Introduction

Carrageenan is a generic name for a family of gel-forming and viscosifying polysaccharides,

which are obtained by extraction from certain species of red seaweeds. The main species
responsible for carrageenan production,

Eucheuma
Kappaphycus
Iridaea
Chondrus
Giartina

Irish moss, Chondrus crispus was first used as the raw material for carrageenan extraction. Later
Gigartina sp. was found to be another important source of carrageenan. These two genera have
been the chief raw material for carrageenan production in the United States for long time.

Commercial preparations of carrageenan are nearly odorless powders that are yellowish, tan, or
white in color (FAO, 2007). Carrageenan is soluble in hot water (80oC) and variably soluble in
room temperature water (20oC); depending on the polysaccharide types present (FMC
Biopolymers, 2010). Carrageenan will disperse more readily in water if the powder is first
moistened with alcohol, glycerin, or a saturated glucose or sucrose solution (FAO, 2007).
Carrageenan is also soluble in boiling milk.
By the chemical studies on the carrageenan structure it has been known that carrageenan from
different species of carrageenophytes essentially may be divided by the structural feature into the
Beta, Kappa and Lambda families. Again they are sub classified into 13 types depending upon the
position of sulfate groups. But among these only kappa, iota and lambda carrageenans are of
commercial significance, because they are the main components in carrageenophytes, which have
abundant sources, and possess the properties applicable in food, pharmaceutical and other uses.
Kappa-carrageenan is the main product, widely used in food industry as a gelling agent. Recently
iota-carrageenan has also been used in food and other industries, owing to its peculiar properties
which are different from that of Kappa's. Lambda-carrageenan is extensively used in food products
as the stabilizer and emulsifier due to its non-gelling and high viscosity properties. With their
different properties, their processing and extraction differ somewhat from each other.

Type of Carrageenan & their production method

There are different types of carrageenan based on their chemical structure & properties, it can be
three types based on chemical structure & also based on the processing method there are four
types. But generalize step include two type of processing methods,
KCl processing
Alcohol processing

The gel-press and alcohol preparation method are the same with the exception of how the
carrageenan is purified and recovered as a solid from a concentrated solution. Basically there are
four types of carrageenan based on processing methods that can be produce from Seaweed those
are,

Refined carrageenan
Semi Refined carrageenan (SRC)
Alkali Treated Cottonii (ATC)
Processed Euchema Seaweed (PES)
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Refined carrageenan
Refined carrageenan is the original carrageenan and was simply called carrageenan. It is now
sometimes called filtered carrageenan. It was first made from Chondrus crispus, but now the
process is applied to all of the algae such as,

Kappaphycusalvarezii
Eucheuma denticulatum
Gigartina skottsbergii
Sarcothalia crispata

The seaweed is washed to remove sand, salts and other foreign matter. It is then heated with water
containing an alkali, such as sodium hydroxide, for several hours, with the time depending on the
seaweeds being extracted and determined by prior small-scale trials, or experience. Alkali is used
because it causes a chemical change that leads to increased gel strength in the final product. The
seaweed that does not dissolve is removed by centrifugation or a coarse filtration, or a
combination. The solution is then filtered again, in a pressure filter using a filter aid that helps to
prevent the filter cloth becoming blocked by fine, gelatinous particles. At this stage, the solution
contains 1-2 percent carrageenan and this is usually concentrated to 2-3 percent by vacuum
distillation and ultrafiltration.

The processor now has a clear solution of carrageenan and there are two methods for recovering it
as a solid,
An alcohol-precipitation method can be used for any of the carrageenans
A gel method can be used for kappa-carrageenan only

Alcohol-precipitation method
In the alcohol method, isopropanol is added until all the carrageenan is precipitated as a fibrous
coagulum that is then separated using a centrifuge or screen (a fine sieve). The coagulum is
pressed to remove solvent and washed with more alcohol to dehydrate it further. It is then dried
and milled to an appropriate particle size, 80 mesh or finer. For the process to be economical the
alcohol must be recovered, both from the liquids and the dryer, and recycled.
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Gel method
The gel method relies on the ability of kappa carrageenan to form a gel with potassium salts. The
gel may be formed in various ways. For the freeze-thaw process it is convenient to form it as
spaghetti-like pieces by forcing the carrageenan solution through fine holes into a potassium
chloride solution. The fine "spaghetti" is collected and washed with more potassium chloride to
remove more water, pressed to remove surplus liquid and then frozen. When allowed to thaw,
separation of water occurs by synaeresis; the pieces are washed with more potassium chloride,
chopped up and dried in a hot air dryer. Inevitably the product contains some potassium chloride.
After squeezing for several hours the sheets of gel are chopped, dried in a hot air dryer and milled
to an appropriate particle size.

Semi Refined Carageenan

Semi-refined carrageenan (SRC) is a type of carrageenan and in this method in which the
carrageenan is never actually extracted from the seaweed. The semi refined process developed
originally to produce high gel strength, cheap carrageenan for use in the pet food industry. It has
since developed into the fastest growing carrageenan technology. In this method, carrageenan is
not technically extracted out of the seaweed; rather, water and alkali are used to wash all other
compounds (e.g., soluble proteins, carbohydrates, cellulose) away from the carrageenan. Because
this method does not involve expensive steps like centrifugation, concentration, and precipitation,
it is cheaper than alcohol preparation or gel-press methods (McHugh, 2003). Semi-refined
carrageenan originally had high bacteria counts making it unsuitable for human consumption
unless used in canned products, since the canning process kills the bacteria.
In semi refined process seaweed, either Eucheuma cottonii or Eucheuma spinosum, is first washed.
The washed weed is then treated in a hot alkali mix with a very high potassium level. Many people
use 5-8% potassium hydroxide. If the cooking temperature is kept below 80oC (for Eucheuma
cottonii) then the seaweed does not dissolve and the mu to kappa conversion is completed with the
carrageenan still within the seaweed. The hot alkali and subsequent washing removes residual
minerals,proteins and fats leaving behind the converted carrageenan and some residual cellulose
from the cell walls. Hence semi refined carrageenan always contains residual cellulose and will
never be clear. Semi refined carrageenan has experienced strong growth in the meats industry and
in the dairy industry where clarity is not an issue. The main advantage of semi refined carrageenan
is the low cost although it has been claimed that semi refined products are actually superior to
refined in meat processing. (Phil).

Seaweed

Water Wash

Alkali soak

Chopping

Water Wash

Drying

Grinding

Blending

Semi refined carrageenan production process

Processed Euchema seaweed (PES)

Producers of carrageenan in the Philippines now add an additional step to the semi- refined
extraction method so that the product, referred to as processed Euchema seaweed or PES, is
suitable for human consumption. After alkali treatment, the carrageenan solution is treated with
bleach, and drying occurs in a closed dryer system. In some cases, the dried carrageenan is then
washed with ethanol and vacuum evaporated, or treated with superheated steam, to eliminate
bacterial contamination. PES contains 8 to 15% acid insoluble materials, opposed to only 2% for
carrageenan that is produced through the alcohol preparation or gel-press methods. The acid
insoluble materials are mostly cellulose and protein materials from the algae that result in different
solubility characteristics between PES and carrageenan extracts. Both products are regulated as the
food additive carrageenan by the FDA and must adhere to the same standards for microbial
contamination and limits for other contaminants such as heavy metals.

Seaweed

Water Wash

Alkali soak

Chopping

Bleaching

Water Wash

Drying

Grinding

Blending
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Alkali Treated Cottonii(ATC)

However, the seaweed flour is colored, often has a high bacterial count and is not suitable for
human consumption. Nevertheless, there is a large market for pet food because it is a good gelling
agent and is much cheaper than Refined Carrageenan. The temperature used in the canning process
destroys any bacteria so that bacterial count in SRC is not a problem. Sometimes the dried product
is just chopped into pieces, not milled and sold as raw material to Refined Carrageenan processors.
It is called Alkali Treated Cottonii (ATC) or Alkali Treated Cottonii
Chips (ATCC) or simply Cottonii chips.

Uses
1. In food
Carrageenan has been used as a natural food additive for over 600 years, and is today recognized
as a harmless food additive without nutritional value. Nowadays, it is used in food primarily as
gelling, thickening or stabilizing agents. A vast amount of carrageenans are applied for the dairy
products and water products such as,

Milkshake and instant breakfast powder: -carrageenan is used to suspend the ingredients
and to impart a richness and body to these drinks. The use level is 0.10.2%.

Cooked flans and custards

Cooked pudding and pie fillings

Cold prepared flans and custards

Chocolate milk: A typical chocolate milk containing 1% cocoa, 6% sugar and 0.025
0.035% carrageenan.

Chocolate syrup

Ice cream and sherbet

Filled and skim milk

Cottage and cream cheese products

Evaporated milk (canned)

Infant formulations
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Ready-to-eat milk puddings (canned)

Whipping cream:

Aerosol spray cream topping

Yogurt: K-Carrageenan is used to stabilize yogurt to which fruit is added.

Frozen whipped toppings

Imitation milk

Dessert gels

Fruit drinks

Low-calorie jellies: A jelly containing K- and - or K-carrageenans (0.51.0%) combination

with artificial sweetness.

Pet foods: K-Carrageenan (0.20.5%)

Fish gels

Frozen fish coating: A solution of about 0.4% of the mixture containing K-carrageenan,
locust bean gum and potassium chloride forms a gelled film that coats frozen fish,
protecting it from freezer burn and mechanical disintegration during processing

Relishes, Pizza, Barbecue sauces

2. Pharmaceutical uses

Mineral oil and insoluble drug preparations: -Carrageenan (0.10.5%) gives stable
emulsions and suspensions for mineral oil and insoluble drug preparations.

Antacid gels

Drugs for peptic and duodenal ulcers: Carrageenan has been proved to be effective for the
symptomatic relief and cure of peptic and duodenal ulcers.

Barium sulfate suspensions: Carrageenan is used as a dispersant for Barium sulfate

3. Other industrial uses

Toothpastes: Carrageenan (0.81.2%) is used to prevent separation of the liquid portion

and abrasive, and to impart short texture and good rinseability characteristics to tooth paste.

Lotions and creams: -Carrageenan (0.11.0%) is used in hand lotions and creams to
provide slip and improved rub-out.

Water-based paints

Air-freshener gels

Immobilization of enzymes and cells: Carrageenan gel beads formed with cations are the
excellent media for entrapping enzymes or cells used for catalyzing the chemical syntheses
and conversions.
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Refined Carrageenan will therefore give a clear solution, while Semi-Refined Carrageenan (PES)
gives a cloudy solution. If clarity of the users end-products is not a concern, PES is good enough
e.g. canned food, pet food, meat, ham, etc. Whereas if clarity of the end-product is critical, Refined
Carrageenan is more suitable e.g. dessert jelly.

Summary
Carrageenans are the polysaccharides extracted with hot water from certain genera of red seaweeds
such as Chondrus, Gigartina, Eucheuma, Furcellaria, Phyllophora, etc. Commercial preparations
of carrageenan are nearly odorless powders that are yellowish, tan, or white in color.
The major difference between Refined Carrageenan and Semi-Refined Carrageenan (PES) is that
PES contains the cellulose that was in the original seaweed, while in Refined Carrageenan this has
been removed by the filtration process.

References

http://www.fao.org/docrep/006/y4765e/y4765e0b.htm#TopOfPage
http://www.fao.org/docrep/x5822e/x5822e05.htm

http://www.fao.org/docrep/field/003/ab730e/ab730e03.htm

http:// www.wiley-vch.de/books/biopoly/pdf_v06/bpol6009_245_250.pdf
http:// www.fao.org/docrep/x5822e/x5822e05.htm
www.agarlab.com/carrageenan-processes tml

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