Title of Invention	PROCESS FOR PURIFICATION OF FATTY ACID ALKYL ESTERS AND USE OF AGENTS TO FACILITATE SUCH PURIFICATION
Abstract	A use of a flocculating and sequestering agent as an agent facilitating the purification of an organic solution comprising fatty acid alkyl esters. Also provided is a process for purification of the organic solution, which process comprises adding a flocculating and sequestering agent to the organic solution so as to facilitate the purification, and removing a portion from the organic solution, which portion comprises the flocculating and sequestering agent, and impurities.

Title of Invention

PROCESS FOR PURIFICATION OF FATTY ACID ALKYL ESTERS AND USE OF AGENTS TO FACILITATE SUCH PURIFICATION

Abstract

A use of a flocculating and sequestering agent as an agent facilitating the purification of an organic solution comprising fatty acid alkyl esters. Also provided is a process for purification of the organic solution, which process comprises adding a flocculating and sequestering agent to the organic solution so as to facilitate the purification, and removing a portion from the organic solution, which portion comprises the flocculating and sequestering agent, and impurities.

Full Text	PROCESS FOR PURIFICATION OF FATTY ACID ALKYL ESTERS AND USE OF AGENTS TO FACILITATE SUCH PURIFICATION Technical field of the invention The present invention relates to the use of certain agents to facilitate the purification of an organic solution of fatty acid alkyl esters. The present invention also relates to a process for purification of the fatty acid alkyl esters suitable for use as biodiesel. Technical background Fatty acid alkyl esters (mono alkyl esters of fatty acids such as methyl and ethyl esters of fatty acids) derived from, vegetable oils or animal fats are known to be used as biodiesel- Known processes to produce such fatty acid alkyl esters comprise transesterification of triglycerides included in vegetable oils or animal fats in presence of an alcohol and a catalyst. It is well known in the art to use catalysts such as acid catalysts or more commonly alkali metal catalysts/ e g sodium and potassium hydroxide or a metal alkoxide such as sodium or potassium methoxide. In fact, a metal alkoxide is a compound formed by the reaction of an alcohol with an alkali metal. In summary, the transesterification reaction can generally be described as follow: Among vegetable oils or animal fats that can be used are coconut oil, palm oil, seed oil, olive oil, sunflower oil, Soya oil, rapeseed oil and tallow. Suitable alcohols that can be used are aryl alcohols such as methanol, ethanol, propanol and butanol. Due to low cost, polarity and short chain, methanol is normally used in biodiesel production. Due to high activity, an alkali catalyst such as potassium hydroxide is usually used on industrial scale, A well-known process for producing fatty acid alkyl esters comprises heating, for example, a vegetable oil to a temperature of normally between 30*C and 110"C. The process further comprises adding an alcohol and a catalyst to the heated oil. The reaction will result in two phases, one including produced glycerol and the other including produced fatty acid alkyl ester. In addition, the process comprises removing the produced glycerol phase from the produced fatty acid alkyl ester phase. Fatty acid alkyl esters produced according to known processes as described above normally comprises to high levels of impurities to comply with regulatory norms concerning fatty acid alkyl esters, e g the European norm EN-14214 for fatty acids methyl esters, which especially limits the impurities originating from the metals K, Na, Mg and Ca. Accordingly, there is a need for purification of the produced fatty acid alkyl esters. Known processes for purification include steps of neutralization and washing with water, which will wash out the impurities and produce fatty acid alkyl ester that complies with the regulatory norms and thus can be used as biodiesel. After each step of washing, the water can be separated from the fatty acid alkyl esters by any method known in the art such as await for the mixture to settle into two phases and thereafter drain off the water phase, or by centrifugation of the mixture. The total amount of water used can typically range from 20 to 100% water of the produced volume of fatty acid alkyl esters: After purification is completed, the traces of water comprised in the fatty acid alkyl esters have to be removed, for example, by re-heating the fatty acid, alkyl esters. In addition, the water normally contains impurities that in turn needs to be removed, e g by filtrating the water and/or running the water through an ion exchange medium. The water can then be re-used or simply treated as wastewater. A drawback with known procedures for purification of fatty acid alkyl esters by using water is that it is difficult to reduce the amount of metal impurities, e g calcium and magnesium impurities, to levels that comply with the regulatory norms concerning fatty acid alkyl esters, even when large amount of water is used for purification. Another drawback with known procedures of purifying the fatty acid alkyl esters using water is that the manufacturing of biodiesel, for example, requires high energy input and becomes time-consuming and costly, since the process, for example, requires a large amount of water for purification, which in turn, needs to be purified. Summary of the invention In view of the aforementioned respects of known processes, an object of the present invention to provide a use of certain agents as well as a process for purification of fatty acid alkyl esters, which wholly or partly eliminate drawbacks of known techniques and which allow a production of fatty acid alkyl esters which is easy to handle resulting in high quality fatty acid alkyl esters suitable for use as biodiesel. The invention is defined by the independent claims. Embodiments are evident from the dependent claims and from the following description and examples According to a first aspect, there is provided a use of a flocculating and sequestering agent as an agent facilitating the purification of an organic solution comprising fatty acid alkyl esters. By a ^flocculating and sequestering agent" is meant a reagent, usually a polyelectrolyte, added to a suspension to unite fine particles to form flocks. Further, the term includes an agent that can form several bonds to a metal ion, such as calcium and magnesium. In addition, the term also relates to an agent that forms an aqueous phase within an organic solution, which phase also attracts ions. By an "organic solution of fatty acid alkyl esters" is understood a phase mainly comprising said fatty acid alkyl esters, but also small amounts of impurities such as the reactants and products of the transesterification process of triglycerides, e g soap, and ions and salts of metals. The use of a flocculating and sequestering agent facilitates the removal of impurities such as calcium, magnesium, potassium and sodium impurities. In addition, the treatment with this flocculating and sequestering agent will not affect the acid number of the product, e g measured as free fatty acids and as other acidity, when added and removed properly. The acid number of free fatty acid methyl esters, for example, according to EN 14214 is restricted to 0,5 mg KOH/kg oil (for further discussion see below). In one embodiment, the flocculating and sequestering agent is selected from the group consisting of polyaluminium coagulants. Such polyaluminium coagulants facilitate to high extent a process, in which impurities, such as calcium, magnesium, potassium and sodium impurities, are to be removed, even from the nonpolar environment of the organic solution of fatty acid alkyl esters. In one embodiment, the flocculating and sequestering agent is polyaluminium hydroxychloride. Polyaluminium hydroxychloride facilitate to high extent the removal of impurities in the nonpolar environment of the organic solution of fatty acid alkyl esters, attracting metal ions such as calcium and magnesium ions. In addition, the polyaluminium hydroxychloride also forms an aqueous phase within the organic solution, which phase also attracts ions such as sodium and potassium ions. Moreover, the chloride ions aid in the removal of ions such as potassium and sodium. In one embodiment, the organic solution is essentially anhydrous. The term "essentially anhydrous" should be understood in the context of that no effective amount of free water is present in the organic solution. An effective amount is the amount that is sufficient to achieve a noticeable reduction in impurities according to the known purification processes using water to wash out impurities without addition of the flocculating and sequestering agent. Amounts of water known to be effective in such processes exceed 10% {by weight), typically around 10 to 60% (by weight) relative the organic solution. In its strict definition, the term means that no free water is needed for the purification and therefore not added to the organic solution during a purification process using the flocculating and sequestering agent. This means that the only water present at any time during the purification process is the water remaining from previous treatment such as a transesterification process, and additions of compounds during the purification. The addition of a flocculating and sequestering agent adds to,the water content, and which addition depends on the added amount of agent. To some extent, small amounts of water, e g less than 1000 ppm by weight, will aid the creation of a phase within the organic solution, which phase attracts ions such as sodium and potassium ions. But, using to high amounts of water together with the flocculating and sequestering agent might affect the purification of the organic solution in a negative way, i e the flocculating and sequestering agent will not facilitate the removal of impurities. Notwithstanding, in a preferred embodiment the maximum water content of the organic solution can be up to 10% (w/w) . In a more preferred embodiment the maximum water content of the organic solution Can be up to 9.5, 9.0, 8,5, 8.0, .7.5, 7.0, 6.5, 6.0, 5.5, 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, 0.43 or 0.10 % (w/w). In a more preferred embodiment, the water content is around 100 to 1000 ppm. (w/w), and even more preferred around 500 ppm. Each of these embodiments will allow small amounts water as long as the total water content is well below an effective amount of water as mentioned above, and that the purification is not affected in a negative way. According to a second aspect, there is provided a process for purification of an organic solution of fatty acid alkyl esters suitable for use as biodiesel, comprising: - adding a flocculating and sequestering agent to the organic solution so as to facilitate the purification, and - removing a portion from the organic solution, which portion comprises the flocculating and sequestering agent, and impurities. Such a process for purification of fatty acid alkyl esters makes it possible to reduce the amount of metal impurities, e g calcium and magnesium impurities, to levels that comply with the regulatory norms concerning fatty acid alkyl esters. In one embodiment of the process, the removing of the portion, from the organic solution comprises a step of centrifugation of the organic solution so as to remove the flocculating and sequestering agent together with impurities, which are solid, polar and/or have different densities than the fatty acid alkyl esters. Such a process will enable less energy input and becomes less time-consuming and less costly, as compared to the known processes using water to purify the organic solution. In addition, the efficiency of the process is easy to control and the process will demand very little monitoring. Moreover, the process can accomplish a system with low water content throughout the process. Such a process requires no water for purification, which in turn needs to be purified. In addition, the process yields a high amount of purified fatty acid alkyl esters that are suitable for use as biodiesel. Such a process will also enable the production of fatty acid alkyl esters without the need of separate neutralization with, for example, an acetic solution. Within the European norm (see above) there is a demand for the limitation of the acid number, which includes both free fatty and mineral acids in the biodiesel. The maximum value is 0.5 expressed as mg KOH/g of biodiesel. There is no demand for pH value in biodiesel, but the need for neutralization is assumed to create metal salts as a by-product of the neutralization. As an example, when fatty acid methyl esters are produced using methanol and alkali, the organic solution can contain rather high levels of alkali, which in turn leads to a pH up to around 11. In known processes, an acetic solution has to be added to the material. In one embodiment of the process, the centrifugation is performed under low pressure in order to remove water from the organic solution. In one embodiment of the process, essentially no water is added to the organic solution during the process to remove impurities. The term "essentially no added water" should be understood in the context of the term ^essentially anhydrous' as discussed above, i e the process comprises that the purification is performed in the absence of an effective amount of free water. According to one embodiment, the water content of the organic solution of fatty acid alkyl esters throughout the process can be up to 10% (w/w) . in a more preferred embodiment the maximum water content of the organic solution throughout the process can be up to 9.5, 9.0, 8,5, 8.0, 7.5, 7.0, 6.5, 6.0, 5.5, 5.0, 4.5, 4.0r 3.5, 3.0, 2.5/ 2.0, 1.5, 1.0, 0.5 0.43 or 0.10 % (w/w). In a more preferred embodiment, the water content is around 100 to 1000 ppm (w/w), and even more preferred around 500 ppm. Each of these embodiments will allow . small amounts water as long as the total water content is well below an effective amount of water as mentioned above, and that the purification is not affected in a negative way. In one embodiment of the process, the impurities comprise glycerol, soap, free fatty acid and/or metal impurities. The process for purification of fatty acid alkyl esters makes it possible to reduce the amount of such impurities. In one embodiment of the process, the metal impurities originate from metals comprising calcium, magnesium, potassium and/or sodium. The process for purification of fatty acid alkyl esters makes it especially possible to reduce the amount of such metal impurities, and even to reduce the amounts of the metal impurities in the final product to be used as biodiesel, so as to comply with regulatory norms. In one embodiment of the process, the flocculating and sequestering agent is selected from the group . consisting of polyaluminium coagulants. In one embodiment, the flocculating and sequestering agent is polyaluminium hydroxychloride. The processes and the use according to the different aspects of the invention will now be described in more detail with reference to embodiments and examples. Detailed description of the invention and embodiments The invention relates to the use of a flocculating and sequestering agent as an agent facilitating the purification of an organic solution comprising fatty acid alkyl esters, in particular mono alkyl esters of long fatty acids that are suitable for use as biodiesel. In one aspect, the invention also relates to a process for purification of the organic solution of fatty acid alkyl esters. The process makes use of a flocculating and sequestering agent to facilitate the purification, and removing a portion from the organic solution, which portion comprises the flocculating and sequestering agent, and impurities. The organic solution of fatty acid alkyl esters to be purified is a product of vegetable oils or animal fats. In one embodiment, the oils or fats used are freshly refined oils or fats, meaning that the oils or fats have never been used. In another embodiment, the oils and fats used are re-used crude oils and fats such as oils that have been used as frying oils. Examples of vegetable oils freshly refined or re-used, are coconut oil, palm oil, olive oil, sunflower oil Soya oil and rapeseed oil. The organic solution for purification can be produced according processes known in the art. Examples of such processes are those that comprise either acid or base catalysts. Examples of such catalysts are the hydroxides from sodium and potassium., alkoxides of potassium and sodium as well as anhydrous sulphuric and acetic acids. In a process of fatty acid alkyl esters, such as methyl esters of fatty acids, it is desirable to accomplish a system with low water content throughout the process. Such a system will disable production of process water, increase the produced yield of fatty acid alkyl esters, and decrease the production of by-products such as soaps. The final product to be used as biodiesel should preferably contain less than 500 ppm water. Accordingly, it is desirable to use catalysts not producing, or producing very small amount of water during preparation or theirs addition. One example of a catalyst in this context is the methoxide of sodium or potassium, which in turn can be formed by the reaction of methanol with sodium or potassium. One example of a process for producing methyl esters of fatty acid comprises heating a vegetable oil to a temperature of normally between 30ºC and 110ºC, depending on the oil used, for example 80 to 90°C when using used cooking oil, 50°C when using rape seed oil and slightly lower when using more unsaturated oils. The process further comprises adding methanol and potassium or sodium methoxide to the heated oil. The amounts of potassium or sodium methoxide and methanol added depend on, for example, the amount of free fatty acid present in the oil, and the average molecular weight of the oil, each of which can be decided as is known to those skilled in the art. The methanol is usually added in excess. The reaction will result in two phases, one including produced glycerol and the other including produced methyl esters of fatty acids. In addition, the process comprises removing the produced glycerol phase, typically constituting around 15 to 20 % (w/w) of the two phases, from the produced methyl ester phase, e g by gravity or two-phase centrifugation. Further, the methanol is removed by evaporation with help of under pressure or with a temperature above the boiling point of methanol. This process will yield an organic solution comprising up to 99 % (w/w) methyl esters of fatty acids, which organic solution needs to be purified according to the invention. Turning now to one aspect of the invention, wherein the flocculating and sequestering agent is used to aid the separation of impurities from the organic solution of fatty acid alkyl esters. The use of a flocculating and sequestering agent was surprisingly found to be useful in the almost xionpolar environments of the organic solution for attracting metal ions of various kinds. In addition, the flocculating and sequestering agent, was found to aid the separation of impurities other than metal ions from the organic solution, such as free fatty acids, soap and glycerol, which are polar as compared to the organic solution. Examples of such flocculating and sequestering agents are polyaluminium coagulants. Polyaluminium coagulants have a polymeric structure, and are known to be soluble in water. The length of the polymerised chain, molecular weight and number of ionic charges is determined by the degree of polymerisation. On hydrolysis, various mono- and polymeric species are formed. These highly polymerised sequestering agents include, for example: polyaluminium chloride, aluminium hydroxychloride, and polyaluminium hydroxychloride; marketed as, for example, Ekoflock 54, and Sweflock 10. The advantages of vising polyaluminium coagulants are, for example, that they are cheap, non-carcinogenic and that they also will attract the ions from sodium and potassium in a chloride solution. Examples of other conceivable types of sequestering agents available on the market are polyaluminium ferric chloride, EDTA and acryl amides. The flocculating and sequestering agent together with the impurities can be separated and removed from the organic solution by methods such as centrifugation and filtration or just by gravity letting the mixture settle into two phases, or by any other mechanical means as is known to those skilled in the art. In a preferred embodiment, the impurities are separated and removed by at least one step of centrifugation. In one embodiment, polyaluminium hydroxychloride is used as the flocculating and sequestering agent, which is known as a satisfactory sequestering agent in water for metal ions, such as calcium and magnesium. The sequestering agent polyalurainium hydroxychloride was found to be useful in the nonpolar environment of the organic solution of fatty acid alkyl esters, attracting metal ions such as calcium and magnesium ions. In addition, the polyaluminium hydroxychloride also forms an aqueous phase within the organic solution, which phase also attracts ions such as sodium and potassium ions. Accordingly, even if less than 100% of the ions such as calcium and magnesium ions are sequestered by the flocculating and sequestering agent, a sufficient level of the remaining ions will be able to enter the aqueous phase. It should be noted that the traces of "water content" increases in the organic solution after addition of polyaluminiura hydroxychloride that by its addition releases up to 1000 ppm (w/w) of water to the organic solution, depending on the amount of polyaluminium hydroxychloride added. In one embodiment, the flocculating and sequestering agent is added when the pH in the organic solution is 9 to 12. Preferably, the pH is 10-11. Accordingly, the flocculating and sequestering agent is preferably added short after the transesterification process is completed and the methanol and glycerol has been removed, since the pH is high, around 10.3 to 10.5, and which pH will decrease in time. In a preferred embodiment, the organic solution is essentially anhydrous, when the flocculating and sequestering agent is added, meaning that no effective amount of free water is present in the organic solution. An effective amount is the amount that is sufficient to achieve a noticeable reduction in impurities according to the known purification processes using water to wash out impurities without addition of the flocculating and sequestering agent. Amounts of water known to be effective in such processes exceed 10% (by weight), typically around 10 to 60% (by weight) relative the organic solution. In its strict definition, the term means that no free water is needed for the purification and therefore not added to the organic solution during a - purification process using the flocculating and sequestering agent. This means that the only water present at any time during such purification process is the water remaining from previous treatment such as a transesterification process, and additions of compounds during the purification. The addition of a flocculating and sequestering agent adds to the water content, and which addition depends on the,added amount of agent. To some extent, small amounts of water, e g less than 1000 ppm by weight, will aid the creation of a phase within the organic solution, which phase attracts ions such as sodium and potassium ions. But, using to high amounts of water together with the flocculating and sequestering agent might affect the purification of the organic solution in a negative way, i e the flocculating and sequestering agent will not facilitate the removal of impurities as will be exemplified by the comparative examples 7 to 10. Notwithstanding, in one embodiment the maximum water content of the organic solution can be up to 10% (w/w) . In a more preferred embodiment the maximum water content of the organic solution can be up to 9.5, 9.0, 8,5, 8.0, 7.5, 7.0, 6.5, 6.0, 5.5, 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, 0.43 or 0.10 % (w/w). In a more preferred embodiment, the water content is around 100 to 1000 ppm (w/w), and even more preferred around 500 ppm. Each of these embodiments will allow small amounts water as long as the total water content is well below an effective amount of water as mentioned above, and that the purification is not affected in a negative way. The concentration of water of the final product to be used as biodiesel should comply with the regulatory norms, and be equal or less than 500 ppm (w/w). According to one aspect of the invention, the process for purification of the organic solution of fatty acid alkyl esters is provided. The process comprises a step of adding a flocculating and sequestering agent to the organic solution so as to facilitate the purification. In addition, the process comprises a step of removing a portion from the organic solution, which portion comprises the flocculating and sequestering agent, and impurities. In one embodiment of the process, the step of removing a portion from the organic solution comprises a step of centrafugation so as to reduce the amount of impurities and flocculating and sequestering agent in the organic solution. One example of a centrifuges is a centrifuge with a closed bowl, e g model FM600 of Mann- Hummel, which is driven by and working under continuous flow of medium to be separated- The inlet of the centrifuge can be connected to a mixing tank/vessel and a pump, and the outlet for the purified solution can in turn also be connected to said tank/vessel. It is noted that any suitable centrifuge as is known to those skilled in the art can be used. During the centrifugation, compounds that are solids, polar or/and have different densities than the fatty acid alkyl esters are separated and removed from the organic solution, such as the flocculating and sequestering agent and impurities. The total amount of impurities can constitute around 1 to 5 % (w/w) of the organic solution. Examples of such compounds are impurities such as salts and ions of metals, free fatty acids, glycerol and soap. In one embodiment, using a bowl centrifuge (e g model FM600 of Mann-Hummel), a portion comprising free fatty acids, glycerol and soap together with the flocculating and sequestering agent create a phase in the bowl, which phase is polar as compared to the organic solution of fatty acid alkyl esters and which is drained off after centrifugation. Metal ions are also localized in this portion and thereby removed simultaneously. In one working embodiment, the centrifugation. is performed using the bowl centrifuge of model EM600 (Mann-Hummel) at around 4200 rpm for six hours under continuous recirculation flow. In one embodiment, the centrifugation is performed under low pressure, e g -0.9 bar. The low pressure was shown to provide, for example, a reduction of water content, wherein the final water content in the organic solution is less than 500 ppia. The amount of impurities can, for example, be lowered from around 5% to 1% (w/w) of the organic solution. Typically, the portion drained off from the centrifuge constitutes approximately 1.1 % (w/w) as compared to the initial batch weight. Using a flocculating and sequestering agent such as polyaluminium hydroxychloride in combination with separation by centrifugation lower to high extent the . amount of impurities in the organic solution. The amount of added flocculating and sequestering agent depends on the initial levels of impurities. Saturated levels can be added, and even in excess., as calculated from the initial amount of impurities, which calculation is evident for those skilled in the art. Typical amount is above 0.5 % (w/w)., in particular 0.5 to 2.5 % (w/w), of the organic solution to be purified. The purified organic solution should comply with regulatory norms, e g the European norm EN-14214. In this norm the following limitations are stated: 5 mg/kg for potassium plus sodium and 5 mg/kg for calcium and magnesium. Examples of values before purification and after purification using a process comprising both centrifugation and addition of polyaluminium hydroxychloride are, as shown in the experimental part, for calcium plus magnesium 11 to 14 and 0.3 to 2.2, respectively, and for potassium and sodium 440 to 100 and 3.9 to 4.1, respectively. As discussed above, one embodiment of the process comprises that essentially no water is added during the process. As will be evident from the experimental part, water can even affect the purification in a negative way. In one embodiment, the addition of the flocculating and sequestering agent to the organic occurs before any centrifugation is performed. The addition is followed by at least one centrifugation step to remove the impurities together with the flocculating and sequestering agent. This method demands no or very little supervision by the operator, wherein the purification can be performed with just one step of removing impurities. In another embodiment, the organic solution is subjected to at least one centrifugation step before any addition of the flocculating and sequestering agent occurs and further steps of removing impurities. The advantage with this method is to enable a pre-removal impurities, in particular soap and glycerol in almost pure form, before adding the flocculating and sequestering agent, and thereafter steps of centrifugation. According to an additional aspect of the invention, there is provided a process for producing an organic solution comprising fatty acid alkyl esters, in particular mono alkyl esters of long fatty acids that are suitable for use as biodiesel. The process comprises producing the organic solution to be purified as discussed above, and purifying this organic solution according to the aspects of the invention regarding purification. Examples The invention will now be illustrated further through the non-limiting recital of experiments conducted in accordance therewith. In these experiments the aspects of purification with or without adding a flocculating and sequestering agent were tested as well as different concentrations of the same. Examples 1 to 6 Experimental procedures Each one of the experiment of examples 1 to 6 was based on a batch of organic solution of fatty acid methyl esters produced using one embodiment of above described process for transesterification, wherein sodium or potassium methoxide was used as the catalyst as well as methanol as the alcohol, The catalyst added was for potassium methylate 0.64% by weight of organic solution, and for sodium methylate 0.45% by weight. Methanol was added at a stoichiometric surplus of 50 % by weight. After the transesterification was completed, the glycerol phase was drained off and the excess of methanol was removed under low pressure (-0.9 bar) to leave a remaining batch of the organic solution for purification. The batch size for each experiment was around 3000 kg. Experimental conditions for purification For all experiments, the centrifugation was performed using a bowl centrifuge (model FM600 of Mann- Hummel) at 4,200 rpm for six hours at 55°C under low pressure (-0.9 bar). Polyaluminiuin hydroxy chloride (cat no 1327-41-9, Eka Nobel) was used as the flocculating sequestering and agent. The amount added was from 0 to 2,25 % by weight organic solution. Polyaluminium hydroxychloride was added following the transesterification process and after the glycerol and the excess of methanol has been removed, when pH still is high, which pH was determined to be around 10.3 to 10.5. Metal content analysis The metal levels for Mg, Ca, Na and K were determined with ICP analysis (inductive coupled plasma with argon) using an instrument from Spectro GmbH. The analyses were performed based on the standard methods described by: ASTM D 4951-96, ASTM 5708~95a, ASTM 5185- 95, DIN 51390-4, DIN 51391-3 and DIN 51790-6, whereby the spectrum lines 183,801/393,366, 285,213, 589,592 and 766.490 nm were ,used to determine the metal content concentrations for Ca, Mg, Na and K, respectively, which determination of concentrations is evident for the person skilled in the,art. Water content analysis The water content was analyzed volumetrically by using calcium hydride (CaH2) . The hydride reacts with the water forming a gas pressure, which was measured by a special gauge for this purpose (the gauge meter in the so called Mobil water test kit, no 429950 produced by Signum/ExxonMobil). From the data shown in table 1, it is evident that the metals calcium plus magnesium and potassium plus sodium can amount around 20 and 100 - 450 mg/ kg, respectively, after production of the organic solution comprising fatty acid alkyl esters before any purification. After treating the material with polyaluminium hydroxychloride followed by centrifugation the metal levels were to high extent reduced. In example 3, the results were obtained by a step of centrifugation, but without addition of any flocculating and sequestering agent. The results show that the metal levels are reduced to some extent, but not to the levels obtained by using the purification combination of centrifugation and addition of a flocculating and sequestering agent. For example 5, it should be noted that the results were obtained by using a slightly malfunctioning centrifuge. Results: Example 6 In one experiment the water content of the organic solution was analyzed. The -water content was as highest right before centrifugation and was determined to be 0.43% (w/w) . After centrifugation for two hour, the water content was 0.23% (w/w) and after the centrifugation was completed the water content was determined to be 0.12% (w/w) . The reason for the relatively high amount of water after the completed centrifugation was shown to be a result of a malfunctioning centrifuge. In other experiments the final water content have been determined to be lower than 1000 ppm (w/w), and the final product to be less than 500 ppm (data not shown). Comparative Examples 7 to 10 Experimental procedures Each one of the experiments of examples 7 to 10 was based on a batch of organic solution of fatty acid methyl esters produced as mentioned above in examples 1 to 6. For each experiment, rape seed oil was used as the. starting material. The amount of biodiesel used for purification in each experiment was 100 g per experiment. The purification of the produced organic solution was performed in a similar way as described in examples 1 to 6, with the exception that the step of removal of the portion comprising the impurities was not performed by centrifugation. Instead, the organic solution was washed with water. The washing comprised mixing water with the organic solution, and removing the water from the organic solution. Three steps of washing were performed, wherein 20% (w/w) of water was added and removed in each step. This process resembles methods in the art in which water is used to wash the organic solution. One difference compared to the known methods was that a flocculating and sequestering agent was mixed into the organic solution before any washing with water occurred. The step of mixing flocculating and sequestering agent was performed before the steps of washing. After the washing with water, the remaining traces of water were removed by leaving the organic solution in a water bath at 50°C until the water content was below 500 ppm. From the data shown in table 2, it "is evident that washing water (3 x 20% w/w) without centrifugation together with the flocculating and sequestering agent will not work properly in reducing the metal impurities, even as compared to washing with water without any addition of flocculating and sequestering agent. Only the values for calcium plus magnesium are of approved levels. The reason for the relatively high remaning levels of metal impurities might be due to poor water solubility properties of the complexes formed by the flocculating and sequestering agent. Moreover, as seen from the low remaining chloride concentration of the final product, the mechanism of using washing water might not allow the potassium plus sodium to form chlorides together with the flocculating and sequestering agent. Instead, the chloride ions seem to preferably migrate into the water and thereby being washed away without the metals and the flocculating and sequestering agent. The concentration of chloride ions before purification and after the flocculating and sequestering agent has been added can be up 11 rug/kg. These results also indicate that addition of water with the flocculating and sequestering agent might affect the purification of the organic solution in a negative way, i e the flocculating and sequestering agent will not facilitate the removal of impurities, even when purification process comprises a centrifugation step. Examples 11 and 12 Experimental procedures Each one of the experiment of examples 11 and 12 was based on a batch of organic solution of fatty acid methyl esters produced, purified and analyzed as mentioned above in examples 1 to 6, with the exceptions of a slightly different amount of added catalyst and th&t batch size was around 3000 kg in example 11 and around 16000 kg in example 12. In example ll, the catalyst was potassium methylate in an amount of around 0.78% by weight of organic solution. In example 12, the catalyst was sodium methylate in an amount of around 0.51% by weight of organic solution. Results: Examples 11 and 12 From the data shown in table 3, it is evident that by treating the organic solution of fatty acid methyl esters with polyaluminium hydroxychloride followed by centrifugation the metal levels were to high extent reduced, even in case of sunflower oil as the origin of organic solution. CLAIMS 1. Use of a flocculating and sequestering agent as an agent facilitating the purification of an organic solution comprising fatty acid alkyl esters. 2. The use according to claim 1, wherein the flocculating and sequestering agent is selected from the group consisting of polyaluminium coagulants. 3. The use according to claim 2, wherein the flocculating and sequestering agent is polyaluminium hydroxychloride. 4. The use according to any one of the preceding claims, wherein the organic solution is essentially anhydrous. 5. The use according to claim 4, wherein the water content of the organic solution is less than 10 % by weight, preferably equal or less than 9.5, 9.0, 8.5, 8.0, 7.5, 7.0, 6.5, 6.0, 5.5, 5,0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, 0.43 or 0.10 % (w/w), and more preferred around 100 to 1000 ppm (w/w), and even more preferred around 500 ppm (w/w). 6. A process for purification of an organic solution of fatty acid alkyl esters suitable for use as biodiesel, comprising: - adding a flocculating and sequestering agent to the organic solution so as to facilitate the purification, and - removing a portion from the organic solution, which portion comprises the flocculating and sequestering agent, and impurities. 7. The process according to claim 6, wherein the removing of the portion from the organic solution comprises a step of centrifugation of the organic solution so as to remove the flocculating and sequestering agent together with impurities, which are solid, polar and/or have different densities than the fatty acid alkyl esters. 8. The process according to claim 7, wherein the centrifugation is performed under low pressure in order to remove water from the organic solution 9- The process according to any one of claims 6 to 8, wherein essentially no water is added to the organic solution during the process. 10. The process according to claim 9, wherein the water content of the organic solution of fatty acid alkyl esters throughout the process is less than 10 % by weight, preferably equal or less than 9.5, 9.0, 8.5, 8.0, 7.5, 7.0, 6.5, 6.0, 5.5, 5,0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, 0.43 or 0.10 % (w/w), and more preferred around 100 to 1000 ppm (w/w), and even more preferred around 500 ppm (w/w). 11. The process according to any one of claims 6 to 10, wherein the impurities comprises glycerol, soap, free fatty acid and/or metal impurities. 12. The process according to claim 11, wherein the metal impurities originates from metals comprising calcium, magnesium, potassium and/or sodium. 13. The process according to any one of claims 6 to 12, wherein the flocculating and sequestering agent is selected from the group consisting of polyaluminium coagulants. 14. The process according to claim 13, wherein the flocculating and sequestering agent: is polyaluminium hydroxychloride. A use of a flocculating and sequestering agent as an agent facilitating the purification of an organic solution comprising fatty acid alkyl esters. Also provided is a process for purification of the organic solution, which process comprises adding a flocculating and sequestering agent to the organic solution so as to facilitate the purification, and removing a portion from the organic solution, which portion comprises the flocculating and sequestering agent, and impurities.

Full Text

PROCESS FOR PURIFICATION OF FATTY ACID ALKYL ESTERS AND
USE OF AGENTS TO FACILITATE SUCH PURIFICATION
Technical field of the invention
The present invention relates to the use of certain
agents to facilitate the purification of an organic
solution of fatty acid alkyl esters. The present
invention also relates to a process for purification of
the fatty acid alkyl esters suitable for use as
biodiesel.
Technical background
Fatty acid alkyl esters (mono alkyl esters of fatty
acids such as methyl and ethyl esters of fatty acids)
derived from, vegetable oils or animal fats are known to
be used as biodiesel- Known processes to produce such
fatty acid alkyl esters comprise transesterification of
triglycerides included in vegetable oils or animal fats
in presence of an alcohol and a catalyst. It is well
known in the art to use catalysts such as acid catalysts
or more commonly alkali metal catalysts/ e g sodium and
potassium hydroxide or a metal alkoxide such as sodium or
potassium methoxide. In fact, a metal alkoxide is a
compound formed by the reaction of an alcohol with an
alkali metal. In summary, the transesterification
reaction can generally be described as follow:

Among vegetable oils or animal fats that can be used
are coconut oil, palm oil, seed oil, olive oil, sunflower
oil, Soya oil, rapeseed oil and tallow. Suitable alcohols
that can be used are aryl alcohols such as methanol,
ethanol, propanol and butanol. Due to low cost, polarity

and short chain, methanol is normally used in biodiesel
production. Due to high activity, an alkali catalyst such
as potassium hydroxide is usually used on industrial
scale,
A well-known process for producing fatty acid alkyl
esters comprises heating, for example, a vegetable oil to
a temperature of normally between 30*C and 110"C. The
process further comprises adding an alcohol and a
catalyst to the heated oil. The reaction will result in
two phases, one including produced glycerol and the other
including produced fatty acid alkyl ester. In addition,
the process comprises removing the produced glycerol
phase from the produced fatty acid alkyl ester phase.
Fatty acid alkyl esters produced according to known
processes as described above normally comprises to high
levels of impurities to comply with regulatory norms
concerning fatty acid alkyl esters, e g the European norm
EN-14214 for fatty acids methyl esters, which especially
limits the impurities originating from the metals K, Na,
Mg and Ca. Accordingly, there is a need for purification
of the produced fatty acid alkyl esters. Known processes
for purification include steps of neutralization and
washing with water, which will wash out the impurities
and produce fatty acid alkyl ester that complies with the
regulatory norms and thus can be used as biodiesel. After
each step of washing, the water can be separated from the
fatty acid alkyl esters by any method known in the art
such as await for the mixture to settle into two phases
and thereafter drain off the water phase, or by
centrifugation of the mixture. The total amount of water
used can typically range from 20 to 100% water of the
produced volume of fatty acid alkyl esters: After
purification is completed, the traces of water comprised
in the fatty acid alkyl esters have to be removed, for
example, by re-heating the fatty acid, alkyl esters. In
addition, the water normally contains impurities that in
turn needs to be removed, e g by filtrating the water

and/or running the water through an ion exchange medium.
The water can then be re-used or simply treated as
wastewater.
A drawback with known procedures for purification
of fatty acid alkyl esters by using water is that it is
difficult to reduce the amount of metal impurities, e g
calcium and magnesium impurities, to levels that comply
with the regulatory norms concerning fatty acid alkyl
esters, even when large amount of water is used for
purification. Another drawback with known procedures of
purifying the fatty acid alkyl esters using water is that
the manufacturing of biodiesel, for example, requires
high energy input and becomes time-consuming and costly,
since the process, for example, requires a large amount
of water for purification, which in turn, needs to be
purified.
Summary of the invention
In view of the aforementioned respects of known
processes, an object of the present invention to provide
a use of certain agents as well as a process for
purification of fatty acid alkyl esters, which wholly or
partly eliminate drawbacks of known techniques and which
allow a production of fatty acid alkyl esters which is
easy to handle resulting in high quality fatty acid alkyl
esters suitable for use as biodiesel.
The invention is defined by the independent claims.
Embodiments are evident from the dependent claims and
from the following description and examples
According to a first aspect, there is provided a
use of a flocculating and sequestering agent as an agent
facilitating the purification of an organic solution
comprising fatty acid alkyl esters.
By a ^flocculating and sequestering agent" is meant
a reagent, usually a polyelectrolyte, added to a
suspension to unite fine particles to form flocks.
Further, the term includes an agent that can form several

bonds to a metal ion, such as calcium and magnesium. In
addition, the term also relates to an agent that forms an
aqueous phase within an organic solution, which phase
also attracts ions.
By an "organic solution of fatty acid alkyl esters"
is understood a phase mainly comprising said fatty acid
alkyl esters, but also small amounts of impurities such
as the reactants and products of the transesterification
process of triglycerides, e g soap, and ions and salts of
metals.
The use of a flocculating and sequestering agent
facilitates the removal of impurities such as calcium,
magnesium, potassium and sodium impurities. In addition,
the treatment with this flocculating and sequestering
agent will not affect the acid number of the product, e g
measured as free fatty acids and as other acidity, when
added and removed properly. The acid number of free fatty
acid methyl esters, for example, according to EN 14214 is
restricted to 0,5 mg KOH/kg oil (for further discussion
see below).
In one embodiment, the flocculating and
sequestering agent is selected from the group consisting
of polyaluminium coagulants.
Such polyaluminium coagulants facilitate to high
extent a process, in which impurities, such as calcium,
magnesium, potassium and sodium impurities, are to be
removed, even from the nonpolar environment of the
organic solution of fatty acid alkyl esters.
In one embodiment, the flocculating and
sequestering agent is polyaluminium hydroxychloride.
Polyaluminium hydroxychloride facilitate to high
extent the removal of impurities in the nonpolar
environment of the organic solution of fatty acid alkyl
esters, attracting metal ions such as calcium and
magnesium ions. In addition, the polyaluminium
hydroxychloride also forms an aqueous phase within the
organic solution, which phase also attracts ions such as

sodium and potassium ions. Moreover, the chloride ions
aid in the removal of ions such as potassium and sodium.
In one embodiment, the organic solution is
essentially anhydrous.
The term "essentially anhydrous" should be
understood in the context of that no effective amount of
free water is present in the organic solution. An
effective amount is the amount that is sufficient to
achieve a noticeable reduction in impurities according to
the known purification processes using water to wash out
impurities without addition of the flocculating and
sequestering agent. Amounts of water known to be
effective in such processes exceed 10% {by weight),
typically around 10 to 60% (by weight) relative the
organic solution. In its strict definition, the term
means that no free water is needed for the purification
and therefore not added to the organic solution during a
purification process using the flocculating and
sequestering agent. This means that the only water
present at any time during the purification process is
the water remaining from previous treatment such as a
transesterification process, and additions of compounds
during the purification. The addition of a flocculating
and sequestering agent adds to,the water content, and
which addition depends on the added amount of agent. To
some extent, small amounts of water, e g less than 1000
ppm by weight, will aid the creation of a phase within
the organic solution, which phase attracts ions such as
sodium and potassium ions. But, using to high amounts of
water together with the flocculating and sequestering
agent might affect the purification of the organic
solution in a negative way, i e the flocculating and
sequestering agent will not facilitate the removal of
impurities.
Notwithstanding, in a preferred embodiment the
maximum water content of the organic solution can be up
to 10% (w/w) . In a more preferred embodiment the maximum

water content of the organic solution Can be up to 9.5,
9.0, 8,5, 8.0, .7.5, 7.0, 6.5, 6.0, 5.5, 5.0, 4.5, 4.0,
3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, 0.43 or 0.10 % (w/w).
In a more preferred embodiment, the water content is
around 100 to 1000 ppm. (w/w), and even more preferred
around 500 ppm. Each of these embodiments will allow
small amounts water as long as the total water content is
well below an effective amount of water as mentioned
above, and that the purification is not affected in a
negative way.
According to a second aspect, there is provided a
process for purification of an organic solution of fatty
acid alkyl esters suitable for use as biodiesel,
comprising:
- adding a flocculating and sequestering agent to
the organic solution so as to facilitate the
purification, and
- removing a portion from the organic solution,
which portion comprises the flocculating and
sequestering agent, and impurities.
Such a process for purification of fatty acid alkyl
esters makes it possible to reduce the amount of metal
impurities, e g calcium and magnesium impurities, to
levels that comply with the regulatory norms concerning
fatty acid alkyl esters.
In one embodiment of the process, the removing of
the portion, from the organic solution comprises a step of
centrifugation of the organic solution so as to remove
the flocculating and sequestering agent together with
impurities, which are solid, polar and/or have different
densities than the fatty acid alkyl esters.
Such a process will enable less energy input and
becomes less time-consuming and less costly, as compared
to the known processes using water to purify the organic
solution. In addition, the efficiency of the process is
easy to control and the process will demand very little
monitoring. Moreover, the process can accomplish a system

with low water content throughout the process. Such a
process requires no water for purification, which in turn
needs to be purified. In addition, the process yields a
high amount of purified fatty acid alkyl esters that are
suitable for use as biodiesel. Such a process will also
enable the production of fatty acid alkyl esters without
the need of separate neutralization with, for example, an
acetic solution. Within the European norm (see above)
there is a demand for the limitation of the acid number,
which includes both free fatty and mineral acids in the
biodiesel. The maximum value is 0.5 expressed as mg KOH/g
of biodiesel. There is no demand for pH value in
biodiesel, but the need for neutralization is assumed to
create metal salts as a by-product of the neutralization.
As an example, when fatty acid methyl esters are produced
using methanol and alkali, the organic solution can
contain rather high levels of alkali, which in turn leads
to a pH up to around 11. In known processes, an acetic
solution has to be added to the material.
In one embodiment of the process, the
centrifugation is performed under low pressure in order
to remove water from the organic solution.
In one embodiment of the process, essentially no
water is added to the organic solution during the process
to remove impurities.
The term "essentially no added water" should be
understood in the context of the term ^essentially
anhydrous' as discussed above, i e the process comprises
that the purification is performed in the absence of an
effective amount of free water.
According to one embodiment, the water content of
the organic solution of fatty acid alkyl esters
throughout the process can be up to 10% (w/w) . in a more
preferred embodiment the maximum water content of the
organic solution throughout the process can be up to 9.5,
9.0, 8,5, 8.0, 7.5, 7.0, 6.5, 6.0, 5.5, 5.0, 4.5, 4.0r
3.5, 3.0, 2.5/ 2.0, 1.5, 1.0, 0.5 0.43 or 0.10 % (w/w).

In a more preferred embodiment, the water content is
around 100 to 1000 ppm (w/w), and even more preferred
around 500 ppm. Each of these embodiments will allow .
small amounts water as long as the total water content is
well below an effective amount of water as mentioned
above, and that the purification is not affected in a
negative way.
In one embodiment of the process, the impurities
comprise glycerol, soap, free fatty acid and/or metal
impurities.
The process for purification of fatty acid alkyl
esters makes it possible to reduce the amount of such
impurities.
In one embodiment of the process, the metal
impurities originate from metals comprising calcium,
magnesium, potassium and/or sodium.
The process for purification of fatty acid alkyl
esters makes it especially possible to reduce the amount
of such metal impurities, and even to reduce the amounts
of the metal impurities in the final product to be used
as biodiesel, so as to comply with regulatory norms.
In one embodiment of the process, the flocculating
and sequestering agent is selected from the group .
consisting of polyaluminium coagulants.
In one embodiment, the flocculating and
sequestering agent is polyaluminium hydroxychloride.
The processes and the use according to the
different aspects of the invention will now be described
in more detail with reference to embodiments and
examples.
Detailed description of the invention and embodiments
The invention relates to the use of a flocculating
and sequestering agent as an agent facilitating the
purification of an organic solution comprising fatty acid
alkyl esters, in particular mono alkyl esters of long
fatty acids that are suitable for use as biodiesel. In

one aspect, the invention also relates to a process for
purification of the organic solution of fatty acid alkyl
esters. The process makes use of a flocculating and
sequestering agent to facilitate the purification, and
removing a portion from the organic solution, which
portion comprises the flocculating and sequestering
agent, and impurities.
The organic solution of fatty acid alkyl esters to
be purified is a product of vegetable oils or animal
fats. In one embodiment, the oils or fats used are
freshly refined oils or fats, meaning that the oils or
fats have never been used. In another embodiment, the
oils and fats used are re-used crude oils and fats such
as oils that have been used as frying oils. Examples of
vegetable oils freshly refined or re-used, are coconut
oil, palm oil, olive oil, sunflower oil Soya oil and
rapeseed oil.
The organic solution for purification can be
produced according processes known in the art. Examples
of such processes are those that comprise either acid or
base catalysts. Examples of such catalysts are the
hydroxides from sodium and potassium., alkoxides of
potassium and sodium as well as anhydrous sulphuric and
acetic acids. In a process of fatty acid alkyl esters,
such as methyl esters of fatty acids, it is desirable to
accomplish a system with low water content throughout the
process. Such a system will disable production of process
water, increase the produced yield of fatty acid alkyl
esters, and decrease the production of by-products such
as soaps. The final product to be used as biodiesel
should preferably contain less than 500 ppm water.
Accordingly, it is desirable to use catalysts not
producing, or producing very small amount of water during
preparation or theirs addition. One example of a catalyst
in this context is the methoxide of sodium or potassium,
which in turn can be formed by the reaction of methanol
with sodium or potassium. One example of a process for

producing methyl esters of fatty acid comprises heating a
vegetable oil to a temperature of normally between 30ºC
and 110ºC, depending on the oil used, for example 80 to
90°C when using used cooking oil, 50°C when using rape
seed oil and slightly lower when using more unsaturated
oils. The process further comprises adding methanol and
potassium or sodium methoxide to the heated oil. The
amounts of potassium or sodium methoxide and methanol
added depend on, for example, the amount of free fatty
acid present in the oil, and the average molecular weight
of the oil, each of which can be decided as is known to
those skilled in the art. The methanol is usually added
in excess. The reaction will result in two phases, one
including produced glycerol and the other including
produced methyl esters of fatty acids. In addition, the
process comprises removing the produced glycerol phase,
typically constituting around 15 to 20 % (w/w) of the two
phases, from the produced methyl ester phase, e g by
gravity or two-phase centrifugation. Further, the
methanol is removed by evaporation with help of under
pressure or with a temperature above the boiling point of
methanol. This process will yield an organic solution
comprising up to 99 % (w/w) methyl esters of fatty acids,
which organic solution needs to be purified according to
the invention.
Turning now to one aspect of the invention, wherein
the flocculating and sequestering agent is used to aid
the separation of impurities from the organic solution of
fatty acid alkyl esters. The use of a flocculating and
sequestering agent was surprisingly found to be useful in
the almost xionpolar environments of the organic solution
for attracting metal ions of various kinds. In addition,
the flocculating and sequestering agent, was found to aid
the separation of impurities other than metal ions from
the organic solution, such as free fatty acids, soap and
glycerol, which are polar as compared to the organic
solution. Examples of such flocculating and sequestering

agents are polyaluminium coagulants. Polyaluminium
coagulants have a polymeric structure, and are known to
be soluble in water. The length of the polymerised chain,
molecular weight and number of ionic charges is
determined by the degree of polymerisation. On
hydrolysis, various mono- and polymeric species are
formed. These highly polymerised sequestering agents
include, for example: polyaluminium chloride, aluminium
hydroxychloride, and polyaluminium hydroxychloride;
marketed as, for example, Ekoflock 54, and Sweflock 10.
The advantages of vising polyaluminium coagulants are, for
example, that they are cheap, non-carcinogenic and that
they also will attract the ions from sodium and potassium
in a chloride solution. Examples of other conceivable
types of sequestering agents available on the market are
polyaluminium ferric chloride, EDTA and acryl amides.
The flocculating and sequestering agent together
with the impurities can be separated and removed from the
organic solution by methods such as centrifugation and
filtration or just by gravity letting the mixture settle
into two phases, or by any other mechanical means as is
known to those skilled in the art. In a preferred
embodiment, the impurities are separated and removed by
at least one step of centrifugation.
In one embodiment, polyaluminium hydroxychloride is
used as the flocculating and sequestering agent, which is
known as a satisfactory sequestering agent in water for
metal ions, such as calcium and magnesium. The
sequestering agent polyalurainium hydroxychloride was
found to be useful in the nonpolar environment of the
organic solution of fatty acid alkyl esters, attracting
metal ions such as calcium and magnesium ions. In
addition, the polyaluminium hydroxychloride also forms an
aqueous phase within the organic solution, which phase
also attracts ions such as sodium and potassium ions.
Accordingly, even if less than 100% of the ions such as
calcium and magnesium ions are sequestered by the

flocculating and sequestering agent, a sufficient level
of the remaining ions will be able to enter the aqueous
phase. It should be noted that the traces of "water
content" increases in the organic solution after addition
of polyaluminiura hydroxychloride that by its addition
releases up to 1000 ppm (w/w) of water to the organic
solution, depending on the amount of polyaluminium
hydroxychloride added.
In one embodiment, the flocculating and
sequestering agent is added when the pH in the organic
solution is 9 to 12. Preferably, the pH is 10-11.
Accordingly, the flocculating and sequestering agent is
preferably added short after the transesterification
process is completed and the methanol and glycerol has
been removed, since the pH is high, around 10.3 to 10.5,
and which pH will decrease in time.
In a preferred embodiment, the organic solution is
essentially anhydrous, when the flocculating and
sequestering agent is added, meaning that no effective
amount of free water is present in the organic solution.
An effective amount is the amount that is sufficient to
achieve a noticeable reduction in impurities according to
the known purification processes using water to wash out
impurities without addition of the flocculating and
sequestering agent. Amounts of water known to be
effective in such processes exceed 10% (by weight),
typically around 10 to 60% (by weight) relative the
organic solution. In its strict definition, the term
means that no free water is needed for the purification
and therefore not added to the organic solution during a -
purification process using the flocculating and
sequestering agent. This means that the only water
present at any time during such purification process is
the water remaining from previous treatment such as a
transesterification process, and additions of compounds
during the purification. The addition of a flocculating
and sequestering agent adds to the water content, and

which addition depends on the,added amount of agent. To
some extent, small amounts of water, e g less than 1000
ppm by weight, will aid the creation of a phase within
the organic solution, which phase attracts ions such as
sodium and potassium ions. But, using to high amounts of
water together with the flocculating and sequestering
agent might affect the purification of the organic
solution in a negative way, i e the flocculating and
sequestering agent will not facilitate the removal of
impurities as will be exemplified by the comparative
examples 7 to 10.
Notwithstanding, in one embodiment the maximum
water content of the organic solution can be up to 10%
(w/w) . In a more preferred embodiment the maximum water
content of the organic solution can be up to 9.5, 9.0,
8,5, 8.0, 7.5, 7.0, 6.5, 6.0, 5.5, 5.0, 4.5, 4.0, 3.5,
3.0, 2.5, 2.0, 1.5, 1.0, 0.5, 0.43 or 0.10 % (w/w). In a
more preferred embodiment, the water content is around
100 to 1000 ppm (w/w), and even more preferred around 500
ppm. Each of these embodiments will allow small amounts
water as long as the total water content is well below an
effective amount of water as mentioned above, and that
the purification is not affected in a negative way. The
concentration of water of the final product to be used as
biodiesel should comply with the regulatory norms, and be
equal or less than 500 ppm (w/w).
According to one aspect of the invention, the
process for purification of the organic solution of fatty
acid alkyl esters is provided. The process comprises a
step of adding a flocculating and sequestering agent to
the organic solution so as to facilitate the
purification. In addition, the process comprises a step
of removing a portion from the organic solution, which
portion comprises the flocculating and sequestering
agent, and impurities.
In one embodiment of the process, the step of
removing a portion from the organic solution comprises a

step of centrafugation so as to reduce the amount of
impurities and flocculating and sequestering agent in the
organic solution. One example of a centrifuges is a
centrifuge with a closed bowl, e g model FM600 of Mann-
Hummel, which is driven by and working under continuous
flow of medium to be separated- The inlet of the
centrifuge can be connected to a mixing tank/vessel and a
pump, and the outlet for the purified solution can in
turn also be connected to said tank/vessel.
It is noted that any suitable centrifuge as is
known to those skilled in the art can be used. During the
centrifugation, compounds that are solids, polar or/and
have different densities than the fatty acid alkyl esters
are separated and removed from the organic solution, such
as the flocculating and sequestering agent and
impurities. The total amount of impurities can constitute
around 1 to 5 % (w/w) of the organic solution. Examples
of such compounds are impurities such as salts and ions
of metals, free fatty acids, glycerol and soap. In one
embodiment, using a bowl centrifuge (e g model FM600 of
Mann-Hummel), a portion comprising free fatty acids,
glycerol and soap together with the flocculating and
sequestering agent create a phase in the bowl, which
phase is polar as compared to the organic solution of
fatty acid alkyl esters and which is drained off after
centrifugation. Metal ions are also localized in this
portion and thereby removed simultaneously. In one
working embodiment, the centrifugation. is performed using
the bowl centrifuge of model EM600 (Mann-Hummel) at
around 4200 rpm for six hours under continuous
recirculation flow. In one embodiment, the centrifugation
is performed under low pressure, e g -0.9 bar. The low
pressure was shown to provide, for example, a reduction
of water content, wherein the final water content in the
organic solution is less than 500 ppia. The amount of
impurities can, for example, be lowered from around 5% to
1% (w/w) of the organic solution. Typically, the portion

drained off from the centrifuge constitutes approximately
1.1 % (w/w) as compared to the initial batch weight.
Using a flocculating and sequestering agent such as
polyaluminium hydroxychloride in combination with
separation by centrifugation lower to high extent the .
amount of impurities in the organic solution. The amount
of added flocculating and sequestering agent depends on
the initial levels of impurities. Saturated levels can be
added, and even in excess., as calculated from the initial
amount of impurities, which calculation is evident for
those skilled in the art. Typical amount is above 0.5 %
(w/w)., in particular 0.5 to 2.5 % (w/w), of the organic
solution to be purified.
The purified organic solution should comply with
regulatory norms, e g the European norm EN-14214. In this
norm the following limitations are stated: 5 mg/kg for
potassium plus sodium and 5 mg/kg for calcium and
magnesium. Examples of values before purification and
after purification using a process comprising both
centrifugation and addition of polyaluminium
hydroxychloride are, as shown in the experimental part,
for calcium plus magnesium 11 to 14 and 0.3 to 2.2,
respectively, and for potassium and sodium 440 to 100 and
3.9 to 4.1, respectively.
As discussed above, one embodiment of the process
comprises that essentially no water is added during the
process. As will be evident from the experimental part,
water can even affect the purification in a negative way.
In one embodiment, the addition of the flocculating
and sequestering agent to the organic occurs before any
centrifugation is performed. The addition is followed by
at least one centrifugation step to remove the impurities
together with the flocculating and sequestering agent.
This method demands no or very little supervision by the
operator, wherein the purification can be performed with
just one step of removing impurities.

In another embodiment, the organic solution is
subjected to at least one centrifugation step before any
addition of the flocculating and sequestering agent
occurs and further steps of removing impurities. The
advantage with this method is to enable a pre-removal
impurities, in particular soap and glycerol in almost
pure form, before adding the flocculating and
sequestering agent, and thereafter steps of
centrifugation.
According to an additional aspect of the invention,
there is provided a process for producing an organic
solution comprising fatty acid alkyl esters, in
particular mono alkyl esters of long fatty acids that are
suitable for use as biodiesel. The process comprises
producing the organic solution to be purified as
discussed above, and purifying this organic solution
according to the aspects of the invention regarding
purification.
Examples
The invention will now be illustrated further
through the non-limiting recital of experiments conducted
in accordance therewith. In these experiments the aspects
of purification with or without adding a flocculating and
sequestering agent were tested as well as different
concentrations of the same.
Examples 1 to 6
Experimental procedures
Each one of the experiment of examples 1 to 6 was
based on a batch of organic solution of fatty acid methyl
esters produced using one embodiment of above described
process for transesterification, wherein sodium or
potassium methoxide was used as the catalyst as well as
methanol as the alcohol, The catalyst added was for
potassium methylate 0.64% by weight of organic solution,

and for sodium methylate 0.45% by weight. Methanol was
added at a stoichiometric surplus of 50 % by weight.
After the transesterification was completed, the glycerol
phase was drained off and the excess of methanol was
removed under low pressure (-0.9 bar) to leave a
remaining batch of the organic solution for purification.
The batch size for each experiment was around 3000 kg.
Experimental conditions for purification
For all experiments, the centrifugation was
performed using a bowl centrifuge (model FM600 of Mann-
Hummel) at 4,200 rpm for six hours at 55°C under low
pressure (-0.9 bar).
Polyaluminiuin hydroxy chloride (cat no 1327-41-9,
Eka Nobel) was used as the flocculating sequestering and
agent. The amount added was from 0 to 2,25 % by weight
organic solution.
Polyaluminium hydroxychloride was added following
the transesterification process and after the glycerol
and the excess of methanol has been removed, when pH
still is high, which pH was determined to be around 10.3
to 10.5.
Metal content analysis
The metal levels for Mg, Ca, Na and K were
determined with ICP analysis (inductive coupled plasma
with argon) using an instrument from Spectro GmbH. The
analyses were performed based on the standard methods
described by: ASTM D 4951-96, ASTM 5708~95a, ASTM 5185-
95, DIN 51390-4, DIN 51391-3 and DIN 51790-6, whereby the
spectrum lines 183,801/393,366, 285,213, 589,592 and
766.490 nm were ,used to determine the metal content
concentrations for Ca, Mg, Na and K, respectively, which
determination of concentrations is evident for the person
skilled in the,art.

Water content analysis
The water content was analyzed volumetrically by
using calcium hydride (CaH2) . The hydride reacts with the
water forming a gas pressure, which was measured by a
special gauge for this purpose (the gauge meter in the so
called Mobil water test kit, no 429950 produced by
Signum/ExxonMobil).

From the data shown in table 1, it is evident that
the metals calcium plus magnesium and potassium plus
sodium can amount around 20 and 100 - 450 mg/ kg,
respectively, after production of the organic solution
comprising fatty acid alkyl esters before any
purification. After treating the material with
polyaluminium hydroxychloride followed by centrifugation
the metal levels were to high extent reduced.
In example 3, the results were obtained by a step
of centrifugation, but without addition of any
flocculating and sequestering agent. The results show

that the metal levels are reduced to some extent, but not
to the levels obtained by using the purification
combination of centrifugation and addition of a
flocculating and sequestering agent.
For example 5, it should be noted that the results
were obtained by using a slightly malfunctioning
centrifuge.
Results: Example 6
In one experiment the water content of the organic
solution was analyzed. The -water content was as highest
right before centrifugation and was determined to be
0.43% (w/w) . After centrifugation for two hour, the water
content was 0.23% (w/w) and after the centrifugation was
completed the water content was determined to be 0.12%
(w/w) . The reason for the relatively high amount of water
after the completed centrifugation was shown to be a
result of a malfunctioning centrifuge. In other
experiments the final water content have been determined
to be lower than 1000 ppm (w/w), and the final product to
be less than 500 ppm (data not shown).
Comparative Examples 7 to 10
Experimental procedures
Each one of the experiments of examples 7 to 10 was
based on a batch of organic solution of fatty acid methyl
esters produced as mentioned above in examples 1 to 6.
For each experiment, rape seed oil was used as the.
starting material. The amount of biodiesel used for
purification in each experiment was 100 g per experiment.
The purification of the produced organic solution was
performed in a similar way as described in examples 1 to
6, with the exception that the step of removal of the
portion comprising the impurities was not performed by
centrifugation. Instead, the organic solution was washed
with water. The washing comprised mixing water with the

organic solution, and removing the water from the organic
solution. Three steps of washing were performed, wherein
20% (w/w) of water was added and removed in each step.
This process resembles methods in the art in which water
is used to wash the organic solution. One difference
compared to the known methods was that a flocculating and
sequestering agent was mixed into the organic solution
before any washing with water occurred. The step of
mixing flocculating and sequestering agent was performed
before the steps of washing. After the washing with
water, the remaining traces of water were removed by
leaving the organic solution in a water bath at 50°C
until the water content was below 500 ppm.

From the data shown in table 2, it "is evident that
washing water (3 x 20% w/w) without centrifugation

together with the flocculating and sequestering agent
will not work properly in reducing the metal impurities,
even as compared to washing with water without any
addition of flocculating and sequestering agent. Only the
values for calcium plus magnesium are of approved levels.
The reason for the relatively high remaning levels of
metal impurities might be due to poor water solubility
properties of the complexes formed by the flocculating
and sequestering agent. Moreover, as seen from the low
remaining chloride concentration of the final product,
the mechanism of using washing water might not allow the
potassium plus sodium to form chlorides together with the
flocculating and sequestering agent. Instead, the
chloride ions seem to preferably migrate into the water
and thereby being washed away without the metals and the
flocculating and sequestering agent. The concentration of
chloride ions before purification and after the
flocculating and sequestering agent has been added can be
up 11 rug/kg.
These results also indicate that addition of water
with the flocculating and sequestering agent might affect
the purification of the organic solution in a negative
way, i e the flocculating and sequestering agent will not
facilitate the removal of impurities, even when
purification process comprises a centrifugation step.
Examples 11 and 12
Experimental procedures
Each one of the experiment of examples 11 and 12
was based on a batch of organic solution of fatty acid
methyl esters produced, purified and analyzed as
mentioned above in examples 1 to 6, with the exceptions
of a slightly different amount of added catalyst and th&t
batch size was around 3000 kg in example 11 and around
16000 kg in example 12. In example ll, the catalyst was
potassium methylate in an amount of around 0.78%

by weight of organic solution. In example 12, the
catalyst was sodium methylate in an amount of around
0.51% by weight of organic solution.
Results: Examples 11 and 12

From the data shown in table 3, it is evident that
by treating the organic solution of fatty acid methyl
esters with polyaluminium hydroxychloride followed by
centrifugation the metal levels were to high extent
reduced, even in case of sunflower oil as the origin of
organic solution.

CLAIMS
1. Use of a flocculating and sequestering agent as
an agent facilitating the purification of an organic
solution comprising fatty acid alkyl esters.
2. The use according to claim 1, wherein the
flocculating and sequestering agent is selected from the
group consisting of polyaluminium coagulants.
3. The use according to claim 2, wherein the
flocculating and sequestering agent is polyaluminium
hydroxychloride.
4. The use according to any one of the preceding
claims, wherein the organic solution is essentially
anhydrous.
5. The use according to claim 4, wherein the water
content of the organic solution is less than 10 % by
weight, preferably equal or less than 9.5, 9.0, 8.5, 8.0,
7.5, 7.0, 6.5, 6.0, 5.5, 5,0, 4.5, 4.0, 3.5, 3.0, 2.5,
2.0, 1.5, 1.0, 0.5, 0.43 or 0.10 % (w/w), and more
preferred around 100 to 1000 ppm (w/w), and even more
preferred around 500 ppm (w/w).
6. A process for purification of an organic solution
of fatty acid alkyl esters suitable for use as biodiesel,
comprising:
- adding a flocculating and sequestering agent to
the organic solution so as to facilitate the
purification, and
- removing a portion from the organic solution,
which portion comprises the flocculating and
sequestering agent, and impurities.

7. The process according to claim 6, wherein the
removing of the portion from the organic solution
comprises a step of centrifugation of the organic
solution so as to remove the flocculating and
sequestering agent together with impurities, which are
solid, polar and/or have different densities than the
fatty acid alkyl esters.
8. The process according to claim 7, wherein the
centrifugation is performed under low pressure in order
to remove water from the organic solution
9- The process according to any one of claims 6 to
8, wherein essentially no water is added to the organic
solution during the process.
10. The process according to claim 9, wherein the
water content of the organic solution of fatty acid alkyl
esters throughout the process is less than 10 % by
weight, preferably equal or less than 9.5, 9.0, 8.5, 8.0,
7.5, 7.0, 6.5, 6.0, 5.5, 5,0, 4.5, 4.0, 3.5, 3.0, 2.5,
2.0, 1.5, 1.0, 0.5, 0.43 or 0.10 % (w/w), and more
preferred around 100 to 1000 ppm (w/w), and even more
preferred around 500 ppm (w/w).
11. The process according to any one of claims 6 to
10, wherein the impurities comprises glycerol, soap, free
fatty acid and/or metal impurities.
12. The process according to claim 11, wherein the
metal impurities originates from metals comprising
calcium, magnesium, potassium and/or sodium.
13. The process according to any one of claims 6 to
12, wherein the flocculating and sequestering agent is
selected from the group consisting of polyaluminium
coagulants.

14. The process according to claim 13, wherein the
flocculating and sequestering agent: is polyaluminium
hydroxychloride.

A use of a flocculating and sequestering agent as an agent facilitating the purification of an organic solution comprising
fatty acid alkyl esters. Also provided is a process for purification of the organic solution, which process comprises adding
a flocculating and sequestering agent to the organic solution so as to facilitate the purification, and removing a portion from the
organic solution, which portion comprises the flocculating and sequestering agent, and impurities.

Documents:

02869-kolnp-2008-abstract.pdf

02869-kolnp-2008-claims.pdf

02869-kolnp-2008-correspondence others.pdf

02869-kolnp-2008-description complete.pdf

02869-kolnp-2008-form 1.pdf

02869-kolnp-2008-form 3.pdf

02869-kolnp-2008-form 5.pdf

02869-kolnp-2008-international exm report.pdf

02869-kolnp-2008-international publication.pdf

02869-kolnp-2008-international search report.pdf

02869-kolnp-2008-others pct form.pdf

02869-kolnp-2008-pct priority document notification.pdf

02869-kolnp-2008-pct request form.pdf

2869-KOLNP-2008-(09-06-2014)-AMANDED PAGES OF SPECIFICATION.pdf

2869-KOLNP-2008-(09-06-2014)-ANNEXURE TO FORM 3.pdf

2869-KOLNP-2008-(09-06-2014)-CLAIMS.pdf

2869-KOLNP-2008-(09-06-2014)-CORRESPONDENCE.pdf

2869-KOLNP-2008-(10-12-2013)-ABSTRACT.pdf

2869-KOLNP-2008-(10-12-2013)-AMENDED CLAIMS.pdf

2869-KOLNP-2008-(10-12-2013)-ANNEXURE TO FORM 3.pdf

2869-KOLNP-2008-(10-12-2013)-CORRESPONDENCE.pdf

2869-KOLNP-2008-(10-12-2013)-GPA.pdf

2869-KOLNP-2008-(10-12-2013)-OTHERS.pdf

2869-KOLNP-2008-(10-12-2013)-PETITION UNDER RULE 137.pdf

2869-KOLNP-2008-(25-07-2012)-ASSIGNMENT.pdf

2869-KOLNP-2008-(25-07-2012)-CORRESPONDENCE.pdf

2869-KOLNP-2008-(25-07-2012)-FORM-1.pdf

2869-KOLNP-2008-(25-07-2012)-FORM-2.pdf

2869-KOLNP-2008-(25-07-2012)-FORM-3.pdf

2869-KOLNP-2008-(25-07-2012)-FORM-5.pdf

2869-KOLNP-2008-(25-07-2012)-FORM-6.pdf

2869-KOLNP-2008-(25-07-2012)-PA-CERTIFIED COPIES.pdf

2869-KOLNP-2008-ASSIGNMENT.pdf

2869-KOLNP-2008-CORRESPONDENCE 1.2.pdf

2869-KOLNP-2008-CORRESPONDENCE-1.1.pdf

2869-KOLNP-2008-FORM 1.1.1.pdf

2869-KOLNP-2008-FORM 13.pdf

2869-KOLNP-2008-FORM 18.pdf

2869-KOLNP-2008-FORM 3-1.1.pdf

2869-KOLNP-2008-FORM 3.1.1.pdf

2869-KOLNP-2008-GPA.pdf

2869-KOLNP-2008-PCT PRIORITY DOCUMENT NOTIFICATION 1.1.pdf

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Patent Number

265556

Indian Patent Application Number

2869/KOLNP/2008

PG Journal Number

10/2015

Publication Date

06-Mar-2015

Grant Date

27-Feb-2015

Date of Filing

15-Jul-2008

Name of Patentee

ALFA LAVAL CORPORATE AB

Applicant Address

PO BOX 73 SE-221 00 LUND, SWEDEN

Inventors:

#	Inventor's Name	Inventor's Address
1	FRYKERAS, DAVID	STRANDHUGGSVAGEN 18,, S-605 97 NORRKOPING
2	WARNQVIST, JAN	HOGASVAGEN 1,, S-665 93 KIL

PCT International Classification Number

C07C 67/58C11C 3/10

PCT International Application Number

PCT/SE2007/000016

PCT International Filing date

2007-01-11

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0600050-9	2006-01-12	Sweden