US20100251600A1 - Hydropyrolysis of biomass for producing high quality liquid fuels - Google Patents
Hydropyrolysis of biomass for producing high quality liquid fuels Download PDFInfo
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- US20100251600A1 US20100251600A1 US12/419,535 US41953509A US2010251600A1 US 20100251600 A1 US20100251600 A1 US 20100251600A1 US 41953509 A US41953509 A US 41953509A US 2010251600 A1 US2010251600 A1 US 2010251600A1
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Definitions
- This invention relates to an integrated process for thermochemically transforming biomass into high quality liquid fuels.
- this invention relates to a substantially self-sustaining process for creating high quality liquid fuels from biomass.
- this invention relates to a multi-stage hydropyrolysis process for creating high quality liquid fuels from biomass.
- this invention relates to a hydropyrolysis process for transforming biomass into high quality liquid fuels in which all of the process fluids are provided by the biomass.
- this invention relates to a hydropyrolysis process for transforming biomass into high quality liquid fuels in which the process outputs are substantially only liquid product and CO 2 .
- the water miscible liquid product is highly oxygenated and reactive, with total acid numbers (TAN) in the range of 100-200, has low chemical stability for polymerization, is incompatible with petroleum hydrocarbons due to water miscibility and very high oxygen content, on the order of about 40% by weight, and has a low heating value.
- TAN total acid numbers
- transport and utilization of this product are problematic and it is difficult to upgrade this product to a liquid fuel due to the retrograde reactions that typically occur in conventional pyrolysis and in conventional fast pyrolysis.
- hydropyrolysis is a catalytic pyrolysis process carried out in the presence of molecular hydrogen.
- the objective of conventional hydropyrolysis processes has been to maximize liquid yield in one step, and even in one known case in which a second stage reaction was added, the objective was to maximize yield while obtaining high oxygen removal.
- this approach compromises economy, creates a system which requires an external source of H 2 , and must be carried out at excessive internal pressures.
- such conventional hydropyrolysis processes produce excessive H 2 O which must then be disposed of.
- self-sustaining we mean that, once initiated, the process requires no input of additional reactants, heat, or energy from external sources.
- liquid product refers to hydrocarbon products, typically —C 5 +liquids, produced by the process of this invention.
- a multi-stage, self-sustaining process for producing liquid products from biomass in which the biomass is hydropyrolyzed in a reactor vessel containing molecular hydrogen and a deoxygenating catalyst, producing a partially deoxygenated pyrolysis liquid, char, and first-stage process heat.
- the partially deoxygenated pyrolysis liquid is hydrogenated using a hydroconversion catalyst, producing a substantially fully deoxygenated pyrolysis liquid, a gaseous mixture comprising CO and light hydrocarbon gases (C 1 -C 4 ), and second-stage process heat.
- the gaseous mixture is then reformed in a steam reformer, producing reformed molecular hydrogen.
- the reformed molecular hydrogen is then introduced into the reactor vessel for the hydropyrolysis of additional biomass.
- the hydropyrolysis and hydroconversion steps are operated at conditions under which about 40-60% of oxygen in the biomass is converted to H 2 O and about 40-60% of the oxygen is converted to CO and C0 2 . That is, the ratio of oxygen in H20 produced therein to the oxygen in the CO and CO 2 produced therein equals about 1 (i.e. H 2 O/(CO+CO 2 ) ⁇ 1).
- process pressures for the hydropyrolysis and hydroconversion steps are in the range of about 300 psig to about 800 psig and are about the same for both steps.
- Pressures greater than about 800 psig result in a higher liquid product yield, which is the driving force behind the operating parameters employed by conventional processes for maximizing liquid product yield; however, such higher pressures also produce higher amounts of water, as a result of which the overall process is driven out of balance, requiring, for example, the introduction of additional hydrogen into the hydropyrolysis reactor vessel from an external source to complete the process. In addition, the excess water produced at the higher pressures must then be purified and disposed of.
- temperatures for the hydropyrolysis and hydroconversion steps are in the range of about 650° F. to about 900° F.
- FIG. 1 is a schematic flow diagram of the self-sustaining process for producing liquid fuels from biomass in accordance with one embodiment of this invention.
- the process of this invention is a compact, balanced, integrated, multi-stage process for thermochemically transforming biomass into gasoline plus diesel liquid product suitable for use as a transportation fuel without the need for externally provided H 2 , CH 4 , or water.
- the first reaction stage of this process employs a pressurized, catalytically-enhanced, hydropyrolysis reactor vessel 10 to create a low-char, partially deoxygenated, hydropyrolysis liquid product from which the char is removed.
- the second reaction stage (subsequent to char removal) employs a hydroconversion reactor vessel 11 in which a hydroconversion process is carried out at substantially the same pressure as the first reaction stage.
- the product from the second reaction stage is then cooled and separated into liquid and gaseous fractions using high pressure separators 12 , 13 and low pressure separator 14 .
- CO plus C 1 -C 4 light gases produced in the two stages are then steam reformed in a steam reformer 15 to produce H 2 using water which is also produced in the process.
- a key aspect of this invention is that the heat energy required in the process is supplied by the heat of reaction of the deoxygenation reaction, which is exothermic, occurring in both the first and second stages.
- Another key aspect of this invention is that the biomass feed need not be severely dried and, in fact, the addition of water either in the feed or as a separate feed is advantageous to the process because it enhances in-situ H 2 formation through a water-gas-shift reaction.
- the integrated, balanced process of this invention is carried out under conditions which balance the levels of decarboxylation, decarbonylation, and hydrodeoxygenation so that 40-60% of the oxygen present in the biomass is rejected as CO and CO 2 and the remaining 40-60% of the oxygen in the biomass is rejected as H 2 O at the end of the process where it is easily separated from the hydrophilic liquid products produced by the process for use in the reforming process.
- each step of the process of this invention can yield a variety of products depending on the catalyst, pressure, temperature, and time on stream employed, only when these processes are integrated in the specific series of steps and process conditions of this invention is it possible to provide a balanced process wherein all of the H 2 , CH 4 , and water demands of the overall process are supplied by the biomass, which is critical for creating a fungible fuel that can be sold at a reasonable cost.
- biomass and molecular hydrogen are introduced into a reactor vessel 10 containing a deoxygenation catalyst in which vessel the biomass undergoes hydropyrolysis, producing an output comprising a low-char, partially deoxygenated, hydropyrolysis liquid product, pyrolysis vapors (C 1 -C 4 gases), H 2 O, CO, CO 2 , and H 2 .
- a reactor vessel 10 containing a deoxygenation catalyst in which vessel the biomass undergoes hydropyrolysis, producing an output comprising a low-char, partially deoxygenated, hydropyrolysis liquid product, pyrolysis vapors (C 1 -C 4 gases), H 2 O, CO, CO 2 , and H 2 .
- the preferred reactor vessel is a fluidized bed reactor.
- the hydropyrolysis process employs a rapid heat up of the biomass fuel such that the residence time of the pyrolysis vapors in the reactor vessel is less than about 5 minutes.
- the residence time of the char 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 sufficiently small to enable them to be carried out with the vapors exiting proximate the top of the reactor vessel.
- Hydropyrolysis is carried out in the reactor vessel at a temperature in the range of about 800° F. to about 950° F. and a pressure in the range of about 300 psig to about 800 psig.
- the objective is to maximize liquid product yield, which requires operation at substantially higher pressures, e.g. 2000 psig. This is because decarboxylation is favored at lower pressures whereas hydrodeoxygenation is favored at higher operating pressures.
- pressures in the process of this invention in the range of 300 to 800 psig, most preferably at about 500 psig, decarboxylation and dehydrodeoxy genation are balanced, but liquid product yield is reduced. At higher pressures, hydrodeoxygenation is favored and the reactions become unbalanced.
- the solid biomass feed is rapidly heated, preferably in a hot fluidized bed, resulting in liquid product yields comparable to and possibly better than yields obtained with conventional fast pyrolysis.
- the pyrolysis vapors now are in the presence of a catalyst and a high partial pressure of H 2 within the fluidized bed, which provides hydrogenation activity and also some deoxygenation activity.
- Hydrogenation activity is very desirable for preventing reactive olefins from polymerizing, thereby reducing the formation of unstable free radicals.
- deoxygenation activity is important so that the heat of reaction from pyrolysis is supplied by the exothermic deoxygenation reaction, thereby obviating the need for external heating.
- hydropyrolysis avoids the retrograde reactions of pyrolysis, which is usually carried out in an inert atmosphere, most certainly in the absence of H 2 and usually in the absence of a catalyst, thereby promoting the undesirable formation of polynuclear aromatics, free radicals and olefinic compounds that are not present in the original biomass.
- the first stage hydropyrolysis process of this invention operates at a temperature hotter than is typical of a hydroconversion process, as a result of which the biomass is rapidly devolatilized.
- the process requires an active catalyst to stabilize the hydropyrolysis vapors, but not so active that it rapidly cokes.
- any deoxygenation catalyst suitable for use in the temperature range of this process may be employed in the hydropyrolysis process, catalysts in accordance with preferred embodiments of this invention are as follows:
- Glass-ceramic catalysts are extremely strong and attrition resistant and can be prepared as thermally impregnated (i.e. supported) or as bulk catalysts.
- the resulting catalyst is an attrition resistant version of a readily available, but soft, conventional NiMo, Ni/NiO, or Co-based catalyst.
- Glass-ceramic sulfided 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 supported catalyst, but in a much more robust, attrition resistant form.
- the attrition rate of the catalyst will typically be less than about 2 weight % per hour, preferably less than 1 weight % per hour as determined in a standard, high velocity jet cup attrition test index test.
- This catalyst may be impregnated on carbon as a separate catalyst or impregnated directly into the biomass feedstock itself.
- Bauxite is an extremely cheap material and, thus, may be used as a disposable catalyst. Bauxite may also be impregnated with other materials such as Ni, Mo, or be sulfided as well.
- Small size spray-dried silica-alumina catalyst impregnated with low amounts of NiMo or CoMo and sulfided to form a low activity hydroconversion catalyst Commercially available NiMo or CoMo catalysts are normally provided as large size 1 ⁇ 8- 1/16 tablets for use in fixed or ebullated beds. In the instant case, NiMo is impregnated on spray dried silica alumina catalyst and used in a fluidized bed. This catalyst exhibits lower activity with lower NiMo loadings than a conventional NiMo catalyst but would be of the right size for use in a fluidized bed.
- char is removed from the pyrolysis liquid product.
- Char removal has been a major barrier in conventional fast pyrolysis because the char tends to coat filters and react with oxygenated pyrolysis vapors to form viscous coatings which can blind hot process filters.
- Char may be removed in accordance with the process of this invention by filtration from the vapor stream, or by way of filtering from a wash step—ebullated bed. Back pulsing may be employed in removing char from filters, as long as the hydrogen used in the process of this invention sufficiently reduces the reactivity of the pyrolysis vapors.
- Electrostatic precipitation or a virtual impact or separator may also be used to remove char and ash particles from the hot vapor stream before cooling and condensation of the liquid product.
- hot gas filtration may be used to remove the char.
- the char is removed by bubbling first stage product gas through a recirculating liquid.
- the recirculated liquid used is the high boiling point portion of the finished oil from this process and is thus a fully saturated (hydrogenated), stabilized oil having a boiling point above 650° F. Char or catalyst fines from the first reaction stage are captured in this liquid.
- a portion of the liquid may be filtered to remove the fines and a portion may be recirculated back to the first stage hydropyrolysis reactor.
- a recirculating liquid provides a way to lower the temperature of the char-laden process vapors from the first reaction stage to the temperature desired for the second reaction stage hydroconversion process while removing fine particulates of char and catalyst.
- Another advantage of employing liquid filtration is that the use of hot gas filtration with its attendant, well-documented problems of filter cleaning is completely avoided.
- large-size NiMo or CoMo catalysts deployed in an ebullated bed, are used for char removal to provide further deoxygenation simultaneous with the removal of fine particulates.
- Particles of this catalyst should be large, preferably about 1 ⁇ 8- 1/16 inch in size, thereby rendering them easily separable from the fine char carried over from the first reaction stage, which is typically less than 200 mesh ( ⁇ 70 micrometers).
- the pyrolysis liquid, together with H 2 , CO, CO 2 , H 2 O, and C 1 -C 4 gases from the first reaction stage hydropyrolysis step is introduced into a hydroconversion reactor vessel 11 in which it is subjected to a second reaction stage hydroconversion step, which preferably is carried out at a lower temperature (600-800° F.) than the first reaction stage hydropyrolysis step to increase catalyst life and at substantially the same pressure (300 -800 psig) as the first reaction stage hydropyrolysis step.
- the liquid hourly space velocity (LHSV) of this step is in the range of about 0.3 to about 0.7.
- the catalyst used in this step should be protected from Na, K, Ca, P, and other metals present in the biomass which can poison the catalyst, which will tend to increase catalyst life.
- This catalyst also should be protected from olefins and free radicals by the catalytic upgrading carried out in the first reaction stage process.
- Catalysts typically selected for this step are high activity hydroconversion catalysts, e.g. sulfided NiMo and sulfided CoMo catalysts.
- the catalyst is used to catalyze a water-gas-shift reaction of CO+H 2 0 to make CO 2 +H 2 , thereby enabling in-situ production of hydrogen in the second reaction stage reactor 11 , which, in turn, reduces the hydrogen required for hydroconversion.
- NiMo and CoMo catalysts both catalyze the water-gas-shift reaction.
- the objective in this second reaction stage is once again to balance the deoxygenation reactions. This balancing is done by using relatively low pressures (300-800 psig) along with the right choice of catalyst. In conventional hydrodeoxygenation processes, pressures in the range of about 2000 psig to about 3000 psig are typically employed. This is because the processes are intended to convert pyrolysis oils, which are extremely unstable and difficult to process at lower pressures of H 2 .
- the oil product will be substantially totally deoxygenated so that it can be directly utilized as a transportation fuel, after it is separated by means of high pressure separators 12 , 13 and low pressure separator 14 , by distillation into gasoline and diesel portions.
- a key aspect of this process is to adjust temperature and pressure and space velocity to balance the level of decarbonylation, decarboxylation and hydrodeoxygenation so that all the H 2 required for the process can be made by reforming the light gases that are produced within the process. If too much hydrodeoxygenation occurs, then too much H 2 will be required for the process and the system will be driven out of balance. Likewise, if too much decarboxylation or decarbonylation occurs, too much carbon will be lost to CO 2 and CO instead of being converted into liquid product, as a result of which liquid yields will be reduced.
- the effluent therefrom is cooled substantially so that gasoline and diesel boiling materials condense and only the light gases remain in the vapor phase.
- gases containing CO, CO 2 , CH 4 , ethane, propane, butanes, heptanes, etc.
- These gases are sent to the steam reformer 15 together with water from the process for conversion into H 2 and CO 2 .
- a portion of these gases are burned in a furnace or other combustor to heat up the remaining portion of gases to the operating temperature of the steam reformer, about 1700° F.
- Steam reformers have a 3/1 steam-to-hydrocarbon ratio in their feed to push the reaction equilibrium, but this is far more than the amount required for reaction. The steam is recovered and recycled around inside the steam reformer.
- the CO 2 is removed from the process by pressure swing absorption (PSA) and the H 2 is recirculated back to the first reaction stage (hydropyrolysis) of the process.
- PSA pressure swing absorption
- the product liquid is separated into diesel and gasoline fraction which are suitable for use as transportation fuels.
- this process is also balanced with respect to water so that enough water is made in the process to provide all the water needed in the steam reforming step.
- the amount of water employed is such that the overall process output contains substantially only CO 2 and liquid products, thereby avoiding an additional process step for excess water disposal.
- the use of steam reforming in combination with hydropyrolysis and hydroconversion steps as set forth herein only makes sense where the objective is to provide a self-sustaining process in which the ratio of O 2 in H 2 O to O 2 in CO and CO 2 produced by the process is about 1.0. In the absence of such an objective, steam reforming is not necessary because H 2 required for the hydropyrolysis process would still be provided by external sources. If one were to employ steam reforming in the absence of the objectives stated herein, one would not end up with the self-sustaining process of this invention in which the process output consists essentially of liquid product and CO 2 .
- the heat generated in the second reaction stage may be used to supply all or part of the heat needed to drive the hydropyrolysis process in the first reaction stage.
- the process also employs recirculation of the heavy finished products as a wash liquid in the second step as stated herein above to capture process fines exiting the first stage pyrolysis reactor and control the heat of reaction.
- this liquid is also recirculated to the hydroconversion and possibly to the first stage hydropyrolysis step to regulate the generation of heat in each step.
- the rate of recirculation is preferably in the range of about 3-5 times the biomass feed rate. This is necessary because hydrodeoxygenation is a strongly exothermic reaction.
- the biomass feed is a high lipid containing biomass such as algae, enabling production of the same deoxygenated diesel oil which would be made from lipids extracted from the algae plus additional gasoline and diesel which can be made from the remainder of the algae biomass.
- This is particularly attractive because lipid extraction is expensive.
- conventional fast pyrolysis of algae biomass would be very unattractive because the uncontrolled thermal reactions characteristic of fast pyrolysis would degrade these lipids.
- the integrated process of this invention is ideal for algae conversion because it can be carried out on algae which are usually only partially dewatered and still produce high quality diesel and gasoline product.
- the process of this invention provides several distinct advantages over conventional fast pyrolysis-based processes in that it produces a negligible to low-char, partially deoxygenated, stabilized product from which residual char can be easily separated by hot gas filtration or contacting with a recirculated liquid; clean, hot hydropyrolysis oil vapors can be directly upgraded to a final product in a close-coupled second catalytically-enhanced process unit operated at almost the same pressure as was employed upstream; and upgrading is carried out quickly before degradation can occur in the vapor produced from the hydropyrolysis step.
- the liquid product produced by this process should contain less than 5% oxygen and preferably less than 2% oxygen with a low total acid number (TAN) and exhibit good chemical stability to polymerization or a reduced tendency to reactivity.
- TAN total acid number
- the water and hydrocarbon phases will easily separate out in any normal separation vessel because the hydrocarbon phase has become hydrophobic. This is a significant advantage when compared to conventional pyrolysis in which the water is miscible with and mixed in with the highly oxygenated pyrolysis oil.
- Table 1 presents an estimated material balance for a balanced hydropyrolysis+hydroconversion process in accordance with this invention utilizing a mixed hardwood feed.
- any excess water produced from this process is relatively free of dissolved hydrocarbons and will likely contain less than 2000 ppm dissolved total organic carbon (TOC), rendering it suitable for irrigation in arid areas. Additionally, the finished hydrocarbon product is now easily transportable, has low total acid number (TAN), and excellent chemical stability.
- the pyrolysis oils typically contain 50-60% oxygen in the form of oxygenated hydrocarbons and 25% dissolved water. Therefore, final products transportation costs for the integrated hydropyrolysis+hydroconversion process of this invention are less than half of the costs for conventional fast pyrolysis. Furthermore, water produced in the proposed process becomes a valuable byproduct especially for arid regions.
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Priority Applications (42)
Application Number | Priority Date | Filing Date | Title |
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US12/419,535 US20100251600A1 (en) | 2009-04-07 | 2009-04-07 | Hydropyrolysis of biomass for producing high quality liquid fuels |
US12/685,352 US8492600B2 (en) | 2009-04-07 | 2010-01-11 | Hydropyrolysis of biomass for producing high quality fuels |
EP10761974.4A EP2417222B1 (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
CN201080025189.XA CN102459518B (zh) | 2009-04-07 | 2010-04-05 | 用于产生高品质液体燃料的生物质加氢热解 |
MX2011010501A MX2011010501A (es) | 2009-04-07 | 2010-04-05 | Hidropirolisis de biomasa para producir conbustibles liquidos de alta calidad. |
BRPI1011219-7A BRPI1011219B1 (pt) | 2009-04-07 | 2010-04-05 | Processo para produzir produtos líquidos a partir de biomassa |
AU2010235214A AU2010235214C1 (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
CN201080015232.4A CN102378748B (zh) | 2009-04-07 | 2010-04-05 | 用于生产高质量液体燃料的生物质的加氢热解 |
CA2757651A CA2757651C (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
ES10761974T ES2862929T3 (es) | 2009-04-07 | 2010-04-05 | Hidropirólisis de biomasa para producir combustibles líquidos de alta calidad |
JP2012504670A JP5521031B2 (ja) | 2009-04-07 | 2010-04-05 | 高品質液体燃料を製造するためのバイオマスの水素化熱分解 |
CA2756819A CA2756819A1 (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
NZ621616A NZ621616A (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
UAA201504986A UA116115C2 (uk) | 2009-04-07 | 2010-04-05 | Гідропіроліз біомаси для отримання високоякісних рідких палив |
CA2912814A CA2912814C (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
DK10761974.4T DK2417222T3 (da) | 2009-04-07 | 2010-04-05 | Hydropyrolyse af biomasse til fremstilling af flydende brændstoffer af høj kvalitet |
PL10761974T PL2417222T3 (pl) | 2009-04-07 | 2010-04-05 | Hydropiroliza biomasy do wytwarzania wysokiej jakości paliw ciekłych |
RU2011144864/04A RU2539598C2 (ru) | 2009-04-07 | 2010-04-05 | Гидропиролиз биомассы для получения высококачественных жидких топлив |
PCT/US2010/001019 WO2010117436A1 (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
PE2011001776A PE20121004A1 (es) | 2009-04-07 | 2010-04-05 | Hidropirolisis de biomasa para producir combustibles liquidos de alta calidad |
MX2011010471A MX2011010471A (es) | 2009-04-07 | 2010-04-05 | Hidropirolisis de biomasa para producir combustibles liquidos de alta calidad. |
PCT/US2010/001020 WO2010117437A1 (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
MYPI2011004768A MY175354A (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing idgh quality liquid fuels |
NZ596155A NZ596155A (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
MX2015008231A MX351040B (es) | 2009-04-07 | 2010-04-05 | Hidropirolisis de biomasa para producir combustibles liquidos de alta calidad. |
AU2010235215A AU2010235215B2 (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
MYPI2011004771A MY158044A (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
RU2011144858/04A RU2535343C2 (ru) | 2009-04-07 | 2010-04-05 | Гидропиролиз биомассы для получения высококачественного жидкого горючего |
JP2012504669A JP5789596B2 (ja) | 2009-04-07 | 2010-04-05 | 高品質液体燃料を製造するためのバイオマスの水素化熱分解 |
CN201510140464.7A CN104845654B (zh) | 2009-04-07 | 2010-04-05 | 用于生产高质量液体燃料的生物质的加氢热解 |
BRPI1015303-9A BRPI1015303B1 (pt) | 2009-04-07 | 2010-04-05 | Processo para produzir produtos líquidos a partir de biomassa |
PE2011001761A PE20120999A1 (es) | 2009-04-07 | 2010-04-05 | Hidropirolisis de biomasa para producir combustibles liquidos de alta calidad |
MX2013011082A MX341855B (es) | 2009-04-07 | 2010-04-05 | Hidropirolisis de biomasa para producir combustibles liquidos de alta calidad. |
UAA201113018A UA106609C2 (uk) | 2009-04-07 | 2010-05-04 | Гідропіроліз біомаси для отримання високоякісного рідкого пального |
UAA201113017A UA109635C2 (uk) | 2009-04-07 | 2010-05-04 | Гідропіроліз біомаси для отримання високоякісних рідких палив |
US12/815,743 US8915981B2 (en) | 2009-04-07 | 2010-06-15 | Method for producing methane from biomass |
CL2011002488A CL2011002488A1 (es) | 2009-04-07 | 2011-10-06 | Proceso para producir productos liquidos desde biomasa que comprende las etapas de introduccion de h2 refeormado y biomasa en reactor, hidropirolisis, remoscion de carbocillo, hidroconversion, reformado y reciclado del producto liquido. |
ECSP11011432 ECSP11011432A (es) | 2009-04-07 | 2011-11-01 | Hidropirólisis de biomasa para la producción de combustibles líquidos de alta calidad |
ECSP11011431 ECSP11011431A (es) | 2009-04-07 | 2011-11-01 | Hidropirólisis de biomasa para la producción de combustibles líquidos de alta calidad |
CL2011003096A CL2011003096A1 (es) | 2009-04-07 | 2011-12-06 | Proceso para producir productos liquidos de biomasa que comprende a) introducir biomasa e hidrogeno molecular reformado en un reactor de hidropirolisis, b) remover residuo de carbon del liquido de hidropirolisis; c) hidroconvertir dicho liquido en un reactor de hidroconversion y d) producir hidrogeno reformado para usar en a). |
US13/843,367 US9447328B2 (en) | 2009-04-07 | 2013-03-15 | Hydropyrolysis of biomass for producing high quality liquid fuels |
JP2014078152A JP5898253B2 (ja) | 2009-04-07 | 2014-04-04 | 高品質液体燃料を製造するためのバイオマスの水素化熱分解 |
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US12/815,743 Continuation-In-Part US8915981B2 (en) | 2009-04-07 | 2010-06-15 | Method for producing methane from biomass |
US13/843,367 Continuation-In-Part US9447328B2 (en) | 2009-04-07 | 2013-03-15 | Hydropyrolysis of biomass for producing high quality liquid fuels |
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CA (1) | CA2756819A1 (es) |
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AU2010235214C1 (en) | 2013-09-12 |
MX341855B (es) | 2016-09-05 |
CN102378748A (zh) | 2012-03-14 |
CN102378748B (zh) | 2015-05-13 |
JP5789596B2 (ja) | 2015-10-07 |
AU2010235214B2 (en) | 2012-11-15 |
CA2756819A1 (en) | 2010-10-14 |
UA106609C2 (uk) | 2014-09-25 |
AU2010235214A1 (en) | 2011-10-27 |
UA109635C2 (uk) | 2015-09-25 |
MY175354A (en) | 2020-06-22 |
BRPI1015303B1 (pt) | 2018-08-07 |
PE20121004A1 (es) | 2012-08-01 |
RU2011144858A (ru) | 2013-05-20 |
CN104845654A (zh) | 2015-08-19 |
MX2011010501A (es) | 2011-10-19 |
ECSP11011432A (es) | 2012-06-29 |
RU2535343C2 (ru) | 2014-12-10 |
CN104845654B (zh) | 2018-09-14 |
JP2012523473A (ja) | 2012-10-04 |
BRPI1015303A2 (pt) | 2016-10-04 |
WO2010117436A1 (en) | 2010-10-14 |
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