BAHAN INDUSTRI HASIL PERTANIAN

PROF. SIMON BW Ph.D. KARAGENAN

Carrageenan
is obtained by extraction with water or alkaline water of certain species of the class Rhodophyceae (red seaweed)

CHONDRUS CRISPUS : ganggang merah

Sea weed for carrageenan manufacture

CARRAGEENAN PRODUCTION

CARRAGEENAN MANUFACTURE

 Pengolahan karagenan masih jarang dilakukan. Padahal prosesnya hampir sama dengan pengolahan agar-agar. Kalau pada waktu ekstrasi untuk mendapatkan agar-agar memakai asam, maka untuk mendapatkan karagenan memakai basa. Bila penanganan pascapanen telah sempurna, proses selanjutnya dapat dilakukan secara sederhana untuk skala rumah tangga dan dapat juga dilakukan untuk skala industri.

Produksi Karaginan untuk Skala Rumah Tangga

1. Rumput laut direndam dalam air tawar selama 12 24 jam, kemudian dibilas dan ditiriskan. 2. Setelah bersih rumput laut direbus dalam air dengan perbandingan rumput laut dengan air sebesar 1 : 15, suhu 120 C selama 15 menit. Perebusan memakai pressure cooker, selanjutnya dilakukan perebusan lagi tanpa tekanan pada suhu 10 C selama 2 3 jam. 3. Rumput laut yang lunak dihancurkan dengan blender dan ditambahkan air panas (90 C). Perbandingan 1 : 30. Hasilnya disaring dengan kain kasa halus. 4. Filtrat diendapkan menambahkan metil alkohol dengan perbandingan 2,5 : 1, bisa juga dengan menambahkan alkohol 90 % atau membekukannya pada suhu -10 C- 6 C selama 24 48 jam. 5. Endapan yang bercampur alkohol disaring dngan kain kasa. Hasil saringan masih berupa keraginan basah. Filtrat yang beku perlu dicairkan dahulu untuk selanjutnya disaring lagi. 6. Karagenan basah dikeringkan selama 3 4 hari. Tepung karagenan dapat diperoleh setelah proses penggilingan.

Produksi Karagenan Untuk Skala Industri

1. Rumput laut dicuci dengan air tawar kemudian dikeringkan sampai kadar air menjadi 15 25 %. 2. Rumput laut kering diesktraksi dengan ditambah air panas dan kalsium hidroksida atau natrium hidrosida. Selama ekstraksi terjadi penghancuran dan hasilnya berupa pasta. Penghancuran ini bertujuan untuk memperluas permukaan rumput laut sehingga proses pelarutan karaginan akan lebih mudah. 3. Pasta selanjutnya dimasukkan ke tangki atau bejana dan dipanaskan selama 24 jam pada suhu 90 95 C. 4. Setelah itu pindahkan ke tangki lain atau bejana dan dipanaskan selama 24 jam pada suhu 90 95 C. 5. Setelah mendidih disaring dengan filter aid atau tanah diatomea. Hasilnya disaring lagi dengan filter press. 6. Filtrate yang dihasilkan dipompa ke dalam tangki yang berisi propil alkohol dan akan didapatkan serat karaginan. 7. Serat karaginan dipress, kemudian dicuci dengan alkohol segar dan dipress lagi.

Standar Mutu
Indonesia belum mempunyai standar mutu karaginan. Standar mutu yang dikenal adalah EEC Stabilizer Directive dan FAO/WHO Specification. Tepung karaginan mempunyai standar 99 % lolos saringan 60 mesh, tepung yang terendap alcohol 0,7 dan kadar air 15 % pada RH 50 dan 25 % pada RH 70.

CHEMICAL STRUCTURE

Struktur Carrageenan

Kappa carrageenan

Iota carrageenan

Lambda carrageenan

Powder characteristics and Storage Stability

Carrageenan is sold as a powder. The color ranges from white to brownish depending on raw material and process used. A typical mesh specification is 99% through a 60 mesh (0.25 mm) sieve. A typical powder density of an alcohol precipitated carrageenan is 0.7. A typical equilibrium water content of an alcohol precipitated carrageenan is 15% at 50% r.h. 25% at 70% r.h. Carrageenan is insoluble in organic solvents such as alcohol, ether, and oil. Solubility in water depends on the structure of the particular carrageenan, the medium, and the temperature. Generally the gelling carrageenans must be heated to dissolve whereas non-gelling carrageenans may be dissolved in cold water.

Solubility
Carrageenan exhibits the solubility characteristics normally shown by hydrophilic colloids. It is water soluble and insoluble in most organic solvents. Water miscible alcohols and ketones, while themselves non-solvents for carrageenan, are tolerated in admixture with carrageenan solutions at levels up to 40%. More highly polar solvents, such as formamide and N,N-dimethylformamide, are tolerated in still higher proportion and alone cause a marked swelling of the polymer. The solubility characteristics of carrageenan in water are influenced by a number of factors most important of which are: a. the type of carrageenan b. counter ions present c. other solutes d. temperature e. pH

TYPE OF CARRAGEENAN
The many forms of carrageenan possible through variation in structural detail, provide much variability in regard to solubility properties. For practical purposes, however, it is convenient to speak in terms of several general structural types and to equate solubility with the overall balance of hydrophilicity as provided by the hydrophilic sulfate and hydroxyl groups on one hand and the more hydrophobic 3.6-anhydro-D-galactose residues on the other. Thus, lambda carrageenan, by definition void of 3.6-anhydro-D-galactose units and being highly sulfated is easily soluble under most conditions. Kappa carrageenan containing 3.6-anhydro-D-galactose as part of the repeating unit and fewer sulfate groups is less hydrophilic and less soluble. Intermediate is iota carrageenan, more hydrophilic by virtue of its 2-sulfate which in addition to its position counteracts the less hydrophilic character of the 3.6-anhydro-D-galactose residue.

SOLUBILITY CARRAGEENAN IN MEDIUM/SOLVENTS

Medium Hot water Kappa Soluble above 60C (140F) Iota Soluble above 60C (140F) Lambda Soluble

Cold water

Sodium salt soluble. Potassium and calcium salt, insoluble

Sodium salt soluble Calcium salts gives thixotropic dispersions

Soluble

Hot milk

Soluble

Soluble

Soluble

Cold milk

Sodium salt, calcium salt and potassium salt insoluble, but swells markedly
Soluble hot

Insoluble

Soluble

Concentrated sugar solutions Concentrated salt solutions

Not easily soluble

Soluble hot

Insoluble

Soluble hot

Soluble hot

USAGE & STANDARDIZATION OF CARRAGEENAN

Carrageenan is used in concentrations from as low as 0.005% to as high as 3.0% in a broad variety of products. Many types of carrageenan are made, some being standardized for general use as a gelling agent in water or milk systems and some being controlled by application tests, designed in cooperation between the user and the manufacturer. Standardization is done by blending different batches of carrageenan and/or by blending with an inert material such as sucrose or dextrose. Standardization of carrageenan with sugar is recognized in the EU stabilizer directive and the FAO/WHO-specification.

QUALITY CONTROL
Carrageenan has a high (natural) ash content, originating from the sulfate half ester groups and the cations. On ashing, some of the sulfate evaporates as SO3, and the ash content is accordingly found to be lower than expected from SO4 and cation content

STABILITY
Carrageenan will depolymerize slowly when stored. As the two most important properties of carrageenan, gel strength and protein reactivity, are hardly dependent on degree of polymerization, the loss in strength over a period of one year at room temperature is undetectable. It is generally undesirable to blend a carrageenan powder with other powdered or crystalline ingredients of an acidic nature. However, when specific precautions are taken, it is possible to make stable blends of carrageenan and citric acid for example.

Gel Properties

Gel Formation
Carrageenan is a thermoreversible gelling agent. Gel formation is obtained only in the presence of potassium ions (kappa and iota carrageenan) or calcium ions (iota carrageenan). When potassium ions are present, and the system is cooled below the gelling temperature, the carrageenan gels instantaneously.

GELLING PROPERTIES
Kappa
Effect of cations

Iota

Lambda
Non-gelling

Gels most strongly Gels most strongly with potassium ions with calcium ions

Type of gel

Strong and brittle with syneresis

Elastic and cohesive Non-gelling without syneresis

Synergistic effect with locust bean gum

Freeze/thaw stability

High

High

None

None

Stable

None

SELECTION GUIDE FOR CARRAGEENAN

GENULACTA types find application in milk systems GENUGEL types find application in water systems GENUVISCO types are used as thickening agents/stabilizing agents

Tugas membaca
Find out : Baca Perbedaan gelling properties of AGAR dengan CARRAGEENAN.