DE2814664A1 - PROCESS FOR PREPARING STARCH XANTHANE COMPOSITIONS - Google Patents

Description

United States of America as represented by the Secretary of Commerce, NTIS, Washington, D.C, U. S. A.

Process for making starch-xanthan compositions

The invention relates to a method of making stable starch gel compositions which exhibit minimal syneresis .

The subject of the invention thus forms the production of starch-xanthan compositions, in particular the production of starch-xanthan compositions which have improved viscosity, solubility and gelling properties as well as minimal syneresis.

Rubber compounds in the form of natural, biosynthetic or modified polysaccharides are known. ^{Such rubber compositions} are hou ^^ ^{0 c} ^ Lvc ^ ^a 's additives for

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Chin lircMiieii / IJivnicii Office: Posilaili / PO Box IO 71 11 IVItlstritlii'2-l. M 2H00 Hmnen 1 Ίι · 1ι · ρΐΗ) π. (0421) 7 40 44
UkkopifixT 'Iflccopicr Kaiik Χιτοχ 400 Ii-lqjr./Cables: Diagram Hri'incii Ί> · Ιι · \ 2} IQ ¹ SH hop.! I (I

909813/0656

Accounts flriMucr Hank. Minnen

(BI./. 290 700 "5O) 1112002

PSiIiA I laiiihuiji

(BI.Z 200 100 20) 12H) 81 Biirn Munich / Munich OllVi ·: Posiradi / PC) Box 14 01 SihlolIliaiin-slraKi ¹ I) -SOOO Miiiidii-n "5

p Tcli-gr. / Cables Ielepalenl Munich

ORIGINAL INSPECTED

BOliHMüR'I & HOHHMFRr _{Λ ΛΙ}

28U664

improving or controlling the properties of a product used. Rubber compounds have unique properties in terms of viscosity, pseudoplasticity, and more Shear rates, acid and heat stability and serve as suspending and emulsifying agents, which are suitable for various uses have proven beneficial. It has been shown to have specific properties Rubber compositions can be improved. For example, a gel that solidifies at room temperature can be used by the interaction of xanthan gum and tare gum. This gel is both acid degradable as well as syneresis (release of liquid during freeze-thaw or heat-cool cycles). Low Concentrations of xanthan gum, alone and in conjunction with other gums, are used to improve the Body, thickness and dispersion quality of food are known. Make excellent instant pudding masses produced from the gelling reaction between xanthan gum and locust bean gum (Canadian Patent 797 202).

When a combination of xanthan gum, locust bean gum and sodium pyrophosphate is mixed with cold milk, it solidifies the combination to a good quality pudding body. The well-known use of rubber masses in Puddings and gels are based on the interaction of the rubber combination with sodium pyrophosphate, which creates the product yields. The concentration of the rubber compounds in relation to the amount of granular starch used for Gelation and interaction with xanthan gum in these food compositions available is on the order of 0.001 to 0.01 g xanthan gum per 100 g starch.

909813/0656

H () .-: HMHR'I, ν BOKfMI-HT

2-8U664

It is also known that starch granules are insoluble in water at room temperature. It is also known that, when a water suspension of unmodified grains is heated the grains initially slowly and reversibly absorb water, with limited swelling, and that the grains swell irreversibly and suddenly rapidly at a defined temperature, which is typically above 70 ° C. If the temperature is increased to more than 70 C, more molecular starch diffuses out of the grains, and the starch appears to become soluble and translucent at a temperature range of about 80 ° C to 10 ° C. These Temperatures vary with the different types of starch. It is also known that starch can diffuse away by heating must be removed from the grains in order to be accessible to enzymatic hydrolysis by means of amylases will.

The invention is based on the object of producing gels and other starch compositions which are improved Have viscosity, solubility and gelling properties and show minimal syneresis. Furthermore, according to the invention a method of making such gels and compositions based on starch can be provided which one requires less energy than the known methods.

According to the invention, this object is achieved in a method of initially mentioned type solved in that starch granules and xanthan in an aqueous medium to form a aqueous starch-xanthan dispersion are dispersed, wherein the amount of xanthan is in the range of 2 to 20 parts per 100 parts of starch on a dry weight basis; that the Starch-xanthan dispersion at a temperature in the range of 3 to 30 ° C below the normal gelatinization temperature

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BOiiHMEin & BOBHMFRT

2-8U664

the starch is cooked; and that the cooked dispersion is cooled to a gelling temperature.

Accordingly, the invention thus provides gels and other compositions which have minimal syneresis have and have unexpected viscosity, solubility and gelling properties by being in an aqueous Medium xanthan and freely available starch are made to react. The inventive method requires less energy than the methods previously available for making gels and compositions from starch alone. The compositions according to the invention can be used as thickening and gelling agents in foods and use in other industrial products.

The xanthan gum which can be used in the present invention is the extracellular polysaccharide, which is obtained from Xanthomonas campestris. Xanthan gum, which Can be used in the present invention can be prepared by a process as described in U.S. Patent 3,507,664 is. Suitable starches include corn or spritz starches made from wheat, corn, potatoes, rice and Tapioca. Other wet or dry milled fractions containing not less than 10 parts of granular starch used for Complete hydration and gelation available, are also suitable as starting materials.

Each type of starch with a different content of amylose and amylopectin have significantly different physical properties Properties.

The starch is dispersed in water or other aqueous medium in an amount of about 2 to 30 percent by weight. Xanthan gum

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is incorporated into the dispersion in an amount ranging from 0.2 to 2% by weight of the dispersion and in an amount from 2 to 20 parts per 100 parts starch on a dry weight basis incorporated. The preferred amount of xanthan gum is 6 to 10 Parts per 100 parts starch.

The cooking of the starch is done by making the starch-xanthan dispersion at a temperature 3 ° to 30 ° C below the normal gelatinization temperature of the starch if there is no xanthan gum, is heated. The gelatinization temperature corresponds to the temperature of the initial increase in viscosity that occurs when stirring, or the minimum temperature to which the Starch must be heated to form a gel when it cools. Wheat starch usually gels at 85 C, corn starch at 74 ° C, rice starch at 83 ° C, potato starch at 64 ° C and tapioca starch at 62 ° C. The dispersion will Boiled at least until the viscosity begins to increase and the dispersion becomes a paste. The paste is then brought to a setting temperature (around room temperature) cooled, whereupon the paste can be built up as a gel there. Alternatively, the paste can also be used dried before cooling so as to give a stable powder. Any conventional drying process, such as freeze drying, spray drying and drum drying can be used. Powdered starch-xanthan compositions, produced in this way are easily soluble in hot or cold water and gel if allowed to solidify at room temperature. Gels, which are made either directly from the paste or from the re-watered powder are in pH ranges from about 3 to 10 are stable to brine solution and seawater salt-resistant and can be frost and

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BOSHMERT & BOEHMEKT

Tolerate heat cycles with minimal syneresis.

Alternative methods of making the original starch-xanthan dispersion include adding Starch added to the xanthan gum broth during the final stages of xanthan gum making and the addition of xanthan gum to the final stage of starch wet grinding.

Starch-xanthan compositions can, as described, in the presence of acids, salts, vegetable protein and sucrose can be produced without the interaction or the development of the viscoelastic and gelling properties would be hindered. When starch and xanthan gum are acidic pH values are reacted, becomes the initial gelatinization temperature reduced even more, resulting in translucent gels. Bleached and unbleached Soft wheat flours at pH values of 4.6 and 5.7 show a 4 to 10-fold increase in the hot paste viscosity and begin to thicken at a temperature that is 20 ° lower than the case with flours without the addition of xanthane is. Proteins in soft wheat flours do not interfere with the increase in viscosity and gel formation. Processed soybean, Peanut and cottonseed proteins can also be starch-xanthan compositions can be added in amounts of 60 to 90% without detrimental effect on gelation. These High protein gels can be used as meat substitutes for animal products without an extender.

Sucrose gels can be made from starch-xanthan compositions which are stable at acidic and neutral pH. These starch-xanthan compositions can specially designed to replace cross-linked starches that are normally used to counteract the hydrolytic effects of acid

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BOEHMERT & BOEHMHRT

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in acidic foods, such as fruit pie fillings to act. The rapid break in paste, the normal in heated starch suspensions which contain acid and sucrose takes place is through the use of starch-xanthan compositions reduced to an I'ininun. Fruit juices and fruit pulp can be added during gelation, thereby creating a wide variety of natural flavorings jellies and confectionery (5 to 40% sucrose).

In another embodiment, it has been found that adding starch to xanthan gum leads to a reduction the energy required for hydrolysis. Usually starch must be gelatinized before it can be fermented Sugars can be hydrolyzed during malting. But it turned out that the starch pulp completely fermentable in the presence of xanthan without prior gelatinization with malt enzymes at 60 ° C Sugar can be hydrolyzed. The preferred amount of xanthan gum required to achieve this result is about 0.5 to 5% based on the dry weight of the starch.

Xanthan-amylose combinations can become pliable, firm transparent films or foils can be cast. Glycerine is added as a plasticizer to reduce brittleness. A special property of the film is that it has an affinity for water absorption, whereby the film differs from conventional amylose films. The water absorption of these films is better than that of powdered xanthan gum alone, which often has a disadvantage in terms of xanthan gum solubility. Expands in water the foil and exhibits many of the properties of xanthan itself.

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BOF.HMF.RT & BOEHMKRT

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The compositions according to the invention can be used as substitutes for gelatinized, crosslinked or modified Starch used in food and industrial products. The practical usability can be expand in many ways in a manner familiar to those skilled in the art.

In the following, the invention is explained individually on the basis of exemplary embodiments, with all parts being given as parts by weight, unless otherwise stated.

example 1 Manufacture of starch-xanthan compositions

Mashes consisting of 4 to 50 parts (dry weight) of wheat starch and 0.25 to 1.0 parts (dry weight) xanthan gum per 100 parts of water were prepared by 1) heating the mashes to 75 ° C. with stirring and the resulting translucent thickened paste was freeze-dried to a fine powder, and that 2) the masas were heated with stirring to 7 5 ° C, the thickened paste was spray-dried (spray conditions: 100 ⁰ C, flow rate of 2 to 4.1 liters / h).

Reactant viscosity (cps.)

wheat
strength Xanthan gum water Dry cons
travel Before the
dry Again
posed 8.0 0.25 100 Lyophili-
ization 13 60 1365 8.0 0.25 100 Sprühge
dries 1364 1956 8.0 0.25 100 Spray dry 200
net (without before
previous heating) 564

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HOKHMKR '·' & B (JEI-IiVi '·; KJ

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28U664

Example 2

Threshold xanthan concentrations required to exhibit a synergistic viscosity effect with starch on heating

Mashes containing 3 9.0 parts of wheat starch and 0 to 4.5 parts of xanthan in 500 ml of water (pH 6.5) were heated to 95 C at a rate of 1.5 ° C per minute, there held for 15 minutes and then cooled to room temperature at a rate of 1.5 ° C per minute. The viscosity the suspension was measured automatically during this process. The paste viscosities were at 60 C, 95 C and 22 C measured after the heated paste had cooled to room temperature.

Viscosity (Braybender Units)

Wheat starch Xanthan gum, g. 60 ° C 95 ° C 22 ° C 39 0.0 0 280 650 39 0.05 0 285 640 39 0.09 0 270 660 39 0.18 0 330 900 39 0.45 10 340 -2) 39 0.90 25th 415 - 39 1 .80 35 550 - 39 3.15 40 665 - 39 4.50 65 780 _

The viscosity of xanthan alone is subtracted from the values shown.

Viscosities above 1000 Braybender units were not determined.

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BC «KHMEHT (Si 13OEHMIiRT

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Example 3 Interaction of corn, potato and rice starch with xanthan gum

Compositions of xanthan gum and corn, potato and rice starch were prepared (pH 6.5 to 7.0); the viscosities were determined in the manner given in Example 2 to show that these starches are also compositions form with increased viscosity and gel properties.

Reaction partner G- Xanthan gum, G· temperature
of the beginning
TH f * Ή on Viscosity ¹ ^ chilled
paste strength
variety Strength, 0.0 Viscosity
increased cooked 1130 Corn 40 0.18 74 350 1440 Corn 40 1 .80 62 420 - Corn 40 0.0 61 560 600 potato 20th 0.18 64 520 825 potato 20th 0.0 61 550 760 rice 25th 0.18 83 280 1240 rice 25th 65 570

Braybender units of viscosity

Example 4

Influence of pH and salt on the viscosity of starch when heated

Wheat starch-xanthan compositions were prepared; the viscosities were in the manner indicated in Example 2 except that the pH of the water was adjusted to 4.6.

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BOF-HMFRT > k ΗΟΕΗΓνίΚΚΤ

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-4Ψ-

Reaction dartner G. Xanthan gum, G- PH temperature
of the beginning
chen viscose Braybender
viscosity gexunlte
paste Strength, 0.0 6.5 in good faith cooked 650 39 0.18 6.5 85 280 900 39 1.80 6.5 63 370 950 39 0.0 4.6 57 550 800 39 0.18 4.6 85 265 960 39 1.80 4.6 64 370 1700 39 60 610

Pulps or slurries made from 4 parts of wheat starch and 0.125 part of xanthan, on a dry weight basis, consisted in 100 parts of water, were heated to 95 ° C for Maintained at this temperature for 15 minutes and then cooled to room temperature. The viscosity of the pulp was at pH values of 2.2, 6.3 and 10.2 before and after adding 2 parts of sodium chloride. Slurry from only 4 parts of wheat starch in 100 parts of water were also heated to 95 C, held there for 15 minutes and then cooled to room temperature.

Brookfield viscosity (cps.

Slurry pH

6.3 2.2

10.2

6.3 2.2

10.2

NaCl, g.

2 2 2

strength just strength with xanthan gum 484 1008 456 1200 936 1536 _ 1200 336 1230 352 1124

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Example 5

Starch-xanthan compositions were prepared. the Viscosities were determined in the manner indicated in Example 2, with the exception that the starch was bleached through and unbleached common wheat flour was replaced and the pH values were different.

Reaction partner G· Xanthan gum, G- 4th pH Temperature, Hot pastes Flour, 0.0 4th .6 where the
Pulp itself viscosity
9 5 ° C Type of flour 39 1 .80 6th .6 to thicken
starts, ⁰ C 100 bleached 39 0.0 6th .5 74 4 80 bleached 39 1 .80 .5 51 70 unbleached 39 76 370 unbleached 53 Example 6

Influence of xanthan on the amount of starch diffusing into the solution during heating

Slurries consisting of 19 parts of wheat starch and 0 to 0.18 part of xanthan gum, on a dry weight basis, in 500 parts Passed water, were heated in the manner described in Example 2 to various temperatures. The suspensions were cooled to room temperature and centrifuged to separate residual starch granules from the soluble material. The soluble ingredients were dried and weighed.

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ΒΟΠ IM ^ RT & BOIiHMKM

2614664

-Away-

Reaction partner

Starch, g. Xanthan gum, g. Suspensions
temperature Percent sol
lighter strength 19th 0.0 22nd 0 19th 0.18 22nd 5-7 19th 0.0 55 1-2 19th 0.18 55 10-15 19th 0.0 80 3-10 19th 0.18 80 50-75 Example 7

Color intensities of soluble starch (SO) and starch xanthan (SX); Soluble components showing amylopectin

4 g of soluble starch material (SO or SX), obtained according to Example 6, were redissolved and then colored with iodine (0.2 parts iodine per 100 parts water) to determine the color changes caused by the amylopectin branched chain Starch in the soluble ingredients were effected. A shift in the color intensities to 550 nm shows one increased diffusion of amylopectin during heating of starch with xanthan gum.

⁰ C SO soluble
Components SX soluble
Components Temporary door, 550 nm. 6 50 nm. 550 nm. 650 nm. 50
80
95 no diffusion
.428 .692
.405 .892 .400 .700
.488 .600
.520 .623

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IiObHMERT &

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Example 8 Enzymatic hydrolysis of starch in the presence of xanthan gum

Wheat starch (7-10% by weight) and 0.05 to 0.5% by weight xanthan gum in water were heated to 60 ° C and held there for 15 minutes. The slurry was cooled back to room temperature and enzymatically hydrolyzed with malt enzymes at 40 C for 15 minutes. The amount of starch hydrolyzed was measured analytically as glucose.

Example 9

Corn starch was used instead of wheat starch and under the experimental conditions as described in Example 8 are hydrolyzed.

Example 10

Instead of wheat starch, rice starch was used and under the conditions as described in Example 8 are hydrolyzed.

Percent hydrolyzed starch

Starch with xanthan gum without xanthan gum

Wheat 95-100 35-40

Corn 90-95 35-40

Rice 85-90 30-3 5

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15OEHMHkT & IJOHHMrIRT

Example 11

Xanthan amylose portfolio softened with glycerine

Potato amylose (2.5 g) and xanthan (2.5 g) were intensively dispersed in 400 ml of water. 1 ml of glycerine was used as Plasticizer added. The mixture was brought to the boil, carefully evacuated to remove bubbles and Poured hot into polymethyl methacrylate bowls and air-dried. A film with flexible cast properties resulted and good tensile strength.

Example 12 Manufacture of sucrose starch xanthan gels

Slurries consisting of 7.8 parts of starch (wheat) and 1.8 parts of xanthan in 100 ml of water were heated under the conditions described in Example 2 and cooled down. The pastes were diluted with various sucrose solutions in such a way that the original paste was diluted in half. The viscosity of the solutions was measured using a Brookfield viscometer.

Viscosity (cps.) Added Sugar, g. Starch xanthan gum

0 784

3 904

9 940

12 1132

15 1288

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Claims (12)

BOLI-ΙΜΕΛΤ & BOEHMERT 28H664 UX 124 claims A method of making stable starch gel compositions which have minimal syneresis, characterized in that starch granules and xanthan gum are dispersed in an aqueous medium to form an aqueous starch-xanthan gum dispersion, the amount of xanthan gum in the range of 2 to 20 parts per 100 parts starch , on a dry weight basis, is; that the starch-Xanthandispersion at a temperature in the range of 3-30 ⁰ C is cooked below the normal gelatinization temperature of the starch; and that the cooked dispersion is cooled to a gelling temperature. 2. The method according to claim 1, characterized in that Wheat starch is used as starch and the cooking temperature is in the range of 55 ° to 82 ° C. 3. The method according to claim 1, characterized in that performic starch is used as starch and the cooking temperature in the range from 44 ° C to 71 ⁰ C. 4. The method according to claim 1, characterized in that rice starch is used as starch and the cooking temperature is in the range of 53 ° C to 80 ° C. ⁴¹¹ 909813/0656 ORIGINAL INSPECTED BOLI-IMEOT & 3OEHMERT 28U664 5. The method according to claim 1, characterized in that potato starch is vprwpndet as a strength and the cooking temperature in the range from 34 ° C to 61 ⁰ C. 6. The method according to claim 1, characterized in that tapioca starch is used as the starch and the cooking temperature is in the range of 32 ° C to 59 ° C. 7. The method according to claim 1, characterized in that the starch-xanthan dispersion contains 5 to 40 wt .-% sucrose. 8. A method for accelerating the hydrolysis of starch, characterized in that a starch mixture that of 7.0 to 10.0% by weight of freely available starch and from 0.05 contains up to 0.5 wt .-% xanthan, is heated to about 60 C; that the mixture is held at 60 ° C for about 15 minutes; that the pulpy mixture is cooled to about 20 to 22 ° C will; and that the starch is enzymatically hydrolyzed with malt enzymes at about 40 C for about 15 minutes. 9. The method according to claim 8, characterized in that the starch is obtained from wheat. 10. The method according to claim 8, characterized in that the starch is obtained from corn. 11. The method according to claim 8, characterized in that the starch is obtained from rice. 12.Methods for making transparent, flexible, Edible films with high tensile strength, characterized in that in an aqueous medium the same weight 909813 / OG 56 3CEHMRPvT & DOEHMERl ' 28U664 parts amylose and xanthan gum are mixed; that glycerine is added to the mixture; that the mixture is boiling is heated; pouring the hot mixture onto a pouring surface; and that the resulting film is air dried will. 9Q3813 / 0656