Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
  • C08L5/12—Agar or agar-agar, i.e. mixture of agarose and agaropectin; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
  • C08L5/14—Hemicellulose; 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

Definitions

• the present invention describes the remarkable synergistic properties of gel strength between agar having a low gel strength and galactomannan flours as well as a process for producing this agar of weak gel having optimal properties to obtain the best synergy.
• agar has unique gelling properties which have been used in several food or industrial applications for millennia; the agar is a polyssacharide extracted from red algae of the gelidium or glacilaria type; its chemical structure is composed of (3 -> 6) ⁇ -L anhydrogalactose linked in (l ⁇ 4) ⁇ -D galactopyranose (1- »3). It can also be functionalized by a sulfate, methoxyl and pyruvate group. The position and the proportion of these groups can vary according to the red alga used for the extraction (Gelidium, Glacilaria, Pterocladia etc.). The molecular weight of the agar is between 40,000 and 200,000.
• the agar gel strength is commonly measured by the nikan method or the stevens method. These methods measure the compressive force necessary to break the agar gel at 1.5% concentration.
• the nikan method measures the weight supported by a flat-bottomed piston of 1 cm2 of surface necessary for the rupture of the agar gel contained in a cassette of dimension of 3cm in thickness, 6 cm in width and 30 cm in length. After several determinations the result is expressed in grams / cm2 and which corresponds to the weight to which the gel would have resisted the piston for 20 seconds.
• the Stevens method uses the "LFRA texture analyzer" device manufactured by the company STEVENS; Dunmow Essex; United Kingdom United.
• This device makes it possible to use pistons with different surfaces of 3 cm2, 2 cm2, 1 cm2 or 0.5 cm2 and to program the speed and the penetration distance of these pistons.
• the apparatus will subject the gel contained in a beaker 7 cm in diameter and 9 cm in height to increasing compression by a flat piston of 1 cm2; at a penetration speed of 15 m / min until the gel breaks.
• the gel strength is expressed in grams / cm2 and corresponds to the maximum recorded.
• the gelling agar has a gel strength for a concentration of 1.5% generally between 300 and 1000 g / cm2 for the nikan method and from 400 to 1000 g / cm2 for the stevens method. that there is no direct correlation between these two measurement methods.
• the Stevens method remains more sensitive for the measurement of low gel forces using flat or conical pistons with a surface of 2 or 3 cm2 and allows the measurement of gel strength greater than 1000 g / cm2 using a 0.5 cm2 flat-bottomed piston.
• carob flour extracted from the albumen of seeds of CERATONIA SILIQUA
• tara flour extracted from the albumen of seeds of CAESALPINIA SPINOSA
• guar flour extracted from the albumen of the seeds of CYAMOPSIS TETRAGONOLOBUS
• the number of galactose connected is statistically 1 galactose for 4 mannoses for carob flour, 1 galactose for 3 mannoses for tara flour, and 1 galactose for 2 mannoses for guar flour.
• galactomannan flours dissolved in l water at 1% concentration develops a viscosity between 1500 and 5000 Cps.
• carob flour solubilized at 80 ° C develops a viscosity between 1500 and 4000 Cps
• tara flour solubilized at 80 ° C develops a viscosity between 3000 and 5000 Cps
• cold solubilized guar flour develops a viscosity between 1500 and 5000 Cps.
• the present invention shows that the phenomenon of synergy is detected from the incorporation of carob flour at 10% compared to the low gel agar, that this phenomenon is at its maximum when the agar / carob flour mixture is 50/50% and this phenomenon is reduced when the proportion of carob flour is increased to more than 150%.
• Curve 2 describes this result.
• the present invention also shows that the maximum synergy is obtained with a low gel strength agar having a value between 50 and 100 g / cm2 by the Stevens method at 1.5% concentration or ⁇ 50 g / cm2 at 0.75% of concentration) (value not detected by the nikan method).
• Figure 2 specifies the multiplying factor of the gel strength of the mixture.
• the present invention proposes to provide a new very effective process for producing with high precision an agar having a gel strength of 1.5% concentration between 50 and 100 g / cm 2 by the Stevens method without pollution induced by the reagents.
• agar with low gel strength consists in combining the following operations:
• a ⁇ the agar molecules are extracted in hot water at temperatures between 100 and 140 ° C from red algae of the gelidium or glacilaria type in autoclaves under pressure or in the open air.
• the juice obtained at a concentration of about 1% agar is filtered hot to remove solid impurities and to clarify it.
• the pH of this juice is adjusted between 9 and 10 with a 0.1 soda solution. mol / 1.
• This juice is then percolated at temperatures between 60 and 95 ° C in columns of cationic ion exchange resins of macroporous or gel type which are in acid form.
• This acid form can be obtained by regeneration ion exchange resin with a non-expensive mineral acid such as hydrochloric or sulfuric acid.
• the agar molecules developing any gel strength from 400 to 1000 g / cm2 then undergo immediate and controlled degradation which makes it possible to reduce the molecular weight of the agar in one single pass over the resin column.
• This result is all the more remarkable since the speed of passage through a column and the height of the bed of ion exchange resins make it possible to control the degradation of the molecular weight of the agar and ultimately to control the desired gel strength.
• This novelty has been confirmed by dissolving agar powder with known gel strength in boiling water at 1% concentration, by adjusting the pH of this solution between 9 and 10 and then by perforating this solution through a column. ion exchange resin in H + form.
• the degraded agar is recovered in the form of powder according to the experimental process described in the chapters below.
• the other advantage of this ultrafiltration is to increase the concentration of the agar juice from 1% up to 10%).
• the agar juice thus concentrated by ultrafiltration forms gels strong enough to be mechanically pressed or frozen - thawed and incidentally allows the traditional agar production processes recognized by those skilled in the art to be used and which remain very economical. .
• the co-processed mixture of agar with low gel strength and galactomannan has a gel strength of between 100 and 1000 g / cm2, a gel point of 35 and 45 ° C and a melting point of between 70 and 85 ° C and a viscosity at 1% of between 300 AND 3000 Cps.
• Figure n ° 3 presents the diagram of an installation for the implementation of the process and Examples of application carried out in this installation: these Examples were implemented according to the general experimental process described below:
• the collected juice is quickly filtered through a buchner (5) on ashless filter paper and on a layer of 10 cm of diatomaceous earth.
• the juice is then percolated through a column thermostatically controlled at 80 ° C (7) variable temperature between 60 and 95 ° C), with a diameter of 50 mm and a height of 1200 mm.
• this column contains cationic resin, the volume of which is adjusted to have a variable bed height between 300 and 1000 mm, ie a resin volume of between 0.6 and 2 liters.
• a flow control pump (6) maintains a constant flow.
• the juice after passing over resin is collected in a tank thermostatically controlled at 80 ° C. (8) ..
• Polyethersulfone type GR81PP having a retention threshold of 10,000 on an ultrafiltration laboratory model type LabStak from the company DSS, Denmarque having a membrane surface of 0.174 m2.
• the juice is pumped into the ultrafiltration module with a flow rate of 81 / min and the average recirculation time is
• the agar juice is collected in a tank to allow it to gel overnight (10); then it is pressed in mechanical presses (1 l) at pressures of 7 to 16 kg / cm2 or else frozen (12) at temperatures between -18 to -22 ° C for 16 hours and then thawed at room temperature.
• the pressed agar is obtained in the form of a cake having a humidity of between 60 and 75% while the frozen-thawed agar is recovered in the form of a micelle having a humidity of 60 to 80% > .
• the agar is dried in a fluidized bed drier (13) to obtain a final humidity of less than 20%.
• the dry agar granules are then ground (14) to obtain a fine powder.
• the agar thus produced has a low gel strength of between 50 and 100 g / cm2, a gelation temperature of between 35 and 42 ° C and a melting temperature of between 70 and 85 ° C.
• This agar needs to be boiled to be dissolved properly.
• This agar can be subjected to an extrusion treatment (15) to make it instantly soluble; as described in our invention following our European patent
• the galactomannans can be introduced by direct solubilization of the powdered flours in the concentrated juice at a temperature of 80 ° C (10). This introduction can also be done by adding a solution or the galactomannan flour is dissolved beforehand at a concentration preferably equal to that of agar juice. (16); just after the ultrafiltration step (9) while the juice is hot at 80 ° C or just after the passage of the extraction juice over the column of ion exchange resin (7). The rest of the process being similar from steps 10 to 15.
• the juice collected (5) has a minerality of 2 meq / 1 of CL-, 4 meq / l of Ca ++; its viscosity at 80 ° C is 6 cps and its gel strength 850 g / cm2 by stevens method the pH of the juice is adjusted to 9 by adding 2 ml of a caustic soda solution of 0.1 mol / 1.
• the column contains a cationic resin of the macroporous type "Amberlite 200 D" of polystyrenic skeleton having a sulphonic group as functional group and the cation H + as counter-cation. It is thermostatically controlled at 80 ° C.
• the volume of resin is 1 liter for a bed height of 500 mm. Passing the juice through the column (7) with a flow rate of 5 volumes of juice / volume of resin / hour makes it possible to obtain a juice having a pH of 5.5, a viscosity of 2 cps at 80 ° C .; and a gel strength of 30 g / cm2 by the stevens method.
• the recovered juice undergoes an ultrafiltration treatment (9) as described above or the initial juice of 15 liters is concentrated in the retentate until 2 1 is obtained in the end; or a concentration of 7; 5 times.
• This concentrated juice has a pH of 6 and a gel strength of 300 g / cm2. . It is then gelled, pressed, dried and ground (10.1 l, 13 and 14). It gives an agar yield of low gel strength of 18% compared to the starting dry alga. this powder has a gel strength of 1.5% of 45 g / cm2 and .75% of 20 g / cm2;. a pH of 6.6 and a viscosity of 2 cps.
• the juice obtained (5) has a minerality of 2 meq / 1 of Cl-, 7.5 meq / 1 of Ca ++ and a pH equal to 6.4.
• the gel strength of this juice is 1000 G: cm2 according to the Stevens method and its viscosity is 6 Cps.
• the pH is adjusted to 9.3 by adding 30 ml of 0.1 mol / l caustic soda solution; the column contains a cationic resin of gel type "Amberlite IRC 86" of acrylic skeleton having a sulphonic group as functional group and the cation H + as counter-cation.
• the volume of resin is 0.75 liter for a bed height of 400 mm. Passing the juice through the column (7) with a flow rate of 4 volumes of juice / volume of resin / hour makes it possible to obtain a juice having a pH of 6.1, a viscosity of 1.5 cps at 80 ° C; and a gel strength of 70 g / cm2 by the stevens method.
• the recovered juice undergoes an ultrafiltration treatment (9) as described above or the initial juice of 15 liters is concentrated in the retentate until 3 1 is obtained in the end; a concentration of 5 times. This concentrated juice at a pH of 6 and a gel strength of 320 g / cm2. It is then gelled, pressed, dried and ground (10.1 l, 13 and 14).
• This powder has a gel strength of 1.5% of 85 g / cm2 and .75% of 55 g / cm2. A pH of 6.8 and a viscosity of 3 cps.
• This powder is dissolved at 7.5 g in 1 liter of boiling water and then 7.5 grams of carob flour with an initial viscosity of 3000 cps are incorporated.
• the solution thus obtained has a viscosity of 1960 cps at 80 ° C. which on cooling will form a gel having a gel strength of 525 g / cm 2.
• the phenomenon of synergy makes it possible to multiply in this case the gel force by 9.5 times.
• the juice collected (5) has a minerality of 2.5 meq / 1 of Cl-, 9.2 meq / l of Ca ++; its viscosity at 80 ° C is 4.8 cps and its gel strength 660 g / cm2 by stevens method.
• the pH of the juice is adjusted to 9.5 by adding 28 ml of a caustic soda solution at 0.1 mol / I.
• the column contains a cationic resin of the macroporous type "Amberlite 200 C" of polystyrenic skeleton having a sulfonic group as functional group and the cation H + as counter-cation.
• the volume of resin is 0.6 liter for a bed height of 300 mm. Passing the juice through the column (7) with a flow rate of 8 volumes of juice / volume of resin / hour makes it possible to obtain a juice having a pH of 5.5, a viscosity of 2 cps at 80 ° C; and a gel strength of 100 g / cm2 by the Stevens method.
• the recovered juice undergoes an ultrafiltration treatment as described above or the initial juice of 15 liters is concentrated in the retentate until 4 1 is obtained in the end; or a concentration of 3.75 times.
• This concentrated juice at a pH of 6.3 and a gel strength of 425 g / cm2. It is then gelled, frozen - thawed, dried and crushed (10,12,13 and 14). It gives a low gel strength agar yield of 23% compared to the starting dry alga.
• this powder has a gel strength of 1.5% of 125 g / cm2 and .75% of 85 g / cm2. a pH of 6.4 and a viscosity of 2.7 cps.
• This powder is dissolved at 7.5 g in 1 liter of boiling water and then 7.5 grams of carob flour with an initial viscosity of 3200 cps are incorporated.
• the solution thus obtained has a viscosity of 2000 Cps at 80 ° C which on cooling will form a gel having a gel strength of 650g / cm2.
• the synergy phenomenon allows to multiply in this case the gel force of 7.6 times
• the column contains a cationic resin of the gel type "Amberlite 1200 H" of a polystyrenic skeleton having a sulphonic group as a functional group and the cation H + as a counter cation. It is thermostated at
• the resin volume is 1.2 liters for a bed height of 600 mm.
• the passage of the juice through the column (7) with a flow rate of 3 volumes of juice / volume of resin / hour makes it possible to obtain a juice having a pH of
• This powder has a 1.5% gel strength of 595 g / cm2 and a pH of 6.8 and a viscosity of 1600 cps.
• the column contains a cationic resin of the macroporous type "Amberlite 200 D" of polystyrenic skeleton having a sulfonic group as a functional group and the cation H + as a counter cation. It is thermostatically controlled at 80 ° C.
• the resin volume is 1.5 liters for a bed height of 800 mm. Passing the juice through the column (7) with a flow rate of 6 volumes of juice / volume of resin / hour makes it possible to obtain a juice having a pH of 5.5, a viscosity of 1.8 cps at 80 ° C .; and a gel strength of 40 g / cm2 by the stevens method.
• the recovered juice undergoes an ultrafiltration treatment (9) as described above or the initial juice of 15 liters is concentrated in the retentate until 12 1 is obtained in the end; or a concentration of 1.25 times.
• This concentrated juice at a pH of 6 and a gel strength of 70 g / cm2.
• 180 g of carob flour having a 1% viscosity of 3500 cps is dissolved with vigorous stirring in 12 liters of water at 80 ° C as described in step (16).
• This solution is then mixed with the concentrated juice of agar and then gelled overnight (10). ).
• the gel strength of this mixture of solutions is 620 g / cm2 by the Stevens method.
• this powder has a gel strength of 1.5% of 690 g / cm2 and .75% of 450 g / cm2,. a pH of 6.4 and a viscosity of 1900 cps.
• the column contains a cationic resin of the macroporous type "PUROLITE Cl 55" of polystyrenic skeleton having a sulfonic group as functional group and the cation H + as counter-cation. It is thermostatically controlled at 80 ° C.
• the resin volume is 1 liter for a bed height of 500 mm. Passing the juice through the column (7) with a flow rate of 7 volumes of juice / volume of resin / hour makes it possible to obtain a juice having a pH of 5.7, a viscosity of 2.2 cps at 80 ° C .; and a gel strength of 85 g / cm2 by the Stevens method.
• the recovered juice undergoes an ultrafiltration treatment (9) as described above or the initial juice of 15 liters is concentrated in the retentate until 10 1 is obtained in the end; or a concentration of 1.5 times.
• This concentrated juice at a pH of 6 and a gel strength of 140 g / cm2 by the Stevens method.
• carob flour having a viscosity at 1% of 2000 cps is dissolved with vigorous stirring in 10 liters of water at 80 ° C as described in step (16). This solution is then mixed with the concentrated juice of agar and then gelled overnight (10). It is then frozen - thawed (12); dried (13) and then ground (14). It produces a mixture of low gel strength agar and locust bean flour of 406 g. This powder has a gel strength of 1.5% > 520 g / cm2 and .75% of 310 g / cm2,. A pH of 6.2 and a viscosity of 1400 cps.
• the juice collected (5) has a minerality of 2.8 meq / 1 of Cl-, 8.4 meq / l of Ca ++; its viscosity at 80 ° C is 3.6 cps and its gel strength 710 g / cm2 according to the Stevens method.
• the pH of the juice is adjusted to 9.4 by adding 29 ml of a caustic soda solution of 0.1 mol / 1.
• the column contains a cationic resin of the macroporous type "Amberlite 200 D" of polystyrenic skeleton having a sulfonic group as a functional group and the cation H + as a counter cation. It is thermostatically controlled at 80 ° C.
• the resin volume is 0.8 liters for a bed height of 400 mm. Passing the juice through the column (7) with a flow rate of 3 volumes of juice / volume of resin / hour makes it possible to obtain a juice having a pH of 5.1, a viscosity of 1.5 cps at 80 ° C; and a gel strength of 25 g / cm2 by the Stevens method.
• the recovered juice undergoes an ultrafiltration treatment as described above or the initial juice of 15 liters is concentrated in the retentate until 3 1 is obtained in the end; a concentration of 5 times.
• This concentrated juice at a pH of 6 and a gel strength of 175 g / cm2 ... It is then gelled, pressed, dried and then ground (10, 11, 13 and 14).
• This powder has a gel strength of 1.5% of 80 g / cm2 and .75% of 30 g / cm2.
• This powder is dissolved at 7.5 g in 1 liter of boiling water then incorporate 7.5 grams of guar flour with an initial viscosity of 3200cps.
• the solution thus obtained has a viscosity of 2100 cps at 80 ° C which, on cooling, will form a gel having a gel strength of 65 g / cm2.
• the synergy phenomenon makes it possible to multiply in this case the gel strength by 2.3 times.

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