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Chemical composition of sunflower seed hulls

Article  in  Journal of the American Oil Chemists' Society · October 1971

DOI: 10.1007/BF02544577

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Chemical Composition
PAUL CANCALON ,2 Ecole Superieure r,'Application
des Corps Gras, 5 Boulevard Latour Maubourg 75, Paris 7, France
ABSTRACT
The major components of the sunflower seed hull,
lipids, proteins and carbohydrates were studied
Lipids represent 5.17% of the t01al hull weights,
2.96% of which is wax composed of long chain fa1ty
acids (CI4-C28, mainly C20) and fatty alcohols
(Cl2-C30, mainly C22, C24, C26J. Hydrocarhon,
sterol and triterpene aJcohol frac; ions were also
examined. The rest of the lipid fraction is an oil with
a composition relatively similar to that of the kernel
oil. The protein fraction (4% of the tDtal huIJ weight)
is similar to the protein fraction uf the oil cake,
although it contains hydroxyproline. The carbohy-
drate fraction is composed mainly of cellulose, but
also of reducing sugars (25.7%), mainly pentoses.
INTRODUCTION
TIle sunflower (Heliarithus annus) w's considered as an
ornamental f]o\ver until the 19th century after which time
it was cultivated as an oilseed plant in Rvssia (I).
Research done in Russia made possjb]~ an increase in the
oil percentage of the seed from 25% to 46%. This increase
of the oil percentage was possible owing not only to the
increase in oil of the kernel, but mainly 10 a decrease of the
ratio of weight between the hull and the kernel. Today the
sunflower is one of the oilseed plants which gives the
highest oil yield (2).
Because of its high B vitamin and protein content, and
also its balance in amino acid composition, the sunflower
oil cake can r-e favorably compared to the best oil cakes
(soya, peanut). However, a rebtively high percentage of
cellulose (7-15%) may limit its usefulness as feed for animal
other than ruminants (3).
The only unused part left of the sunflower seed is the
hull. As with the other oilseeds, the utilization of the hull is
an important industrial problem (4). The production of the
oil liberates an enormous quantity of this byproduct, the
dt'Dsity of which is very low. It therefore needs a very large
v01ume for storage and the factory must get rid of it.
Because of the low economical value of the hull, it is
difficult to find a really profitable way of using it. The
following uses have been recommended (5): heating (but
the o]orific power is less than 3700 calories/g) (6), cattle
feeding (7), fertilizer (8), production of agglomerated
panels, extractions of xyloses (9), and production of
furfural (4).
In the prest'nt study, we hope to establish the relative
importance of the various constituents of the sunflower
hull (lipids, amino acids, carbohydrates). Consequently, this
information should be of some help in finding belter uses
for this b\'DToduct.
EXPERIMENTAL PROCEDURES
Pre[12rction of the Hull
The sunflower seed huJls we used came from an
-industrial source. We therefore handpicked the hulls to
1Submitted in partial fulfi!lment for the Degree of Jngenicur
SpeciaEstc at I 'Ecole Superieure d'Application des Corps Gras, Paris,
France. - -
2Pie~~nt address: Department of Biochemistry,
.State Univcr;:ity of New York at Buffalo, Buffalo, New York 14214.
of Sunflower Seed Hulls
eliminate aH fragments, especiaJly 1he pieces of kernel.
Then the compound was ground in an ordinary coffee
grinder to have homogeneous particles, or 2 mm long, at
most.
Lipids
Extraction of the Total Lipids. Lipids were extracted
from the hulls with petroleum ether in a soxh]et for 20 hr.
111e huH was dried and reextracted for 24 hr. The solvent
was eliminated by distillation on a water ba tho The last
tr<Jces of solvent were eliminated under a stream of
nitrogen. The percentage of lipids extracted from] 0 g of
hull was 5.17%. A large scale experiment was also per-
formed: 500 g of hull were ex tracted with petroleum ether
in a metaHic percolator for 20 hr and again for 24 hr. This
/
method yielded 3.92% lipids.
The characteristics of these lipids were determined by
the following methods: acid number (10); iodine number,
Wijs' method (J I); and unsaponifiabJe (] 2).
Extraction of the Wax. The wax was crystaJlized from
the total lipid extract from petroleum ether (J 0% solution)
at 4 C for 36 hr, and recrystaJlized under the same
conditions for 24 hr. The wax was fiJtered and washed with
cold petroleum ether (13). The characteristics of the wax
were determined by the following methods: acid number;
same method as for the oil (J 0), except that the wax was
dissolved in benzene; iodine number, Hoffmann-Green
method; and hydroxy] value, IUPAC.
Saponification of the Wax. Since the wax was very
resistant to saponification, we used the folJawing method.
100 mg of wax is dissolved in the mixture 50:50 (2 N KOH
ethanolic-petroJeum ether) and refluxed for J 0 hr (14). The
unsaponifiable material was extracted according to the
AOAC official method (12). The solvent was evaporated on
a water bath. The traces of water were eJiminated by
addition of 6 ml of acetone and distilJation. The fatty-
alcohols were in the unsaponfiable Jayer while the fatty
acid soaps were in the aqueous layer.
Acid Composition of the Wax. The fatty acids. were
- liberated from the soap by boiling in 10 ml of 0.2 N HC!.
The methyl esters were prepared as described by Metcalfe
and Schmitz (15).
Alcohol Composition of the Wax. The alcohols were
acetyJated by refluxing wi1h an excess of acetic anhydride
for 45 min, the acetates being analyzed by GLC. Since the
lengths of the alcohols were very different, we used a polar
phase for the short alcoho]s (C 12 to C2 3) and a nonpolar
phase for the long alcoho]s (C23 to C32)'
Hill! Oil Fatty Acid Cnmpositioll. The fatty acids were
analyzed by GLC under the same conditions as for the wax
fatty acids.
Hydrocarbon Composition. The hydrocarbons were
isolated from the unsaponifiable fraction by column chro-
matography (Merck, acid-washed 100-200 mesh alumina)
according to the Kuksjs procedure (J 6). TIle purified
hydrocarbons represented 1.55% of 1he total lipid extract
and were analyzed by GLC under the same conditions as
for 1he wax Jong a]coh01s.
Separation a~ld QZ!llI1tiiatil'e Study of the Othcr Crll1stit-
lIClIts of tllf> U/J.wponifiab/c Extract. TIle other constituents
(sterols and triterpenic alcohols) were separated by TLC
(20 x 20 em) on aJumina G (0.25 mm thick). '
A 0.5 ml strip of lms3ponifiab1c solutjon (40 mg!m]) W3S
Capen Hall, stre<1ked on to the p]ates which wae developed with
hexane-ether (80:20). Each pl3te was sprayed with dich]o-
 1
T ABLE I TABLE II

Analytical Characterization of the Lipid Fractions Wax Fatty Acids Composition

Total lipid Fatty acids Per centa

Methods extract Wax HuB oil
Myristic 1.94
Acid number 64.5 13.5 91.2 Pentadecanoic 0.4
Iodine number 18.2 0.92 Palmitic 6.8
Hydroxyl number 43 Heptadecanoic 0.2
Un sa ponifia ble 9.3% 98% 6.4<;: Iso-stearic 0.35
Melting point 81-82 C Stearic 5.6
Oleic 4.72
Nonadecylic 3.07
Linoleic 0.78
rofluorescein 0.2%. and examined under short wave UV Iso-arachidic 1.3
.
light (I7). After development, the areas corresponding to Arachidic 46.5
the sterols and to tlHJ triterpenic alcohols were removed Iso-medullic 0.9
Medullic O~
from the plate. The compounds were extracted with ether, Behenic 16~
dried, and the residue weighed (I 8). The sterols were also Tricosanoic 0.53
titrated by digitonin precipitation (I9). Lignoceric 4.5
Sterol and Triterpenic Alcohol Composition. The trite- Pentacosanoic 0.23
Monlanic 2.2
rpenic alcohols and sterols isolated by TLC were analyzed
by GLC under the same conditions as for the wax alcohols. aUnknown peaks account for the difference between the tolal
The peaks were identified according to Capella (20). and 100%.
GtC Methods. The GLC analyses were conducted on a
Carlo Erba Fractovap, Model C chromatograph, equipped
'With a flame ionization detector and using nitrogen as Quantitative Results. We assumed that the area of the
carrier gas (gas flow 42 ml/min). spots was proportional to the quantity of .amino acids. By
The fatty acid esters and short alcohol acetates (0.2 pI interpolation bet wee:: different reference samples, we can
per injection) were dctcrmined on a 2 m x 3 mm stainless ev?luate the quantit~ of each amino acid present in the
steel column packed with 11.5% polyethylene-glycol succi- solutions being analyzed.
nate on 60-80 mesh Gaschrom P. Injection and column
temperatures were respcctively 240 and j 80 C. Carbohydrates
The long alcohol acetates, hydrocarbons, sterols and Titration of the Cellulose and the Lignin. Cellulose and
triterpenic alcohols (0.2 pI per inhection) were detcrmined lignin were titrated by the AOAC official method (27).
on a 1.5 x 3 mm stainless steel column packed with A%
Extraction of the Carbohydrates. The carbohydrates
silicone grease SE30 on 60-80 mesh ChromosorD"W.
were hydrolyzed by boiling in N HCI for 80 min. Then the
Injection and column temperatures were respectively 300
proteins were precipitated by addition of alcohol (80%).
and 250 C.
The sugars were purified by ion exchange column chroma-
tography on Dowex 50 x 4. The water was eliminated by
The Amino Acids distilIation in vacuo.
The percentage of protein nitrogen was detcrmi::H~-,Lby Titration of the Reducing Sugars. The reducing sugars
the Kjeldahl method (21). were titrated by the Shaffer Hartmann method (28).
Hydrolysis of the Proteins and Purification of the Amino Qualitative Analysis of the Carbohydrates. The carbo-
Acids. The proteins (0.1 mg N2/ml) were submitted to acid hydrates were analyzed by paper chromatography (29) and
or alkaline hydrolysis by boiling in 6N NCI for 20 hr or in 5 the spots were detected by spraying with a solution of
N Na OH for 15 hr (22). The hydrolyzate was dried by aniline phosphate (1 g aniline, 2 g H3P04, in 100 ml of
distillation in vacuo. . ethyl alcohol) (30).
The amino acids were purified by column ion exchange One-Dimensional Chromatography. The carbohydrates
chromatography on 200-400 mesh Dowex 50 x 4 as were chromatographed on Whatmann No. I (50 x 55 em)
described by Thompson et al. (23). paper in butanol-acetic acid-H2O (40:10:50) for 48 hI. On
One-Dimensional Chromatography. The amino acids each sheet 4 pI of an aqueous solution (50 /-lg/jJl) of each of
were chromatographed on Whatmann No. I (50 x 55 cm) eight known carbohydrates and 4 and 6 pI of the unknown
paper in each of the following solvents: butanol-acetic solution were spotted. The area of each spot was measured
acid-water (40:10:50) (24) and phenol-water (80:20) in by pJanimetry.
ammoniacal atmosphere (25). Two-Dimensional Chromatography. This was done by
On each sheet, 0.4 pI of an aqueous solution (50 mg/ml) using t he following solvents: butanol-acetic acid-H2O
of each of 15 known amino acids was spotted. Also, 0.6 pI (40: J0:50) and in the perpendicular direction: phenol/H2O
of the mixture of the IS known amino acids and (80:20), and quantitated by planimetry.
0.1-0.4-0.6 pI of the unknown solution were spotted.
Asn, Moisture
Even though the solvent front reached the bottom of the
sl1eet (24 hr), this was insufficient to allow separation of all The ash percentage was determined by ignition of the
the amino acids. Therefore, thQY were allowed to dcvelop hull and weighing the residue (31)- The moisture was
for 48 hr. Then the shcets were dried and the spots determined bv the air-oven method (32).
detected by spraying with a solution of 0.2% of ninhydrin
in methanol. The area of each spot was measured by RESULTS AND DISCUSSION
planimetry.
Two-Dimensional Chromatography. The amino acids Lipids
were chromatographed in the solvent (butanol-acetic acid- Total Lipid Extract. The total lipid extract reprcsents
water) for 24 hr and in the perpendicular direction with the 5.17% of the total hu]J weight. TIJe extract is a greenish
solvent (phenol-water) in an ammoniacal atmosphere for yellow compound having the consistency of honey, without
24 hI. The spots were identified by their relative positions a real melting point (Table I).
(26). The Wax. -nJe wax is a white crystallized material and
 TABLE III TABLE V

Wax Fatty Alcohols Composition Sterol Composition

AJcohol Per centa Sterol Per cen t

-Dodecanol 0.16 CampesteroJ 11.38
Tridecanol 0.24 Stigmasterol 9.17
ntradecanol .- traces I3-Sitosterol 68.81
Pentadecanol tra ces Unidentified sterol 10.64
Hexadecanol 0.2
Heptadecanol 0.17
Octadecanol 3.0
0.15 TABLE VI
OIeHo!
Nonad~c:mol 0.17
Triterpcnic Alcohol Composition
Bcosanol 2
Heneicosanol 0.5 Triterpenic alcohols Per cent
Docosanol 12
Tric(J~3nol 0.4
Euphol 9.1
Tetracusanol 34.6
I3-Amyrine 7.'
Pentacosanol 3.45
Cycloartenol 79
Hcxacosanol 14.35
24 Methylene cycloartenol 4.3
Octacosanol 6.65
NODacosanol 5.75
Triacontanol 2.17
The sterols represent only 57% of the compounds
aUnknovm peaks account for the difference between the total precipitated by the digitonin. From the color of the
and 100%. Liebermann-Burchard reaction, and from the position of
the peaks from GLC chromatogram, we assumed that the
represents 2.96% of the total lipid extract (Table I). unidentified compounds were diterpenes (18). {3-Sitosterol
The sunflower hull wax is essentially composed of esters represents almost 70% of the total sterol content of the hull
of long fatty acids and fatty aJcohols. Acids and aJcohols (Table V). I

are almost exchlsively saturated. TIle majority of the acids Trilerpenic Alcohols. They are present in a very small
are in C2O,C22, the aJcohols being longer (C22-C29) quantity; 0.36% of the total lipid extract. The cyc1oartenol
(Tables 11,111). represents 79% of the total triterpenic alcohols (Table VI).
Hull Oil. This oil consists of the total lipid extract
without wax. Its color and consistency are very similar to Amino Acids
those of the total lipid extract (Table I). The hull contains 4.0% protein. Its amino acid composi-
The fatty acid composjtion is very similar to the tion was determined by paper chromatography. This very
composition of the sunflower kernel oil. small percentage of protein in the hull explains why this
Ifydrocarbol1s. They represent J.5 5% of the total lipid material has a very poor food value. The percentage of each
extract. The composition is somewhat different from that amino acid is not very different from that fO}lnd in the oil
found by Kuksis (16) for the sunflower oil. However, cake protein (3). However, we found some differences,
heptacosane, nonacosane and hentriacontane also represent especially in that the hull protein contains hydroxyproline.
about 70% of the total hydrocarbons (Table IV). Since the planimetry method is not very precise, the
Slerols. The precipitation .by.di,gitonin gives a greater quantitative results have only relative value (Table VII).
percentage of sterols than by TLCj)ecause with digitonin
compounds which are not sterols ;u:.ealso extracted. Thus, TABLE VII
total lipid extract is by TLC 0.78%, by digitonin, 1.16%.
Composition of the Protein
Fraction of the Sunflower Seed Hull
TABLE IV':::...:
Amino acid Per cent
Hydrocarbon Composition
Aspartic acid 13.4
Glut~mic acid 10.1
Hydrocarbon Per cent
Serine 7.3
Tetradecane .-
- 0.19 Glycine 7.3
llneonine 5.8
Pen tadecnne 0.1
A~par:1gine 5.8
Hexadecane 5.6
Hy dro x y proline 9.1
Heptadecane 0.55
3.43 Alanine 8
Octadecane
Histidine 2.5
Nonadecane 0.73
1.40 Tryptophane 4.4
Bcosane
Valine 1.64
Iso-he ncicosane 0.23
Methionine 3.1
Nc neicosane 3.21
Proline 7.3
Docosane 3.03
Lysine 5.1
Tricosane 1.95
1.59 Argi"ine 3.6
Tetracosane
0.32 Leucine 2.2
Iso-rentacosane
Penf::,cQsane 1.91 Phenylalanine 3.25
Iso-hexacosane 0.35
Hexacosane 1.26
lso-heptaccsane 0.23 TABLE VIII
Heptacosane 6.65
lso-oct~cosane 0.32 Reducing Sugars of the Hull
Octacosane 3.1
Nonacosane 27.2 Su b3 r Per cent
Triacontane 1.83
Hcntri~contane 35.5 Xylose 52
Dotri3con ta:Je 0.18 Ar2oinose 27
Tritrj~cont~ne 1.88 G?la ct ose 8.6
Tetr3t riacontane 2.75 c'alacturonic acid 12.4
Carhohydrates tion of Official Agricultural Chemists, Washingrof), D.C., 1955, .
26.30.
CeUulose and lignin (almost 50% of the entire hull 11. HOr\,itz, W., Ibid., 26.18.
weight) are the principal constituents of the huH. The 12. Hr"witz, W., Ibid.. 26-35.
reuucinc sugars (25.7% of the entire hull weight) are the 13. Guil!3umin, R., and 1'. Drouhin, Itev. Fr. Corps ~ras 1965:10.
14. Guilbumin, R., and N. Drouhin. Ibid. 1966:3. :
second ~major constituent of the hull, ~vllich explains why 15. Metcalfe, L.D., and A.A. Schmitz, Anal. Chem. 33:363 (1961).
the huH can be used for the extraction of xylose and 16. Kuksis, A., Biochemistry 3:1086 (1964).
production of furfural (Table VIII). Carbohydrates are 17. Walbecg. M., Rev. Fr. Curps Gras 1965:12.
thereforc the only compounds present in the hull in a large 18. Wolff, J.P., and M. Walbecg, ITERG Journees d'elude sur les
consti Juants des corps gras 1965: 27.
enough quantity to permit an industrial cxtration.
19. Boughton, B., and V.R. \Vheatley, l3iochem. J. 73:144 (1959).
20. Capella, P., E. Fedeli and M. Cirimele, Chern. Ind. 39:1590
Ashes, IVaistu re (1963).
21. Horwitz, W., Editor, "Official Methods of Analysis," Associa.
The h:.J1lcontains 8.2% of water of the total hull weight. tion of Official AgricuJtural chemists, Washing1on, D.C., 1955,
TIle ashes represent 2.1'70 of the total weight. 2-23.
22. BJock, R.J., LL. Dunun and G. Zweig, "A Manual of Paper
Chromatography and Paper Electrophurisis," Academic Press,
ACKNOWLEDGMENTS New York, 1958.
23. Thompson, J.F., J. Morris and R.K. Gering, .Lilla!. Chem.
J.P. Wolff and M. WaJbecg gave technical advice. J.D. Klingman 31:1028 (1959).
helped in the preparation of the manuscript. 24. Partridge, S.N., Biochem. J. 42:241 (1948).
25. Condsen, R., A.H. Gord!)n and A.P. Martin, Ibid. 38:224
REFERENCES (1944).
26. Biserte. G., Th. Plaquet, P. Boulanger and P. Paysant, J. Chrom
1. Andr~, D., ITERG Journees d'information sur'Ie tournesol 3:25 (1961).
1965:71. 27. Hon\itz, W., Editor, "Official Methods of Analysis," Associa-
2. Guilh\umaud, M.Y., ITERG Ibid. 1965:15. tion of Official Agricultural Chemists, Washing1on, D.C., 1955,
3. Jacquot, R., and P. Ferrando, "Les Tourteaux" Vigot Frere, 22-33.
Paris,1957. 28. Shaffer, P.A., and A.F. Hartmann, J. BioI. Chem, 45:365
4. Fran! ois, R., lTERG Journees d'information sur Ies produits (J 920).
deriv\ s de I'huilerie 1964: 60. 29. Dedonder, R., BulL Soc. Chern, BioL 34:157 (1952).
5. Fetrow, G., and S. Dimakon, Maslob, Zhir, Delo. 36:40 (1932). 30. Bryson. J.L., and T.1. ~litchell, Nature 167:864 (1951).
6. Nefedov, S.A., Maslob. Zhir. Prom. 25:4,38 (I 959). 31. Hon\;tz, W., Editor "Official Methods of Analysis," Associa.
7. K.itch;guine, Y.P., Maslob. Zhir. I'rom. 24:12,30 (1958). tion of Official Agricultural Chemists, Washington, D.C., 1955,
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7:1008,1028 (1934).
10. Hor"itz, W., Editor, "Official Methods of Analysis," Associa-

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