Title of Invention	PROCESS FOR PRODUCTION OF HIGHLY ENRICHED FRACTIONS OF NATURAL COMPOUNDS FROM PALM OIL WITH SUPERCRITICAL AND NEAR CRITICAL FLUIDS
Abstract	From palm oil valuable compounds like the tocochromanols, carotenoids, phytosterols, and others can be derived. Enrichment to highly concentrated fractions is hindered by the enormous number of components involved, the very low volatility, the very low solubility of many of the compounds in organic solvents, and the high viscosity of the mixtures to be processed. Starting materials for the new process are enriched fractions of tocochromanols (about 20 to about 50 wt.-%) and/or carotenoids (about 10 to 30 wt.-%) from palm oil obtained by conventional processes, or by counter current multistage processes with supercritical carbon dioxide. These processes, not addressed here, may comprise: Removal of free fatty acids, transesterification of the triglycerides to methyl or ethyl esters, removal of the esters, e.g. by short path distillation, separation of the tocochromanol fraction from the carotenoid fraction by cooling. In the new process, fractions derived from crude palm oil, already enriched to some extent in tocochromanols, carotenoids, phytosterols, and others, are being treated by supercritical fluid technology in a unique combination of counter current separation with selective adsorption and desorption using supercritical fluids. A first enrichment, comprising one or more separation steps by application of a near critical or a supercritical fluid in a single or multistage (counter current) separation process is combined appropriately with a second enrichment step wherein the product of the first enrichment step is directly adsorbed on an adsorbent (silicagel) by passing the product flow over a fixed bed of adsorbent without substantial pressure change, and subsequent desorption with the same (or an other) near critical or supercritical fluid at the same or a different pressure as in the first separation, or by a pre-designed sequence of pressures and temperatures. For the tocochromanol enrichment, carbon dioxide at near critical conditions above the critical temperature of carbon dioxide is used. For the carotenoid enrichment, propane at near critical conditions below the critical temperature of propane is used.

Title of Invention

PROCESS FOR PRODUCTION OF HIGHLY ENRICHED FRACTIONS OF NATURAL COMPOUNDS FROM PALM OIL WITH SUPERCRITICAL AND NEAR CRITICAL FLUIDS

Abstract

From palm oil valuable compounds like the tocochromanols, carotenoids, phytosterols, and others can be derived. Enrichment to highly concentrated fractions is hindered by the enormous number of components involved, the very low volatility, the very low solubility of many of the compounds in organic solvents, and the high viscosity of the mixtures to be processed. Starting materials for the new process are enriched fractions of tocochromanols (about 20 to about 50 wt.-%) and/or carotenoids (about 10 to 30 wt.-%) from palm oil obtained by conventional processes, or by counter current multistage processes with supercritical carbon dioxide. These processes, not addressed here, may comprise: Removal of free fatty acids, transesterification of the triglycerides to methyl or ethyl esters, removal of the esters, e.g. by short path distillation, separation of the tocochromanol fraction from the carotenoid fraction by cooling. In the new process, fractions derived from crude palm oil, already enriched to some extent in tocochromanols, carotenoids, phytosterols, and others, are being treated by supercritical fluid technology in a unique combination of counter current separation with selective adsorption and desorption using supercritical fluids. A first enrichment, comprising one or more separation steps by application of a near critical or a supercritical fluid in a single or multistage (counter current) separation process is combined appropriately with a second enrichment step wherein the product of the first enrichment step is directly adsorbed on an adsorbent (silicagel) by passing the product flow over a fixed bed of adsorbent without substantial pressure change, and subsequent desorption with the same (or an other) near critical or supercritical fluid at the same or a different pressure as in the first separation, or by a pre-designed sequence of pressures and temperatures. For the tocochromanol enrichment, carbon dioxide at near critical conditions above the critical temperature of carbon dioxide is used. For the carotenoid enrichment, propane at near critical conditions below the critical temperature of propane is used.

Full Text	Process for production of highly enriched fractions of natural compounds from Palm Oil with supercritical and near critical fluids Background of the invention From palm oil valuable compounds like the tocochromanols, ca- rotenoids, phytosterols, and others can be derived. Enrichment to highly concentrated fractions is hindered by the enormous number of components involved, the very low volatility, the very low solubility of many of the compounds in organic sol- vents, and the high viscosity of the mixtures to be processed. As an example for the production of pre-concentrated frac- tions, the Carotech-process may be taken (Fig. 1). Caromin™, is a carotenoid enriched derivate of crude palm oil, contain- ing approximately 10% of carotenoids. The integrated process for extracting carotenoids and tocotrienols (vitamin E) is carried out according to U.S. Patent 5,157,142 and is summa- rized in Fig. 1. It involves the transesterification of crude palm oil (CPO) to methyl esters (FAME), followed by vacuum distillation and other steps, resulting in a carotene-rich layer and a tocotrienol-rich layer. The carotene-rich layer, as well as the tocotrienol-rich layer are further concentrated to produce highly concentrated products of a maximum content of 30 % for carotenoids, and a maximum content of about 50 % for tocochromanols, mostly tocotrienols. Further enrichmebnt with conventional methods proved to be not possible because of the high viscosity, very low volatility, and low solubility in conventional organics solvents. Although a number of investi- gations have been carried out on various mixtures, mostly to- copherols, with supercritical fluids, no process was able to produce fractions of high concentrations for both the to- cochromanols and the carotenoids from crude palm oil or other natural sources. Fig. 1. Process for production of concentrated fractions of mixed carotenoid and tocotrienols (U.S. Patent 5,157,142). Carotenes, which impart the distinctive orange-red colour to palm oil, together with tocopherols contribute to the stabil- ity and nutritional value of the oil. To a great extent these and other minor constituents determine the quality character- istics of palm oil Carotenoids are often recovered from natu- ral fat or oil, particularly from palm oil. Carotenoids can be extracted from unsaponified distillation residue. They can be also extracted employing adsorbent in some stage of the proc- ess. During the extraction, large amounts of organic solvents are needed. Adsorptive processes so far have not led to higher concentrated carotene fractions from natural sources. Reasons are the initial low concentrations, the high viscosity of carotene fractions, and the instability of carotenes on most adsorbents. Numerous attempts to design a process for produc- ing higher concentrated fractions of carotenes have been made. Carotenoids are the most widespread and important pigments in living organisms. The most widely known carotenes are the -, - and -carotenes, and lycopene. Beside their colour, carote- noids, especially -carotene, are well known to possess pro- vitamin A activity as they can be transformed into vitamin A in vitro. They have also been found to inhibit anti-cancer properties due to their ability to deactivate oxy-radicals. As the carotenes are natural compounds with vitamin A property, they played a positive role in commercial applications for pharmaceutical and nutritional products synthesis. [1, 2]. Carotenoids are found in numerous vegetable oils, including groundnut oil, rapeseed oil, sunflower-seed oil and cottonseed oil. The concentration of carotenoids in these oils is gener- ally low, less than 100ppm. Among these, palm oil is the rich- est natural plant source of carotene in terms of retinol equivalent, with Malaysia contributing the highest percentage of world palm oil production. Palm oil contains the highest known concentration of carotenoids, ranging from 500 to 3000ppm, depending on the species of the palm fruit from which the oil is obtained. [1, 2] The concentration of carotenes in crude palm oil from Malaysia varies between 500 to 700ppm, with - and -carotene form up to 90% of the total carotenes. [3]. Nowadays, carotenes found on the market are chemically syn- thetic -carotene or carotene extracted from algae Dunaliella. Since carotenoids are most probably to grow in importance and value, the recovery of carotenoids from palm oil and its by- products becomes important. Various extracting methods for re- covering carotenes from palm oil have been developed over the years including saponification, urea processing, selective solvent extraction, molecular distillation, separation by ad- sorption, crystallization, and transesterification followed by distillation of esters. [1,4,5]. Tocochromanols: Vitamins are important substances for the hu- man health. They are regulating various processes in the body and have positive effects on many vital functions. In general terms vitamins act as coenzymes or pro-hormones while most of their other functions like anti-carcinogen or anti-oxidizing effects are yet to be researched. Most of the vitamins cannot be synthesized by the human body and therefore these nutrients have to be ingested with the food. Since vitamins vary in their structure and their functions, a first approach is to categorize them into water soluble and oil soluble groups. Wa- ter soluble vitamins are distributed within the whole body and there-fore they are taking effect in almost all organs, while oil soluble vitamins are mostly present in the membranes. The transport in the blood stream and the digestion of these vita- mins can only be done if a sufficient amount of oil lipids and micelles are present. Vitamin E is the generic term for eight substances from the group of the tocochromanols that possess a Vitamin E activity. The tocochromanols can be subdivided into two groups: the to- cochromanols and the tocotrienols: with the tocotrienols pos- sessing three unsaturated double bonds in their hydrocarbon chain and the tocopherols possessing a completely unsaturated hy-drocarbon chain. Both tocopherol and -trienol subgroups consist of: four homologous, designated as -, -, -, and - tocopherol (-trienol), depending on the substitutes of their chroman-ring. The tocochromanols are oil soluble anti-oxidants which are mostly found in the cell membrane of organs, - tocopherol has the highest anti-oxidant activity and therefore it is mostly used as anti-oxidant in the food and cosmetic in- dustry. Nevertheless recent studys report further functions of the other tocochromanol homologous like anti-carcinogen or anti-tumor properties. As a consequence the demand on natural tocochromanol mixtures consisting of all homologous is steadily increasing. The fruits of the malaysian oil palm possess the highest content of tocochromanols in the world. Crude palm oil (CPO) consist of 94 wt.% tryglycerides, 3-4 wt.% free fatty acids (FFA), and only 1 wt.% of the CPO consist of tocochromanols, carotinoids and phytonutrients. Palm oil is available in large quantities and at a comparatively low price. It is the largest source for tocotrienols. Tocotrienols can be recovered from the distil- late fractions obtained during the refining and deodorisation of the crude palm oil. The carotenoids are destroyed during this process. It is therefore reasonable to try to recover both groups of valuble compounds in one process sequence. The most economic way would be to adsorb these compounds from the crude palm oil on an appropriate adsorbent and remove the com- pounds subsequently from the adsorbent. Numerous attempts have been made. So far no success was obtained. Therefore, the need for another approach led to the transesterification of the triglycerides of palm oil to fatty acid methyl esters and their removal by vacuum distillation. The further process of generating higher concentrated fractions is limited by the mentioned properties of the mixtures. The needs for a differ- ent process are obvious. Here, supercritical fluid extraction (SFE) is an alternative to conventional extraction with organic solvents. SFE is able to yield in a solvent free extract and due to its low critical temperature can be used for the treatment of temperature sen- sitive substances like vitamins. Supercritical fluids can dis- solve the low volatile components and carry them through any process via the gaseous phase. Furthermore, highly viscous liquid solutions dissolve a great amount of supercritical flu- ids, in particular carbon dioxide and propane, with the effect of a much reduced viscosity. Then, even the liquid solutions can be handled in a process. Although these facts have each for itself been known for some time, the surprising effects for a further enrichment of the tocochromanols and the carotenoids by applying appropriate combinations of counter current SFE separation and SFE- adsorptions with subsequent selective SFE-desorption have not been recognized. The state of the art achieved so far is re- viewed in the following. State of the art Tocochromanols: The research done on extraction of natural materials with su- percritical carbon dioxide is increasing these days. The critical parameters of carbon dioxide is 7,4MPa and 304,21K [6]. Because of these low critical parameters, using super- critical carbon dioxide is resulting in low operation cost and because of the low critical temperature even temperature sen- sitive materials can be extracted. In contrary to organic sol- vent, carbon dioxide is non toxical, non inflammable, and in- ert. Moreover, carbon dioxide is easy available and can be re- moved completely from the desired product without residues. The solubility of carbon dioxide can be adjusted by the den- sity, therefore it can be adjusted to the feed material. These are the reasons for the enormous amount of research work in the field of supercritical carbon dioxide extraction. Ill'es et al. [7] and Gnayfeed et al. [8] for example were research- ing the extraction of red pepper and pepper oil with super- critical C02 and subcritical propane in respect to the toco- pherol and carotine content. It was found that the solubility of the supercritical carbon dioxide was not sufficient to dis- solve carotine. The solubility of the tocopherols in both sol- vents was good, and it was possible to dissolve tocopherols in both C02 and propane. Nagesha et al. [9] and Shishikura et al. [10] have researched the enrichment of tocopherols from soy deodorizer distillate by supercritical uid extraction. Further research work has been done on the enrichment of squalene from an intermediate of the olive oil production (Dreschner et al.[ll]) and the enrichment of tocopherolacetate and toco- pherol (Fleck [12]) . The adjustment of the solubility of the supercritical carbon dioxide through the density gives the supercritical extraction a high flexibility. But because of the lacking polarity of the carbon dioxide the solubility for polar substances is limited. One possibility to increase the solubility is to add a modi- fier to the supercritical carbon dioxide. Common modifiers are iso-propanol, ethanol and propane. It should not be neglected that an increase of solubility with modifiers is often paired with a decrease in selectivity. Thus recent studies focus on an additional adsorption process prior the supercritical ex- traction. Due to the additional adsorption, the selectivity of the process can be increased, since the adsorbent has a dif- ferent affinity to the different components. The result is that the components are adsorbed and desorbed to a different extent. Wang et al. [13] researched the separation of - tocopherol and squalene using a pressure swing adsorption technique with supercritical carbon dioxide as solvent. In the first stage of the process the feed is mixed with supercriti- cal CO2 and enters a column filled with silica gel at low pres- sure, where the feed adsorbs on the silica gel. In the second stage the adsorbt is desorbed off the silicagel with pure su- percritical carbon dioxide under high pressure. During these experiments Wang et al. was able to enrich -tocopherol from a 20 wt.% feed to 60 wt.% and squalene from 80 wt.% to 98 wt.%. Theoretical work on adsorption and desorption in supercritical carbon dioxide has been done by Reverchon et al. [14] and Goto et al. [15]. The research group of Reverchon used a Langmuir similar multi component adsorption isotherm in order to de- scribe the adsorption behaviour of a complex terpene mixture under supercritical conditions, wheras the research group of Goto used the BET adsorption isotherm to do their simulation. Both works lead to mathematical models which are capable to simulate experimental data with a high accuracy. Lee et al.. [16] published a work on the adsorption kinetics of phospholipids from treated soy oil on regenerated clay. The research group of Lee used a reaction kinetic equation in or- der to describe the adsorption process by measuring the con- centration before and after the adsorber. This was a totally different approach then the authors before, since no adsorp- tion isotherm is used at all to describe the system. Neverthe- less the research group of Lee was able to derive a reaction equation which is capable to predict the experimental data. The regeneration of modified clay with supercritical carbon dioxide was researched by Cavalcante et al. [17] and Carneiro et al. [18]. Modified clay is an important adsorbent in the environmental technology, since its ability to adsorb organic substances is very important in the field of water treatment. Therefore the regeneration of the clay is an important eco- nomical issue for the economical efficiency of the process. Zetzl [19] dealt with the separation of avors from lemon oil by applying a selective adsorption on silicagel followed by a desorption under supercritical carbon dioxide. The desorption curve of limonen and citral was researched and a model was in- troduced which described the experimental data with a high ac- curacy. A patent for the separation technique of selective adsorption followed by a desorption with supercritical CO2 was filed for separating terpenes out of essential oils. The European patent EP 0363971 A2 [20] describes such a process. The oil is mixed by stirring at a constant temperature with the adsorbent and then it is; extracted with supercritical CO2. This is possible because of the low viscosity of the treated oil. Carotenoicls: The Japanese patent JP200226723 [21] presents a method for the enrichment of carotene from palm oil. Palm oil is first trans- esterified. The ester is then extracted with a hydrophilic solvent such as methanol to separated it into a concentrated ester phase. This concentrate is then applied to a column packed with silica gel to adsorb carotene. Carotene is then desorbed using hexane which contains around 4000 ppm aceton. Adsorptive concentration of the carotene-rich concentrate was also employed in U.S. Pat. No. 6072092 [22], where silica gel is used ass adsorbent and a large amount of non-polar solvent is used to recover carotene. European patent EP0242148 [23] describes a similar method us- ing silica gel or activated alumina as adsorbent and a non po- lar solvent containing certain amounts of polar solvents as eluant for the enrichment of carotene. Japanese patent JP63132871 [24] describes a process to enrich carotene applying Zeolite as adsorbent and a non polar sol- vent, such as carbon tetrachloride as eluant. U.S. Pat. No. 5157132 [25] describes a process recovering carotene from oil through transesterification and saponifica- tion. The enriched carotene can be extracted from the saponi- fied residue with an organic solvent. The obtained residue has a carotene content of 20%. Also European patent EP1398311 [26] describes a similar process. 10% to 20% of carotene con- centrate can be obtained. German patent DE 4429506 [27] presents the extraction of caro- tenoids from dried material with propane or butane. It was found that the solubility of both gases can be greatly im- proved when a co-solvent is used. These patents require organic solvents in a large amount as eluant and recovery of the solvents by distillation to obtain the carotenoids concentrate. In the new process only propane and supercritical CO2 are used as solvents at low temperatures to obtain the concentrate. These solvents can be easily re- moved by expansion. Most techniques described in literature that use supercritical carbon dioxide or other compressed gases for the enrichment of both phytosterols and tocochromanols from edible oil start from very low concentrations of the here-treated components. Hence, the main focus of these works lies on depleting the oil from substances like triglycerides or FAME, because these are the by far most prominent substances when dealing with crude or esterified oil, respectively. Additionally, most described processes are batch-wise operated. Thus, the here-described approach, starting from an already enriched palm oil deriva- tives and employing a combination of a continuously operated extraction column with an adsorption/desorption operation on the one side and a subsequent extraction has not yet been ap- plied. Description of the Invention: General description The vitamin compounds of the group of the tocochromanols and carotenoids are enriched from mixtures derived from natural oils in the process described below. These mixtures contain fatty acid methyl esters or fatty acid ethyl esters, squalene, monoglycerides, diglycerides, sterols, and the target com- pounds. With supercritical carbon dioxide as solvent, in a first sepa- ration sequence (Fig. 2, columns Cl and C2), from the to- cochromanols or the carotenoids are removed the compounds more soluble in supercritical carbon dioxide than the target com- pounds at the top of a counter currently operated separation column, and the less solube soluble compounds at the bottom. This process leads to concentrations for the tocochromanols of about 70 wt.-%, and for the carotenoids of about 30wt.-%. The details of this separation are given below. In a second sequence, directly following the countercurrent process, the mixtures are processed by selective adsorption and desorption steps (Fig. 2, adsorbers A1, A2, A3). Adsorp- tion takes place from the mass flow taken from the countercur- rent separation comprising a supercritical or near-critical fluid and the target compounds, and is directly deposited on the adsorbent. In this way, the handling of the highly viscous solution or solid solution is made possible. Subsequently, de- sorption is carried out from the fixed bed loaded with the feed mixture. Desorption may be carried out with the same su- percritical or near critical fluid, or a different one, or in a sequence of two or more of such solvents. Desorption is also carried out at different conditions compared to the adsorp- tion, i.e. different values of pressure, temperature, flow rate of gas. Supercritical or near critical solvents may com- prise mixtures of supercritical or near critical fluids, pref- erably of carbon dioxide and propane. It was found that the separation by adsorption and desorption can be improved by not filling the whole adsorbent with the feed mixture, but only part of it. During desorption a se- quence of adsorption and desorption steps take place, which increase the separation efficiency, and thus the concentra- tions of the separated fractions. The ratio of the first ad- sorbed section to the free section of the fixed bed of adsorb- ent is variable, usually from (3.5 to 0.1. Fig. 2. Flow sheet of the process for concentrating tocochro- manols and carotenoids by SFE technology. Tocochromanols The new process for the production of highly enriched to- cochromanol-fractions, containing mostly tocotrienols from palm oil derived mixtures combines a continuous countercurrent multistage; separation using a supercritical fluid, preferably carbon dioxide, to remove the lighter volatile (i.e. the com- pounds more soluble in supercritical compound, resp. carbon dioxide) over the top of the column. The bottoms of the column are an enriched fraction in tocotrienols with a relatively high content in sterols and other somewhat polar compounds. This bottom fraction is passed over a suitable adsorbent. Silicagel was found to be an applicable adsorbent. The ad- sorbed mixture is desorbed by a supercritical fluid, prefera- bly carbon dioxide in two desorption steps. The first is car- ried out at a pressure of about 140 bar and removes more vola- tile or more in supercritical carbon dioxide soluble com- pounds. In the second desorption step, carried out at about 250 bar, highly enriched tocochromanol fractions, containing mostly tocotrienols, are extracted. The extracted fractions can be split further by collecting them in different vessels. Depending on the cut of the fractions, the concentration of tocotrienols is in the range of 85 to nearly 100% with a yield of about 50% of the feed mixture. The adsorbent is regenerated with liquid solvents like ethanol etc. and reused for the ad- sorption step. The process starts with a pre-enriched fraction, which may be obtained by several methods, one may comprise transesterifica- tion of the glycerides with methanol and removing the obtained fatty acid esters by short-path-distillation or by extraction with supercritical fluids, like carbon dioxide. For example, the starting material for the first extraction step was a palm oil derivatives that among other substances contained 56 wt.-% tocochromanols (with -tocotrienol, -tocotrienol, and - tocopherol being the major components), 16 wt.-% squalene, 5 wt-% phytosterols (with -sitosterol and campesterol being the most prominent species), and 11 wt.-% mono- and diglycerides. This material was fed into a continuously operated extraction column, employing supercritical carbon dioxide as solvent. The column was packed with a structured Sulzer EX packing and has an inner diameter of 17.5 mm and a total height of 7 m, of which 6 m are packed. Employing pressures of 20-30 MPa and temperatures of 323 to 358 K, it was possible to produce a sterol- and tocochromanol-free top product, only extracting specifically FAME, squalene, and monoglycerides, hence obtain- ing a bottom product enriched to about 70% tocochromanols with phytosterols and other most probably more polar compounds com- prising the rest. A longer column would have completely depleted the bottom phase from the higher-volatile components. With chemical engi- neering methods the necessary height for complete separation of FAME, squalene, and monoglycerides from tocochromanols, sterols, and other low-volatile components was calculated. The results are that a complete separation of these components is possible with 13 theoretical separation stages, corresponding to a height of the column of about 15 m, a solvent-to-feed ra- tio of 80 to 140, with a reflux ratio of 6 to 12, at a tem- perature of 323 K, and a pressure of 20-25 MPa. Theoretically, the further enrichment of tocotrienols should be possible by employing another countercurrent separation us- ing a supercritical fluid. Experimental investigations re- vealed that the solubility of the tocotrienol-enriched bottom product in supercritical carbon dioxide is too low to be con- sidered as a solvent for a separation process. Therefore, modifiers were mixed with the basic supercritical fluid, car- bon dioxide, in order to increase the solubility. The follow- ing solvent compositions were investigated: CO2 + propane with a propane content of 29, 55, and 83%, as well as CO2 + liquid organic solvent, namely ethanol, iso-propanol, 1-butanol, and ethyl acetate, each in a concentration of 5 and 10 wt.-%, re- spectively. The measurements were conducted in a pressure range of 5-30 MPa and at temperatures of 323, 343, and 358 K, respectively, in case of experiments with propane and at a fixed pressure of 20 MPa and at temperatures of 323 and 343 K in case of the liquid modifiers. At all conditions investi- gated the concentration of the low volatile compounds was en- riched in the gaseous phase, but the selectivity with respect to tocotrienols was reduced to such an extent that sterols were dissolved in the gas-phase, hence making it impossible to enrich the tocotrienol concentration further. Surprisingly it was found that the separation factors remained high, even increased, if the bottom material was mixed with special silica gels and then desorbed or extracted from this adsorbent with supercritical carbon dioxide. The bottom prod- uct from the first enriching step was mixed with certain amounts of adsorbent (silica gel) in a ration of 4 to 10. The mixture was introduced into a column as fixed bed. Then, ap- plying a supercritical fluid (carbon dioxide) at a pressure of about 14 at a temperature of about 333 K, remaining high vola- tile components such as fatty acid esters and squalene were desorbed. In a second desorption (extraction)-step, at about the same temperature, but a higher pressure of about 25 MPa tocotrienols were desorbed with high concentration. With a ra- tio of adsorbent to feed of 10, a solvent ratio of supercriti- cal carbon dioxide of about 300 [kgCO2/kg Feed and hour], a fraction of 27% of the feed was obtained during 1 h with a concentration of 75% tocotrienols, after that fraction, an- other fraction of 25% of the feed with a 100% concentration of tocotrienols could be recovered in another hour. Experiments with a mixture of carbon dioxide and propane showed that the solubility could be enhanced while the selectivity was main- tained. Therefore, the solvent ratio can be lower than with pure CO2. Description of the invention:Carotenoids. A carotenoid concentrate (1 to 10 wt.-%) is fed into a con- tinuously operated extraction device, constructed as a five- stage high pressure mixer-settler. In three separation se- quences with this apparatus, employing pressures of 20-30 MPa and temperatures of 323 to 358 K, it was possible to produce a product, containing up to 30 wt.-% of carotenoids. This prod- uct is passed over the adsorbent, a special silica gel, pref- erably Zeofree 5170, whereby the mixture of carotenoids, ster- ols and other substances, and the fatty acid esters are ad- sorbed. The mixing ratio is in the range of 4 to 10. Subse- quently, the loaded adsorbent is brought into contact first with suspercritical carbon dioxide, and then with near criti- cal propane at conditions of the state, e.g. 5 MPa and 323 K, preferably in the range of 2 to 7 MPa and 313 to 343 K. With carbon dioxide, mainly non-carotenoids are desorbed and eluted, and with near critical propane, the carotenoids are desorbed. The solvent ratio of propane to feed is in the range of 20 to 100 preferably about 30. Concentration of the eluted carotenoids were enhanced, if during the adsorption step only a fraction of the adsorbent was loaded with the feed. Examples: Tocochromanols. Example 1: First Extraction Step. A continuous operated multi-stage supercritical extraction was conducted with pure carbon dioxide as solvent and a feed mix- ture containing 50 wt.-% tocochromanols (with -tocotrienol, - tocotrienol, and a-tocopherol being the major components), 16 wt.-% squalene, 3 wt-% phytosterols (with -sitosterol and campesterol being the most prominent species), and 11 wt.-% mono- and diglycerides. The employed column had an effective height of 6 m and was packed with a structured Sulzer EX pack- ing. Operating conditions were as follows: 20 MPa, 323 K, sol- vent-to-feed ratio = 19.8, reflux ratio = 7.3. These condi- tions resulted in a top phase product consisting of 2 wt.-% FAME, 58 wt.-% squalene and it was completely depleted from tocochromanols and phytosterols. The bottom product consisted of 8 wt.-% squalene, 58 wt.-% tocochromanols, 4 wt.-% phytos- terols, and it was completely FAME-free. Example 2: First Extraction Step. A continuous operated multi-stage supercritical extraction was conducted with pure carbon dioxide as solvent and a feed mix- ture containing 50 wt.-% tocochromanols (with -tocotrienol, - tocotrienol, and -tocopherol being the major components), 16 wt.-% squalene, 3 wt-% phytosterols (with -sitosterol and campesterol being the most prominent species), and 11 wt.-% mono- and diglycerides. The employed column had an effective height of 6 m and was packed with a structured Sulzer EX pack- ing. Operating conditions were as follows: 20 MPa, 343 K, sol- vent-to-feed ratio = 4 0.3, reflux ratio = 1.3. These condi- tions resulted in a top phase product consisting of 2 wt.-% FAME, 60 wt:.-% squalene, 2 wt.-% tocochromanols, and 1 wt.-% sterols. The bottom product consisted of 7 wt.-% squalene, 54 wt.-% tocochromanols, 4 wt.-% phytosterols, and it was com- pletely FAME-free. Example 3: Production of Concentrated Fractions of Tocotrie- nols -1 1 g of the bottom product obtained from example 1 was used as feed material and mixed with 10 g of silica gel, Zeofree 5170. The mixture is introduced into an empty vessel and supercriti- cal CO2 was used to desorb FAME and squalene at 13 MPa and 333 K for 120 minutes. The pressure was increased to 25MPa and af- ter 60 minutes, a fraction (0.27g), which contains 80 wt.~% of tocochormanols, was collected. The pressure was held constant for another 60 minutes, another fraction (0.24g) was col- lected. This fraction contains approximately 100% tocochro- manols. Example 4: Production of Concentrated Fractions of Tocotrie- nols -2. 2.4 g of the bottom product obtained from example 1 was used as feed material and mixed with 10 g of silica gel, Zeofree 5170. The mixture is introduced into an empty vessel and su- percritical CO2 was used to desorb FAME and squalene at 13 MPa and 333 K for 60 minutes. The pressure was increased to 19MPa and after another 120 minutes, a fraction(1.59g) was col- lected. It contains 80 wt.-% of tocochromanols. Example 5: Carotenoids. The carotenoids concentrate containing approximately 10 wt% of carotenoids was passed over the adsorbent in an high pressure pipe with an internal volume of 50 ml. Silica gel with a mini- mum surface area of 165m2/g was used as the adsorbent with a ratio of 4:1 (12g:3g) to the amount of feed. Extraction was then carried out first with supercritical carbon dioxide at 150 bar and 60 °C, and then with supercritical carbon dioxide at 250 bar and 60 °C. In third step, near critical propane was used at 7 MPa, 60 oC. The fractions are collected. The last fraction consisted of about 60 % carotenoids. References: 1. Y.M. Choo: Palm Oil Carotenoids. The United Nations Univer- sity Press,, Food and Nutrition Bulletin, 15 (1994). 2. C. Lenfant, F.C. Thyrion: Extraction of Carotenoids From Palm Oil, I. Physical and Chemical Properties of -Carotene, Voir OCL 3,3 (1996) 220-226. 3. S.H. Goh, Y.M. Choo, S.H. Ong: Minor Constituents of Palm Oil, J. Am. Oil Chem. Soc. 62 (1985) 237-240. 4. B.S. Baharin, L.L. You, Y.B.. Che Man, and S. Takagi: Effect of Degumming Process on Chromatographic Separation of Caro- tenes from Crude and Degummed Palm Oil, Journal of Food Lipids 8 (2001) 27-35. 5. C. Lenfant, F.C. Thyrion, Extraction of Carotenoids From Palm Oil, II. Isolation Methods, Voir OCL 3,4 (1996) 294-307. 6. VDI : VDI W armeatlas. VDI Verlag GmbH (1988) . 7. V.Ill'es,H.G.Daood,P.A.Biacs, M.H.Gnayfeed, B.M'esz' aros: Supercritical CO2 and Subcritical Propane Extraction of Spice Red Pepper Oil with Special Regard to Carotenoid and Toco- pherol Content. Journal of Chromatographic Science, Vol.37 (1999). 8. M.H.Gnayfeed, H.G.Daood, V.Ill'es, P.A.Biacs: Supercritical CO2 and Subcritical Propane Extraction of Pungent Paprika and Quantification of Carotenoids, Tocopherols and Capsaicinoids. J. Agric. Food Chem. 49, 2761-2766 (2001). 9. G.K.Nagesha, B.Manohar, K.Udaya Sankar: Enrichment of toco- pherols in modified soy de-odorizer distillate using super- critical carbon dioxide extraction. Eur. Food Res. Technol. 217:427- 433 (2003). 10. A.Shishikura, K.Fujimoto, T.Kaneda, K.Arai, S.Saito: Con- centration of Tocopherols from Soybean Sludge by Supercritical Fluid Extraction. J. Jpn. Oil Chera. Soc. 37, No.l (1988). 11. M.Dreschner, M.Bonakdar: Anreicherung des Kohlenwass- erstoffes Squalen in einem Zwischenprodukt der Olivenölher- stellung durch Extraktion mit verdichtetem Kohlendioxid. Che- mie Ingenieur Technik 73, S.338-342 (2001). 12. U. Fleck: Reinigung schwer flüchtiger Substanzen mittels Extraktion mit überkritischen Gasen. Dissertation, Technische Universität Hamburg-Harburg (2000). 13. H.Wang, M.Goto, M.Sasaki, T.Hirose: Separation of - Tocopherol and Squalene by Pressure Swing Adsorption in Super- critical Carbon Dioxide. Ind. Eng. Chem. Res. 43, 2753-2758 (2004). 14. E.Reverchon, G.Lamberti, P.Subra: Modelling and simulation of the supercritical adsorption of complex terpene mixtures. Chemical Engineering Science 53, 3537-3544 (1998). 15. M.Goto, B.C.Roy, A.Kodama, T.Hirose: Modelling Supercriti- cal Fluid Extraction Process Involving Solute-Solid Interac- tion. Journal of Chemical Engineering of Japan 31, 171-177, (1998). 16. C.H.Lee, C.I.Lin: Kinetics of Adsorption of Phospholipids from Hydrated and Alkali-Refined Soy Oil Using Regenerated Clay. Journal of Chemical Engineering of Japan 37, 764-771 (2004) . 17. A.M. Cavalcante, L.G.Torres, G.L.V. Coelho: Adsorption of Ethyl Acetate onto Modified Clays and its Regeneration with Supercritical CO2. Brazilian Journal of Chemical Engineering, Vol.22, No.l, 75-82 (2005). 18. D.G.P. Carneiro, M.F. Mendes, G.L.V. Coelho: Desorption of Toluene from Modified Clays using Supercritical Carbon Diox- ide. Brazilian Journal of Chemical Engineering Vol.21, No.4, 641-646 (2004). 19. C. Zetzl: Desorption von Sauerstoffverbindungen des Zitru- sols durch überkritisches CO2. Diplomarbeit, Institut fur Ther- mische Verfahrenstechnik an der Universitat Karlsruhe, (1994) . 20. European patent EP 0363971 A2 21. Japanese patent JP200226723 22. U.S. Pat. No. 6072092, 23. European patent EP0242148 24. Japanese patent JP63132871 25. U.S. Pat. No. 5157132 26. European patent EP1398311 27. German patent DE 4429506 Claims 1. A process for the production of highly enriched fractions of natural compounds (tocotrienols, carotenoids, and ster- ols) from Palm oil or Palm oil derivatives, characterized by a first separation step comprising countercurrent multi- stage separation with supercritical and/or near critical fluids removing the higher volatile (better soluble in the supercritical or near critical fluid) over top, yielding a bottom fraction enriched in the natural compounds and an- other countercurrent multistage separation with supercriti- cal and/or near critical fluids removing the target natural compounds over top, thus cleaning it from low volatile im- purities, and a second step comprising selective adsorption and desorption by directly adsorbing the fraction from the countercurrent separation containing the supercritical or near critical fluid on an adsorbent, and subsequently eluting the mixture from the adsorbent by the same or an other supercritical or near critical fluid and collecting different fractions. 2. A process for the production of highly enriched fractions of natural compounds (tocotrienols, carotenoids, and ster- ols) from Palm oil or Palm oil derivatives, according to claim 1 using supercritical carbon dioxide and/or near critical propane at operating conditions for the tempera- ture of 313 to 383 K, preferably between 323 and 363 K, and pressures of 5 to 45 MPa, preferably between 10 and 30 MPa, a solvent-to-feed ratio of 1 to 500, preferably between 50 and 300, using a reflux of extract at the top of the column in the range of 0.1 to 50, preferably between 2 and 20. 3. A process for the production of highly enriched fractions of natural compounds (tocotrienols, carotenoids, and ster- ols) from Palm oil or Palm oil derivatives, according to claim 1, wherein a second step comprising selective adsorp- tion and desorption by directly adsorbing the fraction from the countercurrent separation containing the supercritical or near critical fluid carbon dioxide and/or propane, at the same pressure and temperature or at reduced density, on an adsorbent, silica gel, preferably a special silica gel, commercial name Zeofree, in a ratio of 4 to 10, in such a way that only some part of the adsorbent is loaded with the incoming feed material. Desorption (elution, or extraction) is carried out with the same or another supercritical or near critical fluid in one or more steps, preferably in two pressure steps. In a first elution step, at lower pressure in the range of 12 to 15 MPa, the higher volatile compounds still remaining in the adsorbed mixture are being removed. In a subsequent second elution, at an enhanced pressure in the range of 22 to 35 MPa, preferably 25 MPa, at tempera- tures between 313 and 373 K the lower volatile compounds are extracted. A third elutions step comprises the use of near critical propane at conditions of 3 to 10 MPa, pref- erably 5 to 7 MPa. 4. A process for the production of highly enriched fractions of natural compounds from Palm oil or Palm oil derivatives, according to claims 1 to 3, for tocochromanol fractions. 5. A process for the production of highly enriched fractions of natural compounds from Palm oil or Palm oil derivatives, according to claims 1 to 3, for carotenoid fractions. 6. A process for the production of highly enriched fractions of natural compounds from Palm oil or Palm oil derivatives, according to claims 1 to 3, for sterol fractions. 7. A process for the production of highly enriched fractions of natural compounds from Palm oil or Palm oil derivatives, according to claims 1 to 3, for coenzyme Q10. From palm oil valuable compounds like the tocochromanols, carotenoids, phytosterols, and others can be derived. Enrichment to highly concentrated fractions is hindered by the enormous number of components involved, the very low volatility, the very low solubility of many of the compounds in organic solvents, and the high viscosity of the mixtures to be processed. Starting materials for the new process are enriched fractions of tocochromanols (about 20 to about 50 wt.-%) and/or carotenoids (about 10 to 30 wt.-%) from palm oil obtained by conventional processes, or by counter current multistage processes with supercritical carbon dioxide. These processes, not addressed here, may comprise: Removal of free fatty acids, transesterification of the triglycerides to methyl or ethyl esters, removal of the esters, e.g. by short path distillation, separation of the tocochromanol fraction from the carotenoid fraction by cooling. In the new process, fractions derived from crude palm oil, already enriched to some extent in tocochromanols, carotenoids, phytosterols, and others, are being treated by supercritical fluid technology in a unique combination of counter current separation with selective adsorption and desorption using supercritical fluids. A first enrichment, comprising one or more separation steps by application of a near critical or a supercritical fluid in a single or multistage (counter current) separation process is combined appropriately with a second enrichment step wherein the product of the first enrichment step is directly adsorbed on an adsorbent (silicagel) by passing the product flow over a fixed bed of adsorbent without substantial pressure change, and subsequent desorption with the same (or an other) near critical or supercritical fluid at the same or a different pressure as in the first separation, or by a pre-designed sequence of pressures and temperatures. For the tocochromanol enrichment, carbon dioxide at near critical conditions above the critical temperature of carbon dioxide is used. For the carotenoid enrichment, propane at near critical conditions below the critical temperature of propane is used.

Full Text

Process for production of highly enriched fractions of natural
compounds from Palm Oil with supercritical and near critical
fluids
Background of the invention
From palm oil valuable compounds like the tocochromanols, ca-
rotenoids, phytosterols, and others can be derived. Enrichment
to highly concentrated fractions is hindered by the enormous
number of components involved, the very low volatility, the
very low solubility of many of the compounds in organic sol-
vents, and the high viscosity of the mixtures to be processed.
As an example for the production of pre-concentrated frac-
tions, the Carotech-process may be taken (Fig. 1). Caromin™,
is a carotenoid enriched derivate of crude palm oil, contain-
ing approximately 10% of carotenoids. The integrated process
for extracting carotenoids and tocotrienols (vitamin E) is
carried out according to U.S. Patent 5,157,142 and is summa-
rized in Fig. 1. It involves the transesterification of crude
palm oil (CPO) to methyl esters (FAME), followed by vacuum
distillation and other steps, resulting in a carotene-rich
layer and a tocotrienol-rich layer. The carotene-rich layer,
as well as the tocotrienol-rich layer are further concentrated
to produce highly concentrated products of a maximum content
of 30 % for carotenoids, and a maximum content of about 50 %
for tocochromanols, mostly tocotrienols. Further enrichmebnt
with conventional methods proved to be not possible because of
the high viscosity, very low volatility, and low solubility in
conventional organics solvents. Although a number of investi-
gations have been carried out on various mixtures, mostly to-
copherols, with supercritical fluids, no process was able to
produce fractions of high concentrations for both the to-
cochromanols and the carotenoids from crude palm oil or other
natural sources.

Fig. 1. Process for production of concentrated fractions of
mixed carotenoid and tocotrienols (U.S. Patent 5,157,142).
Carotenes, which impart the distinctive orange-red colour to
palm oil, together with tocopherols contribute to the stabil-
ity and nutritional value of the oil. To a great extent these
and other minor constituents determine the quality character-
istics of palm oil Carotenoids are often recovered from natu-
ral fat or oil, particularly from palm oil. Carotenoids can be
extracted from unsaponified distillation residue. They can be
also extracted employing adsorbent in some stage of the proc-
ess. During the extraction, large amounts of organic solvents
are needed. Adsorptive processes so far have not led to higher
concentrated carotene fractions from natural sources. Reasons
are the initial low concentrations, the high viscosity of
carotene fractions, and the instability of carotenes on most
adsorbents. Numerous attempts to design a process for produc-
ing higher concentrated fractions of carotenes have been made.
Carotenoids are the most widespread and important pigments in
living organisms. The most widely known carotenes are the -,
- and -carotenes, and lycopene. Beside their colour, carote-
noids, especially -carotene, are well known to possess pro-
vitamin A activity as they can be transformed into vitamin A
in vitro. They have also been found to inhibit anti-cancer
properties due to their ability to deactivate oxy-radicals. As
the carotenes are natural compounds with vitamin A property,
they played a positive role in commercial applications for
pharmaceutical and nutritional products synthesis. [1, 2].
Carotenoids are found in numerous vegetable oils, including
groundnut oil, rapeseed oil, sunflower-seed oil and cottonseed
oil. The concentration of carotenoids in these oils is gener-
ally low, less than 100ppm. Among these, palm oil is the rich-
est natural plant source of carotene in terms of retinol
equivalent, with Malaysia contributing the highest percentage

of world palm oil production. Palm oil contains the highest
known concentration of carotenoids, ranging from 500 to
3000ppm, depending on the species of the palm fruit from which
the oil is obtained. [1, 2] The concentration of carotenes in
crude palm oil from Malaysia varies between 500 to 700ppm,
with - and -carotene form up to 90% of the total carotenes.
[3].
Nowadays, carotenes found on the market are chemically syn-
thetic -carotene or carotene extracted from algae Dunaliella.
Since carotenoids are most probably to grow in importance and
value, the recovery of carotenoids from palm oil and its by-
products becomes important. Various extracting methods for re-
covering carotenes from palm oil have been developed over the
years including saponification, urea processing, selective
solvent extraction, molecular distillation, separation by ad-
sorption, crystallization, and transesterification followed by
distillation of esters. [1,4,5].
Tocochromanols: Vitamins are important substances for the hu-
man health. They are regulating various processes in the body
and have positive effects on many vital functions. In general
terms vitamins act as coenzymes or pro-hormones while most of
their other functions like anti-carcinogen or anti-oxidizing
effects are yet to be researched. Most of the vitamins cannot
be synthesized by the human body and therefore these nutrients
have to be ingested with the food. Since vitamins vary in
their structure and their functions, a first approach is to
categorize them into water soluble and oil soluble groups. Wa-
ter soluble vitamins are distributed within the whole body and
there-fore they are taking effect in almost all organs, while
oil soluble vitamins are mostly present in the membranes. The
transport in the blood stream and the digestion of these vita-
mins can only be done if a sufficient amount of oil lipids and
micelles are present.

Vitamin E is the generic term for eight substances from the
group of the tocochromanols that possess a Vitamin E activity.
The tocochromanols can be subdivided into two groups: the to-
cochromanols and the tocotrienols: with the tocotrienols pos-
sessing three unsaturated double bonds in their hydrocarbon
chain and the tocopherols possessing a completely unsaturated
hy-drocarbon chain. Both tocopherol and -trienol subgroups
consist of: four homologous, designated as -, -, -, and -
tocopherol (-trienol), depending on the substitutes of their
chroman-ring. The tocochromanols are oil soluble anti-oxidants
which are mostly found in the cell membrane of organs, -
tocopherol has the highest anti-oxidant activity and therefore
it is mostly used as anti-oxidant in the food and cosmetic in-
dustry. Nevertheless recent studys report further functions of
the other tocochromanol homologous like anti-carcinogen or
anti-tumor properties.
As a consequence the demand on natural tocochromanol mixtures
consisting of all homologous is steadily increasing. The
fruits of the malaysian oil palm possess the highest content
of tocochromanols in the world. Crude palm oil (CPO) consist
of 94 wt.% tryglycerides, 3-4 wt.% free fatty acids (FFA), and
only 1 wt.% of the CPO consist of tocochromanols, carotinoids
and phytonutrients. Palm oil is available in large quantities
and at a comparatively low price. It is the largest source for
tocotrienols. Tocotrienols can be recovered from the distil-
late fractions obtained during the refining and deodorisation
of the crude palm oil. The carotenoids are destroyed during
this process. It is therefore reasonable to try to recover
both groups of valuble compounds in one process sequence. The
most economic way would be to adsorb these compounds from the
crude palm oil on an appropriate adsorbent and remove the com-
pounds subsequently from the adsorbent. Numerous attempts have
been made. So far no success was obtained. Therefore, the need
for another approach led to the transesterification of the

triglycerides of palm oil to fatty acid methyl esters and
their removal by vacuum distillation. The further process of
generating higher concentrated fractions is limited by the
mentioned properties of the mixtures. The needs for a differ-
ent process are obvious.
Here, supercritical fluid extraction (SFE) is an alternative
to conventional extraction with organic solvents. SFE is able
to yield in a solvent free extract and due to its low critical
temperature can be used for the treatment of temperature sen-
sitive substances like vitamins. Supercritical fluids can dis-
solve the low volatile components and carry them through any
process via the gaseous phase. Furthermore, highly viscous
liquid solutions dissolve a great amount of supercritical flu-
ids, in particular carbon dioxide and propane, with the effect
of a much reduced viscosity. Then, even the liquid solutions
can be handled in a process.
Although these facts have each for itself been known for some
time, the surprising effects for a further enrichment of the
tocochromanols and the carotenoids by applying appropriate
combinations of counter current SFE separation and SFE-
adsorptions with subsequent selective SFE-desorption have not
been recognized. The state of the art achieved so far is re-
viewed in the following.
State of the art
Tocochromanols:
The research done on extraction of natural materials with su-
percritical carbon dioxide is increasing these days. The
critical parameters of carbon dioxide is 7,4MPa and 304,21K
[6]. Because of these low critical parameters, using super-
critical carbon dioxide is resulting in low operation cost and
because of the low critical temperature even temperature sen-
sitive materials can be extracted. In contrary to organic sol-
vent, carbon dioxide is non toxical, non inflammable, and in-

ert. Moreover, carbon dioxide is easy available and can be re-
moved completely from the desired product without residues.
The solubility of carbon dioxide can be adjusted by the den-
sity, therefore it can be adjusted to the feed material. These
are the reasons for the enormous amount of research work in
the field of supercritical carbon dioxide extraction. Ill'es
et al. [7] and Gnayfeed et al. [8] for example were research-
ing the extraction of red pepper and pepper oil with super-
critical C02 and subcritical propane in respect to the toco-
pherol and carotine content. It was found that the solubility
of the supercritical carbon dioxide was not sufficient to dis-
solve carotine. The solubility of the tocopherols in both sol-
vents was good, and it was possible to dissolve tocopherols in
both C02 and propane. Nagesha et al. [9] and Shishikura et al.
[10] have researched the enrichment of tocopherols from soy
deodorizer distillate by supercritical uid extraction. Further
research work has been done on the enrichment of squalene from
an intermediate of the olive oil production (Dreschner et
al.[ll]) and the enrichment of tocopherolacetate and toco-
pherol (Fleck [12]) .
The adjustment of the solubility of the supercritical carbon
dioxide through the density gives the supercritical extraction
a high flexibility. But because of the lacking polarity of the
carbon dioxide the solubility for polar substances is limited.
One possibility to increase the solubility is to add a modi-
fier to the supercritical carbon dioxide. Common modifiers are
iso-propanol, ethanol and propane. It should not be neglected
that an increase of solubility with modifiers is often paired
with a decrease in selectivity. Thus recent studies focus on
an additional adsorption process prior the supercritical ex-
traction. Due to the additional adsorption, the selectivity of
the process can be increased, since the adsorbent has a dif-
ferent affinity to the different components. The result is
that the components are adsorbed and desorbed to a different

extent. Wang et al. [13] researched the separation of -
tocopherol and squalene using a pressure swing adsorption
technique with supercritical carbon dioxide as solvent. In the
first stage of the process the feed is mixed with supercriti-
cal CO2 and enters a column filled with silica gel at low pres-
sure, where the feed adsorbs on the silica gel. In the second
stage the adsorbt is desorbed off the silicagel with pure su-
percritical carbon dioxide under high pressure. During these
experiments Wang et al. was able to enrich -tocopherol from a
20 wt.% feed to 60 wt.% and squalene from 80 wt.% to 98 wt.%.
Theoretical work on adsorption and desorption in supercritical
carbon dioxide has been done by Reverchon et al. [14] and Goto
et al. [15]. The research group of Reverchon used a Langmuir
similar multi component adsorption isotherm in order to de-
scribe the adsorption behaviour of a complex terpene mixture
under supercritical conditions, wheras the research group of
Goto used the BET adsorption isotherm to do their simulation.
Both works lead to mathematical models which are capable to
simulate experimental data with a high accuracy.
Lee et al.. [16] published a work on the adsorption kinetics of
phospholipids from treated soy oil on regenerated clay. The
research group of Lee used a reaction kinetic equation in or-
der to describe the adsorption process by measuring the con-
centration before and after the adsorber. This was a totally
different approach then the authors before, since no adsorp-
tion isotherm is used at all to describe the system. Neverthe-
less the research group of Lee was able to derive a reaction
equation which is capable to predict the experimental data.
The regeneration of modified clay with supercritical carbon
dioxide was researched by Cavalcante et al. [17] and Carneiro
et al. [18]. Modified clay is an important adsorbent in the
environmental technology, since its ability to adsorb organic
substances is very important in the field of water treatment.
Therefore the regeneration of the clay is an important eco-

nomical issue for the economical efficiency of the process.
Zetzl [19] dealt with the separation of avors from lemon oil
by applying a selective adsorption on silicagel followed by a
desorption under supercritical carbon dioxide. The desorption
curve of limonen and citral was researched and a model was in-
troduced which described the experimental data with a high ac-
curacy.
A patent for the separation technique of selective adsorption
followed by a desorption with supercritical CO2 was filed for
separating terpenes out of essential oils. The European patent
EP 0363971 A2 [20] describes such a process. The oil is mixed
by stirring at a constant temperature with the adsorbent and
then it is; extracted with supercritical CO2. This is possible
because of the low viscosity of the treated oil.
Carotenoicls:
The Japanese patent JP200226723 [21] presents a method for the
enrichment of carotene from palm oil. Palm oil is first trans-
esterified. The ester is then extracted with a hydrophilic
solvent such as methanol to separated it into a concentrated
ester phase. This concentrate is then applied to a column
packed with silica gel to adsorb carotene. Carotene is then
desorbed using hexane which contains around 4000 ppm aceton.
Adsorptive concentration of the carotene-rich concentrate was
also employed in U.S. Pat. No. 6072092 [22], where silica gel
is used ass adsorbent and a large amount of non-polar solvent
is used to recover carotene.
European patent EP0242148 [23] describes a similar method us-
ing silica gel or activated alumina as adsorbent and a non po-
lar solvent containing certain amounts of polar solvents as
eluant for the enrichment of carotene.

Japanese patent JP63132871 [24] describes a process to enrich
carotene applying Zeolite as adsorbent and a non polar sol-
vent, such as carbon tetrachloride as eluant.
U.S. Pat. No. 5157132 [25] describes a process recovering
carotene from oil through transesterification and saponifica-
tion. The enriched carotene can be extracted from the saponi-
fied residue with an organic solvent. The obtained residue has
a carotene content of 20%. Also European patent EP1398311
[26] describes a similar process. 10% to 20% of carotene con-
centrate can be obtained.
German patent DE 4429506 [27] presents the extraction of caro-
tenoids from dried material with propane or butane. It was
found that the solubility of both gases can be greatly im-
proved when a co-solvent is used.
These patents require organic solvents in a large amount as
eluant and recovery of the solvents by distillation to obtain
the carotenoids concentrate. In the new process only propane
and supercritical CO2 are used as solvents at low temperatures
to obtain the concentrate. These solvents can be easily re-
moved by expansion.
Most techniques described in literature that use supercritical
carbon dioxide or other compressed gases for the enrichment of
both phytosterols and tocochromanols from edible oil start
from very low concentrations of the here-treated components.
Hence, the main focus of these works lies on depleting the oil
from substances like triglycerides or FAME, because these are
the by far most prominent substances when dealing with crude
or esterified oil, respectively. Additionally, most described
processes are batch-wise operated. Thus, the here-described
approach, starting from an already enriched palm oil deriva-
tives and employing a combination of a continuously operated
extraction column with an adsorption/desorption operation on

the one side and a subsequent extraction has not yet been ap-
plied.
Description of the Invention: General description
The vitamin compounds of the group of the tocochromanols and
carotenoids are enriched from mixtures derived from natural
oils in the process described below. These mixtures contain
fatty acid methyl esters or fatty acid ethyl esters, squalene,
monoglycerides, diglycerides, sterols, and the target com-
pounds.
With supercritical carbon dioxide as solvent, in a first sepa-
ration sequence (Fig. 2, columns Cl and C2), from the to-
cochromanols or the carotenoids are removed the compounds more
soluble in supercritical carbon dioxide than the target com-
pounds at the top of a counter currently operated separation
column, and the less solube soluble compounds at the bottom.
This process leads to concentrations for the tocochromanols of
about 70 wt.-%, and for the carotenoids of about 30wt.-%. The
details of this separation are given below.
In a second sequence, directly following the countercurrent
process, the mixtures are processed by selective adsorption
and desorption steps (Fig. 2, adsorbers A1, A2, A3). Adsorp-
tion takes place from the mass flow taken from the countercur-
rent separation comprising a supercritical or near-critical
fluid and the target compounds, and is directly deposited on
the adsorbent. In this way, the handling of the highly viscous
solution or solid solution is made possible. Subsequently, de-
sorption is carried out from the fixed bed loaded with the
feed mixture. Desorption may be carried out with the same su-
percritical or near critical fluid, or a different one, or in
a sequence of two or more of such solvents. Desorption is also
carried out at different conditions compared to the adsorp-
tion, i.e. different values of pressure, temperature, flow
rate of gas. Supercritical or near critical solvents may com-

prise mixtures of supercritical or near critical fluids, pref-
erably of carbon dioxide and propane.
It was found that the separation by adsorption and desorption
can be improved by not filling the whole adsorbent with the
feed mixture, but only part of it. During desorption a se-
quence of adsorption and desorption steps take place, which
increase the separation efficiency, and thus the concentra-
tions of the separated fractions. The ratio of the first ad-
sorbed section to the free section of the fixed bed of adsorb-
ent is variable, usually from (3.5 to 0.1.
Fig. 2. Flow sheet of the process for concentrating tocochro-
manols and carotenoids by SFE technology.
Tocochromanols
The new process for the production of highly enriched to-
cochromanol-fractions, containing mostly tocotrienols from
palm oil derived mixtures combines a continuous countercurrent
multistage; separation using a supercritical fluid, preferably
carbon dioxide, to remove the lighter volatile (i.e. the com-
pounds more soluble in supercritical compound, resp. carbon
dioxide) over the top of the column. The bottoms of the column
are an enriched fraction in tocotrienols with a relatively
high content in sterols and other somewhat polar compounds.
This bottom fraction is passed over a suitable adsorbent.
Silicagel was found to be an applicable adsorbent. The ad-
sorbed mixture is desorbed by a supercritical fluid, prefera-
bly carbon dioxide in two desorption steps. The first is car-
ried out at a pressure of about 140 bar and removes more vola-
tile or more in supercritical carbon dioxide soluble com-
pounds. In the second desorption step, carried out at about
250 bar, highly enriched tocochromanol fractions, containing
mostly tocotrienols, are extracted. The extracted fractions
can be split further by collecting them in different vessels.
Depending on the cut of the fractions, the concentration of

tocotrienols is in the range of 85 to nearly 100% with a yield
of about 50% of the feed mixture. The adsorbent is regenerated
with liquid solvents like ethanol etc. and reused for the ad-
sorption step.
The process starts with a pre-enriched fraction, which may be
obtained by several methods, one may comprise transesterifica-
tion of the glycerides with methanol and removing the obtained
fatty acid esters by short-path-distillation or by extraction
with supercritical fluids, like carbon dioxide. For example,
the starting material for the first extraction step was a palm
oil derivatives that among other substances contained 56 wt.-%
tocochromanols (with -tocotrienol, -tocotrienol, and -
tocopherol being the major components), 16 wt.-% squalene, 5
wt-% phytosterols (with -sitosterol and campesterol being the
most prominent species), and 11 wt.-% mono- and diglycerides.
This material was fed into a continuously operated extraction
column, employing supercritical carbon dioxide as solvent. The
column was packed with a structured Sulzer EX packing and has
an inner diameter of 17.5 mm and a total height of 7 m, of
which 6 m are packed. Employing pressures of 20-30 MPa and
temperatures of 323 to 358 K, it was possible to produce a
sterol- and tocochromanol-free top product, only extracting
specifically FAME, squalene, and monoglycerides, hence obtain-
ing a bottom product enriched to about 70% tocochromanols with
phytosterols and other most probably more polar compounds com-
prising the rest.
A longer column would have completely depleted the bottom
phase from the higher-volatile components. With chemical engi-
neering methods the necessary height for complete separation
of FAME, squalene, and monoglycerides from tocochromanols,
sterols, and other low-volatile components was calculated. The
results are that a complete separation of these components is
possible with 13 theoretical separation stages, corresponding

to a height of the column of about 15 m, a solvent-to-feed ra-
tio of 80 to 140, with a reflux ratio of 6 to 12, at a tem-
perature of 323 K, and a pressure of 20-25 MPa.
Theoretically, the further enrichment of tocotrienols should
be possible by employing another countercurrent separation us-
ing a supercritical fluid. Experimental investigations re-
vealed that the solubility of the tocotrienol-enriched bottom
product in supercritical carbon dioxide is too low to be con-
sidered as a solvent for a separation process. Therefore,
modifiers were mixed with the basic supercritical fluid, car-
bon dioxide, in order to increase the solubility. The follow-
ing solvent compositions were investigated: CO2 + propane with
a propane content of 29, 55, and 83%, as well as CO2 + liquid
organic solvent, namely ethanol, iso-propanol, 1-butanol, and
ethyl acetate, each in a concentration of 5 and 10 wt.-%, re-
spectively. The measurements were conducted in a pressure
range of 5-30 MPa and at temperatures of 323, 343, and 358 K,
respectively, in case of experiments with propane and at a
fixed pressure of 20 MPa and at temperatures of 323 and 343 K
in case of the liquid modifiers. At all conditions investi-
gated the concentration of the low volatile compounds was en-
riched in the gaseous phase, but the selectivity with respect
to tocotrienols was reduced to such an extent that sterols
were dissolved in the gas-phase, hence making it impossible to
enrich the tocotrienol concentration further.
Surprisingly it was found that the separation factors remained
high, even increased, if the bottom material was mixed with
special silica gels and then desorbed or extracted from this
adsorbent with supercritical carbon dioxide. The bottom prod-
uct from the first enriching step was mixed with certain
amounts of adsorbent (silica gel) in a ration of 4 to 10. The
mixture was introduced into a column as fixed bed. Then, ap-
plying a supercritical fluid (carbon dioxide) at a pressure of
about 14 at a temperature of about 333 K, remaining high vola-

tile components such as fatty acid esters and squalene were
desorbed. In a second desorption (extraction)-step, at about
the same temperature, but a higher pressure of about 25 MPa
tocotrienols were desorbed with high concentration. With a ra-
tio of adsorbent to feed of 10, a solvent ratio of supercriti-
cal carbon dioxide of about 300 [kgCO2/kg Feed and hour], a
fraction of 27% of the feed was obtained during 1 h with a
concentration of 75% tocotrienols, after that fraction, an-
other fraction of 25% of the feed with a 100% concentration of
tocotrienols could be recovered in another hour. Experiments
with a mixture of carbon dioxide and propane showed that the
solubility could be enhanced while the selectivity was main-
tained. Therefore, the solvent ratio can be lower than with
pure CO2.
Description of the invention:Carotenoids.
A carotenoid concentrate (1 to 10 wt.-%) is fed into a con-
tinuously operated extraction device, constructed as a five-
stage high pressure mixer-settler. In three separation se-
quences with this apparatus, employing pressures of 20-30 MPa
and temperatures of 323 to 358 K, it was possible to produce a
product, containing up to 30 wt.-% of carotenoids. This prod-
uct is passed over the adsorbent, a special silica gel, pref-
erably Zeofree 5170, whereby the mixture of carotenoids, ster-
ols and other substances, and the fatty acid esters are ad-
sorbed. The mixing ratio is in the range of 4 to 10. Subse-
quently, the loaded adsorbent is brought into contact first
with suspercritical carbon dioxide, and then with near criti-
cal propane at conditions of the state, e.g. 5 MPa and 323 K,
preferably in the range of 2 to 7 MPa and 313 to 343 K. With
carbon dioxide, mainly non-carotenoids are desorbed and
eluted, and with near critical propane, the carotenoids are
desorbed. The solvent ratio of propane to feed is in the range
of 20 to 100 preferably about 30. Concentration of the eluted

carotenoids were enhanced, if during the adsorption step only
a fraction of the adsorbent was loaded with the feed.
Examples: Tocochromanols.
Example 1: First Extraction Step.
A continuous operated multi-stage supercritical extraction was
conducted with pure carbon dioxide as solvent and a feed mix-
ture containing 50 wt.-% tocochromanols (with -tocotrienol, -
tocotrienol, and a-tocopherol being the major components), 16
wt.-% squalene, 3 wt-% phytosterols (with -sitosterol and
campesterol being the most prominent species), and 11 wt.-%
mono- and diglycerides. The employed column had an effective
height of 6 m and was packed with a structured Sulzer EX pack-
ing. Operating conditions were as follows: 20 MPa, 323 K, sol-
vent-to-feed ratio = 19.8, reflux ratio = 7.3. These condi-
tions resulted in a top phase product consisting of 2 wt.-%
FAME, 58 wt.-% squalene and it was completely depleted from
tocochromanols and phytosterols. The bottom product consisted
of 8 wt.-% squalene, 58 wt.-% tocochromanols, 4 wt.-% phytos-
terols, and it was completely FAME-free.
Example 2: First Extraction Step.
A continuous operated multi-stage supercritical extraction was
conducted with pure carbon dioxide as solvent and a feed mix-
ture containing 50 wt.-% tocochromanols (with -tocotrienol, -
tocotrienol, and -tocopherol being the major components), 16
wt.-% squalene, 3 wt-% phytosterols (with -sitosterol and
campesterol being the most prominent species), and 11 wt.-%
mono- and diglycerides. The employed column had an effective
height of 6 m and was packed with a structured Sulzer EX pack-
ing. Operating conditions were as follows: 20 MPa, 343 K, sol-
vent-to-feed ratio = 4 0.3, reflux ratio = 1.3. These condi-
tions resulted in a top phase product consisting of 2 wt.-%

FAME, 60 wt:.-% squalene, 2 wt.-% tocochromanols, and 1 wt.-%
sterols. The bottom product consisted of 7 wt.-% squalene, 54
wt.-% tocochromanols, 4 wt.-% phytosterols, and it was com-
pletely FAME-free.
Example 3: Production of Concentrated Fractions of Tocotrie-
nols -1
1 g of the bottom product obtained from example 1 was used as
feed material and mixed with 10 g of silica gel, Zeofree 5170.
The mixture is introduced into an empty vessel and supercriti-
cal CO2 was used to desorb FAME and squalene at 13 MPa and 333
K for 120 minutes. The pressure was increased to 25MPa and af-
ter 60 minutes, a fraction (0.27g), which contains 80 wt.~% of
tocochormanols, was collected. The pressure was held constant
for another 60 minutes, another fraction (0.24g) was col-
lected. This fraction contains approximately 100% tocochro-
manols.
Example 4: Production of Concentrated Fractions of Tocotrie-
nols -2.
2.4 g of the bottom product obtained from example 1 was used
as feed material and mixed with 10 g of silica gel, Zeofree
5170. The mixture is introduced into an empty vessel and su-
percritical CO2 was used to desorb FAME and squalene at 13 MPa
and 333 K for 60 minutes. The pressure was increased to 19MPa
and after another 120 minutes, a fraction(1.59g) was col-
lected. It contains 80 wt.-% of tocochromanols.
Example 5: Carotenoids.
The carotenoids concentrate containing approximately 10 wt% of
carotenoids was passed over the adsorbent in an high pressure
pipe with an internal volume of 50 ml. Silica gel with a mini-
mum surface area of 165m2/g was used as the adsorbent with a
ratio of 4:1 (12g:3g) to the amount of feed. Extraction was

then carried out first with supercritical carbon dioxide at
150 bar and 60 °C, and then with supercritical carbon dioxide
at 250 bar and 60 °C. In third step, near critical propane was
used at 7 MPa, 60 oC. The fractions are collected. The last
fraction consisted of about 60 % carotenoids.

References:
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sity Press,, Food and Nutrition Bulletin, 15 (1994).
2. C. Lenfant, F.C. Thyrion: Extraction of Carotenoids From
Palm Oil, I. Physical and Chemical Properties of -Carotene,
Voir OCL 3,3 (1996) 220-226.
3. S.H. Goh, Y.M. Choo, S.H. Ong: Minor Constituents of Palm
Oil, J. Am. Oil Chem. Soc. 62 (1985) 237-240.
4. B.S. Baharin, L.L. You, Y.B.. Che Man, and S. Takagi: Effect
of Degumming Process on Chromatographic Separation of Caro-
tenes from Crude and Degummed Palm Oil, Journal of Food Lipids
8 (2001) 27-35.
5. C. Lenfant, F.C. Thyrion, Extraction of Carotenoids From
Palm Oil, II. Isolation Methods, Voir OCL 3,4 (1996) 294-307.
6. VDI : VDI W armeatlas. VDI Verlag GmbH (1988) .
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Supercritical CO2 and Subcritical Propane Extraction of Spice
Red Pepper Oil with Special Regard to Carotenoid and Toco-
pherol Content. Journal of Chromatographic Science, Vol.37
(1999).
8. M.H.Gnayfeed, H.G.Daood, V.Ill'es, P.A.Biacs: Supercritical
CO2 and Subcritical Propane Extraction of Pungent Paprika and
Quantification of Carotenoids, Tocopherols and Capsaicinoids.
J. Agric. Food Chem. 49, 2761-2766 (2001).
9. G.K.Nagesha, B.Manohar, K.Udaya Sankar: Enrichment of toco-
pherols in modified soy de-odorizer distillate using super-
critical carbon dioxide extraction. Eur. Food Res. Technol.
217:427- 433 (2003).

10. A.Shishikura, K.Fujimoto, T.Kaneda, K.Arai, S.Saito: Con-
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11. M.Dreschner, M.Bonakdar: Anreicherung des Kohlenwass-
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12. U. Fleck: Reinigung schwer flüchtiger Substanzen mittels
Extraktion mit überkritischen Gasen. Dissertation, Technische
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Tocopherol and Squalene by Pressure Swing Adsorption in Super-
critical Carbon Dioxide. Ind. Eng. Chem. Res. 43, 2753-2758
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Claims
1. A process for the production of highly enriched fractions
of natural compounds (tocotrienols, carotenoids, and ster-
ols) from Palm oil or Palm oil derivatives, characterized
by a first separation step comprising countercurrent multi-
stage separation with supercritical and/or near critical
fluids removing the higher volatile (better soluble in the
supercritical or near critical fluid) over top, yielding a
bottom fraction enriched in the natural compounds and an-
other countercurrent multistage separation with supercriti-
cal and/or near critical fluids removing the target natural
compounds over top, thus cleaning it from low volatile im-
purities, and a second step comprising selective adsorption
and desorption by directly adsorbing the fraction from the
countercurrent separation containing the supercritical or
near critical fluid on an adsorbent, and subsequently
eluting the mixture from the adsorbent by the same or an
other supercritical or near critical fluid and collecting
different fractions.
2. A process for the production of highly enriched fractions
of natural compounds (tocotrienols, carotenoids, and ster-
ols) from Palm oil or Palm oil derivatives, according to
claim 1 using supercritical carbon dioxide and/or near
critical propane at operating conditions for the tempera-
ture of 313 to 383 K, preferably between 323 and 363 K, and
pressures of 5 to 45 MPa, preferably between 10 and 30 MPa,
a solvent-to-feed ratio of 1 to 500, preferably between 50
and 300, using a reflux of extract at the top of the column
in the range of 0.1 to 50, preferably between 2 and 20.
3. A process for the production of highly enriched fractions
of natural compounds (tocotrienols, carotenoids, and ster-
ols) from Palm oil or Palm oil derivatives, according to
claim 1, wherein a second step comprising selective adsorp-

tion and desorption by directly adsorbing the fraction from
the countercurrent separation containing the supercritical
or near critical fluid carbon dioxide and/or propane, at
the same pressure and temperature or at reduced density, on
an adsorbent, silica gel, preferably a special silica gel,
commercial name Zeofree, in a ratio of 4 to 10, in such a
way that only some part of the adsorbent is loaded with the
incoming feed material. Desorption (elution, or extraction)
is carried out with the same or another supercritical or
near critical fluid in one or more steps, preferably in two
pressure steps. In a first elution step, at lower pressure
in the range of 12 to 15 MPa, the higher volatile compounds
still remaining in the adsorbed mixture are being removed.
In a subsequent second elution, at an enhanced pressure in
the range of 22 to 35 MPa, preferably 25 MPa, at tempera-
tures between 313 and 373 K the lower volatile compounds
are extracted. A third elutions step comprises the use of
near critical propane at conditions of 3 to 10 MPa, pref-
erably 5 to 7 MPa.
4. A process for the production of highly enriched fractions
of natural compounds from Palm oil or Palm oil derivatives,
according to claims 1 to 3, for tocochromanol fractions.
5. A process for the production of highly enriched fractions
of natural compounds from Palm oil or Palm oil derivatives,
according to claims 1 to 3, for carotenoid fractions.
6. A process for the production of highly enriched fractions
of natural compounds from Palm oil or Palm oil derivatives,
according to claims 1 to 3, for sterol fractions.
7. A process for the production of highly enriched fractions
of natural compounds from Palm oil or Palm oil derivatives,
according to claims 1 to 3, for coenzyme Q10.

From palm oil valuable compounds
like the tocochromanols, carotenoids, phytosterols,
and others can be derived. Enrichment to highly
concentrated fractions is hindered by the enormous
number of components involved, the very low
volatility, the very low solubility of many of the
compounds in organic solvents, and the high
viscosity of the mixtures to be processed. Starting
materials for the new process are enriched fractions
of tocochromanols (about 20 to about 50 wt.-%)
and/or carotenoids (about 10 to 30 wt.-%) from
palm oil obtained by conventional processes, or by
counter current multistage processes with supercritical
carbon dioxide. These processes, not addressed
here, may comprise: Removal of free fatty acids,
transesterification of the triglycerides to methyl or
ethyl esters, removal of the esters, e.g. by short path
distillation, separation of the tocochromanol fraction
from the carotenoid fraction by cooling. In the new process, fractions derived from crude palm oil, already enriched to some
extent in tocochromanols, carotenoids, phytosterols, and others, are being treated by supercritical fluid technology in a unique
combination of counter current separation with selective adsorption and desorption using supercritical fluids. A first enrichment,
comprising one or more separation steps by application of a near critical or a supercritical fluid in a single or multistage (counter
current) separation process is combined appropriately with a second enrichment step wherein the product of the first enrichment
step is directly adsorbed on an adsorbent (silicagel) by passing the product flow over a fixed bed of adsorbent without substantial
pressure change, and subsequent desorption with the same (or an other) near critical or supercritical fluid at the same or a different
pressure as in the first separation, or by a pre-designed sequence of pressures and temperatures. For the tocochromanol enrichment,
carbon dioxide at near critical conditions above the critical temperature of carbon dioxide is used. For the carotenoid enrichment,
propane at near critical conditions below the critical temperature of propane is used.

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Patent Number

268480

Indian Patent Application Number

2644/KOLNP/2008

PG Journal Number

36/2015

Publication Date

04-Sep-2015

Grant Date

31-Aug-2015

Date of Filing

30-Jun-2008

Name of Patentee

CAROTECH SDN. BHD.

Applicant Address

LOT 56442, 7/12 MILE, JALAN IPOH CHEMOR 31200 CHEMOR, PERAK

Inventors:

#	Inventor's Name	Inventor's Address
1	KUMAR, SENDIL	ADOLF-WAGNER-STRASSE 10, 21073 HAMBURG
2	CHAN, WAN, PING	51 JALAN CHIN HWA, TAWAN CHATEAU, IPOH, 30250 PERAK
3	BRUNNER GERD	HAGEDORNSTRASSE 24, 20149 HAMBURG
4	CHUANG, MENG-HAN	ALTER POSTWEG 26, 21075 HAMBURG
5	CHAN, PHILIP	FLOTTKAMP 38A, 24568 KALTENKIRCHEN
6	GAST, KAI	PEIFFERSWEG 7, 22307 HAMBURG

PCT International Classification Number

C11B 1/10,B01D 11/04

PCT International Application Number

PCT/EP2007/000802

PCT International Filing date

2007-01-31

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	06002687.9	2006-02-10	EUROPEAN UNION