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Abstract: The objective of this work was to investigate the effect of six
individual strains of fungi on the reduction of gossypol levels and nutritional
value during solid substrate fermentation of cottonseed meal (CSM). Six
groups of disinfected CSM substrate were incubated for 48 h after
inoculation with either of the fungi C. capsuligena ZD-1, C. tropicalis ZD-3,
S. cerevisae ZD-5, A. terricola ZD-6, A. oryzae ZD-7, or A. niger ZD-8. One
not inoculated group (substrate) was used as a control. Levels of initial and
final free gossypol (FG), crude protein (CP), amino acids (AA) and in vitro
digestibility were assayed. The experiment was done in triplicate.
References:
[3] AOCS, 1989. Free and Total Gossypol Methods, Official and Tentative
Methods of the AOCS, 4th Ed. American Oil Chemists’ Society, Chicago.
[4] Barraza, M.L., Coppock, C.E., Brooks, K.N., Wilks, D.L., Saunders,
R.G., Latimer, G.W., 1991. Iron sulfate and feed elleting to detoxify FG in
cottonseed diets for dairy cattle. J. Dairy Sci., 74(10):3457-3467.
[5] Berardi, L.C., Goldblatt, L.A., 1980. Gossypol. In: Liener, I.E. (Ed.),
Toxic Constituents of Plant Foodstuffs, 2nd Ed. Academic Press, NY, p.183-
237.
[7] Cherry, J.P., Gray, S., 1981. Methylene chloride extraction of gossypol
from cottonseed products. J. Food Sci., 46(6):1726-1733.
[9] Francis, G., Makkar, H.P.S., Becker, K., 2001. Antinutritional factors
present in plant-derived alternate fish feed ingredients and their effects in
fish. Aquaculture, 199(3-4): 197-227.
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Title:
**Method for removal of gossypol from cottonseed meal by the use of
urea in a borate containing buffer
Document Type and Number:
United States Patent 5277909
Link to this page:
http://www.freepatentsonline.com/5277909.html
Abstract:
Plant material may be treated for the removal of gossypol therefrom to
provide a protein-rich product and/or oil relatively free of gossypol. The
process includes the steps of: a. grinding the plant material to form a meal,
b. adding an amine and a buffer to the meal and mixing to form a slurry and
react the gossypol in the plant material with the amine and buffer to form a
gossypol/amine/buffer complex, c. allowing the slurry to form a crystal layer
of the complex above a layer of the meal having gossypol removed
therefrom, d. separating the crystal layer from the layer of meal. The
gossypol containing complex recovered also possesses insecticidal activity.
Inventors:
Schmidt, John H. (Leland, MS, US)
Wells, Randy (Raleigh, NC, US)
Bailey, Jack C. (Leland, MS, US)
Application Number:
572070
Filing Date:
08/24/1990
Publication Date:
01/11/1994
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Assignee:
The United States of America, as represented by the Secretary of
(Washington, DC)
Primary Class:
424/776
Other Classes:
530/377
International Classes:
A61K 035/78, A61K 035/80
Field of Search:
424/195.1 530/377
US Patent References:
4340676 Jul, 1982 Bourque 435/232.
4546004 Oct, 1985 Rhee 426/656.
Other References:
The Merck Index 9th Ed., Merck & Co. Rahway N.J. 1976 #4377.
J. H. Schmidt & R. Wells, "Recovery of Soluble Proteins from Glanded
Cotton Tissues with Amines," Anal. Biochem. 154: 244-249 (1986).
E. E. King, "Extraction of Cotton Leaf Enzymes with Borate,"
Phytochemistry 10: 2337-2341 (1971).
S. P. Clark et al., "Removal of Gossypol from Cottonseed Meats with
Aliphatic Amines," Oil Mill Gazeteer 69: 16-21 (1965).
W. G. Bickford et al., "The Antioxidant and Antipolymerization Properties
of Gossypol, Dianilinogossypol, and Related Materials," J. Am. Oil Chem.
Soc. 31: 91-93 (1954).
J. H. Schmidt & R. Wells, "Evidence for the Presence of Gossypol in
Malvaceous Plants Other than Those in the Cotton Tribe," J. Agric. Food
Chem. 38: 505-508 (1990).
Primary Examiner:
Wityshyn, Michael G.
Assistant Examiner:
Gitomer, Ralph
Attorney, Agent or Firm:
Silverstein; M. Howard, Fado; John D., Deck; Randall E.
Claims:
We claim:
a. grinding cottonseed,
b. adding an amine and a buffer to said meal and mixing to form a slurry and
react gossypol in said cottonseed with said amine and said buffer to form a
gossypol:amine:buffer complex,
c. allowing said slurry to form a crystal layer comprising said complex, said
crystal layer being formed above a layer of the meal having gossypol
removed therefrom,
1. Field of Invention
Any plant material containing gossypol can be treated using the process of
this invention. Plant material from the tribes Gossypeae or Hibiscadeae may
be treated, and particularly cottonseed, cotton leaves, okra, or the meal
therefrom.
The amine and buffer employed may be varied and may be readily
determined by one skilled in the art. Suitable amines must be capable of
reacting with a carbonyl group of gossypol and include, for example,
ammonium sulfate and particularly urea. Suitable buffers have ionic groups
or metal-containing ionic groups capable of hydrogen bonding with
gossypol, and include solutions of weak acids and/or their salts. Preferred
buffers include those containing boric acid and/or borate, particularly
Tris/sodium tetraborate buffer. In this preferred embodiment, a
gossypol/urea/borate complex is formed.
Treatment conditions also may be varied. Suitable urea concentrations range
between about 2 and 10M, while the buffer may have an ionic strength
between about 0.01 and 1M with 0.1M being preferred. The effective range
of pH for the complexing reaction is between about 7.0 and 8.0, with 7.6
providing for peak activity. The temperature of the complexing reaction may
be between about 0.degree. C. and 60.degree. C., although the rate of
reaction is slower below 25.degree. C. Formation and drying of the crystals
after the complexing reaction may also proceed within this same temperature
range. However, for substantially faster crystal formation and drying,
heating of the slurry is preferred, particularly between about 55.degree. C.
and 60.degree. C. One skilled in the art will recognize that the reaction time
and the crystal formation and drying time will vary with temperature and
may be readily determined.
To be effective, the agent must be applied to the locus of, or the vicinity of,
the pest to be controlled. When the agent is intended as a stomach poison, it
is applied in conjunction with its carrier to the pest diet. In the case of plants,
the composition will typically be applied to the leaf surfaces or else
systemically incorporated. Alternatively, when the agent is to be applied as a
contact poison, any method of topical application, such as direct spraying on
the pest or on a substrate which is likely to be contacted by the pest, would
be appropriate. In any of these embodiments, the agent may be incorporated
with a bait as will be recognized within the art.
EXAMPLE
Cottonseed meal was prepared for treatment by grinding the seed until a fine
powder was obtained. The powdered meal was then mixed in a slurry with
8M urea in 0.1M Tris/sodium tetraborate buffer (pH 7.6) at a ratio of 1 g
meal to 5 ml buffer. Mixing was continued for 1 hr to allow reaction of the
gossypol with the urea and borate and formation of gossypol/urea/borate
complex. After reaction, the slurry was allowed to settle and then heated to
55.degree. C. for 24 hr. A crystal layer containing the gossypol/urea/borate
complex formed above the meal during this step, which was subsequently
separated from the remaining meal.
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Title:
**Removal of toxins from cottonseed
Document Type and Number:
United States Patent 4747979
Link to this page:
http://www.freepatentsonline.com/4747979.html
Abstract:
A method is disclosed for removal of toxins and oil from cottonseed by
contact of the toxin/oil containing cottonseed with a chlorinated hydrocarbon
solvent and a protic or aprotic solvent. Batch, semicontinuous and
continuous methods of contacting are also described.
Inventors:
Gimber, Gerald A. (Lake Jackson, TX, US)
Haschke, Elliot M. (Lake Jackson, TX, US)
Application Number:
701846
Filing Date:
02/14/1985
Publication Date:
05/31/1988
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Assignee:
The Dow Chemical Company (Midland, MI)
Primary Class:
554/14
Other Classes:
426/430, 426/630
Field of Search:
426/430, 630 260/412.4
US Patent References:
1260656 Mar, 1918 Bollmann 426/430.
1653201 Dec, 1927 Bollmann 260/412.
2475419 Jul, 1949 Battistella 260/412.
2484831 Oct, 1949 Hutchins et al. 260/412.
2680754 Jun, 1954 Stapelberg 260/412.
3721569 Mar, 1973 Steinkraus 260/412.
4008210 Feb, 1977 Steele et al. 426/430.
4062984 Dec, 1977 Lindquist 426/430.
4279811 Jul, 1981 Gray et al. 426/430.
4460504 Jul, 1984 Rubin et al. 260/412.
Other References:
Fore et al, "J. Am. Oil Chemists Soc.", vol. 47, No. 1, pp. 17-18, (1969),
Reprint.
Vix et al, "Chem. Eng. Progress Symp. Series", vol. 65, No. 93 (1969) pp.
49-56 (Reprint).
Primary Examiner:
Evans, J. E.
Attorney, Agent or Firm:
Baker; Glwynn R., Ancona; A. Cooper
Parent Case Data:
CROSS REFERENCE TO THE RELATED APPLICATION
1. A method for simultaneous toxin (gossypol and aflatoxin) and oil removal
from cottonseed meal which comprises
8. The method of claim 1 wherein said solvent mixture is from 0.5 to about
20 percent by weight of methanol based on the chlorinated solvent.
9. The method of claim 1 wherein said solvent mixture is from 0.5 to about
20 percent by weight of ethanol based on the chlorinated solvent.
10. The method of claim 1 wherein said solvent mixture is from 0.5 to about
20 percent by weight of dimethyl formamide based on the chlorinated
solvent.
11. The method of claim 1 wherein said solvent mixture is from 0.5 to about
20 percent by weight of dimethyl sulfoxide based on the chlorinated solvent.
12. The method of claim 1 wherein said solvent mixture is from 0.5 to about
20 percent by weight of isopropyl alcohol based on the chlorinated solvent.
Description:
BACKGROUND OF THE INVENTION
Various solvents have been employed to extract oil from cottonseed meal.
Hexane is the most extensively used solvent in the cottonseed processing
industry. While cottonseed oil is very soluble in hexane, the toxic
components such as aflatoxin and gossypol are not, and thus much of this
toxic material remains in the extracted meal following hexane extraction,
lowering the value of the meal. The gossypol is in the form of free gossypol,
which is toxic, and bound gossypol, in combination with lysine, which is not
toxic but decreases the protein content of the meal. The aflatoxin remaining
with the meal is a toxic residue which reduces the value of the meal
In accordance with the present invention the meal, (flake, ground meal or
expanded) obtained from cottonseed is contacted with a solvent mixture
composed of a chlorinated hydrocarbon solvent and either an aprotic or
protic solvent. The treatment is carried out in a batchwise, semi-continuous
or continuous manner, at ambient temperature or an elevated temperature up
to the boiling point of the solvents. The contacting maybe carried out by
contacting the solvent with the meal batchwise or in counter current
percolation flow through a bed, deep or shallow with or without mild
agitation, e.g. mechanical, ultrasonic or the like. It is of course understood
that the solvent mixture may be vaporized and passed through a mass or
body of flake or meal condensing onto the meal dissolving the toxins into
the condensate. The method of contacting is not critical so long as the meal
is essentially contacted with a sufficient amount of solvent to maintain the
solvent substantially below its saturation point, with respect to the toxins and
oil, in the final contact.
The toxins (e.g. gossypol and aflatoxin) in the solvent/oil solution can be
removed by conventional refining, which are well understood process steps.
Suitable aprotic and/or protic solvents are the lower C.sub.1 to C.sub.4
alcohols (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl,
and tertiary butyl alcohols), alkyl ethers, ketones, as well as dimethyl
formamide, dimethyl sulfoxide and the like. Again, because of public
sentiment lower alcohols are preferred. However, dimethyl formamide
(DMF) and dimethyl sulfoxide (DMSO) are the most efficient solvents in
combination with methylene chloride.
The proportions of the two classes of solvents used in accordance with the
present invention are not critical but for economic and time efficiency from
about 0.5 to about 20 percent by weight of the aprotic or protic solvent is
generally preferred.
EXAMPLE 1
1. MeCl.sub.2 (100%)
The cottonseed meal was placed in a thimble and installed in the soxhlet
apparatus. Low heat was applied which allowed a slow thimble immersion
cycle rate, simulating the percolation process commonly used in the
industry. Extracted meal was dried and analyzed for residual free gossypol.
______________________________________
Residual Free Gossypol (% Wt.)
Total Total Total
Cycles Time Cycles
Time Cycles
Time
Solvent 3 (min) 5 (min) 10 (min)
______________________________________
MeCl.sub.2
0.21 70 0.12 105 0.083 210
MeCl.sub.2 /6%
0.096 70 0.063
105 0.041 210
MeOH
MeCl.sub.2 /10%
0.20 70 0.15 105 0.063 210
Acetone
______________________________________
EXAMPLE 2
Cottonseed meal was extracted with various solvent blends for oil and
gossypol removal. This method employed agitating the samples on a wrist
action shaker for extraction. The blends used were:
1. 7% MeOH in MeCl.sub.2
2. 5% EtOH* in MeCl.sub.2
6. MeCl.sub.2 (control)
Data is as follows:
______________________________________
Solvent Free Gossypol (Wt. %)
______________________________________
MeOH/MeCl.sub.2
0.051
EtOH/MeCl.sub.2
0.058
Ethyl ether/MeCl.sub.2
0.140
DMF/MeCl.sub.2 0.0236
DMSO/MeCl.sub.2
0.0123
MeCl.sub.2 0.135
______________________________________
The process of course can be conveniently carried out in any of the myriad
of equipment conventionally employed by the industry and the solvent
recovered in stills and reused.
The toxins may be isolated from the oil/solvent solution for purification or
removed via conventional refining for disposal.
EXAMPLE 3
In the MeCl.sub.2 extraction, fresh flakes were first percolated with miscella
(MeCl.sub.2 +oil) containing 6.8% oil, followed by successive miscellas of
3.3% oil and 1.0% oil, and a clean MeCl.sub.2 final percolation, simulating
a four stage countercurrent extraction. Solvent to flake ratio (wt) was held at
2:1 for each percolation stage.
______________________________________
Initial Oil in Flakes
Residual Oil in Meal
(% wt) (% wt)
______________________________________
MeCl.sub.2
29.8 1.17
Hexane 29.8 1.57
______________________________________
EXAMPLE 4
______________________________________
Extracted Meal Toxin Residuals
Free
Feed Analysis Aflatoxins Gossypol
Solvent (B.sub.1 + B.sub.2, ppb)
%
______________________________________
Feed Analysis 194 .426
MeCl.sub.2 140 .048
MeCl.sub.2 + .5% EtOH.sup.1
123 .043
MeCl.sub.2 + 2.1% EtOH
2 .034
MeCl.sub.2 + 5.0% EtOH
1 .012
MeCl.sub.2 + 10% EtOH
1 .003
Feed Analysis 183 .449
MeCl.sub.2 + 2% EtOH.sup.1 + .5% H.sub.2 O
1 .022
MeCl.sub.2 + 2% EtOH + 1% H.sub.2 O
.5 .118
Feed Analysis 207 .494
MeCl.sub.2 152 .045
MeCl.sub.2 + .52% MeOH.sup.1
63 .052
MeCl.sub.2 + 2.1% MeOH
.6 .016
MeCl.sub.2 + 2% MeOH + .32% H.sub.2 O
.5 .011
MeCl.sub.2 + 5.2% MeOH
.5 .012
Feed Analysis 195 .456
MeCl.sub.2 139 .030
MeCl.sub.2 + .5% DMSO.sup.1
147 .033
MeCl.sub.2 + 2% DMSO
139 .006
MeCl.sub.2 + 2% DMSO, H.sub. 2 O sat.
2 .018
MeCl.sub.2 + 5% DMSO
2 .006
Feed Analysis 213 .422
MeCl.sub.2 122 .067
MeCl.sub.2 + .05% ISOH.sup.1
131 .056
MeCl.sub.2 + 2% ISOH
118 .037
MeCl.sub.2 + 2% ISOH, H.sub.2 O Sat.
3 .035
MeCl.sub.2 + 5% ISOH
158 .015
______________________________________
.sup.1 EtOH = 95% ethyl alcohol 5% water; MeOH methyl alcohol;
DMSO =
dimethylsulfoxide; ISOH = isopropyl alcohol.
EXAMPLE 5
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Presented in part at the AOCS Annual Meeting, Atlanta, GA, May 8–12,
1994.
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.
The residual toxicity of treated cottonseed meals cannot be explained on the
basis of their free gossypol content as analyzed for meals with high values
gave better growth performance than some with lower levels of free
gossypol. There were also very marked differences in final body weight after
8 weeks of feeding six different treated cottonseed meal samples having
practically the same free gossypol
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**Wen-Ju Zhanga, b, Zi-Rong Xua, , , Shun-Hong Zhaob, Jun-Fang
Jianga, Yan-bo Wanga and Xiang-Hua Yana
a
Key Laboratory of Molecular Animal Nutrition, Ministry of Education,
Animal Science College, Zhejiang University, Hangzhou 310029, PR China
b
College of Animal Science and Technology, Shihezi University, Shihezi,
Xinjiang 832003, PR China
Received 6 January 2006; revised 11 May 2006. Available online 19 May
2006.
Abstract
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The recent "Guideline for Edible Cottonseed Protein Flours and Related
Products" (Food and Nutrition Bulletin, vol. 2, no. 3) provided up-to-date
information on cottonseed products and processes for their production.
A pilot plant was built for the continuous processing of cottonseed meal to
achieve gossypol reduction. Two arrangements for solids were tested, one
using a bag collector and the other using a cyclone separator. The
arrangement using the cyclone worked well, while the other method was less
satisfactory. Several runs were made at different temperatures and flow
rates. It was found possible to obtain a homogeneous product with a final
gossypol content of 0.04 per cent. Trying to reduce it further by increasing
the temperature is not recommended because of a higher lysine loss.
Gossypol reduction was a function of temperature, residence time, initial
gossypol content, and amount of chemical additives, but not of meal flow
rate.
The dry continuous process has the following advantages over the new
technologies that the Guideline makes reference to (liquid cyclone, acetone,
membrane, aqueous extraction):
i. it can be adapted to existing commercial processes;
ii. the investment is minimal relative to the alter natives; and
iii. it does not need special solvents, special equipment, or a new plant.
Carlos Rolz
Head, Applied Research Division
Instituto Centroamericano de Investigatión y Tecnología Industrial
Guatemala
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Thirty-two lactating cows were fed ad libitum diets with 1) 18.7% soybean
meal, 2) diet 1 plus 500 ppm supplemental Fe from FeSO4.H2O, 3) 15%
whole cottonseed, or 4) diet 3 plus 500 ppm Fe from FeSO4.H2O. Dry matter
intakes were similar except for cows fed diet 2, which was lower. Cows fed
whole cottonseed diets ingested 23 g/d of free gossypol per cow. Free
gossypol apparently excreted was lower than its intake. Iron excretion was
similar to Fe intake. Blood metabolites and productive performance did not
differ among the diet groups. No signs of gossypol toxicity were observed.
Twelve neonatal Holstein male calves were fed a commercial milk replacer
for 4 wk, then were allowed ad libitum access to diets with 1) 27% soybean
meal, 2) 50% whole cottonseed, or 3) diet 2 plus 500 ppm Fe from
FeSO4.H2O. Dry matter intakes were similar but slightly lower for calves fed
diet 3. Daily individual intakes of free gossypol from diets 2 and 3 were 2 g,
which was lower than the expected 4 g due to an apparent effect of pelleting.
Blood metabolites did not differ among the groups, and calves averaged
about .6 kg of daily gain on these diets. A follow-up study showed that
pelleting reduced free gossypol by as much as 70% in whole cottonseed and
by 48% in cottonseed meal. Pelleting represents a mechanism to decrease the
toxicity of gossypol in cottonseed products.
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**Article
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The results of these experiments point to the conclusion that cottonseed meal
free of pigment glands is devoid of any toxic principle as judged by the
growth of rats and histopathological examination of visceral organs. Our
results would indicate that hexane-extracted meal is not completely devoid
of toxic principles or appetite-depressing factors, as judged by inhibition in
the growth of rats on a diet containing 15% or more of the meal. This
inhibition in growth cannot be accounted for completely by the slight
difference in food consumed between rats on this diet and the controls or rats
on a lower dietary intake of hexane-extracted meal. It would appear at first
sight that the toxicity of hexane-extracted meal (15% level) may be due to
the gossypol present in the meal, since 0.256% of pigment glands
(equivalent to 0.096% gossypol) in the diet of rats produced an inhibition in
growth comparable to that produced by the diet containing 15% of hexane-
extracted meal. However, it is doubtful if gossypol is the chief responsible
constituent, since rats on the 0.256% pigment gland diet processed from
seeds stored for approximately 6 months were not similarly affected. This
difference in toxicity of the two samples of pigment glands used may be
accounted for on the basis of storage time before processing for removal of
the pigment glands. The gossypol content of the two pigment-gland diets
was extremely small, 0.096 and 0.0934%, respectively, as compared to
0.16% for the diet containing 15% of hexane-extracted meal. Comparable
chronic toxicity studies of gossypol were not made, because of the
unavailability of enough gossypol at the time the studies with cottonseed
meal and pigment glands were being carried out.
From the acute and subacute oral toxicological data obtained, it is concluded
that the toxicity of cottonseed pigment glands and gossypol is low. Single
oral doses of pigment glands of up to 3,000 mg/kg, or gossypol in doses of
up to 800 mg/kg each, did not appear to produce any toxic symptoms.
The repeated administration of cottonseed pigment glands in doses of 2,000
mg/kg three times at 7-day intervals caused the rats to lose weight, depressed
appetite, and produced diarrhea. Similarly, the repeated oral administration
of gossypol in doses of 500 mg/kg at 5-day intervals had an effect similar to
that of the pigment glands except that it did not produce diarrhea. Lower
doses of pigment glands or gossypol were without effect.
The experimental data raise the question of whether or not chemical assay of
cottonseed pigment glands for gossypol is a reliable index, since a difference
has been observed in the toxicity of pigment glands processed at different
times, while the gossypol content was approximately the same.
Since the completion of this work a paper by Lillie and Bird (’50) on chicks
has appeared in which our findings on the toxicity of cottonseed pigment
glands and gossypol are confirmed.
It was observed that the use of warm water (50 C), in preparing the ferrous
sulfate-cotton-seed meats mixture, improved the combination of iron and
gossypol to the extent that free gossypol in the redried meats was reduced
from 1.17 to .01%.
Footnotes 1 Paper No. 5397 of the Journal series of the North Carolina
Agricultural Experiment Station, Raleigh. The use of trade names in this
publication does not imply endorsement by the North Carolina Agriculture
Experiment Station of the products named, nor critisism of similar ones not
mentioned.
2
Present address: Venezuelan Ministry of Agriculture, Maracoibo,
Venezuela.
3
Animal Science Department.
4
Appreciation is expressed to Cotton Incorporated for support of this project.