Patent Application
20090199462
The present invention generally relates to fatty acid esters, more particularly, to a method for preparation and separation of fatty acid esters. A multitude of energy crises stemming from supply disruption as well as significantly increasing demand for fossil fuels by industrialized nations in the past few decades have spawned motivation for development of alternative fuel sources. Additionally, since there are finite reserves of crude oil from which petroleum based fuels are derived, there is also motivation to develop renewable fuel sources. A substantial amount of effort has recently been made to develop biodiesel fuels from renewable sources.
Soy methyl ester (SME) or methyl soyate, the chemical description of which is provided below, is a common organic acid ester precursor for producing biodiesel. Organic acids, as the name indicates, are organic compounds with acid-like properties. One common group of organic acids are carboxylic acids, which have a “—COOH tail.” Esters constitute a class of organic acid compounds where at least one —OH member is replaced by an alkoxy group (—O—CnH2+1). In the case of methyl acetate ester, for example, a methoxy group (—O—CH3), which is the simplest form of an alkoxy, has replaced the —OH group in acetic acid CH3COOH. This results in CH3COOCH3, or methyl acetate ester. This chemical reaction is commonly termed esterification. Diagram 1, found below, shows the chemical bond structures for these compounds.
Fatty acids consist mainly of carbon chains and hydrogen atoms. These chains can be short with a small number of carbon atoms, e.g., butyric acid (CH3CH2CH2COOH), or long with large number of carbon atoms, e.g., oleic acid CH3(CH2)7CH═CH(CH2)7COOH. Fatty acids may include single and double bonds between carbon atoms. A saturated fatty acid has the maximum number of hydrogen atoms covalently bound to each carbon atom in the chain of carbon atoms, i.e., a saturated fatty acid has no double bonds. An unsaturated fatty acid has at least one double bond between two carbon atoms. Diagram 2, found below, shows an example of saturated and unsaturated fatty acids.
SME is produced by the transesterification of soybean oil with methanol in the presence of a catalyst. Transesterification results in a class of organic reactions where one ester is transformed into another ester by interchanging at least one alkoxy. The catalyst is often an acid or base.
SME profile by percent and by molecular weight is given in Table 1, below.
Biodiesel produced by typical methods suffers from a crystallization phenomenon when temperatures decrease. Although this crystallization phenomenon is not limited to biodiesel, the temperature at which biodiesel begins to crystallize is substantially higher than petroleum-based diesel fuel. The crystallized constituents can clog fuel filters in vehicles using biodiesel and thereby cut off the fuel supply to the engine. The temperature at which two phases, i.e., the liquid and solid phases start to separate, thus producing a cloudy mixture, is referred to as cloud point (C.P.). Saturated fatty acid esters constituents have a higher C.P. than unsaturated fatty acid esters. To lower the temperature at which crystallization occurs and thereby lower the C.P. of the fuel, several techniques are often used, examples of which include blending with petroleum-based diesel, introducing additives, and winterization. Winterization refers to removal of saturated fatty acids, e.g., C16:0 and C18:0, and in some cases mono-unsaturated fatty acids, e.g., C18:1, that cause the biodiesel product to crystallize at an undesirably high temperature. The removal process is typically by filtration of the crystallized particles of the saturated and in some cases mono-unsaturated fatty acids which leaves a mixture having a greater amount of unsaturated fatty acids compounds with lower C.P., thereby lowering the C.P. of the biodiesel so produced.
The winterization process has gained more interest in recent years. Winterization by itself produces low yields, i.e., a substantial portion of the starting material is lost during the filtration process. Therefore, use of compounds which improve the winterization process, typically referred to as “improvers,” is essential. One process which includes the addition of improvers is referred to as fractionation, which uses the crystallization properties of esterified fatty acids to separate a mixture into low and high melting point liquid fractions. During fractionation, these improvers create inclusion compounds/complexes. This process includes a host constituent having a series of cavities or landing sites for attachment by a second chemical constituent, commonly referred to as the guest. The compound resulting from the combination of the host and the guest is called an “inclusion compound.” The forces that hold the host and the guest constituents together are van der Waals type forces. That is, no covalent bonds form between the guest and the host. Clathrates are one type of inclusion compound in which the spaces in the host constituent are enclosed on all sides, causing a “trapping effect.”
There are three different types of fractionation: dry fractionation, detergent fractionation, and solvent fractionation. Solvent fractionation has received a substantial amount of interest in recent years. It is an efficient process by which one group of esterified fatty acid constituents are separated from another group. The differing solubility of the groups is the key to success with this process. Several advantages are offered by solvent fractionation as compared to dry fractionation. For example, dry fractionation requires a longer crystallization period than solvent based fractionation; and solvent fractionation substantially increases the chance of crystallization in one round rather than multiple stages as may be the case with dry fractionation. Conversely, solvent based fractionation requires more energy and the solvents are costly, although in many cases they are recovered in solvent recovery schemes.
The prior art method of thermal crystallization (winterization) followed by filtration (with or without solvent) utilizes the difference in crystallization temperature of the saturated and unsaturated components of SME. The saturated components crystallize at a higher temperature and can be removed via filtration, centrifugation, etc. However, a significant amount of co-crystallization occurs. Co-crystallization occurs when during the winterization process certain unsaturated components also crystallize and are thus also removed, resulting in high losses of the preferred unsaturated fatty acid methyl esters (FAME). To obtain a C.P. of −16° C., almost 75% of the starting material was removed in the work reported by Dunn et al. See R. O. Dunn, M. W. Shockley, and M. O. Bagby, “Improving the Low-Temperature Properties of Alternative Diesel Fuels: Vegetable Oil-Derived Methyl Esters,” JAOCS, Vol. 73, No. 12 (1996), PP 1720-1721. Additionally, these techniques involve cooling to very low temperatures and require processing times of days.
Also, the amount of saturated or monounsaturated molecules which are extracted from the fatty acid compound has been shown to have an effect on the C.P. For instance, Dunn et al. in two published articles suggest a linear relationship in the depression in C.P. as a function of reduction of saturate constituents. See, Dunn et al. “Improving the low-temperature properties of alternative diesel fuels: Vegetable oil-derived methyl esters” published in 1996, and “Winterized Methyl Esters from Soybean Oil: An Alternative Diesel Fuel with Improved Low-Temperature Flow Properties” published in 1997. In the latter article, Dunn et al. describe a linear relationship between total concentration of saturate constituents and C.P., as described in equation (1), found below:
CP=1.4403*(Total Saturates)−24.8 (1)
In the 1996 article, Dunn et al. reported a winterization process resulting in a C.P. of −16° C. having final components of C16:0 (4.3, % by wt), C18:0 (1.3, % by wt), C18:1 (30.3, % by wt), C18:2 (49.6, % by wt), C18:3 (11.9, % by wt), and others (2.6, % by wt). In the same paper, Dunn et al. suggested a laboratory experiment resulting in a C.P. of −23° C. C.P. for a pure solution of unsaturated C18 components, presumably C18:1, C18:2, and C18:3, i.e., a saturate concentration of 0. That is, according to Dunn et al., a drop of 7° C. is to be expected in going from a normal winterization process having a C.P. of −16° C., to −23° C. with zero concentration of saturated components. Extension of the linear relationship, as shown in
In other prior art work, urea, also known as carbamide with the chemical formula (NH2)2CO, has been used in the winterization process. Urea is used to form inclusion compounds with long chain organic compounds. This was first discovered and reported by F. Bengen in a German patent filed in 1940. See Bengen, F., German Patent Application 0. Z. 12438, Mar. 18, 1940. Later studies from the late forties to the early fifties reported the selectivity of urea in forming complexes with long chain organic molecules. (See citations in the Reference section.) This selectivity was found to be based on: a) Carbon chain length, b) presence of unsaturation in the molecule, and c) degree of unsaturation. The formation of these complexes was found to be a useful technique for the separation of a mixture of saturated and unsaturated organic compounds, e.g., fractionation of a mixture of free fatty acids. Various techniques for the formation of such complexes were also studied, however, with little or no focus on process parameters. Hayes et al. worked on the fractionation of fatty acids and studied various process parameters that affect the formation of urea inclusion complexes, product yields, and the composition of fractions obtained. U.S. Pat. Nos. 5,106,542 and 5,243,046 to Traitler et al. describe the art of fractionating fatty acid mixtures via urea inclusion. U.S. Pat. No. 5,679,809 to Bertoli et al. (“the '809 patent”) describes the concentration of polyunsaturated fatty acid ethyl esters via urea inclusion.
In solvent fractionation, urea dissolves in ethanol, methanol, or other solvents as an early step in producing inclusion compounds. The goal of solvent-based fractionation, as explained in the '809 patent, is to remove saturated and monounsaturated fatty acid ethyl esters. The '809 patent teaches heating the mixture of ester, urea, and ethanol to a particular temperature until the urea is dissolved. The mixture is then cooled to allow certain molecules to form a solid phase. The solid phase is separated from the liquid phase by filtration or centrifugation. The liquid phase is further processed to partly remove ethanol, and the desired ethyl esters enriched with polyunsaturated fatty acids are then extracted by washing the remaining liquid phase with an acidic liquid.
As cloud points of approximately −20° C. are too high for many cold weather uses of biodiesel, such as in vehicles, there is still a need for an improved process to lower C.P. of biodiesel to an acceptable level.
The above references 1-30 are incorporated herein by reference.
Embodiments of the present teachings are related to lowering cloud point of a vegetable derived composition having methyl esters by fractionating saturated and mono-unsaturated components of methyl esters in the composition.
According to one exemplary embodiment, a composition is disclosed having methyl esters derived from vegetable oils. The methyl esters comprise less than about 3% by weight of saturated fatty acid methyl esters. The composition has a cloud point of less than about −30° C.
The methyl esters in certain embodiments comprise methyl oleate, methyl linoleate and methyl linolenate. The methyl linolenate may comprise less than about 10% by weight of the methyl esters. The methyl stearate comprises less than about 0.1% by weight of the methyl esters. The methyl linoleate comprises at least about 50% or at least about 60% by weight of the methyl esters.
Cloud point of the composition can be selected, but for most cold weather applications envisioned, the composition has a cloud point that is less than about −35° C. In another embodiment, the composition has a cloud point that less than about −40° C. In still another embodiment, the composition has a cloud point less than about −45° C.
In another embodiment, the composition has a cloud point less than about −50° C.
In yet another embodiment, the composition has a cloud point is less than about −55° C.
In one embodiment, the methyl esters in the composition comprise less than about 2% saturated methyl esters. In another embodiment, the methyl esters in the composition comprise less than about 1.5% saturated methyl esters. In another embodiment, the methyl esters in the composition comprise less than about 0.5% saturated methyl esters.
In one embodiment, the vegetable from which the composition is derived comprises soy oil. In another embodiment, the composition includes material comprising a petroleum based component, wherein the petroleum based component comprises fossil fuel derived diesel fuel. In another embodiment, the composition includes material comprising animal fat derived methyl esters.
In one embodiment, the composition comprises less than about 1% methyl stearate. In another embodiment the composition comprises less than about 0.5% methyl stearate. In yet another embodiment the composition comprises less than about 0.1% methyl stearate.
In one exemplary embodiment, a method of lowering the cloud point of methyl esters derived from vegetable oil is disclosed. The method includes mixing vegetable derived methyl esters, urea and alcohol with sufficient heat to form a homogenous mixture. The homogeneous mixture is cooled to a temperature where a solid phase and a liquid phase are formed, the solid phase being enriched in saturated fatty acid methyl esters and the liquid phase being enriched in unsaturated fatty acid methyl esters. The solid phase is separated from the liquid phase, and methanol and unused urea are removed from the liquid phase to form a liquid composition having a cloud point of less than about −30° C. and less than about 3% by weight saturated fatty acid methyl esters.
In one embodiment of the above method, the alcohol comprises methanol. Also, the method further comprises, before the step of forming the homogeneous mixture, the step of mixing vegetable derived oil, sodium hydroxide and methanol to form the vegetable derived methyl esters. In certain embodiments, the homogeneous mixture contains methanol in an amount of about 3 to 10 times by weight of the amount of the fatty acid methyl ester. Excess methanol is provided in the step of mixing the vegetable derived oil, sodium hydroxide and methanol to form the vegetable derived methyl esters. Adding methanol during the step of forming the homogeneous mixture is therefore unnecessary.
In another embodiment, the method further comprises separating glycerin from the vegetable derived methyl esters before the step of forming the homogeneous mixture. In another embodiment of the method, the ratio of urea to methyl esters in the homogeneous mixture is from about 0.9:1 to about 1:1. In another embodiment, the solid phase is separated from the liquid phase by filtration, centrifugation, sedimentation, or decantation of the liquid phase. In yet another embodiment, the liquid composition comprises less than about 2 percent by weight of saturated fatty acid methyl esters. In another embodiment of the method, the liquid composition comprises less than about 1.5 percent by weight of saturated fatty acid methyl esters. In yet another embodiment of the method, the step of removal of methanol is by evaporation. Alternatively, the step of removal of methanol can be by applying vacuum. In another embodiment of the method, unused urea is removed by washing with acidified water, and the washed unused urea can be separated by a liquid-liquid centrifugal extractor or by a gravity separation.
In one embodiment of the method, the yield of the liquid composition is at least 43% by weight of the vegetable-derived methyl esters used to form the homogeneous mixture and the cloud point of the liquid composition is less than −34° C. The cloud point of the liquid composition, however, can be less than −40° C. or less than −50° C.
The above-mentioned and other advantages of the present invention and the manner of obtaining them, will become more apparent and the invention itself will be better understood by reference to the following description of the embodiments of the invention taken in conjunction with the accompanying drawings, wherein:
a is a schematic showing process steps involved in producing SME;
b is a schematic showing process steps involved in fractionation of SME in accordance with the current teachings;
a is a graph of C.P. vs. percent saturates illustrating how the current teachings differ from prior art predictions;
b is a graph of C.P. vs. percent saturated fatty acids, monounsaturated fatty acids, and polyunsaturated fatty acids;
The embodiments of the present invention described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that others skilled in the art may appreciate and understand the principles and practices of the present invention.
These teachings relate to the fractionation/separation of fatty acid methyl esters, e.g., SME, into saturated fatty acid-rich and unsaturated fatty acid-rich fractions via the use of urea inclusion/urea complexation. Operation of diesel engines using renewable energy sources including triglycerides-derived fuels is known, as is the challenge of overcoming negative properties of these triglycerides-derived fuels, e.g., the gelling of bioderived diesel (biodiesel) at higher temperatures than petroleum derived fuels. The composition of typical un-winterized biodiesel from SME is as given in table 2.
1 The parenthetical reference (Cnn:n) indicates the number of carbon atoms of the molecule on the left side of the colon followed by the number of carbon-carbon double bonds in the molecule on the right hand side of the colon.
Referring to
Typically, the transesterification of fatty acids from soy oil is considered “commercially complete” after a reaction time of from one to three hours at reaction conditions. Total time of reactants in the reaction vessel may exceed these times if it is necessary to heat reactants to reaction temperature in situ. In commercial settings, completion of the transesterification occurs when continuation of the transesterification cannot economically be maintained. Commercial completion may be influenced by many factors related to the equipment involved. Examples of these factors are capital cost/depreciation status, operating expense, size, geometry, separation equipment available, raw material cost, labor cost, or even the time of day as it relates to an operator's shift change.
The range of possible fat sources is not limited. Commercial fat sources are generally chosen from oilseeds, often locally produced, such as soybeans and canola. The carbon content of fatty acids from such sources ranges from 16 to 22 carbon atoms per fatty acid molecule.
In one embodiment, transesterification of raw materials of fats is most commonly accomplished by supplying fats and alcohol in the molar ratio of 1 mole fat (triglycerides) to 3 moles alcohol. Although the process is operable outside this ratio, unreacted raw materials result. The reaction is observed to be nearly stoichiometric although it may be advantageous to add excess alcohol to the esterification step as will be discussed below. One percent catalyst by weight of fat is sufficient to facilitate the reaction at a commercially acceptable rate. Insufficient catalyst results in a slowed reaction; excess catalyst is not observed to significantly increase the reaction rate and may require additional separation effort at the completion of the reaction.
An example of the transesterification process is shown in
Transesterification of soy oil with methanol in a vessel was completed with 6 molar parts methanol to 2 molar parts refined soy oil. NaOH as a catalyst at the rate of 1% by weight of soy oil was included. The liquid components were heated to 65° C. The condition was maintained for one hour with continuous mixing. The resulting two phases (upper layer—soybean methyl esters, methanol, impurities; bottom layer-glycerol, residual catalyst, impurities) were separated by decantation, using a 1000 ml separatory funnel. Analysis of the methyl ester phase disclosed the composition by weight in Table 3a.
For purpose of comparison, compositions of other vegetable oils are listed in table 3b, while compositions of the fats of some land and marine animals are listed in table 3c.
Biodiesel derived from SME has proven to be an extender, additive, or replacement for petroleum-based diesel fuel and heating oil. Studies are ongoing for using biodiesel as an aviation turbine fuel extender. A challenge posed by biodiesel is its poor cold flow properties. The total content of saturates is about 14-15% (wt/wt) and causes the C.P. to be about 0° C. and pour point to be about −2° C. to −4° C. This limits the use of SME at low temperatures. Various efforts have been made to reduce or depress the C.P. of SME, e.g., 1) removal of saturated components, 2) use of cold flow additives, 3) use of branched chain alcohol esters, and 4) combinations thereof.
The popular method for removal of saturate components is winterizing or cold filtering. Various studies have been conducted; however, these methods have very low yields for any significant reduction in the C.P. Cold flow additives have been successful in lowering the P.P. (Pour Point), but have little or no effect on the C.P.
These teachings disclose a C.P. reduction ranging from about −2° C. to about −57° C. by a controlled removal of the saturated, and in some cases, mono-unsaturated fractions by clathration and subsequent separation. The remaining polyunsaturated fatty acid fractions yields range from 98%-41% of the starting material, i.e., SME. The process parameters of greater significance are: 1) urea/FAME/Alcohol (weight/weight/weight ratio), and 2) the temperature to which the methyl ester clathrate mixture is cooled. The rate of cooling appears to play a lesser role in the formation of urea clathrates and therefore separation of saturated from unsaturated fatty acid methyl ester.
Referring to
Subsequent to heating, the mixture in reactor 100 is cooled to precipitate the clathrates. The mixture is cooled to a final temperature of between 20-25° C. While the rate of cooling does not have an important effect in the final composition of the mixture, the final temperature is a crucial parameter in the process affecting yield and the amount by which saturated components are removed from the mixture. For example, cooling down to 20-25° C. has provided acceptable yields while removing high amounts of saturated compounds. Constant stirring is important throughout the process. The cooling will result in a fractional crystallization of the mixture, giving rise to the formation of two phases: 1) solid phase or precipitate having urea complexes (mainly clathrates of saturated fatty acids and urea); and 2) liquid phase or filtrate having methanol (mainly unsaturated fatty acids and urea). This fractionation process can be repeated in several steps, generally referred to as step fractionation, on the same sample to obtain the desired composition and properties of the final product.
The liquid-solid mixture is transferred to liquid-solid separation station 102 where centrifugation, filtration, or other techniques may be employed to separate liquids from solid clathrates. Extraction and purification of the mixture having mainly unsaturated fatty acids and urea is accomplished by centrifugal separation, vacuum filtration, or by using conical decantation tank to precipitate the solids. The liquid that is separated from the solid clathrates is then transferred to solvent recovery station 104 to remove the solvent. Solvent recovery station 104 is a closed vessel in which the liquid is heated to evaporate and recover the solvent, e.g., methanol 105. Solvent recovery can also be accomplished by applying vacuum to the closed vessel. In one embodiment, an evaporator equipped with an internal detector can be used which stops the heating process whenever the evaporator detects that no more solvent is being evaporated. In another embodiment a rotary evaporator can be used having a water-bath that is at about 60° C., having a vacuum of between 15-25 mm Hg. The recovered methanol 105 is then transferred to reactor 100 to supplement the solvent used in the starting material. The solvent recovered liquid extract is then washed by acidified water in mixer 106 (60° C., pH 3-4) to dissolve the remaining urea (around 100 ml water for each 170 g of urea), before going through liquid-liquid separation station 108 to extract low C.P. SME 124 as well as urea brine 116. Optionally, hexane or another suitable organic solvent can be added to improve the extraction of the remaining unsaturated methyl esters. The water/solvent phases are separated either by a liquid-liquid centrifugal extractor or by gravity separation (decantation) of phases.
Raffinate solids 110 extracted from liquid-solid separation station 102 are mixed with water in mixer 112 and transferred to liquid-liquid separation station 114 to extract urea brine 116 and high C.P. SME 120. The raffinate solids 110 are washed with warm water to dissolve the urea inclusion compounds (UIC). The upper layer containing the methyl esters is decanted or siphoned in liquid-liquid separation station 114. Urea brine 116 coming from liquid-liquid separation stations 108 and 114 is combined and dried in dryer 122 to produce urea 118 that can be re-used in reactor 100. If this results in a hardened form of urea, it is recommended to grind it before recycling it into the process.
Depending upon the desired C.P. reduction, a particular proportion of urea/FAME/Alcohol as starting material is chosen. Affecting the C.P. reduction is also the terminal temperature to which the mixture is cooled in reactor 100. In one embodiment of the current teachings, the mixture is allowed to cool to room temperature. Additionally, the fatty acid starting materials in the transesterification process affect the cloud point. Various combinations of these parameters are possible for the same C.P. reduction. The urea/FAME ratio may range from 0.0:1 to 1:1 wt/wt. The alcohol/FAME ratio may range from 3:1 to 10:1 wt/wt.
Exemplary methods in accordance with these teachings add an alcohol, such as methanol, as a urea solvent and urea for fractionation or clathration. By weight, the ratio of urea to FAME may be in the range from 0.1:1 to 1:1. It is also envisioned that a ratio greater than 1 part urea to 1 part FAME can be used if a very low CP is desired. Urea forms solid phase clathrates with the saturated fatty acid esters.
Sufficient alcohol should be added to dissolve all urea that is added. A sufficient amount of alcohol results in a ratio of alcohol to the methyl ester which ranges from 3:1 to 10:1 wt/wt. Excess alcohol decreases the tendency to produce urea clathrates, thus, decreases the efficiency of the process. Alcohol present after clathrate formation is often separated from the predominantly unsaturated ester by methods utilizing the relative vapor pressures of the two components, for example, distillation or flash evaporation. Economic considerations encourage limiting alcohol to an amount necessary to dissolve the added urea.
Methanol is preferred for esterification. Use of methanol as the solvent for urea in preference to C2-C4 alcohols eliminates the need to store and handle additional reagents for separation of fatty acid methyl esters. After formation of the FAME and glycerin, a convenient manufacturing sequence separates the glycerin phase from the fatty acid ester phase, followed by addition of urea and alcohol to the FAME. The urea and alcohol may be added separately or as a solution of urea dissolved in alcohol. An option afforded by the use of methanol as urea solvent is the convenient continuation of the process by conducting the subsequent clathration step in the same vessel used for the ester formation. By continuing the process in the same vessel with methanol as the solvent, capital investment is reduced by eliminating additional process steps to first remove residual methanol prior to addition of C2-C4 alcohols.
In one embodiment, excess methanol may be provided in the esterification step such that the addition of solvent during the clathration stage can be reduced or eliminated. In another embodiment it is possible to proceed directly from esterification to clathration without removing glycerin. In this embodiment, glycerin is removed as a final stage, as are clathrates.
Dissolution of urea in methyl ester is accomplished by stirring alcohol in the solution at temperatures in the range of 50-75° C. The rate of heating of the mixture has not been observed to have a significant effect on the yield of the product or the C.P. achieved.
It has been observed that the cooling rate has little influence on the C.P. Yields are impacted more significantly by the terminal temperature to which a mixture is cooled. Cooling the mixture of saturated fatty acid esters urea clathrates, unsaturated fatty acid methyl esters, excess/unreacted methyl alcohol, excess/unreacted urea, and optionally, glycerin, to temperatures of 20 to 25° C. provides economically acceptable yields resulting in high clathrate formation of saturated esters compounds and thereby in high removal of saturates without the need for refrigeration.
The solid phase including clathrates of the saturated methyl esters may be separated from the liquid phase comprising unsaturated-methyl-esters, methanol, dissolved urea, and optionally, glycerin by convenient solid-liquid separation means such as filtration or centrifuge, as indicated by liquid-solid separation station 102.
If present, glycerin may be removed from the liquid phase. Alcohol present in the liquid phase that is rich in unsaturated fatty acid esters may be recovered by evaporation at a temperature between 30-50° C. (e.g., in a closed vessel under vacuum, as indicated by solvent recovery station 104). The remaining filtrate is then washed with warm acidic water (60-70° C., pH 3-4) to remove urea and alcohol, as indicated by liquid-liquid separation station 108. The water wash may be carried out in steps, washing the filtrate with warm, acidified water in each step, or in a continuous manner. Suitable purity of filtrate may be achieved with single or multiple step washes with water volumes equal to the filtrate volume. Continuous washing is successful with 3-4 water volumes.
The saturate rich fraction, indicated by high temperature SME 120 in
The exemplary technique is illustrated by the following examples. A summary of these examples is found in table 4. In Table 4 FAME constituents are listed for each example. Additionally, resulting C.P., cooling rate, % by weight of starting SME and the proportions of SME to urea to ethanol is listed for each example.
Soy methyl ester prepared as described is analyzed for composition. The starting soy methyl ester had the composition and properties according to Table 5:
24.1 g of soy methyl ester and 10.1 g of urea were added to 160 mL of ethanol and the mixture was heated to 67° C., with constant stirring. A homogenous mixture was obtained with all the urea dissolving at this temperature. The mixture was then cooled at a rate of 1.2° C./min to a final temperature of 20° C. The urea inclusion compounds (clathrates) formed were separated by filtration. The filtrate was then heated to 30° C. and 70% of the starting volume of ethanol was recovered via evaporation under vacuum. The remaining filtrate was twice washed with equal volumes of water (60° C., pH 3). 18.8 g of fractionated soy methyl ester (78.4% by wt of the starting soy methyl ester) was recovered with the composition and properties according to Table 6. Recovered ethanol is available for re-use in the process.
24.1 g of soy methyl ester having the composition according to Table 5 and 18.0 g of urea were added to 160 mL of ethanol and the mixture was heated to 73° C., with constant stirring. A homogenous mixture was obtained with all the urea dissolving at this temperature. The mixture was then cooled at a rate of 1.2° C./min to a final temperature of 20° C. The urea inclusion compounds formed were then separated by filtration. The filtrate was then heated to 30° C. and 52% of the starting volume of ethanol was recovered via evaporation under vacuum. The filtrate was twice washed with equal volumes of water (60° C., pH 3). 16.0 g of fractionated soy methyl ester (66.4% by wt of the starting soy methyl ester) was recovered with the composition and properties according to Table 7.
24.1 g of soy methyl ester having the composition according to Table 5 and 16.0 g of urea were added to 160 mL of ethanol and the mixture was heated to 72° C., with constant stirring. A homogenous mixture was obtained with all the urea dissolving at this temperature. The mixture was then cooled at a rate of 1.3° C./min to a final temperature of 30° C. The urea inclusions compounds formed were then separated by filtration. The filtrate was then heated to 30° C. and 63% of the starting volume of ethanol was recovered via evaporation under vacuum. The filtrate was twice washed with equal volumes of water (60° C., pH 3). 18.3 g of fractionated soy methyl ester (75.9% by wt of the starting soy methyl ester) was recovered with the composition and properties according to Table 8.
24.1 g of soy methyl ester having the composition according to Table 5 and 16.0 g of urea were added to 160 mL of ethanol and the mixture was heated to 72° C., with constant stirring. A homogenous mixture was obtained with all the urea dissolving at this temperature. The mixture was the cooled at a rate of 10.7° C./min to a final temperature of 20° C. The urea inclusions compounds formed were then separated by filtration. The filtrate was then heated to 30° C. and 63% of the starting volume of ethanol was recovered via evaporation under vacuum. The filtrate was twice washed with equal volumes of water (60° C., pH 3). 15.6 g of fractionated soy methyl ester (64.9% by wt of the starting soy methyl ester) was recovered with the composition and properties in Table 9.
Fuel for turbine engines is specified by ASTM standard D-1655. Plant sourced oils have limited penetration in to the market for turbine fuel.
A commercially sourced soybean oil derived fatty acid methyl ester, the properties of which are described in Table 5, was fractionated as described herein. The “as obtained” fraction analysis and the fraction analysis after processing appears in Table 11. The fractionated soy methyl ester of Examples 5-7 was then blended with the Commercial Jet A fuel to yield the properties which are listed in Table 10.
The fractionated soy methyl ester was blended with Jet A fuel in the ratios indicated in Table 10 which yielded the properties that are indicated in Table 10. The blended fuel has demonstrated that the requirements of ASTM D-1655 are attainable with blends including soy methyl ester.
Combustion studies of soy methyl ester blends with commercial Jet A show non-critical deviation from the combustion of commercial Jet A fuel. An Allison stationary 250 turbine having a relatively low compression ratio of 6.2:1 was used for the combustion study.
Controlled emissions for Jet A and soy methyl ester blends are shown in
24.0 g of soy methyl esters and 16.8 g of urea were added to 120 mL of methanol and the mixture was heated to 55° C., with constant stirring. The starting SME was prepared according to the example which followed the discussion of transesterification process and which was titled “Transesterification of soy oil to produce un-winterized SME example.” A homogenous mixture was obtained with all the urea dissolving at this temperature. The mixture was then cooled in a water bath to 25° C. The urea clathrates were then separated by filtration. Methanol was recovered from the filtrate by flash evaporation. The filtrate was washed two times with equal volumes of water (60° C., pH of 3). 12.4 g of fractionated soy methyl ester (51.7 by wt of the starting soy methyl ester) was recovered with the composition and properties according to Table 12.
24.0 grams of soy methyl esters, prepared according to transesterification of soy oil to produce un-winterized SME example, and 19.2 grams of urea were added to 120 ml of methanol. The mixture was heated to 55° C., with constant stirring. After all components were dissolved, the mixture was cooled down to 25° C. in a water bath; the urea clathrates formed were separated by filtration. The methanol from the filtrate was removed by flash evaporation. The filtrate was then washed twice with equal volume of water (60° C., pH of 3). 10.7 g of fractionated SME (yield=44.6%) was recovered with the composition and properties according to Table 13.
24.0 g of soy methyl ester, prepared according to transesterification of soy oil to produce un-winterized SME example, and 24.0 g of urea were added to 120 mL of methanol. The mixture was heated to 55° C., with constant stirring. The homogenous mixture obtained was then cooled in a water bath to 25 to 20° C. The urea clathrates were separated by filtration. Methanol was removed from the filtrate by flash evaporation. The filtrate was washed two times with equal volumes of water (60° C., pH of 3). 10.3 g of fractionated soy methyl ester (42.9% by wt of the starting soy methyl ester) was recovered with the composition and properties according to Table 14.
Referring to
Each bar in
A solid line connecting the C.P. data points is shown in
Additionally,
As discussed above, the prior art teachings of Dunn et al., predict a straight line relationship between the amount of saturated components removed and the reduction in cloud point. Dunn et al. predicted that this straight line can be extrapolated to compositions having no saturated components. However, quite surprisingly and remarkably, the inventors of the instant application have found that the reduction in cloud point as the last few percent of saturated components is removed is not linear. In stark contrast to the teachings of Dunn et al., the inventors have found that the cloud point of composition having very low amounts of saturated components is far lower than Dunn et al. predicted. For example, one of skill in the art can readily recognize that the slope of the line extending from left to right in
In addition, it can be observed from
Another observation that can be made from
Referring to
The graph in
It is envisioned that experimental results using different starting material as indicated in
In addition to the effect of the amount of urea in the urea/FAME/alcohol mixture on the C.P., the starting material in the transesterification process, i.e., the source of starting fatty acid, also affects the C.P. Referring to
Further referring to
The amount of saturated fatty acids, i.e., C16:0 and C18:0, that remain at the end of the clathration process controls the cloud point. This concept is shown in
In experiments 10 and 15, for example, the amounts of PUFA and MUFA are approximately the same, i.e., 36.7% vs. 37.1, and 61.5% vs. 61.6%. However, the SFA are different by 0.5%, i.e., 1.8% vs. 1.3%. The difference in percent SFA results in a drop in C.P. of 10° C. In contrast to these experiments, experiments 1 and 2 reveal a much smaller lowering of C.P. in the presence of a much larger drop in SFA. For example, a difference of 2.6% in SFA, i.e., 14.1% vs. 11.5%, results in a 5° C. drop in C.P. This observation further strengthens the point that very small amounts of SFA remaining in the end composition could produce ultra low C.P., lower than −30° C. Moreover, as the percent SFA remaining in the end composition reaches about 1-2%, further removing small amounts of SFA, e.g., 0.5%, results in larger drops in C.P., e.g., 10° C. This shows that the relationship between the amount of saturated fatty acids and CP becomes nonlinear after most of the saturated fatty acids are removed. Conversely, where large amounts of SFA remain in the end composition, e.g., about 11-14%, further removing large amounts of SFA, e.g., 2.6%, results in relatively smaller drops in C.P., e.g., 5° C.
In another embodiment, the product from the fractionation process, according to the current teachings, can be used to treat petroleum based fuel to improve cold flow properties of the petroleum based diesel fuel. Two types of diesel fuel are commonly used. Diesel number 2, which contains a higher amount of paraffin, has a cloud point of about −28° C. Diesel number 1 has a cloud point of about −40° C. Traditionally, diesel number 1 is blended with diesel number 2 for cold-weather operation. Adding fractionated esters from the current process, which is rich in polyunsaturated fatty acids, to diesel number 2 will improve C.P. of the blend. This is advantageous since blending fuel with diesel number 1 in large quantities is not desirable for diesel engine operation due to lubricity difference between diesel number 1 and number 2. However, addition of polyunsaturated-rich fractionated esters to diesel number 2 will not have the same lubricity disadvantages. It is well known that addition of polyunsaturated-rich fractionated esters will actually improve lubricity.
Referring to
Referring to
Applicants' method as disclosed enables the fractionation of fatty acid methyl esters based on saturated vs. unsaturated molecules from mixtures of saturated and unsaturated fatty acid methyl esters. Separated fractions may be achieved with the desired unsaturated fraction comprising from 15 to 0% by weight saturated fatty acid methyl esters, from 10 to 45% by weight monounsaturated fatty acid methyl esters, and from 50 to 85% polyunsaturated fatty acid methyl esters.
The C.P. for mixtures of saturated and unsaturated fatty acid methyl esters may be reduced by preferably 10° C., more preferably 25° C. to 60° C. below the C.P. of the unfractionated fatty acid methyl ester mixture.
It is envisioned that for many cold weather uses, biodiesel in accordance with these teachings should have a cloud point that is less than about −30° C. Other cold weather applications may require the biodiesel to have a cloud point less than about −40° C., or less than about −45° C., or even less than about −50° C. These teachings provide a composition having a cloud point of as low as −57° C. (see Example 10) and a method of making the same.
As one of skill in the art can appreciate from the examples above, these surprisingly low cloud points are achieved when almost all of the saturated fatty acid components, i.e., more than about 97%, are removed. In accordance with these teachings, the amount of saturated fatty acid components in the final product should be less than about 3%, more preferably less than about 2%. To achieve cloud points of less than −40° C. or less than about −50° C., the amount of saturated fatty acid components should be less than about 3%, depending on the feedstock.
The experiments above also empirically show that surprisingly low cloud points are achieved in a composition with a small relative amount of C18:3 components. With reference to
Additionally, empirical data show that very low C.P.'s may be achieved without a significant corresponding sacrifice in yields. For example, to achieve a cloud point of −23° C., yield was about 52% (resulting SME compared to starting SME), whereas for a cloud point of −57° C., yield was about 43%. Surprisingly, yield was substantially unaffected when lowering cloud point from −34° C. to −57° C., as the yield was lowered only by about 2%.
While exemplary embodiments incorporating the principles of the present invention have been disclosed hereinabove, the present invention is not limited to the disclosed embodiments. Instead, this application is intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
This application is a continuation-in-part of U.S. patent application Ser. No. 11/690,540, filed Mar. 23, 2007, which claims priority to U.S. patent application Ser. No. 11/668,865, filed Jan. 30, 2007, now abandoned, which claims priority to U.S. patent application Ser. No. 11/068,104, filed Feb. 28, 2005, which claims priority to U.S. Provisional Patent Application Ser. No. 60/547,992, filed Feb. 26, 2004, all of which are hereby incorporated by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11690540 | Mar 2007 | US |
| Child | 12261806 | US |
