Visiting adress: Skaraborgsvägen 3 Postal adress: 501 90 Borås Website: www.hb.se/ths Thesis for the Degree of Master in Science with a major in Textile Engineering The Swedish School of Textiles 2014-06-26 Report no. 2014.14.04 Extraction of β-carotene from orange peel and carrot waste for cotton dyeing Susan Hecker
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4.2. DRYING OF THE CARROT AND ORANGE PEEL RESIDUE 17
4.3. EXTRACTION METHOD 17
4.4. ANALYSIS OF THE DYESTUFF, PURITY AND YIELD 18
4.5. COTTON DYEING 18
4.6. SPECTROPHOTOMETRIC MEASUREMENTS 20
4.7. FASTNESS PROPERTIES TESTS 21
4.7.1. XENON TEST (ISO-NORM B02) 21
4.7.2. WASH FASTNESS TEST (ISO 105 – C) 21
5. RESULTS AND DISCUSSION 22
5.1. DETERMINATION OF Β-CAROTENE SPECTRUM 22
5.2. RESULTS OF THE RP-HPLC ANALYSIS 23
5.3. MORDANTING AND DYEING 26
5.4. SPECTROPHOTOMETRIC COLOUR MEASUREMENTS 28
5.5. RESULTS OF THE WASH FASTNESS TEST (ISO 105 – C) 30
5.6. RESULTS OF THE XENON TEST (ISO-NORM B02) 31
VIII Master thesis by Susan Hecker
6. CONCLUSIONS 33
7. FUTURE RESEARCH 34
REFERENCES 35
APPENDIX I
APPENDIX I II
AQUEOUS EXTRACTION II
ORGANIC SOLVENTS EXTRACTION WITH ETHANOL III
RESULTS OF THE HPLC ANALYSIS IV
APPENDIX II VI
CHEMICAL STRUCTURES OF THE SOLVENTS USED VI
APPENDIX III VII
VAT DYE VII
APPENDIX IV VIII
HPLC RESULTS VIII
APPENDIX V XII
SPECTROPHOTOMETRIC AND FASTNESS PROPERTY RESULTS XII
Master thesis by Susan Hecker IX
Table List
TABLE 1: TOTAL CAROTENOIDS AND THE CONTENT OF DIFFERENT CAROTENE AND XANTHOPHYLLS IN CARROTS
AND ORANGE PEEL IN MG/G CARROTS/ORANGE PEEL ............................................................................ 7 TABLE 2: SOLVENT PROPERTIES OF THE USED SOLVENTS ............................................................................ 9 TABLE 3: AMOUNTS OF THE DRIED RESIDUES (G) AND SOLVENTS (ML) THAT WERE USED FOR THE HPLC
SAMPLES AND THE DYESTUFF EXTRACTION FOR THE COTTON DYEING. ................................................. 17 TABLE 4: COMPOSITION OF THE USED Β-CAROTENE DYESTUFF OF CARROT AND ORANGE PEEL RESIDUE THAT
WAS USED FOR THE DYEING OF 0,8 G COTTON FABRIC. ....................................................................... 19 TABLE 5: FINAL DYE RECEIPT. AMOUNT PER LITRE WATER AND THE CALCULATED AMOUNT THAT WAS USED FOR
THE DYEING OF 0,8 G COTTON FABRIC IS LISTED. ............................................................................... 20 TABLE 6: THREE DIFFERENT CONCENTRATIONS USED FOR THE HPLC-STANDARD CURVE ............................ 23 TABLE 7: Β-CAROTENE CONTENT IN CARROTS AND ORANGE PEEL (MG/G OF CARROTS OR ORANGE PEEL) ...... 25 TABLE 8: COLOUR COORDINATION OF THE DYED COTTON FABRICS WITH CARROT EXTRACT .......................... 28 TABLE 9: COLOUR COORDINATION OF THE DYED COTTON FABRICS WITH ORANGE PEEL EXTRACT ................. 29 TABLE 10: RESULTS OF THE WASH FASTNESS TEST OF UNMORDANTED AND POST MORDANTED (ALUM) DYED
COTTON FABRICS OF ORANGE PEEL AND CARROT EXTRACT................................................................. 30 TABLE 11: RESULTS OF THE XENON LIGHT FASTNESS TEST OF UNMORDANTED AND POST MORDANTED (ALUM)
DYED COTTON FABRICS OF ORANGE PEEL AND CARROT EXTRACT. ....................................................... 31 TABLE 12: Β-CAROTENE CONTENT IN CARROTS AND ORANGE PEEL (ΜG/G) ................................................... IV TABLE 13: DIFFERENT PARAMETERS FOR VAT DYEING ON COTTON FABRIC .................................................. VII TABLE 14: RESULTS OF THE DETERMINATION OF Β-CAROTENE BY HPLC ................................................... VIII TABLE 15: COLOUR COORDINATION OF THE ALL DYED COTTON FABRICS WITH CARROT EXTRACT .................. XII TABLE 16: COLOUR COORDINATION OF THE ALL DYED COTTON FABRICS WITH ORANGE PEEL EXTRACT ......... XII TABLE 17: RESULTS OF THE WASH FASTNESS TEST OF ALL UNMORDANTED AND POST MORDANTED (ALUM)
DYED COTTON FABRICS OF ORANGE PEEL AND CARROT EXTRACT. ...................................................... XIII TABLE 18: RESULTS OF THE LIGHT FASTNESS TEST OF ALL UNMORDANTED AND POST MORDANTED (ALUM)
DYED COTTON FABRICS OF ORANGE PEEL AND CARROT EXTRACT. ...................................................... XIII
X Master thesis by Susan Hecker
Figure List
FIGURE 1: FRUITS AND VEGETABLE WASTE FROM JUICE PRESSING OF BRÄMHULTS JUICE AB IN TONS PER
YEAR. ................................................................................................................................................ 2 FIGURE 2: WASTE HANDLING OF BRÄMHULTS JUICE AB. WASTE IN TONS PER YEAR. ..................................... 3 FIGURE 3: ALL-TRANS Β-CAROTENE ............................................................................................................ 4 FIGURE 4: CAROTENOIDS CLASSIFICATIONS ................................................................................................ 5 FIGURE 5: Β-CAROTENE SYNTHESIS BY WITTIG REACTION ............................................................................ 6 FIGURE 6: 9-CIS-Β-CAROTENE .................................................................................................................... 6 FIGURE 7: DESICCATOR SILICA UNDER VACUUM CONTAINING ORANGE PEEL AND CARROT PIECES ................. 17 FIGURE 8: GRINDING DRIED ORANGE PEEL AND CARROTS IN A MORTAR ....................................................... 17 FIGURE 9: EXTRACTION FROM CARROTS IN PETROLEUM ETHER .................................................................. 17 FIGURE 10: GRAPH OF THE DETERMINED WAVELENGTH OF Β-CAROTENE AT 450 NM. ................................... 22 FIGURE 11: HPLC-STANDARD CURVE OF Β-CAROTENE .............................................................................. 23 FIGURE 12: HPLC GRAPH AT 450 NM SHOWING Β-CAROTENE, Α-CAROTENE AND ZEAXANTHIN EXTRACTED
FROM CARROT RESIDUE .................................................................................................................... 24 FIGURE 13: HPLC GRAPH AT 450 NM SHOWING Β-CAROTENE, Α-CAROTENE AND ZEAXANTHIN EXTRACTED
FROM ORANGE PEEL RESIDUE ........................................................................................................... 24 FIGURE 14: Β-CAROTENE DYESTUFF OF CARROT RESIDUE, DYED ON COTTON, MORDANTED AND UNMORDANTED
....................................................................................................................................................... 27 FIGURE 15: Β-CAROTENE DYESTUFF OF ORANGE PEEL RESIDUE, DYED ON COTTON, MORDANTED AND
UNMORDANTED ................................................................................................................................ 27 FIGURE 16: HPLC FROM CARROT EXTRACT IN AQUEOUS SOLUTION AT 450 NM ............................................ IV FIGURE 17: HPLC FROM ORANGE PEEL EXTRACT IN AQUEOUS SOLUTION AT 450 NM .................................... IV FIGURE 18: HPLC FROM CARROT EXTRACT IN 80 % AQUEOUS ETHANOL SOLUTION AT 450 NM ..................... IV FIGURE 19: HPLC FROM ORANGE PEEL IN 80 % AQUEOUS ETHANOL SOLUTION AT 450 NM............................ V FIGURE 20: HPLC GRAPH OF SAMPLE 1 Β-CAROTENE FROM ORANGE PEEL, EXTRACTED IN ETHYL ACETATE VIII FIGURE 21: HPLC GRAPH OF SAMPLE 7 Β-CAROTENE FROM ORANGE PEEL, EXTRACTED IN ETHYL ACETATE .. IX FIGURE 22: HPLC GRAPH OF SAMPLE 3 Β-CAROTENE FROM ORANGE PEEL, EXTRACTED IN HEXANE/ACETONE
........................................................................................................................................................ IX FIGURE 23: HPLC GRAPH OF SAMPLE 9 Β-CAROTENE FROM ORANGE PEEL, EXTRACTED IN HEXANE/ACETONE
........................................................................................................................................................ IX FIGURE 24: HPLC GRAPH OF SAMPLE 2 Β-CAROTENE FROM ORANGE PEEL, EXTRACTED IN PETROLEUM ETHER
........................................................................................................................................................ IX FIGURE 25: HPLC GRAPH OF SAMPLE 8 Β-CAROTENE FROM ORANGE PEEL, EXTRACTED IN PETROLEUM ETHER
......................................................................................................................................................... X FIGURE 26: HPLC GRAPH OF SAMPLE 4 Β-CAROTENE FROM CARROT, EXTRACTED IN ETHYL ACETATE ............ X FIGURE 27: HPLC GRAPH OF SAMPLE 10 Β-CAROTENE FROM CARROT, EXTRACTED IN HEXANE/ACETONE....... X FIGURE 28: HPLC GRAPH OF SAMPLE 6 Β-CAROTENE FROM CARROT, EXTRACTED IN HEXANE/ACETONE......... X FIGURE 29: HPLC GRAPH OF SAMPLE 12 Β-CAROTENE FROM CARROT, EXTRACTED IN HEXANE/ACETONE...... XI FIGURE 30: HPLC GRAPH OF SAMPLE 5 Β-CAROTENE FROM CARROT, EXTRACTED IN PETROLEUM ETHER ...... XI FIGURE 31: HPLC GRAPH OF SAMPLE 11 Β-CAROTENE FROM CARROT, EXTRACTED IN PETROLEUM ETHER .... XI
Master thesis by Susan Hecker XI
List of Abbreviations
Abbreviation Unit Definition
Å Ångström
a*
Red-green b*
Blue-yellow
C*
Chroma FTIR
Fourier transform infrared spectroscopy
h Hue HPLC
High Performance Liquid Chromatography
K/S
Kubelka Munk, colour strength or colour uptake L*
Lightness
NaOH
Sodium hydroxide Owf
Of the weight fraction
RP-HPLC
Reverse-Phase High Performance Liquid Chromatography
TLC
Thin Layer Chromatography UV
Ultra violet
v
Volume
V Volt
ΔE
Colour difference between uncoloured and coloured fabric
μg Microgram λ max
Maximal absorption
2 Master thesis by Susan Hecker
1. Introduction
Plant material like fruits, berries, roots, barks, vegetables, leaves etc. have been used for
textile dyeing over hundreds of years (Cardon, 2007). With the industrialisation and the
invention of synthetic dyes, natural dyes disappeared almost entirely in the textile industry
(Cardon, 2007, Hardman and Pinhey, 2009). With their well-known structures synthetic dyes
became easier in handling, higher in process safety and better in reproducibility compared to
natural dyes and so a success for dye houses. Nevertheless different researchers
investigated in the recent years again in new methods on dyeing with natural material and
their extracts. The used extraction methods are mostly organic-solvent extraction (Saleh et
al., 2013, Yi and Yoo, 2010). The article by Saleh et al. (2013) shows great potential of
dyeing cotton fabric with β-carotene containing dyestuff extracts, extracted from banana
leaves by organic solvent extraction. The results evidenced high tensile strength, high colour
strength, and high fastness properties for the dyed cotton fabrics.
Brämhults Juice AB, Borås has 8100 tons of orange peel waste and 570 tons of carrots
waste from juice pressing each year (Figure 1). In this state after the juice pressing the
vegetable and fruit residues still contain a lot of natural resources such as colorants and
pigments (Brämhults Juice AB, 2014). A further use of the waste could be the textile dyeing
industry (Guinot et al., 2007, Saleh et al., 2013). With extraction and purification of the
pigments, dyes comparable to synthetically textile dyes can be achieved.
Figure 1: Fruits and vegetable waste from juice pressing of Brämhults Juice AB in tons per year.
8100
570 630
Orange peel
Carrots
Others
Master thesis by Susan Hecker 3
β-carotene is a natural yellow-red pigment. Its chemical formula is C40H56. Its sources are
mainly plants, vegetables and fruits with a yellow-red colour as carrots and oranges. It is an
important precursor for vitamin A since it cannot be synthesised in the human body. The
intake has to be over the diet (Schlieper, 2005). As colorant it is used in the food industry
under the numbers E160 a-f (Domke et al., 2004).
The total amount of residue of the juice pressing of all vegetables and fruits from Brämhults
Juice is 9300 tons per year.
Figure 2: Waste handling of Brämhults Juice AB. Waste in tons per year.
This is composed of 8300 tons that is used for the biogas production and fodder, 500 tons for
fodder and 500 tons for waste disposal (Figure 2) (Brämhults Juice AB, 2014). A suitable
extraction method of β-carotene from orange peel and carrot residue would gain an
additional value to their waste. The further use of the residues can be economically beneficial
for both the juice pressing and the textile dyeing industry. Synthetically produced β-carotene
and the extracted β-carotene from natural sources have the same chemical structure and are
therefore comparative with each other.
8300
500 500
Biogas production and fodder
Fodder
Waste disposal
4 Master thesis by Susan Hecker
2. Literature review
The following literature review gives a look into the physical and chemical properties of β-
carotene, its synthesis and uses today. It gives an overview on the existing research in the
field of extraction of β-carotene and other natural pigments and their appliance in different
dyeing methods. It is shown how much β-carotene other researchers could extract from
orange peel and carrots. An investigation on different solvents and their suitability for β-
carotene extraction was done. Different dyeing methods used for water insoluble dyes and
on cotton and the usage of mordants is described as well.
2.1. β-carotene
β-carotene is a natural yellow-red coloured pigment with the chemical structure C40H56,
(Figure 3). It occurs mainly in plants, fruit and vegetables. It belongs to the group of
carotenes that together with xanthophyll belongs to the upper-level grouping of carotenoids
(Bergmann, 2004). Chemically β-carotene is classified as tetraterpene (Koskinen, 2012).
Carotenoids are divided in oxygen containing molecules (xantophylls) and non-oxygen
containing molecules (carotene) (Domke et al., 2004), Figure 4. The lack of hydroxyl groups
makes β-carotene hydrophobic. Due to its two cyclic rings at each end of the molecule chain,
β-carotene is a dicyclic compound, composed of 8 isoprene-units (C5H8). The high amount of
conjugated double bonds is called chromophor and is responsible for the colour impression
(Bergmann, 2004). β-carotene absorbs light of the wavelength 450 nm of the visible part of
the spectrum (Bauernfeind, 1981).
Figure 3: All-trans β-carotene
In the nature carotenoids have an indispensable protective role for chlorophyll and the
human eyes by absorbing and dissipating excessive light energy that would damage them
Master thesis by Susan Hecker 5
(Campbell, 2003). β-carotene is the most common carotene (Schlieper, 2005). β-carotene is
very sensitive to light, heat and oxygen. It can change its chemical structure due to oxidation,
degradation or isomerization. The latter doesn’t have any effect on the colour impression of
β-carotene because the double bonds do not break (Liaaen-Jensen, 1989). The handling of
carrots and orange peel residue for the β-carotene pigment extraction and the later dyeing
process therefore has to be handled with care. Too high exposures to light, heat and oxygen
have to be avoided. The storing is recommended under frozen conditions. According to Qian
et al. (2012) the β-carotene stability against degradation is higher at a pH between 4-8.
Natural β-carotene occurs in trans- and cis-isomers whereas synthetically produced β-
carotene is mostly all-trans-form, due to its higher absorbance for the human body
(Bundesinstitut für Risikobewertung, 2013).
Figure 4: Carotenoids classifications
The β-carotene synthesis is either produced by employing a Wittig reaction or a Grignard
reaction (Koskinen, 2012). The following reaction (Figure 5) is by Wittig. It shows a trans-
selective Wittig olefination of aldehydes II—synthesis of β-carotene from a dialdehyde.
Carotenoids
Carotene
(hydrophobic)
β-carotene α-carotene
Lycopene etc.
Xantophylls
(hydrophillic)
Lutein Zeaxanthin
etc.
6 Master thesis by Susan Hecker
Figure 5: β-carotene synthesis by Wittig reaction
As vitamin A precursor, synthetically produced β-carotene is especially important for the use
in the food industry as completion to the natural, in the food existing β-carotene. As food
additive with the purpose of a food colorant it is known under the numbers E160 a-f. (Domke
et al., 2004)
Figure 6: 9-cis-β-carotene
Master thesis by Susan Hecker 7
2.2. Carrots and Orange peel
Carrots and orange peels are a rich source for carotenoids. Carotenoids, especially β-
carotene is present in both of them and is responsible for their yellow-orange colour. Main
compounds in carrots and orange peel are β-carotene, α-carotene, lutein and zeaxanthin
(Table 1), (Heinonen, 1990, Wang et al., 2008, Curl and Bailey, 1956). Additionally orange
peel contains flavonoids, phenolic acids, pectin and waxes (Wang et al., 2008). The
compounds in orange peels extracts are by some researches tested on their UV-protective
properties and antimicrobial activity (Hou et al., 2013, Yi and Yoo, 2010). The total
carotenoids content and the amount of some xantophylls and carotenes of carrots and
orange peel are listed below.
Table 1: Total carotenoids and the content of different carotene and xanthophylls in carrots and orange peel in mg/g carrots/orange peel
Carrots Article Orange peel Article
Total
carotenoids 0,16 – 0,38
Mustafa et al.
(2012) 0,45 Wang et al. (2008)
Carotenes (hydrophobic carotenoids)
β-carotene 0,046 – 0,10 Heinonen
(1990) 0,05 – 0,056
Dumbravă et al.
(2010), Wang et al.
(2008)
α -carotene 0,022 – 0,049 Heinonen
(1990) 0,017 – 0,019
Curl and Bailey
(1956)
Xanthophylls (hydrophilic carotenoids)
Lutein 0,0011 – 0,0056 Heinonen
(1990) 0,029 Wang et al. (2008)
Zeaxanthin 0,0574 Curl and Bailey
(1956) 0,027 Wang et al. (2008)
8 Master thesis by Susan Hecker
2.3. Extraction methods and solvent properties
In literature different extraction methods for β-carotene (carotenes) from orange peel, carrots
and other fruits, vegetables and plants are described. The most common method is the
organic solvent extraction. It was described by several different researches for the extraction
of β-carotene from orange peel (Ghazi, 1999), (Dumbravă et al., 2010) and carrots (Biswas
et al., 2011), (Fikselova et al., 2008), (Livny et al., 2003), (Marx et al., 2000), but also from
other vegetables and plants as tomato, paprika (Levy et al., 1995) and from the algae
Dunaliella salina (Marchal et al., 2013), (Mojaat et al., 2008).
Several other extraction methods for β-carotene were researched. So were investigations on
supercritical fluid extraction of β-carotene done by Kaur et al. (2012), Chandra and Nair
(1997) and Benelli et al. (2010) for carrots and the latter one for orange peel. “Ultrasound
assisted extraction of β-carotene from Spirulina platensis”, a cyanobacteria was researched
by Dey and Rathod (2013). A microwave-assisted extraction of β-carotene from carrots was
done by Hiranvarachat et al. (2013) and the effect of enzymes on carotene extraction in
carrots was investigated by Jaramillo‐Flores et al. (2005).
The “Relative solubility, stability, and absorptivity of lutein and β-carotene in organic solvents
were tested by Craft and Soares (1992). The solubility of both carotenoids (β-carotene and
lutein) was best in tetrahydrofuran, whereas the least solubility for lutein was in hexane and
for β-carotene methanol and acetonitrile. Organic solvents can be classified due to their
chemical structure, according their solubility in water they are grouped into polar and non-
polar solvents (Smallwood, 1996). A good solubility for β-carotene was shown by some
organic solvents of the category hydrocarbons (same chemically classification as β-
carotene), ethers, esters, chlorinated solvents and ketones (Craft and Soares, 1992). For the
selection of a suitable solvent for β-carotene extraction a low boiling point is advantageous.
The solvent has to be removed by rotary evaporator after the extraction to achieve pure β-
carotene, with a low boiling point the thermal sensitive β-carotene can be preserved.
Two articles used the organic solvent mixture of acetone and hexane (1:1 v/v) for the
“Extraction of β-carotene from orange peel” (Ghazi, 1999) and from carrot juices (Marx et al.,
2000). Ghazi (1999) concluded that the organic solvent mixture of acetone and hexane
achieves the highest extracted yield of β-carotene. Biswas et al. (2011) extracted amongst
others β-carotene from carrots with four different organic solvents; acetone, diethyl ether,
Master thesis by Susan Hecker 9
acetonitrile and methanol. With acetone the highest yield was achieved followed by diethyl
ether. In another study β-carotene was extracted from orange (Citrus sinensis L.) fruits peel
extracts by three different organic solvents; ethanol, benzene and petroleum ether. Only in
the petroleum ether extract, β-carotene could be identified. The amount in the ethanol and
benzene extract was too little (Dumbravă et al., 2010). Ishida and Chapman (2009)
compared ethyl lactate as an environmentally friendly solvent with the, for the food industry
commonly used solvents ethyl acetate and ethanol for the carotenoid extraction. It was
mentioned that ethyl acetate is a good solvent for β-carotene and lutein and less good for all-
trans isomer of lycopene. That could help to achieve a higher purity of the extracted β-
carotene. Therefore ethyl acetate was chosen instead of ethyl lactate, which was slightly
better in the extraction of β-carotene.
The following table are the solvents that were used in this thesis for the β-carotene extraction
from orange peel and carrot residue. They are listed after their solvent classification. The
solubility of β-carotene (mg/L) and the stability after 10 days in % of the initial absorbance of
β-carotene at λmax (Craft and Soares, 1992), values of the boiling point (°C) and the polarity
of the solvents are given (Smallwood, 1996).
Table 2: Solvent properties of the used solvents
1 (Craft and Soares, 1992); 2 (Smallwood, 1996)
Solvent
Solubility of β-carotene mg/L
1
Stability after 10 days % of initial absorbance of β-carotene at λmax.