Patent Application
20100212217
The present invention concerns a method for the manufacture of an ether of 5-hydroxymethylfurfural (5-(hydroxymethyl)-2-furaldehyde, or HMF) from HMF and olefins.
Fuel, fuel additives and various chemicals used in the petrochemical industry are derived from oil, gas and coal, all finite sources. Biomass, on the other hand, is considered a renewable source. Biomass is biological material (including biodegradable wastes) which can be used for the production of fuels or for industrial production of e.g. fibres, chemicals or heat. It excludes organic material which has been transformed by geological processes into substances such as coal or petroleum.
Production of biomass derived products for non-food applications is a growing industry as interest in sustainable fuel sources is growing. Bio based fuels are an example of an application with strong growing interest. Biomass contains sugars (hexoses and pentoses) that may be converted into value added products. Current biofuel activities from sugars are mainly directed towards the fermentation of sucrose or glucose into ethanol or via complete breakdown via Syngas to synthetic liquid fuels.
EP 0641 854 describes the use of fuel compositions comprising of hydrocarbons and/or vegetable oil derivatives containing at least one glycerol ether to reduce particulate matter emissions.
More recently, the acid catalysed reaction of fructose has been re-visited, creating HMF as an intermediate of great interest. Most processes investigated have the disadvantage that HMF is not very stable at the reaction conditions required for its formation. Fast removal from the water-phase containing the sugar starting material and the acid catalyst has been viewed as a solution for this problem. Researchers at the University of Wisconsin-Madison have developed a process to make HMF from fructose. HMF can be converted into monomers for plastics, petroleum or fuel extenders, or even into fuel itself. The process by prof. James Dumesic and co-workers first dehydrates the fructose in an aqueous phase with the use of an acid catalyst (hydrochloric acid or an acidic ion-exchange resin). Salt is added to salt-out the HMF into the extracting phase. The extracting phase uses an inert organic solvent that favors extraction of HMF from the aqueous phase. The two-phase process operates at high fructose concentrations (10 to 50 wt %), achieves high yields (80% HMF selectivity at 90% fructose conversion), and delivers HMF in a separation-friendly solvent (DUMESIC, James A, et al. “Phase modifiers promote efficient production of Hydroxymethylfurfural from fructose”. Science. 30 juni 2006, vol. 312, no. 5782, p. 1933-1937). Although the HMF yields from this process are interesting, the multi-solvent process has cost-disadvantages due to the relatively complex plant design and because of the less than ideal yields when cheaper and less reactive hexoses than fructose, such as glucose or sucrose, are used as a starting material. HMF is a solid at room temperature which has to be converted in subsequent steps to useful products. Dumesic has reported an integrated hydrogenolysis process step to convert HMF into dimethylfuran (DMF), which is assumed to be an interesting gasoline additive.
In WO 2006/063220 a method is provided for converting fructose into 5-ethoxymethylfurfural (EMF) at 60° C., using an acid catalyst either in batch during 24 hours or continuously via column elution during 17 hours. Applications of EMF were not discussed.
Nonetheless, there remains an interest in a much more efficient and faster method for the manufacture of HMF ethers without the formation of by-products and uncontrolled degradation and without the restriction of using the ethanol reagent as the reaction solvent. The inventors have set out to overcome this shortfall.
In a companion patent application, the inventors have described a method for the manufacture of an ether of 5-hydroxymethylfurfural by reacting a fructose and/or glucose-containing starting material with an olefin in the presence of an acid catalyst. This reaction is believed to proceed through the intermediate HMF, which is then reacted with olefin in the presence of the acid catalyst. The inventors have found that the same products may be made from HMF itself, for instance when the HMF is made by any of the prior art processes and isolated for further derivatization.
Accordingly, the current invention provides a method for the manufacture of an ether of 5-hydroxymethylfurfural through hydro-alkoxy-addition by reacting 5-hydroxymethylfurfural with an olefin in the presence of an acid catalyst.
When the reaction product of the above method is used as such or when it is used as an intermediate for a subsequent conversion the selectivity of the reaction is preferably high as the product is preferably pure. However, when the reaction product of the above method is used as a fuel, a fuel additive or as a fuel or a fuel additive intermediate, the reaction product does not necessarily need to be pure. Indeed, the HMF starting material may contain non-interfering components or components with an alcoholic functionality which may be converted to their ethers at the same time. Other hydroxymethylfuran derivatives will also be converted into their corresponding tert-butoxymethyl ether derivatives. The ultimate reaction product may therefore contain non-interfering components such as other furan ethers and levulinic acid derivatives. For ease of reference, however, the method and the reaction product are described in terms of the reaction of HMF starting material with an olefin, resulting in an ether of HMF.
The current invention also provides for the use of the reaction product made according to the present invention as fuel or as fuel additive. Fuels for blending with the product of the present invention include but are not limited to gasoline and gasoline-ethanol blends, kerosene, diesel, biodiesel (refers to a non-petroleum-based diesel fuel consisting of short chain alkyl (methyl or ethyl) esters, made by transesterification of vegetable oil, which can be used (alone, or blended with conventional petrodiesel) in unmodified diesel-engine vehicles), Fischer-Tropsch liquids (for example obtained from GTL, CTL or BTL gas-to-liquids/coal-to-liquids/biomass to liquids processes), diesel-biodiesel blends and green diesel and blends of diesel and/or biodiesel with green diesel (green diesel is a hydrocarbon obtained by hydrotreating biomass derived oils, fats, greases or pyrolysis oil; see for example the UOP report OPPORTUNITIES FOR BIORENEWABLES IN OIL REFINERIES FINAL TECHNICAL REPORT, SUBMITTED TO: U.S. DEPARTMENT OF ENERGY (DOE Award Number: DE-FG36-05GO15085)). The product is a premium diesel fuel containing no sulfur and having a cetane number of 90 to 100). Fuels for blending with the product of the present invention may also include one or more other furanics, wherein the expression furanics is used to include all derivatives of furan and tetrahydrofuran. The invention also provides a fuel composition comprising a fuel element as described above and the reaction product made according to the present invention. The HMF ethers of the invention can also be used as or can be converted to compounds that can be used as solvent, as monomer in a polymerization, as fine chemical intermediate, or in other applications.
The synthesis of HMF from fructose, glucose and sucrose as a biomass source is a hot topic. HMF has been obtained in processes using both homogeneous and heterogeneous catalysts, using different diluent systems such as water, 2 phase systems for extracting the HMF into an organic phase after its formation, or using diluent systems such as acetone, dmso or ionic liquids.
The olefin used in the method of the current invention is preferably an olefinically unsaturated compound that is susceptible to electrophilic attack. It would thus appear that concurrent with the dehydration of the monosaccharide, a hydro-alkoxy-addition occurs. The addition of alcohols and phenols to the double bond of an olefinically unsaturated compound is discussed in Chapter 15 of Advanced Organic Chemistry, by Jerry March, and in particular under reaction 5-4. (3rd ed., © 1985 by John Wiley & Sons, pp. 684-685). This reference book, however, provides no information on the preparation of renewable liquid fuel (additives). Surprisingly, the in-situ preparation of the HMF is not hampered by the hydro-alkoxy-addition.
This reaction is therefore different, and the products are therefore different from the 2,3-unsaturated o-glycosides synthesized by Filho J. R. DE FREITAS et al, “Synthesis of new 2,3-unsaturated o-glycosides through ferrier rearrangement”, in Journal of Carbohydrate Chemistry, 2001, vol. 20, pages 561-568. In this synthesis, an unsaturated o-glycal is converted into an unsaturated glycoside, by Sn2′ attack of the alcohol oxygen at C1, with subsequent elimination of the complexed O-acetyl group, as opposed to the hydroxyl-alkoxy-addition where the unsaturated carbon-carbon bond is reacted away.
Preferred olefins contain 4 carbon atoms or more. Ethylene and propylene are also possible but will be very slow to react, whereas isobutylene has been found to be very useful. Indeed, preferred olefins are cycloolefins and substituted iso olefins such as isobutene, 2-methyl-2-butene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, 1-methylcyclopentene, the C7 iso olefins and similar C8 and higher olefins. Also suitable are dienes such as butadiene and isoprene and terpenes such as pinene and limonene. These olefins may be represented by the general formulae
HRC=CR′R″
H2C=CR′R″
wherein each R, R′ and R″ independently represents an alkyl, aralkyl and alkenyl group which may be linear, branched or cyclic with up to 7 carbon atoms, or R and R′ jointly represent an alkenyl group with up to 7 carbon atoms. Of these, substituted olefins having up to 8 carbon atoms in total are preferred, with isobutylene being most preferred. The iso olefins used as reagents are generally used in mixture with other hydrocarbons of similar boiling points. For instance isobutene feedstocks usually are C4 cuts from Fluid Catalytic Cracking (FCC) plants, from Steam Cracking plants or from field butanes Dehydrogenation/Isomerization plants. Depending on their origin, these C4 cuts usually contain between 20 and 50 wt % isobutene. The hydro-alkoxy addition reaction is highly selective so that nearly only the isoolefins are converted to ethers.
Another class of olefins found to be suitable are cyclic olefins, such as cyclopentene, cyclohexene and alkyl-substituted derivatives thereof. These olefinically unsaturated compounds may contain elements other than carbon, such as oxygen, provided the olefinically unsaturated bond remains susceptible to electrophilic attack and provided that the other functional groups are compatible with the acid catalysed dehydration reactions and with the hydrolytic cleavage reactions.
The amount of olefin used during the manufacture of the HMF ether is preferably at least equimolar to the HMF content in the feedstock, but it is typically used in much greater excess. Indeed, the olefin (such as dihydropyran) may be used as solvent or co-solvent. In such a case, a sufficient amount of olefin is present to form the HMF ether. The catalyst is preferably selected such that the olefins are not reacting to dimers, oligomers and or polymers.
The acid catalyst in the method of the present invention can be selected from amongst (halogenated) organic acids, inorganic acids, Lewis acids, ion exchange resins and zeolites or combinations and/or mixtures thereof. It may be a homogeneous catalyst, but heterogeneous catalysts (meaning solid) are preferred for purification reasons. The HMF ethers can be produced with a protonic, Brønsted or, alternatively, a Lewis acid or with catalysts that have more than one of these acidic functionalities.
The protonic acid may be organic or inorganic. For instance, the organic acid can be selected from amongst oxalic acid, levulinic acid, maleic acid, trifluoro acetic acid (triflic acid), methanesulphonic acid or para-toluenesulphonic acid. Alternatively, the inorganic acid can be selected from amongst (poly)phosphoric acid, sulphuric acid, hydrochloric acid, hydrobromic acid, nitric acid, hydroiodic acid, optionally generated in situ.
Certain salts may be used as catalyst, wherein the salt can be any one or more of (NH4)SO4/SO3, ammonium phosphate, pyridinium chloride, triethylamine phosphate, pyridinium salts, pyridinium phosphate, pyridinium hydrochloride/hydrobromide/perbromate, DMAP, aluminium salts, Th and Zr ions, zirconium phosphate, Sc and lanthanide ions such as Sm and Y as their acetate or trifluoroactate (triflate) salt, Cr—, Al—, Ti—, Ca—, In-ions, ZrOCl2, VO(SO4)2, TiO2, V-porphyrine, Zr—, Cr—, Ti-porphyrine.
Lewis acids selected as dehydration catalyst can be any one of ZnCl2, AlCl3, BF3. Ion exchange resins can be suitable dehydration catalysts. Examples include Amberlite™ and Amberlyst™, Diaion™ and Levatit™. Other solid catalyst that may be used include natural clay minerals, zeolites, supported acids such as silica impregnated with mineral acids, heat treated charcoal, metal oxides, metal sulfides, metal salts and mixed oxides and mixtures thereof. If elevated reactions temperatures are used, as defined hereafter, then the catalyst should be stable at these temperatures.
An overview of catalysts that may be used in the method of the current invention may be found in Table 1 of the review article prepared by Mr. Lewkowski: “Synthesis, chemistry and applications of 5-hydroxymethylfurfural and its derivatives” Arkivoc. 2001, p. 17-54.
The amount of catalyst may vary, depending on the selection of catalyst or catalyst mixture. For instance, the catalyst can be added to the reaction mixture in an amount varying from 0.01 to 40 mole % drawn on the HMF content of the feedstock, preferably from 0.1 to 30 mole %, more preferably from 1 to 20 mole %.
In the preferred embodiment, the catalyst is a heterogeneous catalyst.
The temperature at which the reaction is performed may vary, but in general it is preferred that the reaction is carried out at a temperature from 50 to 200 degrees Celsius, preferably from 50 to 150 degrees Celsius, more preferably from 75 to 125 degrees Celsius. In general, temperatures higher than 150 degrees are less preferred as the selectivity of the reaction reduces and as many by-products occur. Performing the reaction below the lowest temperature is also less preferable because of the low reaction rate. If the reactions are carried out above the boiling temperature of water, then the reactions are preferably carried out under pressure, e.g., 10 bar nitrogen or higher.
The HMF starting material is typically dissolved in a solvent, which can also be the olefin reactant, in order to facilitate the reaction. The solvent system may be selected from the group consisting of water, sulfoxides, preferably DMSO, ketones, preferably methyl ethylketone, methylisobutylketone and acetone, ethylene glycol ethers, preferably diethyleneglycol dimethyl ether (diglyme) or the reactant olefin or mixtures of two or more of the above solvents. Also so-called ionic liquids may be used. The latter refers to a class of inert ionic compounds with a low melting point, which may therefore be used as solvent. Examples thereof include e.g., 1-H-3-methyl imidazolium chloride, discussed in “Dehydration of fructose and sucrose into 5-hydroxymethylfurfural in the presence of 1-H-3-methyl imidazolium chloride acting both as solvent and catalyst”, by Claude Moreau et al, Journal of Molecular Catalysis A: Chemical 253 (2006) 165-169.
The amount of solvent is preferably sufficient to dissolve the starting material and to limit undesired side-reactions.
The method of the current invention may be carried out in a batch process or in a continuous process, with or without recycle of (part of) the product stream to control the reaction temperature (recycle via a heat exchanger). For instance, the method of the invention can be performed in a continuous flow process. In such method, homogenous catalysts may be used and the residence time of the reactants in the flow process is between 0.1 second and 10 hours, preferably from 1 second to 1 hours, more preferably from 5 seconds to 20 minutes.
Alternatively, the continuous flow process may be a fixed bed continuous flow process or a reactive (catalytic) distillation process with a heterogeneous acid catalyst. To initiate or regenerate the heterogeneous acid catalyst or to improve performance, an inorganic or organic acid may be added to the feed of the fixed bed or reactive distillation continuous flow process. In a fixed bed process, the liquid hourly space velocity (LHSV) can be from 1 to 1000, preferably from 5 to 500, more preferably from 10 to 250 and most preferably from 25 to 100 min−1.
The above process results in a stable HMF ether, which can then be used as such or be converted into a further derivative before being used as fuel and/or as fuel additive. The HMF ethers of the invention can also be used as or can be converted to compounds that can be used as solvent, as monomer in a polymerization (such as 2,5-furandicarboxylic acid or FDCA, as fine chemical or pharmaceutical intermediate, or in other applications. Oxidation of 5-(tertbutoxymethyl)furfural using an appropriate catalyst under appropriate conditions such as for example described for p-xylene with a NHPI/Co(OAc)2/MnOAc)2 catalyst system in Adv. Synth. Catal. 2001, 343, 220-225 or such as described for HMF with a Pt/C catalyst system at pH<8 in EP 0 356 703 or or such as described for HMF with a Pt/C catalyst system at pH>7 in FR 2 669 634, all with air as an oxidant, resulted in the formation of 2,5-furan dicarboxylic acid (FDCA).
The invention further concerns the use of the HMF ethers prepared by the method of the current invention as fuel and/or as fuel additive. Of particular interest is the use of the ethers in diesel, biodiesel or “green diesel”, given its (much) greater solubility therein than ethanol. Conventional additives and blending agents for diesel fuel may be present in the fuel compositions of this invention in addition to the above mentioned fuel components. For example, the fuels of this invention may contain conventional quantities of conventional additives such as cetane improvers, friction modifiers, detergents, antioxidants and heat stabilizers, for example. Especially preferred diesel fuel formulations of the invention comprise diesel fuel hydrocarbons and HMF ether as above described together with peroxidic or nitrate cetane improvers such as ditertiary butyl peroxide, amyl nitrate and ethyl hexyl nitrate for example.
The addition of the HMF ether of the invention to diesel fuel results in similar NOx emissions and slightly higher CO emissions; however, the use of sufficient amounts of cetane improvers can be utilized to improve the NOx and CO emissions well below the base reference fuel.
Examples are enclosed to illustrate the method of the current invention and the suitability of the products prepared there from as fuel. The examples are not meant to limit the scope of the invention.
In a 7.5 ml batch reactor, 0.077 mmol HMF, dissolved in diglyme, was reacted with 0.3 mmol isobutene and 0.9 mg acid catalyst at a temperature 90, 120 or 150 degrees Celsius for 1.5 or 6 hours. Two main furan peaks were observed in the UV spectra. Mass spectrometry identified these products as HMF and 5-(tertbutoxymethyl)furfural (tBMF). Selectivities and conversions for catalysts used in this example can be found in table below.
Conversion of substrate, selectivity and yield of furan derivatives were calculated according to the following formulae:
X=100*mr substrate/m0 substrate
X conversion (%)
mr substrate amount of reacted substrate (mg)
m0 substrate amount of substrate in feed (mg)
Scompound=100*nr substrate/n0 substrate
Scompound selectivity to compound (%)
nr substrate moles of substrate reacted
n0 substrate moles of substrate in feed
Yield=100*nproduct/n0 substrate
Yield yield (%)
nproduct moles of product formed
Analytical Method
The reaction products were quantified with the aid of HPLC-analysis with an internal standard (saccharine, Sigma Aldrich). An Agilent 1100 series chromatograph, equipped with UV and ELSD detectors, was used. Stationary phase was reverse phase C18 (Sunfire 3.5 μm, 4.6×100 mm, Waters) column. A gradient elution at a constant flow 0.6 ml/min and temperature 40° C. was used according to the following scheme.
The product was characterized with 1H NMR and LC-MS (CI) (See pictures below). Molecular mass of tBMF is 182.2 g/mol. See
Fuel Solubility
Fuel solubility is a primary concern for diesel fuel applications. Not all highly polar oxygenates have good solubility in the current commercial diesel fuels. Results show that in the 5 vol %, in the 25 vol % and in the 40 vol % blends of tBMF with commercial diesel, both liquid blend components are completely miscible. In a comparative set of experiments it was shown that ethoxymethylfurfural (EMF) is completely miscible in a 5 vol % blend with commercial diesel, but that phase separation occurs with the 25 vol % and with the 40 vol % blends of EMF and diesel.
Cetane Number
Oxygenated fuel additives may reduce the natural cetane number of the base diesel fuel. A 0.1 vol % blend of tBMF with additive free diesel fuel was prepared at an outside laboratory for cetane determination according to an ASTM D 6890 certified method. While the reference additive-free diesel showed an average cetane number of 52.5, surprisingly, the 0.1 vol % tBMF blend showed an increase with 0.5 to an average cetane number of 53.0.
Oxidation Stability
Likewise, oxygenated fuel additives, certainly when containing an aldehyde functional group, often reduce the oxidation stability of the base diesel fuel. A 0.1 vol % blend of tBMF with additive free diesel fuel was prepared at an outside laboratory for oxidation stability determination according to NF en ISO 12205 certified methods. Surprisingly, both the reference additive-free diesel and the 0.1 vol % tBMF blend showed the same oxidation stability, indicating that the oxygenated tMBF added to an additive free diesel base fuel does not decrease the oxidation stability of the blend relative to the pure base diesel.
In a D9B diesel engine of a citroen Berlingo test car, comparative testing is performed with normal commercial diesel as a fuel and the same commercial diesel to which 25 vol. % 5-(t-butoxymethyl)furfural (tBMF) was added, respectively. tBMF is added as a liquid and does not yield any mixing or flocculation problems up to a 40 vol % blend ratio. The engine is run stationary with regular diesel initially, after which the fuel supply is switched to the 40 vol % tBMF-diesel blend.
During stationary operation with the commercial diesel fuel and with the 25 vol % tBMF blend, the following measurements were made: total particulate matter, volume, O2, CO, CO2, NOx (NO+NO2) and total hydrocarbons.
Total particulate matter was sampled according to NEN-EN 13284-1
Particle size distribution was sampled according to VDI 2066-5
Volume was measured according to ISO 10780
Gases were sampled according to ISO 10396
O2, CO and CO2 were analysed according to NEN-ISO 12039
NOx (NO+NO2) was analysed according to NEN-ISO 10849
Total hydrocarbons were analysed according to NEN-EN 13526.
Table 1, gas analysis results of 100% commercial diesel fuel.
In a typical experiment, 0.27 mmol of HMF, 0.8 ml of diglyme and 0.1 ml 2-methyl-1-pentene (MP) were added in a reactor, coated inside with Teflon. The mixture reacted under nitrogen (12.5 bar) in the presence of a acid catalyst (6.5 mg) for 4 h at 90° C. The main peaks observed in the UV spectrum were identified as HMF and 5-(1,1-dimethylbutoxymethyl)furfural (MPMF). In this experiment, the selectivity was calculated slightly different, based on the formula:
Selectivity=100*nt (product)/[n0 (substrate)−nt (substrate)]
n0—the initial number of moles
nt—the number the moles of a compound at time “t”.
| Number | Date | Country | Kind |
|---|---|---|---|
| 07075772.9 | Sep 2007 | EP | regional |
This application is the National Stage of International Application No. PCT/EP2008/007411, filed Sep. 5, 2008, which claims priority to European Application No. 07075772.9, filed Sep. 7, 2007, the entire contents of each of which are incorporated by reference herein.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2008/007411 | 9/5/2008 | WO | 00 | 4/22/2010 |
