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WO2010023128A1 - Compositions jaunes de curcuma contenant une faible quantité de solvant résiduel - Google Patents

Compositions jaunes de curcuma contenant une faible quantité de solvant résiduel Download PDF

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WO2010023128A1
WO2010023128A1 PCT/EP2009/060630 EP2009060630W WO2010023128A1 WO 2010023128 A1 WO2010023128 A1 WO 2010023128A1 EP 2009060630 W EP2009060630 W EP 2009060630W WO 2010023128 A1 WO2010023128 A1 WO 2010023128A1
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solvent
turmeric
curcuminoid
oleoresin
composition
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Venancio Hidalgo Garcia
Luis Hernandez Vera
Bjoern Madsen
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Chr Hansen AS
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Chr Hansen AS
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources

Definitions

  • the present invention relates to turmeric curcuminoids/curcumin compositions with a very low amount of residual solvents, processes for making such low solvent turmeric compositions and use of these low solvent compositions for e.g. colouring a food/feed product.
  • Turmeric or "yellow root” is a general term for plants and plant materials having a high content of curcuminoids, compounds that have a strong colouring effect and which are used extensively in the colouring of e.g. food products.
  • Turmeric plants belong to rhizomatous Curcuma species and have been known for centuries for their flavouring and colouring properties. The plants are grown commercially, particularly in India, but also in Bangladesh, China, Sri Lanka, Indonesia, Taiwan, Haiti, Jamaica and Peru.
  • Curcuma plant materials contain three different curcuminoid compounds including, as the predominant colouring compound, curcumin having a strong yellow colour, and minor yellow and brownish-red compounds, i.e. the term "curcuminoids” include curcumin (C), reddish orange and with two methoxy groups; demethoxy curcumin (DMC), orange-yellow with one methoxy group and bis-demethoxy curcumin (BDMC), yellow and without a methoxy group.
  • curcuminoids include curcumin (C), reddish orange and with two methoxy groups; demethoxy curcumin (DMC), orange-yellow with one methoxy group and bis-demethoxy curcumin (BDMC), yellow and without a methoxy group.
  • the Curcuma rhizomes including the primary or mother rhizomes and several long cylindrical multi-branched secondary rhizomes growing downward from the primary rhizomes, that contain the curcuminoid compounds in an oily cell phase, are harvested at maturity, typically 8 to 9 months after planting.
  • the rhizomes are cured in a process essentially comprising cooking the fresh rhizomes in water. This cooking step aids in producing a product of fairly uniform colour due to the diffusion of the yellow pigments from the individual oil containing cells into the surrounding tissues. After cooking, the material is spread and allowed to dry in the sun. When properly dried, the rhizomes become hard, almost horny and brittle, and of uniform yellow colour.
  • This cured and dried turmeric product is marketed as bulbs and fingers, each type in polished and unpolished forms.
  • This turmeric raw material is then made available to bulk purchase as a starting material for further processing resulting in commercial colouring agents. In figure 1 herein, this turmeric raw material is termed turmeric plant rhizomes.
  • the next step involves conventional extraction methods typically using organic solvents.
  • the solvents are generally solvents of defined purity allowed by national and international food laws for the processing of food additives.
  • acetone for industrial production is normally used acetone in this extraction step, since curcuminoid are very soluble in acetone.
  • desolventation is obtained by e.g. performing a standard evaporation step.
  • the curcuminoid-containing phase that is obtained by the above extraction methods is in the form of an oleoresin comprising essential oils containing the curcuminoids.
  • the curcuminoid content of the oleoresin is typically in the range of 30-50% by weight.
  • this extraction step is step (1 ) and the extracted material is termed turmeric oleoresin.
  • the essential oil fraction of the turmeric oleoresin has a very strong and bitter flavour, which for many purposes, such as colouring of food products, is undesirable.
  • turmeric oleoresin may be processed further.
  • the oleoresin may subsequently be subjected to a so-called crystallisation step resulting in the obtainment of a curcuminoid crystal powder of a relatively high purity (typically >90% by weight) in respect of curcuminoids.
  • step (2) this so-called crystallisation step is step (2) and the obtained crystal composition is termed curcuminoid crystal powder.
  • Solvents used in this so-called crystallisation step are also solvents allowed by national and international food laws. In the European Union is e.g. permitted use of ethyl acetate and isopropanol is allowed in e.g. USA and by the Joint FAO/WHO Expert Committee on Food Additives (JECFA).
  • JECFA Joint FAO/WHO Expert Committee on Food Additives
  • Acetone - normally used in the extraction step - is normally not used commercially in the subsequent so-called crystallisation step. According to the prior art, one reason for this is that the curcuminoids are too soluble in acetone to efficiently obtain the curcuminoid crystals.
  • solubility of curcumin in some organic solvents is: acetone > ethyl methyl ketone > ethyl acetate > methanol > ethanol > 1 ,2 dichloroethane > isopropanol > ether > benzene > hexane.
  • curcumin in hexane Due to the low solubility of curcumin in hexane it is often used to wash/remove the oils from the turmeric oleoresin, e.g. by washing the turmeric oleoresin with hexane.
  • Step (2) (i): Crystallisation step in a different solvent wherein the curcuminoids are relatively less soluble (e.g. Ethyl acetate (EU) or Isopropanol (USA)) to get the curcuminoid crystal powder.
  • the curcuminoids are relatively less soluble (e.g. Ethyl acetate (EU) or Isopropanol (USA)) to get the curcuminoid crystal powder.
  • EU Ethyl acetate
  • Isopropanol USA
  • the chromatograms of the article also indicate presence of acetone.
  • the article on page 248 "the acetone peak has resulted from the degradation of curcumin by alkali”. This means that the authors believed that the acetone was present due to that the acetone is a degradation product derived from the alkali induced 10 degradation of curcumin. Said in other words, the author's prima facie believed that acetone was not present in the analysed curcuminoid crystal powder before the analysis was actually made by use of the alkali.
  • Verghese and Joy (Flavour & Fragrance J. VoI 4, 31-32, 1989) describes a process 15 wherein the solvent ethyl acetate is used in both the extraction step [step (1 ) in figure 1 herein] and the subsequently so-called crystallization step [(step (2) in figure 1 herein].
  • step (1 ) in figure 1 herein the extraction step
  • step (2) in figure 1 the crystallization step
  • the residual amount of ethyl acetate in the curcuminoid crystal powder is said to be 300 20 ppm. It is not explained how the residual amount of the ethyl acetate has been measured.
  • EP1313808B1 Chor. Hansen A/S
  • GB2132205A J.V.
  • curcumin is known for its antitumor, antioxidant, antiarthritic, anti-amyloid and anti-inflammatory properties. Accordingly, there are numerous prior art documents that relates to special 35 pharmaceutical relevant compositions of curcumin. As known to the skilled person, an active pharmaceutical ingredient (API) shall generally be in a very pure form. Accordingly, the art also describes very detailed and sophisticated methods to make curcumin preparations to be used in curcumin pharmaceutical compositions. An example of such a detailed and sophisticated method is described in e.g. US5861415, which relates to use of a special curcuminoid composition for neutralizing free radicals in a patient. As evident to the skilled person, the economic value/profit for a pharmaceutical curcuminoid product is generally significantly higher than for a natural curcuminoid food colouring product.
  • the problem to be solved by the present invention may be seen in the provision of a turmeric curcuminoid composition that comprises less unwanted impurities as compared to prior art comparable turmeric compositions.
  • the turmeric composition may in particular be used for food/feed colouring.
  • the solution of the present invention may essentially be seen in the removal of residual organic solvents in particular residual organic solvents that have been used as organic solvents in the extraction step (1 ) of figure 1 herein.
  • the residual organic solvents are unwanted impurities.
  • the present inventors analysed residual solvent content in a number of commercially available turmeric oleoresin and curcuminoid crystal powder compositions. The results are shown in table 1 of example 2 herein.
  • all tested products comprised significant amounts of e.g. the extraction solvent acetone.
  • acetone is used as extraction solvent and not in the subsequent so-called crystallization process.
  • the extraction solvent is removed by evaporation. Consequently, one would prima facie NOT have expected to identify significant amount of acetone in commercially available turmeric oleoresin and curcuminoid crystal powder compositions.
  • example 1 is based on JECFA well known standard described analytical methods - except that N,N-dimethyl-formanide (DMF) is used as a solvent in stead of water.
  • DMF N,N-dimethyl-formanide
  • the difference is that DMF can dissolve the curcuminoid crystals, which water can not do in a significant way.
  • DMF can dissolve the curcuminoid crystals, which water can not do.
  • a substantial amount of the residual solvents identified by use of DMF as solvent are in fact solvents trapped within curcuminoid crystals lattice. Since water is not able to dissolve the curcuminoid crystals, use of water as solvent will not be able to measure such curcuminoid crystals trapped solvents, since in water the un-dissolved crystals will "keep" the trapped solvents within it and it will therefore not be identified/measured.
  • the so-called crystallization step (step (2) of figure 1 ) is in fact not a "real" crystallization - but may be seen as simply the separation of already existing curcuminoid crystals from the complex matrix of the turmeric oleoresin.
  • the theory is that the curcuminoid crystals are mainly already formed during the evaporation of the extraction solvent step (step (1 ) (ii) of figure 1 ) and NOT during the so-called crystallization step (step (2) of figure 1 ).
  • turmeric oleoresin Today there is industrially produced a lot of bulk turmeric oleoresin in countries such as India. This turmeric oleoresin is distributed to many different production facilities to make e.g. relatively pure curcuminoid crystal powder compositions. From the present invention, it is evident that the majority of this - in e.g. India - bulk produced turmeric oleoresin will actually be contaminated with acetone without anyone actually knows it. As explained this acetone will then also be present - trapped in the crystals - in the final curcuminoid crystal powder products - also without anyone actually is aware of it today.
  • turmeric oleoresin and curcuminoid crystal powder compositions with very low amounts of residual solvents.
  • the present inventors developed novel methods that essentially are based on crystallisation of the curcuminoid in the oleoresin matrix without the presence of the extraction solvent.
  • the inventors identified that one may remove the extraction solvent relatively rapidly - before crystallisation has started - and crystal formation can then under adequate conditions (e.g. stirring etc) be made in the oleoresin matrix as such.
  • the curcuminoid crystals will be formed in the oleoresin matrix without the presence of the extraction solvent (e.g. acetone) and thereby one can get a low solvent oleoresin with essentially no residual solvent (e.g. acetone) trapped within the crystals.
  • the extraction solvent e.g. acetone
  • a first aspect of the invention relates to a low solvent turmeric oleoresin composition that comprises essential oils and from 25 to 50% curcuminoids, characterised by that the turmeric oleoresin comprises from 1 ppm to 100 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin and wherein the amount of trapped residual organic solvent(s) are measured by the analytical method as described in example 1 herein, wherein the amount of residual organic solvents are measured by making two separate measurements - one using water as solvent and in the second N,N-dimethyl-formanide (DMF) as solvent - and the amount of residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin is then the difference between the amount measured by using DMF as solvent minus the amount measured by using water as solvent.
  • DMF N,N-dimethyl-formanide
  • example 1 is based on JECFA well known standard described analytical methods - except that N,N-dimethyl-formanide (DMF) is used as a solvent in stead of the "official" water.
  • DMF N,N-dimethyl-formanide
  • DMF can dissolve the curcuminoid crystals, which water can not do in significant way. Accordingly, when DMF is used one measures total amount of residual solvents in the sample (solvent trapped in crystals plus "extra free” solvent) and when water is used one only measures the "extra free” solvent.
  • example 1 the analytical method of example 1 can easily be made and based on this can the skilled person routinely identify the total amount of residual organic solvent(s) trapped within the curcuminoid crystals.
  • the separation may e.g. be done by addition of a suitable solvent (e.g. isopropanol) to the low solvent oleoresin - stirring until homogeneous solution is obtained - following by filtration to isolate the curcuminoid crystals.
  • a suitable solvent e.g. isopropanol
  • the other components e.g. oils
  • the curcuminoid crystals flouting around (suspended) in the homogeneous solution are easily isolated/separated by filtration - the crystals will be recovered on the filter and the oils etc will simply pass through the filter. See e.g. working example 4 herein for further details.
  • a second aspect of the invention relates to a low solvent turmeric curcuminoid crystal powder composition that comprises at least 80% curcuminoids by weight of the composition, characterised by that the turmeric curcuminoid crystal powder comprises from 1 ppm to 200 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the powder and wherein the amount of trapped residual organic solvent(s) are measured by the analytical method as described in example 1 herein, wherein the amount of residual organic solvents are measured by making two separate measurements - one using water as solvent and in the second N,N-dimethyl-formanide (DMF) as solvent - and the amount of residual organic solvent(s) trapped within the curcuminoid crystals present in the powder is then the difference between the amount measured by using DMF as solvent minus the amount measured by using DMF as solvent.
  • DMF N,N-dimethyl-formanide
  • a third aspect of the invention relates to a process for making a low solvent turmeric oleoresin composition of first aspect, wherein the process comprises following steps:
  • a fourth aspect of the invention relates to a process for making a low solvent turmeric oleoresin composition of first aspect, wherein the process comprises following steps: (i): starting with a turmeric plant rhizome composition comprising curcuminoids; (ii): extracting the curcuminoids by use of a suitable organic extraction solvent; (iii): removing the solvent used in (b) to get a oleoresin sample essentially free from the solvent used in (b);
  • the process of the third and fourth aspect are both based on crystallisation of the curcuminoid in the oleoresin matrix essentially without the presence of the extraction solvents. Without being limited to theory, it is believed that the present invention for the first time describes this principle.
  • a fifth aspect of the invention relates to a process for making a low solvent turmeric curcuminoid crystal powder composition of second aspect, wherein the process comprises following steps:
  • the process of the fifth aspect is based on that one may simply separate the - in the oleoresin - already formed crystals (without trapped solvent) from the other components (e.g. oils) of the oleoresin.
  • the present invention for the first time describes that the crystal are already present/formed in the oleoresin.
  • a sixth aspect of the invention relates to a use of a (I) a low solvent turmeric oleoresin composition of first aspect; or (II) a low solvent turmeric curcuminoid crystal powder composition of second aspect; for colouring a product of interest.
  • a seventh aspect of the invention relates to a low solvent turmeric oleoresin composition of the first aspect obtainable by the process of the third aspect or the process of the fourth aspect.
  • An eight aspect of the invention relates to a low solvent turmeric curcuminoid crystal powder composition of the second aspect obtainable by the process of the fifth aspect.
  • Fig. 1 It illustrates the general prior art plus some of the novel technical discoveries as described herein.
  • an object of an aspect of the invention e.g. a "turmeric oleoresin composition of first aspect” it should herein be understood as it refers to the object (e.g. turmeric oleoresin) of the aspect (e.g. first aspect) plus all the herein described related embodiments to this aspect.
  • a "turmeric oleoresin composition of first aspect” it should herein be understood as it refers to the object (e.g. turmeric oleoresin) of the aspect (e.g. first aspect) plus all the herein described related embodiments to this aspect.
  • turmeric oleoresin is well known to the skilled person.
  • a turmeric oleoresin composition comprises essential oils and typically from 25 to 50% curcuminoids.
  • the ratio of the three curcuminoids in the turmeric oleoresin is typically: curcumin about 50-70%, demethoxy curcumin about 10-30% and bis-demethoxy curcumin about 10-30% the sum of the three compounds being 100%.
  • a turmeric oleoresin is made by solvent extraction of the curcuminoids from curcuminoids containing plants.
  • the plant specie include a plant of the genus Curcuma.
  • Useful curcuminoid producing species of this genus include Curcuma longa L, C. aromatica Salisb., C. amada Roxb., C. zedoaria Rose, and C. xanthorrhiza Roxb.
  • the weight of the low solvent turmeric oleoresin composition of the first aspect may be from 10 kg to 500 kg, such as from 20 kg to 200 kg.
  • the weight relates to the weight of the composition as such within a suitable package.
  • turmeric curcuminoid crystal powder is well known to the skilled person.
  • the turmeric curcuminoid crystal powder is derived from the turmeric oleoresin, i.e. it is made by use of turmeric oleoresin as starting material (see e.g. figure 1 herein).
  • the low solvent turmeric curcuminoid crystal powder composition of second aspect is a composition that comprises at least 90% curcuminoids by weight of the composition.
  • Commercial curcuminoid crystal powder compositions typically comprise at least 90% curcuminoids by weight of the composition.
  • the ratio of the three curcuminoids in the turmeric curcuminoid crystal powder is typically: curcumin about 50-70%, demethoxy curcumin about 10-30% and bis-demethoxy curcumin about 10-30% the sum of the three compounds being 100%.
  • turmeric curcuminoid crystal powder compositions are normally produced in large scale - e.g. the production fabric makes a large scale bulk composition.
  • the weight of the low solvent turmeric powder composition of the second aspect may be from 10 kg to 500 kg, such as from 20 kg to 200 kg.
  • the weight relates to the weight of the composition as such within a suitable package. Residual organic solvent(s) - amounts (ppm):
  • the first aspect relates to a low solvent turmeric oleoresin characterised by that the turmeric oleoresin comprises from 1 ppm to 100 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin.
  • the low solvent turmeric oleoresin comprises from 1 ppm to 75 ppm, more preferably from 1 ppm to 50 ppm, even more preferably from 1 ppm to 30 ppm and most preferably 1 ppm to 20 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin.
  • the lower limit of "1 ppm" may be seen as relating to that one in practice can not remove all residual solvents. If e.g. acetone is used for the extraction one will at the end of the day have at least very small amounts of such residual acetone in a final curcuminoid composition as described herein.
  • the range is from 1 ppm to 200 ppm.
  • the upper range is a bit higher than for the turmeric oleoresin - this is logical due to in the powder the essential oils etc are removed and thereby concentrated - giving a higher ppm number for the similar absolute amount of solvent(s).
  • the low solvent turmeric curcuminoid crystal powder comprises from 1 ppm to 150 ppm, more preferably from 1 ppm to 100 ppm, even more preferably from 1 ppm to 60 ppm and most preferably 1 ppm to 40 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin.
  • ppm means parts-per-million.
  • the ppm numbers here relates to the total amount of solvent(s) trapped within the curcuminoid crystals - i.e. there may be one or more different types of solvents (e.g. acetone, EtAc etc).
  • Residual organic solvent(s) preferred types:
  • turmeric colour compositions are commercially used solvents such as acetone, ethyl methyl ketone, ethyl acetate (EtAc), methanol, ethanol, dichloromethane, isopropanol , hexane, n-butanol and/or ethylene dichloride (EDC).
  • solvents such as acetone, ethyl methyl ketone, ethyl acetate (EtAc), methanol, ethanol, dichloromethane, isopropanol , hexane, n-butanol and/or ethylene dichloride (EDC).
  • the 1 ppm to 100 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin of the first aspect includes at least one solvent selected from the group consisting of acetone, ethyl methyl ketone, ethyl acetate (EtAc), methanol, ethanol, dichloromethane, isopropanol , hexane, n-butanol and ethylene dichloride (EDC).
  • EtAc ethyl methyl ketone
  • EtAc ethyl acetate
  • methanol ethanol
  • dichloromethane isopropanol
  • hexane hexane
  • n-butanol ethylene dichloride
  • This embodiment should be understood as a limitation of the first aspect in the sense that measurable amounts of at least one of above listed solvents shall be present as a residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin.
  • solubility of curcumin in some organic solvents is: acetone > ethyl methyl ketone > ethyl acetate > methanol > ethanol > 1 ,2 dichloroethane (EDC) > isopropanol > ether > benzene > hexane.
  • acetone is normally used as an extraction solvent [step 1 (i) of figure 1 herein] due to the solubility of curcumin is high in acetone.
  • the 1 ppm to 100 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin of the first aspect includes at least one solvent which has a higher solubility of curcumin as compared to the solubility of ethyl acetate.
  • the at least one solvent which has a higher solubility of curcumin as compared to ethyl acetate is one or more solvent(s) that in total is/are present in an amount of 1 ppm to 50 ppm or in an amount of 1 ppm to 25 ppm.
  • the 1 ppm to 100 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin of the first aspect includes at least the solvent acetone.
  • acetone is present it is typically present in an amount of 1 ppm to 50 ppm, more preferably in an amount of 1 ppm to 25 ppm and even more preferably in an amount of 1 ppm to 10 ppm.
  • the residual solvents trapped in a oleoresin will at least to some degree also still be present in a low solvent turmeric curcuminoid crystal powder as described herein - since such a crystal powder preferably are made by a "simply” separating already crystal from the oleoresin.
  • the 1 ppm to 200 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the powder of the turmeric curcuminoid crystal powder of second aspect includes at least one solvent selected from the group consisting of acetone, ethyl methyl ketone, ethyl acetate (EtAc), methanol, ethanol, dichloromethane, isopropanol, hexane, n-butanol and ethylene dichloride (EDC).
  • the 1 ppm to 200 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the powder of the second aspect includes at least one solvent which has a higher solubility of curcumin as compared to ethyl acetate.
  • the at least one solvent which has a higher solubility of curcumin as compared to ethyl acetate is one or more solvent(s) that in total is/are present in an amount of 1 ppm to 100 ppm, more preferably in an amount of 1 ppm to 50 ppm.
  • the 1 ppm to 200 ppm of residual organic solvent(s) trapped within the curcuminoid crystals present in the powder of the second aspect includes at least the solvent acetone. If acetone is present it is typically present in the powder in an amount of 1 ppm to 100 ppm, more preferably in an amount of 1 ppm to 50 ppm and even more preferably in an amount of 1 ppm to 20 ppm.
  • the process of the third and fourth aspect are both based on crystallisation of the curcuminoid in the oleoresin matrix essentially without the presence of extraction solvents.
  • the present invention for the first time describes this principle. Based on this principle is in working example 3 described how to prepare low solvent turmeric oleoresin compositions with very low amounts of residual solvents.
  • step (a) started with a turmeric oleoresin composition that comprises significant amounts of residual organic solvent(s) trapped within the curcuminoid crystals present in the oleoresin.
  • turmeric oleoresin composition This may herein be considered a prior art turmeric oleoresin composition.
  • the skilled person were - before the present disclosure - not aware of the problem with the significant presence of e.g. extraction solvents like acetone in commercially relevant turmeric oleoresin compositions.
  • steps (b) to (e) is the trapped residual solvent removed to get a low solvent turmeric oleoresin composition of the first aspect.
  • step (b) is curcuminoid crystals dissolved in a suitable solvent.
  • this step (b) is to dissolve the crystals it is preferred to use a solvent wherein the solubility of curcumin is relatively high such as e.g. acetone.
  • acetone is used in example 3 herein.
  • another suitable solvent as known to the skilled person - plus one may use a combination of two or more different solvents.
  • step (b) one should dissolve the oleoresin and thereby the crystals within it under suitable conditions.
  • suitable conditions may include stirring, adequate temperature (e.g. room temperature) under atmospheric pressure.
  • step (c) is removed the solvent used in (b) to get a sample essentially free from the solvent used in (b).
  • This step (c) shall be seen in conjunction with step (d) - saying that the crystallization shall take place without the presence of significant amount of the solvent used in step (b).
  • step (c) is the solvent relatively rapid removed - to get it removed before significant start of crystallisation in step (d).
  • the solvent may be relatively rapid removed by using an adequate temperature (e.g. from 8O 0 C to 110 0 C) under suitable vacuum conditions for a suitable time (e.g. from 20 to 80 minutes).
  • a suitable time e.g. from 20 to 80 minutes.
  • the skilled person can optimize the conditions of step (c) to get solvent removed.
  • step (d) is initiated the crystallisation so the curcuminoid crystals are created without presence of significant amount of the solvent used in (b) - i.e. the crystals will comprise low amounts of trapped solvents.
  • start of crystallisation As known to the skilled person a number of factors may influence start of crystallisation. For instance one may add seeds crystals to catalyze the start of crystallisation.
  • step (d) appropriate stirring of the sample is suitable way to properly initiate the crystallisation in step (d).
  • a sample after step (c) i.e. a desolventised oleoresin
  • viscosity lowering substance such as propylene glycol (PG)
  • step (d) was done by adding propylene glycol or by increasing stirring temperature to 70-80°C.
  • viscosity lowering substance such as propylene glycol (PG)
  • PG propylene glycol
  • an alternative different viscosity lowering substance may for example be mineral oil, ethylene glycol, glycerol etc.
  • step (e) is continued crystallisation until it is essentially completed and thereby getting the low solvent turmeric oleoresin composition of first aspect.
  • step (i) started with a turmeric plant rhizome composition comprising and in step (ii) made extracting the curcuminoids by use of a suitable organic extraction solvent.
  • steps (i) and (ii) may herein be seen as standard steps made according to the art - i.e. correspond to step (1 ) (i) as illustrated in figure herein.
  • - acetone may be a good extraction solvent.
  • Steps (iii) and (iv) may be seen as the novel important steps and technically essentially corresponds to steps (c) and (d) of the third aspect as discussed above. Accordingly, the preferred embodiments/details for steps (c) and (d) are also preferred embodiments/details for these steps (iii) and (iv).
  • step (v) technically essentially corresponds to steps (e) of the third aspect. Accordingly, the preferred embodiments/details for step (e) are also preferred embodiments/details for this step (v).
  • the process of the fifth aspect is based on that one may simply separate the - in the oleoresin - already formed crystals (without trapped solvent) from the other components (e.g. oils) of the oleoresin.
  • the present invention for the first time describes that the crystal are already present/formed in the oleoresin.
  • the separation may e.g. be done by addition of a suitable solvent (e.g. isopropanol) to the low solvent oleoresin - stirring until homogeneous solution is obtained - following by filtration to isolate the curcuminoid crystals.
  • a suitable solvent e.g. isopropanol
  • step (A) is started with a low solvent turmeric oleoresin of the first aspect.
  • step (B) is isolated, by use of a suitable organic solvent, turmeric curcuminoid crystals from the turmeric oleoresin of step (A).
  • isolated could alternatively have been termed “separating”, i.e. separating the crystals from other parts (e.g. oils) of the oleoresin.
  • suitable solvents are ethyl acetate, methanol, ethanol, isopropanol or n- butanol.
  • suitable examples are ethyl acetate, methanol, ethanol, isopropanol or n- butanol.
  • a mixture of methonal/hexane also worked well.
  • step (B) by be performed by adding suitable solvent to the low solvent turmeric oleoresin of step (A); mixing at adequate temperature to get a homogenous mixture with the crystals suspended in the mixture and isolating the crystals by e.g. filtration.
  • Step (B) Based on the information herein (see e.g. example 4) and common general knowledge the skilled person can routinely perform this Step (B).
  • step (C) is simply dried the in step (B) isolated turmeric curcuminoid crystals to get the turmeric curcuminoid crystal powder colour composition of the second aspect. This is a routine step.
  • the sixth aspect of the invention relates to a use of a (I) a low solvent turmeric oleoresin composition of first aspect; or (II) a low solvent turmeric curcuminoid crystal (TCC) powder composition of second aspect; for colouring a product of interest.
  • a (I) a low solvent turmeric oleoresin composition of first aspect or (II) a low solvent turmeric curcuminoid crystal (TCC) powder composition of second aspect; for colouring a product of interest.
  • TCC low solvent turmeric curcuminoid crystal
  • the product to be coloured may e.g. be a food or feed product. It may be a solid or liquid food/feed product.
  • the products may be in any conventional form including products in tablet or capsule dosage forms that may comprise separate compartments which can be coloured separately.
  • the product may be textile.
  • textile refers to any filament, fibre or yarn that can be made into fabric or cloth and used in e.g. wearing apparel, household linens and beddings, upholstery, draperies and curtains, wall coverings, rugs and carpets.
  • the product may also be a medical/pharmaceutical product, wherein the low solvent turmeric composition as described herein beside the colouring effect could also have a medical/pharmaceutical effect.
  • An example could be an antitumor, antioxidant, antiarthritic, anti-amyloid or anti-inflammatory effect as known in the art.
  • a separate aspect of the invention relates to use of a
  • the analytical method of this example 1 is based on JECFA well known standard described analytical methods - except that N,N-dimethyl-formanide (DMF) is used as a solvent in stead of the "official" water.
  • DMF N,N-dimethyl-formanide
  • the difference is that DMF can dissolve the curcuminoid crystals, which water can not do in significant way. Accordingly, when DMF is used one measures total amount of residual solvents in the sample (solvent trapped in crystals plus "extra free” solvent) and when water is used one only measures the "extra free” solvent. Consequently, by measuring the difference between the amount measured by using DMF as solvent minus the amount measured by using water as solvent - one identifies the amount of residual organic solvent(s) trapped within the curcuminoid crystals.
  • results of the "water” reference measurement may be seen as results the skilled person probably prima facie could have expected - i.e. results that show some relatively limited residual solvents in the commercial samples.
  • results of table 1 were very surprising for the present inventors.
  • the results of table 1 show that there are significant residual organic solvent(s) trapped within the curcuminoid crystals of the analysed commercially available turmeric colour compositions.
  • EXAMPLE 3 Making low solvent turmeric oleoresin composition followed by separation of crystals to get a turmeric curcuminoid crystal powder composition
  • Residual solvents Measured as described in example 1 using DMF as solvent. .
  • the technique developed consists in dissolving the oleoresin turmeric (ORT) in acetone (the best solvent for curcumin, and with the lower boiling point of the solvents allowed in EU, except dichloromethane which is out of question being an halogenated), and removing it as fast as possible, to avoid the start of crystallisation until the solvent is removed.
  • ORT oleoresin turmeric
  • ORT (ca. 20 g) was dissolved in 200 ml. acetone, different amounts of propylene glycol were added, and the solution was desolventised for 30-60' minutes at 90 or 100°C under vacuum (500 mm Hg) and air current (1 L/min).
  • the residual solvent of oleoresins treated this way ranged from 2 to 7 mg/Kg acetone when PG was present, and 10-30 mg/Kg in 25 40% ORT without PG.
  • desolventised oleoresins are initially dark brown and homogeneous, and were left at ambient temperature alternatively with and without stirring, When stirring was applied, it took 10-15' to see visible turbidity and crystallisation, while in the samples stored without stirring it takes several days to see the first crystals.
  • the crystallisation is very advanced when we add solvent to obtain the crystals, so very little solvent is trapped, while in other cases part of the crystallisation takes place when the solvent reduces the viscosity and then the crystals contain a lot of solvent.
  • the tables 3 and 4 below show the results of e.g. yield of colour and residual solvent in the curcuminoid crystal powder compositions.
  • the crystals were separated from the low solvent oleoresin - made as described above in this example - by the separation method as described in the material and methods section of this example 3 - i.e. a separation method using methanol/hexane.
  • ORT+PG stirring. Ambient temperature of table 3 and the term “ORT + stirring. HOT temperature” of table 4 refers to how the low solvent oleoresin was made as described above.
  • the target yield of curcumin crystals from the experiments was that obtained from the original oleoresins: T30-01-01 : 63-68% T40-01 -02: 59-60%
  • the crystals were then separated from the low solvent turmeric oleoresin and there was obtained low solvent curcuminoid crystal powder compositions.
  • the starting material was turmeric oleoresin compositions with curcuminoid crystals present in the oleoresin.
  • the experiments included an addition of solvent to the oleoresin and stirring at ambient temperature until a homogeneous suspension was achieved and then filtrated. Filtration of the homogeneous suspension was performed and the crystals were recovered from the filter. After recovery the crystals were dried at 1 10 0 C for one hour.
  • the solvent simply removes essential oils/resins from the precipitated crystals, and the crystals can be separated from the mother liquid.
  • the crystals are already formed in the oleoresin. One can only expect to isolate these crystals as turmeric powder. It is not possible to isolate more colour as powder. The time needed to free the crystals is the time it takes to "dissolve" the oleoresin in the solvent. None is gained by prolonged contact with the solvent.
  • lsopropanol is a good solvent for production of curcumin powder.
  • the ratio used today gives a wet filter cake that needs washing with fresh solvent, which means loss of product.
  • the product is legal in the US.
  • n-butanol would work just as well as isopropanol but the solvent seems not to be used commercially.
  • Methanol can be used to produce legal powders for both the EU and the US. The yield would be lower than when using isopropanol.
  • Ethanol could be used instead of methanol with a higher yield than for methanol (but still lower than for isopropanol) giving legal powders for both the EU and the US.
  • Ethyl acetate can be used to produce legal powders for the EU. The yield would be lower than when using isopropanol. Actually, the yield will be the lowest of all the solvents.
  • Methanol/hexane can be used to produce powders of high purity and maximum yield legal for both the EU and the US.
  • the system, including the washing, should be adapted to each individual oleoresin.
  • step (A) of the fifth aspect a low solvent turmeric oleoresin as described herein
  • step (B) and (C) of the fifth aspect - as done in this example 4 - then one gets a low solvent turmeric curcuminoid crystal powder composition as described herein.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Medicines Containing Plant Substances (AREA)

Abstract

Cette invention concerne des compositions curcuminoïdes/jaunes de curcuma contenant une très faible quantité de solvants résiduels, des procédés de fabrication de ces compositions de curcuma à faible teneur en solvant et leur utilisation, par exemple dans la coloration d'un produit alimentaire.
PCT/EP2009/060630 2008-08-29 2009-08-17 Compositions jaunes de curcuma contenant une faible quantité de solvant résiduel Ceased WO2010023128A1 (fr)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
US20160151440A1 (en) * 2013-08-19 2016-06-02 Aurea Biolabs Private Limited A Novel Composition of Curcumin with Enhanced Bioavailability
WO2018020302A1 (fr) * 2016-07-29 2018-02-01 Synthite Industries Limited Procédé d'extraction et d'isolement de curcuminoïdes
CN112898359A (zh) * 2019-12-03 2021-06-04 晨光生物科技集团股份有限公司 一种低溶残晶体的制备方法

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US3340250A (en) * 1963-09-18 1967-09-05 Griffith Laboratories Extracting values from turmeric
GB2132205A (en) * 1982-12-15 1984-07-04 Mccormick & Co Inc Colouring agents
ES2081264A1 (es) * 1994-08-03 1996-02-16 A C Pharmaceutical Internation Procedimiento para la obtencion de extractos apolares y polares de curcuma y aplicaciones de los mismos.
EP1837030A1 (fr) * 2006-03-09 2007-09-26 INDENA S.p.A. Complexes phospholipidiques de curcumin ayant une biodisponibilité améliorée

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DE658958C (de) * 1933-10-10 1938-04-20 Temmler Werke Verfahren zur Gewinnung der Gesamtpigmentstoffe der Curcuma-Drogen
US3340250A (en) * 1963-09-18 1967-09-05 Griffith Laboratories Extracting values from turmeric
GB2132205A (en) * 1982-12-15 1984-07-04 Mccormick & Co Inc Colouring agents
ES2081264A1 (es) * 1994-08-03 1996-02-16 A C Pharmaceutical Internation Procedimiento para la obtencion de extractos apolares y polares de curcuma y aplicaciones de los mismos.
EP1837030A1 (fr) * 2006-03-09 2007-09-26 INDENA S.p.A. Complexes phospholipidiques de curcumin ayant une biodisponibilité améliorée

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160151440A1 (en) * 2013-08-19 2016-06-02 Aurea Biolabs Private Limited A Novel Composition of Curcumin with Enhanced Bioavailability
WO2018020302A1 (fr) * 2016-07-29 2018-02-01 Synthite Industries Limited Procédé d'extraction et d'isolement de curcuminoïdes
CN112898359A (zh) * 2019-12-03 2021-06-04 晨光生物科技集团股份有限公司 一种低溶残晶体的制备方法

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