[0001] This application claims the benefit of Provisional U.S. Patent Application Serial No. 61/782,276, filed on March 14, 2013, pending, which is incorporated by reference herein in its entirety.

TECHNICAL FIELD

[0002] The invention relates generally to the synthesis of alcohols, diols, cyclic ethers and lactones from biomass, and specifically to the production of such compounds via the combination of the chemical transformations of dehydration, decarbonylation,

hydrogenation, hydrogenolysis and oxidation applied to pentose and hexose carbohydrates, such carbohydrates being derived from renewable biomass, e.g. pentose monosaccharides such as xylose and arabinose, hexose monosaccharides such as glucose, galactose, mannose and fructose, hexose disaccharides such as sucrose, trehalose, and cellobiose, and oligomers of pentoses and hexoses.

BACKGROUND

[0003] An estimated 170 billion metric tonnes of biomass are generated globally on an annual basis (D.L. Klass, Academic Press, 1998). In the United States alone, the US

Department of Energy and US Department of Agriculture concluded that just over 1 billion metric tonnes of biomass are available in the US alone. ("Biomass as Feedstock for A Bioenergy and Bioproducts Industry: The Technical Feasibility of a Billion-ton Annual Supply", US Department of Energy, US Department of Agriculture, 2005)

[0004] The range of molecules produced biologically from biomass for fuel purposes (i.e. biofuels) includes not only ethanol but also n-butanol, /so-butanol, and longchain hydrocarbons, and these may also be produced by fermentation processes: examples are 1- butanol (WO20101511706A1), iso-butanol (WO2009059253A2, US20090215137A1, WO2011085223A1), and alkanes (Andreas Schirmer et al, Science, 329, 559-562 (2010)).

[0005] Of specific interest is the use of primary alcohols such as 1-butanol and 1-pentanol as precursors to the terminal alkenes 1-butene and 1-pentene. These alkenes are feedstock for the production of jet fuel via oligomerization chemistry developed by the United States Navy. (Michael E. Wright et al, Energy & Fuels, 22, 3299-3302 (2008)). [0006] However, the same renewable, carbohydrate feedstock and the same technologies used to produce biofuels may also be used to produce molecules having primary value as commodity chemicals rather than as fuels. Current examples include lactic acid, succinic acid, 1,3-propandiol, 1,4-butanediol, adipic acid, glucaric acid, 3-hydroxypropionic acid, and others. Of particular interest are those molecules that can be used as monomers in the production of polymers such as polyesters. For example, the use of Ι,ω-diols such as 1,3- propanediol (PDO) and 1,4-butanediol (BDO) in polyesters is well known, and longer, homologous Ι,ω-diols such as 1,5-pentanediol (PeDO) and 1,6-hexanediol (HDO) are known to have similar utility. At present there is no published biological route to either PeDO or HDO, that is, a route using natural or engineered metabolic pathways and run as a whole cell process consuming fermentable sugar as the carbon source, such as carbohydrates.

[0007] The plant sources used to produce fermentable sugars for use in the fermentive production of molecules with utility as commodity chemicals are also primary food crops. This has led to concern that as the conversion from petroleum feedstock for chemical production to bio-based feedstock for chemical production increases, there will be conflict with the demands of such crops for food. In an effort to avoid this conflict, the use of nonfood biomass for the production of fermentable carbon. This effort is directed to the production of mono-saccharides from lignocellulosic biomass that is not useful as food and a very large, global effort has been mounted to deconstruct lignocellulosic biomass in a manner that provides fermentable sugars. The US National Renewable Energy Laboratory (NREL) has investigated this issue for well over a decade, and a standard benchmark process using heat and dilute acid is publicly available.

[0008] Unfortunately, the weakness of such processes generally is that they produce compounds that inhibit fermentation of the resulting sugars. Such inhibitory compounds are formed by chemical reactions that occur during the processes, and typically these are furfurals, organic acids, and related compounds that are toxic to the organisms most widely used for the fermentive production of bio-based chemicals and biofuels.

[0009] The problem of toxic molecules contaminating the fermentable sugars which are produced from lignocellulosic biomass can be overcome by utilizing such compounds as lime, or using more elaborate processes that avoid the use of acidic conditions. While some of these processes do claim to generate sugars with little or no toxic compounds present, they are complicated, expensive, and use materials such as ionic liquids (including hydrates of hydrogen chloride) or ammonia, each of which must be recovered with extremely high efficiencies and which require special materials of construction for containment and handling during their use.

[0010] Another problem is that the process of fermentation itself requires considerable capital expense for the fermentation equipment, and the efficiency of the conversion of compounds to biofuels via fermentation is dictated by biological pathways. Thus, the theoretical maximum efficiency for the production of PDO from glucose 54% by weight respectively, i.e. one tonne of glucose can theoretically be fermented to 540 kgs of PDO. The practically efficiency is necessarily reduced by the use of the fermentable sugars for the biological processes that do not produce ethanol or butanol, but maintain the integrity of the cell. In practice, the losses of efficiency due to the required, non-productive biological process of the cell may range from 10% to over 30% of the theoretical maximum.

[0011] A further practical problem is that the concentration of the chemical being produced is that it cannot exceed relatively low concentrations in the fermentation broth as it may be toxic to the cell performing the fermentation; this is true whether the compound is to be used as a chemical or a fuel. Continuous separation and removal of the molecule from the aqueous fermentation broth may thus be required. This requires further equipment and energy.

[0012] These issues may be summarized in the following manner:

1. Yield (Conversion): A fermentation process requires the microbial agent performing the fermentation to grow and perform other necessary biological activities (such as maintenance of the cell membrane, etc.); this requires that at least some of the input biomass be consumed by metabolic processes that do not produce the desired product. Further, the metabolic pathways themselves may not be chemically efficient from the perspective of maximum conversion of input material to desired product. In practice, the losses of efficiency due to the essential but non-productive biological processes of the cell may range from 10% to over 30% of the theoretical maximum.

2. Concentration (Titer): Because the product of the fermentation may be toxic to the micro-organism that is producing it, the concentration of product in the fermentations is generally limited. For example, in butanol fermentations the practical limit is about 2.0%. (Qureshi and Blaschek, 2000 Food Bioprod. Process, 78, 139-144) Therefore, it is necessary to remove the butanol from the fermentation broth as it is formed broth in order to keep it below its toxic concentration; this requires energy and equipment that might otherwise be avoided.

3. Rate (Productivity): Fermentations generally require several days to produce an amount of product that is commercially useful; current ethanol fermentations require approximately 2 days, while butanol fermentations require 4 to 5 days.

[0013] It is thus advantageous to avoid the production of desired products via a

fermentation process due to its inherent limitations of yield, rate and concentration described above. It is more specifically advantageous to practice a process that has a greater efficiency of conversion from biomass to the desired chemical or fuel molecule than allowed by biological methods such as fermentation, avoids the potential need to continuously remove the chemical being produced from the biological process, and can convert a given amount of starting material to the desired product at higher concentration and in less time than can be achieved using a fermentation process.

[0014] It is of further advantageous to generate chemicals and fuels in a manner that avoids not only the toxicity issues with fermentable sugars produced by the pre-treatment methods, but also avoids the need for the elaborate pre-treatment processes generally.

[0015] It is known that the compounds produced during the various bio-mass pretreatment processes and having toxicity towards fermentation processes belong to the general class of furfuryl aldehydes; specifically furfuraldehyde (also known as furfural and termed "FF" in this document) and 5-hydroxymethyl furfuraldehyde, commonly called "HMF".

[0016] Furfural is produced by the triple dehydration of the pentose sugars, principally xylose which is the main component of the hemicellulose fraction of lignocellulosic biomass. More than 300,000 metric tons/year of furfural are produced from biomass for commercial use every year (Montane, D. et al, Biomass & Bioenergy 22, 295-304 (2002))

[0017] The production of furfural from sugars is well know and was practiced commercially by Quaker Oats in the US (US Patent 1735084), and is currently practiced by lllovo Sugar in South Africa (www.illovo.co.za/Our_Products/Downstream_Products.aspx). The direct treatment of the raw biomass with strong acid at elevated temperatures catalyzes the conversion of biomass pentose sugars to furfural in high yield. The following schematic illustrates the dehydration of pentoses (xylose shown) to form FF.

Xylose

Furfuraldehyde

Carbohydrate biomass C ₅ H ₄ 0 ₂

(pentoses, C ₅ H ₁₀ O ₅ ) FF

[0018] The treatment of 6-carbon sugars such as glucose and fructose with heat and acid produces hydroxymethylfurfural (HMF), and yields in the 50-75% range are reported in the earlier literature and patents (Verendel, J. Johan et al, Synthesis 2011, 1649-1677; Chheda, Juben N. et al, Catalysis Today 123, 59-70 (2007)). A wide variety of supported acid catalysts can be used, and this general process can also be adapted to produce levulinic acid as well as HMF (US7317116B2). Sucrose and other disaccharides can be used as well with hydrolysis to individual sugars (e.g. fructose and glucose from sucrose) presumably occurring as the first step under the acidic conditions (GB600871A). The following schematic illustrates the dehydration of hexoses (fructose and glucose shown) to form HMF

Fructose Glucose 5-hydroxymethyl-2-furfural

C6H ₆ 0 ₃

HMF

Carbohydrate biomass

(hexoses, C ₆ H ₂ 0 ₆ )

[0019] The formation of HMF has even been reported following the treatment of algal cells with sub-critical hot water (S.Daneshvar et al, Ind. Eng. Chem. Res. 51, 77-84 (2012)).

[0020] Both FF and HMF are susceptible to decarbonylation, hydrogenation and

hydrogenolysis, and combinations of these chemical transformations can be anticipated to give a variety of molecules of value both as chemicals and fuels, and in efficiencies that exceed the efficiencies achievable by fermentation or FT technologies.

[0021] The production of 1-butanol and 1-pentanol have been reported during the hydrogenation and hydrogenolysis of FF, although in low yield. Previous work has been directed to the production of furfuryl alcohol using platinum supported on Si0 ₂ , Al ₂ 0 ₃ , MgO, or Ti0 ₂ (Kijenski, J. et al, Applied Catalysis A-General 233, 171-182 (2002)) or using copper chromite supported on carbon (Rao, R. S. et al, Catalysis Letters 60, 51-57 (1990)). [0022] Other efforts at FF reduction have been attempted, using Raney nickel (Liu, B. J. et al, Applied Catalysis A-General 171, 117-122 (1998)), nickel amorphous alloys (Lee, S. P. et al, Industrial & Engineering Chemistry Research 38, 2548-2556 (1999)), and homogeneous complexes of Rh, Ru and Pt (Burk, M. J. et al, Tetrahedron Letters 35, 4963-4966 (1994)) have been disclosed in the literature . Granted patents also offer some examples of catalyst development for FF hydrogenation (US7064222, US4185022) but this work ignores other possible hydrogenation products and pathways beyond furfuryl alcohol. Still other efforts have noted low levels of production of THF and 1-pentanol in reactions designed to produce MeTHF from FF (US2010/0048922A1) using copper and precious metals.

[0023] The hydrogenation of furan to give THF is known with catalysts containing group VIII metals. (Jackson, S. D. et al, Industrial & Engineering Chemistry Research 42, 5489-5494 (2003)) The hydrogenation of furan is generally performed using Ni and Pd and little other work exists. Even with supported Ni and Pd catalysts, little has been reported in terms of the actual reaction catalytic cycle. In particular, catalyst deactivation is a serious hurdle. Experimental evidence points to carbon deposition from decomposition reactions of strongly adsorbed furan and THF moieties on metal sites as the main source for catalyst deactivation. (Jackson, S. D. et al, Studies in Surface Science and Catalysis (Catalyst

Deactivation) 126, 453-456 (1999))

[0024] Decarbonylation of FF has been revealed in the patent literature using Pd and the deliberate addition of water to the reaction (US2011/0196126A1). A patent application by the same inventor (US2011/201832A1) appears to reveal improvements such as the need for the Pd to be supported on alumina, to be activated by cesium carbonate, and to be operated in the temperature range of 300°C to 500°C.

[0025] Decarbonylation of benzaldehyde, an aromatic compound with an exo-cyclic carbonyl group analogous to FF, has been studied using Ni catalysts (A. Saadi et al, J. Mol. Cat. A: Chemical 253 (2006) 79-85, A. Saadi et al, J. Mol. Cat. A: Chemical 164 (2000) 205- 216) but the authors did not extend this work to FF or HMF, and the reported yields for decarbonylation are under 50%. Hydrogenation of FF has been studied (Surapas Sitthisa et al, Catal. Lett. (2011) 141:784-791). While the conversion of FF to furan, THF and furfuryl alcohol are reported, the yields are generally low, with the exception of a 71% yield of furfuryl alcohol reported under one set of conditions. No use of combined metal catalysts was reported. [0026] The use of precious metals such as platinum, palladium, rhenium and rhodium for hydrogenation is well known, and the use of rare earth metals such as cesium is also reported. However, these metals are expensive, their prices volatile, and cost-reduction in processes using such metals requires the collection and recovery of the metal from spent catalysts; such collection and recovery requirements lead to more complicated and costly processes overall. It is therefore advantageous to use catalysts that do not contain rare earth or precious metals. The metal chromium, although not considered a rare earth or precious metal, possess considerable toxicity. Thus it is also advantageous to avoid the use of chromium in any catalyst.

[0027] 1-Butanol and 1-pentanol have been observed as an adventitious byproduct in reactions of furfural with hydrogen using Cu/Zn/AI/Ca/Na and Cu/Cr/Ni/Zn/Fe catalysts. A reaction pathway has been proposed and is shown in the illustration below. (Zheng, H. Y. et al, Journal of Molecular Catalysis A-Chemical 246, 18-23 (2006)). The following schematic shows the reaction pathways for the production of 1-butanol and 1-pentanol proposed by Zheng et al.

FF = furfural

FFalc = furfuryl alchol

THF = tetrahydrofuran

VL = valerolactone

MeF = 2-methylfuran

MeTHF = 2-methyltetrahydrofuran

HMTHF = 2-hydroxymethylTHF

„OH

VJ HC HC = hydrocarbon species

MeF 1-pentanol from over-reduction

MeTHF 2-pentanone 2-pentanol

[0028] Zheng et al reference an earlier literature report for the production of PeDO from 2- hydroxymethylTHF (HMTHF) (J. Kijenski et al, Appl. Catal. A: Gen. 233 (2002) 171-182) and briefly note that a small amount of PeDO was observed in their own work.

[0029] While production of PeDO from FF is recognized as generally valuable, the use of non-precious metal catalysts such as copper chromite or Raney Nickel give such low yields as to have no practical utility. (S. Koso et al, Chemical Communications (2009) 2035-2037; Yoshinao Nakagawa et al, Catalysis Today 195 (2012) 136- 143). [0030] Hydrogenation of FF over supported Ni catalysts giving high yields of tetrahydrofurfuryl alcohol and some furfuryl alcohol is reported (Yoshinao Nakagawa et al, ChemCatChem 2012, 4, 1791 - 1797). However, this publication notes that the catalyst required particle sizes of less then 4 nanometers to have useful activity, and reactions time of at least 30 minutes were required to achieve high yields of tetrahydrofurfuryl alcohol.

[0031] The chemical processes of decarbonylation, hydrogenolysis and hydrogenation that are reported for FF will apply to HMF, and HMF does provide a convenient bio-based starting material for a variety of non-biological chemical process leading to commodity chemicals. Work by Dumesic et al (Nature, 447, 982-985 (2007)) shows that HMF can be full hydrogenated to give 2,5-dimethyl furan, also an aromatic compound although with greater utility as a fuel, rather than a chemical feedstock or monomer. In this process,

carbohydrates are converted to HMF in a biphasic extractive reaction system using NaCI as a dehydrating agent, and several reactor conditions are reported to give conversions of fructose to HMF in the 80% range. Fructose is clearly the best hexose carbohydrate starting material for conversion to HMF in this system, and several conditions showing yields of HMF from fructose of approximately 84% are reported (US7572925B2, WO2007146636A1).

Hydrogenolysis of the HMF over a Cu/Ru catalyst is reported to give yields of 2,5- dimethylfuran at approximately 70% from HMF. To add a biological aspect to the chemical process, a combination of enzymatic isomerization of either glucose or mannose to fructose, followed by mild chemical conversion has been revealed in the patent literature, and arranged as a continuous process for the production of HMF (WO2011124639A1).

[0032] HMF may undergo decarbonylation to give furfuryl alcohol (FFalc), and it will be clear that such furfuryl alcohol may then participate in the chemical pathways proposed by Zheng et al. It will be equally clear that furfuryl alcohol produced by decarbonylation of HMF may be subsequently oxidized to give FF, and that FF formed in this manner may then participate in the chemical pathways proposed by Zheng et al and described above, including subsequent decarbonylation. The following schematic illustrates the formation of furfural (FF) and furfuryl alcohol from HMF.

5-hydroxymethyl Furfurlyl Furfural

2-furfural alcohol (FF)

(HMF) (FFalc) SUMMARY OF THE INVENTON

[0033] A method is provided which comprises:

a) mixing an input starting material comprising furfural (FF) or

hydroxymethylfurfural (HMF) with hydrogen gas, and optionally with a carrier fluid, in such a manner that a fluid mixture results;

b) allowing the fluid mixture to reside in a reactor assembly in the presence of a catalyst at a temperature (T) and pressure (P) and for a time (t) such that the catalyst, in the presence of the hydrogen gas, promotes decarbonylation, hydrogenolysis and/or hydrogenation of the furfural or hydroxymethylfurfural to produce a primary alcohol, a- olefin, secondary alcohol, ketone, aldehyde, alkane, alkene, cyclic ether, lactone and/or 1, ω-diol in a product mixture; and

c) collecting the product mixture.

[0034] A catalyst comprising at least three metallic elements is also provided wherein the metallic elements are selected from the group consisting of scandium, titanium, vanadium, manganese, iron, cobalt, nickel, copper and zinc, wherein the catalyst is capable of catalyzing the reaction of hydrogen with furfural (FF) or hydroxymethylfurfural (HMF).

BRIEF DESCRIPTION OF THE DRAWINGS

[0035] FIG. 1 illustrates the reaction pathways from FF and HMF starting materials, showing the location of decarbonylation, hydrogenation and hydrogenolysis reactions in the pathways, and the end products.

DETAILED DESCRIPTION

[0036] The present invention is a process that uses renewable lignocellulosic biomass and hydrogen to produce a family of molecules via non-biological chemical reactions which use FF or HMF or both as the starting material. The reactions and product molecules are summarized graphically in FIG. 1.

[0037] The present invention uses FF or HMF formed from biomass as the input starting material to a catalytic reactor. This gives an advantage in that the formation of FF or HMF that occurs in many biomass pre-treatment processes does not have to be avoided, and in fact, biomass pre-treatment processes that leads to the formation of FF or HMF may be deliberately practiced for this purpose. [0038] The present invention uses either FF or HMF as starting material, the FF or HMF being formed, either separately or in combination, from pentoses and hexoses found in renewable biomass. FF is produced by the triple dehydration of pentose sugars and HMF is produced by the triple dehydration of the hexose sugars and FF or HMF as illustrated in Step 1 of FIG. 1. The biomass-derived FF or HMF is contacted with catalysts comprised of a number of metals, and such catalyst may or may not be supported, for example on a substrate such as silica, alumina, titania or carbon.

[0039] The carbonyl group of FF or HMF may be removed in a decarbonylation step (Step 2 in FIG. 1), or left present, and the use of appropriate metals in the catalyst, such as cobalt or Ni can facilitate the decarbonylation reaction. If desired, the decarbonylation reaction can be made to occur in a separate reactor physically distinct from the reactor in which the hydrogenation and hydrogenolysis reactions are performed.

[0040] The addition of hydrogen leads to a series of hydrogenolysis and hydrogenation reactions shown in FIG. 1 as Hydrogenation Steps 3a, 3b, 3c, 3d and 3x and 3z. It will be clear that following decarbonylation of HMF to furfuryl alcohol (FFalc), the chemistry will proceed through the same pathways as for furfuryl alcohol produced by hydrogenation of the carbonyl groups of FF.

[0041] Specifically, Step 3a is the hydrogenation of the carbonyl group of either FF or HMF to give a hydroxymethyl group in either case. Step 3b is the hydrogenolysis of the hydroxyl function of the hydroxymethyl group to leave a methyl group and produce water as a byproduct; it is believed that this hydrogenolysis most usually occurs if the furan ring has not been hydrogenated to the tetrahydrofuran species. Step 3c is the hydrogenation of the double bonds in the furan ring to give a tetrahydrofuran species, and Step 3d is

hydrogenolysis of the furan ring which causes the ring to open; this allows production of the acyclic products 1-butanol, 1-pentanol, and 2-pentanol. Step 3e is a combination of a hydrogenolysis reaction to open the tetrahydrofuran ring plus further hydrogenation reactions which reduce the presumed intermediate double bonds and aldehyde leaving the Ι,ω diols 1,5-pentanediol (PeDO) or 1,6-heaxanediol (HDO) from FF or HMF respectively.

[0042] Loss of carbon can occur via a hydrogenolysis reaction that Zheng et al report, that is, the hydrogenolysis of the entire hydroxymethyl group of furfuryl alcohol to leave furan with the presumed production of methanol; this is shown as Step 3x in FIG. 1. [0043] Specifically, in the pathway of reactions beginning with input FF and in which decarbonylation of FF takes place to give furan as the immediate product, Hydrogenolysis Step 3d opens the furan intermediate to 1-butanol, while Hydrogenation Step 3e simple takes the furan product of FF decarbonylation to tetrahydrofuran (THF). Hydrogenation Step 3z is shown for completeness; this take the carbon monoxide produced by

decarbonylation to methanol and on the methane.

[0044] In the pathway of reactions beginning with input FF and in which decarbonylation of FF does not occur, Hydrogenation Step 3a is the hydrogenation of the aldehyde carbonyl of furfural to produce furfuryl alcohol. Hydrogenation Step 3b is the hydrogenolysis of the hydroxyl group of furfuryl alcohol to produce methylfuran. Hydrogenation Step 3c is the hydrogenation of the double bonds of the furan ring. When this hydrogenation step occurs in the pathway of reactions where decarbonylation does previously occur, THF is produced. When this hydrogenation step occurs in the pathway of reactions where decarbonylation does not previously occur, MeTHF is produced. Hydrogenation Step 3d is the combined hydrogenolysis of the ether linkage of the furan ring with hydrogenation of the double bonds in the resulting ring-opened intermediate. In the pathway of reactions where decarbonylation does occur, Hydrogenation Step 3d produces 1-butanol from furan. In the pathway of reactions where decarbonylation does not occur, Hydrogenation Step 3d produces 1-pentanol from methylfuran. Hydrogenation Step 3x is the hydrogenolysis of the entire hydroxymethyl group, forming furan from furfuryl alcohol plus water as a by-product.

[0045] In the pathway of reactions where HMF is input instead of FF, and in which decarbonylation takes place, the immediate product is furfuryl alcohol (FFalc). It will be readily apparent from FIG. 1 that all further Hydrogenation Steps 3b, 3c, 3d, 3e and 3x and 3z will proceed as described above for the case in which FF is the input material and decarbonylation does not occur.

[0046] In the pathway of reactions where HMF is the input starting material and

decarbonylation does not occur, Step 3a is the hydrogenation of the aldehyde carbonyl of HMF to produce furan-2,5-dimethanol (FDM). Step 3b is the same hydrogenolysis reaction as described above, operating on one or both of the hydroxymethyl groups of FDM to produce 2,5-dimethylfuran (diMeF). As previously described, Step 3c is the hydrogenation of the double bonds of the furan ring to leave a tetrahydrofuran species giving

terahydrofuran-2,5-dimethanol (THFdiM). Also as previously described, Step 3e is a combination of a hydrogenolysis reaction to open the tetrahydrofuran ring plus hydrogenation reactions to reduce the presumed intermediate aldehyde functions to finally yield the Ι,ω-diol 1,6,-hexandiol (HDO).

[0047] According to some embodiments, the catalyst comprises copper, zinc, iron, nickel and cobalt. According to some embodiments, the catalyst comprises 10-80% Cu, 10-70 % Co, 4-20% Ni, 0.1-5% Zn and 0.1-5% Fe, wherein the percentages are given in atomic weight percentages.

[0048] According to some embodiments, the catalyst comprises 70-80% Cu, 9-25% Co, 2-8% Ni, 2-4% Zn and 0.5-2% Fe, wherein the percentages are given in atomic weight percentages.

[0049] According to some embodiments, the catalyst does not contain chromium.

[0050] Nine catalysts numbered PH0 through PH8 are made separately but following the same procedure in each case.

[0051] General Procedure for Catalyst Preparation

[0052] Using the atomic ratios given in list below, the required mass of copper, cobalt, nickel, iron, and zinc nitrates are calculated and weighed out. For each separate catalyst, the nitrate salts are combined in a beaker and 250 mL of water is added, and the mixture was stirred until the salts dissolved.

[0053] A I M solution of ammonium carbonate is made up in distilled water, and both the ammonium solution and metal solution are charged into separate burettes. A I L beaker is placed onto a magnetic stir-plate and the burettes were clamped in place above the beaker. A pH probe is placed in the 1 L beaker along with enough water to submerge the bottom of the probe. A stir bar is placed in the beaker and stirring is commenced. The burette containing the metal nitrate salts solution is opened first and the solution dripped into the beaker until the pH reaches approximately a value of 6. Then the burette containing the ammonium solution is opened and the stream of ammonium carbonate is adjusted to maintain the pH of the contents of the 1L beaker at near pH 6. A solid precipitate forms quickly, and the addition of both the nitrate salts solution and the ammonium carbonate solution are continued until all of the metal nitrate solution is used; stirring is continued at ambient temperature for approximately another 10 to 15 minutes.

[0054] The precipitate is recovered by simple vacuum filtration, and washed three times with water distilled water, and the recovered solid is placed in a drying oven at

approximately 100-110 ° C for 24 hours. The dried solid is then broken in to smaller particles using a mortar and pestle, and the ground material is calcined in an oven under nitrogen at 575 ° C for 24 hours. Upon cooling, the final material is further crushed using a mortar and pestle and separated into varying particle sizing using a stacked array of sieve screens. The desired catalysts particles are collected between sieve screens of 60 and 80 mesh and stored in an air tight container until required for use.

Table of Catalyst Compositions

[0055] General Procedure for Catalyst Use

[0056] In the examples, the reactions are carried out using a flow microreactor. Typically, a tubular fixed-bed reactor is used; 500mm in length with an internal diameter of 12mm. The reactor is charged with approximately 1 g of catalyst, and the reactor purged with a stream of H ₂ /N ₂ (5:95) at 1 atm. The reactor is gradually heated until it reaches 270°C and held at this temperature for about 10 minutes. The temperature is then set to the desired temperature, generally between 150°C and 300°C, and the gas flow is switched to 100% H ₂ .

[0057] The reactant, either FF or HMF, can be introduced into the reactor assembly in a continuous stream. For FF, this may be achieved by evaporating FF into the input gas stream, or by direct liquid injection using a syringe pump. For HMF, direct liquid injection is used.

[0058] The output of the reactor is analyzed using a GC/MS system, and the results are displayed in the tables below. Each table shows the relative mass amounts of each of the listed products for one catalyst across a range of temperatures using FF as the input substrate. RESULTS OF FF INPUT TO CATALYSTS PHO THROUGH PH8; RELATIVE MASS AMOUNTS (%) OF PRODUCTS CATALYST PHO

CATALYST PHI

CATALYST PH2

CATALYST PH3

CATALYST PH4

CATALYST PH5

CATALYST PH6

CATALYST PH7

CATALYST PH8

[0060] In one embodiment, the present invention may be used to produce THF from FF by using a catalyst comprising a metal or a combination of metals that promotes the decarbonylation of FF to furan (Step 2). Promoting Hydrogenation Step 3c relative to Hydrogenation Step 3d by lowering the temperature, reducing the residence time in the reactor, reducing the molar ratio of H ₂ , using metals known to favor hydrogenation over hydrogenolysis, or any combination of these, leads to the production of THF.

[0061] In a related embodiment, the present invention may be used to produce 1-butanol from FF by using a catalyst comprising a metal or a combination of metals that promotes the decarbonylation of FF to furan. Promoting Hydrogenation Step 3d relative to Hydrogenation Step 3c by increasing the temperature, increasing the residence time in the reactor, increasing the molar ratio of H ₂ , using metals known to favor hydrogenolysis over hydrogenation, or any combination of these, leads to the production of 1-butanol.

[0062] In another embodiment, the present invention may be used to produce MeTHF from FF by using a catalyst comprising a metal or a combination of metals that suppresses the decarbonylation of FF to furan while promoting Hydrogenation Step 3a, so that furfuryl alcohol is produced, and no is furan produced for further reaction. Further, in this embodiment, Hydrogenation Step 3b is promoted so that methylfuran is produced. Promoting Hydrogenation Step 3c relative to Hydrogenation Step 3d by lowering the temperature, reducing the residence time in the reactor, reducing the molar ratio of H ₂ , using metals known to favor hydrogenation over hydrogenolysis, or any combination of these, leads to the production of MeTHF.

[0063] In a another embodiment of the invention, FF may be provided as the input material and the catalyst composition and reaction conditions are chosen to avoid the decarbonylation of FF to furfuryl alcohol, i.e. avoid Step 2 shown in FIG. 1, allowing subsequent hydrogenation and hydrogenolysis reactions leading to PeDO.

[0064] In a another embodiment of the invention, HMF may be provided as the input material and the catalyst composition and reaction conditions chosen to promote the decarbonylation of HMF to furfuryl alcohol, i.e. enhance Step 2 shown in FIG. 1, such that furfuryl alcohol formed in good yield and will be available for subsequent hydrogenation and hydrogenolysis reactions leading to the formation of methylfuran, methyltetrahydrofuran, 1-pentanol, and the corresponding products of further hydrogenolysis, i.e. tetrahydrofuran and 1-butanol.

[0065] In a another embodiment of the invention, HMF may be provided as the input material and the catalyst composition and reaction conditions are chosen to avoid the decarbonylation of HMF to furfuryl alcohol, i.e. avoid Step 2 shown in FIG. 1, or reduces it to such a degree that any furfuryl alcohol formed is at a sufficiently low concentration that it does not interfere with the desired, subsequent hydrogenation and hydrogenolysis reactions leading to HDO.

[0066] In any embodiment of the present invention, the introduction of the starting materials FF or HMF and hydrogen into the reactor assembly containing the catalyst may be performed in any manner that provides a convenient fluid stream to the reactor assembly. The input fluid stream may be a liquid, a gas, or a combination of both. Non-limiting examples of such a fluid input stream include;

a) a mixture of FF vapor mixed with H ₂ , and

b) a mixture of FF vapor mixed with H ₂ and an optional carrier fluid such as N ₂ , water- vapor, C0 ₂ , or an organic solvent vapor, and

c) a liquid stream containing FF or HMF in a suitable organic solvent which is mixed with H ₂ or H ₂ and an optional carrier fluid, and

d) a stream of FF or HMF in a supercritical fluid that is mixed with H ₂ and an optional

carrier fluid which may also be in a supercritical state, or dissolved or entrained in the supercritical fluid.

[0067] It will also be clear that the introduction of the hydrogen to the process may be performed in a manner such that the hydrogen is first mixed with the fluid input stream prior to entering the reactor assembly, or the hydrogen may be input to the reactor assembly as a separate input stream. In either case, the hydrogen may be presented as a gas, or as a mixture or solution of hydrogen in a carrier fluid or a carrier gas.

[0068] The degree of reaction for a given starting material over a given catalyst may be controlled by adjusting the following parameters:

1) Temperature of the reactor 2) Flow rate of the combined reactant stream and H ₂ stream through the reactor (i.e. residence time)

3) Molar ratio of H ₂ to reactant in the input stream.

[0069] It will also be clear that in any embodiment of the present invention in which the decarbonylation step (Step 2 in FIG. 1) is desired, the decarbonylation step may be performed in a separate reactor assembly that is connected in series to a second reactor assembly in which the reactions with hydrogen are performed while still being part of the overall process. In this manner, a catalyst comprising a metal known to promote decarbonylation, such as Pd or Pt, may be used at a temperature also known to promote decarbonylation, but which is different than the temperature required for optimizing further reactions with hydrogen, such as Steps 3a through 3d previously described.

[0070] Similarly, in an embodiment of the present invention in which decarbonylation (Step 2 in FIG. 1) is to be avoided and Step 3a is desired, Step 3a may be performed in a separate reactor assembly that is connected in series to a second reactor assembly in which the subsequent reactions with hydrogen are performed while still being part of the overall process. In this manner, a catalyst known to promote Step 3a may be used at a temperature also known to promote Step 3a, but which is different than the temperature required for optimizing further reactions with hydrogen as shown in FIG. 1.

[0071] The catalyst contained in the reactor assembly may be unsupported, or on a support. In the case of a supported catalyst, the support may be chosen to promote or suppress other chemical reactions. For example, use of an acidic support, such as Si0 ₂ , will promote dehydration of primary alcohols. For example, 1-butanol may be undergo further reaction to give 1-butene and 1-pentanol may react to give 1-pentene.

[0072] Various aspects of the present invention may be used alone, in combination, or in a variety of arrangements not specifically discussed in the embodiments described in the foregoing and is therefore not limited in its application to the details and arrangement of components set forth in the foregoing description or illustrated in the drawings. For example, aspects described in one embodiment may be combined in any manner with aspects described in other embodiments. [0073] Use of ordinal terms such as "first," "second," "third," etc., in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements.

[0074] Also, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of "including," "comprising," or "having,"

"containing," "involving," and variations thereof herein, is meant to encompass the items listed thereafter and equivalents thereof as well as additional items.

[0075] The present invention provides among other things novel methods for the production of specific chemical compounds. While specific embodiments of the subject invention have been discussed, the above specification is illustrative and not restrictive. Many variations of the invention will become apparent to those skilled in the art upon review of this specification. The full scope of the invention should be determined by reference to the claims, along with their full scope of equivalents, and the specification, along with such variations.

[0076] All publications, patents and patent applications cited above are incorporated by reference herein in their entirety for all purposes to the same extent as if each individual publication or patent application were specifically indicated to be so incorporated by reference.