Patent Grant
8236972
Provided herein is a process for enhancing molecular mass of biomass reactants. More specifically, the process involves preparing unsaturated organic compounds with one or more electron withdrawing groups from biomass-derived aldehydes or ketones such as furfurals. These compounds can then be further convened to branched hydrocarbons (e.g. alkanes or alkenes) by hydrodeoxygenation and/or hydrodenitrogenation to reduce unsaturation, oxygen, and/or nitrogen content.
In light of energy prices and environmental concerns, processes for the production of fuels from renewable feedstocks are needed. The most common process involves producing ethanol from corn. Unfortunately, using corn and the like as precursors competes with food and feed supplies.
Some processes employ lignocellulosic biomass as a feedstock because it is readily available and competitively priced. Lignocellulosic biomass often comprises polymeric carbohydrates (cellulose and hemicelluose), complex poly-aromatics (lignin), extractives and ashes and thereby does not compete with food and feed supplies.
WO 2007/103858, incorporated herein by reference, describes using biomass-derived carbohydrates to form alkanes. An aldol condensation of acetone with furfural or 5-hydroxymethyl furfural (HMF) followed by reduction of the coupled product in hydrogen gives alkanes having from approximately 8 to 18 carbon atoms. Unfortunately, the described process has numerous disadvantages. For example, the reactions often require a high strength base. Moreover, the low degree of branching of the derived alkanes also results in a low octane numbers which limit their use in izasoline. Therefore, the production of practical gasoline fuels from biomass using prior art methods requires additional processing steps adding to the cost and inefficiencies.
Accordingly, new processes are needed for use in making biofuels which are more efficient and more cost effective.
The instant invention provides new processes for use in making biofuels which are often efficient and may also be cost effective. In one embodiment, the instant invention relates to a process for enhancing molecular mass of biomass reactants comprising first forming a substituted or unsubstituted furfural from a biomass. Next, the substituted or unsubstituted furfural is reacted with an activated methylene compound comprising at least one electron withdrawing group in the presence of a catalyst. This results in the formation of a substituted or unsubstituted furan compound comprising one or more electron-withdrawing groups.
In another embodiment, the instant invention relates to a process for enhancing molecular mass of biomass reactants comprising first forming a substituted or unsubstituted aldehyde or ketone from a biomass. Next, the substituted or unsubstituted aldehyde or ketone is reacted with an activated methylene compound comprising at least one electron withdrawing group in the presence of a catalyst to form a substituted or unsubstituted Knoevenagel product. The substituted or unsubstituted Knoevenagel product is then reacted with H2, or another reducing agent to form a hydrodeoxygenated and/or hydrodenitrogenated product.
The instant invention relates to a process for enhancing molecular mass of biomass reactants. The process comprises first forming a substituted or unsubstituted aldehyde such as furfural, substituted or unsubstituted ketone, or mixture thereof from a biomass. The origin and type of the biomass employed is not particularly critical so long as it supplies the desired substituted or unsubstituted compound. A particularly preferable biomass is a lignocellulosic biomass, i.e., a plant biomass typically comprised of for example, cellulose, hemicellulose, poly(aromatics), such as lignin, extractives, ash, and mixtures thereof. Such lignocellulosic biomasses often comprise carbohydrate polymers (cellulose and hemicelluloses) tightly bound to the lignin, by hydrogen and covalent bonds. Biomass comes in many different types, which may be grouped into a few main categories: wood residues, including sawmill and paper mill discards, municipal paper waste, algae agricultural residues, including corn stover (stalks and straw), and sugarcane bagasse, and dedicated energy crops, which are mostly composed of fast growing tall, woody grasses.
Any of the aforementioned may find use in the instant invention. A particularly preferable biomass comprises one wherein greater than about 50, preferably greater than 60 weight percent of the biomass comprises carbohydrates.
The specific substituted or unsubstituted aldehyde, or ketone compound is not particularly critical so long as it is capable of being reacted with an activated methylene compound comprising at least one electron withdrawing group. i.e., a group capable of drawing electrons away from a reaction center, in the presence of a catalyst and, if desired, a solvent to form a Knoevenagel product.
Typical Knoevenagel reactants include substituted or unsubstituted aldehydes or ketones such as furan derivatives. The products typically include olefins and comprise one or more electron withdrawing groups and one or more carbon-carbon double bonds. Particularly preferable starting substituted or unsubstituted aldehyde or ketone compounds may be selected from the group consisting of substituted or unsubstituted aldehydes or ketones having from about five to about 9 carbon atoms. Suitable aldehydes or ketones include substituted or unsubstituted furfural, other bio-mass-derived aldehydes or ketones, as well as, mixtures thereof. Particularly preferable furfurals comprise unsubstituted furfural, 5-hydroxymethyl-furfural, and mixtures thereof.
The reaction between the substituted or unsubstituted aldehyde or ketone compound and activated methylene compound may occur in any convenient vessel, at any convenient temperature, and any convenient pressure. The reaction time, temperature, and pressure to be employed will vary depending upon the ingredients, desired products, and other reaction conditions. In this vein, closed pressure reactors or vessels equipped with condensers may be employed. Typically, while the reaction may be conducted at gentle reflux, the higher the temperature the faster the reaction will occur. Useful temperatures are often greater than about 50, preferably greater than about 60, preferably greater than 70, preferably greater than 75° C. Pressures typically range from atmospheric to elevated pressures generated autogenously in closed vessels.
The activated methylene compound employed may be any methylene compound capable of donating a proton when used with, for example, a basic catalyst. Useful activated methylene compounds may comprise a methylene group (CH2) associated with one or two electron withdrawing groups such as carboxylic acids, ester or nitrile groups. Particularly preferable activated methylene compounds comprise substituted or unsubstituted malonic acid, its esters or derivatives thereof, as well as, malononitrile or a suitable derivative thereof, and substituted or unsubstituted levulinic acid, its esters or derivatives thereof. Suitable malonic acid esters may include any ester of malonic acid, preferably methyl and ethyl esters of malonic acid. Employing malonic acid as the activated methylene compound in a reaction with unsubstituted furfural, 5-hydroxymethyl-furfural, or mixtures thereof in the instant process usually results in Knoevenagel products comprising 2-((furan-2-yl)methylene)malonic acid, 2-((5-(hydroxymethyl)furan-2-yl)methylene)malonic acid, or a mixture thereof. Also, depending on the catalyst used, decarboxylation of the primary product may yield the following unsaturated mono-carboxylic acids: 3-(5-(hydroxymethyl)furan-2-yl)acrylic acid and 3-(furan-2-yl)acrylic acid.
The catalyst for the reaction between the substituted or unsubstituted aldehyde or ketone compound such as furfural and activated methylene compound varies depending upon, for example, the ingredients and reaction conditions. Typically, the catalyst comprises a base capable of extracting a proton from the activated methylene to form the desired substituted or unsubstituted Knoevenagel products or mixture thereof. Fortunately, such bases may often be of less strength than those required in, for example, aldol condensation. Bases with a strength (pKB) of less than 6, preferably from about 3 to about 4 are often useful in the present invention. Typically, a suitable catalyst has a high surface area so that a high concentration of basic sites are exposed. Suitable catalysts include a catalyst selected from the group consisting of supported organic bases (e.g. ethylenediamine supported on poly(styrene), 3-aminopropyl-functionalized silica, dimethylaminopyridine on poly(styrene)), a solid base such as MgO, basic alumina, hydrotalcites, oxynitrides, alkali exchanged zeolites, and mixtures thereof.
Depending on the ingredients a solvent may be useful for the reaction between the substituted or unsubstituted aldehyde or ketone compounds and activated methylene compound. The specific solvent to be employed is usually not particularly critical so long as it is capable of significantly dissolving either the aldehyde or ketone or the activated methylene compounds. In some cases, one or both reactants can be used as solvents themselves. Thus, useful solvents may vary depending upon, for example, the ingredients and reaction conditions. Suitable solvents may include those selected from the group consisting of tetrahydrofuran (THF), ethyl acetate, diethyl ether, toluene, hexanes, water, isopropanol, and mixtures thereof.
Illustrative embodiments of the aforementioned process are described in
The substituted or unsubstituted Knoevenagel products formed in the aforementioned process may be further reacted to, for example, remove oxygen and/or nitrogen and form alkenes, alkanes, oxygenates or mixtures thereof which may be useful in or as fuels. Such further reactions processes may include, for example, hydrodeoxygenating and/or hydrodenitrogenating the substituted or unsubstituted Knoevenagel product to form a partially or fully reduced product. That is a hydrodeoxygenated product has at least one fewer oxygen atoms than the precursor Knoevenagel product, i.e., it is partially hydrodeoxygenated. Preferably, hydrodeoxygenated products have about 50% up to substantially all of the oxygen atoms removed, i.e., it is fully hydrodeoxygenated. Useful hydrodeoxygenating and hydrodenitrogenating steps are described in, for example, U.S. 20070135316 incorporated herein by reference. This may be readily accomplished by reacting the substituted or unsubstituted Knoevenagel product with H2, or another reducing agent to form a product which is hydrodeoxygenated, hydrodenitrogenated, or both.
Advantageously, hydrodeoxygenated and/or hydrodenitrogenated products of the present invention are often characterized by one or more of the following characteristics: (1) a viscosity (as measured by ASTM D7042-04) of less than the substituted or unsubstituted Knovenagel product; (2) an energy density (as measured by ASTM D240-02) of greater than the substituted or unsubstituted Knovenagel product; or (3) a physical and/or chemical stability (as measured by ASTM D6468-06) of greater than the substituted or unsubstituted Knovenagel product.
Often, depending upon the reaction and starting materials, the hydrodeoxygenated and/or hydrodenitrogenated products are advantageously comprised of a significant amount of substituted or unsubstituted branched alkenes or alkanes. Branched alkenes and alkanes are desirable because when fully hydrogenated branched alkenes and alkanes will usually have a higher octane rating than for fully hydrogenated n-alkenes and n-alkanes with the same molecular weight. Similarly, branched partially reduced products containing some oxygen generally have a higher octane rating than a corresponding straight chain partially reduced products containing substantially the same or the same oxygen-containing functional groups. Alkenes are particularly desirable because they often have a higher octane rating than alkanes. Moreover, the presence of the double bond in the ydrodeoxygenated and/or hydrodenitrogenated products allows for further increase of the molecular weight by dimerization or addition reactions. Further increasing the molecular weight through, for example, oligomerization, followed by hydrogenation to improve thermal and oxidative stability often makes the resulting compounds more useful in fuels such as diesel.
The oligomerization of olefins has been well reported in the literature, and a number of commercial processes are available. See, for example, U.S. Pat. Nos. 4,417,088; 4,434,308, 4,827,064; 4,827,073; 4,990,709; 6,703,535. Various types of reactor configurations may be employed, with the fixed catalyst bed reactor being used commercially. More recently, performing the oligomerization in an ionic liquids media has been proposed, since the contact between the catalyst and the reactants is efficient and the separation of the catalyst from the oligomerization products is facilitated. Preferably, the oligomerized product will have an average molecular weight at least 10 percent higher than the initial feedstock, more preferably at least 20 percent higher. The oligomerization reaction will proceed over a wide range of conditions. Typical temperatures for carrying out the reaction are between about 0° C. and about 425° C. Other conditions include a space velocity from 0.1 to 3 LHSV and a pressure from 0 to 2000 psig. Catalysts for the oligomerization reaction can be virtually any acidic material, such as, for example, zeolites, clays, resins BF3 complexes, HF, H2SO4, AlCl3, ionic liquids (preferably ionic liquids containing a Bronsted or Lewis acidic component or a combination of Bronsted and Lewis acid components), transition metal-based catalysts (such as Cr/SiO2), superacids, and the like. In addition, non-acidic oligomerization catalysts including certain organometallic or transition metal oligomerization catalysts may be used, such as, for example, zirconocenes.
A solution of 0.192 g furfural and 0.208 g malonic acid in 8 ml THF was prepared in a pressure tube and 25 mg 3-aminopropyl on silica on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 13 h a conversion of 99% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 8 ml THF was prepared in a pressure tube and 25 mg 3-aminopropyl on silica was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 24 h a conversion of 71% (aldehyde) was observed.
A solution of 0.192 g furfural and 0.208 g malonic acid in 8 ml THF was prepared in a pressure tube and 10 mg dimethylaminopyridine on polystyrene was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 13 h a conversion of 8% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 8 ml THF was prepared in a pressure tube and 25 mg 3-aminopropyl on silica was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 13 h a conversion of 66% (aldehyde) was observed.
A solution of 0.192 g furfural and 0.208 g malonic acid in 8 ml THF was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 13 h a conversion of 49% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 8 ml THF was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 13 h a conversion of 81±6% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.08 g malonic acid in 10 ml ethyl acetate was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 1 h a conversion of 53% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml diethyl ether was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 1 h a conversion of 52% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml isopropanol was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 1 h a conversion of 54% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml THF was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 69% (aldehyde) was observed.
A solution of 0.192 g furfural and 0.208 g malonic acid in 10 ml isopropanol was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 1 h a conversion of 42% (aldehyde) was observed.
A solution of 0.192 g furfural and 0.208 g malonic acid in 10 ml ethyl acetate was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 1 h a conversion of 41% (aldehyde) was observed.
A solution of 0.192 g furfural and 0.208 g malonic acid in 10 ml THF was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 1 h a conversion of 40% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml THF was prepared in a 2 two-neck flask with a reflux condenser and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The flask was placed in an oil bath that was heated to 70° C. After a reaction time of 5 h a conversion of 71% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml THF was prepared in a pressure tube and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 62% (aldehyde) was observed.
A solution of 0.48 g furfural and 0.520 g malonic acid in 25 ml THF was prepared in a two-neck flask and 30 mg ethylenediamine on poly(styrene) was added as catalyst. The flask was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 65% (aldehyde) was observed.
A solution of 0.64 g HMF and 0.502 g malonic acid in 25 ml THF was prepared in a two-neck flask and 30 mg ethylenediamine on poly(styrene) was added as catalyst. The flask was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 79% (aldehyde) was observed.
A solution of 0.96 g furfural and 1.04 g malonic acid in 10 ml THF was prepared in a pressure tube and 18 mg homogeneous ethylenediamine was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 4 h a conversion of 89±4% (aldehyde) was observed.
A solution of 0.196 g furfural and 0.208 g malonic acid in 10 ml THF was prepared in a three-neck flask and 12 mg ethylenediamine on poly(styrene) was added as catalyst. The flask was placed in an oil bath that was heated to 70° C. After a reaction time of 4 h a conversion of 43% (aldehyde) was observed.
A solution of 0.196 g furfural and 0.208 g malonic acid in 10 ml THF was prepared in a pressure tube and 10 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 4 h a conversion of 53% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml THF was prepared in a three-neck flask and 10 mg ethylenediamine on poly(styrene) was added as catalyst. The flask was placed in an oil bath that was heated to 80° C. After a reaction time of 10 h a conversion of 90% (aidehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml THF (with BHT inhibitor) was prepared in a pressure tube and 20 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 70% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml THF (with BHT inhibitor) was prepared in a pressure tube and 30 mg ethylenediamine on polystyrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 86% (aldehyde) was observed.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml THF (with BHT inhibitor) was prepared in a pressure tube and 40 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 90% (aldehyde) was observed in several experiments.
A solution of 0.252 g HMF and 0.123 g malononitrile in 10 ml THF (with BHT inhibitor) was prepared in a pressure tube and 10 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 96% (aldehyde) was observed.
A solution of 0.196 g furfural and 0.123 g malononitrile in 10 ml THF (with BHT inhibitor) was prepared in a pressure tube and 10 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 95% (aldehyde) was observed.
A solution of 0.196 g furfural and 0.123 g malonic acid in 10 ml THF (with BHT inhibitor) was prepared in a pressure tube and 10 mg magnesium oxide was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 10% (aldehyde) was observed. The relatively low observed conversion could possible be due to the deactivation of the catalyst.
A solution of 0.252 g HMF and 0.123 g malononitrile in 10 ml THF (with BUT inhibitor) was prepared in a pressure tube and 2 μl ethylenediamine (homogeneous) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 99% (aldehyde) was observed.
The conversion of biomass may result in mixtures of pentoses and hexoses that can possibly be dehydrated to furfural and hydroxymethylfurfural (HMF), respectively. The Knoevenagel reaction for mixtures of the two aldehydes was investigated by preparing a solution of 0.252 g HMF, 0196 g furfural, and 0.208 g malonic acid in 10 ml THF in a pressure tube. Twelve mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 1 h a conversion of 20±1 and 19±1% was observed for HMF and furfural, respectively.
A solution of 0.252 g HMF and 0.208 g malonic acid in 10 ml THF was prepared in a pressure tube and 10 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 5 h a conversion of 64±5% (aldehyde) was observed with a selectivity for the di-acid of 99%. The decarboxylated HMF product was identified with a selectivity of 1%.
A solution of 0.196 g furfural and 0.208 g malonic acid in 10 ml THF was prepared in a pressure tube and 10 mg ethylenediamine on poly(styrene) was added as catalyst. The tube was placed in an oil bath that was heated to 80° C. After a reaction time of 5 h a conversion of 50% (aldehyde) was observed with a selectivity for the di-acid of 95%. The decarboxylated furfural product was identified with a selectivity of 5%.
A solution of 0.196 g furfural and 0.208 g malonic acid in 10 ml THF was prepared in a pressure tube and 30 mg 3-aminopropyl on silica was added as catalyst. The tube was placed in an oil bath that was heated to 70° C. After a reaction time of 5 h a conversion of 53% (aldehyde) was observed with a selectivity for the di-acid of 99%.
A solution of 2 mmol (0.252 g) HMF and 2 mmol (0.208 g) malonic acid in 10 ml ethyl ether or 10 ml ethyl acetate was prepared and 10 mg of ethylenediamine on poly(styrene) was added as catalyst. The mixture was heated to 80° C. for 5 hours. In both cases, the solid product 2-((5-(hydroxymethyl)furan-2-yl)methylene)malonic acid precipitated out of the solution in approximately 50% yield and 99% selectivity.
Samples of the product of some of the above examples were analyzed by NMR.
All publications and patent applications mentioned in this specification are herein incorporated by reference to the sane extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be readily apparent to those of ordinary skill in the art in light of the teachings of this invention that certain changes and modifications may be made thereto without departing from the spirit or scope of the appended claims.
| Number | Name | Date | Kind |
|---|---|---|---|
| 4417088 | Miller | Nov 1983 | A |
| 4434308 | Larkin et al. | Feb 1984 | A |
| 4827064 | Wu | May 1989 | A |
| 4827073 | Wu | May 1989 | A |
| 4990709 | Wu | Feb 1991 | A |
| 6518440 | Lightner | Feb 2003 | B2 |
| 6703535 | Johnson et al. | Mar 2004 | B2 |
| 7850841 | Koivusalmi et al. | Dec 2010 | B2 |
| 7880049 | Dumesic et al. | Feb 2011 | B2 |
| 20070135316 | Koivusalmi et al. | Jun 2007 | A1 |
| Number | Date | Country |
|---|---|---|
| WO 2007103858 | Sep 2007 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20100029926 A1 | Feb 2010 | US |
