, like a current 136, from the second reaction stage 134 through a second process heat exchanger 140 (which can also be used to produce process steam and which, depending on the needs of the process, can be optional) and for a high pressure separator 142 to form, produce, or separate the process stream into a gas fraction (referred to as vapors) 144, hydrocarbon fraction 146 and a water fraction 148.
[050] The hydrocarbons leaving the high pressure separator 142 are directed to a distillation column 150 that separates the hydrocarbons into a fraction of gasoline 152 and a fraction of diesel 154.
[051] The rated diesel product stream 154 leaving the distillation column 150 is split, with one portion forming a diesel outlet stream 156 and another portion 158 being passed back to the top of a hydrocarbon absorber 160 afterwards having been passed through the heat exchanger 162 (which depending on the needs of the process can be optional).
[052] The vapor stream 144 leaving the high pressure separator 142 is directed to the bottom of the hydrocarbon absorber 160 so that the hydrocarbon absorber 160 receives two streams, one emanating from the high pressure separator 142 and the other emanating from the distillation column 150 and subsequently passing through heat exchanger 162 (which again depending on the needs of the process may be optional). The hydrocarbon absorber 160 also has two outlets. An output stream 164 (separate hydrocarbon stream) joins the hydrocarbon output of the high pressure separator 142 and is directed to the distillation column 150, as mentioned above. The other outlet is mainly gaseous and exits the top of the hydrocarbon absorber 160 as a stream 166 and is directed as for an H2S scrubber 168, as described below.
[053] Steam stream 144 typically contains non-condensing hydrocarbon vapors (such as methane, ethane, propane and butane), other non-condensing vapors (CO2, CO, and H2), and depending on the efficiency of the high pressure separator 142 , some H2S and NH3 vapors.
[054] These gases (typically include one or more of CO, CO2, CH4, ethane, and propane) are sent to the packaging stream reformer and PSA / MSS 170 unit along with the process water for conversion to H2 and CO2 . A portion of these gases is burned in a furnace or other combustion chamber to accelerate the heating of the remaining portion of gases to the operating temperature of the steam reformer, around 925 ° C. Steam reformers typically require a vapor- 3/1 parahydrocarbon in its feed to promote reaction equilibrium, but this is much more than the amount needed for reaction. The steam is recovered and recycled within the steam reformer. CO2 is removed from the process by pressure alternating adsorption (PSA), a suitable membrane separation system (MSS), or by other means known to those skilled in the art of separating H2 from a mixture of gases and H2 is recirculated again for the first reaction stage (hydropyrolysis) of the process.
[055] In addition, this process is preferably balanced with respect to water so that enough water is made in the process to supply all the water needed in the steam reforming step. According to an embodiment of this invention, the amount of water used is such that the overall process yield contains substantially only CO2 and liquid hydrocarbon products, thereby avoiding an additional process step for disposing of excess water. It will be assessed by those skilled in the art that the use of vapor reform in combination with hydropyrolysis and hydroconversion steps as presented here makes sense where the goal is to provide a self-sufficient process in which the ratio of O2 in H2O to O2 in CO and CO2 produced by the process is about 1.0. In the absence of such an objective, steam reform is not necessary because the H2 needed for the hydropyrolysis stage can still be supplied by external sources. If a person were to use steam reform in the absence of the objectives set out here, they would not end the self-sufficient process of this invention in which the process yield consists essentially of liquid hydrocarbon products and CO2.
[056] According to an embodiment of this invention, the heat generated in the second reaction stage can be used to supply all or part of the heat necessary to conduct the hydropyrolysis step in the first reaction stage. According to an embodiment of this invention, the process also employs recirculation of the heavy finished products as a washing liquid in the second stage as set forth above to capture process fines that come out of the first stage pyrolysis reactor and control the heat of the reaction. According to an embodiment of this invention, this liquid is also recirculated for hydroconversion and possibly for the first stage hydropyrolysis step to regulate heat generation at each step. The recirculation rate is preferably in the range of about 3 to 5 times the biomass feed rate. This is necessary because hydrodeoxygenation is a strongly exothermic reaction.
[057] According to an embodiment of this invention, the biomass feed is any aquatic biomass containing a high lipid content such as algae or an aquatic plant such as lemna. In a form where lipids have not been extracted, gasoline and diesel can be manufactured directly from the aquatic biomass feed. This is particularly attractive because lipid extraction is expensive. Otherwise, with the process of this invention, materials at the boiling point of gasoline and diesel can be manufactured from a delipidated aquatic biomass such as algae or an aquatic plant such as lemna. In contrast, conventional rapid pyrolysis of algae and other aquatic biomass would be very unattractive because the uncontrolled thermal reactions characteristic of rapid pyrolysis would degrade these lipids. Thus, the integrated process of this invention is ideal for the conversion of aquatic biomass because it can be carried out in aquatic biomass which is usually only partially dehydrated and still produces high quality diesel and gasoline products.
[058] The process of this invention provides several distinct advantages over processes based on conventional rapid pyrolysis in which it produces a low, partially deoxygenated, stabilized low-carbon animal product from which charcoal and residual particles can be easily separated by hot gas filtration or contact with a recirculated liquid; hot, clean hydropyrolysis oil vapors can be directly upgraded to a final product in a closely linked secondary catalytically enhanced process unit operated at almost the same pressure as was used upstream; and the improvement is carried out quickly before degradation can occur in the steam produced from the hydropyrolysis step.
[059] The liquid hydrocarbon products produced by this process should contain less than 5% oxygen and preferably less than 2% oxygen with a low total acid number (TAN) and should exhibit good chemical stability. polymerization or a reduced tendency to exhibit chemical reactivity. In a preferred embodiment of this invention in which the total oxygen content of the product is reduced below 2%, the water and hydrocarbon phases will easily separate in any normal separation vessel because the hydrocarbon phase has become hydrophobic. This is a significant advantage when compared to conventional pyrolysis in which water is miscible with and mixed with highly oxygenated pyrolysis oil.
[060] Because the fungible fuels produced in the disclosed process are low in oxygen, any excess water produced from this process is relatively free of dissolved hydrocarbons and is likely to contain less than 2000 ppmv of total dissolved organic carbon (TOC), that makes it suitable, for example, for use in irrigation in arid areas. In addition, the finished hydrocarbon product can now be easily transported, has a low total acid number (TAN), and excellent chemical stability. In conventional rapid pyrolysis, pyrolysis oils typically contain 50 to 60% oxygen in the form of oxygenated hydrocarbons and 25% dissolved water and must be chemically stabilized before transport. Therefore, costs of transporting final products alone for the hydropyrolysis and integrated hydroconversion process of this invention can be less than half the costs for conventional rapid pyrolysis. In addition, the water produced in the proposed process becomes a valuable by-product especially for arid regions.
[061] If desired and as shown in FIG. 1, the process desirably can take into account the recovery of ammonium sulfate. In this regard, the gas fraction 166 is therefore directed to the H2S scrubber 168 and H2S 172 extractor which act by mutual agreement to release a stream of gas 174 free of H2S and MM3 to the packaged steam reformer-PSA / MSS unit 170 the purpose of which is to supply a stream of pure hydrogen 176 to the hydropyrolysis reactor 116 and to reject residual CO2 (via a stream 178) from which additional heat can be recovered to provide another source of process heat to dry the biomass or for other purposes. Because this CO2 is derived entirely from biomass it does not contribute to the burning of Greenhouse Gas (GHG) in the process.
[062] As shown in FIG. 1.0 The high pressure separator 142 releases an aqueous current 148 containing ammonia and hydrogen sulfide in solution to a former acid water tractor 180. The acid water extractor 180, separates the aqueous stream 148 received from the water separator high pressure 142 in a stream of water 182 rich in ammonia and H2S as well as a stream of relatively pure water 184 which with further purification by means of a suitable water purifier 186 to remove all sulfur compounds provides a source of water of purity high 188 for the packaged steam reformer-PSA / MSS unit 170. The rejected water from the water purifier 186, shown as a stream 190, can be disposed of or recycled to the acid water extractor 180. The aqueous stream 182 of the extractor acid water 180 and H2S extractor 172 are combined and directed to an oxidation reactor 192 where the combined currents can be reacted with oxygen in a non-catalytic, thermal conversion zone to convert substances initially dissolved ammonium sulfide (NH4) 2S to ammonium sulfate (NH4) 2SO4 and thiosulfate. The stream can also be contacted with oxygen and an oxidation catalyst according to the method disclosed in Gillespie, US Patent 5,470,486 or, alternatively, the inlet aqueous stream can be reacted with oxygen, in the presence of an appropriate catalyst, according to the method disclosed in US Patent 5,207,927 (Marinangeli, et al.). Using any technology, within the pH ranges, mol in ratio of oxygen to sulfur, pressure, temperature, and net hourly spatial speeds shown in these patents, an aqueous stream 194 containing ammonia NH3 and (NH4) 2SO4 is thus obtained, and these compounds can then be recovered and sold as fertilizer. A variety of methods for obtaining ammonium sulfate from an aqueous stream containing ammonium sulfite and dissolved ammonia are currently in use and the examples cited above serve to illustrate what established technologies exist to effect this conversion. Excessive O2 and unreacted N2 are discarded from the oxidation reactor as a current 196.
[063] Finally, the pure H2 produced by the packaged steam reformer unit - PSA / MSS 170 is directed to a steam driven compressor 198 where it is compressed and then passed to the hydropyrolysis reactor 116. Note that the steam used to driving the compressor 198 is provided with heat exchanger 130 and heat exchanger 140 (which, depending on the needs of the process, can be optional). Residual heat from the steam that drives the 198 hydrogen compressor is available to provide lower levels of process heat. Also note that the hydrogen released to the hydropyrolysis reactor 116 will have been cooled down a bit, which poses no challenge to the process since the exothermic nature of the hydropyrolysis reaction is sufficient to supply all the heat required by the hydropyrolysis reactor 116 .
[064] FIG. 2 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, such a process generally designated by reference numeral 210.
[065] Process 210 is generally similar to process 110, described above. In particular, in process 210, biomass (such as through a stream 212) and molecular hydrogen (such as through a stream 214) are introduced into a vessel in the hydropyrolysis and hydroconversion reactor 216, such as having a catalyst replacement port 218, to produce an output stream 220 comprising a liquid hydropyrolysis product at least partially deoxygenated, pyrolysis vapors (C1-C3 gases), H2O, CO, CO2, H2, and charcoal. The outlet process stream 220 is passed to and through an optional char separator 224, a barrier filter 226 (such as to remove catalyst fines) and a process heat exchanger 230 that can be used to produce steam of process. The product stream free of animal charcoal and particle 232 passes from the heat exchanger 230 to a second reaction stage that employs a hydroconversion reactor vessel 234 in which a hydroconversion step is performed to complete the deoxygenation and hydrogenation of the hydrocarbon product. received from the hydropyrolysis reactor 216. The completely deoxygenated product passes, like a current 236, from the second reaction stage 234 through a second process heat exchanger 240 (which can also be used to produce process steam and which, depending on the process requirements can be optional) and for a high pressure separator 242 to form, produce or separate into a gas fraction (designated as vapors) 244, hydrocarbon fraction 246 and a water fraction 248.
[066] In process 210, the gas / steam fraction 244 and water fraction 248 are processed in a similar manner to that in process 110 and will not be described in more detail here.
[067] Also similarly, the hydrocarbons leaving the high pressure separator 242 are directed to a distillation column 250 that separates the hydrocarbons into a fraction of gasoline 252 and a fraction of diesel 254. The rated diesel product stream 254 exiting the distillation column 250 is divided, with one portion forming a diesel outlet stream 256 and another portion 258 being passed back to the top of a hydrocarbon absorber 260 after it has been passed through heat exchanger 262 (which depending on the process needs can be optional).
[068] Process 210 primarily differs from process 110 in which the rated diesel product stream 254 is further divided such that a portion of the diesel product stream is diverted via a diesel recirculation circuit 255 back to the inlet the hydroconversion reactor 234 to retrace its path through the high pressure separator 242 and the distillation column 250 and thereby improve the quality of the diesel. That is, a portion of the materials in the boiling range of the diesel is added to the feed of hydropyrolysis product free of animal coal and particle to the hydroconversion reactor 234, for example.
[069] As shown, process 210 may, if desired, include one or more features, such as an H2S 268 scrubber, a steam reformer-PSA / MSS 270 unit, an H2S 272 extractor, an extractor acid water 280, a suitable water purifier 286, an oxidation reactor 292 and a compressor 298, similar to those shown in FIG. 1.
[070] FIG. 3 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, such a process generally designated by reference numeral 310.
[071] Process 310 is generally similar to process 110, described above. In particular, in process 310, biomass (such as through a stream 312) and molecular hydrogen (such as through a stream 314) are introduced into a vessel in the hydropyrolysis and hydroconversion reactor 316, such as having a catalyst replacement port 318, to produce an output stream 320 comprising a liquid hydropyrolysis product at least partially deoxygenated, pyrolysis vapors (gases C1-C3), H2O, CO, CO2, H2, and animal charcoal. The output process stream 320 is passed to and through an optional char separator 324, a barrier filter 326 (such as to remove catalyst fines) and a process heat exchanger 330 that can be used to produce process steam. The animal-free particle stream 332 passes from heat exchanger 330 to a second reaction stage that employs a hydroconversion reactor vessel 334 in which a hydroconversion step is performed to complete deoxygenation of the hydrocarbon product received from the reactor hydropyrolysis 316. The completely deoxygenated product passes, like a current 336, from the second reaction stage 334 through a second process heat exchanger 340 (which can also be used to produce process steam and which, depending on process needs may be optional) and a high pressure separator 342 to form, produce or separate in a gas (designated as vapors) fraction 344, hydrocarbon fraction 346 and a fraction of water 348.
[072] Also similarly, the hydrocarbons leaving the high pressure separator 342 are directed to a distillation column 350 that separates the hydrocarbons into a fraction of gasoline 352 and a fraction of diesel 354. The rated diesel product stream 354 that the distillation column 350 is split, with one portion forming a diesel outlet stream 356 and another portion 358 being passed back to the top of a hydrocarbon absorber 360 after it has been passed through heat exchanger 362 (which , depending on process needs may be optional).
[073] Process 310 differs mainly from process 210 in that it illustrates another option for diesel product recirculation that allows a portion of the diesel fraction exiting the distillation column 350 to be recirculated again at the first fluidized bed hydropyrolysis and hydroconversion reactor 316 through the diesel recirculation circuit 355 and for this reason it steps back its steps to the hydroconversion reactor 334, the high pressure separator 342, and returns to the distillation column 350.
[074] As shown, process 310 may, if desired, include one or more features, such as an H2S 368 scrubber, a PSA / MSS 370 steam reformer unit, an H2S 372 extractor, an extractor acid water 380, a suitable water purifier 386, an oxidation reactor 392 and a compressor 398, similar to those shown in FIG. 1.
[075] FIG. 4 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, such a process generally designated by reference numeral 410.
[076] Process 410 is generally similar to process 110 described above. In particular, in process 410, biomass (such as through a stream 412) and molecular hydrogen (such as through a stream 414) are introduced into a vessel in the hydropyrolysis and hydroconversion reactor 416, such as having a catalyst replacement port 418, to produce an output stream 420 comprising a liquid hydropyrolysis product at least partially deoxygenated, pyrolysis vapors (C1-C3 gases), H2O, CO, CO2, H2 and animal charcoal. The output process stream 420 is passed to and through an optional char separator 424, a barrier filter 426 (such as to remove catalyst fines) and a process heat exchanger 430 that can be used to produce process steam. The animal-free particle stream 432 passes from heat exchanger 430 to a second reaction stage that employs a hydroconversion reactor vessel 434 in which a hydroconversion step is performed to complete deoxygenation of the hydrocarbon product received from the reactor hydropyrolysis 416. The completely deoxygenated product passes, as a current 436, from the second reaction stage 434 through a second process heat exchanger 440 (which can also be used to produce process steam and which, depending on process needs may be optional) and a high pressure separator 442 to form, produce or separate into a gas (designated as vapors) fraction 444, hydrocarbon fraction 446 and a water fraction 448. The hydrocarbons leaving the high pressure separator 442 are directed to a distillation column 450 that separates hydrocarbons into a fraction of gasoline 452 and a fraction of diesel 454. The diesel product stream n The terminal 454 exiting the distillation column 450 is divided, with one portion forming a diesel outlet chain 456 and another portion 458 being passed back to the top of hydrocarbon absorber 460 after having been passed through heat exchanger 462 (which, depending on process needs can be optional).
[077] Process 410 differs mainly from process 110 in that process 410 now provides the additional chemical improvement of gasoline and diesel boiling materials, 452 and 456, respectively. More specifically, process 410 includes: 1) an improvement of catalytic gasoline step 455 that receives the fraction of gasoline 452 from partial distillation step 450 and therefore allows the production of an improved fraction of gasoline 457, and 2) a catalytic bed reactor drip tank 459 which produces an ultra low sulfur diesel (ULSD) product 461 which, depending on the performance of the partial distillation apparatus 450, may contain a small portion of gasoline which has been directed to the drip bed catalytic reactor 459.
[078] As shown, process 410 may, if desired, include one or more features, such as an H2S 468 scrubber, a PSA / MSS 470 steam reformer unit, an H2S 472 extractor, an extractor of acidic water 480, a suitable water purifier 486, an oxidation reactor 492 and a compressor 498, similar to those shown in FIG. 1.
[079] FIG. 5 illustrates a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, such a process generally designated by reference numeral 510.
[080] The process shown 510 is generally similar to the process 410 described above in that the gasoline and diesel boiling materials are still chemically suitable for further processing. To that end, more particularly, in process 510, biomass (such as through a stream 512) and molecular hydrogen (such as through a stream 514) are introduced into a vessel of the hydropyrolysis and hydroconversion reactor 516 , such as having a catalyst replacement port 518, to produce an output stream 520 comprising a liquid hydropyrolysis product at least partially deoxygenated, pyrolysis vapors (C1-C3 gases), H2O, CO, CO2, H2, and animal charcoal. Output process current 520 is passed to and through an optional charcoal separator 524, a barrier filter 526 (such as to remove catalyst fines) and a process heat exchanger 530 that can be used to produce process steam. The animal-free particle stream 532 passes from heat exchanger 530 to a second reaction stage that employs a hydroconversion reactor vessel 534 in which a hydroconversion step is performed to complete deoxygenation of the hydrocarbon product received from the reactor hydropyrolysis 516. The completely deoxygenated product passes, like a stream 536, from the second reaction stage 534 through a second process heat exchanger 540 (which can also be used to produce process steam and which, depending on process needs optional) and a high pressure separator 542
[081] In process 510, however, the high pressure separator 542 is operated at a higher temperature, such as to produce a gas hydrocarbon stream 544, a diesel product stream 556 and a water stream 548, as opposed to to the process shown in FIG. 4 in which the separator 442 produces a vapor stream hydrocarbon which is then passed to a hydrocarbon absorber 460. In the process embodiment shown in FIG. 5, the hydrocarbon gas stream 544 discharged through the separator 542 is passed directly to an improvement of catalytic gasoline step 563 whose product is cooled in a heat exchanger 565 (which, depending on process needs can be optional) before be passed to a separator 567 that diverts a fraction of gas 569 (Ci gas through C4 hydrocarbons with other process gases) to an H2S scrubber 568 and an H2S extractor 572 similar to the process shown in FIGS. 1 to 4, while a 557 enhanced liquid gas fraction is produced as a product process.
[082] Similar to process 410, process 510 includes a drip bed catalytic reactor 559 that processes diesel product 556 to produce an ultra low sulfur diesel (ULSD) product 561 that can contain a small portion of gasoline.
[083] Note in this embodiment that the gas exhaust from separator 542 does not contain vapors, but only gas. As opposed to the process, the embodiments shown in FIGS. 1 to 4, where the exhaust of the separator was kept at a lower temperature so that vapors were subjected to exhaust to a hydrocarbon absorber, in this and following the process embodiments, the gases leaving the separator will have a temperature more high suitable for the introduction to an improvement of catalytic gasoline step. Otherwise, the balance of this embodiment of the process remains similar to that described in FIG. 4.
[084] As shown, process 510 may, if desired, include one or more features, such as a steam reformer-PSA / MSS 570 unit, a former acid water tractor 580, a suitable water purifier 586, an oxidation reactor 592 and a compressor 598, similar to those shown in FIG. 1.
[085] While the processes of the invention were shown in the figures described above with the inclusion of a second hydrotreating reactor, those skilled in the art and guided by the teachings here will provide that the broader practice of the invention is not necessarily limited in this way. For example, in a case where sufficiently active catalysts are available that can produce a completely deoxygenated hydrocarbon product in the fluid bed reactor 116, 216, 316, 416 and 516, for example, a separate second hydroconversion reactor can become not necessary. Thus, it should be understood that the processes shown in FIGS. 1 to 5 can, in such examples, be suitably modified accordingly. That is, if desired, the processes of the invention can be carried out with or without a second reactor hydrotreatment and that the presence or absence of such a second reactor hydrotreatment does not necessarily create a fundamentally different process.
[086] FIG. 6 illustrates a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, such a process generally designated by reference numeral 610.
[087] Process 610 is similar to process 510 in that in process 610, biomass (such as through a stream 612) and molecular hydrogen (such as through a stream 614) are introduced into a hydropyrolysis reactor vessel and hydroconversion 616, such as having a catalyst replacement port 618, to produce an output stream 620 comprising a liquid hydropyrolysis product at least partially deoxygenated, pyrolysis vapors (C1-C3 gases), H2O, CO, CO2 , H2, and animal charcoal. The outlet process stream 620 is passed to and through an optional charcoal separator 624, a barrier filter 626 (such as to remove catalyst fines) and a process heat exchanger 630 that can be used to produce steam. process.
[088] Process 610 differs from process 510 in that a second hydro-conversion reactor, such as 534, has been suppressed such that the stream of animal-free product and particle 632 passes from heat exchanger 630 to a separator high pressure 642. Similar to process 510 described above, the high pressure separator 642 is operated at a sufficiently high temperature such as to produce a gaseous hydrocarbon stream 644, a diesel product stream 656 and a water stream 648.
[089] The 644 hydrocarbon gas stream is passed directly to a step 663 catalytic gasoline enhancement whose product is cooled in a 665 heat exchanger (which, depending on process needs can be optional) before being passed to a separator 667 that diverts a fraction of gas 669 (gaseous hydrocarbons Ci to C4 with other process gases) to an H2S scrubber 668 and H2S extractor 672 similar to the process shown in FIGS. 1 to 4, while a fraction of 657 enhanced liquid gasoline is produced as a product process.
[090] Also similar to process 510, process 610 includes a drip bed catalytic reactor 659 which processes diesel product 656. Process 610 differs from process 510 in which process 610 includes a partial distillation unit 671 which receives a product stream ULSD 661 from the 659 drip bed reactor which may contain some small fraction of gasoline. The partial distillation unit 671 separates the remaining material gasoline into the ULSD 661 product stream and passes it, such as through a 673 stream, to the 667 separator when it is mixed with an already improved gasoline product from the catalytic gasoline unit upgrade. 663 in order to form the product stream 657. Partial distillation unit 671 can then discharge a legitimate ULSD product stream 675 (i.e., a product stream that is substantially free of a fraction of gasoline).
[091] As shown, process 610 can, if desired, include one or more features, such as a steam reformer-PSA / MSS 670 unit, an acid water extractor 680, a suitable water purifier 686, an oxidation reactor 692 and a compressor 698, similar to those shown in FIG. 1.
[092] As will still be understood, a hydroconversion reactor can be added, such as the following 630 heat exchanger, if desired or necessary, as well as to properly maintain product quality.
[093] FIG. 7 illustrates an embodiment process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, such a process generally designated by reference numeral 710.
[094] As described in more detail below, process 710 is generally similar to process 610 described above with process 710, however, using enhanced H2 extraction.
[095] In particular, in process 710, biomass (such as via a stream 712) and molecular hydrogen (such as via a stream 714) are introduced into a vessel in the 716 hydropyrolysis and hydroconversion reactor, such as having a catalyst replacement port 718, to produce an output stream 720 comprising a liquid hydropyrolysis product at least partially deoxygenated, pyrolysis vapors (gases C1-C3), H2O, CO, CO2, H2 and animal charcoal. The outlet process stream 720 is passed to and through an optional charcoal separator 724, a barrier filter 726 (such as to remove catalyst fines) and a process heat exchanger 730 that can be used to produce steam. process. The product stream free of charcoal and particle 732 passes from the heat exchanger 730 to a high pressure separator 742. The high pressure separator 742 is desirably operated at a sufficiently high temperature such as to produce a gas hydrocarbon stream 744, a stream of diesel product 756 and a stream of water 748.
[096] The hydrocarbon gas stream 744 is passed directly to a step 763 catalytic gasoline enhancement. The process efficiency for process 710 is improved over the embodiment shown in FIG. 6, however, by introducing a separator membrane 777 after catalytic enhancement of step 763. The membrane separator 777 desirably serves to separate hydrogen from the product stream of the catalytic enhancement step of gasoline 763 and directs that hydrogen to the process gases entering an H2S 768 scrubber and an H2S 772 extractor similar to the process shown in FIGS. 1 to 4. As a result, the amount of gas passing through heat exchanger 765 and gas / separator liquid 767 can be significantly reduced compared to the same point in process 610.
[097] Similar to the same point in process 610 described above, the product, now from the membrane separator 777, is cooled in a heat exchanger 765 (which, depending on process needs can be optional) before being passed to a separator 767 that diverts a fraction of gas 769 (gaseous hydrocarbons Ci to Cs with other process gases) to an H2S 768 scrubber and an H2S 772 extractor, while an enhanced liquid gasoline fraction 757 is produced as a product process.
[098] Similar to the embodiment described above, process 710 includes a drip bed catalytic reactor 759 that processes diesel product 756. Process 710 includes a partial distillation unit 771 that receives a stream of ULSD product 761 from the reactor of drip bed 759 which may contain some small fraction of gasoline. Partial distillation unit 771 separates material gasoline remaining in the ULSD product stream 761 and passes, as through a stream 773, to separator 767 when mixed with an already processed improved gasoline product from the catalytic gasoline unit 763 enhancement and forms product stream 757 and gas fraction stream 769. Partial distillation unit 771 can then discharge a legitimate ULSD product stream 775 (i.e., a product stream that is substantially free of a fraction of gasoline).
[099] As shown, process 710 may, if desired, include one or more features, such as a steam reformer-PSA / MSS 770 unit, a former acid water tractor 780, a suitable water purifier 786, an oxidation reactor 792 and a compressor 798, similar to those shown in FIG. 1.
[0100] While in FIG. 7, the illustrated embodiment is shown again without the inclusion of a second hydroconversion reactor, as shown in the embodiments described in FIGS. 1 to 5, a hydroconversion reactor can be added, such as following the heat exchanger 730, if desired or necessary, as well as to properly maintain the quality of the product.
[0101] FIG. 8 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, such a process generally designated by reference numeral 810.
[0102] Process 810 is generally similar to process 610 described above except through the inclusion of solid sorbent beds to provide an improved ga-soline product.
[0103] In process 810, biomass (such as via a stream 812) and molecular hydrogen (such as via a stream 814) are introduced into a vessel in the 816 hydropyrolysis and hydroconversion reactor, such as having a catalyst replacement port 818, to produce an output stream 820 comprising a liquid hydropyrolysis product at least partially deoxygenated, pyrolysis vapors (C1-C3 gases), H2O, CO, CO2, H2 and animal charcoal. The outlet process stream 820 is passed to and through an optional char separator 824, a barrier filter 826 (such as to remove catalyst fines) and a process heat exchanger 830 that can be used to produce process steam. The product stream free of charcoal and particles 832 passes from the heat exchanger 830 to a high pressure separator 842. The high pressure separator 842 is desirably operated at a sufficiently high temperature such as to produce a gas hydrocarbon stream 844, a stream of diesel product 856 and a stream of water 848.
[0104] The hydrocarbon gas stream 844 is passed to a step 863 catalytic gasoline upgrade whose product is cooled in an 865 heat exchanger (which, depending on process needs can be optional) before being passed to a bank. solid sorbent beds 881 and 883. Note that heat exchanger 865 may be optional and is shown to highlight a possibly suitable method for maintaining the inlet temperature of gas entering the solid sorbent beds at an appropriate value.
[0105] Solid sorbent beds 881 and 883 are generally configured so that a bed receives gas from the heat exchanger 865 which absorbs the enhanced gasoline product and exhaust gases suppressed from the improved gasoline product to the H2S scrubber 868 while the others solid sorbent beds have been removed from the line while gasoline that has been adsorbed in this way is appropriately desorbed and directed to exhaust the improved gasoline product 857. At an appropriate time when the offline solid sorbent beds have been suppressed from gasoline adsorbed and the other solid sorbent beds become completely charged, processing through the solid sorbent beds is appropriately changed and the process continued, such that the solid sorbent beds are in the reception of the gas communication whose gasoline is adsorbed with gases suppressed from the gasoline 869 directed to the H2S 868 scrubber and H2S 872 extractor, while the other exhausts es of the sorbent beds of desorbed solids improved the gasoline for the exhaustion of the product 857.
[0106] As shown, process 810 may, if desired, include one or more features, such as a drip bed catalytic reactor 859, a steam reformer-PSA / MSS 870 unit, a partial distillation unit 871, an acidic water extractor 880, a suitable water purifier 886, an oxidation reactor 892 and a compressor 898, as corresponding to those shown in the embodiments described above.
[0107] As with FIGS. 6 and 7, FIG. 8 shows an embodiment method in which the second hydroconversion reactor shown in the embodiments of the process described in FIGS. 1 to 5 has been deleted. As noted above, following the 830 heat exchanger, a hydroconversion reactor can be added, if necessary, to maintain product quality.
[0108] FIG. 9 is a schematic flow diagram of a process for producing hydrocarbon fuels from biomass according to another embodiment of the invention, such a process generally designated by reference numeral 910.
[0109] Process 910 is sometimes similar to process 810, described above, except that process 910 employs gasoline adsorption. More particularly, FIG. 9 shows an embodiment of the process in which a hydrocarbon absorber is added in place of the double solid sorbent beds and along with the inclusion of other process modifications serves to provide an improved gasoline product.
[0110] In process 910, biomass (such as via a 912 stream) and molecular hydrogen (such as via a 914 stream) are introduced into a 916 hydropyrolysis and hydroconversion reactor vessel, as having a catalyst replacement port 918, to produce an output stream 920 comprising a liquid hydropyrolysis product at least partially deoxygenated, pyrolysis vapors (C1-C3 gases), H2O, CO, CO2, H2, and charcoal. The output process stream 920 is passed to and through an optional charcoal separator 924, a barrier filter 926 (such as to remove catalyst fines) and a process heat exchanger 930 that can be used to produce process steam. The product stream free of charcoal and particle 932 passes from the heat exchanger 930 to a high pressure separator 942. The high pressure separator 942 is desirably operated at a sufficiently high temperature such as to produce a gaseous hydrocarbon stream 944, a stream of diesel product 956 and a stream of water 948.
[0111] The hydrocarbon gas stream 944 is passed to a step 963 catalytic gasoline enhancement whose product is cooled in a 965 heat exchanger (which, depending on process needs can be optional) before being passed to a fuel absorber. hydrocarbon. As noted above, the heat exchanger 965 can be optional and is included in the illustrated embodiment to show a method for maintaining the inlet temperature of gas entering a hydrocarbon absorber at an appropriate value. As opposed to the double solid sorbent beds shown in FIG. 8, in FIG. 9, the two solid sorbent beds are replaced by a single hydrocarbon absorber 985. Hydrocarbon absorber 985 desirably serves to continuously discharge a gasoline-free gas stream 969 to the H2S scrubber 968 while providing a stream rich in separate gasoline 987 to a partial distillation unit 971. The distillation unit 971 also receives a chain 961 containing ULSD and gasoline from the drip bed reactor 959. The partial distillation unit 971 serves to supply a chain 975 of legitimate ULSD product, an improved gasoline chain 957 and a gasoline containing chain 989 that is directed to a heat exchanger 991 before being directed to the hydrocarbon absorber 985. The heat exchanger 991 can be optional and is included in this embodiment to show a method to maintain the inlet temperature of the gas entering a 985 hydrocarbon absorber at an appropriate value. Through this arrangement, the 971 distillation unit produces two product streams, an enhanced gasoline stream 957 and a legitimate ULSD stream 975.
[0112] As shown, process 910 may, if desired, include one or more additional features, such as a steam reformer-PSA / MSS 970 unit, an H2S 972 extractor, an acidic water extractor 980, a suitable water purifier 986, an oxidation reactor 992 and a compressor 998, as corresponding to those shown in the embodiments described above.
[0113] As in FIGS. 6 to 8, FIG. 9 shows an embodiment process in which the second hydroconversion reactor shown in the embodiments of the process described in FIGS. 1 - 5 has been deleted. As noted above, following the 930 heat exchanger, a hydroconversion reactor can be added, if necessary, to maintain product quality.
[0114] In view of the above, it should be appreciated that the present invention extends to biomass processing, as described in US Serial Patent Applications No. 12 / 419,535 identified above, filed on April 7, 2009; Serial N2 12 / 685,352, filed on January 11, 2010; Serial N2 13 / 089.010, deposited on April 18, 2011 and Serial N2 13 / 196.645, deposited on August 2, 2011, for processing where diesel fuels with ultra-low sulfur content and enhanced fractionated gasoline can be process chains of output. Using partial distillation and integration with other processes similar to the refinery, at least two separate fungible fuel streams can be produced, one dominated by liquids in the gasoline boiling range and the other by liquids in the gas boiling range. diesel. In addition, the inventors have developed a variety of process schemes up to and including multi-stage distillation units connected to a series of reactors located to accept these boiling point ranges as well as perhaps a jet fuel range that can be upgraded catalytic to remove impurities and create fuels in the JP-8 boiling range. Clearly, these distillation bands can be modified to optimize the hydrocarbons produced from a single fuel (for example, wood produces high grade gasoline but diesel fuel of poorer quality, motto produces superior diesel fuel but relatively average gasoline and combinations of two fuels for producing interesting ranges of hydrocarbon fuels that should benefit from carefully configured partial distillation cuts linked to downstream enhancement catalytic reactors). Thus, the method described here allows the direct production of several fuels from a single biomass processing reactor, thereby improving the process economy, improving the process in a versatile way and considering a self-contained process that can operate independently without no need for a refinery to produce a final finished gasoline or diesel fuel.
[0115] Although in the preceding specification, this invention has been described in relation to certain preferred embodiments of it and many details have been presented for the purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain details described here can be varied considerably without departing from the basic principles of the invention.

权利要求:
Claims (20)
[0001]
1. Process for producing hydrocarbon fuels from biomass, CHARACTERIZED by the fact that the process comprises: (a) hydrotreating biomass under hydrotreating reaction conditions to produce a hydrotreating product comprising (i) a gas mixture comprising non-condensable vapors and (ii) a deoxygenated hydrocarbon product including fractions in the boiling point range of gasoline and diesel, said hydrotreatment comprising: hydropyrolysing biomass in a reactor containing molecular hydrogen and a catalyst for deoxygenation and addition of hydrogen under conditions hydropyrolysis reaction to produce a deoxygenated hydrocarbon hydropyrolysis product comprising animal charcoal and vapors; separating substantially all said animal charcoal and particles from said deoxygenated hydrocarbon hydropyrolysis product to produce a hydropyrolysis product substantially free of animal charcoal and particle; (b) separating said gas mixture comprising non-condensable vapors from said hydrotreating product and directing said gas mixture to a vessel to remove H2S from said gas mixture; (c) separating each of said fractions in the boiling point range of gasoline and diesel from said hydrotreating product and from one another to provide a fraction in the range of the separate gasoline boiling point and a fraction in the range of the boiling point boiling of the separated diesel; (d) improve said fractions in the boiling point range of separate gasoline and diesel, in which, in said step of improving (d), said fraction in the boiling point range of separate diesel is treated in a diesel drip bed with ultra low sulfur content to produce a diesel product with ultra low sulfur content.
[0002]
2. Process according to claim 1, CHARACTERIZED by the fact that the ultra-low sulfur diesel drip bed reactor produces a product stream primarily comprising the ultra low sulfur diesel product and some residual gasoline, said process further comprising separating at least a portion of said residual gasoline from said ultra low sulfur diesel product.
[0003]
3. Process according to claim 1 or 2, CHARACTERIZED by the fact that in step (d), said fraction in the boiling point range of the separated gasoline is catalytically improved under catalytic gasoline improvement conditions to form a product enhanced gasoline.
[0004]
Process according to any one of claims 1 to 3, CHARACTERIZED by the fact that said hydrotreating product additionally comprises an aqueous fraction.
[0005]
5. Process according to claim 4, CHARACTERIZED by the fact that it further comprises separating said aqueous fraction from said hydrotreating product.
[0006]
6. Process, according to claim 5, CHARACTERIZED by the fact that: said fraction in the gasoline boiling point range and said gas mixture comprising non-condensable vapors are separated simultaneously from said hydrotreating product and, in step ( d), are subjected to the improvement of catalytic gasoline in conditions of improvement of catalytic gasoline to form a catalytic gasoline improvement product comprising catalytically enhanced gasoline and a gaseous product and further comprising separating said gaseous product from said catalytically enhanced gasoline.
[0007]
7. Process according to claim 6, CHARACTERIZED by the fact that it additionally comprises: separating hydrogen from said catalytic gasoline enhancement product before separating other gaseous components from it.
[0008]
8. Process according to claim 6 or 7, CHARACTERIZED by the fact that said separation of said gaseous product from said catalytically enhanced gasoline comprises processing said catalytic gasoline enhancement product by means of an effective sorbent bed for absorb catalytically enhanced gasoline.
[0009]
9. Process, according to claim 6, CHARACTERIZED by the fact that said separation of said gaseous product from said catalytically enhanced gasoline comprises processing said catalytic gasoline enhancement product by means of a hydrocarbon adsorber to produce a stream of gaseous effluent and a stream rich in gasoline.
[0010]
10. Process according to any one of claims 1 to 9, CHARACTERIZED by the fact that said hydrotreatment further comprises: hydroconverting said hydropyrolysis product substantially free of animal coal and particle in a separate hydroconversion reactor using a hydroconversion catalyst under hydroconversion reaction conditions to produce the hydrotreating product comprising (i) the gas mixture comprising non-condensable vapors and (ii) the deoxygenated hydrocarbon product including fractions in the boiling range of gasoline and diesel.
[0011]
11. Process according to any one of claims 1 to 10, CHARACTERIZED by the fact that at least a portion of said fraction in the boiling point range of separate diesel is added to the hydropyrolysis product substantially free of animal charcoal and particle.
[0012]
12. Process according to any one of claims 1 to 11, CHARACTERIZED by the fact that at least a portion of said fraction in the range of the boiling point of the separated diesel is recirculated to the reactor.
[0013]
13. Process according to any one of claims 1 to 12, CHARACTERIZED by the fact that it additionally comprises replacing the catalyst in the reactor that has been spent by friction or decomposed through a replacement port arranged in the reactor.
[0014]
14. Process according to any one of claims 1 to 13, CHARACTERIZED by the fact that said reactor comprises a hydropyrolysis and hydroconversion reactor.
[0015]
15. Process for producing hydrocarbon fuels from biomass, CHARACTERIZED by the fact that the process comprises: (a) hydropyrolysing biomass in a hydropyrolysis reactor vessel containing molecular hydrogen and a deoxygenation and hydrogen addition catalyst, to produce a hydropyrolysis and hydroconversion product comprising a hydropyrolysis gas comprising CO2, CO and C1-C3 gases, a partially deoxygenated hydropyrolysis product, water and animal charcoal; (b) removing substantially all of said animal charcoal and particles from at least said partially deoxygenated hydropyrolysis product to form a partially deoxygenated hydropyrolysis product substantially free of animal charcoal and particle; (c) hydroconverting said partially deoxygenated hydropyrolysis product substantially free of animal charcoal and particle in a separate hydroconversion reactor vessel using a hydroconversion catalyst in the presence of hydropyrolysis gas to produce a deoxygenated hydrocarbon liquid including fractions in the range from the boiling point of gasoline and diesel, a gas mixture comprising CO, CO2, and light hydrocarbon gases (C1-C3) and water; (d) steam reforming at least a portion of said gas mixture using water produced in at least one of said hydropyrolysis and hydroconversion steps to produce reformed molecular hydrogen; (e) introducing at least a portion of said reformed molecular hydrogen into said vessel of the hydropyrolysis reactor; (f) separating each of said fractions in the range of the boiling point of gasoline and diesel from said deoxygenated hydrocarbon liquid and from each other to provide a fraction in the range of the boiling point of the separate gasoline and a fraction in the range of the boiling of the separated diesel; and (g) improve said fractions in the boiling point range of separate gasoline and diesel, in which, in said step of improving (g), said fraction in the boiling point range of separate diesel is treated to provide a product of diesel with ultra-low sulfur content, when contacting said fraction in the boiling point range of the separated diesel with a second portion of said reformed molecular hydrogen.
[0016]
16. Process according to claim 15, CHARACTERIZED by the fact that said separation of each of said fractions in the range of the boiling point of gasoline and diesel from said deoxygenated hydrocarbon liquid and one from the other comprises first separating said fractions in the range of the boiling point of gasoline and diesel of said deoxygenated hydrocarbon liquid followed by separation of said fractions in the range of the boiling point of gasoline from said fractions in the range of the boiling point of diesel.
[0017]
17. Process, according to claim 15 or 16, CHARACTERIZED by the fact that: said fraction in the gasoline boiling point range and said gas mixture are separated simultaneously and, in step (g), are subjected to improvement of catalytic gasoline in conditions for improving catalytic gasoline to form a catalytic gasoline enhancement product comprising catalytically enhanced gasoline and a gaseous product and further comprising separating said gaseous product from said catalytically enhanced gasoline.
[0018]
18. Process, according to claim 16 or 17, CHARACTERIZED by the fact that it further comprises replacing the catalyst in the reactor that has been frayed or decomposed through a replacement port arranged in the hydropyrolysis reactor vessel.
[0019]
19. Process according to any one of claims 1 to 14, CHARACTERIZED by the fact that it further comprises steam reforming of at least a portion of said gas mixture, after removal of the H2S in step (b), to produce a molecular hydrogen retired.
[0020]
20. Fuel hydrocarbon CHARACTERIZED by the fact that it is produced by the process, as defined in any of claims 1 to 14 or 19, or the process as defined in any of claims 15 to 18.

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法律状态:
2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-05-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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