Field of the Invention
The present invention relates to an improved process for the preparation of curcuminoids
from turmeric (Curcuma longa L.) oleoresin.
Background of the Invention
Turmeric (Curcuma longa L.) belongs to the family Zingiberaceae which is the largest family
of the order Zingiberales found through out the tropics but is predominantly Asian: The wellestablished,
rhizomatous, aromatic economic spices of this family are the genus Zingier
(ginger), Curcuma,(turineric), Alpinia (galangal) and Icaemfera. Turmeric belong to
rhizomatous Curcuma species and have been lcnown for their flavouring and colouring
properties. Turmeric is grown mainly in India, China, Indonesia, Malaysia, Sri%Lanka,
. -
Jamaica and Peru. Turmeric is one of the major spices grown in India. The annual production
was 8,30,200 MT from an area of 1,74,600 hectares in 2010-1 1.. The export was 51,500 MT
during 2010-1 1.
After harvesting, the rhizomes are subjected to a process comprising the steps of 1)
coolcing in water and 2) drying in the sun to produce a product of fairly uniform colour. The
cured turmeric fingers so obtained are hard, brittle and yellow in colour due to.the presence
of the phenolic compounds called curcuminoids. The curcuminoids, which are present in an
oily cell phase, are mainly curcumin (reddish 'orange) with two methoxy group,
demethoxycurcu~nin (orange-yellow) with one methoxy group and bis - demethoxycurcu~nin
(yellow) without any methoxy group. The cured turmeric is marketed as bulbs and fingers for
use as a spice and also as a bulk raw material for commercial processing. As used herein,
the expression curcumin crystals obtained from oleoresin includes material derived from
plant species include plants of the genus Czlrcuma longa L, C.aromaticaSalisb,
C.amadaRoxb., C. zedoarialiosc. andxanthorrhizaRoxb A curcu~ninoidsc ontaining starting
material can be selected that has one of the above mentioned species I mixture of the species.
for example Curcurna longa L. includes varieties like aleppy, Salem, Mysore local,
Chamarajanagara, North eastern region Lakadang etc.
The commercially important 'turmeric products are turmeric powder, debittered. turmeric
powder, oleoresin and curcuminoids. Oleoresin extracted from turmeric powder using
solvents such as methyl ethyl ketone, acetone, ethylene dichloride, comprises essential oil,
fatty oil and curcuminoids (30-50% by weight). However the essential oil, fraction of the
turmeric/oleoresin has a very strong flavour and bitter taste, and as such is not desirable for
colouring food products. In order to meet the increasing demand for a flavour and taste free
curcuminoids (neutraceuticals) rich product, the oleoresin may be processed further. Thus,
the oleoresin is subjected to crystallization step using organic solvents to obtain curcuminoids
rich (90-95 %) powder of a relatively high purity in respect of curcuminoids. The residual
material that remains after the separation of curcuminoids crystals called mother liquor or
curcumin removed turmeric oleoresin (CRTO) is a by product/industrial waste which contain
about 15-16% non crystalisablecurcuminoids. However, this residual material is unsuitable as
a colouring agent due to the extensive undesirable taste, flavour and relatively low colouring
effect in food .applications. Hence turmeric powder or its oleoresin is not directly i~tilized as.
colourant commercially. Curcuminoids (30-50ppm) is a promising substitute for the synthetic.
colourstartrazine (80-100ppm) and sun set yellow (30-50~~1in )th e food products.
There are several patents on preparation of curcuminoids, curcuminoids -rich
fractions and its application. The Indian 'patent No. 1689/DEL/10 provides a process for the
preparation of bland turmeric powder (colourant) with enhanced curcu~ninoids after
selectively removing the non-colouring substances from turmeric for food applications. The
Indian patent No. 401/DEL/01 provides a process for the .preparation of formulations using
turmeric oleoresin for food applicatidn and IP No.l68/DEL/02, states that the method of
recovery of curcuminoids from industrial waste (CRTO) and IP194592 provides methods for
pigment (curcuminoids) stabilization or prevention of fading. JP 2007037448 gives a method
. . for reducing bitter taste of turmeric extract. W0200704358 provides a process for producing
enriched fractions of tetrahydroxy-curcumin frorn the extracts of Czrrcuma longa. US41 63803
on eliminating the bitter principal from turmeric or extractives of turmeric such as solvent
extracts or debittered solvent extracts by the addition of glycine. I11 US6497908 patent
entitled turmeric containing coolting oils and fats, oil soluble ingredients of turmeric, which
are eluted from a rhizome of turmeric and low molecular substances generated by I
decomposing macromolecular substances in the turmeric. JP 200312578 provided a process
to prepare turmeric alcohol extract to prepare refreshing beverages. Hover there is no patents
on preparation of high purity curcumini.e 98-100%. I . . I
I Turmeric is conventionally processed by the solvent extraction process using solvents
like acetone or.' ethylene dichloride to obtain a resinous mass called oleoresin. The
conventional oleoresin has 25-40% curcumin, the rest being volatile oil, fatty oil and resinous
constituents. Pure curcumin is recovered from the oleoresin by crystallization method using
appropriate organic solvents to overall recovery of curcumin being 50-55% on raw material
basis (turmeric powder). Thereof 45-50% of curcumin remains unrecovered in the mother
liquor called CRTO (curcumin removed turmeric oleoresin). Hence, there is a need to
develop alternative methods to recover maximum curcuminoids frorn turmeric oleoresin in
almost pure form. The present invention, relates to the preparation of high purity
curcuminoids (colourant) from turmeric oleoresin is free from non-colouring constituents
viz., bitter principles, essential oil, fixed oil, resinous matter etc. This improved process for
the preparation of curcumin powder containing 98-100% curcuminoids from turmeric'
(Curcuma longa L.) oleoresin is achieved for the first time using acetic acid (edible).
-
Summary of invention
Accordingly the present invention pertains- to "An improved process for the
preparation of curcuminoidsfrom turmeric (Curcurnu longu L.) oleoresin" the method
comprising the step of (i) defatting of turmeric oleoresin using hydrocarbon solvent to yield
defatted oleoresin and filtrate (ii) subjecting the defatted turmeric oleoresin for crystallization
using acetic acid to yield curcuminoids crystals and filtrate (iii) further washing of the
curduminoids crystals with acetic acid followed by water (iv) drying of the curcuminoids
crystals at low temperaturelshade to yield 98- 100% pure curcuminoids (v) distillation of
filtrates' from step (i) and step (ii) to obtain turmeric flavourant (volatile and non-volatile
oils) and curcurnin removed turmeric resin (CRTR) containing 10-15% non crystallisable
curcuminoids.
Brief description of figures
. .
.Fig 1 : Flow chart of the process
Object of the invention
A major objective of this present invention is to provide "An improved process for the I
preparation of curcuminoidsfrom turmeric (Curcuma longa L.) oleoresin" without using . , I organic solvents which results in the co~ninerciallyv aluable. yellow crystals (colourant) with
98-100% curcuminiods. As used the expression "curcuminoids (colourant) with high purity
curcuminoids " includes colouring material containing analogous viz. curcurnin(C),
demethoxycurcumin(DMC) and bis-detnethoxycurcumin(BDMC) in the range of 76.9-79.8,
16.5-19.1, and. 2.9-5.3%. The curcumin, De-methoxy curcumin 'and Bis- . . I
DemethoxyCurcumin were isolated and quantified by TLC in pure for'in and characterized by
HPLC and ' ~ n u l e a r maganeticresonancespectroscopy( 'HNMR) in our laboratory. The
curcumin and its analogs demethoxycurcumin and bis-demethoxycurcurnin were present' in
the ratio of 5.0:1,.0:0.2 in curcuminoids prepared by this new process. Also the percentage
curcuminoids content were determined by spectrophotometric method (AOAC) and found ,
that the prepared curcuminoids content by. improved method was 100% when compare to
curcuminoids content of standard 95.0% (Sigma).
Accordingly "An improved process for the preparation of curcuminoidsfroln turmeric
(Curcurnu longa L.)oleoresin "is provided.
1. The extraction steps in'the process of the present invention includes:
a) defatting of turmeric oleoresin with petroleuln ether 60-80°C in extraction vessel
using electric stirrer at room temperature, followed by filtration through sintered
funnel under vacuum to yield defatted oleoresin residue and filtrate.
b) drying of the defatted oleoresin residue from step (a) in drier at 40-50°C for 2-3
'. hr. to yield defatted oleoresin powder,
c) loading of the defatted oleoresin powder obtained from step [b] and acetic acid in
to the crystallisation vessel maintaining the ratio of material to acid (1 : 1 to 1 : lo),
mixing the mass using magnetic stirrer for a period of 1.0 - 3.0 h followed by
filtration through sintered filnnel under vacuuln to obtain curcumin. crystals and
filtrate. This process was repeated (twolthree times) maintaining the material to
acetic acid ratio preferably 1:3 each time.
d) washing of the crystalls from step (c) with water to remove any water soluble
impurities viz. acetic acid etc.
e) drying of the cfystals fiom step (d) at 40-50°C in mechanical drier to yield high
purity curcuminoids crystals (98-1 00%).
f ) subjecting the filtrates from step [a] and [dl separately to desolventization process
initially under atmospheric pressure till up to 95 % of the solvent is recovered and
subsequently under vacuum to yield . byproducts turmeric flavourant and
curcuminoidsremoved turmeric resin (CRTR)respectively.
In an embodiment of the present invention it provides an improved process for the
preparation of curcuminoids from turmeric (Cz~rcunza longa L.) oleoresin colnprising
steps :
a) Providing turmeric oleoresin;
b) dissolving oleoresin obtained in step a with solvent in an extraction vessel
followed by filtration by known methods to obtain defatted oleoresin residue and
filtrate;
c) drying the defatted oleoresin residue as obtained from step (b) in drier at 40-50°C
for 2-3 hr,
d) characterized in adding acetic acid to the powder obtained in step (c),
e) loading the lnixture obtained in step (d) to the crystallisation vessel in the ratio of
material to acid ranging from 1 : 1 to 1 : 10;
f) mixing the mass obtained in step (e)'for a period of 1.0 - 3.0 hours followed by
filtration under vacuum to obtain curcumin crystals and filtrate.
g) washing the curcumin crystals obtained in step (f) with water to remove any
water soluble impurities;
h) drying of the curculnin crystals obtained in step (g) at 40-50°C to obtain
curcuminoids;
i) optionally, subjecting the filtrates obtained in step and [h] separately to
desolventization process initially under atlnospheric pressure and subsequently
under vacuum to obtain by-products turmeric viz., flavourant and curcumin
removed turmeric resin (CRTR) respectively.
In yet another embodiment the invention provides a process wherein, the essential'oil and
, fatty oil are selec'tively extiacted from the turmeric oleoresin using solvents selected from
the group comprising of petroleum ether,
In yet another embodiment the invention provides a process wherein, defatted turmeric
oleoresin powder from step (b), can be optionally used without defatting for the
I . . curcuminoids ciystallization process followed by defatting of the curcurnin crystals.
In yet another embodiment the invention provides a process wherein, the material to acetic
acid ratio is preferably 1 :3.
I In an embodiment of the invention, the essential oil and fatty oil are selectively extracted
from the turmeric oleoresin in step (a) can be replaced with any hydrocarbon / fat solvents
viz. hexane, petroleum ether (40-60°C) etc.
In another embodiment of the invention, the drying of defatted oleoresin residue from step (b)
can be replaced with shade drying etc.
In another embodiment of the invention, the solvents used in step (c) can be replaced with
any mineral or organic acids.
In yet another ernbodilnent of the invention, in place of defatted turmeric oleoresin powder
from step (b), can be replaced with turlileric oleoresin (without defatting) for the
curcuminoids crystallization process followed by defatting of the curcumin crystals,
In another embodiment of the invention, the product obtained from the step (e) is
curcuminoidscrystals with 98-1 00% purity having characteristics of (1) Appearance: bright /
dark yellow (2) Texture: free flowing powder (3) Aroma: bland (4) taste: bland (5) Residual
solvent: - nil -,
In another embodiment of the invention, the by-product obtained from the step (f) is a
turmeric flavourant with characteristics of (1) Appearance: yellowish free flowing liquid (2)
Specific gravity: 0.93401 (3) Optical rotation: + 3.132 (4) Refractive index: 1.5102 (5)
Aroma: Mild turmeric (6) ~ksiduhls olvent: below 50 ppm. (7) Volatile oil content (% v/v):
PPQ BELMI 1 3 - O : P - L B $ 5 15': 4 4 >
In yet another embodiment of the. invention, the filtration of the mass using sintered fi~nnel
from step (d) can be replaced by centrifugation method.
In yet another embodiment of the invention, the high purity curcuminoids crystals prepared as
described is suitable to use as a raw material to prepare pure curcuminoids viz. curcumin
. (reddish orange), demethoxycurcu~nin (orange-yellow) and bis- de~nethoxycurcumin (yellow)
by adapting techniques such preparatory HPLC, colu~nnc hromatography separation method,
phase separation techniques, etc. for food and pharmaceutical application.
Detailed disclosure of the invention
Novelty
1. This is an improved process wherein first time the edible organic acid (acetic acid ) is
used to obtain curcu~ninoids crystals from turmeric oleoresin which is free from
solvent residue.
2. The product obtained is of 100% pure curcuminoids crystals which can be further
processed for the preparation of individual curcuminoids having different. colour
shade and bi.oactivity viz., curcumin (reddish orange) with two methoxy groups,
demethoxycurcu~nin (orange-yellow) with one methoxy group and bis -
de~nethoxycurcumin (yellow) without any methoxy groups.
3. The by-products obtained from this process are turmeric flavoura~lct ontaining volatile
oil (60.6%) and curcumin removed turmeric resin (CRTR) containing noncrystalizablecurcumini.
ods (15%). The by-products can find food and pharmaceutical
applications .
EXAMPLES
The following examples are given by way of illustration of the present invention and
therefore should not be construed to limit the scope of the present invention.
Example 1
Turmeric oleoresin salnple was procured from Synthite, Kochi, India was used as the ' I
1
raw material. The turmeric oleoresin (1.0 kg) was loaded in an extractor SS vessel, defatted ,
with 2.5litres petroleum ether using electric stirrer for1 hour a d decanted the extract I i
I
.: (2.0litres). The extraction process was repeated one time using 2.50 litres of petroleum ether I
' . I
and decanted the extract (2.0litres). The residue removed from the extractor dried in drier, at !
50-60 "C to yield 716g (71.7%) 'defatted turmeric oleoresin powder. The extract obtained
during defatting of turmeric oleoresin was desolventized in a rotary evaporator at atmospheric
pressure ti'll nearly 95% of the solvent was recovered. Rest of the distillation was carried out
under reduced pressure of 20 - 26 inches and a temperature of less than 60°C using a suction I
pump till solvent was almost completely removed to yield 1 log byprod~lct a yellowish
aromatic flavourant.
Example 2 I
The defatted turmeric oleoresin powder (100g) was loaded in to 500m1 glass stopper conical
flask and added acetic acid (3001nI) and homogenized on ,magnetic stirrer for 3.0 h. and the
mass was filtered through sint'ered funnel using vacuum to obtain curcumin crystals and
filtrate separately. The above recrystallization process was repeated two times maintaining
the material to acetic acid ratio 1:3. The curcuminoids crystals from the funnel were
subjected 'to water washing to remove acetic, acid residuesltill neutral to p1-I. The water
washed curcuminoids crystal were dried at 40- 50°C in oven to yield curcu~ninoidsc rystals
(46.6 g) with a purity of 97.0%. The acetic acidic filtrates obtained above during
crystallization of curcuminoids from defatted turmeric oleoresin was pooled and
desolventized in a rotary evaporator at atmospheric pressure till nearly 95% of the acid was
recovered. Rest of the distillation ,was carried out under reduced pressure of 20 - 26 inches at
temperature less than 60°C using a suction pump till acid was completely removed to yield
54.48 dark brown resinous matter called curcuminoids removed turmeric resin (CRTR)
containing 9.3% non crystalisablecurcu~ninoids.
Example -3
The defatted turmeric oleoresin powder (100g) was loaded in to 5001nl glass stopper conical
flask and added acetic acid (400ml) and homogenized on magnetic stirrer for 3.0h and the
mass was filtered through sintered funnel using vacuum to obtain curculninoids crystals and
filtrate separately. Further the above recrystallization process repeated two times maintaining
the material to acetic acid. ratio 1:3. The curculninoids crystals from the finnel were
subjected to water washing to remove acetic acid residues/till neutral tp pH. . After water
washing curcuminoids crystal were dried at 40- 50°C in oven to yield curculninoids crystals
(43.68) with a purity of 98.0 % The acetic acid filtrates obtained above during crystallization
of curcuminoids'from defatted turmeric oleoresin was desolventized in a rotary evaporator at
atmospheric pressure till nearly 95% of the acid was recovered. Rest of the distillation was
carried out under reduced pressure of 20 - 26 inches and a temperature of less than 60°C
using a suction pump till acid was almost completely removed to yield 56.4 g dark brown
, resinous matter called curcu~ninoids removed ti~rmeric resin (CRTR) containing non-
Example 4
The defatted turmeric oleoresin powder (100g) was loaded in to lOOOml glass stopper conical.
flask and added acetic acid (500ml) and homogenized on a magnetic stirrer for 3.0 h. and the
The curcuminoids crystals from the funnel were subjected to water washing to remove acetic
acid residues/till neutral to pH. The curcurninoids crystals from the funnel were dried at 40-
50°C in oven to yield 39.6.g curcumin crystals of purity 100%. The acidic filtrates obtained
above during crystallization of curcurnin was pooled and desolventized in a rotary evaporator
at atlnospheric pressure till nearly 95% of the acetic acid was recovered. Rest of the
distillation was carried out under reduced pressure of 20 - 26 inches at a temperature of less
than 60°C using'a suction pump till acetic acid wa's almost completely removed to yield63.3
g dark brown resinous matfer called'curcumin removed turme'ric resin (CRTR). The noncrystalisablecurcuminoids
content of C R T R ' W ~15~.0 % .The results of the above examples is
given in Table. 1 . ,
Example 5 I
Pure curcuminoids obtained from the abive examples was characterized by standard
methods. The curcumin, De-methoxy curc~~tniann d Bis-DemethoxyCurcumin were isolated
and quantified by TLC (Fig. 1 & Table 2) in pure form and characterized by HPLC (Fig.2)and
'H NulearMaganetic Resonance Spectroscopy ( 'HNMR) (Fig.3). The curcurnin and its I
analog~tes demethoxycur~umin and bis-demethoxycurcumin were present in'.the: ratio of
5.0:1.0:0.2 in curcuminoids prepared by this new process. The percentage curcuminoids
content were determined by spectrophotometric method (AOAC) and found that the prepared
curcuminoids content by improved method was 100% compared to curciuninoids standard
95.0% (Sigma).
Table 1: Data on yield, analysis of curcuminoids and resin obtained from
defatted turmeric oleoresin
Particulars
CurcurninoidsCrystals Curculnin removed- turtneric resin
(CRTR)
Table 2: Ratio of three curcuminiods in the high purity
bands eluted with methanol by TLC of curcuminoids powder (25mg) using Methanol
and chloroform (5:95) as nob bile phase)
Curcuminoids Crystals
Curcumin
Specification
TLC method.
De~nethoxy-c urcumin
Product: Turmeric curcuminoids
1 . Nature: yellow colourant
HPLC method
Yield of pigments (mg)
19.30
03.90
13
- - -
I P Q D E b H I 1 3 - O % - E Q 1 5 1 5 1 4 4
. % Recovery
79.60
2. Appearance:
3. Texture:
4. Moisture (%):
Fine bright yellow crystals
Free flowing
1.00-2.00 '
By-product: Turmeric flavourant
(1) Nature Rich in volatile & fatty oil constituents
(2) Appearance Yellowish free flowing liquid
(3) ,Specific gravity : 0.93401
(4) Optical rotation : t-3.132
(6) Refractive index: 1.5102
(8) Aroma Mild appealing turmeric aroma
(9) Residua1,solvent : < 50ppm hexane
(10) Volatile oil (%) : 60.00 to 70.00
(1 1) Applicatibn Food flavourant and phar~naceutical
By-pr.oduct: Curcumin removed turmeric resin (CRTR)
(1) Nature Resinous viscous matter
(2) Appearance Dark brown
. .
(3)Aroma Mild turmeric aroma
(4) Application As flavourant and colourant in foods
Advantages:
1. The high purity curcumin is a yellow/bioactive molecule which can find varied
applications as a natural yellow colourant in food / pharmaceutical industries.
2. The cryitallization of curcuminoids using acetit acid is a two stage simple process
which involves defatting of turmeric oleoresin with a hydrocarbon solvent followed
by acetic acid to yield yellow crystals having 98-100% curcuminoids
3. The acetic acid used for crystallization of' curcuminoids from defatted turmeric
oleoresin is edible and overco~nesth e problem of residual solvent which is presently
facing by,the industries.
, 4. The byproduct CRTR can.be processed to obtain low colour value yellow colourant in
powder form, since i t contains non-~r~stali~ablecurcurniann d is free from flavour
constituents ( volatile) and fatty oil (nonvolatile).
5. The by-product flavourant is having mild turmeric odor and aroma, which can be used
to impart' turmeric flavour of predetermined levels to food preparations.
6. The by-products can also be used to prepare powderlliquid for~nulations of various
flavour strengths for food application. In pharlnaceutical preparations, it can be used
as antiseptic in ointments and bandages etc.
7. The process is amenable for scale -up.

We Claim:
1. An improved process for the preparation of curcuminoids from turmeric (Curczinza'longa
L.) oleoresin" comprising steps :
j) Providing turmeric oleoresin;
k) dissolving oleoresin obtained in step a with solvent in an extraction vessel
followed by filtration by known methods to obtain defatted oleoresill residue and
filtrate;
1) drying the defatted oleoresin residue as obtained from step (b) in drier at 40-50°C
for 2-3 hr,
m) characterized in adding acetic acid to the powder obtained in step (c),
n) loading the mixture obtained in step (d) to the crystallisation vessel in the ratio of
material to acid ranging from 1 : 1 to 1 : 10;.
o) mixing the mass obtained in step (e) for a period of 1.0 - 3.0 hours followed by
filtration under vacuum to obtain curcumin crystals and filtrate.
p) washing the curcumin crystals obtained in step ( f ) with water to remove any
water soluble impurities;
q) drying of the curci~min crystals obtained in step (g) at 40-50°C to obtain
. .
curcuminoids;
r) optionally, subjecting the filtrates obtained in 'step [.TJ and [h] separately to
desolventization process initially under atmospheric pressure and subsequently
under vacuum to obtain by-products turmeric viz., fl'avourant and curcumin
removed turmeric resin (CRTR) respectively
.2. The process as clai~ned in claim 1, wherein, the essential oil and fatty oil are selectively
extracted from the turmeric oleoresin using solvents selected from the group comprising
of petroleum ether, Dimethylsulphoxide, Dimethyl formamide etc.
3. The process as claimed in claim I wherein, defatted turmeric oleoresin powder from step (b), can be optionally used without defatting for the curcuminoids crystallization process followed by defatting of the curcumin crystals.
4. The process as claimed in claim I wherein the material to acetic acid ratio is preferably 1:3.