WO2010138004A1 - Method for producing cold-soluble semi-refined carrageenan and applications of cold-soluble semi-refined carrageenan - Google Patents

Method for producing cold-soluble semi-refined carrageenan and applications of cold-soluble semi-refined carrageenan Download PDF

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Publication number
WO2010138004A1
WO2010138004A1 PCT/PH2009/000006 PH2009000006W WO2010138004A1 WO 2010138004 A1 WO2010138004 A1 WO 2010138004A1 PH 2009000006 W PH2009000006 W PH 2009000006W WO 2010138004 A1 WO2010138004 A1 WO 2010138004A1
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carrageenan
cold
semi
seaweeds
refined
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PCT/PH2009/000006
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French (fr)
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Michael U. Tan
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Tan Michael U
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Publication of WO2010138004A1 publication Critical patent/WO2010138004A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L13/00—Meat products; Meat meal; Preparation or treatment thereof
    • A23L13/40—Meat products; Meat meal; Preparation or treatment thereof containing additives
    • A23L13/42—Additives other than enzymes or microorganisms in meat products or meat meals
    • A23L13/422—Addition of natural plant hydrocolloids, e.g. gums of cellulose derivatives or of microbial fermentation gums
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L13/00—Meat products; Meat meal; Preparation or treatment thereof
    • A23L13/50—Poultry products, e.g. poultry sausages
    • A23L13/55—Treatment of original pieces or parts
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L13/00—Meat products; Meat meal; Preparation or treatment thereof
    • A23L13/70—Tenderised or flavoured meat pieces; Macerating or marinating solutions specially adapted therefor
    • A23L13/72—Tenderised or flavoured meat pieces; Macerating or marinating solutions specially adapted therefor using additives, e.g. by injection of solutions
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/256—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin from seaweeds, e.g. alginates, agar or carrageenan
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0036—Galactans; Derivatives thereof
    • C08B37/0042—Carragenan or carragen, i.e. D-galactose and 3,6-anhydro-D-galactose, both partially sulfated, e.g. from red algae Chondrus crispus or Gigantia stellata; kappa-Carragenan; iota-Carragenan; lambda-Carragenan; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation

Definitions

  • This invention relates to a method for producing a cold soluble kappa- and iota- semi- refined carrageenan (“SRC”) or Processed Eucheuma Seaweed (“PES”) from carrageenan- containing seaweed wherein the solubility temperature is below 25 0 C to about 4 0 C or to lower temperatures as long as solution is still formed and applications of the same.
  • SRC cold soluble kappa- and iota- semi- refined carrageenan
  • PES Processed Eucheuma Seaweed
  • Carrageenan are polysaccharides which occurs naturally in certain red seaweeds species such as Rhodophyceae and gigartinaceae families and chemically, a linear polysaccharides consisting of repeating units of sulfated D-galactose and 3 ,6-anhydro-D-galactose.
  • Carrageenan molecules give flexibility of structure in the seaweeds as these molecules are distributed inside the plant stems in the spaces between the plant cells.
  • carrageenan The ionic nature of carrageenan gives its unique functionality and is used in many applications in foods, pharmaceutical and other industrial use. It has the ability to react with other ionic molecules such as proteins and ionic gums and even forms synergistic reactions with some of these. Carrageenan thickens in water solutions and some types can form gels in water. It has also a pronounced reactivity with some types of ions such as potassium, calcium and ammonium. These characteristics of carrageenan made it usable as binder, thickener, suspending agent and gelling agent in applications with a water environment such as processed meats, air freshener and dessert gels, dairies, etc.
  • Carrageenan are categorized according to chemical structure which are named as mu-, kappa-, nu-, iota-, lambda-, theta-, and xi-carrageenan depending on their sulfate and anhydro-D-galactose contents. Since carrageenan is negatively ionic in nature, therefore in its powder form, a certain amount of balancing cations or positive ions such as potassium, calcium or sodium are also present. The cations present in carrageenan are the results of the methods of processing used because different manufacturers used different types of chemicals with different cations in these chemicals.
  • Kappa type carrageenan exhibits some properties such as: - soluble above 75 0 C if the inherent cations are potassium or calcium ions; - soluble in cold water if the inherent cations are sodium ion; - gels most strongly with potassium in which the gels formed is strong, brittle and with syneresis.
  • Iota type carrageenan exhibits properties such as; - soluble above 75 0 C if the inherent cations are potassium or calcium; - gives a thixotropic dispersion in cold water in solutions of calcium ions; - soluble in cold water if the inherent cations are sodium; - gels most strongly with calcium in which the gels formed is elastic and no syneresis.
  • Lambda type carrageenan exhibits some properties such as; - soluble in hot and cold solutions in any type of cations present; - does not form gels in water.
  • Kappa- and iota-Carrageenan solubility in water is mainly affected by the cations and the type of cations present.
  • these positive ions namely potassium and calcium ions
  • the carrageenan molecules which are arranged in helical structures and piled side by side with other carrageenan helices, and the positive ions will be arranged in between these gaps.
  • These gaps have specific distance for a certain type of carrageenan.
  • the negatively ionic sulfate side chains of carrageenan molecule causes the attraction of these positive ions between these gaps.
  • the sodium ion does not meet the requirement for stability in fitting on these gaps due to its different size, thus, if the inherent cations in carrageenan and in the water solution is sodium while the potassium and calcium ions is reduced to a minimal amount, the kappa- and iota-carrageenan solubility is increased and even at cold temperatures (below 25 0 C) these carrageenan types still dissolves.
  • the cold solubility of the carrageenan is greatly reduced. From these principles that the object of this invention is utilized.
  • Kappa and Iota Carrageenan are manufactured according to two major processing methods which are; (1) refined processing method, a method involving treatment of seaweed using strong alkali solution at elevated temperatures of 50 - 95 0 C and extraction of carrageenan from the treated seaweed by filtration and excluding other constituents of the seaweed, and precipitation of the carrageenan extract solution using alcohol or salt of potassium or calcium; and (2) semi-refined carrageenan processing method, of which involves treatment of seaweed with strong alkali solution at elevated temperatures of 50 - 95 0 C, washing and neutralizing and optional bleaching of the treated seaweed and grinding to convert them to powder form in which the other seaweeds constituents principally cellulose forms part of the powder.
  • a cold soluble semi-refined carrageenan powder provides advantages in many applications of carrageenan.
  • Such application in processed meat for example where the brine solution is at cold temperatures (less than 10 0 C) the incorporation of carrageenan as binder, texturizer and water holder needs to be heated in order to fully utilize the carrageenan effect.
  • An application of carrageenan in air freshener gels, wherein the carrageenan acts as gelling agent and carrier of perfume, a cold soluble type will be most efficient because the dissipation of perfume due to heating is reduced.
  • step (c2) soaking the seaweeds in sodium sulfate salt solution repeated multiple times depending on the desired cold solubility of the final powder.
  • Other sodium containing salt may also be used in step (c2) wherein the sodium containing salt does not contain potassium or calcium ion.
  • the preferred embodiment of commercial scale method of the present invention for producing cold soluble semi-refined carrageenan combines traditional method of producing semi-refined carrageenan and additional processing steps and chemicals which are described in detail in this invention.
  • the common practice in manufacture of semi-refined carrageenan involves the following steps: (I) A dried seaweeds of Eucheuma cottonii or Eucheuma spinosum specie of about 30 to 50% moisture is used as the starting raw material is pre-washed with water to remove excess salts and sands and other impurities, an optional mechanical agitator maybe employed to make the pre-washing more effective and also multiple pre-washings maybe chosen; (2) after the seaweeds is pre-washed, the seaweeds is submerged in a hot solution containing alkali of either sodium hydroxide or potassium hydroxide (other alkalis may also be used.).
  • the purpose of the alkali treatment is to catalyze the conversion of the pre-cursor mu or nu type carrageenan into its corresponding kappa or iota type (chemically it is the formation of 3,6-anhydro-galactose in the molecule of the kappa and iota type carrageenan) .
  • the temperature may range from 50 0 C to 95 0 C depending on the type of carrageenan present in the seaweed specie. For iota types seaweed such as Eucheuma spinosum, the temperature needed is lower at about 50 - 70 0 C, this is because the iota seaweed type is easily melted at high temperature.
  • Kappa type Eucheuma cottonii seaweed is usually heated from 80 to 95 0 C.
  • the seaweed is washed with water in series of washings to remove the excess alkali and other unwanted pigments from the seaweeds. These washing steps also neutralize the seaweeds to some degree.
  • the washed seaweed is bleached using common bleaching agents employed in food manufacture such as hypochlorites or peroxides.
  • the seaweed is rinsed with water to remove the excess bleach.
  • the seaweed is chopped in smaller size about 2 to 4 inched or as chosen in order to facilitate more efficient drying at the latter stage.
  • the seaweed is dried using a mechanical dryer or sundrying method to about 15% moisture.
  • the dried seaweeds or called seaweed chips is ground into powder using mechanical grinders.
  • Ground powder is homogenized in a blender. (11) The powder is packed in desired packaging.
  • the described method above was already an established and stable process for producing a SRC kappa or iota type which are hot soluble since the majority of inherent cations are potassium or calcium.
  • the reason for employing these cations (K + , Ca +2 ) is to prevent the seaweeds from melting during the heated alkali treatment and washing steps.
  • Dried seaweeds with about 40% moisture are normally containing around 20 to 30% inherent salt that is absorbed by the seaweeds from the seawater and containing a significant amount of potassium and calcium salts.
  • the amount of inherent potassium and calcium salt is significantly enough to cause the produced powder not to exhibit cold solubility even if the cooking steps preferred to use alkali not containing potassium or calcium.
  • the heated alkali treatment step and the inherent potassium and calcium ions content of the natural seaweed increase the difficulty of producing a cold soluble semi-refined carrageenan type. This is the reason that the methods in this invention is not known or utilized in the art. There has never been mentioned of a process which produces a semi- refined carrageenan in which the inherent cation is sodium and which its semi-refined carrageenan powder produced is cold soluble
  • the preferred embodiment of this invention is described below which can produced a cold soluble semi-refined carrageenan on a commercial scale.
  • the method of producing cold soluble semi-refined carrageenan in commercial scale (1)
  • the dried Eucheuma cottonii or Eucheuma spinosum seaweed specie to about 20 - 50% moisture is pre-washed to remove impurities and excess salts.
  • calcium chloride salt is used as aid to prevent seaweeds from melting.
  • the seaweed is washed multiple times with water.
  • the seaweed is soaked in ionic solution multiple times. In this preferred embodiment, the seaweed is soaked in 0.5% calcium chloride.
  • the seaweeds is soaked in sodium sulfate solution to abstract and precipitate the calcium ion into the solution and to exchange calcium or potassium ions inside the seaweeds stems with sodium ions , (6)
  • the seaweeds is bleached by a suitable bleaching agent employed in the conventional method.
  • the seaweed is rinsed with water for suitable number of times.
  • the seaweed is chopped (9)
  • the chopped seaweed is dried (10)
  • the dried seaweed chips is ground (1 1)
  • the powder is homogenized (12) The powder is packed.
  • the semi-refined carrageenan powder produced from the preferred embodiment of this invention is subjected to tests to determine its cold solubility.
  • the powder that is dispersed in de- ionized water solution must be able to form homogenous solution appearance as evidence by its smoothness instead of a swollen dispersion or presence of spherical hydrated powder, and as would also appear like the solution of a regular hot soluble semi-refined carrageenan which is heated and dissolved.
  • the powder in question must also form viscous solution and if the powder viscosity is essentially near or the same to the viscosity of the same powder that has been heated and cooled, and most importantly if the dispersed powder at cold water temperature (below 25 C) which is added with Potassium Chloride forms a gel, then is presumed that the powder is cold-water soluble.
  • Another test is also employed wherein the powder from this embodiment which is a kappa-semi-refined carrageenan is read of its gel strength as known in the art. Since the powder in test may not have sufficient potassium or calcium ions inherently present from the powder, the test includes addition of 0.2% Potassium Chloride into the solution of carrageenan. Below are the typical data from the powders produced from this preferred embodiment.
  • the viscosity is read using Brookfield LVT viscometer and the gel strength is read using TAXT2 Texture Analyzer by Stable Microsystems. The results of the tests indicate that the produced semi-refined carrageenan is cold-soluble.
  • the preferred preparation of the brine involves dispersing about 0.8 - 1.7 % cold- soluble semi-refined carrageenan in soft water or de-ionized water with a temperature of approximately 0 - 4 0 C for about 2 - 3 minutes using high speed stirrer; adding and dissolving well about 6 - 7 % sodium chloride in the solution; adding and dissolving thoroughly about 4- 5 % sodium tripolyphosphate in the solution; adding other ingredients as desired for added flavor enhancement and other advantageous characteristics; injecting the brine solution into the chicken meat providing about 20 - 30 % added weight to the meat; packaging and storing of the injected chicken meat in the freezer.
  • the cold-soluble SRC exhibits advantageous characteristics in mousse, an increase in the overrun or volume yield of mousse prepared using cold-soluble kappa carrageenan blend , as compared when lambda carrageenan is used.
  • the preferred preparation of Mousse involves dry blending of about 8 - 12 % skimmed milk powder, 5 - 8 % powdered sugar, 0.4 - 1.2 % cocoa powder and 0.8 - 1.5 % cold- soluble kappa carrageenan blend; dispersing the mix in approximately 23 - 40 % full cream milk chilled to achieve about 5 - 10 0 C; adding about 44 - 48 % all purpose cream in the 1 _ mixture; whipping the mixture at highest speed for about 3 - 5 minutes; pouring into container.
  • the preferred preparation of whipped cream using cold-soluble semi-refined carrageenan comprising the steps of: chilling of all purpose cream to achieve a temperature of about 3 - 5 0 C; whipping using until it becomes slightly soft; pre-mixing about 0.05 - 0.25 - _ % cold-soluble semi-refined carrageenan with about 5 - 10 % confectioners sugar; adding the stabilizer mix to the whipping cream; beating until stiff peak forms.

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Abstract

A method of producing cold soluble kappa and iota semi-refined carrageenan or Processed Eucheuma Seaweed from a carrageenan containing seaweeds wherein the solubility temperature is below 25 °C. Applications of this cold soluble semi-refined carrageenan is found advantageous in processed poultry meat wherein the yield increased to about 5% when used in brine preparation, and also in Mousse and Whipped Cream preparation wherein volume yield has increased when compared to lambda refined carrageenan which is typically used for this application.

Description

METHOD FOR PRODUCING COLD-SOLUBLE SEMI-REFINED CARRAGEENAN AND APPLICATIONS OF COLD-SOLUBLE SEMI-REFINED CARRAGEENAN
Field of Invention
This invention relates to a method for producing a cold soluble kappa- and iota- semi- refined carrageenan ("SRC") or Processed Eucheuma Seaweed ("PES") from carrageenan- containing seaweed wherein the solubility temperature is below 25 0C to about 4 0C or to lower temperatures as long as solution is still formed and applications of the same.
Background to the Invention
Carrageenan are polysaccharides which occurs naturally in certain red seaweeds species such as Rhodophyceae and gigartinaceae families and chemically, a linear polysaccharides consisting of repeating units of sulfated D-galactose and 3 ,6-anhydro-D-galactose.
Carrageenan molecules give flexibility of structure in the seaweeds as these molecules are distributed inside the plant stems in the spaces between the plant cells.
The ionic nature of carrageenan gives its unique functionality and is used in many applications in foods, pharmaceutical and other industrial use. It has the ability to react with other ionic molecules such as proteins and ionic gums and even forms synergistic reactions with some of these. Carrageenan thickens in water solutions and some types can form gels in water. It has also a pronounced reactivity with some types of ions such as potassium, calcium and ammonium. These characteristics of carrageenan made it usable as binder, thickener, suspending agent and gelling agent in applications with a water environment such as processed meats, air freshener and dessert gels, dairies, etc.
Carrageenan are categorized according to chemical structure which are named as mu-, kappa-, nu-, iota-, lambda-, theta-, and xi-carrageenan depending on their sulfate and anhydro-D-galactose contents. Since carrageenan is negatively ionic in nature, therefore in its powder form, a certain amount of balancing cations or positive ions such as potassium, calcium or sodium are also present. The cations present in carrageenan are the results of the methods of processing used because different manufacturers used different types of chemicals with different cations in these chemicals. Common types of carrageenan in the market are kappa, iota and lambda, also these carrageenan varies in characteristics depending on the inherent cations present in the powder. Kappa type carrageenan exhibits some properties such as: - soluble above 75 0C if the inherent cations are potassium or calcium ions; - soluble in cold water if the inherent cations are sodium ion; - gels most strongly with potassium in which the gels formed is strong, brittle and with syneresis. Iota type carrageenan exhibits properties such as; - soluble above 75 0C if the inherent cations are potassium or calcium; - gives a thixotropic dispersion in cold water in solutions of calcium ions; - soluble in cold water if the inherent cations are sodium; - gels most strongly with calcium in which the gels formed is elastic and no syneresis.
Lambda type carrageenan exhibits some properties such as; - soluble in hot and cold solutions in any type of cations present; - does not form gels in water.
Kappa- and iota-Carrageenan solubility in water is mainly affected by the cations and the type of cations present. In the presence of these positive ions, namely potassium and calcium ions, the carrageenan molecules which are arranged in helical structures and piled side by side with other carrageenan helices, and the positive ions will be arranged in between these gaps. These gaps have specific distance for a certain type of carrageenan. The negatively ionic sulfate side chains of carrageenan molecule causes the attraction of these positive ions between these gaps. The interaction and stability caused by these positive ions in the carrageenan helical structure in water solution causes the carrageenan molecules to resist the dissolution in water, since in order to dissolve the carrageenan molecules in water, the individual molecules must be separated from each other and hence water must be inserted and arranged in between these molecules. For the kappa type, potassium ion has the most pronounced effect on its solubility because the gaps between its molecules most precisely fit these positive ions, while for iota type, calcium exhibits the most effect. However, for both types, the sodium ion does not meet the requirement for stability in fitting on these gaps due to its different size, thus, if the inherent cations in carrageenan and in the water solution is sodium while the potassium and calcium ions is reduced to a minimal amount, the kappa- and iota-carrageenan solubility is increased and even at cold temperatures (below 25 0C) these carrageenan types still dissolves. However, even a significantly minimal amount of potassium or calcium ion when present in the solution whether coming from the inherent ions of the carrageenan or from the ions originally present in the solution, the cold solubility of the carrageenan is greatly reduced. From these principles that the object of this invention is utilized.
Kappa and Iota Carrageenan are manufactured according to two major processing methods which are; (1) refined processing method, a method involving treatment of seaweed using strong alkali solution at elevated temperatures of 50 - 95 0C and extraction of carrageenan from the treated seaweed by filtration and excluding other constituents of the seaweed, and precipitation of the carrageenan extract solution using alcohol or salt of potassium or calcium; and (2) semi-refined carrageenan processing method, of which involves treatment of seaweed with strong alkali solution at elevated temperatures of 50 - 95 0C, washing and neutralizing and optional bleaching of the treated seaweed and grinding to convert them to powder form in which the other seaweeds constituents principally cellulose forms part of the powder.
There are already common methods employed in industry in producing semi-refined carrageenan. An improved method using shear stress method is also mentioned in US Patent 7,018,635 and 7,189,843 which can produce semi-refined carrageenan that may also exhibit near cold solubility, for instance the iota produced by this method may hydrate about 30 0C and the kappa type about 50 0C. However, this method requires a special equipment to apply shear stress in the carrageenan containing seaweeds. Also mentioned in US patent 5801240 an improved method of producing semi-refined carrageenan by monitoring the reaction progress of the desulfation in the chemical reaction step during the alkali treatment step in order to effectively convert the carrageenan containing seaweed into its kappa or iota form. However, this method will also produce kappa and iota type with the intention to increase the proportion of kappa and iota carrageenan fraction in the powder form. These methods all require special equipment and will incorporate potassium or calcium ions as significantly present inherently in the powder form, thus the carrageenan that will be produced is not cold soluble. These methods have not taken into account a specific method to purposely produce a cold soluble semi-refined carrageenan of kappa and iota type in which the solubility temperature is below 25 0C for both types.
A cold soluble semi-refined carrageenan powder provides advantages in many applications of carrageenan. Such application in processed meat for example where the brine solution is at cold temperatures (less than 10 0C), the incorporation of carrageenan as binder, texturizer and water holder needs to be heated in order to fully utilize the carrageenan effect. An application such as frozen meat and seafood like shrimp where the carrageenan is used as water holder and coating, a cold soluble is preferred since an extra heating step to dissolve the carrageenan is eliminated. An application of carrageenan in air freshener gels, wherein the carrageenan acts as gelling agent and carrier of perfume, a cold soluble type will be most efficient because the dissipation of perfume due to heating is reduced. Since manufacture of carrageenan of the soluble types can be done easily using refined carrageenan processing method as common in the industry, there is a disadvantage of high cost. There is a need for a commercial method for producing a cold soluble kappa- and iota- semi-refined carrageenan because this method is far cheaper and more practical in most applications than using the refined processing method as known by practitioners in the art.
Summary of the Invention
Accordingly, a method of producing cold soluble kappa and iota semi-refined carrageenan wherein the solubility temperature is below 25 0C, from a carrageenan containing seaweeds in which the method of producing conventional semi-refined carrageenan by the processing steps of: (a) pre-washing of carrageenan containing seaweeds; (b) treating the seaweeds in heated alkali solution to cause conversion of the precursor carrageenan type naturally present in the seaweeds into the kappa and iota type carrageenan; (c) washing, optional bleaching and rinsing of seaweeds in water; (d) chopping and drying the seaweed; (e) grinding the dried seaweed chips; there is disclosed an improvement of method to produce a cold soluble semi-refined carrageenan by incorporating the following steps in step (c) wherein added the sub-steps of: (cl) soaking the seaweeds in calcium chloride solution to facilitate ion exchange of potassium inside the seaweeds with calcium ion. (c2) soaking the seaweeds in sodium sulfate salt solution repeated multiple times depending on the desired cold solubility of the final powder. Other sodium containing salt may also be used in step (c2) wherein the sodium containing salt does not contain potassium or calcium ion.
Detailed Description of Preferred Embodiments of the Invention
The preferred embodiment of commercial scale method of the present invention for producing cold soluble semi-refined carrageenan combines traditional method of producing semi-refined carrageenan and additional processing steps and chemicals which are described in detail in this invention.
Manufacture of conventional Semi-refined Carrageenan(SRC)
The common practice in manufacture of semi-refined carrageenan involves the following steps: (I) A dried seaweeds of Eucheuma cottonii or Eucheuma spinosum specie of about 30 to 50% moisture is used as the starting raw material is pre-washed with water to remove excess salts and sands and other impurities, an optional mechanical agitator maybe employed to make the pre-washing more effective and also multiple pre-washings maybe chosen; (2) after the seaweeds is pre-washed, the seaweeds is submerged in a hot solution containing alkali of either sodium hydroxide or potassium hydroxide (other alkalis may also be used.). The purpose of the alkali treatment is to catalyze the conversion of the pre-cursor mu or nu type carrageenan into its corresponding kappa or iota type (chemically it is the formation of 3,6-anhydro-galactose in the molecule of the kappa and iota type carrageenan) . The temperature may range from 50 0C to 95 0C depending on the type of carrageenan present in the seaweed specie. For iota types seaweed such as Eucheuma spinosum, the temperature needed is lower at about 50 - 70 0C, this is because the iota seaweed type is easily melted at high temperature. Kappa type Eucheuma cottonii seaweed is usually heated from 80 to 95 0C. (3) After the alkali treatment at elevated temperature, the seaweed is washed with water in series of washings to remove the excess alkali and other unwanted pigments from the seaweeds. These washing steps also neutralize the seaweeds to some degree. (4) Optionally, the washed seaweed is bleached using common bleaching agents employed in food manufacture such as hypochlorites or peroxides. (5) The seaweed is rinsed with water to remove the excess bleach. (6) Neutralization of the alkalinity of the seaweeds to desired pH of the final powder (pH to about 8 to 1 1) using water or optionally adding acids. (7) optionally, the seaweed is chopped in smaller size about 2 to 4 inched or as chosen in order to facilitate more efficient drying at the latter stage. (8) The seaweed is dried using a mechanical dryer or sundrying method to about 15% moisture. (9) The dried seaweeds or called seaweed chips is ground into powder using mechanical grinders. (10) Ground powder is homogenized in a blender. (11) The powder is packed in desired packaging.
Manufacture of Cold Soluble Semi-refined Carrageenan
The described method above was already an established and stable process for producing a SRC kappa or iota type which are hot soluble since the majority of inherent cations are potassium or calcium. The reason for employing these cations (K+, Ca+2) is to prevent the seaweeds from melting during the heated alkali treatment and washing steps. Dried seaweeds with about 40% moisture are normally containing around 20 to 30% inherent salt that is absorbed by the seaweeds from the seawater and containing a significant amount of potassium and calcium salts. The amount of inherent potassium and calcium salt is significantly enough to cause the produced powder not to exhibit cold solubility even if the cooking steps preferred to use alkali not containing potassium or calcium.
The heated alkali treatment step and the inherent potassium and calcium ions content of the natural seaweed increase the difficulty of producing a cold soluble semi-refined carrageenan type. This is the reason that the methods in this invention is not known or utilized in the art. There has never been mentioned of a process which produces a semi- refined carrageenan in which the inherent cation is sodium and which its semi-refined carrageenan powder produced is cold soluble
The preferred embodiment of this invention is described below which can produced a cold soluble semi-refined carrageenan on a commercial scale. Presented is the method of producing cold soluble semi-refined carrageenan in commercial scale. (1) Optionally, the dried Eucheuma cottonii or Eucheuma spinosum seaweed specie to about 20 - 50% moisture is pre-washed to remove impurities and excess salts. (2) The seaweeds subjected to heated alkali treatment at 80 - 95 0C for Eucheuma cottonii or 50 - 70 0C for Eucheuma spinosum for about 1 to 3 hours long using potassium hydroxide or other strong alkali and addition of potassium chloride or calcium chloride to prevent the seaweeds from dissolving. In this preferred embodiment, calcium chloride salt is used as aid to prevent seaweeds from melting. (3) After the heated alkali treatment, the seaweed is washed multiple times with water. (4) The seaweed is soaked in ionic solution multiple times. In this preferred embodiment, the seaweed is soaked in 0.5% calcium chloride. (5) The seaweeds is soaked in sodium sulfate solution to abstract and precipitate the calcium ion into the solution and to exchange calcium or potassium ions inside the seaweeds stems with sodium ions , (6) The seaweeds is bleached by a suitable bleaching agent employed in the conventional method. (7) The seaweed is rinsed with water for suitable number of times. (8) the seaweed is chopped (9) The chopped seaweed is dried (10) The dried seaweed chips is ground (1 1) The powder is homogenized (12) The powder is packed.
The semi-refined carrageenan powder produced from the preferred embodiment of this invention is subjected to tests to determine its cold solubility. In order to conclude the solubility of the semi -refined carrageenan produced, the powder that is dispersed in de- ionized water solution must be able to form homogenous solution appearance as evidence by its smoothness instead of a swollen dispersion or presence of spherical hydrated powder, and as would also appear like the solution of a regular hot soluble semi-refined carrageenan which is heated and dissolved. The powder in question must also form viscous solution and if the powder viscosity is essentially near or the same to the viscosity of the same powder that has been heated and cooled, and most importantly if the dispersed powder at cold water temperature (below 25 C) which is added with Potassium Chloride forms a gel, then is presumed that the powder is cold-water soluble. Another test is also employed wherein the powder from this embodiment which is a kappa-semi-refined carrageenan is read of its gel strength as known in the art. Since the powder in test may not have sufficient potassium or calcium ions inherently present from the powder, the test includes addition of 0.2% Potassium Chloride into the solution of carrageenan. Below are the typical data from the powders produced from this preferred embodiment.
Viscosity(cps) of Viscosity(cps) of Gel Strength (grams) cold-dispersed 2% w/w powder of 2% w/w powder +
2% w/w powder heated to 75 0C and 0.2% KCl dissolved
@ 15 0C cooled, read @ 15 0C at 20 0C and after
4 hours ageing in 20 0C
Cold Soluble SRC 276 310 127 Regular SRC 8 90 no sel formed
The viscosity is read using Brookfield LVT viscometer and the gel strength is read using TAXT2 Texture Analyzer by Stable Microsystems. The results of the tests indicate that the produced semi-refined carrageenan is cold-soluble.
Cold-soluble SRC Applications
Some applications of the cold soluble semi-refined carrageenan were determined to give advantages on these applications as mentioned below. Brine Solution Using Cold-Soluble Semi-Refined Carrageenan for Fresh Poultry
The cold-soluble SRC carrageenan application on meat .processing resulted in increased water retention of the poultry meat during cold storage and after cooking caused by using the cold-soluble carrageenan in the brine and injecting the brine in the meat as compared to regular hot soluble semi-refined carrageenan.
The preferred preparation of the brine involves dispersing about 0.8 - 1.7 % cold- soluble semi-refined carrageenan in soft water or de-ionized water with a temperature of approximately 0 - 4 0C for about 2 - 3 minutes using high speed stirrer; adding and dissolving well about 6 - 7 % sodium chloride in the solution; adding and dissolving thoroughly about 4- 5 % sodium tripolyphosphate in the solution; adding other ingredients as desired for added flavor enhancement and other advantageous characteristics; injecting the brine solution into the chicken meat providing about 20 - 30 % added weight to the meat; packaging and storing of the injected chicken meat in the freezer.
A reduction of about 4- 6 % thawing loss is observed in injected chicken meat using cold- soluble semi-refined carrageenan against regular carrageenan as shown below.
% Loss First Thawing Cycle Second Thawing Cycle
Using cold soluble SRC 3 3
Using regular SRC 7 9
A reduction of about 5 - 7 % cooking loss is observed in injected chicken meat using cold- soluble semi-refined carrageenan against regular carrageenan as shown below.
% Cooking Loss
Using Cold soluble SRC 14
Using regular SRC 20 Mousse Preparation Using Cold-Soluble Semi-Refined Carrageenan
The cold-soluble SRC exhibits advantageous characteristics in mousse, an increase in the overrun or volume yield of mousse prepared using cold-soluble kappa carrageenan blend , as compared when lambda carrageenan is used.
The preferred preparation of Mousse involves dry blending of about 8 - 12 % skimmed milk powder, 5 - 8 % powdered sugar, 0.4 - 1.2 % cocoa powder and 0.8 - 1.5 % cold- soluble kappa carrageenan blend; dispersing the mix in approximately 23 - 40 % full cream milk chilled to achieve about 5 - 10 0C; adding about 44 - 48 % all purpose cream in the 1 _ mixture; whipping the mixture at highest speed for about 3 - 5 minutes; pouring into container.
Whipped Cream Preparation Using Cold-Soluble Semi-Refined Carrageenan
It is observed that an increase in the overrun or volume yield of whipped cream . ^ prepared using cold-soluble semi-refined carrageenan blend as compared when lambda carrageenan is used.
The preferred preparation of whipped cream using cold-soluble semi-refined carrageenan comprising the steps of: chilling of all purpose cream to achieve a temperature of about 3 - 5 0C; whipping using until it becomes slightly soft; pre-mixing about 0.05 - 0.25 - _ % cold-soluble semi-refined carrageenan with about 5 - 10 % confectioners sugar; adding the stabilizer mix to the whipping cream; beating until stiff peak forms.

Claims

What is Claimed is:
1. A method of producing cold soluble kappa and iota semi-refined carrageenan from carrageenan containing seaweeds in which the method of producing conventional semi- refined carrageenan by the processing steps of:
(a) pre-washing of carrageenan containing seaweeds;
(b) treating the seaweeds in heated alkali solution to cause conversion of the precursor carrageenan type naturally present in the seaweeds into the kappa and iota type carrageenan; (c) washing, optional bleaching and rinsing of seaweeds in water;
(e) chopping and drying the seaweed;
(f) grinding the dried seaweed chips; incorporates the following steps to produce a cold soluble semi-refined carrageenan in step (c) wherein added the sub-steps of: (cl) soaking the seaweeds in calcium chloride solution to facilitate ion exchange of potassium ion inside the seaweeds with calcium ion;
(c2) soaking the seaweeds in sodium sulfate salt solution repeated multiple times depending on the desired cold solubility of the final powder. Other sodium containing salt may also be used wherein the sodium containing salt does not contain potassium or calcium ion.
2. The seaweed before the drying step from claim 1 is not melted and suitable for mechanical- or sun- drying.
3. The salt used in step (c2) of claim 1 can be any sodium containing salt and not containing potassium or calcium.
4. The concentration of salt in step (c2) of claim 1 range from 0.001% up to the saturation concentration of the salt or at any practical salt concentration depending on the desired number of salt soakings required to efficiently and practically abstract the inherent potassium and calcium ions from the seaweed and whereby preventing the dissolving of the seaweed into the solution.
5. The solubility temperature of the semi-refined carrageenan produced from claim 1 is cold soluble wherein cold soluble is defined as soluble in both hot temperature and cold temperature, wherein hot temperature is defined as greater than 25 0C and cold temperature is defined as less than or equal to 25 0C up to lower temperatures as long as solution is still formed.
6. A brine preparation for poultry meat using cold soluble semi-refined carrageenan as active ingredient replacing regular hot soluble semi-refined carrageenan to decrease lost of incorporated water upon and after thawing and cooking of the poultry meat.
7. A Mouse preparation using cold soluble semi-refined carrageenan as replacement for lambda refined carrageenan to increase the overrun or volume yield of mousse prepared.
8. A Whipped Cream preparation using cold soluble semi-refined carrageenan as replacement for lambda refined carrageenan to increase the overrun or volume yield of Whipped Cream prepared.
PCT/PH2009/000006 2009-05-28 2009-05-28 Method for producing cold-soluble semi-refined carrageenan and applications of cold-soluble semi-refined carrageenan WO2010138004A1 (en)

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WO2020076698A1 (en) * 2018-10-11 2020-04-16 Cargill, Incorporated Seaweed flour

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CN102775510A (en) * 2012-08-06 2012-11-14 青岛德慧海洋生物科技有限公司 Preparation technique of low-temperature instant carrageenan
WO2020076698A1 (en) * 2018-10-11 2020-04-16 Cargill, Incorporated Seaweed flour

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