# Patent

## Title
Catalysts and methods for reforming oxygenated compounds

## Abstract

Disclosed are catalysts and methods that can reform aqueous solutions of oxygenated compounds such as ethylene glycol, glycerol, sugar alcohols, and sugars to generate products such as hydrogen and alkanes. In some embodiments, aqueous solutions containing at least 20 wt % of the oxygenated compounds can be reformed over a catalyst comprising a Group VIII transition metal and a Group VIIB transition metal, preferably supported on an activated carbon-supported catalyst. In other embodiments, catalysts are provided for the production of hydrogen or alkanes at reaction temperatures less than 300° C.

## Background
This application is a 371 of PCT/US2006/048030 filed Dec. 18, 2006, which claims the benefit of provisional application SN 60/752,485 filed Dec. 21, 2005.


FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
This invention was made with United States government support awarded by DOC NIST ATP Grant No 70NANB3H3014 and DOE Grant No. DE-FG36-04GO14258. The United States has certain rights in this invention.


TECHNICAL FIELD
The present invention is directed to catalysts and methods for reforming oxygenated compounds, including biomass-derived compounds, to form products such as hydrogen or alkanes via reforming processes, such as aqueous-phase reforming. Catalysts and processes disclosed herein can be used, for example, to reform aqueous solutions of glycerol, sugar alcohols, sugars or polyols such as ethylene glycol and propylene glycol, as well as hydrocarboxylic acids.
BACKGROUND
There are finite quantities of nonrenewable fossil fuels such as crude oil and natural gas that are currently being utilized to generate energy. Biomass (plant-derived material) is one the most important renewable energy resources. The conversion of biomass to fuels, chemicals, materials and power reduces the dependence on foreign oil and natural gas. Currently, biomass provides the only renewable alternative for liquid transportation fuel. Biomass use strengthens rural economies, decreases America's dependence on imported oil, reduces air and water pollution, and reduces greenhouse gas emissions.
A key challenge for promoting and sustaining the vitality and growth of the industrial sector is to develop efficient and environmentally benign technologies for generating fuels, such as hydrogen, from renewable resources. The generation of energy from renewable resources such as biomass, reduces the net rate of production of carbon dioxide, an important greenhouse gas that contributes to global warming. This is because the biomass itself consumes carbon dioxide during its life cycle.
Aqueous-Phase Reforming (APR) is a catalytic reforming process that generates hydrogen-rich fuel gas from oxygenated compounds derived from biomass (glycerol, sugars, sugar alcohols). The resulting fuel gas may be used as a fuel source for electricity generation via PEM fuel cells, solid-oxide fuel cells, internal combustion engines genset, or gas turbine genset. APR processes may generate light hydrocarbons (e.g. methane, ethane, propane, butane, propane, and hexane) and/or hydrogen by the reaction of oxygenated compounds with liquid water at low temperatures (e.g., less than 300° C.). The key breakthrough of the APR process is that the reforming can be done in the liquid phase. The APR process can occur at temperatures (e.g., 150° C. to 270° C.) where the water-gas shift reaction is favorable, making it possible to generate hydrogen with low amounts of CO in a single chemical reactor. Advantages of the APR process include: (i) performing the reaction at pressures (typically 15 to 50 bar) where the hydrogen-rich effluent can be effectively purified; (ii) generation of hydrogen-rich fuel gas at low temperatures without the need to volatilize water, which represents a major energy saving; (iii) operation at temperatures where the water-gas shift reaction is favorable, making it possible to generate high quality fuel gas with low amounts of CO in a single chemical reactor, (iv) operation at temperatures which minimize undesirable decomposition reactions typically encountered when carbohydrates are heated to elevated temperatures, and (v) utilization of agricultural derived feedstocks found in the United States.
The APR process takes advantage of the thermodynamic properties of oxygenated compounds containing a C:O stoichiometry of 1:1 to generate hydrogen from these oxygenated compound at relatively low temperatures in a single reaction step (see FIG. 1), in contrast to certain multi-reactor systems used for producing hydrogen via steam reforming of hydrocarbons. FIG. 1 was constructed from thermodynamic data obtained from Chemical Properties Handbook, C. L. Yaws, McGraw Hill, 1999.
Reaction conditions for producing hydrogen from hydrocarbons can be dictated by the thermodynamics for the steam reforming of the alkanes to form CO and H2 (reaction 1) and the water-gas shift reaction to form CO2 and H2 from CO (reaction 2).

CnH2n+2+nH2O⇄nCO+(2n+1)H2  (1)

CO+H2O⇄CO2+H2  (2)

FIG. 1 shows changes in the standard Gibbs free energy (ΔGo/RT) associated with reaction 1 for a series of alkanes (CH4, C2H6, C3H8, C6H14), normalized per mole of CO produced. The steam reforming of alkanes is thermodynamically favorable (i.e., negative values of ΔGo/RT) at temperatures higher than about 675 K. Oxygenated hydrocarbons having a C:O ratio of 1:1 produce CO and H2 according to reaction 3.

CnH2yOn⇄nCO+yH2  (3)

Relevant oxygenated hydrocarbons having a C:O ratio of 1:1 include methanol (CH3OH), ethylene glycol (C2H4(OH)2), glycerol (C3H5(OH)3), and sorbitol (C6H8(OH)6). On FIG. 1, dotted lines show values of 1n(P) for the vapor pressures versus temperature of CH3(OH), C2H4(OH)2, C3H5(OH)3, and C6H8(OH)6 (pressure in units of atm). FIG. 1 shows that steam reforming of these oxygenated hydrocarbons to produce CO and H2 may be thermodynamically favorable at significantly lower temperatures than those required for alkanes with similar numbers of carbon atoms. Accordingly, the steam reforming of oxygenated hydrocarbons having a C:O ratio of 1:1 would offer a low-temperature route for the formation of CO and H2. FIG. 1 also shows that the value of ΔGo/RT for water-gas shift of CO to CO2 and H2 is more favorable at lower temperatures. Therefore, it is possible to produce H2 and CO2 from steam reforming of oxygenated compounds utilizing a single-step catalytic process, since the water-gas shift reaction is favorable at the same low temperatures where steam reforming of carbohydrates is possible.
While FIG. 1 shows that the conversion of oxygenated compounds in the presence of water to H2 and CO2 is highly favorable at this low temperature, the subsequent reaction of H2 and CO2 to form alkanes (CnH2n+2) and water is also highly favorable at low temperatures. For example, the equilibrium constant at 500 K for the conversion of CO2 and H2 to methane (reaction 4) is of the order of 1010 per mole of CO2.

CO2+4H2⇄CH4+2H2O  (4)

The reforming reaction can be optimized not only to yield hydrogen, but to yield hydrocarbons. For example, the complete reforming of sorbitol yields 13 moles of hydrogen for every 6 moles of CO2 produced:

C6H14O6+6H2O→6CO2+13H2  (5)

However, the more thermodynamically favored reaction consumes the hydrogen to yield a mixture of water and hydrocarbons:

C6H14O6+xH2→aH2O+bCH4+cC2H6+dC3H8+eC4H10+fC5H12+gC6H14  (6)

Referring to FIG. 2, the individual reactions for the production of methane, ethane, and hexane are all thermodynamically favored (i.e., ΔGo/RT<0) across the entire temperature range presented in the graph. Moreover, production of these hydrocarbons is more favorable than the generation of hydrogen from the reaction of water with sorbitol. The thermodynamics for the formation of propane, butane, and pentane fit smoothly within the homologous series (between ethane and hexane), but these traces have been omitted from FIG. 2 for clarity. Thus, as described in full below, the present reaction can be optimized to yield a product mixture comprising almost exclusively hydrocarbons rather than hydrogen. FIG. 2 was constructed from thermodynamic data obtained from Chemical Properties Handbook, C. L. Yaws, McGraw Hill, 1999.
U.S. Pat. No. 6,699,457 to Cortright et al., as well as published U.S. patent application US 2005/0207971 A1 with Ser. No. 11/124,717 and filed May 9, 2005, which are incorporated herein by reference, disclose a method of producing hydrogen from oxygenated hydrocarbon reactants, including examples showing conversion of feedstocks comprising up to 10% glycerol, glucose, or sorbitol to hydrogen. The method can take place in the vapor phase or in the condensed liquid phase. The method can include the steps of reacting water and a water-soluble oxygenated hydrocarbon having at least two carbon atoms, in the presence of a metal-containing catalyst. The catalyst contains a metal selected from the group consisting of Group VIII transitional metals, alloys thereof, and mixtures thereof. The disclosed method can be run at lower temperatures than those used in the conventional steam reforming of alkanes.
U.S. Pat. No. 6,953,873 to Cortright et al., which is incorporated herein by reference, discloses a method of producing hydrocarbons from oxygenated hydrocarbon reactants, such as glycerol, glucose, or sorbitol. The method can take place in the vapor phase or in the condensed liquid phase (preferably in the condensed liquid phase). The method can include the steps of reacting water and a water-soluble oxygenated hydrocarbon having at least two carbon atoms, in the presence of a metal-containing catalyst. The catalyst can contain a metal selected from the group consisting of Group VIIIB transitional metals, alloys thereof, and mixtures thereof. These metals can be supported on supports that exhibit acidity or the reaction is conducted under liquid-phase conditions at acidic pHs. The disclosed method allows the production of hydrocarbon by the liquid-phase reaction of water with biomass-derived oxygenated compounds.
U.S. Pat. Nos. 6,964,757 and 6,964,758 to Cortright et al., which are incorporated herein by reference, disclose a method of producing hydrogen from oxygenated hydrocarbon reactants, such as methanol, glycerol, sugars (e.g. glucose and xylose), or sugar alcohols (e.g. sorbitol). The method can take place in the condensed liquid phase. The method can include the steps of reacting water and a water-soluble oxygenated hydrocarbon in the presence of a metal-containing catalyst. The catalyst contains a metal selected from the group consisting of Group VIIIB transitional metals, alloys thereof, and mixtures thereof. The disclosed method can be run at lower temperatures than those used in the conventional steam reforming of alkanes.
U.S. Pat. No. 4,223,001 to Novotny et al. discloses methods of generating hydrogen from an aqueous feedstock comprising a water-soluble alcohol, such as methanol or ethylene glycol, using a catalyst comprising a Group VIII metal, such as a homogeneous rhodium-containing catalyst (e.g., RhCl3.3H2O in the aqueous phase.
Cortright et al. describe the conversion of oxygenated compounds, methanol, ethylene glycol, glycerol, sorbitol, and glucose via aqueous phase reforming over a 3% Pt/Al2O3 catalyst. Reaction temperatures ranged from 498 to 538 K, system pressures ranged between 29 and 56 bar, and feed concentrations of 1 wt % oxygenated compound. Cortright, R. D.; Davda, R. R.; Dumesic J. A., Nature, Vol. 418, p. 964, 2002.
Davda et al. describe reaction kinetic studies of aqueous-phase reforming of 10 wt % ethylene glycol solutions over silica-supported metal catalysts. Reaction temperatures for this investigation were 483 and 498 K and reaction pressure of 22 bar. Results from this paper show that the overall catalytic activity of these catalyst decreases in the following order: Pt ̃Ni>Ru>Rh ̃Pd>Ir. Davda, R. R.; Shabaker J. W.; Huber, G. W.; Cortright, R. D.; Dumesic, J. A.; Appl. Cat. B: Environmental, Vol 43, p. 13, 2003.
Shabaker et al. describe reaction kinetic studies of aqueous-phase reforming of 10 wt % ethylene glycol solutions over Pt-black and Pt supported on TiO2, Al2O3, activated carbon, SiO2, SiO2—Al2O3, ZrO2, CeO2, and ZnO. Reaction temperatures were 483 and 498 K, and the reaction pressures were 22.4 and 29.3 bar, respectively. High activity for the production of H2 by aqueous-phase reforming was observed over Pt-black and over Pt supported on TiO2, carbon, and Al2O3; moderate catalytic activity for the production of hydrogen is demonstrated by Pt supported on SiO2—Al2O3 and ZrO2; and lower catalytic activity is exhibited by Pt supported on CeO2, ZnO, and SiO2. Pt supported on Al2O3, and to a lesser extent ZrO2, exhibits high selectivity for production of H2 and CO2 from aqueous-phase reforming of ethylene glycol. Shabaker, J. W.; Huber, G. W.; Davda, R. R.; Cortright, R. D.; Dumesic, J. A.; Catalysis Letters, Vol. 88, p. 1, 2003.
Davda et al. describe reaction conditions desired to generate hydrogen with low concentrations of CO via aqueous-phase reforming of ethylene glycol over a 3% Pt/Al2O3 catalyst. Reaction temperatures ranged from 498 K to 512 K, system pressure between 25.8 to 36.2 bar, and ethylene feed concentrations between 2 and 10 wt %. Davda, R. R; Dumesic J. A.; Angew. Chem. Int. Ed., Vol. 42, p. 4068, 2003.
Huber et al. describe the reaction of sorbitol to produce C1 through C6 alkanes over platinum-based catalyst with varying amounts of hydrogen added as a co-feed. In this paper, the platinum was loaded on either alumina or silica-alumina. This paper discussed the mechanism for this process through a bi-functional route involving acid-catalyzed dehydration reaction followed by a metal catalyzed hydrogenation reaction. Reaction temperatures were between 498 and 538 K, pressures between 25.8 to 60.7 bar, and feed concentrations of 5 wt % sorbitol. Huber, G. W.; Cortright, R. D.; Dumesic, J. A., Angew. Chem. Int. Ed., Vol. 43, p. 1549, 2004.
Davda et al. review aqueous-phase reforming of oxygenated compounds. Discussed are the effects of supports, supported metals, reaction conditions, and reactor configurations. Concentrations of oxygenated compounds were less than 10% in this paper. Davda, R. R.; Shabaker J. W.; Huber, G. W.; Cortright, R. D.; Dumesic, J. A.; Appl. Cat. B: Environmental, Vol 56, p. 171, 2005.
Huber et al. describe the effectiveness of tin modified nickel-based catalyst for the aqueous-phase reforming of oxygenated compounds such as ethylene glycol, glycerol, and sorbitol at 498 K and 538 K. Concentrations of oxygenated compounds studies in this investigation were less than 5 wt %. Huber, G. W.; Shabaker, J. W.; Dumesic, J. A.; Science, Vol. 300, p. 2075, 2003.
Previous patents and literature describe methods for the aqueous-phase reforming of water soluble oxygenated compounds at concentrations of 10 wt % or lower. Energy balances on the APR system indicate that significant energy losses can occur because of vaporization of water in the reactor system to maintain the partial pressure of water in the hydrogen gas bubbles formed in the reactor.
Thus, there exists a need for catalyst systems and processes that have higher activity levels to support high conversion of high concentrations of oxygenated hydrocarbon feedstocks in an aqueous reforming system.
SUMMARY
In a first embodiment, reforming catalysts are provided. The reforming catalysts preferably comprise a mixture of Group VIIB and Group VIII transition metals and mixtures thereof. Preferably, the reforming catalyst comprises Re and at least one transition metal selected from the group consisting of: Ir, Ni, Pd, Pt, Rh and Ru. Optionally, the catalyst further comprises Ce or La. Examples of suitable bimetallic catalysts include: IrRe, NiRe, PdRe, PtRe, Rh3Re, RhRe, and RuRe. Pt1.0Re2.5 is an example of one particularly preferred catalyst.
The reforming catalyst can be adhered to an aqueous-stable support. For example, the catalyst can be adhered to a support comprising one or more materials selected from the group consisting of: carbon, zirconia, titania or ceria. Preferably, the catalyst is adhered to a carbon support. Carbon supports can be modified with other materials such as titanium, vanadium, tungsten or rhenium. In one particular aspect, the catalyst can be adhered to a support such that the combination of the catalyst and the support comprises 0.25%-10% by weight of the Group VIII metal on the catalyst, and the catalyst comprises Re and the Group VIII metal. The atomic ratio of Re to the Group VIII metal is preferably between 0.25 to 10. One preferred catalyst comprises Pt1.0Re2.5 adhered to a carbon support.
In a second embodiment, methods of reforming an oxygenated hydrocarbon from a feedstock solution of oxygenated hydrocarbon are provided that comprise the step of contacting the feedstock solution with a reforming catalyst. The oxygenated hydrocarbon is preferably a water-soluble hydrocarbon, including polyol compounds, with any suitable number of carbon atoms, such as water-soluble oxygenated hydrocarbons with 1 to 12 carbon atoms, preferably 1 to 6 carbons. Examples of preferred oxygenated hydrocarbons include ethylene glycol, glycerol, and sorbitol. Methods of reforming an oxygenated hydrocarbon include methods of producing hydrogen, as well as methods of producing mixtures of hydrogen and alkanes, from one or more oxygenated hydrocarbons in a feedstock. The feedstock solution can be an aqueous solution with at least 20 weight percent of the total feedstock solution of an oxygenated hydrocarbon having at least one oxygen. For example, the feedstock solution can comprise at least about 20%, 30%, 40%, or 50% of the oxygenated hydrocarbon.
The feedstock solution can be contacted with the reforming catalyst under conditions of reaction temperature and reaction pressure effective to produce hydrogen gas, as described herein. The reaction temperature and pressure are preferably selected to maintain the feedstock in the liquid phase. For example, the reaction temperature can be between about 80° C. and about 300° C. and the reaction pressure can be between about 10 bar (145 psi) and about 90 bar (1300 psi). More preferably, the reaction temperature can be between about 120° C. and about 300° C., even more preferably between about 150° C. and about 300° C., and the reaction pressure can be between about 10 bar (145 psi) and about 50 bar (725 psi). Liquid-phase modifiers such as water-soluable salts of alkali or alkali earth metals can optionally be added to the feedstock at a range of between 0.1 to 10 wt % of the aqueous-solution to optimize reaction products. For example, addition of compounds to increase the pH of the feedstock can increase the amount of hydrogen production in the reaction products.
The methods of reforming oxygenated hydrocarbons may produce a variety of useful reaction products, such as hydrogen, carbon dioxide and/or light hydrocarbons (e.g., methane, ethane, propane, butane, and pentane) from a feedstock comprising sorbitol or glycerol. In one aspect, methods of alkane production are provided that include contacting the feedstock solution with a reforming catalyst. The feedstock may include an aqueous solution having about 10-60% of one or more C1-C6 oxygenated hydrocarbon, preferably glycerol, ethylene glycol, and/or sorbitol. The feedstock may be contacted with a catalyst comprising one or more metals selected from the group consisting of platinum, rhodium and rhenium. In another aspect, methods of hydrogen production are provided that includes contacting the feedstock solution with a suitable reforming catalyst, as described herein.
In a third embodiment, methods of making a reforming catalyst are provided. In one aspect, a method of preparing a catalyst can include the step of oxidizing a carbon support by heating the carbon support to a temperature of about 450° C., introducing air to form an activated carbon support, and contacting the carbon support with a catalyst. For example, activated carbon can be heated to a desired temperature in a stream of inert gas, such as nitrogen, and then contacted with a stream of air at a suitable flow rate, added to the nitrogen. The carbon can be treated for a suitable period and then allowed to cool under flowing nitrogen. The method of preparing a catalyst further comprises the step of incorporating a metal oxide in the activated carbon support by incipient wetting of the activated carbon support with a solution comprising a metal alkoxide comprising the metal oxide. Preferably, the metal oxide is incorporated without suspending the carbon support in solvent. For example, functionalized carbon surfaces can be modified by impregnation of metal oxides prior to impregnation of catalyst precursors. Organic solutions of suitable metal oxides, such as titanium n-butoxide or vanadium oxide triisopropoxide in anhydrous isopropanol, can be added by incipient wetting to air oxidation functionalized carbon, and the wetted carbon can be subsequently dried.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph depicting the thermodynamics for the conversion of hydrocarbons and oxygenated hydrocarbons to carbon monoxide and hydrogen (H2);
FIG. 2 is a graph depicting the thermodynamics for the conversion of sorbitol to hydrogen, carbon dioxide, water and various hydrocarbons;
FIG. 3 is a graph depicting the effect of feed composition on thermal efficiency at 100% conversion in an aqueous phase reforming system;
FIG. 4 is a schematic diagram of a reactor system that can be used to evaluate the aqueous phase reforming activity of catalysts according to an embodiment of the present invention; and
FIG. 5 is a graph depicting the conversion of Glycerol to Gas Phase Products using aqueous phase reforming according to one embodiment of the present invention.



DETAILED DESCRIPTION
Various methods are described herein for reforming high concentrations of oxygenated hydrocarbons with water at low temperatures and in the liquid-phase. Unless otherwise indicated, the following terms shall be defined herein as indicated below.
The term “reforming” shall generically denote the overall reaction of an oxygenated hydrocarbon and water to yield a product mixture comprising hydrocarbons and/or hydrogen and CO2, regardless of whether the reaction takes place in the gaseous phase or in the condensed liquid phase. Where the distinction is important, it shall be so noted.
The term “Group VIII” transition metal refers to an element selected from the group consisting of: Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Hs, Mt and Ds, in any oxidation state.
The term “Group VIIB” transition metal refers to an element selected from the group consisting of: Mn, Tc, Re and Bh, in any oxidation state.
When the reforming of oxygenated hydrocarbons is carried out in the liquid phase, the present invention makes it possible to produce hydrocarbons from aqueous solutions of oxygenated hydrocarbons having limited volatility, such as sugars (glucose and xylose) and heavier molecular weight polyols such as xylitol and sorbitol.
Abbreviations and Definitions:
“GC”=gas chromatograph or gas chromatography.
“GHSV”=gas hourly space velocity.
“psig”=pounds per square inch relative to atmospheric pressure (i.e., gauge pressure).
“Space Velocity”=the mass/volume of reactant per unit of catalyst per unit of time.
“TOF”=turnover frequency.
“WHSV”=weight hourly space velocity=mass of oxygenated compound per mass of catalyst per h.
“WGS”=water-gas shift.
Oxygenated Hydrocarbons
Oxygenated hydrocarbons for the reforming processes described herein are preferably water-soluble. Desirably, the oxygenated hydrocarbon has from 1 to 12 carbon atoms, and more preferably from 1 to 6 carbon atoms. For feedstock concentrations of about 30% oxygenated hydrocarbons with 1 to 6 carbon atoms are particularly preferred. Preferred oxygenated hydrocarbons comprise at least 1 oxygen atom in the oxygenated hydrocarbon, and oxygen-to-carbon ratios ranging from 0.50:1.00 to 1.50:1.00, including ratios of 0.25:1.00, 0.33:1.00, 0.66:1.00, 0.75:1.00, 1.00:1.00, 1.25:1.00, 1.5:1.00, as well as ratios therebetween. Preferably oxygenated hydrocarbons have an oxygen-to-carbon ratio of 1:1. The oxygenated hydrocarbon can also be a polyol. Nonlimiting examples of preferred water-soluble oxygenated hydrocarbons can be selected from the group consisting of: methanol, ethanol, ethanediol, ethanedione, acetic acid, propanol, propanediol, propionic acid, glycerol, glyceraldehyde, dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, butanediols, butanoic acid, aldotetroses, tautaric acid, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, and alditols. From among the 6-carbon oxygenated hydrocarbons, aldohexoses and corresponding alditols are particularly preferred, with glucose and sorbitol being the most preferred. Xylose, arabinose, arabinol and xylitol are particularly preferred oxygenated compounds having 5 carbon atoms. Sucrose is a preferred oxygenated hydrocarbon having more than 6 carbon atoms.
Vapor-phase reforming requires that the oxygenated hydrocarbon reactants have a sufficiently high vapor pressure at the reaction temperature so that the reactants are in the vapor phase. In particular, the oxygenated hydrocarbon compounds preferred for use in the vapor phase method of the present invention include, but are not limited to, methanol, ethanol, ethanediol, glycerol, and glyceraldehyde. When the reaction is to take place in the liquid phase, sugars such as sucrose, glucose, xylose and polyols such as xylitol and sorbitol are the most preferred oxygenated hydrocarbons.
In the methods of the present invention, the oxygenated hydrocarbon compound is preferably combined with water to create an aqueous solution. The water-to-carbon ratio in the solution is preferably from about 0.5:1 to about 7:1, including ratios therebetween such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1 and any ratios between these values. This range is provided as one example of a non-limiting, preferred range. Water-to-carbon ratios outside this range are also included within the scope of this invention. The feedstock solution can be an aqueous solution with at least 20 weight percent of the total feedstock solution of an oxygenated hydrocarbon having at least one oxygen. For example, the feedstock solution can comprise at least about 20%, 30%, 40%, 50% or 60% of one or more oxygenated hydrocarbons. Unless otherwise specified, references to a percentage of oxygenated hydrocarbon in the feedstock refers to the total amount oxygenated hydrocarbon species in the feed stock solution, which can include mixtures of multiple oxygenated hydrocarbon species.
Preferably the balance of the feedstock solution is water. In some embodiments, the feedstock solution consists essentially of water, one or more oxygenated hydrocarbons, and, optionally, one or more of the feedstock modifiers described herein, such as alkali or alkali earth salts or acids. The feedstock solution can preferably contain negligible amounts of hydrogen, preferably less than about 1 bar partial pressure. In preferred embodiments, hydrogen is not added to the feedstock.
An aqueous reforming process can be operated at feed concentrations in this range using different catalysts. For example, Shabaker et al. describe the aqueous-phase reforming of 5 and 63 wt % solutions of ethylene glycol of a NiSn catalyst. Shabaker, J. W.; Simonetti, D. A.; Cortright, R. D.; Dumesic, J. A.; J. Catal., Vol. 231, p. 67, 2005. As FIG. 3 shows, the thermal efficiency of the system can be improved by operating the system with higher concentrations of feedstock. FIG. 3 shows that as the feed concentration is increased from 10 wt % to 60 wt %, the calculated efficiency of the system increases from less that 10% to greater than 80% at a 100% conversion of the ethylene glycol. FIG. 3 was constructed using thermodynamic and vapor pressure data taken from Chemical Properties Handbook, C. L. Yaws, McGraw Hill, 1999.
Catalysts
The metallic catalyst systems preferred for use in the present invention comprise of one or more Group VIII metal combined with one or more of a Group VIIB metal. The preferred Group VIIB metals would be rhenium or manganese. The preferred Group VIII metals would be platinum, rhodium, ruthenium, palladium, nickel or combination thereof. Preferred loadings of the Group VIII metals would be in the range of 0.25 wt % to 25 wt % on the carbon including weight percentages of 0.10% and 0.05% increments between these values, such as 1.00%, 5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio of the Group VIIB to the Group VIII metal is in the range of 0.25-to-1 to 10-to-1, including ratios therebetween such as 0.50, 1.00, 2.50, 5.00, and 7.50-to-1.
The preferred catalyst composition is further achieved by the addition of oxides of Group IIIB and the associated rare earth oxides. In this case the preferred components would be oxides of either lanthanium or cerium. The preferred atomic ratio of the Group IIIB compounds to the Group VIII metal is in the range of 0.25-to-1 to 10-to-1, including ratios therebetween such as 0.50, 1.00, 2.50, 5.00, and 7.50-to-1.
Unless otherwise specified, the recitation of a catalyst composition as “X:Y” herein, where X and Y are metals, refers to a group of catalyst compositions comprising at least metals X and Y in any suitable stoichiometric combination, and optionally including other materials. Similarly, the recitation of a catalyst composition as “X1.0Y1.0” refers herein to a composition comprising at least metals X and Y in a 1:1 stoichiometric molar ratio. Accordingly, particularly preferred catalytic compositions are bimetallic metal compositions described by the formula X:Y, where X is a Group VIII metal and Y is a Group VIIB metal. For example, the catalysts designated “Re:Pt” include the bimetallic catalysts Re1.0Pt1.0 and Re2.5Pt1.0. Furthermore, recitation of a bimetallic catalyst X:Y can include additional materials besides X and Y, such as La or Ce. For example, the catalysts designated “Re:Rh” herein include catalysts such as Re1.0Rh1.0, Re1.0Rh3.8, Re1.0Rh2.0Ce2.0, Re1.0Rh1.0Ce1.0, and Re1.0Rh1.0La3.0.
In some embodiments, the catalysts can be provided with a suitable support. Catalyst systems can be supported on a form of support that is stable at the chosen reaction conditions. Any suitable support can be used, but supports are preferably sufficiently stable in a feedstock solution, such as an aqueous feedstock solution, to function at a desired level. One particularly preferred catalyst support is carbon. It is preferred that such carbon supports have relatively high surface areas (greater than 100 square meters per gram). Such carbons include activated carbon (granulated, powdered, or pelletized), activated carbon cloth, felts, or fibers, carbon nanotubes or nanohorns, carbon fullerene, high surface area carbon honeycombs, carbon foams (reticulated carbon foams), and carbon blocks. The carbon may be produced via either chemical or steam activation of peat, wood, lignite, coal, coconut shells, olive pits, and oil based carbon. One preferred support is granulated activated carbon produced from coconuts. Other useful catalyst supports for the practice of the invention include, but are not limited to: silica, silica-alumina, and alumina. Preferably, the catalyst system is platinum on silica or silica-alumina, with the platinum being further alloyed or admixed with nickel or ruthenium. The support may also be treated, as by surface-modification, to modify surface moieties such hydrogen and hydroxyl. Surface hydrogen and hydroxyl groups can cause local pH variations that would affect catalytic efficiency. The support can be modified, for example, by treating it with a modifier selected from the group consisting sulfates, phosphates, tungstenates, and silanes.
It is preferred that the chosen carbon may be pretreated with either steam, oxygen (from air), inorganic acids, or hydrogen peroxide to provide more surface oxygen sites. The preferred pretreatment would be to use either oxygen (from air) or hydrogen peroxide.
The pretreated carbon can be modified by the addition of oxides of Group IVB and Group VB. It is preferred to use oxides of titanium, vanadium, zirconia and mixtures thereof.
The catalyst systems of the present invention can be prepared by conventional methods known to those in the art. These methods include evaporative impregnation techniques, incipient wetting techniques, chemical vapor deposition, wash-coating, magnetron sputtering techniques, and the like. The method chosen to fabricate the catalyst is not particularly critical to the function of the invention, with the proviso that different catalysts will yield different results, depending upon considerations such as overall surface area, porosity and the like.
Reforming Methods
The liquid phase reforming method of the present invention should generally be carried out at a temperature at which the thermodynamics of the proposed reaction are favorable. The pressure selected for the reactions varies with the temperature. For condensed phase liquid reactions, the pressure within the reactor must be sufficient to maintain the reactants in the condensed liquid phase at the reactor inlet.
The vapor phase reforming method of the present invention should be carried out at a temperature where the vapor pressure of the oxygenated hydrocarbon compound is at least about 0.1 atm (and preferably a good deal higher), and the thermodynamics of the reaction are favorable. This temperature will vary depending upon the specific oxygenated hydrocarbon compound used, but is generally in the range of from about 100° C. to about 450° C. for reactions taking place in the vapor phase, and more preferably from about 100° C. to about 300° C. for vapor phase reactions. For reactions taking place in the condensed liquid phase, the preferred reaction temperature should not exceed about 300° C.
The condensed liquid phase method of the present invention may also optionally be performed using a modifier that increases the activity and/or stability of the catalyst system. It is preferred that the water and the oxygenated hydrocarbon are reacted at a suitable pH of from about 1.0 to about 10.0, including pH values in increments of 0.1 and 0.05 therebetween. Generally, the modifier is added to the feedstock solution in an amount ranging from about 0.1% to about 10% by weight as compared to the total weight of the catalyst system used, although amounts outside this range are included within the present invention.
Optionally, alkali or alkali earth salts can be added to the feedstock solution to optimize the proportion of hydrogen in the reaction products. Examples of suitable water-soluble salts include one or more selected from the group consisting of an alkali or an alkali earth metal hydroxide, carbonate, nitrate, or chloride salt. For example, adding alkali (basic) salts to provide a pH of about pH 4 to about pH 10 can improve hydrogen selectivity of reforming reactions.
Methods of alkane production are provided that include contacting the feedstock solution with a reforming catalyst. The feedstock may include an aqueous solution having about 10-60%, preferably 20% or 30% or more, of one or more C1-C6 oxygenated hydrocarbon, preferably glycerol, ethylene glycol, and/or sorbitol. The feedstock may be contacted with a catalyst comprising one or more metals selected from the group consisting of platinum, rhodium and rhenium. As described in the examples, suitable catalysts for use in methods of producing alkanes include PtRe and RhRe catalysts with varying amounts of each metal. Preferred methods for alkane production provide products containing about 3-50%, 5-25% or 10-20% alkanes in the product stream. Preferably, the alkanes produced have 1, 2, 3, 4, 5, 6, 7, 8 or more carbons, and may be straight or branched hydrocarbons.
Optionally, acidic compounds may be added to a feedstock or reactor system to provide increased alkane selectivity of the reforming reactions. It is preferred that the water-soluble acid is selected from the group consisting of nitrate, phosphate, sulfate, and chloride salts, and mixtures thereof. If an optional acidic modifier is used, it is preferred that it be present in an amount sufficient to lower the pH of the aqueous feed stream to a value between about pH 1 and about pH 4. Lowering the pH of a feed stream in this manner can increase the proportion of alkanes in the reaction products.
Described below are methods to generate both hydrogen and alkanes via aqueous-phase reforming of oxygenated hydrocarbons that contain at least one carbon and one oxygen. These methods utilize a combination of Group VIIB and Group VIII metals supported on activated carbon generated from coconut, the carbon may be functionalized either by an acid treatment, treatment with hydrogen peroxide, or treatment with oxygen, the carbon support can further be functionalized by the addition oxides of either titanium, vanadium, tungsten, molybendum. The performance is further enhanced by the addition of oxides of Group IIIB and the associated rare earth. The process is thermally efficient if the process is run at feed concentration of greater than 20 wt % oxygenated compound, preferably greater than 30 wt %, more preferably greater than 40 wt % or 50 wt %.
In one aspect, preferred compositions of matter are provided. The compositions may be isolated before, during or after performing one or more methods or processes described herein, and may be isolated within a portion of a reactor system. One preferred composition comprises in one or more phases: an APR catalyst composition, sorbitol, hydrogen, carbon dioxide, and hydrocarbons such as methane, ethane, propane, butane, pentane, and hexane. Another preferred composition comprises, in one or more phases: an APR catalyst composition, glycerol, hydrogen, carbon dioxide and light hydrocarbons such as methane, ethane, propane, butane and pentane. The catalyst composition in both compositions preferably include one or more metals selected from the group consisting of: platinum, rhenium and rhodium. In particular, a composition comprises a solid phase including a catalyst comprising platinum, rhenium and/or rhodium, an aqueous phase including sorbitol, a gas phase including hydrogen, carbon dioxide, and methane, and organic or gas phases including ethane, propane, butane, pentane and hexane. Another composition comprises a solid phase including a catalyst comprising platinum, rhenium and/or rhodium, an aqueous phase including glycerol, a gas phase including hydrogen, carbon dioxide, and methane, and organic or gas phases including ethane, and propane.
EXAMPLES
The following examples are to be considered illustrative of various aspects of the invention and should not be construed to limit the scope of the invention, which are defined by the appended claims.
Example 1
Method 1
Monometallic catalyst systems supported on activated carbons were prepared by impregnating the carbon with solutions of metal precursors using incipient wetness techniques. (1) Activated carbons to be impregnated were dried under vacuum at  ̃100° C. overnight and stored in sealed containers until used. (2) A solution containing the metal precursor(s), volume equal to incipient wetness volume for the carbon to be impregnated, was applied drop wise, while stirring, to the activated carbon. (3) The wetted carbon was dried under vacuum as in step 1. (4) If additional applications were required to achieve the desired metal loading, steps 2 and 3 were repeated until sufficient metal precursor had been applied.
Example 2
5% wt. Pt on C
A 5 wt % platinum catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, 22.49 g, containing 3.34 g of dihydrogen hexachloroplatinate (IV) hexahydrate was added to 22.49 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh). The mixture was dried at 100° C. under vacuum.
Example 3
5% Ru on C
A 5 wt % ruthenium catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, 38 mL, containing 0.98 g of ruthenium (III) nitrosylnitrate (Alfa Aesar, 1.5% Ru) was added to 47.52 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh). The mixture was dried at 100° C. under vacuum. Three additional applications using 38 mL of this solution, then a last application, using 14 mL of this solution diluted to 38 mL, were performed. The carbon mixture was dried at 100° C. under vacuum between each application.
Example 4
5% wt. Rh on C
A 5 wt % rhodium catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, 38 mL, containing 18.54 g of rhodium nitrate solution(Alfa Aesar, 13.84% Rh) was added to 47.51 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh). The mixture was dried at 100° C. under vacuum.
Example 5
5% wt. Re on C
A 5 wt % rhenium catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, 7.6 mL, containing 0.882 g of perrhenic acid solution (Alfa Aesar, 76.41% HReO4) was added to 9.502 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh). The mixture was dried at 100° C. under vacuum.
Example 6
5% wt. Pd on C
A 5 wt % palladium catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, 7.6 mL, containing 5.916 g of palladium (II) nitrate (Alfa Aesar, 8.5% Pd) was added to 9.501 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh). The mixture was dried at 100° C. under vacuum.
Example 7
5% wt. Ir on C
A 5 wt % iridium catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, 62 mL, containing 5.03 g of dihydrogen hexachloroiridate (IV) hydrate (Strem, 47.64% Ir) was added to 44.87 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh). The mixture was dried at 100° C. under vacuum.
Example 8
15% wt. Ni on C
A 15 wt % nickel catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, 7.3 mL, containing 7.807 g of nickel (II) nitrate hexahydrate (Alfa Aesar, 19.4% Ni) was added to 8.587 g activated carbon (Calgon OLC-AW, sieved to 12-40 mesh). The mixture was dried at 100° C. under vacuum.
Example 9
Catalysts were evaluated for APR activity using test systems illustrated in FIG. 4.
Catalysts are loaded into a stainless steel tube reactor 1 which is installed in an aluminum block heater 2 to maintain isothermal conditions. The reaction temperature is controlled by the temperature control subsystem. The critical components of the temperature control subsystem (not shown in FIG. 4) are a thermocouple inserted into the tube reactor, resistive heaters mounted on the aluminum block, and a PID controller.
Substrate solutions (i.e., feedstock solutions) are continuously fed into the reactor using an HPLC pump 3. The material exiting the reactor is cooled as it passes through heat exchanger 4 before entering the phase separator 5.
Gasses exit the phase separator via the gas manifold 6 which is maintained at constant pressure by the pressure control subsystem. The critical components of the pressure control subsystem are the pressure sensor 7 pressure control valve 8 and PID controller 9. The quantity of gas released by the pressure control valve 8 is measured by mass flow meter 10. The composition of this gas is monitored by gas chromatography.
The liquid level in phase separator 5 is maintained at constant level by the level control subsystem. The components of the level control subsystem include the level sensor 11 in the phase separator, a level control valve 12 and PID controller 13. The aqueous solution drained from the phase separator during a catalyst evaluation experiment is collected and the quantity collected measured gravimetrically. Analysis of this solution may include, pH, total organic carbon concentration, GC to determine the concentrations of unreacted substrate and specific intermediates and side products.
Example 10
Monometallic catalyst systems described in Examples 1 thru 8 were tested in the apparatus described in Example 9. The catalysts were treated under flowing hydrogen at 250° C., before the liquid feed containing 10 wt % ethylene glycol was introduced to the catalyst at 230° C. Table 1 below describes the results of reforming the ethylene glycol solution over the catalyst at 430 psig. Table 1 shows that of the Group VIII carbon-supported monometallic catalytic materials, that platinum and ruthenium show appreciable activity. Carbon-supported rhenium also shows some reforming activity.







TABLE 1







Activity of Monometallic Catalysts for APR of 10% Ethylene Glycol









Gas Composition

















APR
P
WHSV
Conversion
H2
Alkanes
CO2


Catalyst
Example
T(° C.)
(PSIG)
(hr−1)a
to Gas (%)
(%)
(%)
(%)





5% Pt
2
230
430
0.80
13% 
84%
1%
15%


5% Ru
3
230
430
0.77
27% 
 9%
39% 
52%


5% Rh
4
230
430
0.71
0%
NA
NA
NA


5% Re
5
230
430
0.84
4%
67%
4%
29%


5% Pd
6
230
430
0.78
0%
NA
NA
NA


5% Ir
7
230
430
2.38
0%
NA
NA
NA


15% Ni
8
230
430
0.58
0%
NA
NA
NA





aWeight hour space velocities (WHSV) are based on feed rate of oxygenated substrate






Example 11
ReIr Bimetallic Catalyst, 5% wt. Ir, 1 Molar Ratio Re:Ir
Perrhenic acid solution (Alfa Aesar, 76.41% HReO4), 0.87 g was diluted to 7.6 mL with DI water and added by incipient wetting to 10.00 g of 5 wt % Ir on Carbon catalyst from Example 7. The mixture was dried at 100° C. under vacuum.
Example 12
ReNi Bimetallic Catalyst, 5% wt. Ni, 1:16 Molar Ratio Re:Ni
Nickel (II) nitrate hexahydrate (Alfa Aesar, 19.4% Ni), 2.577 g, and Perrhenic acid solution (Alfa Aesar, 76.4% HReO4), 0.163 g were dissolved in enough DI water to make a 7.6 mL solution. This solution was added by incipient wetting to 9.409 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh). The mixture was dried at 100° C. under vacuum.
Example 13
RePd Bimetallic Catalyst, 5% wt. Pd, 1:1 Molar Ratio Re:Pd
An aqueous solution, 7.6 mL, containing 4.577 g Perrhenic acid solution (Alfa Aesar, 76.4% HReO4) and 5.906 g Palladium (II) nitrate (Alfa Aesar, 8.5% Pd) was added to 9.503 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh) by incipient wetting. The mixture was dried at 100° C. under vacuum.
Example 14
RePt Bimetallic Catalyst, 5% wt. Pt, 1:1 Molar Ratio Re:Pt)
A 5 wt % platinum catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, approximately 26 mL, containing 4.261 g of dihydrogen hexachloroplatinate (IV) hexahydrate (Alfa Aesar, 39.85% Pt) was added to 32.34 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh). The mixture was dried at 100° C. under vacuum. An additional application of aqueous solution, 7.6 mL, containing 0.87 g of perrhenic acid solution (Alfa Aesar, 76.41% HReO4) was added to 10.03 g of the dried platinum/carbon mixture. The mixture was dried at 100° C. under vacuum.
Example 15
ReRh Bimetallic Catalyst, 5% wt. Rh, 1:3.8 Molar Ratio Re:Rh
An aqueous solution, approximately 7.6 mL, containing 3.55 g of rhodium (III) nitrate (Alfa Aesar, 13.93% Rh) was added to 9.51 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh) by incipient wetting. The mixture was dried at 100° C. under vacuum. An additional application of aqueous solution, 7.6 mL, containing 0.42 g of perrhenic acid solution (Alfa Aesar 76.41% HReO4) was performed. The mixture was dried at 100° C. under vacuum.
Example 16
ReRh Bimetallic Catalyst, 5% wt. Rh, 1:1 Molar Ratio Re:Rh
An aqueous solution, 24.2 mL, containing 1.60 g perrhenic acid solution (Alfa Aesar, 76.41% HReO4) was added to 10.01 g dry Degussa catalyst G106 NB/W 5 wt % Rh by incipient wetting. The mixture was dried at 100° C. under vacuum.
Example 17
ReRu Bimetallic Catalyst, 5% wt. Ru, 1:1 Molar Ratio Re:Ru)
Perrhenic acid solution (Alfa Aesar, 76.41% HReO4), 1.63 g was diluted to 7.3 mL with DI water and added by incipient wetting to 10.01 g of 5 wt % Ru on Carbon catalyst from Example 3. The mixture was dried at 100° C. under vacuum.
Example 18
The rhenium modified catalyst systems described in Examples 11 thru 17 were tested in the apparatus described in Example 9. The catalysts were treated under flowing hydrogen at 250° C., before the liquid feed containing 10 wt % ethylene glycol was introduced to the catalyst at 230° C. Table 2 below describes the results of reforming the ethylene glycol solution over the catalyst at 430 psig. Table 2 shows that the combination of rhenium and Group VIII metals supported on activated carbon significantly enhances the activity for the reforming of ethylene glycol compared to the results of Example 10.







TABLE 2







Activity of Monometallic Catalysts for APR of 10% Ethylene Glycol











Molar

Gas Composition















Catalyst


Ratios
WHSV
Conversion
H2
Alkanes
CO2


(MRe)
Example
Wt % M
(Re:M)
(hr−1)a
to Gas (%)
(%)
(%)
(%)





IrRe
11
5% Ir
1:1
0.76
76%
39%
19%
35%


NiRe
12
5% Ni
 1:16
0.68
 4%
74%
20%
 6%


PdRe
13
5% Pd
1:1
0.73
20%
54%
27%
19%


PtRe
14
5% Pt
1:1
0.72
74%
38%
36%
28%


RhRe
15
5% Rh
  1:3.8
0.80
75%
65%
 6%
28%


RhRe
16
5% Rh
1:1
1.73
100% 
52%
20%
28%


RuRe
17
5% Ru
1:1
1.98
83%
21%
45%
32%





aWeight hour space velocities (WHSV) are based on feed rate of oxygenated substrate.






Example 19
RhReCe Catalyst, 5% wt. Rh, 1:2:2 Molar Ratio Re:Rh:Ce
An aqueous solution, 7.6 mL, containing 3.64 g of rhodium (III) nitrate (Alfa Aesar, 13.93% Rh), 0.82 g of perrhenic acid solution (Alfa Aesar, 76.49% HReO4), 2.18 Cerium (III) nitrate was added to 9.50 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh) by incipient wetting. The mixture was dried at 100° C. under vacuum.
Example 20
Hydrogen peroxide has been used to functionalize activated carbons to provide improved supports for APR catalysts. S. R. de Miguel, O. A. Scelza, M. C. Roman-Martinez, C. Salinas Martinez de-Lecea, D. Cazorla-Amoros, A. Linares-Solano, Applied Catalysis A: General 170 (1998) 93. Activated carbon, 45 g, was added slowly to 1200 ml of 30% hydrogen peroxide solution. After addition of the carbon was completed, the mixture was left overnight. The aqueous phase was decanted and the carbon was washed three times with 1200 mL of DI water, then dried under vacuum at 100° C.
Example 21
RhReCe Catalyst, 5% wt. Rh, 1:1:1 Molar Ratio Re:Rh:Ce
Hydrogen peroxide functionalized carbon was prepared using the method described in Example 20 and Calgon OLC-AW, sieved to 18-40 mesh. After functionalization, the carbon was dried at 100° C. under vacuum. An aqueous solution, 7.6 mL, containing 2.12 g Cerium (III) nitrate was added by incipient wetting to 9.46 g of the hydrogen peroxide functionalized carbon. The mixture was dried at 100° C. under vacuum. An additional application of aqueous solution, 7.6 mL, containing 3.64 g rhodium (III) nitrate (Alfa Aesar, 12% Rh) and 1.61 g perrhenic acid solution was performed. The mixture was dried at 100° C. under vacuum.
Example 22
RhReLa Catalyst, 5% wt. Rh, 1:1:3 Molar Ratio Re:Rh:La
A 5 wt % rhodium catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, approximately 7.6 mL, containing 3.72 of rhodium (III) nitrate (Alfa Aesar, 13.65 wt % Rh) was added to 9.5 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh). The mixture was dried at 100° C. under vacuum. An additional application of aqueous solution, 7.6 mL, containing 1.60 g perrhemic acid solution (Alfa Aesar, 76.41% HReO4) and 6.33 g Lanthanum (III) nitrate hexahydrate (Alfa Aesar, 99.9% La(NO3)3) was performed. The mixture was dried at 100° C. under vacuum.
Example 23
The Rh/Re catalysts modified with Group IIIB compounds described in Examples 19 thru 22 were tested in the apparatus described in Example 9. The catalysts were treated under flowing hydrogen at 250° C., before the liquid feed containing 10 wt % ethylene glycol was introduced to the catalyst at 230° C. Table 3 below describes the results of reforming the ethylene glycol solution over the catalyst at 430 psig. Table 3 shows the addition of these Group IIIB compounds enhances the selectivity to hydrogen.







TABLE 3







Activity of RhRe Catalysts attenuated with Ce or La for APR of 10% Ethylene Glycol











Molar Ratios

Gas Composition


















(Re:Rh:Ce
WHSV
Conversion
H2
Alkanes
CO2


Catalyst
Example
Wt % Rh
or La)
(hr−1)a
to Gas (%)
(%)
(%)
(%)


















RhRe
16
5%
1:1:0
1.73
100% 
52%
20%
28%


RhReCe
19
5%
1:2:2
1.8
56%
63%
 6%
27%


RhReCe
_21—
5%
1:1:1
2.0
95%
63%
 8%
31%


RhReLa
22
5%
1:1:3
0.5
97%
55%
11%
28%





aWeight hour space velocities (WHSV) are based on feed rate of oxygenated substrate






Example 24
A Pt/Fe on carbon catalyst (Degussa CF105) was tested utilizing various concentrations of glycerol in water. This catalyst contained a loading of 5 wt % Pt and 0.5 wt % Fe. The catalyst was pretreated under flowing hydrogen at 250° C., before the liquid feed containing glycerol was introduced to the catalyst at 230° C. Table 4 shows the results of reforming the different glycerol solutions over this Pt/Fe catalyst.







TABLE 4







Activity of 5 wt % Pt/0.5 wt % Fe on Activated Carbon









Gas Composition














Wt %
APR
P
WHSV
Conversion
H2
Alkanes
CO2


Glycerol
T(° C.)
(PSI)
(hr−1)a
to Gas (%)
(%)
(%)
(%)

















10
230
433
1.8
62%
67%
5%
28%


20
230
428
3.6
32%
66%
4%
30%


30
230
431
5.4
21%
64%
4%
32%


40
235
429
7.2
13%
62%
4%
34%


50
238
432
9.0
 9%
60%
4%
36%


60
237
431
10.8
 6%
56%
3%
41%





aWeight hour space velocities (WHSV) are based on feed rate of oxygenated substrate.






Example 25
PtRe Catalyst, 5% wt. Pt, 2.5:1 Molar Ratio Re:Pt
Dihydrogenhexachloroplatinate (IV) hexahydrate (Alfa Aesar 39.85% Pt) 1.18 g, and Perrhenic acid solution (Alfa Aesar 79.18% HReO4) 1.92 g was diluted to 10.75 mL. The solution was added by incipient wetting to 8.95 g of hydrogen peroxide functionalized (Example 20) UU 60×120 mesh carbon and dried at 100° C. under vacuum.
Example 26
Oxidization with air has been used to functionalize activated carbons to provide improved supports for APR catalysts. Activated carbon, 23 g, was placed in a quartz U tube and heated to 450° C. in a stream of nitrogen, 150 mL/min. Once the temperature was stable, a stream of air, 50 mL/min, was added to the nitrogen. The carbon was treated for 10 hours, then allowed to cool under flowing nitrogen.
Example 27
RhReCe Catalyst, 5% wt. Rh, 1:1:1 Molar Ratio Re:Rh:Ce
Rhodium, rhenium, and ceria were added to activated carbon that has been air oxidized using the method of Example 26. An aqueous solution, 9.3 mL, containing 4.34 g of rhodium (III) nitrate solution (Alfa Aesar, 13.82% Rh), 1.85 g of perrhenic acid solution (Alfa Aesar, 79.18% HReO4), 2.53 Cerium (III) nitrate was added to 11.4 g air-oxidized carbon (Calgon OLC-AW, sieved to 18-40 mesh) by incipient wetting. The mixture was dried at 100° C. under vacuum.
Example 28
PtRe Catalyst, 5% wt. Pt, 2.5:1 Molar Ratio Re:Pt)
Dihydrogenhexachloroplatinate (IV) hexahydrate (Alfa Aesar 39.85% Pt) 1.18 g, and Perrhenic acid solution (Alfa Aesar 79.18% HReO4) 1.92 g was diluted to 10.75 mL. The solution was added by incipient wetting to 8.95 g of air oxidized UU 60×120 mesh carbon and dried at 100° C. under vacuum.
Example 29
RhReCe Catalyst, 5% wt. Rh, 1:1:1 Molar Ratio Re:Rh:Ce
Rhodium (III) Nitrate Dihydrate 1.37 g (Alfa Aesar 31.91% Rh), Perrhenic Acid solution (Alfa Aesar 79.18% HReO4) and Cerium (III) Nitrate Hexahydrate 1.85 g was diluted to 13.2 mL. The solution was added to 8.31 g of UU 120×200 mesh activated carbon by incipient wetting and dried at 100° C. under vacuum.
Example 30
Functionalized carbon surfaces were modified by impregnation of metal oxides prior to impregnation of catalyst precursors. Titanium n-butoxide, 1.95 g, was diluted to 12 mL with anhydrous isopropanol. This solution was added by incipient wetting to air oxidation functionalized carbon (see Example 26 above), 10 g. The wetted carbon was dried under vacuum at 100° C. overnight.
Example 31
RhReCe Catalyst, 5% wt. Rh, 1:1:1 Molar Ratio Re:Rh:Ce
Rhodium(III) Nitrate, 3.86 g, Perrhenic Acid, 1.64 g, and Cerium(III) Nitrate hexahydrate, 2.21 g, were dissolved in enough DI water to make 12 mL of solution. This solution was added by incipient wetting to Titania modified carbon from Example 30, and then dried under vacuum at 100° C. overnight.
Example 32
The catalysts of Examples 25 through 31 were pretreated under flowing hydrogen at 250° C., before the liquid feed containing oxygenated compounds were introduced to the catalyst at the desired reaction temperature. Table 5 shows the results of reforming the different solutions over these catalysts. When compared to the results for the conversion of higher concentrations of glycerol presented in Example 24, Table 5 shows that the combination of rhenium and Group VIII metals supported on activated carbon significantly enhances the activity for the reforming of higher concentrations of oxygenated compounds.







TABLE 5







Activity for APR Catalysts reforming high concentration substrates











Molar Ratios

Gas Composition




















Carbon

(Re:Rh:Ce
WHSV
Conversion
H2
Alkanes
CO2


Feedstock
Catalyst
Ex.
Pretreatment
Wt % M
or Re:Pt)
(hr−1)a
to Gas (%)
(%)
(%)
(%)





30%
RhReCe
27
Air oxided
5% Rh
1:1:1
4.8
47%
61%
10%
29%


Ethylene












Glycerol












30%
PtRe
25
H2O2
5% Pt
2.5:1
2.0
81%
45%
17%
35%


Glycerol












30%
PtRe
28
Air
5% Pt
2.5:1
2.2
57%
36%
12%
47%


Sorbitol


oxided









30%
RhReCe
29
None
5% Rh
1:1:1
2.0
28%
36%
16%
48%


Sorbitol












50%
PtRe
25
H2O2
5% Pt
2.5:1
3.2
66%
43%
16%
40%


Glycerol












50%
RhReCe
31
Air oxided
5% Rh
1:1:1
1.8
81%
49%
19%
35%


Glycerol


Ti Modified









50%
RhReCe
31
Air oxided
5% Rh
1:1:1
1.8
60%
41%
14%
46%


Sorbitol


Ti Modified





aWeight hour space velocities (WHSV) are based on feed rate of oxygenated substrate.






Example 33
Functionalized carbon surfaces were modified by impregnation of with metal oxides prior to impregnation of catalyst precursors. Vanadium oxide triisopropoxide, 0.67 g, was diluted to 12 mL with anhydrous isopropanol. This solution was added by incipient wetting to hydrogen peroxide functionalized carbon (see Example 20 above), 10 g. The wetted carbon was dried under vacuum at 100° C. overnight.
Example 34
RhReCe Catalyst, 5% wt. Rh, 1:1:1 Molar Ratio Re:Rb:Ce)
Rhodium(III) Nitrate, 3.82 g, Perrhenic Acid, 1.69 g, and Cerium(III) Nitrate hexahydrate, 2.21 g, were dissolved in enough DI water to make 12 mL of solution. This solution was added by incipient wetting to Vanadia modified carbon, and then dried under vacuum at 100° C. overnight.
Example 35
The catalysts of Examples 29, 31 and 34 were pretreated under flowing hydrogen at 250° C., before the liquid feed containing oxygenated compounds were introduced to the catalyst at the desired reaction temperature. Table 6 shows the results of reforming 30 wt % sorbitol at 240° C. and 495 psig. This table shows that addition of either Ti or V significantly improves the conversion of sorbitol.







TABLE 6







Activity for APR Catalysts 30% Sorbitol supported on modified carbons.









Gas Composition


















Carbon

Molar Ratios
WHSV
Conversion
H2
Alkanes
CO2


Catalyst
Ex.
Pretreatment
Wt % M
(Re:Rh:Ce)
(hr−1)a
to Gas (%)
(%)
(%)
(%)





RhReCe
29
None
5% Rh
1:1:1
2.0
28%
36%
16%
48%


RhReCe
31
Air oxided
5% Rh
1:1:1
1.8
72%
51%
11%
40%




Ti Modified









RhReCe
34
H2O2
5% Rh
1:1:1
1.8
83%
47%
12%
42%




V Modified





aWeight hour space velocities (WHSV) are based on feed rate of oxygenated substrate.






Example 36
It has been found that the addition of bases significantly increases the amount of hydrogen generated during aqueous-phase reforming. Table 7 shows the effects of adding various amounts of NaOH and KOH.







TABLE 7







Effect of Addition of Base to Feed on Activity and Selectivity for APR Catalysts.











Molar Ratios

Gas Composition






















(Re:Rh:Ce
WHSV
Conversion
H2
Alkanes
CO2


Feedstock
Catalyst
Ex.
Base
Wt % M
or Re:Pt)
(hr−1)a
to Gas (%)
(%)
(%)
(%)





30%
RhReCe
NAb
none
5% Rh
1:1:1
1.8
70%
47%
12% 
40%


Sorbitol












30%
RhReCe
b
0.5%
5% Rh
1:1:1
1.7
71%
53%
8%
39%


Sorbitol


NaOH









30%
RhReCe
b
1.25%
5% Rh
1:1:1
1.8
78%
57%
8%
37%


Sorbitol


NaOH









30%
RhReCe
b
1.5%
5% Rh
1:1:1
1.8
75%
56%
8%
34%


Sorbitol


NaOH









30%
RhReCe
b
1.65%
5% Rh
1:1:1
1.8
73%
56%
8%
34%


Sorbitol


NaOH









30%
PtRe
28
none
5% Pt
2.5:1
2.2
57%
36%
12% 
47%


Sorbitol












30%
PtRe
28
2.5%
5% Pt
2.5:1
2.2
64%
55%
7%
36%


Sorbitol


KOH









50%
RhReCe
31
none
5% Rh
1:1:1
1.8
81%
49%
19% 
35%


Sorbitol












50%
RhReCe
31
1.65%
5% Rh
1:1:1
1.8
75%
57%
12% 
33%


Sorbitol


NaOH





aWeight hour space velocities (WHSV) are based on feed rate of oxygenated substrate.


bpreparation of this catalyst (on H2O2 vanadium modified carbon) was not described in any example, but the procedure was similar to example 34.






Example 37
A 3 wt % platinum catalyst supported on activated carbon was prepared according to the general method of Example 1. An aqueous solution, approximately 9.5 mL, containing 0.75 g of dihydrogen hexachloroplatinate (IV) hexahydrate (Alfa Aesar, 39.85% Pt) and 1.22 g of perrhenic acid solution (Alfa Aesar, 79.18% HReO4) was added to 10.0 g peroxide functionalized carbon (Calgon UU, sieved to 60-120 mesh functionalized using the method of Example 20). The mixture was dried at 100° C. under vacuum.
Example 38
The catalysts of Example 37 was pretreated under flowing hydrogen at 350° C., before the liquid feed containing oxygenated compounds were introduced to the catalyst at the desired reaction temperature. FIG. 5 shows the time-dependent results of fractional conversion to gas for reforming 50 wt % glycerol at 260° C., 600 psig and a WHSV of 0.55 based on the feed rate of glycerol.
Example 39
ReRh Bimetallic Catalyst, 5% wt. Rh, 1:2 Molar Ratio Re:Rh
An aqueous solution, 7.6 mL, containing 0.85 g of perrhenic acid solution (Alfa Aesar 76.41% HReO4) was added to 10.0 g of 5% wt Rh catalyst, Example 4, by incipient wetting. The mixture was dried at 100° C. under vacuum.
Example 40
ReRh Bimetallic Catalyst, 5% wt. Rh, 1:1 Molar Ratio Re:Rh
An aqueous solution, 7.6 mL, containing 1.61 g of perrhenic acid solution (Alfa Aesar 76.41% HReO4) was added to 10.0 g of 5% wt Rh catalyst, Example 4, by incipient wetting. The mixture was dried at 100° C. under vacuum.
Example 41
ReRh Bimetallic Catalyst, 5% wt. Rh, 1:1 Molar Ratio Re:Rh
An aqueous solution, 15 mL, containing 3.15 g of rhodium (III) nitrate (Alfa Aesar) was added to 19.0 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh) by incipient wetting. The mixture was dried at 100° C. under vacuum. An additional application of aqueous solution, 15.2 mL, containing 3.14 g of perrhenic acid solution (Alfa Aesar 79.2% HReO4) performed. The mixture was dried at 100° C. under vacuum.
Example 42
ReRh Bimetallic Catalyst, 5% wt. Rh, 2:1 Molar Ratio Re:Rh
An aqueous solution, 7.6 mL, containing 1.57 g of rhodium (III) nitrate (Alfa Aesar) and 3.11 g of perrhenic acid solution (Alfa Aesar 76.41% HReO4) was added to 9.53 g activated carbon (Calgon OLC-AW, sieved to 18-40 mesh) by incipient wetting. The mixture was dried at 100° C. under vacuum.
Example 43
It has been found that increasing the rhenium loading will enhance the production of alkane products. Table 8 shows the results of reforming two concentrations of ethylene glycol over catalysts with varying ratios of Re to Rh. As this ratio increased, the concentration of alkanes in the product gas increased.







TABLE 8







Effect of increasing Re:Rh ratio on Activity and Selectivity for APR Catalysts.











Molar

Gas Composition






















Ratios
WHSV
Conversion
H2
Alkanes
CO2


Feedstock
Catalyst
Ex.
T (° C.)
Wt % Rh
(Re:Rh)
(hr−1)a
to Gas (%)
(%)
(%)
(%)





10%
RhRe
15
210
5%
  1:3.8
0.8
36%
65%
 7%
27%


Ethylene












Glycol












10%
RhRe
39
210
5%
1:2
0.7
89%
59%
12%
29%


Ethylene












Glycol












10%
RhRe
40
210
5%
1:1
0.7
100% 
48%
24%
27%


Ethylene












Glycol












30%
RhRe
41
230
5%
1:1
2.2
19%
60%
10%
28%


Ethylene












Glycol












30%
RhRe
42
230
5%
2:1
2.1
20%
53%
17%
30%


Ethylene












Glycol





aWeight hour space velocities (WHSV) are based on feed rate of oxygenated substrate.






The described embodiments and examples are to be considered in all respects only as illustrative and not restrictive, and the scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

## Claims

1. A method of reforming oxygenated hydrocarbons in a feedstock solution, the method comprising the steps of
modifying an aqueous-stable support comprising carbon with a member selected from the group consisting of titanium, vanadium and tungsten, and
contacting the feedstock solution with a reforming catalyst on the modified support under conditions of reaction temperature and reaction pressure effective to produce hydrogen gas and alkanes having 1 to 8 carbon atoms,
wherein the feedstock solution comprises oxygenated hydrocarbons in an amount of at least 20 weight percent and
wherein the reforming catalyst comprises rhenium and at least one Group VIII transition metal.

2. The method of claim 1, wherein the conversion to hydrogen gas is greater with the reforming catalyst than the conversion to hydrogen gas using the same feedstock solution and the same catalyst absent rhenium.

3. The method of claim 1, wherein the conversion to alkanes with the reforming catalyst is greater than the conversion to alkanes using the same feedstock solution and the same catalyst absent rhenium.

4. The method of claim 1, wherein the support comprises activated carbon, and wherein the combination of rhenium and the at least one Group VIII transition metal on the activated carbon significantly enhances the activity for reforming the oxygenated hydrocarbon compared to a monometallic catalyst comprising Pt, Ru, Rh, Re, Pd, Ir or Ni.

5. The method of claim 1, wherein the aqueous-stable support comprises activated carbon, and wherein the combination of rhenium and the at least one Group VIII transition metal on the activated carbon significantly enhances the activity for reforming the oxygenated hydrocarbon compared to a Pt/Fe on carbon catalyst.

6. The method of any one of claims 1-5, wherein the reforming catalyst comprises Re and at least one transition metal selected from the group consisting of: Ir, Ni, Pd, Pt, Rh and Ru.

7. The method of any one of claims 1-5, wherein the reforming catalyst further comprises Ce or La.

8. The method of any one of claims 1-5, wherein the aqueous-stable support comprises one or more materials selected from the group consisting of:
carbon, zirconia, titania, ceria and combinations thereof.

9. The method of any one of claims 1-5, wherein the atomic ratio of Re to the Group VIII metal in the catalyst is from 0.25-to-1 to 10-to-1, and the combination of the catalyst and the support comprises from 0.25 wt % to 10 wt % Group VIII metal.

10. The method of any one of claims 1-5, wherein the catalyst is selected from the group consisting of: Re1.0Rh3.8, Re1.0Rh1.0, Ni1.0Re16.0, Re1.0Rh2.0Ce2.0, Re1.0Rh1.0Ce1.0, Re1.0Rh1.0La3.0, and Re2.5Pt1.0.

11. The method of any one of claims 1-5, wherein the feedstock solution comprises at least 50% of the oxygenated compound.

12. The method of any one of claims 1-5, wherein the reaction temperature is between about 80° C. and about 300° C. and wherein the reaction pressure is between about 10 bar (145 psi) and about 50 bar (725 psi).

13. A reforming catalyst prepared by a process comprising the steps of:
(a) impregnating a carbon support with titania, vanadia, tungsten or zirconia;
(b) adhering a catalytic composition to the impregnated carbon support, the catalytic composition comprising Re and a second metal selected from the group consisting of: Ir, Ni, Pd, Pt, Rh and Ru; and
(c) adhering a third metal of Ce or La to the impregnated carbon support or to the catalytic composition.

14. The reforming-catalyst of claim 13, wherein the catalytic composition is selected from the group consisting of: Re1.0Rh3.8, Ni1.0Re16.0, Re1.0Rh2.0Ce2.0, Re1.0Rh1.0Ce1.0, Re1.0Rh1.0La3.0, and Re2.5Pt1.0.

15. A composition of matter comprising
(a) a reforming catalyst comprising rhenium, a Group VIII metal, and Ce or La in which a reforming catalyst is adhered to the modified carbon support, wherein the carbon support has been modified with a member selected from the group consisting of titanium, vanadium and tungsten;
(b) a gaseous phase comprising hydrogen, methane, carbon dioxide and one or more compounds selected from the group consisting of: ethane and propane; and
(c) a liquid phase comprising a C1-C6 oxygenated hydrocarbon.

16. The composition of claim 15, wherein the liquid phase comprises an organic phase comprising hexane, pentane and propane and an aqueous phase comprising sorbitol.

17. The composition of claim 15 or 16, wherein the liquid phase comprises an organic phase comprising propane and an aqueous phase comprising glycerol.

18. The composition of any one of claim 15 or 16, wherein the Group VIII metal comprises one or more materials selected from the group consisting of: Ir, Ni, Pd, Pt, Rh and Ru.