WO2012093355A1 - Process including the metered addition of raw material and enzyme for the production of highly concentrated glucose syrups and maltodextrins from starches - Google Patents
Process including the metered addition of raw material and enzyme for the production of highly concentrated glucose syrups and maltodextrins from starches Download PDFInfo
- Publication number
- WO2012093355A1 WO2012093355A1 PCT/IB2012/050028 IB2012050028W WO2012093355A1 WO 2012093355 A1 WO2012093355 A1 WO 2012093355A1 IB 2012050028 W IB2012050028 W IB 2012050028W WO 2012093355 A1 WO2012093355 A1 WO 2012093355A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- starch
- enzyme
- liquefaction
- stage
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
- C08B30/18—Dextrin, e.g. yellow canari, white dextrin, amylodextrin or maltodextrin; Methods of depolymerisation, e.g. by irradiation or mechanically
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/20—Preparation of compounds containing saccharide radicals produced by the action of an exo-1,4 alpha-glucosidase, e.g. dextrose
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/06—Glucose; Glucose-containing syrups obtained by saccharification of starch or raw materials containing starch
-
- 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
- This invention is related to production processes of malt dextrins and glucose from starches from different plant sources. These processes use characteristic enzymes such as -amylase and glucoamylase, among others. Specifically, amylase is used for liquefaction of starch and production of maltodextrin.
- the CPC International Inc. patent of publication number FR2304675A1 presents a process for the complete conversion of starch to fructose. This process is carried out by mixing starch in water, a bacterial-amylase together with glucoamylase and glucose isomerase, with a pH between 5 and 7 and at a temperature between 40 ° C and 70 ° C in which the starch does not start to gelatinize. The process is maintained until a soluble hydrolyzate is obtained while the residual starch is in a non-gelatinized form.
- the enzymes used act synergistically.
- the aqueous starch suspension preferably has a solids content between 10% and 70%.
- the solubilized starch contains an equivalent dextrose (ED) between 90% and 95%. Unreacted starch is recycled to the enzymatic process.
- ED equivalent dextrose
- the solubilized starch is close to 98%.
- the present invention is novel, because it comprises a liquefaction process with dosed addition of raw material and enzyme that decreases the reaction time, prevents sediment formation or starch retrogradation and improves reactivity from the enzyme to starch, which increases productivity with respect to a liquefaction process with a single dosage of addition of raw material and enzyme, and concentrated syrups are obtained that require less concentration and purification processes to be commercially viable.
- US4612284A (Process for enzymatic hydrolysis of non-gelatinized granulated starch directly to glucose) describes a process for enzymatic hydrolysis of non-gelatinized granular starch directly to glucose and dextrin malt. The process consists of a partial hydrolysis of a suspension of non-gelatinized granular starch at a temperature between 50 ° C and 65 ° C which is below the gelatinization temperature of the granular starch material.
- the starch is contacted with an enzymatic system capable of hydrolyzing it in a non-gelatinized granular form directly to glucose, said enzyme is employed in an amount such that, under the process conditions, the hydrolysis performed is partial to glucose of the starch material , without achieving its total hydrolysis.
- all fatty acids and proteins trapped in starch are released from hydrolyzed starch to be absorbed by non-gelatinized starch. This step facilitates the obtaining and purification of glucose.
- the non-hydrolyzed granular starch material with absorbed protein or fatty acids is cooked at 80 ° C and subsequently subjected to hydrolysis to produce malt dextrins. Finally, the dextrin malt released during hydrolysis at 80 ° C is removed.
- US4612284A patent claims mainly the use of starch that is not hydrolyzed because the fats and proteins present cover it and prevent the enzymatic attack, then at an additional stage at high temperatures and an additional process time they release the trapped starch and hydrolyze it. even sugars.
- this material only represents a maximum of 2% w / w of the raw material and is removed by filtration, dried, and is used in animal feed.
- the present invention is novel, because multiple additions of raw material and enzyme are made during the liquefaction stage which decreases the reaction time and increases the efficiency of the process, with improvements in contact time enzyme / starch increasing productivity. It is also not observed that the process of US4612284A is focused on preventing the increase in viscosity by means of two or more stages of adding raw material and enzyme during liquefaction, as if it is carried out in the present invention.
- the suspension is hydrolyzed to dextrose equivalent (ED) of 15, using 35% hydrochloric acid between 100 ° C and 1 15 ° C.
- ED dextrose equivalent
- the reaction mixture is adjusted to pH 6-7, cooled between 80 ° C and 85 ° C and stirred for 1 to 3 hours in the presence of -amylase.
- the preferred conditions for the formation of other products are for glucose, treatment with -amylase at pH between 6 and 6.5 and then amyloglucosidase at pH 4.2; for maltose, the treatment with -amylase at a pH 7 and then with a -amylase of a fungus of pH between 4.8 and 5.4 and for dextrose the treatment with -amylase at a pH 6.5 and then with -amylase at a pH 6.
- the differences refer to the process of patent WO2004007739A1 having other stages. Specifically in this process the production of malt dextrins is done in a single stage and the purification process includes a step with ion exchange. Specifically in that process the production of malt dextrins is made with inorganic acid and not through an enzymatic process (with cc-amylase) as in the present invention.
- the present invention is novel, since it contains a process with multiple additions of raw material and enzyme during the enzymatic liquefaction stage, which decreases the reaction time and increases the efficiency of the process and improves the time of contact enzyme / starch increasing productivity.
- the publication WO2004007739A1 reports that in order to obtain an ED of 15, 10 hours are required with enzymatic treatment (highlighting that it was previously treated with inorganic acid) and it is not observed that the process is focused on avoiding the increase in viscosity of the process through the implementation of two or more additions of raw material and enzyme during the liquefaction stage controlling the temperature and activity of the enzymes.
- Patent document CN101696437A of China describes a manufacturing process of maltodextrin from rice comprising the immersion steps, pulp formation until the concentration is between 15-16 degrees Be (28 to 30 ° Brix), subsequently It performs enzymatic liquefaction with waste removal, finally it is neutralized and filtered.
- the hydrolysis process is performed with -amylase.
- the filtrate is passed through an ion exchange resin, concentrated and dried for packing.
- This process overcomes the disadvantages in the production of malt dextrins from corn and cassava since the initial handling of the material implies maceration.
- This invention neutralizes and eliminates odor with the incorporation of activated carbon.
- the present invention can be considered novel over said above, because it presents a process of multiple additions of raw material and enzyme during the enzymatic liquefaction stage, which decreases the reaction time, increases the efficiency of the process and improves the processing time. Enzyme / starch contact increasing productivity. It is also not observed that the process of the CN101696437A patent is focused on preventing the increase in viscosity of the process through the realization of the two or more additions of raw material during the liquefaction stage by controlling the temperature and the activity of the enzymes.
- US Patent 4,069,103 describes a process for producing dextrose and dextrins from starch products containing proteins. Starting from a solution with a content of between 7% and 8.5% of starch, the liquefaction takes between 1 and 2 hours and then the second enzyme is added taking the hydrolysis 48 hours (saccharification).
- the process of the present invention during liquefaction can reach concentrations up to 70% w / w, requires less time, less water consumption, generates lower viscosity at a higher concentration of starch and, as a consequence, increases productivity of process.
- the present invention allows the raw material to be incorporated and processed without having rheology problems (high viscosity), in addition the starch is transformed more efficiently because the method of multiple additions of raw material and enzyme during the liquefaction stage takes advantage of the water that It is released at a previous stage due to the effect of the enzyme by breaking the gelatinized starch granules, to condition new starch and make it available for enzymatic attack.
- Figure 1 shows the process for obtaining concentrated glucose dextrins and syrups whose details are specified in example 2.
- the liquefaction stage involves the partial hydrolysis of starch, with the consequent loss of viscosity.
- the gelatinized starch is literally liquefied by partial hydrolysis, by enzymes, which cause the destruction of the starch polymer chains (amylose and amylopectin) giving rise to smaller chains.
- a gelation stage can occur which generates unwanted by-products that reduce the quality of the product and reduces the efficiency of the process because it requires considerable time to be worked at high viscosities, generating higher energy consumption and therefore higher operational costs.
- the enzyme / starch contact times in the gelation stage to achieve the equivalent values of dextrose (ED) and the duration of the general process, are very long affecting productivity. Therefore, the gelation step is avoided with the process of the present invention.
- the liquefaction step of the process of the present invention is carried out gradually, that is to say in the present invention multiple additions of raw material and enzyme are made to the reactor.
- first addition water, starch and enzyme are charged to the reactor, in the second and subsequent additions only starch and enzyme are charged to the reactor.
- the novelty of the process is found in the dosed addition of starch and enzyme to the reactor.
- the process begins by preheating water at 55 ° C, starch is added until a concentration between 6% and 35% w / w is achieved, the pH is adjusted from 4.5 to 6 using a solution of HCI or NaOH and the enzyme is added - Amylase Then, the temperature is raised to 95 ° C gradually, with a heating ramp (between 1 and 6 ° C / min) and allowed to react for 5 to 60 minutes, obtaining an intermediate product called maltodextrin, whose equivalent degree Dextrose (ED) is between 5 and 20, depending on the reaction time mentioned.
- ED equivalent degree Dextrose
- the temperature of the solution is first lowered to 55 ° C, the pH is adjusted again (between 4.5 and 6), fresh starch and enzyme is added maintaining the enzyme / substrate ratio.
- the purpose of reducing the temperature is to completely stop the reaction inside the reactor before adding a new load of fresh material.
- Starch is added to increase its concentration to 70% w / w, with either two or more additions of starch and fresh enzyme.
- the temperature is raised again to 95 ° C and the solution is allowed to react for the time necessary to reach the required ED, depending on the product to be manufactured.
- the water molecules around the granules break the Van deer Waltz type links between the polymeric starch chains inside the granule and they swell increasing the viscosity of the starch suspension.
- the liquefaction enzyme is -amylase (such as Liquozyme supra 2.2X of Novozyme®), and is used at a concentration of 0.40 to 1.5 kg of enzyme per ton of starch (enzyme / substrate ratio).
- the partial hydrolysis of starch is the rupture of the 1 -4 glycosidic bonds of the starch polymer chains, with the enzyme -amylase and in the presence of water, until dextrose equivalents (ED) less than 20 are reached.
- Partial hydrolysis of starch results in maltodextrin which is composed of a mixture of saccharides, polysaccharides and oligosaccharides with wide weight distributions molecular.
- the composition of malt syrups dextrin is commonly associated with ED, so that an ED less than 20 is called dextrin and an ED greater than 20, and less than 100, is called glucose.
- the hydrolyzate is concentrated because no water was added but starch was added, in addition the product dextrins of the initial stage are also hydrolyzed in the second reaction because in its molecules there is presence of 1 -4 glycosidic bonds. If desired, more than two dosed additions of raw material can be made until a solids content of 70% is reached within the reactor.
- the advantage of adding starch and enzyme gradually is because it is possible to hydrolyze as much starch as possible (about 70% w / w); that is to say, there is a hydrolyzate to which, depending on the applications, it is not necessary to remove excess water at later stages of concentration which implies a greater demand for energy, use of equipment, and physical separation processes.
- the hydrolysis described above can be done, for example, in batch reactors ⁇ Multiple Batch Reactor) and / or continuous flow reactors ⁇ Multistage Continuous Reactor, "Submarine") modified so that some stage of the reactor allows temperature modification, and in another the addition of starch and enzyme.
- the starch is gelatinized, the suspension increases the viscosity, but under the conditions of this invention the starch is gelatinized and immediately begins to hydrolyze preventing the viscosity from increasing, facilitating the enzyme-starch interaction thus reducing the time of this stage.
- a saccharification stage is included at the end of the previous process, in which the glucoamylase enzyme in a concentration of 0.8 to 1 .5 is added to the solution of the previous stage. g / kg of substrate.
- the reaction is carried out at a pH between 4 and 6 and at a temperature between 50 ° C and 65 ° C reaching an ED between 40 and 60 in a time between 90 and 120 minutes of reaction.
- the glucoamylase enzyme is deactivated by heating the solution to 95 ° C for 40 minutes.
- Enzymatic processes for glucose production require a saccharification stage after the liquefaction of starch. This stage is carried out with an enzyme known as amyloglucosidase or glucoamylase, of microbial origin, which has the characteristic of being an exoamylase that releases glucose mainly from 1-4 bonds of starch but also from 1-6 bonds, although at a lower rate , which allows hydrolyzing dextrins.
- the enzymes -amylase and gluco-amylase are removed from the products by known physical methods of separation, such as ultrafiltration or centrifugation among others.
- Glucose syrups are a mixture between an aqueous solution of D-glucose, maltose and other oligosaccharides called dextrins. D-Glucose syrups are commonly characterized by their equivalent of dextrose (ED).
- Example 1 Process at the laboratory level using two stages of metered starch and enzyme addition and subsequent saccharification.
- This example illustrates the method established in the present invention to produce glucose syrups from starch (for example cassava starch) at the laboratory level using two (2) steps of dosed addition of raw material and subsequent saccharification, the process is started by charging 370g of water to the reactor and preheating it to 55 ° C, 190 g of starch (12% w / w moisture) are added, the pH of the suspension is adjusted between 4.5 and 6 by the addition of HCI or NaOH, immediately add the enzyme -amylase (for example Liquozyme Supra 2.2X of Novozyme®) between 0.4 and 1.5 Kg and raise the temperature of the suspension to 95 ° C with a heating ramp between 1 and 6 ° C / min , it remains constant between 5 and 60 min and with constant agitation at 150 rpm.
- starch for example cassava starch
- the product resulting from these stages is called dextrin and has the following characteristics: Dextrose equivalent (ED) equal to 20, a percentage of dissolved solids 50 ° Brix at 20 ° C, a percentage of glucose ⁇ 1, a density of 1 .21 g / ml.
- ED Dextrose equivalent
- the temperature is lowered to between 50 and 65 ° C, the pH of the solution is adjusted between 4 and 6 by the addition of 5N HCI or 5N NaOH, between 0.8 and 1.5 Kg of enzyme are added per ton of substrate (For example Dextrozyme GA 1.5X of Novozyme®) and kept at constant temperature and stirring for 180 min.
- Example 2 Application on an industrial scale of the process to produce malt dextrin and glucose syrup, from starch, in batches (batch type) This example is for three stages of dosed addition of starch and enzyme and subsequent saccharification, to reach a concentration of 60% w / w. See Figure 1.
- the process begins with the first stage of liquefaction, loading the reactor (2) with 361 Kg of preheated water at 55 ° C and, by means of an endless screw (1), with 238 Kg of starch (12% humidity ).
- the reactor (2) batch type (CSTR Continuous Stirred Tank Reactor) is interconnected with the filtration system (1 1), centrifugation (7), concentration (12) and drying (13). This reactor allows to maintain turbulent flow regimes and the internal temperature is controlled (through a coil) by passing boiler steam (16) or cooling tower water (18).
- the pH of the suspension is adjusted between 4.5 and 6 by the addition of HCI or NaOH, immediately between 0.4 and 1.5 Kg of enzyme amylase / ton of starch are added and the temperature of the suspension is raised to 95 ° C With a heating ramp of 1 .3 to 1 .8 ° C / min and constant stirring at 500 rpm, the reaction temperature is kept constant for 30 min.
- the suspension is cooled to 55 ° C and 238 kg of starch are added.
- the pH is adjusted between 4.5 and 6, between 0.4 and 1.5 kg / tonne of enzyme starch amylase are added again and heated to 95 ° C. This constant temperature is maintained for 30 min and then cooled again to 55 ° C.
- the suspension is cooled to 55 ° C, 100 kg of starch are added, the pH is adjusted again between 4.5 and 6, and between 0.4 and 1.5 kg of cc-amylase / tonne starch enzyme are added, After completely homogenizing the suspension, the temperature is raised again to 95 ° C and kept constant for 60 min.
- the product of this stage called maltodextrin, has the following characteristics: Dextrose equivalent (ED) 20, percentage of dissolved solids 60 ° Brix at 20 ° C, percentage of glucose ⁇ 1, density 1.22 g / ml.
- ED Dextrose equivalent
- This product can be sent immediately to purification (7 and / or 1 1) or directly to a concentrator (12) or spray dryer (13).
- the product from the previous stage is cooled to 60 ° C and transported to the reactors (3 and / or 4), the pH is adjusted again to 4.5. and between 0.8 and 1.5 Kg of enzyme is added per Ton of substrate. .
- the enzyme can be Dextrozyme Supra 2.2X glucoamylase from Novozyme ®.
- the temperature is kept constant at 60 ° C and stirring of 500 rpm for a period of 120 min.
- the product obtained has the characteristics 60 ° Brix, ED 50 and glucose percentage ⁇ 50% BS.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Emergency Medicine (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
PROCESO CON ADICIÓN DOSIFICADA DE MATERIA PRIMA Y ENZIMA PROCESS WITH DOSED ADDITION OF RAW MATERIAL AND ENZYME
PARA LA PRODUCCIÓN DE MALTODEXTRINAS Y JARABES DE GLUCOSA ALTAMENTE CONCENTRADOS A PARTIR DE ALMIDONES FOR THE PRODUCTION OF MALTODEXTRINES AND GLUCOSE SYRUPS HIGHLY CONCENTRATED FROM ALMIDONES
SECTOR TECNOLÓGICO TECHNOLOGICAL SECTOR
Esta invención está relacionada con procesos de producción de malto dextrinas y glucosa a partir de almidones de diferentes fuentes vegetales. Estos procesos utilizan enzimas características como la -amilasa y glucoamilasa, entre otras. Específicamente se utiliza -amilasa para la licuefacción del almidón y producción de maltodextrina. This invention is related to production processes of malt dextrins and glucose from starches from different plant sources. These processes use characteristic enzymes such as -amylase and glucoamylase, among others. Specifically, amylase is used for liquefaction of starch and production of maltodextrin.
ESTADO DE LA TÉCNICA STATE OF THE TECHNIQUE
La patente de CPC International Inc. de número de publicación FR2304675A1 (Proceso para producir levulosa (fructosa) de un almidón granular) presenta un proceso para la conversión completa de almidón a fructosa. Este proceso se realiza mezclando almidón en agua, una -amilasa bacterial junto con glucoamilasa y glucosa isomerasa, con un pH entre 5 y 7 y a una temperatura entre 40 °C y 70 °C en la cual el almidón no comienza a gelatinizar. El proceso se mantiene hasta que se obtiene un hidrolizado soluble mientras que el almidón residual se encuentra en forma no gelatinizada. Las enzimas utilizadas actúan sinérgicamente. La suspensión acuosa de almidón preferiblemente tiene un contenido de sólidos entre el 10% y el 70%. El almidón solubilizado contiene una dextrosa equivalente (ED) entre el 90% y el 95%. El almidón que no reacciona es reciclado al proceso enzimático. The CPC International Inc. patent of publication number FR2304675A1 (Process for producing levulose (fructose) from a granular starch) presents a process for the complete conversion of starch to fructose. This process is carried out by mixing starch in water, a bacterial-amylase together with glucoamylase and glucose isomerase, with a pH between 5 and 7 and at a temperature between 40 ° C and 70 ° C in which the starch does not start to gelatinize. The process is maintained until a soluble hydrolyzate is obtained while the residual starch is in a non-gelatinized form. The enzymes used act synergistically. The aqueous starch suspension preferably has a solids content between 10% and 70%. The solubilized starch contains an equivalent dextrose (ED) between 90% and 95%. Unreacted starch is recycled to the enzymatic process.
Las principales diferencias consisten en que en el proceso de la patente FR2304675A1 las etapas de gelatinización, licuefacción, sacarificación e isomerización ocurren simultáneamente, pues específicamente en este proceso las enzimas se adicionan simultáneamente y funcionan sinérgicamente, así la licuefacción no presenta al menos dos etapas de adición de materia prima y enzima con las cuales se reduce el tiempo de reacción y tampoco se observan The main differences are that in the process of patent FR2304675A1 the stages of gelatinization, liquefaction, saccharification and isomerization occur simultaneously, because specifically in this process enzymes are added simultaneously and function synergistically, so liquefaction does not present at least two stages of addition of raw material and enzyme with which the reaction time is reduced and neither are observed
i los procesos intermedios característicos de la presente invención en la cual las etapas de gelatinización y licuefacción son simultáneas, además durante la etapa de licuefacción se realizan dos o más adiciones de materia prima y enzima antes de la etapa de sacarificación, es decir las etapas de licuefacción y sacarificación son independientes, y en ese orden. i the intermediate processes characteristic of the present invention in which the gelatinization and liquefaction stages are simultaneous, in addition during the liquefaction stage two or more additions of raw material and enzyme are made before the saccharification stage, that is the liquefaction stages and saccharification are independent, and in that order.
En la presente invención, después de las etapas de gelatinización-licuefacción, el almidón solubilizado es cercano al 98%. Respecto al proceso de la patente FR2304675A1 , la presente invención es novedosa, debido a que comprende un proceso de licuefacción con adición dosificada de materia prima y enzima que disminuye el tiempo de reacción, evita la formación de sedimentos o retrogradación del almidón y mejora la reactividad de la enzima hacia el almidón, lo cual incrementa la productividad respecto a un proceso de licuefacción con una sola dosificación de adición de materia prima y enzima, y se obtienen jarabes concentrados que requieren menos procesos de concentración y purificación para ser comercialmente viables. In the present invention, after the gelatinization-liquefaction steps, the solubilized starch is close to 98%. With regard to the process of the FR2304675A1 patent, the present invention is novel, because it comprises a liquefaction process with dosed addition of raw material and enzyme that decreases the reaction time, prevents sediment formation or starch retrogradation and improves reactivity from the enzyme to starch, which increases productivity with respect to a liquefaction process with a single dosage of addition of raw material and enzyme, and concentrated syrups are obtained that require less concentration and purification processes to be commercially viable.
De lo reportado en la patente FR2304675A1 , con respecto a las actividades enzimáticas, de la -amilasa, glucoamilasa y glucosa isomerasa, de 1 a 25 U/g de almidón, 0,1 a 5 U/g de almidón y 0,1 a 20 U/g de almidón, respectivamente, el tiempo estará definido por la actividad de la glucoamilasa. Comparadas estas actividades con las de la presente invención, (35.000 Ul/g de enzima, 312.202 Ul/g) se concluye que a pesar de que las etapas de gelatinización y licuefacción son simultáneas, y las de sacarificación e isomerización son independientes, el tiempo para transformar el almidón a dextrinas y glucosa es mucho menor. As reported in patent FR2304675A1, with respect to the enzymatic activities, of -amylase, glucoamylase and glucose isomerase, from 1 to 25 U / g of starch, 0.1 to 5 U / g of starch and 0.1 to 20 U / g starch, respectively, the time will be defined by glucoamylase activity. Compared to these activities with those of the present invention, (35,000 Ul / g enzyme, 312,202 Ul / g) it is concluded that although the gelatinization and liquefaction stages are simultaneous, and the saccharification and isomerization stages are independent, the time to transform starch to dextrins and glucose is much lower.
La patente US4612284A (Proceso para la hidrólisis enzimática del almidón granulado no gelatinizado directamente a glucosa) describe un proceso para la hidrólisis enzimática de almidón granular no gelatinizado directamente a glucosa y malto dextrinas. El proceso consiste en una hidrólisis parcial de una suspensión de almidón granular no gelatinizado a una temperatura entre 50 °C y 65 °C que es inferior a la temperatura de gelatinización del material de almidón granular. El almidón se pone en contacto con un sistema enzimático capaz de hidrolizarlo en una forma granular no gelatinizada directamente a glucosa, dicha enzima es empleada en una cantidad tal que, bajo las condiciones de proceso, la hidrólisis realizada es parcial hasta glucosa del material de almidón, sin lograr su hidrólisis total. Igualmente todos los ácidos grasos y proteínas atrapados en el almidón son liberados del almidón hidrolizado para ser absorbidos por parte del almidón no gelatinizado. Este paso facilita la obtención y purificación de la glucosa. El material de almidón granular no hidrolizado con proteína o ácidos grasos absorbidos se cocina a 80 °C y posteriormente es sometido a hidrólisis para producir malto dextrinas. Finalmente se realiza la separación de las malto dextrinas liberadas durante la hidrólisis a 80 °C. US4612284A (Process for enzymatic hydrolysis of non-gelatinized granulated starch directly to glucose) describes a process for enzymatic hydrolysis of non-gelatinized granular starch directly to glucose and dextrin malt. The process consists of a partial hydrolysis of a suspension of non-gelatinized granular starch at a temperature between 50 ° C and 65 ° C which is below the gelatinization temperature of the granular starch material. The starch is contacted with an enzymatic system capable of hydrolyzing it in a non-gelatinized granular form directly to glucose, said enzyme is employed in an amount such that, under the process conditions, the hydrolysis performed is partial to glucose of the starch material , without achieving its total hydrolysis. Likewise all fatty acids and proteins trapped in starch are released from hydrolyzed starch to be absorbed by non-gelatinized starch. This step facilitates the obtaining and purification of glucose. The non-hydrolyzed granular starch material with absorbed protein or fatty acids is cooked at 80 ° C and subsequently subjected to hydrolysis to produce malt dextrins. Finally, the dextrin malt released during hydrolysis at 80 ° C is removed.
Las principales diferencias se refieren a que el proceso de la patente US4612284A tiene etapas diferentes a las reportadas en la presente invención. Específicamente, las enzimas se adicionan conjuntamente y se tiene un paso de absorción de proteínas y ácidos grasos sobre almidón no hidrolizado, el cual posteriormente es utilizado para la producción de malto dextrinas. The main differences concern that the process of US4612284A has different stages than those reported in the present invention. Specifically, the enzymes are added together and there is an absorption step of proteins and fatty acids on non-hydrolyzed starch, which is subsequently used for the production of dextrin malt.
En la patente US4612284A la materia prima, el almidón, tiene un alto contenido de grasas y proteínas, las cuales son tratadas mediante un proceso de cocción y tratamiento enzimático mientras que en la presente invención este material, no soluble en el hidrolizado de almidón, es retirado por filtración. In US4612284A the raw material, starch, has a high content of fats and proteins, which are treated by a process of cooking and enzymatic treatment while in the present invention this material, not soluble in starch hydrolyzate, is filtered out.
Adicionalmente, la patente US4612284A reivindica principalmente el aprovechamiento del almidón que no es hidrolizado porque las grasas y proteínas presentes lo recubren e impiden el ataque enzimático, entonces en una etapa adicional a altas temperaturas y un tiempo adicional de proceso liberan el almidón atrapado y lo hidrolizan hasta azúcares. En la presente invención este material solo representa máximo del 2% p/p de la materia prima y es retirado por filtración, secado, y es utilizado en alimentación animal. En la patente US4612284A reportan un tiempo de hidrólisis de almidón (para ED 25) entre 24 y 96 horas, mientras que en la presente invención para alcanzar una conversión de ED de 50, se requieren menos de 2 horas. Additionally, US4612284A patent claims mainly the use of starch that is not hydrolyzed because the fats and proteins present cover it and prevent the enzymatic attack, then at an additional stage at high temperatures and an additional process time they release the trapped starch and hydrolyze it. even sugars. In the present invention this material only represents a maximum of 2% w / w of the raw material and is removed by filtration, dried, and is used in animal feed. In US4612284A they report a starch hydrolysis time (for ED 25) between 24 and 96 hours, while in the present invention to achieve an ED conversion of 50, less than 2 hours are required.
Respecto a la patente US4612284A, la presente invención es novedosa, debido a que se hacen múltiples adiciones de materia prima y enzima durante la etapa de licuefacción lo que disminuye el tiempo de reacción e incrementa la eficiencia del proceso, con mejoras en el tiempo de contacto enzima/almidón incrementando la productividad. Tampoco se observa que el proceso de la patente US4612284A esté enfocado a evitar el aumento de viscosidad mediante dos o más etapas de adición de materia prima y enzima durante la licuefacción, como si se realiza en la presente invención. With respect to US4612284A, the present invention is novel, because multiple additions of raw material and enzyme are made during the liquefaction stage which decreases the reaction time and increases the efficiency of the process, with improvements in contact time enzyme / starch increasing productivity. It is also not observed that the process of US4612284A is focused on preventing the increase in viscosity by means of two or more stages of adding raw material and enzyme during liquefaction, as if it is carried out in the present invention.
El documento de la publicación de la solicitud de patente WO2004007739A1 propone que a partir de yuca entera lavada se produzca malto dextrina, glucosa, maltosa y dextrosa, mediante un proceso en el cual las porciones cortadas, lavadas y secadas de yuca son llevadas a sacarificación, con elementos mecánicos de modo que la ralladura y pulverización de una mezcla acuosa en suspensión se lleva a cabo en reactores en donde por la adición de enzimas y/o ácidos y dentro de valores térmicos y de acidez en el pH de dichos licores se van obteniendo los productos mencionados en un alto grado de rendimiento y economía respecto a los sistemas industrializados actuales. Para producir las malto dextrinas la suspensión es hidrolizada hasta dextrosa equivalente (ED) de 15, usando acido clorhídrico al 35% entre 100°C y 1 15°C. La mezcla de reacción es ajustada a pH 6-7, enfriada entre 80 °C y 85 °C y agitada entre 1 y 3 horas en la presencia de -amilasa. Las condiciones preferidas para la formación de otros productos son para glucosa, tratamiento con -amilasa en pH entre 6 y 6,5 y luego amiloglucosidasa en un pH 4,2; para maltosa, el tratamiento con -amilasa en un pH 7 y luego con una -amilasa de un hongo de pH entre 4,8 y 5,4 y para dextrosa el tratamiento con -amilasa en un pH 6,5 y luego con -amilasa en un pH 6. Las diferencias se refieren a que el proceso de la patente WO2004007739A1 tiene otras etapas. Específicamente en este proceso la producción de malto dextrinas se hace en una sola etapa y el proceso de purificación incluye un paso con intercambio iónico. Específicamente en ese proceso la producción de malto dextrinas se hace con ácido inorgánico y no a través de un proceso enzimático (con cc-amilasa) como en la presente invención. The document of the publication of the patent application WO2004007739A1 proposes that from whole washed cassava dextrin malt, glucose, maltose and dextrose be produced, by a process in which the sliced, washed and dried portions of cassava are taken to saccharification, with mechanical elements so that the grating and spraying of an aqueous mixture in suspension is carried out in reactors where by the addition of enzymes and / or acids and within thermal values and acidity in the pH of said liquors are obtained the products mentioned in a high degree of performance and economy with respect to current industrialized systems. To produce the malt dextrins, the suspension is hydrolyzed to dextrose equivalent (ED) of 15, using 35% hydrochloric acid between 100 ° C and 1 15 ° C. The reaction mixture is adjusted to pH 6-7, cooled between 80 ° C and 85 ° C and stirred for 1 to 3 hours in the presence of -amylase. The preferred conditions for the formation of other products are for glucose, treatment with -amylase at pH between 6 and 6.5 and then amyloglucosidase at pH 4.2; for maltose, the treatment with -amylase at a pH 7 and then with a -amylase of a fungus of pH between 4.8 and 5.4 and for dextrose the treatment with -amylase at a pH 6.5 and then with -amylase at a pH 6. The differences refer to the process of patent WO2004007739A1 having other stages. Specifically in this process the production of malt dextrins is done in a single stage and the purification process includes a step with ion exchange. Specifically in that process the production of malt dextrins is made with inorganic acid and not through an enzymatic process (with cc-amylase) as in the present invention.
Respecto a la invención del documento WO2004007739A1 , la presente invención es novedosa, pues contiene un proceso con múltiples adiciones de materia prima y enzima durante la etapa de licuefacción enzimática, lo que disminuye el tiempo de reacción e incrementa la eficiencia del proceso y mejora el tiempo de contacto enzima/almidón incrementando la productividad. La publicación WO2004007739A1 reporta que para obtener un ED de 15 se requieren 10 horas con tratamiento enzimático (resaltando que previamente fue tratado con ácido inorgánico) y tampoco se observa que el proceso esté enfocado a evitar el aumento de viscosidad del proceso a través de la realización de dos o más adiciones de materia prima y enzima durante la etapa de licuefacción controlando la temperatura y la actividad de las enzimas. With respect to the invention of WO2004007739A1, the present invention is novel, since it contains a process with multiple additions of raw material and enzyme during the enzymatic liquefaction stage, which decreases the reaction time and increases the efficiency of the process and improves the time of contact enzyme / starch increasing productivity. The publication WO2004007739A1 reports that in order to obtain an ED of 15, 10 hours are required with enzymatic treatment (highlighting that it was previously treated with inorganic acid) and it is not observed that the process is focused on avoiding the increase in viscosity of the process through the implementation of two or more additions of raw material and enzyme during the liquefaction stage controlling the temperature and activity of the enzymes.
El documento de patente CN101696437A de la China, describe un proceso de manufactura de maltodextrina a partir de arroz que comprende los pasos de inmersión, formación de pulpa hasta llevar la concentración entre 15 -16 grados Be (28 a 30°Brix), posteriormente se realiza la licuefacción enzimática con remoción de residuos, finalmente se neutraliza y filtra. El proceso de hidrólisis se realiza con -amilasa. El filtrado se pasa por una resina de intercambio iónico, se concentra y seca para empaque. Este proceso supera las desventajas en la producción de malto dextrinas provenientes de maíz y yuca ya que el manejo inicial del material implica maceración. Esta invención neutraliza y elimina el olor con la incorporación de carbón activado. Finalmente el refinado se hace por intercambio iónico con cierta cantidad de pirosulfito para mejorar la estabilidad del azúcar. Esta invención utiliza un evaporador de película cuádruple y un evaporador estándar para alcanzar la concentración deseada. El producto de malto dextrina es incoloro, con buena fluidez y un alto valor biológico. Patent document CN101696437A of China describes a manufacturing process of maltodextrin from rice comprising the immersion steps, pulp formation until the concentration is between 15-16 degrees Be (28 to 30 ° Brix), subsequently It performs enzymatic liquefaction with waste removal, finally it is neutralized and filtered. The hydrolysis process is performed with -amylase. The filtrate is passed through an ion exchange resin, concentrated and dried for packing. This process overcomes the disadvantages in the production of malt dextrins from corn and cassava since the initial handling of the material implies maceration. This invention neutralizes and eliminates odor with the incorporation of activated carbon. Finally the refining is done by ion exchange with a certain amount of pyrosulfite to improve the stability of sugar. This invention uses an evaporator of Quad film and a standard evaporator to reach the desired concentration. The product of malt dextrin is colorless, with good fluidity and a high biological value.
La presente invención puede considerarse novedosa por sobre dicha anterioridad, debido a que presenta un proceso de múltiples adiciones de materia prima y enzima durante la etapa de licuefacción enzimática, lo que disminuye el tiempo de reacción, incrementa la eficiencia del proceso y mejora el tiempo de contacto enzima/almidón incrementando la productividad. Igualmente tampoco se observa que el proceso de la patente CN101696437A esté enfocado a evitar el aumento de viscosidad del proceso a través de la realización de las dos o más adiciones de materia prima durante la etapa de licuefacción controlando la temperatura y la actividad de las enzimas. The present invention can be considered novel over said above, because it presents a process of multiple additions of raw material and enzyme during the enzymatic liquefaction stage, which decreases the reaction time, increases the efficiency of the process and improves the processing time. Enzyme / starch contact increasing productivity. It is also not observed that the process of the CN101696437A patent is focused on preventing the increase in viscosity of the process through the realization of the two or more additions of raw material during the liquefaction stage by controlling the temperature and the activity of the enzymes.
La patente US 4,069,103 describe un proceso para producir dextrosa y dextrinas de productos de almidón que contienen proteínas. Parten de una solución con un contenido de entre 7% y 8.5% de almidón, la licuefacción toma entre 1 y 2 horas y luego se agrega la segunda enzima tomando la hidrólisis 48 horas (sacarificación). US Patent 4,069,103 describes a process for producing dextrose and dextrins from starch products containing proteins. Starting from a solution with a content of between 7% and 8.5% of starch, the liquefaction takes between 1 and 2 hours and then the second enzyme is added taking the hydrolysis 48 hours (saccharification).
En general el proceso de la presente invención durante la licuefacción se puede llegar a concentraciones hasta del 70% p/p, requiere menor tiempo, menor consumo de agua, genera menor viscosidad a mayor concentración de almidón y, como consecuencia, se aumenta la productividad del proceso. In general, the process of the present invention during liquefaction can reach concentrations up to 70% w / w, requires less time, less water consumption, generates lower viscosity at a higher concentration of starch and, as a consequence, increases productivity of process.
Respecto a la publicación "Producción de jarabes de fructosa por medio de la hidrólisis enzimática del almidón de yuca de las variedades Corpoica M Tai-8 y Corpoica Orense"; Dyna, Vol. 76, Núm. 160, diciembre, 2009, pp. 121 -130; Universidad Nacional de Colombia; Salcedo M., Jairo G. ; Montes M., Everaldo J.; Pajaro S., José L. en el proceso descrito no se menciona cómo la etapa de gelatinización afecta el proceso de producción de jarabes. La licuefacción se realiza en una sola etapa y posteriormente la sacarificación. No explican tampoco cómo se realiza la desactivación de las enzimas, como se describe en la presente invención, porque el no hacerlo trae como consecuencia la inestabilidad de las propiedades de los productos (ED, concentración glucosa). Regarding the publication "Production of fructose syrups by means of enzymatic hydrolysis of cassava starch of the Corpoica M Tai-8 and Corpoica Orense varieties"; Dyna, Vol. 76, No. 160, December, 2009, pp. 121-130; National university of Colombia; Salcedo M., Jairo G.; Montes M., Everaldo J .; Pajaro S., José L. in the described process it is not mentioned how the gelatinization stage affects the syrup production process. The liquefaction is carried out in a single stage and subsequently the saccharification. They also do not explain how enzyme deactivation is performed, as described in the present invention, because failure to do so results in instability of the properties of the products (ED, glucose concentration).
El objetivo principal de esta publicación es la comparación de almidones de tres variedades de yuca utilizando un proceso reportado en el estado de la técnica. The main objective of this publication is the comparison of starches of three cassava varieties using a process reported in the prior art.
En vista de la información anterior, es claro que en el estado de la técnica existe la necesidad de contar con un proceso de hidrólisis y licuefacción de almidones que requiera un menor tiempo de reacción y garantice un producto sustancialmente libre de compuestos indeseables generados por al descomposición del almidón. In view of the above information, it is clear that in the state of the art there is a need for a starch hydrolysis and liquefaction process that requires a shorter reaction time and guarantees a product substantially free of undesirable compounds generated by decomposition. of starch
La presente invención permite incorporar y procesar la materia prima sin tener inconvenientes de reología (viscosidad elevada), adicionalmente el almidón se transforma con mayor eficiencia debido a que el método de múltiples adiciones de materia prima y enzima durante la etapa de licuefacción aprovecha el agua que se libera en una etapa previa por efecto de la enzima al romper los gránulos de almidón gelatinizado, para acondicionar nuevo almidón y dejarlo disponible para el ataque enzimático. The present invention allows the raw material to be incorporated and processed without having rheology problems (high viscosity), in addition the starch is transformed more efficiently because the method of multiple additions of raw material and enzyme during the liquefaction stage takes advantage of the water that It is released at a previous stage due to the effect of the enzyme by breaking the gelatinized starch granules, to condition new starch and make it available for enzymatic attack.
El estado del arte reporta que solo se tienen resultados exitosos (hidrólisis hasta lograr jarabes con ED de 94) hasta una concentración del 30% de sólidos, por lo cual se deduce que la licuefacción se realiza en una sola etapa, mientras que el proceso de múltiples etapas de licuefacción de la presente invención se puede trabajar en concentraciones hasta del 70% p/p de almidón en el mismo tiempo. The state of the art reports that only successful results (hydrolysis to achieve syrups with ED of 94) have been achieved up to a concentration of 30% solids, so it follows that liquefaction is carried out in a single stage, while the process of Multiple stages of liquefaction of the present invention can be worked at concentrations up to 70% w / w starch at the same time.
FIGURAS FIGURES
En la figura 1 se muestra el proceso para la obtención de dextrinas y jarabes de glucosa concentrados cuyos detalles se especifican en el ejemplo 2. Figure 1 shows the process for obtaining concentrated glucose dextrins and syrups whose details are specified in example 2.
DESCRIPCION DE LA INVENCIÓN El proceso para la producción de maltodextrinas y jarabes de glucosa a partir de almidones está compuesto por las siguientes etapas: DESCRIPTION OF THE INVENTION The process for the production of maltodextrins and glucose syrups from starches is composed of the following stages:
1. Licuefacción 1. Liquefaction
La etapa de licuefacción involucra la hidrólisis parcial del almidón, con la consecuente pérdida de viscosidad. El almidón gelatinizado es literalmente licuado por hidrólisis parciales, mediante enzimas, que producen la destrucción de las cadenas poliméricas del almidón (amilosa y amilopectina) dando lugar a cadenas de menor tamaño. Después de ocurrir la gelatinización puede ocurrir una etapa de gelificación la cual genera subproductos indeseados que desmejoran la calidad del producto y reduce la eficiencia del proceso porque requiere trabajarse un tiempo considerable a altas viscosidades, generando mayores consumos de energía y por ende mayores costos operacionales. Los tiempos de contacto enzima/almidón en la etapa de gelificación para lograr los valores de equivalente de dextrosa (ED) y la duración del proceso general, son muy prolongados afectando la productividad. Por lo anterior, con el proceso de la presente invención se evita la etapa de gelificación. The liquefaction stage involves the partial hydrolysis of starch, with the consequent loss of viscosity. The gelatinized starch is literally liquefied by partial hydrolysis, by enzymes, which cause the destruction of the starch polymer chains (amylose and amylopectin) giving rise to smaller chains. After the gelatinization occurs, a gelation stage can occur which generates unwanted by-products that reduce the quality of the product and reduces the efficiency of the process because it requires considerable time to be worked at high viscosities, generating higher energy consumption and therefore higher operational costs. The enzyme / starch contact times in the gelation stage to achieve the equivalent values of dextrose (ED) and the duration of the general process, are very long affecting productivity. Therefore, the gelation step is avoided with the process of the present invention.
La etapa de licuefacción del proceso de la presente invención, se realiza de manera gradual, es decir en la presente invención se realizan múltiples adiciones de materia prima y enzima al reactor. En la primera adición se carga agua, almidón y enzima al reactor, en la segunda y posteriores adiciones solo se carga almidón y enzima al reactor. La novedad del proceso se encuentra en la adición dosificada de almidón y enzima al reactor. El proceso comienza precalentando agua a 55 °C, se adiciona almidón hasta lograr una concentración entre el 6% y el 35% p/p, se ajusta el pH de 4.5 a 6 utilizando una solución de HCI o NaOH y se adiciona la enzima -amilasa Luego, se eleva la temperatura hasta 95 °C de manera gradual, con una rampa de calentamiento (entre 1 y 6°C/min) y se deja reaccionar de 5 a 60 minutos, obteniéndose un producto intermedio denominado maltodextrina, cuyo grado equivalente de dextrosa (ED) se encuentra entre 5 y 20, dependiendo del tiempo de reacción mencionado. Para la segunda y posteriores adiciones de materia prima, primero se baja la temperatura de la solución a 55 °C, se ajusta nuevamente el pH (entre 4.5 y 6), se adiciona almidón y enzima fresca manteniendo la relación enzima/sustrato. El objeto de reducir la temperatura es detener completamente la reacción dentro del reactor antes de agregar una nueva carga de material freso. Se adiciona almidón para incrementar su concentración hasta el 70% p/p, ya sea con dos o más adiciones de almidón y enzima fresca. Después de la adición de almidón y enzima fresca, se eleva nuevamente la temperatura hasta 95 °C y se deja reaccionar la solución el tiempo necesario hasta alcanzar el ED requerido, dependiendo del producto a fabricar. En esta etapa de licuefacción las moléculas de agua alrededor de los gránulos rompen los enlaces tipo Van deer Vals entre las cadenas poliméricas de almidón en el interior del gránulo y éstos se hinchan aumentando la viscosidad de la suspensión de almidón. The liquefaction step of the process of the present invention is carried out gradually, that is to say in the present invention multiple additions of raw material and enzyme are made to the reactor. In the first addition, water, starch and enzyme are charged to the reactor, in the second and subsequent additions only starch and enzyme are charged to the reactor. The novelty of the process is found in the dosed addition of starch and enzyme to the reactor. The process begins by preheating water at 55 ° C, starch is added until a concentration between 6% and 35% w / w is achieved, the pH is adjusted from 4.5 to 6 using a solution of HCI or NaOH and the enzyme is added - Amylase Then, the temperature is raised to 95 ° C gradually, with a heating ramp (between 1 and 6 ° C / min) and allowed to react for 5 to 60 minutes, obtaining an intermediate product called maltodextrin, whose equivalent degree Dextrose (ED) is between 5 and 20, depending on the reaction time mentioned. For the second and subsequent additions of raw material, the temperature of the solution is first lowered to 55 ° C, the pH is adjusted again (between 4.5 and 6), fresh starch and enzyme is added maintaining the enzyme / substrate ratio. The purpose of reducing the temperature is to completely stop the reaction inside the reactor before adding a new load of fresh material. Starch is added to increase its concentration to 70% w / w, with either two or more additions of starch and fresh enzyme. After the addition of starch and fresh enzyme, the temperature is raised again to 95 ° C and the solution is allowed to react for the time necessary to reach the required ED, depending on the product to be manufactured. At this stage of liquefaction the water molecules around the granules break the Van deer Waltz type links between the polymeric starch chains inside the granule and they swell increasing the viscosity of the starch suspension.
Algunas moléculas cortas de amilosa se disuelven y se difunden fuera de los gránulos, las cuales son inmediatamente hidrolizadas por la enzima; las moléculas más largas de amilosa, que refuerzan la estructura de los gránulos al igual que las de amilopectina se van liberando, gelatinizando e inmediatamente son hidrolizadas, evitando así el aumento fuerte de la viscosidad como se reporta en la literatura técnica para las suspensiones de almidón gelatinizado. Estos cambios tienen lugar sobre un rango de temperatura que es determinado usando un microscopio de polarización equipado con un sistema de calentamiento y se reporta como el Rango de Temperatura de Gelatinización. Some short molecules of amylose dissolve and diffuse out of the granules, which are immediately hydrolyzed by the enzyme; the longer amylose molecules, which reinforce the structure of the granules as well as those of amylopectin, are released, gelatinized and immediately hydrolyzed, thus avoiding a sharp increase in viscosity as reported in the technical literature for starch suspensions gelatinized These changes take place over a temperature range that is determined using a polarization microscope equipped with a heating system and is reported as the Gelatinization Temperature Range.
La enzima de licuefacción es -amilasa (como por ejemplo la Liquozyme supra 2.2X de Novozyme®), y es empleada a una concentración de 0.40 a 1 .5 kg de enzima por tonelada de almidón (relación enzima/sustrato). The liquefaction enzyme is -amylase (such as Liquozyme supra 2.2X of Novozyme®), and is used at a concentration of 0.40 to 1.5 kg of enzyme per ton of starch (enzyme / substrate ratio).
La hidrólisis parcial del almidón, denominada licuefacción, es la ruptura de los enlaces a 1 -4 glucosídicos de las cadenas poliméricas de almidón, con la enzima -amilasa y en presencia de agua, hasta alcanzar equivalentes de dextrosa (ED) inferiores a 20. La hidrólisis parcial del almidón da como resultado la maltodextrina la cual se compone de una mezcla de sacáridos, polisacáridos y oligosacáridos con amplias distribuciones de pesos moleculares. La composición de los jarabes de malto dextrina se asocia comúnmente al ED, de tal forma que un ED inferior a 20 se denomina dextrina y un ED superior a 20, y menor de 100, se denomina glucosa. The partial hydrolysis of starch, called liquefaction, is the rupture of the 1 -4 glycosidic bonds of the starch polymer chains, with the enzyme -amylase and in the presence of water, until dextrose equivalents (ED) less than 20 are reached. Partial hydrolysis of starch results in maltodextrin which is composed of a mixture of saccharides, polysaccharides and oligosaccharides with wide weight distributions molecular. The composition of malt syrups dextrin is commonly associated with ED, so that an ED less than 20 is called dextrin and an ED greater than 20, and less than 100, is called glucose.
Lo que se logra con las múltiples adiciones de almidón y enzima es incrementar gradualmente la concentración de sólidos porque sólo se adiciona agua en la primera licuefacción. Para realizar la segunda y posteriores adiciones de almidón y enzima, primero se disminuye la temperatura lo que disminuye la cinética de la hidrólisis al mínimo, es decir, se detiene la licuefacción, seguidamente se adiciona nuevo almidón y enzima fresca y se ajustan nuevamente las condiciones para continuar con la licuefacción, es decir, se aumenta la temperatura hasta 95 °C, se ajusta pH y se deja el tiempo requerido de reacción hasta lograr el ED deseado. En esta etapa se concentra el hidrolizado porque no se adicionó agua pero sí almidón, además las dextrinas producto de la etapa inicial también son hidrolizadas en la segunda reacción porque en sus moléculas hay presencia de enlaces 1 -4 glucosídicos. Si se desea, se pueden hacer más de dos adiciones dosificadas de materia prima hasta alcanzar un contenido de sólidos de 70% dentro del reactor. What is achieved with the multiple additions of starch and enzyme is to gradually increase the concentration of solids because only water is added in the first liquefaction. To make the second and subsequent additions of starch and enzyme, first the temperature is lowered which decreases the kinetics of the hydrolysis to a minimum, that is, the liquefaction is stopped, then new starch and fresh enzyme are added and the conditions are adjusted again to continue liquefaction, that is, the temperature is increased to 95 ° C, pH is adjusted and the required reaction time is left until the desired ED is achieved. In this stage the hydrolyzate is concentrated because no water was added but starch was added, in addition the product dextrins of the initial stage are also hydrolyzed in the second reaction because in its molecules there is presence of 1 -4 glycosidic bonds. If desired, more than two dosed additions of raw material can be made until a solids content of 70% is reached within the reactor.
La ventaja de adicionar el almidón y la enzima de manera gradual es debido a que se puede hidrolizar la mayor cantidad de almidón posible (cerca al 70% p/p); es decir se tiene un hidrolizado al que, dependiendo de las aplicaciones, no es necesario retirarle el exceso de agua en etapas posteriores de concentración lo cual implica una mayor demanda de energía, uso de equipos, y procesos físicos de separación. La hidrólisis descrita anteriormente se puede hacer, por ejemplo en reactores por lotes {Múltiple Batch Reactor) y/o reactores de flujo continuos {Multistage Continuous Reactor, "Submarine") modificados para que alguna etapa del reactor permita la modificación de la temperatura, y en otra la adición de almidón y enzima. The advantage of adding starch and enzyme gradually is because it is possible to hydrolyze as much starch as possible (about 70% w / w); that is to say, there is a hydrolyzate to which, depending on the applications, it is not necessary to remove excess water at later stages of concentration which implies a greater demand for energy, use of equipment, and physical separation processes. The hydrolysis described above can be done, for example, in batch reactors {Multiple Batch Reactor) and / or continuous flow reactors {Multistage Continuous Reactor, "Submarine") modified so that some stage of the reactor allows temperature modification, and in another the addition of starch and enzyme.
En la presente invención se realizó además una mejora en el proceso de desactivación de las enzimas, pues en la literatura se encuentra que se debe bajar el pH por debajo de 2, dejar 10 minutos y subir nuevamente el pH al valor previo (entre 4.5 y 6) pero este procedimiento no desactiva completamente la enzima. La mejora consiste en que la enzima es desactivada totalmente a pH inferior a 3 durante 40 minutos a 95°C, garantizando que no haya más hidrólisis del almidón y por tanto, las propiedades físico químicas del producto son constantes en el tiempo. Esto se ha probado para almidones de diferentes proveedores. In the present invention an improvement was also made in the process of deactivation of enzymes, since in the literature it is found that the pH must be lowered below 2, leave 10 minutes and the pH raised again to the previous value (between 4.5 and 6) but this procedure does not completely deactivate the enzyme. The improvement is that the enzyme is completely deactivated at pH below 3 for 40 minutes at 95 ° C, ensuring that there is no more hydrolysis of the starch and therefore, the physical chemical properties of the product are constant over time. This has been tested for starches from different suppliers.
El tiempo de contacto enzima/almidón, en la etapa de licuefacción, reportado en la literatura técnica partiendo de suspensiones agua almidón al 30% p/v, que es de 100 minutos, es mejorado dramáticamente en la presente invención, reduciéndose a 30 minutos. Cuando se gelatiniza el almidón, la suspensión aumenta la viscosidad, pero bajo las condiciones de esta invención el almidón se va gelatinizando e inmediatamente comienza a hidrolizarse impidiendo que aumente la viscosidad, facilitando la interacción enzima-almidón disminuyendo así el tiempo de esta etapa. The enzyme / starch contact time, in the liquefaction stage, reported in the technical literature starting from 30% w / v starch water suspensions, which is 100 minutes, is dramatically improved in the present invention, being reduced to 30 minutes. When the starch is gelatinized, the suspension increases the viscosity, but under the conditions of this invention the starch is gelatinized and immediately begins to hydrolyze preventing the viscosity from increasing, facilitating the enzyme-starch interaction thus reducing the time of this stage.
En el estado de la técnica en la etapa de licuefacción con diferentes amilasas para lograr jarabes licuados con un ED entre 4 y 8, se requieren 60 minutos de contacto con la enzima, mientras que con el proceso de esta invención, para lograr ese rango de ED, se requieren entre 15 y 25 minutos. Esto representa una disminución a menos de la mitad del tiempo con el consiguiente ahorro de energía y aumento de la productividad. In the state of the art in the liquefaction stage with different amylases to achieve liquefied syrups with an ED between 4 and 8, 60 minutes of contact with the enzyme are required, while with the process of this invention, to achieve that range of ED, 15-25 minutes are required. This represents a decrease less than half the time with the consequent energy savings and productivity gains.
2. Sacarificación 2. Saccharification
Cuando lo que se desea es la obtención de jarabe de glucosa, se incluye al final del proceso anterior, una etapa de sacarificación, en la cual se adiciona a la solución de la etapa anterior la enzima glucoamilasa en una concentración de 0.8 a 1 .5 g/Kg de sustrato. La reacción es llevada a cabo a un pH entre de 4 y 6 y a una temperatura entre 50 °C y 65 °C alcanzando un ED entre 40 y 60 en un tiempo entre 90 y 120 minutos de reacción. When what is desired is to obtain glucose syrup, a saccharification stage is included at the end of the previous process, in which the glucoamylase enzyme in a concentration of 0.8 to 1 .5 is added to the solution of the previous stage. g / kg of substrate. The reaction is carried out at a pH between 4 and 6 and at a temperature between 50 ° C and 65 ° C reaching an ED between 40 and 60 in a time between 90 and 120 minutes of reaction.
Una vez transcurrido el tiempo requerido de reacción, la enzima glucoamilasa es desactivada calentando la solución hasta 95 °C durante 40 minutos. Los procesos enzimáticos para la producción de glucosa requieren de una etapa de sacarificación después de la licuefacción del almidón. Esta etapa se efectúa con una enzima conocida como amiloglucosidasa o glucoamilasa, de origen microbiano, la cual tiene la característica de ser una exoamilasa que libera glucosa fundamentalmente de enlaces 1 -4 del almidón pero también de enlaces 1 -6, aunque a una velocidad inferior, lo que permite hidrolizar las dextrinas. After the required reaction time has elapsed, the glucoamylase enzyme is deactivated by heating the solution to 95 ° C for 40 minutes. Enzymatic processes for glucose production require a saccharification stage after the liquefaction of starch. This stage is carried out with an enzyme known as amyloglucosidase or glucoamylase, of microbial origin, which has the characteristic of being an exoamylase that releases glucose mainly from 1-4 bonds of starch but also from 1-6 bonds, although at a lower rate , which allows hydrolyzing dextrins.
Las enzimas -amilasa y gluco-amilasa son retiradas de los productos por métodos físicos de separación conocidos, tales como ultrafiltración o centrifugación entre otros. The enzymes -amylase and gluco-amylase are removed from the products by known physical methods of separation, such as ultrafiltration or centrifugation among others.
Los jarabes de glucosa son una mezcla entre una solución acuosa de D- glucosa, maltosa y otros oligosacáridos llamados dextrinas. Los jarabes de D- Glucosa vienen comúnmente caracterizados por su equivalente de dextrosa (ED). Glucose syrups are a mixture between an aqueous solution of D-glucose, maltose and other oligosaccharides called dextrins. D-Glucose syrups are commonly characterized by their equivalent of dextrose (ED).
EJEMPLOS EXAMPLES
Ejemplo 1 : Proceso a nivel de laboratorio utilizando dos etapas de adición dosificada de almidón y enzima y posterior sacarificación. Example 1: Process at the laboratory level using two stages of metered starch and enzyme addition and subsequent saccharification.
Este ejemplo ilustra el método establecido en la presente invención para producir jarabes de glucosa a partir de almidón (por ejemplo almidón de yuca) a nivel de laboratorio utilizando dos (2) etapas de adición dosificada de materia prima y posterior sacarificación, se inicia el proceso cargando al reactor 370g de agua y precalentándola hasta 55 °C, se adicionan 190 g de almidón (12% p/p de humedad), se ajusta el pH de la suspensión entre 4.5 y 6 mediante la adición de HCI o NaOH, inmediatamente se adicionan la enzima -amilasa (por ejemplo Liquozyme Supra 2.2X de Novozyme®) entre 0,4 y 1 ,5 Kg y se eleva la temperatura de la suspensión hasta 95 °C con una rampa de calentamiento entre 1 y 6°C/min, se mantiene constante entre 5 y 60 min y con agitación constante a 150 rpm. Luego se enfría hasta 55 °C y se adicionan 190 g de almidón, después de homogenizar completamente la suspensión por agitación, se ajusta el pH (si es requerido), se agrega nuevamente enzima -amilasa con la relación enzima/sustrato descrita anteriormente, se eleva la temperatura nuevamente a 95°C y se mantiene constante dependiendo de los tiempos y relaciones enzima/sustrato, entre 5 y 60 min. This example illustrates the method established in the present invention to produce glucose syrups from starch (for example cassava starch) at the laboratory level using two (2) steps of dosed addition of raw material and subsequent saccharification, the process is started by charging 370g of water to the reactor and preheating it to 55 ° C, 190 g of starch (12% w / w moisture) are added, the pH of the suspension is adjusted between 4.5 and 6 by the addition of HCI or NaOH, immediately add the enzyme -amylase (for example Liquozyme Supra 2.2X of Novozyme®) between 0.4 and 1.5 Kg and raise the temperature of the suspension to 95 ° C with a heating ramp between 1 and 6 ° C / min , it remains constant between 5 and 60 min and with constant agitation at 150 rpm. It is then cooled to 55 ° C and 190 g of starch are added, after completely homogenizing the suspension by stirring, the pH is adjusted (if required), enzyme-amylase is added again with the enzyme / substrate ratio described above, the temperature is raised again to 95 ° C and is kept constant depending on the times and enzyme / substrate ratios, between 5 and 60 min.
El producto resultante de estas etapas se denomina dextrina y cuenta con las siguientes características: Equivalente de dextrosa (ED) igual a 20, un porcentaje de sólidos disueltos 50 °Brix a 20 °C, un porcentaje de glucosa < 1 , una densidad de 1 .21 g/ml. Para iniciar la sacarificación se baja la temperatura hasta entre 50 y 65 °C, se ajusta el pH de la solución entre 4 y 6 mediante adición de HCI 5N o NaOH 5N, se agregan entre 0,8 y 1 ,5 Kg de enzima por tonelada de sustrato (Por ejemplo Dextrozyme GA 1 .5X de Novozyme®) y se mantiene a temperatura y agitación constantes durante 180 min. The product resulting from these stages is called dextrin and has the following characteristics: Dextrose equivalent (ED) equal to 20, a percentage of dissolved solids 50 ° Brix at 20 ° C, a percentage of glucose <1, a density of 1 .21 g / ml. To start saccharification, the temperature is lowered to between 50 and 65 ° C, the pH of the solution is adjusted between 4 and 6 by the addition of 5N HCI or 5N NaOH, between 0.8 and 1.5 Kg of enzyme are added per ton of substrate (For example Dextrozyme GA 1.5X of Novozyme®) and kept at constant temperature and stirring for 180 min.
Las condiciones generales de licuefacción y sacarificación de almidones se muestran en la tabla 1 The general conditions of liquefaction and saccharification of starches are shown in table 1
Tabla 1 : Condiciones generales de licuefacción y sacarificación de almidones Table 1: General conditions for liquefaction and saccharification of starches
Condiciones de Conditions of
operación Rango Operation Range
Concentración de Almidón 6-70% Starch Concentration 6-70%
pH de la suspensión pH of the suspension
durante la licuefacción 4,5-6,0 during liquefaction 4.5-6.0
pH de la suspensión pH of the suspension
durante la sacarificación 4,0-6,0 during saccharification 4.0-6.0
0,4-1 ,5 Kg / Ton 0.4-1.5 Kg / Ton
Concentración de alfa de almidón (base Starch alpha concentration (base
amilasa seca) dried amylase)
Temperatura de Temperature of
licuefacción 55-95 °C liquefaction 55-95 ° C
Temperatura de Temperature of
sacarificación 50-65 °C saccharification 50-65 ° C
E.D. final 40-60 E.D. final 40-60
Ejemplo 2: Aplicación a escala industrial del proceso para producir malto dextrina y jarabe de glucosa, a partir de almidón, por lotes (tipo batch) Este ejemplo es para tres etapas de adición dosificada de almidón y enzima y posterior sacarificación, para alcanzar una concentración del 60% p/p. Ver Figura 1 . Example 2: Application on an industrial scale of the process to produce malt dextrin and glucose syrup, from starch, in batches (batch type) This example is for three stages of dosed addition of starch and enzyme and subsequent saccharification, to reach a concentration of 60% w / w. See Figure 1.
El proceso se inicia con la primera etapa de licuefacción, cargando el reactor (2) con 361 Kg de agua precalentada a 55 °C y, por medio de un tornillo sin fin (1 ), con 238 Kg de almidón (12% de humedad). El reactor (2) tipo batch (CSTR Continuous Stirred Tank Reactor) está interconectado con el sistema de filtración (1 1 ), centrifugación (7), concentración (12) y secado (13). Este reactor permite mantener regímenes de flujo turbulento y se controla la temperatura interna (a través de un serpentín) pasando vapor de caldera (16) o agua de torre de enfriamiento (18). The process begins with the first stage of liquefaction, loading the reactor (2) with 361 Kg of preheated water at 55 ° C and, by means of an endless screw (1), with 238 Kg of starch (12% humidity ). The reactor (2) batch type (CSTR Continuous Stirred Tank Reactor) is interconnected with the filtration system (1 1), centrifugation (7), concentration (12) and drying (13). This reactor allows to maintain turbulent flow regimes and the internal temperature is controlled (through a coil) by passing boiler steam (16) or cooling tower water (18).
Se ajusta el pH de la suspensión entre 4.5 y 6 mediante la adición de HCI o NaOH, inmediatamente se adicionan entre 0,4 y 1 ,5 Kg de enzima amilasa/tonelada de almidón y se eleva la temperatura de la suspensión hasta 95 °C con una rampa de calentamiento de 1 .3 a 1 .8°C/min y agitación constante a 500 rpm, la temperatura de reacción se mantiene constante por 30 min. Para la segunda adición, se enfría la suspensión hasta 55 °C y se adicionan 238 Kg de almidón. Después de homogenizar completamente la suspensión se ajusta el pH entre 4,5 y 6, se adicionan nuevamente entre 0.4 y 1 .5 Kg/tonelada de almidón de enzima -amilasa y se calienta hasta 95 °C. Se mantiene esta temperatura constante durante 30 min para luego volver a enfriar hasta 55 °C. The pH of the suspension is adjusted between 4.5 and 6 by the addition of HCI or NaOH, immediately between 0.4 and 1.5 Kg of enzyme amylase / ton of starch are added and the temperature of the suspension is raised to 95 ° C With a heating ramp of 1 .3 to 1 .8 ° C / min and constant stirring at 500 rpm, the reaction temperature is kept constant for 30 min. For the second addition, the suspension is cooled to 55 ° C and 238 kg of starch are added. After completely homogenizing the suspension, the pH is adjusted between 4.5 and 6, between 0.4 and 1.5 kg / tonne of enzyme starch amylase are added again and heated to 95 ° C. This constant temperature is maintained for 30 min and then cooled again to 55 ° C.
En la tercera adición, se enfría la suspensión hasta 55 °C, se agregan 100 Kg de almidón, se ajusta nuevamente el pH entre 4.5 y 6 y se agregan entre 0.4 y 1 .5 Kg de enzima cc-amilasa/tonelada de almidón , después de homogenizar completamente la suspensión se eleva nuevamente la temperatura a 95 °C y se mantiene constante durante 60 min. El producto de esta etapa, denominado maltodextrina, cuenta con las siguientes características: Equivalente de dextrosa (ED) 20, porcentaje de sólidos disueltos 60 °Brix a 20 °C, porcentaje de glucosa < 1 , densidad 1 .22 g/ml. Este producto, se puede enviar inmediatamente a purificación (7 y/o 1 1 ) o directamente a un concentrador (12) o secador tipo spray (13). In the third addition, the suspension is cooled to 55 ° C, 100 kg of starch are added, the pH is adjusted again between 4.5 and 6, and between 0.4 and 1.5 kg of cc-amylase / tonne starch enzyme are added, After completely homogenizing the suspension, the temperature is raised again to 95 ° C and kept constant for 60 min. The product of this stage, called maltodextrin, has the following characteristics: Dextrose equivalent (ED) 20, percentage of dissolved solids 60 ° Brix at 20 ° C, percentage of glucose <1, density 1.22 g / ml. This product can be sent immediately to purification (7 and / or 1 1) or directly to a concentrator (12) or spray dryer (13).
Para obtener jarabes de glucosa, el producto de la etapa anterior se enfría hasta 60 °C y se transporta a los reactores (3 y/o 4), se ajusta nuevamente el pH a 4.5. y se adiciona entre 0,8 y 1 ,5 Kg de enzima por Ton de sustrato. . La enzima puede ser la glucoamilasa Dextrozyme Supra 2.2X de Novozyme ®. Se mantiene constante la temperatura a 60 °C y agitación de 500 rpm por un periodo de 120 min. El producto obtenido cuenta con las características 60°Brix, ED 50 y porcentaje de glucosa < 50% BS. To obtain glucose syrups, the product from the previous stage is cooled to 60 ° C and transported to the reactors (3 and / or 4), the pH is adjusted again to 4.5. and between 0.8 and 1.5 Kg of enzyme is added per Ton of substrate. . The enzyme can be Dextrozyme Supra 2.2X glucoamylase from Novozyme ®. The temperature is kept constant at 60 ° C and stirring of 500 rpm for a period of 120 min. The product obtained has the characteristics 60 ° Brix, ED 50 and glucose percentage <50% BS.
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR112013017285A BR112013017285A8 (en) | 2011-01-04 | 2012-01-03 | process with a metered addition of raw materials and enzymes for the production of highly concentrated maltodextrins and glucose syrups from starches |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CO11-000459 | 2011-01-04 | ||
| CO11000459A CO6480105A1 (en) | 2011-01-04 | 2011-01-04 | PROCESS WITH DOSED ADDITION OF RAW MATERIAL AND ENZYME FOR THE PRODUCTION OF MALTO DEXTRINES AND GLUCOSE SYRUPES HIGHLY CONCENTRATED FROM ALMIDONES. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012093355A1 true WO2012093355A1 (en) | 2012-07-12 |
Family
ID=46457274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2012/050028 Ceased WO2012093355A1 (en) | 2011-01-04 | 2012-01-03 | Process including the metered addition of raw material and enzyme for the production of highly concentrated glucose syrups and maltodextrins from starches |
Country Status (5)
| Country | Link |
|---|---|
| AR (1) | AR084785A1 (en) |
| BR (1) | BR112013017285A8 (en) |
| CO (1) | CO6480105A1 (en) |
| PE (1) | PE20140393A1 (en) |
| WO (1) | WO2012093355A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220015399A1 (en) * | 2013-02-05 | 2022-01-20 | Oatly Ab | Liquid oat base |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644126A (en) * | 1969-05-26 | 1972-02-22 | Standard Brands Inc | Method of making a starch conversion syrup |
| GB1448786A (en) * | 1974-03-28 | 1976-09-08 | Dds Kroyer As | Method of preparing starch hydrolysates by enzymatic hydrolysis |
| WO1986002096A1 (en) * | 1984-09-28 | 1986-04-10 | A. E. Staley Manufacturing Company | Use of granular starch to remove fat and/or protein from starch hydrolysate syrups |
| US4596776A (en) * | 1984-02-28 | 1986-06-24 | Cpc International Inc. | Process for making starch hydrolyzates and high fructose syrups |
| EP0255124A2 (en) * | 1986-07-29 | 1988-02-03 | Hitachi, Ltd. | Thermostable glucoamylase, a method for production of glucose using same and a plant for production thereof |
| WO2010036515A1 (en) * | 2008-09-25 | 2010-04-01 | Danisco Us Inc. | Alpha-amylase blends and methods for using said blends |
-
2011
- 2011-01-04 CO CO11000459A patent/CO6480105A1/en unknown
-
2012
- 2012-01-03 BR BR112013017285A patent/BR112013017285A8/en not_active IP Right Cessation
- 2012-01-03 PE PE2013001514A patent/PE20140393A1/en not_active Application Discontinuation
- 2012-01-03 WO PCT/IB2012/050028 patent/WO2012093355A1/en not_active Ceased
- 2012-01-04 AR ARP120100026A patent/AR084785A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644126A (en) * | 1969-05-26 | 1972-02-22 | Standard Brands Inc | Method of making a starch conversion syrup |
| GB1448786A (en) * | 1974-03-28 | 1976-09-08 | Dds Kroyer As | Method of preparing starch hydrolysates by enzymatic hydrolysis |
| US4596776A (en) * | 1984-02-28 | 1986-06-24 | Cpc International Inc. | Process for making starch hydrolyzates and high fructose syrups |
| WO1986002096A1 (en) * | 1984-09-28 | 1986-04-10 | A. E. Staley Manufacturing Company | Use of granular starch to remove fat and/or protein from starch hydrolysate syrups |
| EP0255124A2 (en) * | 1986-07-29 | 1988-02-03 | Hitachi, Ltd. | Thermostable glucoamylase, a method for production of glucose using same and a plant for production thereof |
| WO2010036515A1 (en) * | 2008-09-25 | 2010-04-01 | Danisco Us Inc. | Alpha-amylase blends and methods for using said blends |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220015399A1 (en) * | 2013-02-05 | 2022-01-20 | Oatly Ab | Liquid oat base |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112013017285A2 (en) | 2017-06-20 |
| BR112013017285A8 (en) | 2018-07-03 |
| CO6480105A1 (en) | 2012-07-16 |
| AR084785A1 (en) | 2013-06-26 |
| PE20140393A1 (en) | 2014-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Aiyer | Amylases and their applications | |
| EP0688872B1 (en) | Process for preparing starchy products | |
| Azmi et al. | A review on acid and enzymatic hydrolyses of sago starch. | |
| CN1318602C (en) | Method for preparing porous starch through enzyme method in high temperature | |
| EP1435391A1 (en) | A process for hydrolyzing starch without pH adjustment | |
| JP5828589B2 (en) | Industrial production method of branched glucan having cyclic structure | |
| EP1435390B1 (en) | A process for hydrolyzing starch without ph adjustment | |
| CN104204216A (en) | Method for making high maltose syrup | |
| Sadeghi et al. | Evaluation of different parameters effect on maltodextrin production by–amylase Termamyl 2-x | |
| JP2018075010A (en) | Processes for starch liquefaction | |
| CN112553187A (en) | Polymer immobilized xylanase, preparation method and application thereof | |
| US12359235B2 (en) | Method for producing branched dextrin with improved white turbidity | |
| WO2012093355A1 (en) | Process including the metered addition of raw material and enzyme for the production of highly concentrated glucose syrups and maltodextrins from starches | |
| CN110004128A (en) | Compound saccharification enzyme preparation and method for starch saccharification | |
| Liakopoulou‐Kyriakides et al. | Synergistic hydrolysis of crude corn starch by α‐amylases and glucoamylases of various origins | |
| KR101297474B1 (en) | Enzymatic Hydrolysis method of Law Starch Using Direct Pressure Pre-Treatment | |
| RU2758089C2 (en) | Thermally reversible gelatinized starch | |
| US20150366245A1 (en) | Malt extract | |
| RU2630665C2 (en) | Malto se-containing syrup and method of its production | |
| CN110343729A (en) | A kind of preparation method of low DE value glucose syrup | |
| JP2002101896A (en) | Method for producing maltose liquid | |
| CN112979831B (en) | Method for efficiently preparing raw material medicine icodextrin | |
| US20060160189A1 (en) | High-temperature enzyme starch-to-sugar conversion | |
| BG64008B1 (en) | Glucose syrup with specific properties and method for its preparation | |
| Hemmingsen et al. | Enzyme technology in the manufacture of sugars from cereals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12732418 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 001514-2013 Country of ref document: PE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 12732418 Country of ref document: EP Kind code of ref document: A1 |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112013017285 Country of ref document: BR |
|
| ENP | Entry into the national phase |
Ref document number: 112013017285 Country of ref document: BR Kind code of ref document: A2 Effective date: 20130704 |