USOO7772211 B2

(12) United States Patent (10) Patent No.: US 7,772,211 B2

Tsai et al. (45) Date of Patent: *Aug. 10, 2010
(54) PRODUCTION OF CARRAGEENAN AND 4,859.484 A 8, 1989 Bielskis et al.
CARRAGEENAN PRODUCTS 4,950,752 A 8, 1990 Whitaker
5,089,307 A 2/1992 Ninomiya et al.
(75) Inventors: Albert G. Tsai, New Castle, DE (US); 5,275,803 A 1/1994 Dawson
Linnea K. S. Ledwith, Rockport, ME 5,275,834 A 1/1994 Thibault et al.
(US); Robert Kopesky, Camden, ME 5,342,626 A 8/1994 Winson, Jr. et al.
(US); Maurice Gerard Lynch, Waterloo 5,496,936 A 3, 1996 Thami et al.
(BE); William Ross Blakemore, 5,502,179 A 3, 1996 Larsen
SpyMESS; Peter J. Riley, 5,662,840 A 9/1997 Thomas et al.
s 5,756,123 A 5/1998 Yamamoto et al.
(73) Assignee: FMC Corporation, Philadelphia, PA 5,777,102 A * 7, 1998 Larsen ....................... 536,124
(US) 5,801,240 A 9, 1998 RideOut et al.
6,042,854 A 3/2000 Morris et al.
( c ) Notice: Subject to any disclaimer, the term of this 6,045,780 A * 4/2000 Bixler et al. .................. 424/49
patent is extended or adjusted under 35 6,063,915 A 5, 2000 Hansen et al.
U.S.C. 154(b) by 616 days. 6,146,570 A 1 1/2000 Stern et al.
6,214,376 B1 4/2001 Gennadios
This patent is Subject to a terminal dis- 6,268,191 B1 7/2001 Prudhomme et al.
claimer. 6,331.205 B1 12/2001 Paris et al.
6,375,981 B1 4/2002 Gilleland et al.
(21) Appl. No.: 11/542,936 6,387.354 B1 5/2002 Bixler et al.
(22) Filed: Oct. 4, 2006 6.479,649 B1 * 1 1/2002 Tsai et al. .................. 536,111
6,528,088 B1 3/2003 Gilleland et al.
(65) Prior Publication Data 6,582,727 B2 6/2003 Tanner et al.
6,635,275 B1 10/2003 Scott et al.
US 2007/O112184 A1 May 17, 2007 6,685,978 B1 2/2004 Hauksson ................... 426,573
Related U.S. Application Data 7,018,635 B2* 3/2006 Tsai et al. .............. 424,195.18
(60) Division of application No. 10/450,107, filed as appli
cation No. PCT/US01/47020 on Dec. 10, 2001, now
Pat. No. 7,189,843, which is a continuation-in-part of (Continued)
application No. 09/798.012, filed on Mar. 2, 2001, now
Pat. No. 6,479,649. FOREIGN PATENT DOCUMENTS
(60) Provisional application No. 60/255.279, filed on Dec. CL 125-96 9, 1996
13, 2000.
(51) Int. Cl.
A6 IK3I/73 (2006.01) (Continued)
C7H I/06 (2006.01) OTHER PUBLICATIONS
C7H I/08 (2006.01)
(52) U.S. Cl. ...................................... 514/54:536/123.1 Stancioff D. Carrageenans: Versatile Food Ingredients, Foods Food
(58) Field of Classification Search ....................... None Ingredients J.Japan, 167, 37-47, 1996.
See application file for complete search history. (Continued)
(56) References Cited
Primary Examiner Eric S Olson
U.S. PATENT DOCUMENTS
(57) ABSTRACT
2,620,334 A 12/1952 Nielson et al.
2,620,335 A 12/1952 Nielson et al.
2,624,727 A 1/1953 Le Gloahec
3,094,517 A 6/1963 Stanley The methods of the present invention prepare carrageenan
3,176,003 A 3, 1965 Stancioff products from processed seaweed material having a solids
3,280,102 A 10/1966 Gordon et al. content of less than 25% by weight Solids, using shear stress
3,342,612 A 9, 1967 Foster et al. treatment. The carrageenan products comprise at least about
3,849,395 A 1 1/1974 Moirano et al. 60% by weight of carrageenan and at least about 2% by
3.855,149 A 12, 1974 Bielskis weight of acid insoluble material. The carrageenan products
3,901,873. A 8, 1975 Doi et al. of the present invention are useful as components in food
3,907,770 A 9, 1975 Strong products, such as, dairy products, meats, and dessert gels as
4,112,223. A 9, 1978 Lin et al. well as non-food products, such as, toothpaste formulations,
4,443,486 A 4/1984 Guiseley cosmetics, paints, films and delivery capsules
4,765,886 A 8, 1988 Whitaker s s
4,816,278 A 3, 1989 Sasmoto et al.
4,851,394 A 7, 1989 Kudodera 5 Claims, 1 Drawing Sheet
 US 7,772,211 B2
Page 2

U.S. PATENT DOCUMENTS WO WO90,04333 5, 1990

WO WO94,22921 10, 1994
7,189,843 B2 * 3/2007 Tsai et al. ................... 536,114 WO WO94,22922 10, 1994
2002, 0071861 A1 6, 2002 Blanchin et al. WO WO 98.40412 9, 1998
WO WO99/47249 9, 1999
FOREIGN PATENT DOCUMENTS WO WOOOO6609 2, 2000
EP 0432835 * 6/1991 WO WOOOf 10538 3, 2000
EP O 598 141 A1 5, 1994 WO WOO1,03677 1, 2001
EP O 812545. A 12/1997 WO WOO1? 66O73 A2 9, 2001
EP O812545 * 12/1997
JP 11252 8, 1958 OTHER PUBLICATIONS
JP S48-0912S6 11, 1973 DeRuiter G. Carrageenan Biotechnology, Trends in Food Science &
JP 55-12234 3, 1980 Tech 8(12)389-395, Dec. 1997.
JP S55-12234 3, 1980 Prakash, J., “Proceedings of the Regional Workshop on Seaweed
JP S57-2O875 12/1982 Culture and Marketing.” South Pacific Aquaculture Development
JP S59-1795O2 10, 1984 Project, Adams, T., et al. (Eds.), Nov. 14-17, 1989, 1-86.
JP S60-055O39 3, 1985 Stanley, N., "Chapter 3: Production, properties and uses of car
JP 61254.146 11, 1986 rageenan.' Food and Agriculture Organization of the United Nations,
JP S62-29.947 2, 1987 FAO Fisheries Technical Paper No. 288, McHugh, D.J. (Ed.), 1987,
JP S62-186754 8, 1987 116-146.
JP S63-164858 T 1988 Meiji, et al., “Treating seaweed to enable utilisation of components -
JP S63-216442 9, 1988 by crushing, adjusting water content and extruding.” Derwent Pub
JP H1-211463 8, 1989 lications Ltd., London, XP002 196719, Nov. 28, 1973. 1 page
JP HO3-0 12231 1, 1991 (Abstract).
JP HO3-053873 3, 1991 PCT International Search Report dated Jun. 11, 2002 (PCT/US01/
JP 2 572611 1, 1997 47020).
JP H10-025302 1, 1998
WO WO 84/00761 3, 1984 * cited by examiner
U.S. Patent Aug. 10, 2010 US 7,772.211 B2

FIGURE 1
Brabender Profile V. Feed Moisture Content
E. Cottonii, Examples 1-3
S 200
15
2.
1 g
3R
O
70,00 75.00 80,00 85.00 90.00
%MC in feed
amOn 1st Brabenber Peak, (2nd Brabender Peak
admTemp of 1st Peak"C. IrarTerp. of 2nd Peak C
 US 7,772,211 B2
1. 2
PRODUCTION OF CARRAGEENAN AND or by oxidative depolymerization upon treatment with hydro
CARRAGEENAN PRODUCTS gen peroxide. Upon cleavage of the polymer chains, carrag
eenan products having optimum gelling properties and vis
RELATED APPLICATIONS cosity can be obtained.
In a typical process for making pure carrageenan, crude
This application is a divisional application of U.S. appli seaweed is first washed with cold water to remove sand and
cation Ser. No. 10/450,107, filed Oct. 14, 2003 now U.S. Pat. other particulates that may be present after the seaweed has
No. 7,189,843 allowed May 9, 2006, incorporated herein by been harvested. Carrageenan typically does not Swell during
reference, which is the U.S. National Phase or PCT/US01/ the cold wash, primarily because carrageenan in seaweed is
47020, filed Dec. 10, 2001, which is a continuation in part of 10
U.S. application Ser. No. 09/789,012, filed Mar. 2, 2001 now associated with the structural components of the seaweed,
generally cellulose. Depending on the seaweed species, fol
U.S. Pat. No. 6,479,649 which claims priority on U.S. Provi lowing the cold wash a hot water extraction procedure is
sional Application 60/255.279, filed Dec. 13, 2000. typically performed in which the extracted carrageenan is
FIELD OF THE INVENTION 15
treated with aqueous base at high temperature. Generally, the
base used is an alkali or alkaline earth metal hydroxide Such
The present invention is directed to carrageenan products, as, for example, NaOH, Ca(OH), or KOH. This high tem
perature aqueous base modification leads to the formation of
methods of preparing Such carrageenan products, and to for 3,6-anhydro linkages in the galactose units of the carrageenan
mulations containing carrageenan products according to the polysaccharide. After base modification, the hot extract is
present invention. filtered to remove insoluble material such as cellulose, hemi
BACKGROUND OF THE INVENTION cellulose and other particulates, and acid is added to adjust the
pH to 9 or lower. The filtrate can then be concentrated to
Carrageenan is a complex mixture of sulfated polysaccha about4% carrageenan for further processing. Optional proce
rides comprising linear polymers of 1.3 bound C-D-galactose 25
dural steps after extraction may include centrifugation and
units and 1.4 bound C-D-galactose units with the general bleaching. Pure carrageenan is typically obtained by precipi
formula: tation of the extract from the aqueous solution with KCl oran
alcohol Such as isopropanol.
Preparation of pure carrageenan by extraction on a com
30 mercial scale is expensive because of viscosity and gelling
wherein A and B represent galactose residues derived from properties that limit the rate at which Such carrageenan prod
two different groups. ucts can be processed. After the extraction step, a hot aqueous
Carrageenan is extracted from red seaweeds and consti stream can typically only contain low concentrations of car
tutes the principal structure of the seaweed. It is located rageenan, typically up to about 4%. At higher concentrations
within the cell wall and intracellular matrix of the plant tissue. 35 of carrageenan, the aqueous stream becomes too viscous to be
The carrageenan content of commercially harvested sea processed efficiently. Therefore, a relatively low proportion
weeds is generally between 30% and 80% based on the sea of carrageenan is obtained per unit volume of the aqueous
weed dry weight. process stream.
Carrageenan finds wide applicability as a food ingredient There has been an ongoing search for more cost-effective
and is functional in foods such as dairy products, water des methods of preparing semi-refined carrageenan and other
40
sert gels, meat products, confections, beverages, dressings products as lower cost replacements for conventional carra
and other Such products. Carrageenan is also used in non-food geenan. Semi-refined carrageenan (SRC) products are those
products such as cosmetics, toothpaste, and other personal in which few or none of the structural components of the
care products. The molecular weight of commercial carrag seaweed, principally cellulose, have been removed. During
eenan products is typically from about 100,000 to 1,000,000 45 the preparation of SRC, a salt such as KCl or NaCl typically
Daltons. Carrageenans have the unique ability to form an is added during base modification along with the base. The
almost infinite variety of gels at room temperature, with a presence of sufficient amounts of salt prevents disintegration
variety of gelling and melting points. These gels require no of the seaweed structure and inhibits extraction of carrag
refrigeration, and can be made stable through repeated freeze eenan from the seaweed. An alcohol. Such as isopropanol, can
thaw cycles. Carrageenan Solutions can thicken, Suspend, and 50 also be used to inhibit extraction during the high temperature
stabilize particulates, colloidal dispersions and water/oil base modification step. Following the base modification step,
emulsions. The solutions shearthin, which allows them to be with the seaweed structure still intact, the processed seaweed
pumped easily. Also, the Solutions rapidly rebuild viscosity mixture is typically dried to afford SRC. When the seaweed is
and Suspending power on standing. Depending upon the food a member of the Eucheuma family, the SRC obtained is
application, carrageenan present in a few percent by weight or 55 known as processed Eucheuma seaweed (PES).
less provides gelling, thickening, and binding, and also helps U.S. Pat. No. 5,502,179 is directed to processes wherein
in imparting appropriate texture to the food product. Owing to the seaweed starting (feed) material is mixed with a base and
these qualities, carrageenan is particularly desirable as a fat a solvent in which carrageenan is insoluble. This base-treated
replacement in low fat foods. mixture is washed with an aqueous Solution and then Sub
Carrageenan is generally soluble in warm water, in which 60 jected to shear stress treatment (Such as an extrusion process
it forms viscous solutions. It is insoluble in most organic or by means of a shear mixer). The shear stress treatment is
Solvents, and typically forms complexes with proteins. The said to be performed on seaweed material having a solids
major types of carrageenan are designated as kappa, iota, content of at least 25%, at a temperature between iooaC and
lambda, nu and mu. These are differentiated based on the 175°C., for about 10 to 200 seconds. The carrageenan mate
nature of the repeating galactose units contained in the car 65 rial resulting from the shear stress treatment may be dried and
rageenan. The polymer chains in carrageenan can be cleaved Subjected to comminution, grinding or milling to obtain a
by hydrolytic depolymerization upon treatment with an acid, powder with a particle size in the range of 0.05 to 0.5 mm.
 US 7,772,211 B2
3 4
Conventional carrageenans typically have some advan rageenan product further comprises about 2% to about 15%
tages relative to SRC obtained from the same seaweed. One by weight of a salt. A preferred salt is sodium chloride.
Such advantage is that they typically begin to hydrate, i.e., The present invention further includes foods and other
they begin to swell and solubilize, at a lower temperatures products containing a carrageenan product or products pro
than does SRC. For example, conventional iota carrageenan duced by the foregoing methods. The carrageenan product
obtained from Eucheuma spinosum will hydrate, Swell, and preferably comprises at least about 60% by weight of carra
solubilize at room temperature. PES derived from Eucheuma geenan and at least about 2% by weight of acid insoluble
spinosum, however, does not hydrate, Swell and Solubilize material. For Such carrageenan products produced from
until first heated to above about 60° C. Another such advan Eucheuma cottonii, the onset of hydration can be as low as
tage is that because SRC contains cellulosic and other mate 10 below about 50° C. For such carrageenan products produced
rials which are absent in conventional carrageenan, gels from Eucheuma spinosum, the onset of hydration can be as
formed from SRC have reduced clarity relative to pure carra low as below about 30° C.
geenan gels. Therefore, utility of SRC products has been Other products include toothpaste formulations compris
limited to those applications where the food product is not ing a binder, a humectant, an abrasive, and water, wherein the
required to be clear and can be readily prepared at the high 15 binder is a carrageenan product according to the present
temperatures required for hydration and solubility of carrag invention. It is preferred that the concentration of the binder
eenanto occur. Formany applications, however, it is desirable be from about 0.5 to about 1.5% by weight of the toothpaste
to have an SRC which provides gelling without the need for formulation.
such high temperatures. It is also important that SRC have The present invention further includes methods of making
acceptable color and appearance Suitable for use in products articles containing one or more carrageenan products pro
made for human consumption Such as, for example, cream, duced by the methods of the invention. In one embodiment, a
ice cream, other dairy products, and beverages, as well as Solution comprising the carrageenan-containing product of
non-food products Such as, for example, cosmetics, tooth the invention is heated and at least a portion of the heated
paste, and other personal care products. solution is then subjected to conditions effective to transform
Therefore, there is a need in the art for a low cost processes 25 it into a barrier material. Films can beformed, for example, by
for producing carrageenan products with improved hydration casting the Solution on a cooled rotating drum. Optionally, the
characteristics while maintaining acceptable color and carrageenan-containing film can be fed through a series of
appearance Suitable for use in food products. rollers to counter rotating dies which form, cut, and fill cap
Sules of various sizes.
SUMMARY OF THE INVENTION 30
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention provides methods for preparing a
carrageenan product comprising the steps of providing a car FIG. 1 is a graph showing changes in the Brabender profile
rageenan-containing seaweed material having a seaweed sol with varying levels of feed moisture content.
ids content of less than 25% by weight, and subjecting this 35
seaweed material to shear stress treatment. The carrageenan DETAILED DESCRIPTION OF THE INVENTION
containing seaweed material optionally is treated with base
prior to extrusion. The present invention is directed to processes for preparing
In one embodiment, the carrageenan-containing seaweed carrageenan-containing products from processed seaweed
material is prepared by a process comprising the steps of 40 using shear stress. Representative seaweed species include
washing the seaweed with water to produce washed seaweed; those from the Eucheuma, Gigartina, Chondrus, and Irideae
rinsing the seaweed with water to form rinsed seaweed; and families. Preferred species include Eucheuma spinosum,
washing the rinsed seaweed with water oranaqueous Solution Eucheuma cottonii, and Gigartina radula.
to form the carrageenan-containing seaweed material. Processed seaweed can be obtained by treatment of the
In another embodiment, the methods of the present inven 45 seaweed with a base, followed by neutralization, if needed.
tion comprise washing the seaweed with water, treating the Base modification of the crude seaweed is optional and can be
seaweed with a base at a temperature of about 25°C. to about performed with a base such as NaOH, KOH, or Ca(OH) in
65° C. to form base-modified seaweed; rinsing the base the presence of a salt such as NaCl, or KC1. Subsequent
modified seaweed with water, washing this base-modified aqueous rinses of the modified seaweed can contain salt. As
seaweed with an aqueous Solution of a salt; rinsing this base 50 used herein, the term "salt” refers to the reaction product
modified seaweed with water to form processed seaweed, obtained when a metal displaces a hydrogen atom of an acid.
wherein the processed seaweed comprises less than 25% In the present invention, the salt may be used in the form of an
Solids; extruding this processed seaweed to form extruded aqueous solution. If a salt is to be used in the rinses; it is
seaweed; and drying the extruded seaweed to form a carrag preferable to use the same Salt as was used in the base modi
eenan product. 55 fication procedure. Use of a sodium salt, instead of a potas
In yet another embodiment, the concentration of the aque sium salt, typically affords a final, shear-stressed product
ous salt solution is less than about 40%. It is preferred that the having improved water solubility.
concentration of the aqueous salt Solution be less than about The carrageenan-containing seaweed feed material
15%. It is more preferred that the concentration of the aque obtained prior to shear stress treatment is dried, or is either
ous salt solution be between about 2% and about 15%. 60 semi-dried or wet and has a solids content of less than 25%.
The present invention also includes carrageenan products As used herein, the term "solids content” is the difference
that preferably comprise at least about 60% by weight of between the total weight and the weight of the moisture or
carrageenan and at least about 2% by weight of acid insoluble water content in the seaweed material mixture. The water
material, and have an onset of hydration below about 50°C. In content of the seaweed material prior to extrusion includes
a preferred embodiment, the carrageenan product is derived 65 water that may be bound to the seaweed material (as water of
from Eucheuma spinosum, or any other species containing hydration), or water that has been added to the seaweed mate
iota-carrageenan. In another preferred embodiment, the car rial.
 US 7,772,211 B2
5 6
In some instances, such as, for example, where the carra In another embodiment of the present invention, the carra
geenan containing seaweed feed material is obtained dry, it is geenan-containing feed material is fed into a single screw
typically necessary to add water to the dried seaweed material extruder that is connected to a twin screw extruder. The single
to reconstitute it before extrusion. screw extruder can be, for example, a Wenger Model X-85
It has been observed that when a feedstream of seaweed 5 and the twin screw extruder can be, for example, a Wenger
material has a solids content of 25% or higher, shear stress Model TX-57 (both commercially available from Wenger
treatment typically results in an unacceptable darkening of Manufacturing, Inc., Sabetha, Kans.). Typically, the outlet of
the material. The color of a carrageenan product is typically the single screw extruder is connected to the inlet of the twin
very important to an end user. End users who prepare prod screw extruderby, for example, an insulated, flexible pipe.
ucts for human consumption, for example, typically select 10 While not intending to be limiting, it is believed that in
SRC products that are no darker than off-white, with cheaper, extrusion systems in which a single screw extruder feeds into
more deeply-colored products often finding their way into a twin screw extruder, the heat generated by the single screw
products in which color is not such a concern. extruder thermally prepares the carrageenan-containing sea
While not fully understood, the differences that are weed material for higher shear stress in the twin screw
observed with respect to feedstreams having more than 25% 15 extruder. This heat is believed to pre-hydrate, or begin to
solids may be due to the effect that the water has on the heat solubilize, the carrageenan in the seaweed feed material.
generated by the shear stress to which the feedstreams are Other means to generate this heat can be used to thermally
exposed. Water tends to dissipate heat created during the prepare the carrageenan-containing seaweed material. Such
extrusion away from the seaweed material, decreasing the as, for example, high-shear and/or high Solids mixers.
extent to which the heat is available to caramelize Sugars in The solids content of wet processed seaweed fed into the
the feedstock, thereby darkening the final product. Thus, extruder typically is less than 25% by weight. The solids
where there is more water to dissipate heat, lighter products content of the processed seaweed can, for example, be about
are produced. 24%. In one embodiment, the carrageenan-containing sea
Color changes that occur during shear stress treatment can weed material or processed seaweed comprises about 23%
be monitored with the human eye or with a suitable measure 25 Solids. In another embodiment, the processed seaweed com
ment device. In accordance with preferred embodiments of prises about 22% solids. In a further embodiment, the pro
the present invention, the amount of color development that cessed seaweed comprises about 21% solids. In yet a further
occurs during shear stress treatment will correspond to less embodiment, the processed seaweed comprises about 20%
than about 4.0 L * units as measured using a Macbeth Color solids. In a still further embodiment, the processed seaweed
Eye 3000 colorimeter and dry powders having a particle size 30 comprises about 18% solids. In another embodiment, the
characterized in that at least 99% of the powder passes processed seaweed comprises about 16% solids. In a pre
through a 100 mesh screen. ferred embodiment, the solids content of the carrageenan
To maintain the uniformity of the color and appearance of containing seaweed material is between about 10% and about
the carrageenan products and formulations containing Such 20% by weight. In a more preferred embodiment, the solids
products, the carrageenan-containing seaweed material 35 content of the carrageenan-containing seaweed material is
should be fed into the extruder as a relatively dilute feed between about 13% and about 17% by weight.
stream. Such a dilute feedstream typically leads to a final The extruder screw proffie is designed to provide a level of
product with improved aesthetics (believed to be a result of shear that is sufficient to disrupt the cellulose structure of the
optimal hydration of the carrageenan contained in the sea seaweed. A typical Screw comprises five high shearing sec
weed). Moreover, water typically does not have to be 40 tions made up of conveying elements, mixing blocks, and
removed from the carrageenan containing seaweed product reverse elements for three of the high shear sections. Convey
prior to feeding it into the extruder, which leads to a cost ing elements transport the processed seaweed material along
effective process for the preparation of a carrageenan product the extruder. Reverse elements increase the residence time in
as the seaweed is more efficiently sheared under Such condi the mixing blocks where some shearing occurs. The first,
tions. Wet processed seaweed can be in the form of chips, 45 second and seventh barrels contain only conveying elements.
preferably about 2 cm to 5 cm. A screw cap secures a die plate to the extruder exit leaving a
Extrusion is a convenient method of shear stress treatment. relatively small air gap. The air gap may be adjusted to
Extrusion equipment with various designs can be used for achieve Sufficient back pressure for adequate shearing. For
extrusion of wet processed seaweed. Examples of extruders example, with the Clextral Model BC45, an air gap of 1.75
include, but are not limited to, twin-screw extruders such as 50 mm is used. Here, the die plate contains three holes, each
the Clextral Model BC45 (Clextral, Inc., Tampa, Fla.) and being 6 mm in diameter.
Werner-Pfliederer Model ZSK-30 (Werner-Pfliederer Corp., To provide adequate shearing, a screw speed of at least
Ramsey, N.J.). Selection of the appropriate equipment and about 200 rpm is needed. It is preferred that the screw speeds
extrusion conditions will be apparent to those skilled in the art be at least about 500 rpm, more preferably, at least about 600
in view of the examples described below. 55 rpm.
In one embodiment of the present invention, a Clextral Extrusion temperatures can be adjusted to achieve optimal
Model BC45 twin screw extruder is used. This extruder has and efficient extrusion. Elevated extrusion temperatures can
eight barrels, each barrel having an internal diameter of 50 assist in disrupting the seaweed structure, thereby liberating
mm and a length of 200 mm. The screws are 1600 mm long, carrageenan from the structural components of the seaweed.
having a center-to-center distance of 45mm. Wet processed 60 A suitable extrusion temperature is at least about 90° C., and
seaweed can be fed into the open top of the first barrel by a preferably about 120° C.
loss-in-weight twin screw feeder. Additional water may be Preferably, the conditions inside the extruder are such that
pumped into the first barrel to adjust the solids content. The a phenomenon called 'steam explosion’ occurs. Steam
remaining barrels are equipped with induction heating coils explosion is the rapid discharge of material from the extruder
and water circulation for temperature control. A venting 65 die as a result of steam pressure inside the extruder. Specifi
option to allow the escape of steam may also be provided, cally, by operating the extruderata Sufficiently high tempera
preferably on the seventh barrel. ture and pressure, steam becomes pressurized in the extruder
 US 7,772,211 B2
7 8
and, as a result, the carrageenan-containing seaweed material posites as contrasted with simple admixture or blending, as
is rapidly discharged to atmospheric pressure through the described, for example, in U.S. Pat. No. 5,441,753 at col. 5,
extruder's exit die. It is believed that the trapped steam inside line 32 et seq.
the extruded material expands at the die’s orifice and results The throughput rate of wet processed seaweed can be var
in a change in the morphology of the exiting material. Typi ied. For example, when employing a Clextral Model BC45
cally, the exiting material changes from Solid strands to finely having an air gap of 1.75 mm, the throughput rate of the wet
divided, highly expanded, open structured granules. Such processed seaweed is typically from about 40 pounds per hour
granules have an increased surface area relative to granules up to about 200 pounds per hour. Generally, for a particular
formed in the absence of steam explosion. extruder, residence time of processed seaweed in the extruder
There are several advantages to operating the extruder 10 decreases as the throughput rate increases. For example, for
under conditions that promote steam explosion. One Such the Clextral extruder, a throughput rate of about 80 pounds of
advantage is that the increased Surface area of the granular wet processed seaweed per hour results in a residence time of
carrageenan-containing seaweed material allows the product about 50 seconds. Solubility of extruded processed seaweed
to cool faster. Hot products often stick to each other, whereas is generally better at lower throughput rates, presumably
cool products typically do not. Thus, material handling is 15 because of the greater residence time of processed seaweed in
improved when the product has an increased surface area. The the extruder. Greater residence time allows for more shearing
increased Surface area of the 'steam exploded granules also in the mixing blocks. Accordingly, improved solubility of wet
allows the granules to dry faster and to hydrate faster. processed seaweed can be obtained at higher throughput rates
In other embodiments of the invention, the carrageenan if the residence time is also increased. Increased residence
containing seaweed feed material may be either admixed or time can be achieved by increasing the extruder length or
co-processed with hydrocolloids and/or other additives to increasing the number of reverse elements. Also, at high
enhance functionality and/or to improve economics by low throughput rates, the barrels are fuller, which further
ering cost or expanding applications. For example, if the enhances shearing in the mixing blocks.
carrageenan product is intended for use in toothpaste, the Cold solubility temperature of extruded processed sea
carrageenan-containing feed material (e.g., processed sea 25 weed from Eucheuma spinosum is affected by the salt content
weed or washed seaweed) may be admixed or co-processed of the product. Generally, for lower temperature solubility, a
with a food grade cellulosic Such as cellulose, microcrystal preferred salt is NaCl. An effective salt concentration is typi
line cellulose (MCC) and/or chemically modified cellulose cally less than about 25% by weight, preferably less than
such as carboxymethyl cellulose (CMC), methyl cellulose about 15% by weight. More preferably, the salt concentration
(MC), hydroxyethyl cellulose (HEC), hydroxylpropyl cellu 30 is between about 2% and 15% by weight. The desired salt
lose (HPC) and hydroxypropyl methylcellulose (HPMC), concentration may be obtained by rinsing the processed sea
and with humectants, buffers, surfactants, emulsifiers, weed material with water or abrine solution priorto extrusion.
sequestrants, other bleaching or color agents, odor control Processed seaweed material from Eucheuma spinosum sea
agents and the like. Similarly, processed Euchena cottonii, weed, having a salt concentration of about 25%, typically has
processed Euchena spinosum, and Euchena wet seaweed 35 a maximum swelling temperature of about 92°C. Depending
feed materials may be either admixed or co-processed with upon the extrusion conditions and the salt concentration
one or more of (i) such cellulose, MCC and/or chemically employed in the methods of the present invention, the maxi
modified celluloses; (ii) other seaweed extracts such as fur mum swelling temperature may be lowered to about 10°C. to
cellaran, agar and alginates including their salts and/or about 70° C. For example, extrusion of processed Eucheuma
chemically modified derivatives, e.g., propylene glycol algi 40 spinosum seaweed material having a sodium chloride con
nate; (iii) natural gums and gum exudates, such as gum arabic centration of about 10% lowers the maximum swelling tem
and gum karaya, polymannans Such as locust bean gum, guar perature to about 25°C.
and konjac, and plant extracts such as pectins and amidated The carrageenan products of the present invention com
pectins; (iv) biosynthetic gums such as Xanthan, gellan and prise carrageenan and acid insoluble material, and preferably
dextran, (v) proteins such as gelatin and chitin; (vi) Synthetic 45 have an onset of hydration below about 50° C. The carrag
hydrocolloids such as polyvinylpyrrolidone (PVP), carbox eenan products of the present invention preferably comprise
yvinyl polymers (e.g., Carbopol products), methylvinyl at least 70% by weight carrageenan and at least 2% acid
ether/maleic anhydride polymers (e.g., GantreZAN products) insoluble material. In one embodiment of the present inven
and ethylene oxide polymers (e.g., Polyox products); (vii) tion, the onset of hydration is below 350C. In a further
starches, modified Starches, dextrins, dextrose, Sugars, Sur 50 embodiment, the onset of hydration is below 25°C. In a
factants, emulsifiers and salts; and/or other additives such as, preferred embodiment, the carrageenan product of the
for example, microreticulated proteins, microcrystalline present invention is derived from Eucheuma spinosum, which
starch, and the like. The additives may be selected to provide affords iota carrageenan. The acid insoluble material com
enhanced functionality including dispersion, hydration, Solu prises structural components of the seaweed, predominantly
bility and other properties desired in the carrageenan-contain 55 cellulosic material.
ing products of the invention and in food and other products The carrageenan products of the present invention typi
for which the carrageenan-containing products are intended. cally contain up to about 20% by weight water, preferably
Such additives, functionality and properties are known, as about 10% by weight. In a preferred embodiment, the carra
described, for example, in U.S. Pat. No. 5,502,179 at column geenan products further comprise about 2% to about 20% by
5, line 21 et seq. The additives may be introduced before, 60 weight of salt, preferably sodium chloride. It is more pre
during, or after the shearing operation or to the carrageenan ferred that the carrageenan product comprise about 2% to
containing product resulting from the shearing. The additives about 5% salt.
may also be co-processed with the carrageenan-containing It is preferred that the carrageenan products of the present
seaweed feed material prior to or as part of the shearing invention have a particle size in the range of about 50 microns
operation, or may be coprocessed with the carrageenan-con 65 to about 200 microns. The desired particle size depends upon
taining product resulting from the shearing. "Co-processing the particular application. For example, some applications,
or similar term, as used herein, means the formation of com Such as meats, require a very fine particle size Such that the
 US 7,772,211 B2
10
carrageenan products can fit through an injection needle, 80 pounds per hour and having a salt concentration of about
hence, a product having an average particle size on the low 10% NaCl, heated to 50° C., forms a gel having a break
end of this range is typically employed. In other applications, strength of about 150 g.
Such as, for example, toothpaste, the particle size of the car The carrageenan products of the present invention are fur
rageenan product is less important and, hence, a product ther directed to a multiplicity of applications. Such applica
having an average particle size on the high end of this range is tions include products made for human consumption Such as,
typically employed. for example, meats, salad dressings, sauces, dairy products
The onset of hydration of a carrageenan product according Such as, for example, cream, milk ice cream, and nutritional
to the present invention is determined by measuring the vis and pharmaceutical capsules, as well as non-food industrial
cosity of its aqueous solution, preferably with a Brabender 10 products Such as, for example, toothpastes, cosmetics, paints,
viscometer. As measured by a Brabender viscometer, the oil drilling fluids, and airplane de-icing fluids. It has been
onset of hydration is the point at which one observes a change found that in any one of these product applications, a final
in slope of a curve plotting the Viscosity of the solution as a product can be prepared wherein pure carrageenan extract has
function of time and temperature. To measure the onset of been extensively replaced with a carrageenan product accord
hydration by employing a Brabender viscometer, a test solu 15 ing to the present invention.
tion is prepared. The test solution preferably consists of the For example, the carrageenan products of the present
carrageenan product in water Such as by mixing 10.0 g of the invention may be used as a binder in toothpaste formulations.
product in 490.0 g of deionized water. The cup speed on the Toothpaste formulations of the present invention comprises a
Brabender viscometer is set at 75 rpm. More preferably, the binder, a humectant, an abrasive, and water, wherein the
test solutions consist of formulations representative of the binder is the carrageenan product It is preferred that the
particular product application intended for the carrageenan binder be in a concentration of less than about 1.5% by weight
product. For example, the following formulations can be of the toothpaste formulation.
used: In addition, the carrageenan products according to the
Sorbitol/glycerin toothpaste elixir 8.0 g sample, 2.0 g invention can be used (either alone or with other components
Sodium saccharin, 2.5 g tetrasodium pyrophosphate, 11.0 g 25
such as fillers, plasticizers and/or binders) to form films and
sodium monophosphate, 170.0 g sorbitol, 100.0 g glycerin, other types of barriers. A barrier according to the invention is
220.0 g deionized water. a material that separates two or more Substances of interest to,
Glycerin toothpaste elixir 8.8 g. sample, 2.2 g sodium sac for example, control and/or limit the extent to which they
charin, 2.8 g. tetrasodium pyrophosphate, 8.4 g sodium interact. Examples of barriers according to the invention
monophosphate, 242.0 g glycerin, 236.0g deionized water. 30
include films, capsules and beads such as, for example, gel
Meat brine 7.5 g sample, 7.5 g sodium tripolyphosphate, microbeads and the like.
33.8g dextrose, 22.5g sodium chloride, 429.0g deionized Carrageenan-containing films according to the invention
Water.
Soft scrub elixir 4.9 g sample, 1.2 g terra alba, 12.2 g can be formed by depositing one or more carrageenan-con
propylene glycol, 482.0 g deionized water. 35
taining layers upon a Substrate. Such films can, for example,
be in the form of a sheet or web, and can be applied or affixed
Once the test solution is prepared, the Brabender viscometer to the Substrate concurrently or sequentially. Carrageenan
performs a temperature profile to determine onset of hydra containing capsules, as well as other types of barriers accord
tion. Preferred temperature profiles for the above formula ing to the invention, can be used to Surround and protect
tions are as follows: various Substances such as nutritionals, antioxidants, preser

Hold Heating at Hold Cooling at Hold

C. min. 1.5°C. min. C. min. 1.5°C./min. min.

2% in water 25 60 25 to 82 82 15
Sorbitol/glycerin 25 15 25 to 65 65 15 65 to 25 25 15
elixir
Glycerin elixir 25 15 25 to 71 71 15 71 to 25 25 15
Meat brine 45 to 71 71 15 71 to 25
Soft scrub elixir 25 60

Note:
All Brabender viscometer profiles were performed at 75 rpm.

The carrageenan products of the present invention exhibit Vatives, and the like. As will be recognized, carrageenan
enhanced gel-forming properties. For example, when a 2% containing barrier materials according to the invention can be
solution of an SRC prepared according to the methods of the disposed upon or under a variety of other types of materials to
present invention is heated to about 50° C. and allowed to gel form a multilayer structure.
thereafter, the break strength of the gel is about 100 to about Carrageenan capsules according to the invention can be
250 g. By comparison, a 2% solution of processed seaweed eitherhard or softgel capsules and can also be used to deliver
heated to 50° C. does not form a geland, when heated to 72 finished dosage forms of active ingredients such as, for
C., forms only a weak gel having a break strength of about 90 65 example, pharmaceutical compounds for ingestion or topical
g. In comparison, a 2% solution of a carrageenan product application. Such capsules also can be used to deliver com
prepared in a Clextral extruder at 120° C., at a throughput of ponent(s) in a process at a critical phase of manufacturing the
 US 7,772,211 B2
11 12
final product. Examples of the types of soft-gel capsules that using feedstocks having about 86%, about 79% and about
can be made with the carrageenan products produced accord 74% moisture content, obtained by blending these three cot
ing to the invention can be found in U.S. Pat. No. 6,214.376 tonii materials. A small ribbon blender (estimated at approxi
and International Publication No. WO 01/03677 A1, both of mately 8-10 ft capacity) was used to prepare the feedstocks
which are herein incorporated by reference. When the carra by combining the three cottonii raw materials and additional
geenan products of the invention are used in hard gel capsule water as required. Materials were blended for 10-15 minutes
applications, the texture of the carrageenan-containing cap to equilibrate.
sule wall can be controlled, as recognized by those skilled in Extrusion system: The extrusion system employed was as
the art, through component selection. Gel beads used to follows:
deliver component(s) in manufacturing processes such as, for 10
example, to immobilize enzymes for use in non-aqueous Feeder/feedrate AccuRate brand device commercially
enzymatic reactions, are described in U.S. Pat. Nos. 6,268, available from AccuRate, Whitewater, Wis., calibrated
191 and 5,662,840, both of which are herein incorporated by to 54 kg/hr using 77% moisture material;
reference. Single screw extruder Wenger X-20 operating at 500
Carrageenans produced in accordance with the present 15 rpm, exit temperature at 95-100° C.;
invention can be used in a variety of manufacturing processes Twin screw extruder Wenger TX-52 operating at 454
to form delivery systems such as, for example, the carrag rpm, exit temperature at 120-180°C.;
eenan-containing capsules and gel beads described above. Twin screw exit die plate—single 4 mm diameter hole;
Such delivery systems can be made, for example, by joining Twin screw exit pressure manually adjusted with die
previously-manufactured, flexible, carrageenan-containing throttle valve to maintain maximum exit pressure and
Strips, by casting a uniform carrageenan-containing coating barrel fill (retention time).
around liquid component (dual nozzle method), or by spray
ing a carrageenan-containing System as a liquid and then Example 1
initiating film/wall formation. Numerous other methods for
capsule/film/barrier formation known to those skilled in the 25 Extrusion of High Moisture Content Feedstock
art are included in the scope of the present invention.
Barriers according to the invention can incorporate colo Processing: Extruder conditions were stable and exit condi
rants, flavorants, and Volatile compounds suitable for use in tions at the TX-52 were easy to maintain.
flavor delivery, masking, or neutralization. Such additional
substances typically are included to modify the overall pre 30 Moisture content: Final measurements of percentage mois
sentation of the dosage form to the user. Ratios of the addi ture in the feedstocks were determined by employing either a
tional Substances to the carrageenan products of the present moisture balance such as, for example, a Denver Instruments
invention can also be used to control/modify the structural IR200 or a Mettler LJ16 or air oven methods. A typical air
integrity, properties, and functions of the finished film, bar oven method is to dry a sample at about 60° C. overnight and
rier, capsule, bead, or caplet. For example, variable dissolu 35 determine the '% moisture by a simple calculation based on
tion rates can be achieved which, in turn, can allow timed the differences of the wet and dry materials. A slight differ
delivery of the various components. Examples of additional ence was observed betweenthese two methods. As seen in the
Substances that can be used to modify the carrageenan struc table below, since the difference and standard deviation are
ture are: starches (native, modified and/or of controlled small, all subsequent discussions will be based on the Aver
reduced molecular weight, microcrystalline, and the like), 40 age data.
polyols, hydrocolloids, proteins (native, polypeptides, amino
acids, enzymes, and combinations, thereof), cellulosic mate Feedstock% moisture content
rials of various sources, sizes and microcrystallinity, Sugars
(mono- and polymerized), and the like. 45
Feed IR2OO 60° owen Average Std. Dev.
The following examples illustrate the present invention A. 86.11 86.42 86.27 O.22
and are not intended to limit the same. In this specification
and claims, all parts and percentages are by weight, all tem
peratures are in degrees Celsius, and all pressures are in mm Brabender hydration profiles: Product hydration rate for the
Hg, unless otherwise specified. 50 feedstock having a moisture content of about 86% was deter
EXAMPLES
mined in a Brabender Viscograph B using the specific test
method detailed in U.S. Pat. No. 5,502,179 at, for example,
Comparative Examples 1-3 column 4, lines 17-23. The results are shown in FIG.1. There
was no significant change in the temperatures of either hydra
Effects of Feedstock Extrusion Versus 96 Moisture
55 tion peak as a function of feedstock. Maximum viscosity of
148-160 BU was observed with feedstock having about 86%
moisture content (FIG. 1).
Materials: The primary raw material used in Examples 1-3
was we alkali modified cottonii seaweed. The material was
made to food grade standards including (1) removing plastic 60 Brabender hydration peaks
ties from the weed prior to processing and (2) bleaching the l" peak 2" peak
weed to remove color. Two batches of raw materials having
different moisture contents were obtained, one batch had Feed % moisture o C. BU o C. BU
about 85% moisture, while the other batch had about 77% A. 86.27 64 160 8O 148
moisture. Furthermore, washed, chopped and dried cottonii 65
having a moisture content of about 27% was also used. Pro BU = maximum attained viscosity in Brabender Units
cesses according to the present invention were performed
 US 7,772,211 B2
13 14
Example 2 Typical product specifications have L* greater than 74-75. A
significant change in product powder color was observed as a
Low Moisture Content Feedstock function offeedstock moisture content. A substantial darken
ing of product color was observed upon decreasing the mois
ture content of the feedstock from about 85% to about 80%.
Processing: Testing was performed to compare the results As seen from the table below, a feedstock moisture content of
obtained using feedstocks with moisture contents lower than about 86% afforded a product having L* (powder color) of
those used in accordance with the present invention. No sig 79.5. Powder color is an aesthetic quality that is important to
nificant processing differences between the three Cottonii customer acceptance of carrageenan products that are used in
feedstocks was observed. Extruder conditions were stable
and exit conditions at the TX-52 were easy to maintain for all
10 food products; lighter colored products are preferred A
three products. The lower moisture feedstocks produced drier change of 1/2-2 L* units is readily noticeable by an untrained
products at the exit. Exit at the twin screw increased with the eye. Knowledgeable end users can detect an even Smaller
lower moisture feedstocks. change in L*.
Moisture content: final measurements of 96 moisture in the 15
feedstocks showed a slight difference between the IR200 and
the air oven method. As the difference and standard deviation Powder color, Li
are Small, all Subsequent discussions will be based on the Feed % MC Product Feed A
Average data.
A. 86.27 79.520 83.294 3.774
B 79.23 74.647 78.550 3.903
C 74.03 73.184 79.655 5.625
Feedstock% moisture content

Feed IR200 60° owen Average Std. Dev.

25 Example 4
B 78.85 79.60 79.23 O.S3
C 73.58 74.47 74.03 O.63 An alkali-dipped Chondrus feedstock was also used to test
the effect of a high shear extrusion system on a different
seaweed. This Chondrus material was made by (1) washing
Brabender hydration profiles: Product hydration rates for 30 the weed in fresh water, (2) chopping the weed to the desired
feedstocks having moisture contents of 79% and 74% were size; (3) drying in a 60° C. air oven; and (4) adjusting the
determined in a Brabender Viscograph E using the specific moisture content to about 30% by spraying with a 0.2N
test method detailed in U.S. Pat. No. 5,502,179 at, for NaOH solution. The moisture content of the Chondrus feed
example, column 4, lines 17-23. No significant difference in stock was adjusted to about 29.9% (measured) with water.
hydration behavior was apparent. There was no significant 35 Measured moisture content before adjustment (as shipped)
change in the temperatures of either hydration peak as a was 22%. The material was too large to uniformly feed
function offeedstock. However, a decrease in maximum vis through the AccuRate so a Fitz mill was used to chop the
cosity with a decrease in feedstock moisture indicated a loss material to about 4-1/2" pieces. A small ribbon blender (esti
of viscosity due to the high shearing effect of the process of mated at approximately 8-10ft capacity) was used to prepare
the invention. While the maximum viscosity observed with 40 the feedstocks. Materials were blended for 10-15 minutes to
feedstock having about 86% moisture content was 148-160 equilibrate. This Chondrus material had a moisture content of
BU, the maximum viscosity observed with a lower feedstock about 29.94% (Actual % moisture). Actual % moisture was
moisture content of about 79% and about 74% was 102-104 measured using a Denver Instruments IR200 moisture bal
BU and 52-68 BU, respectively (FIG. 1). This loss of func ance Set at 150° C.
tionality indicates the process of the present invention is
configured to best handle feedstocks with greater than 80%
45 Extrusion system: the extrusion system employed was as
moisture content. follows:
Feeder/feedrate AccuRate brand device commercially
available from AccuRate, Whitewater, Wis., calibrated
50
to 54 kg/hr using 77% moisture material;
Brabender hydration peaks Single screw extruder Wenger X-20 operating at 500
l" peak
s aa
2" peak
rpm, exit temperature at 95-100° C.
Twin screw extruder Wenger TX-52 operating at 454
Feed % moisture o C. BU o C. BU rpm, exit temperature at 120-180°C.;
B 79.23 63 102 82 104 55
Twin screw exit die plate—single 4 mm diameter hole;
C 74.03 61 68 8O 52 Twin screw exit pressure manually adjusted with die
throttle valve to maintain maximum exit pressure and
BU = maximum attained viscosity in Brabender Units barrel fill (retention time).
Processing: The screw elements of the X-20 in the carrag
Example 3 60 eenan extraction process are configured for maximum shear
and, therefore, were not able to convey the high solids level
Effect of Feedstock Moisture Content on Color chondrus through the extruder. A very dense, Solid plug of
material formed near the end of the X-20 and stopped all flow.
The color of the powder was measured using a Macbeth This plug showed evidence of charring from the thermome
ColorEye 3000 colorimeter on material that was ground to 65 chanical energy input from the extruder and from autocata
99.5% through 100 mesh (150 micron). Powder color is lytic acid hydrolysis from carrageenan decomposition. The
reported in L* units; the lower the L*, the darker the powder. single screw extruder was bypassed and the feed was fed
 US 7,772,211 B2
15 16
directly to the TX-52. Although the twin screw extruder was was smooth. The seaweed was then conveyed to a twin screw
able to convey the feed, product exiting the machine was extruder through a 1.5" diameter pipe engineered to achieve a
charred (with exit temperature up to 180° C.). Both screw closed system transfer.
speed and barrel temperature were reduced to 170 RPM and Extrusion: After pre-pasting, processed cottonii material was
100-130°C., respectively, and with cooling water on the last fed into an 8 barrel Wenger TX-57 co-rotating, intermeshing,
barrel) to minimize charring. It was, however, Suspected that twin screw extruder. The high shear Screw configuration used
the extrusion conditions were still too severe to completely for this sample is proprietary to Wenger. Temperature control
prevent any carrageenan degradation.
was separated into 5 zones. The last four barrel Zones were
Brabender hydration profiles: Brabender hydration profiles 10
heated with steam.
confirmed that the carrageenan contained in the Chondrus
was destroyed during extrusion. Although the Chondrus feed Extrusion exit: A valve just before the 4 mm, 1 hole die at twin
stock showed development of a typical Brabender viscosity screw exit controlled backpressure to ensure steam explosion
peak, the extruded Chondrus showed a complete lack of of extruded processed cottonii material out of the machine.
viscosity. No further testing was performed. The extruded Cottonii resembled fine breadcrumbs as it exited
15 the extruder.
These results illustrate that the process of the invention is a
high shear process suitable only for feedstocks with high Samples: As sample exited the extruder it was transferred to a
moisture content. A model of the process Suggests that a high collection bin by a pneumatic conveyor. This tumbled and
moisture level contributes to (1) a lower feed density; (2) cooled product to prevent it from Sticking together. It was then
partial hydration of the carrageenan in the single screw dried in a Wenger Series VII 3-stage belt dryer.
extruder, (3) increased lubrication at the screw-feed interface; Process settings and readings:
(4) increased thermal energy absorption; and (5) temperature
conditions that minimize carrageenan degradation. It appears
that all of these factors are required to successfully operate the
process. 25 Accu-rate feeder Feed rate 147 kgfnir
As demonstrated in Examples 1-3, the Cottonii products Single screw Exit temp. 95° C.
Screw speed 600 rpm
extruded under constant process conditions from feedstocks Residence time 1 minute
containing between 75-85% moisture were generally very Motor load 22% full load
similar. However, there were two important functionality dif Twin screw Barrel temp Zones (°C.) 46, 125, 129, 140,140
ferences. First, significant loss in product viscosity occurs as Exit temp. 116° C.
30 Screw speed 605 rpm
the moisture content of the feedstock drops below 80%. A Exit rate 147 kg/hr
lower product viscosity is generally unacceptable for a SRC Residence time 1.5 minutes
that is used as a thickening agent. Next, significant darkening Motor load 6% full load
of product powder color occurs as the moisture content of the
feedstock drops below 80%. A darker powder color is unac 35
ceptable for SRC that is used in food products whose color Testing: Dried sample was ground to at least 95% through 100
must be maintained almost colorless or white. mesh for testing. Table 1 shows general quality testing of the
Furthermore, high solids feedstocks, such as the 30% extruded cottonii compared to the starting material to show
moisture Chondrus, are not generally suitable for the pro that no carrageenan degradation occurred during extrusion.
cesses of the invention. The high shear extrusion conditions 40 Table 2 shows solubility improvements of the extruded cot
were too severe in the absence of adequate lubrication by the tonii over the starting material during a 2% in water Bra
water in the feed. In low moisture feedstocks, the carrageenan bender profile. Table 3 shows solubility improvements of the
in the weed is completely degraded in the process. extruded cottonii over the starting material in a meat brine
elixir Brabender profile.
Example 5 45
TABLE 1
Extrusion of Base-Treated Eucheuma cottonii
Feedstock Using a Single and Twin Screw Extruder: General Quality testing
Processed PBS Extruded
50 Test Cottonist. mat. PES coitorii
Starting Material:
1. Modify Eucheuma cottonii feedstock through a standard Moisture content (%) 86-87 85.96
PES process and drain. Viscosity (cP) 85 91
pH 9.00-960 9.03
2. Wash the modified Eucheuma cottonii feedstock in cold KCI (%) O.S.-3.0 2.80
water for 30 minutes and drain. Repeat. 55
Mesh (% through 100 mesh) 90-100 >95
3. Bleach for 30 minutes in 0.17% Ca(OCl), and drain.
4. Wash in cold water for 30 minutes and drain.
TABLE 2
Moisture content of the starting material was 86-87%. KCl
content was 0.5-3.0%. The cottonii was chopped to /2" pieces 60 Brabender Analysis - Solubility Testing - 2% in water
before bleaching.
Processed PES Extruded
Pre-pasting: The chopped cottonii was metered into a Wenger Cottonist. mat. PES coitorii
X-85 single screw extruder using an Accu-rate feeder. Tem Begin Swell: C 68 48
perature in the single screw was controlled to target a material BU 2 3
exit temperature of 95°C. by steam circulating through eight 65 1 peak C no peak 52
individual heads. Processed cottonii was heated and mixed in BU no peak 89
the single screw to breakdown seaweed structure until paste
 US 7,772,211 B2
17 18
TABLE 2-continued TABLE 4
Brabender Analysis - Solubility Testing - 2% in water General Quality Testing
Processed PES Extruded Processed PES cottonii Extruded PES
Cottonist. mat. PES coitorii Test starting material cottoni
2” peak C 77 65 Moisture content (%) 6 not measured
BU 12 35 Viscosity (cP) 160 55
End 82°C. hold BU 8 29 101 gel (gms breakforce) 491 435
10 KCI (%) 1.5 1.4
Mesh (% thru 100 M) 90-100 91

TABLE 3
Brabender Analysis - Solubility Testing - Meat Brine Elixir TABLE 5
15
Processed PES Extruded Brabender Analysis - Solubility Testing - 2% in Water
Cottonist. mat. PES coitorii
Processed PES cottonii Extruded PES
Begin Swell: C 71 66 starting material cottonii
BU 19 2
1 peak C no peak 68 Begin Swell: C 59 56
BU no peak 19 BU 12 12
2" peak (71° C.) BU 35 17 1 peak: C no peak 59
End 71° C. hold BU 35 15 BU no peak 24
2” peak: C 78 75
BU 60 28
At 82° C.: BU 59 27
25
Example 6
Extrusion of Base-Treated Eucheuma cottonii Example 7
Feedstock Using a Twin Screw Extruder
30 Extrusion of Base-Treated Eucheuma spinosum
Starting material: Processed cottonii starting material was Feedstock Using Single and Twin Screw Extruders
prepared by putting Eucheuma cottonii seaweed though a
standard PES process, chopping PES cottonito /2 inch chips, Starting material: PES spinosum starting material was pre
drying, and then grinding to 100 mesh. 35 pared by putting Eucheuma spinosum seaweed through the
following process:
Extrusion: Powdered processed cottonii was fed from a hop 1. Soak seaweed in 25% NaCl for 1 hour and drain.
per into a 12 barrel Werner-Pfleiderer ZSK-30 co-rotating,
intermeshing, twin screw extruder. Total length L/D ratio was 2. Modify in 7.9% NaCl, 2.86% NaOH for 2 hours at 45° C.
37. Water was sprayed into the feed section along with the and drain.
40 3. Wash in 9% NaCl for 30 minutes and drain.
Processed cottonii to create a mixture at 80% moisture. The
high shear screw configuration used for this sample is propri 4. Bleach in 0.25% NaOCl for 30 minutes and drain
etary to Werner-Pfleiderer. Heating and cooling were con 5. Wash in 6% NaCl for 30 minutes and drain.
trolled in barrels 4 thru 10 with electric heating and water 6. Wash in cold water and drain.
cooling. 45
Moisture content of the PES spinosum starting material was
Extrusion exit: No die plate was put onto screw exit. Material 78-82%. NaCl content was 11-15%. The spinosum was
exited with the appearance of elastic, ground, uniform bits. chopped to /2" pieces before bleaching.
Samples: Sample was spread into pans to cool, then dried Pre-pasting: The chopped PES spinosum was metered from
overnight in a 60° C. oven. 50 an Accu-rate feeder into a Wenger X-85 single screw cruder.
Process settings and readings: Temperature in the single screw was controlled to target a
material exit temperature of 100° C. by steam circulating
through eight individual heads and by steam injection. PES
Feeder Feed rate 9 kg/hr
spinosum was heated and mixed in the single screw to break
Twin screw Barrel temps. (C.) 25, 82,90,90, 89, 89,90,90, 90,90
55 down seaweed structure and paste until relatively smooth.
Exit temp. 90° C. Material was then conveyed to a twin screw extruder through
Screw speed 500 rpm a 1.5" diameter pipe engineered to achieve a closed system
Exit rate 9 kg/hr transfer.

60
Extrusion: As PES spinosum paste exited from the single
Testing: Dried sample was ground to 91% through 100 mesh screw, it was fed into an 8 barrel Wenger TX-57 co-rotating,
for testing. Table 4 shows general quality testing of the intermeshing, twin screw extruder. The high shear Screw con
extruded Processed cottonii compared to the starting mate figuration used for this sample is proprietary to Wenger. Tem
rial, to show that no carrageenan degradation occurred during perature control was separated into 5 zones. The last 4 Zones
were heated with steam.
extrusion. Table 5 shows solubility improvements of the 65
extruded Processed cottonii over the starting material during Extrusion exit: A valve just before the 4 mm 1 hole die at twin
a 2% in water Brabender profile. screw exit controlled backpressure to ensure steam explosion
 US 7,772,211 B2
19 20
of the extruded PES spinosum material out of the machine. Moisture content of washed spinosum starting material was
Extruded spinosum exited as fine breadcrumbs. 85-86%. NaCl content was 8%. The washed spinosum was
Sample: As sample exited the extruder it was transferred to a chopped to /2" pieces.
collection bin by a pneumatic conveyor. This tumbled and Pre-pasting: The chopped, washed spinosum was metered
cooled product to prevent it from Sticking together. It was then from an Accu-rate feeder into a Wenger X-20 single screw
dried in a Wenger Series VII 3-stage belt dryer. extruder. Temperature in the single screw was controlled to
Process settings and readings: target a material exit temperature of 95°C. by steam circu
lating through eight individual heads. Washed spinosum was
10 heated and mixed in the single screw to breakdown seaweed
structure and partially paste. Pre-pasted, washed spinosum
Accu-rate feeder Feed rate 144 kg.hr was relatively smooth, but had some remaining weed bits.
Single screw Exit temp.
Screw speed
100° C.
600 rpm
Material was then conveyed to a twin screw extruder through
Motor load 17% full load a 1.5" diameter insulated pipe.
Twin screw Barrel temp Zones (°C.) 48, 124, 128, 138, 136 15 Extrusion: As washed spinosum paste exited from the single
Exit temp. 107° C.
Screw speed 600 rpm screw, it was fed into an 8 barrel Wenger TX-52 co-rotating,
Exit rate 144 kg.hr intermeshing, twin screw extruder. The high shear Screw con
Motor load 5% full load figuration used for this sample is proprietary to Wenger.
Extruder barrels 4 through 6 were heated with circulating hot
oil and steam was injected into barrels 3 and 4.
Testing: Dried sample was ground to at least 95% through 100 Extrusion exit: A valve just before the 4 mm, 3 hole die at twin
mesh for testing. Table 6 shows general quality testing of the screw extruder exit controlled backpressure to ensure steam
extruded PES spinosum compared to the starting material, to explosion of extruded, washed spinosum material out of the
show that no carrageenan degradation occurred during extru machine. Extruded, washed spinosum exits as a mixture of
sion. Table 7 shows solubility improvements of the extruded 25
wet granules and Viscous paste.
PES spinosum over the starting material during a 2% in water
Brabender profile. Samples: Care was used in collecting extruded, washed spi
nosum material to ensure that sample did not stick together.
TABLE 6 Sample was spread into pans to cool, before being dried
30 overnight in a 60° C. oven.
General Quality testing
Process settings and readings:
Processed PES Extruded PES
Test spinostin St. mat spinostin
Moisture content (%) 78-82 81 35 Accu-rate feeder Feed rate 33 kg/hr
Viscosity (cP) 30 38
pH 8.30-890 8.73 Single screw Exit temp. 96° C.
NaCl (%) 11-15 11.72 Screw speed 100 rpm
Motor load 11% fall load
Mesh (% through 100 mesh) 90-100 >95
Twin screw Barrel temps. (C.) 73,73, 95, 119, 119, 120,
120, 120
40 Exit temp. 135° C.
Screw speed 472 rpm
TABLE 7 Exit rate 33 kg/hr
Motor load 9% full load
Brabender Analysis - Solubility Testing - 2% in water
Processed PES Extruded PES
45
spinostin St. mat spinostin Testing: Dried sample was ground to 91% through 100 mesh
Hold at 25°C.: for testing. Table 8 shows general quality testing of the
extruded, washed spinosum compared to the starting mate
Start BU no peak 184 rial, to show that no carrageenan degradation occurred during
End BU no peak 177 extrusion. Table 9 shows improved solubility of the extruded,
Heating peak: C 65 no peak 50
BU 26 no peak washed spinosum over the starting material in 65° C., sorbi
End 82°C. hold BU 26 26 tol/glycerin toothpaste elixir Brabender profile. Table 10
shows solubility improvements of the extruded, washed spi
nosum over the starting material in 71°C., glycerintoothpaste
Example 8 55
elixir Brabender profile.
TABLE 8
Extrusion of Washed, Non-Base-Treated Eucheuma
spinosum Feedstock Using Single and Twin Screw General Quality Testing
Extruders
60 Washed spinosum Extruded washed
Test starting material spinostin
Starting material: Washed spinosum starting material was Moisture content 85-86 85.9
prepared from Eucheuma spinosum seaweed in the following Viscosity (cP) SO-60 41
al pH 7.5-8.5 7.8
1. Soak in cold water for 30 minutes and drain. NaCl (%) 6-10 6.2
65 Mesh (% thru 100 M) 90-100 91
2. Soak in cold 1.5% NaCl and drain.
3. Press out excess water in a Wilmes press.
 US 7,772,211 B2
21 22
TABLE 9 -continued
Brabender Analysis - Solubility Testing - 65° C. Exit temp. 81 C.
Sorbitol/Glycerin Toothpaste Elixir Screw speed 550 rpm
Exit rate 54 kg/hr
Washed spinosum Extruded washed Residence time 2.0 minutes
starting material spinostin Motor load 11 amps
Begin Swell: C 62 44
BU 30 45
End 65 C. hold: BU 44 122 10 Testing: Dried sample was ground to 94% through 100 mesh
Cooled: C 25 25 for testing. Table 11 shows general quality testing of the
BU S4O 8SO extruded PES spinosum compared to the starting material, to
show that no carrageenan degradation occurred during extru
TABLE 10 sion. Table 12 shows solubility improvements of the extruded
15 PES spinosum over the starting material during a 2% in water
Brabender Analysis - Solubility Testing Brabender profile.
21 C. Glycerin Toothpaste Elixir
TABLE 11
Washed spinosum Extruded washed
starting material spinostin General Quality Testing
Begin Swell: C 66 37
BU 23 40 PES spinosum Extruded PES
End 71 C. hold BU 81 89 Test starting material spinostin
Cooled: C 26 37
BU 695 651 Moisture content (%) 83.0 82.5
Viscosity (cP) 28 32
25 pH 9.90 9.1O
NaCl (%) not measured 747
Mesh (% thru 100M) 90-100 97
Example 9
Extrusion of Base-Treated Eucheuma spinosum
Feedstock Using a Twin Screw Extruder 30 TABLE 12
Brabender Analysis - Solubility Testing - 2% in Water
Starting material: PES spinosum starting material was pre PES spinosum Extruded PES
pared by putting Eucheuma spinosum seaweed though the starting material spinostin
following process: 35
Hold at 25°C.
1. Modify in 1.0M NaOH, 3.1MNaCl for 6 hours at 45° C.
and drain. Start BU 8 35
2. Follow modification with two cold, 30-minute 5% NaCl End
1 peak:
BU
C 30
9 122
30
rinses. 3. Neutralize pH in the first rinse. BU 9 65
4. This sample was given an additional 30-minute cold 40 2" peak: C 60 60
water soak at the trial before extruding. End 82° C. hold:
BU
BU
27
59
27
13
Moisture content of PES spinosum starting material was 83%.
The PES spinosum was chopped to /2" pieces.
Extrusion: The chopped PES spinosum was metered from a 45 Examples 10 and 11
volumetric feeder into a 9 barrel Clextral BC-45 co-rotating,
intermeshing, twin screw extruder. The high shear Screw con Examples 10 and 11 demonstrate the applicability of the
figuration used for this sample is proprietary to Clextral. carrageenan products of the present invention as an ingredient
Heating and cooling were controlled on the last eight barrels in toothpaste formulations. Specifically, toothpaste formula
by induction coils and cooling water. 50 tions of the present invention are evaluated for efficacy of the
carrageenan product as a carrageenan binder in the tooth
Extrusion exit: Exit temperature was measured just before a 3 paste. The efficacy of a carrageenan binder in a toothpaste
mm, 3 hole cooling die plate. Extruded PES spinosum exited formulation is determined by measuring the strength, stabil
as opaque, Sticky, spreadable strands. ity, and texture of the toothpaste formulation. A traditional
Samples: Sample was belt conveyed for approximately 15 55 method for measuring toothpaste strength, Stability, and tex
seconds to cool before collecting in pans. The Sticky material ture is by using a Cuban rating system wherein the toothpaste
tended to clump together even when cool, so it had to be Strands are squeezed over a Cuban rack. Ability of the Strands
manually broken into smaller bits before drying overnight in to stay suspended between bars with numbered size incre
a 60° C. Oven. ments determines the 1 to 12 rating given to the toothpaste.
60 Measurements are typically taken over a period of 9 weeks.
Process settings and readings: More particularly, measurements are taken after 1 day, 1
week, 3 weeks, 6 weeks, and 9 weeks at storage temperatures
of about 25°C. and 50° C., to determine toothpaste strength,
Volumetric feeder Feed rate 54 kg/hr stability, texture and degree of “heat shock.” Heat shock is
Twin screw Barrel temps. (C.) 25, 128, 189, 175, 140, 142, 65 defined as a change (increase of decrease) in the strength of
124,99, 79 the toothpaste upon storage at 50° C. A change of more than
3 Cuban ratings is considered undesirable. A disadvantage of
 US 7,772,211 B2
23 24
the Cuban test is that the toothpaste must be prepared and the BU/minute, exhibits an increase of 4 Cuban units, from 5 to 9;
measurements be taken over a period of 9 weeks to make a whereas, the extruded and washed spinosum, with a slope of
quality determination for a particular carrageenan sample. 2.0 BU/minute, shows an increase of only 2 Cuban units, from
The toothpaste formulations according to the present 6 to 8. Although an increase of 2 Cuban units is considered
invention are examined for carrageenan solubility using a acceptable, an increase of 4 Cuban units is unacceptable.
Brabender Viscograph test wherein a toothpaste "elixir is Table 14 compares the same three samples at a process
used to examine carrageenan solubility in the presence of
other toothpaste ingredients. The toothpaste "elixir' formula temperature of 71°C. The negative slopes of the extruded and
contains ingredients in the same ratios as that of a typical washed spinosum and the toothpaste extract indicate they are
toothpaste formulation, except that the "elixir lacks the bulk 10 fully solubilized at this higher process temperature. The
ing agent, the foaming agent and the flavor oil. Brabender higher Cuban ratings also reflect this, as does the lack of heat
temperature profiles typically focus on conditions for carra shock for these three samples.
geenan solubility. It was determined that the Brabender tooth The Brabender elixir test results also provide information
paste "elixir test was an excellent predictor of the perfor regarding the difference in process Viscosity, which Cuban
mance of the carrageenan product of the present invention in 15 ratings do not. Although the extruded and washed spinosum
a toothpaste formulation. The advantage of the Brabender test compares closely to the toothpaste extract in Cuban units and
used in the present invention, relative to the traditional Cuban a high final, cooled Viscosity, process viscosity is signifi
rating system, is that the Brabender test decreases the time cantly lower for the extruded and washed spinosum, as indi
required to make functional quality determinations from 9 cated by the Brabender elixir test results. In this case, the low
weeks to a few hours. process viscosity is advantageous in typical toothpaste prepa
In the following examples, toothpaste "elixirs were ana ration
lyzed using Brabender viscographs to examine carrageenan
solubility in the presence of toothpaste ingredients. The TABLE 13
toothpaste elixir formula contained ingredients in the same
ratios as that of a typical toothpaste system except that the 25 Toothpaste Elixir Solubility Profile Compared to
bulking agent, the foaming agent and the flavor oil were Toothpaste Cuban Rating. 65 C. Processing
absent in the elixir formula. Brabender temperature profiles Slope of
typically focus on conditions for carrageenan Solubility in Begin End End curve (c) 1 day 2 day
order to understand the Solubility potential for carrageenan 65° C. 650 C. 250 C. 65° C. Cuban, Cuban,
under the application-specific process conditions. The Bra 30 (BU) (BU) (BU) (BU/min.) 25° C. 50° C.
bender toothpaste elixir formula and temperature profiles Washed 29 44 538 1.O 3 3
developed for use in the work discussed here were designed to spinostin
track Solubility of carrageenan products intoothpaste systems Extruded, 92 122 837 2.O 6 8
focusing on toothpaste process conditions. washed
spinostin
35
Toothpaste 293 725 1216 28.8 5 9
Example 10 Extract
Blend
Toothpaste Elixir
In this case, toothpaste elixir testing was done at process 40
TABLE 1.4
temperatures of both 65° C. and 71° C.
Toothpaste Cuban ratings measure strength of prepared Toothpaste Elixir Solubility Profile Compared to
toothpaste. Degree of heat shock is determined by the change Toothpaste Cuban Rating, 71° C. Processing
in toothpaste strength after storage at 50° C. for three days. Slope of
The Brabender toothpaste elixir test contributes additional 45
Begin End End curve (c) 1 day 2 day
information regarding the process of making the toothpaste: 71o C. 71 o C. 25 C. 71o C. Cuban, Cuban,
when solubility takes place (at what time and temperature), (BU) (BU) (BU) (BU/min.) 25° C. 50° C.
whether hydration is complete, viscosity contribution during Washed 47 71 850: 1.6 12 12
processing, and Viscosity contribution to the final product. spinostin
Tables 13 and 14 compare the slope and viscosity of the 50 Extruded, 101 89 850: -0.8 11 12
toothpaste elixir solubility curve during the hold at elevated washed
spinostin
temperature to the Cuban rating changes during storage of Toothpaste 8SO 740 1416 -7.3 6 6
actual toothpaste. Extract
Table 13 compares washed spinosum, extruded washed Blend
spinosum, and a toothpaste extract blend at a process tem 55
*Extrapolated from curve.
perature of 65° C. The positive slope during the 65° C. hold
for all three samples suggests that none of them are fully
solubilized. Comparison of washed spinosum to extruded Example 11
washed spinosum shows a small difference in slope between
the two, but a significant improvement in the Cuban ratings 60
Glycerin/Sorbitol Chalk Toothpaste
for the extruded and washed spinosum, indicating improve
ment from extrusion. Comparison of the extruded and washed
spinosum to the toothpaste extract blend shows similar tooth Two extruded, washed spinosum samples (EWS-1 and
paste Cuban ratings for 1 day, 25°C., even though there are EWS-2) were tested in inexpensive, glycerin/sorbitol chalk
large differences in process viscosity. The slope difference for 65 toothpaste at a 65° C. process temperature. The results were
these two samples is highly significant, explaining the differ excellent and showed no heat shock Table 15 compares the
ences in heat shock. The extract, with a slope of 28.8 Cuban ratings of the two toothpastes.
 US 7,772,211 B2
25 26
(1) Fifteen-minute hold at elevated temperature: The viscos
TABLE 1.5 ity and change in Viscosity over time (slope) of the solu
bility curve during the hold at an elevated temperature is a
Toothpaste Performance in Chalk-Based Toothpaste strong indicator of potential toothpaste heat shock. The
1 day Cuban, 25°C. 2 day Cuban, 50° C. steeper this slope, the more chance of heat shock. The
EWS-1 6 5
flatter the slope, the less chance of heat shocks
EWS-2 7 6
(2) Final cooling to 25°C.: The final cooled viscosity of the
processed elixir indicates the potential viscosity contribu
tion a carrageenan sample can make to toothpaste. This
Results (from Examples 10 and 11): 10 final cooled Viscosity is not the same as the process viscos
(1) Using a toothpaste elixir that mimics a toothpaste is a ity.
means to not only gain information about performance of What is claimed is:
stabilizers in a final product, but also important informa 1. A semi-refined iota carrageenan-containing product
tion regarding performance during the toothpaste process made by a process comprising Subjecting a carrageenan-con
1ng. 15 taining seaweed material having a solids content of less than
(2) The occurrence of toothpaste heat shock is directly pro 25% by weight to a shear stress treatment to provide said
portional to increased steepness or positive slope of the carrageenan-containing product, wherein said process further
solubility curve during the process hold at an elevated comprises drying said carrageenan-containing product to
temperature. produce a dried carrageenan-containing product and grinding
(3) Differences in product performance for a sample pro said dried carrageenan-containing product, and wherein said
cessed at two different temperatures can be readily product has a color of greater than about 74 L* units as
observed and explained by the solubility information pro measured using a Macbeth ColorEye 3000 colorimeter and a
vided by an elixir Brabender profile. particle size characterized in that at least 99% of the powder
(4) Process viscosity is not directly proportional to final passes through a 100 mesh screen.
toothpaste strength. 25 2. The product of claim 1 having an onset of hydration
(5) The Brabender toothpaste elixir test is an excellent pre below about 50° C. as measured with a Brabender viscometer
dictor of carrageenan performance in actual toothpaste. It as a 2% by weight Solids aqueous solution.
can reduce the time it takes to make functional quality 3. The product of claim 1 comprising about 1% to about
determinations from weeks or days to hours. 20% by weight of a salt.
(6) Toothpaste process elixir Brabenders tests can be useful in 30 4. A toothpaste formulation comprising a binder, a humec
determining process temperature limitations and ranges for tant, an abrasive, and water, wherein the binder comprises the
any toothpaste system carrageenan-containing product according to claim 1.
Analysis (based on Examples 10 and 11): 5. The toothpaste formulation of claim 4 wherein the
binder comprises less than about 1.5% by weight of the tooth
35 paste formulation.
Two regions of the Brabender solubility profile are useful in
predicting the toothpaste performance for a particular
sample: