CONVERTING BIOMASS TO GASEOUS FUEL HYDROCARBONS |
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| 申请号 | US13202239 | 申请日 | 2010-02-23 | 公开(公告)号 | US20120035403A1 | 公开(公告)日 | 2012-02-09 |
| 申请人 | Maria Flytzani-Stephanopoulos; Branko Zugic; Brian Ricks; Gregory Stephanopoulos; | 发明人 | Maria Flytzani-Stephanopoulos; Branko Zugic; Brian Ricks; Gregory Stephanopoulos; | ||||
| 摘要 | A method includes providing a solution containing a C2-6 carboxylic acid or a C2-6 carboxylate that is derived from biomass; and contacting the solution with a solid catalyst to form a C1-5 hydrocarbon. | ||||||
| 权利要求 | What is claimed is: |
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| 说明书全文 | This application claims the benefit of the priority of U.S. Provisional Application Ser. Nos. 61/154,598 and 61/176,605, filed Feb. 23, 2009 and May 8, 2009, respectively, the contents of which are incorporated herein by reference. This invention was supported by 0304515 awarded by the National Science Foundation. The government has certain rights in the invention. The invention relates to methods of converting biomass to gaseous fuel hydrocarbons. Declining petroleum resources have heightened the interest in biomass as a renewable energy source. Various processing options for biomass have been explored, including gasification to form synthesis gas, pyrolysis and liquefaction to generate bio-oils, and fermentation of sugars formed through hydrolysis of cellulosic and hemicellulosic biomass. The above processing options are described in detail in Huber, G. W. et al., Chem. Rev. 106 (2006) 4044-4098. There is a need in seeking other potentially inexpensive and efficient methods of converting biomass to fuels. In one aspect, the invention relates to a method of converting biomass to fuels (e.g., short-chain hydrocarbon fuels, in particular, a method of decarboxylating a C2-6 carboxylic acid or a C2-6 carboxylate. More specifically, the method includes providing a solution containing a C2-6 carboxylic acid or a C2-6 carboxylate that is derived from biomass and contacting the solution with a solid catalyst to form a C1-5 hydrocarbon. The term “biomass” includes but is not limited to whole plants or parts thereof, organic matter in municipal solid wastes, photosynthetic organisms (e.g. cyanobacteria, macro-algae, and micro-algae) or parts thereof, carbohydrate compounds such as simple sugars (e.g., glucose, xylose, mannose, and arabinose) and their polymers, such as starch, cellulose, hemicellulose, and lignin. The term “solid catalyst” refers to a catalyst in the form of a solid at room temperature and 1 atm. The term “carboxylate” refers to a conjugate base or a salt of the corresponding carboxylic acid (e.g. hydroxybutyrate, sodium acetate, potassium butyrate, or ethyl propionate). The carboxylic acids can be obtained from biomass by a variety of approaches such as thermochemical, catalytic, and biochemical. See, e.g., Corma, A. et al., J. Catal. 257 (2008): 163-171. For instance, short-chain aliphatic carboxylic acids (e.g., butyric acid) or their salts (e.g., butyrate) can be obtained from sugars by hydrolysis followed by fermentation. In another example, municipal waste is first converted to synthesis gas, and the synthesis gas is then converted to a carboxylic acid mixture. The method of this invention can be performed under different conditions. The solution containing the carboxylic acid or the carboxylate can be carried by a gas to effect contact with the solid catalyst. The gas can be hydrogen, an inert gas or a mixture of an inert gas and hydrogen. The solution (e.g., an aqueous solution) can be brought into contact with the solid catalyst at 25-500° C. (e.g., 200-350° C. or 250-400° C.) and at 1-30 atm (e.g., 1-10 atm or 5-15 atm). The solid catalyst includes a metal (e.g., Fe, Co, Ni, Mn, Ru, Rh, Pd, Re, Os, Ir, Pt, Sn, Cu, Ag, Au, or a combination thereof) and a substrate (e.g., a metal oxide, metal sulfide, metal nitride, metal carbide, a zeolite, a molecular sieve, a perovskite, a clay, a carbonaceous material, or a combination thereof). The method can further include purifying thus-obtained C1-5 hydrocarbon by removing the other product CO2 via liquefaction, neutralization, or any other suitable techniques. It can also include recycling the gaseous carrier gas back to the reactor; and/or using some part of it with the CO2 produced to make fuels or chemicals. The condensed liquid effluent can be further treated and discharged or returned to the fermentor down-stream processing units. The term “metal” refers to an elemental metal, a metal alloy, and a metal-containing compound (e.g., a metal oxide or an elemental metal coated with its oxide) that is reducible to form an elemental metal under the conditions described herein. The term “carbonaceous material” refers to material that is rich in carbon, e.g., having 70% of elemental carbon or more by weight. Examples of carbonaceous materials include but are not limited to activated carbon, graphite, charcoal, carbon black, carbon nanotubes, carbon fibers, or a combination thereof. One advantage of the above-described method is that the fuels thus produced are rich in gaseous hydrocarbons such as propane and butane. The gaseous hydrocarbons are particularly desirable since they can easily be integrated into the current pipeline infrastructure. Indeed, propane and butane mixtures comprise the Liquified Petroleum Gas (LPG). Another advantage is that the method, unexpectedly, has a high selectivity for decarboxylation. Namely, other reactions such as decarbonylation are unlikely to take place. A hydrocarbon product rich in alkanes is produced when hydrogen is used as the carrier gas. However, a mixture of alkanes and alkenes, e.g. propane and propylene, is possible, by using an inert carrier gas. Also within the scope of the invention is a solid catalyst described above. The details of one or more embodiments are set forth in the accompanying description below. Other aspects, features, and advantages will be apparent from the following drawing, detailed description of embodiments, and also from the appending claims. This invention relates to a method of decarboxylating a carboxylic acid (e.g., butyric acid) or its salt (e.g., butyrate) to form a hydrocarbon fuel, e.g., a propane rich fuel. The method can thus be applied to make liquefied petroleum gas (LPG). The method includes first providing a solution containing one or more short-chain carboxylic acids (e.g., C2-6 carboxylic acids) or their salts (e.g., C2-6 carboxylates) that are derived from biomass and then contacting the solution, in vapor or liquid phase, with a solid catalyst to form one or more short-chain hydrocarbons (e.g., methane, ethane, ethylene, propane, propene, butane, butene, etc.). Preferably, the catalyst has a high and stable decarboxylation activity at moderate temperatures (e.g., not higher than 400° C.) and moderate pressures (e.g., not higher than 20 atm). Higher pressures (e.g., ˜30 atm) may be used to, e.g., keep the solution in liquid phase during the decarboxylation reaction. The solution can be either aqueous or organic. Before contacting the solution with the catalyst, one can first fully or partially gasify the solution by adjusting the temperature and pressure. Hydrogen gas (99.99%) can be used as a carrier and reactant gas to bring the vapor-phase solution into contact with the catalyst. An inert gas, e.g., nitrogen (N2), helium (He), and argon (Ar), can also be used as a carrier gas and to control the pressure of the decarboxylation process. Hydrogen can also be used to pretreat (e.g. to reduce) the catalyst, to keep the catalyst in its reduced form, or to catalyze the hydrogenation of the carboxylic acids to afford the corresponding alkanes. In one embodiment, the method of this invention is carried out in a continuous, tubular reactor system as shown in The decarboxylation of carboxylic acid or carboxylate is carried out using various supported metal catalysts. In one embodiment, the reactor described above is first loaded with a metal catalyst and quartz beads, the latter being 1.5 times the weight of the former, for even distribution of the catalyst within the reactor. The furnace surrounding the reactor is then heated at a selected rate (e.g., 2° C. per minute) from room temperature up to the reaction temperature (e.g., 200-400° C.) with a pretreatment gas flowing in at a selected rate (e.g., 30 mL/min) and at a pressure ranging from 1 to 20 atm. To ensure uniform heating and to provide sufficient time for catalyst reduction, once the reactor is heated to the desired reaction temperature, it can be kept at that temperature for a certain period of time (e.g., 30 minutes) prior to introducing the carboxylic acid or carboxylate solution. When the catalyst is to be reduced before the decarboxylation reaction, H2 gas or a H2/He (or N2) mixture can be used as a pretreatment gas. On the other hand, when the catalyst is not to be reduced, pure He or N2 can be used as the pretreatment gas. The pretreatment gas may be the same as or different from the carrier gas described above. For example, a 5% H2/He (or N2) gas stream can be used as both the pretreatment gas and carrier gas of the solution. As another example, H2 is used as the pretreatment gas when the reactor is heated to and kept at a predetermined decarboxylation temperature for 30 min, and then is also used as a carrier/reactant gas for the solution when the decarboxylation reaction takes place. One can also control the product yield of the decarboxylation reaction by varying the concentration or flow rate of the carboxylic acid/carboxylate solution. In one embodiment, an aqueous solution of butyric acid is prepared with an acid concentration ranging from 4 wt % to 90 wt % and is pumped into a heated reactor at a rate of 0.01 to 0.05 mL/min. The vapor stream coming out of the outlet of the reactor can be cooled in a condenser where the liquid and gas phases of the stream separate. As already described above, the liquid phase can be sampled at regular intervals throughout the decarboxylation process while the gas phase flows from the top of the condenser to be collected or analyzed by an on-line instrument such as a gas chromatograph (GC) equipped with a flame ionization detector (FID). The collected liquid samples can be analyzed with, e.g., a GC with FID. Without further elaboration, it is believed that the above description has adequately enabled the present invention. The following examples are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. All of the publications cited herein are hereby incorporated by reference in their entirety. A 1 wt % Pt/Al2O3 catalyst was prepared in house by incipient wetness impregnation. To prepare the catalyst, the substrate Al2O3 (Puralox®, SBET=210 m2/g) was impregnated with an aqueous solution of Pt(NH3)4(NO3)2, the volume of which equaled the total pore volume of Al2O3 (˜0.5 ml/g), at room temperature. After impregnation, the sample was dried in vacuum at 80° C. overnight and calcined in air at 200° C. for 1 h. The resulting material had very highly dispersed Pt on the alumina surface. The decarboxylation of aqueous solutions of butyric acid was performed over the Pt/Al2O3 catalyst at atmospheric pressure in the continuous flow reactor described above. The catalyst loading was kept constant at 0.2 g throughout. The weight hourly space velocity (WHSV), defined here as grams of acid per gram catalyst per hour (gacid/gcat/hr) or as h−1 for brevity, was varied (0.9-2.7 h−1) by changing the feed concentration of the reactant butyric acid solution (30-90 wt % butyric acid in water). Prior to reaction the catalyst was reduced with 99.99% H2 gas. In a reduction treatment, the catalyst sample was heated to 300° C. at a rate of 2° C. per minute and held at 300° C. for 30 minutes under a flow of H2 gas flowing at 50 mL/min at atmospheric pressure. The pretreatment gas was also used as a carrier/reactant gas for the decarboxylation reaction. The reaction temperature was varied from 300° C. to 400° C., and cycled back to 350° C. to check for deactivation. The Pt/Al2O3 catalyst reached a steady state after about 30 minutes of time-on-stream. The major product was found to be propane with the two different space velocities resulting in similar conversions, as indicated in Table 1 below shows the selectivity to different gaseous hydrocarbons for each test. As indicated by the results listed in Table 1, the Pt/Al2O3 catalyst is highly selective for catalyzing decarboxylation of butyric acid to form propane. The small amounts of methane and ethane indicate the presence of carbon cracking side reactions at higher temperatures. A small amount of the butyric acid was also hydrogenated to yield butane. The liquid samples collected from the reactor did not show any other products upon analysis by gas chromatography. Only butyric acid was detected, indicating high selectivity towards the hydrocarbon gases. The decarboxylation of butyric acid was carried out using a 5 wt % Pd/C catalyst obtained from Alfa Aesar. The catalyst was reduced at 300° C. using a ramp of 2° C. per minute under 99.99% hydrogen gas. The catalyst was tested using a feed solution of 30 wt % butyric acid at a temperature of 300-400° C., using hydrogen as a carrier/reactant gas. The results are shown in The conversion of butyric acid increased with temperature while the selectivity to propane remained very high. Minimal cracking products were observed at elevated temperatures (400° C.). The analysis of the condensed liquid from the separator indicated no other liquid phase products. Some deactivation was observed while the reaction temperature was maintained at 400° C. This is reflected in the lower conversion to propane upon cycling the temperature back down to 350° C. Tests carried out using lower space velocities (WHSV=0.06-0.24 h−1) with both unreduced and reduced Pd/C catalysts using He and 5% H2/He as the carrier gas at 90 psig exhibited high selectivity for decarboxylation and dehydrogenation, with >95 vol. % of the CO2-free gaseous products being propane and propylene. Other hydrocarbons observed in the gas product mixture were very small amounts of methane and ethane (i.e., products of subsequent carbon cracking reactions) and trace amounts of butane (<0.3 vol. %, product of hydrogenation of butyric acid). Upon comparing the amount of CO2 to the C3 hydrocarbons in the product gas stream, a molar ratio of 0.93 CO2 to 1.0 (propane and propylene) was observed. Butyric acid was the only organic compound found in the liquid stream exiting the bottom of the condenser. A Pt-based catalyst was prepared on multi-walled carbon nanotubes (MWNT) obtained from Cheap Tubes, Inc., (length: 10-30 μm long; 20-30 nm OD). A 1 wt % Pt/MWNT catalyst was prepared by incipient wetness impregnation as described in Example 1. Prior to impregnation, the MWNTs were treated in nitric acid at 120° C. for 4 hours in order to create acidic surface functionality. The catalyst was reduced under 99.99% hydrogen at 400° C. for 30 minutes using a ramp of 1° C. per minute. After reduction, the temperature was reduced to a reaction temperature of 327° C. The reaction was carried out at a space velocity of 9 h−1. Some steady catalyst deactivation was observed as the butyric acid conversion decreased over the course of 48 hours. However, the selectivity to propane remained very high, at a minimum of ˜92%. A Pt-based catalyst, 1 wt % Pt/L-Zeolite, was prepared using the incipient wetness impregnation technique described in Example 1. The L-Zeolite support (pore volume˜0.7 mL/g) was impregnated with Pt(NH3)4(NO3)2. The catalyst (0.2 g) was reduced at 300° C. (using a ramp of 2° C. per minute) under 99.99% H2 gas for 30 minutes under atmospheric pressure. The reaction was conducted using the pretreatment gas as the carrier/reactant and the temperature was varied from 300° C. to 400° C. at a space velocity of 0.9 h−1 (based on catalyst loading and acid flow). The highest butyric acid conversion of ˜50% was observed at 400° C. The selectivity to propane was maintained at 97-100% throughout the reaction. A 3 wt % Au/Co3O4 catalyst was prepared in house. The cobalt oxide powder was prepared in nanoparticle (4-5 nm size) form according to a surfactant-free preparation method described in Nanotech. 18 (2007) 435-602 and the gold was added by a urea-based deposition-precipitation technique aimed at dispersing the gold on the surface of the support, e.g. following the method described in J. Phys. Chem. B 106 (2002) 7634-7642. The catalyst was tested for the decarboxylation of a 30 wt % aqueous butyric acid feed. The catalyst was reduced at 250° C. (heating at 2° C. per minute) for 30 minutes under hydrogen gas. The reaction was carried out in the pretreatment gas (99.99% hydrogen) under atmospheric pressure. The temperature was varied from 250° C. to 400° C. The space velocity based on the butyric acid solution flow rate and the catalyst loading was 1.8 h−1. The catalyst was active at higher temperatures, reaching a total conversion of 15% at 400° C., with the highest selectivity to propylene (˜55%). Selectivity to other hydrocarbon gas products was observed, including propane (˜20%), ethane (˜4%), ethylene (˜6%) and methane (˜15%), indicating some degree of cracking. The above examples demonstrate the suitability of several supported metal catalyst systems for the decarboxylation of aqueous solutions of short-chain carboxylic acids to produce gaseous hydrocarbon fuels. Depending on the choice of metal and its particle size and loading amount as well as the choice of the support, the decarboxylation can take place at mild conditions of pressure and temperature. In some cases, the carrier gas can be hydrogen-free. Examples of the carrier gas include but are not limited to an inert gas (He or nitrogen) and part of the CO2. All of the features disclosed in this specification may be combined in any combination. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features. From the above description, one skilled in the art can easily ascertain the essential characteristics of the present invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. Thus, other embodiments are also within the scope of the following claims. |
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