EP0929690B1 - Glucosesirup mit speziellen eigenschaften und verfahren zu seiner herstellung - Google Patents

Glucosesirup mit speziellen eigenschaften und verfahren zu seiner herstellung Download PDF

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Publication number
EP0929690B1
EP0929690B1 EP96931816A EP96931816A EP0929690B1 EP 0929690 B1 EP0929690 B1 EP 0929690B1 EP 96931816 A EP96931816 A EP 96931816A EP 96931816 A EP96931816 A EP 96931816A EP 0929690 B1 EP0929690 B1 EP 0929690B1
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EP
European Patent Office
Prior art keywords
ranges
fraction
glucose syrup
process according
starch
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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.)
Expired - Lifetime
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EP96931816A
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English (en)
French (fr)
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EP0929690A1 (de
Inventor
Alex René Julien Remi VERPLAETSE
Koenraad Frans Paul Ruttens
Frank Robert Gabriel Maria Van Lancker
Alain Michel Pierre Destexhe
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Tate and Lyle Europe NV
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Tate and Lyle Europe NV
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Classifications

    • 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

Definitions

  • the present invention relates to a new process for preparing enzymatically converted glucose syrups which can be used as countertypes for standard acid converted glucose syrups, i.e. glucose syrups with a DE varying between 30 and 50, and to the new syrups which can be thus obtained.
  • the acid process is generally used for syrups in the range of 30-50 DE (Dextrose Equivalent). The acid conversion always yields a product of specific composition because of the random hydrolysis of the starch. Major disadvantages of this process are the high salt content of the syrup, and the special equipment needed to perform the acid conversion reaction.
  • the acid converted glucose syrups are typically used in hard boiled candy. There they reduce the tendency of sucrose to crystallise, they slow down the tendency to shell-graining and they contribute to the body and "mouthfeel" of the confection on consumption. Glusose syrups are also used in toffees, fudge or fondant where they prevent, slow down or control granulation of sucrose. These acid converted glucose syrups represent a market of more than 400.000 ton dry substance Europe-wide.
  • the acid converted glucose syrups used today are furhter purified by extended demineralisation,which results in better colour stability and improved organoleptic properties. These additional purification steps, which are needed to produce refined products, require additional equipment and cause additional operating costs. For this reason, alternatives for acid converted glucose syrups have been developed, based on acid-enzyme and enzyme-enzyme converted syrups. These products are already used in a number of food applications. These syrups are characterised by a DE which is the same as the DE of the acid converted syrups, but they differ considerably in sugar spectrum and rheological properties.
  • table 1 Comparison of state of the art glucose syrups obtained by: acid conversion acid-enzyme conversion enzyme-enzyme conversion DE - value 42 42 42 Sugar Spectrum (weight percentages) dextrose 19 6 2,5 maltose 14 45 56 maltotriose 12 12 16 maltotetraose 10 3 0,7 maltopentaose 8 2 0,4 maltohexaose 7 2 0,7 higher sugars 30 30 23,7
  • syrups having a sugar spectrum which is closer to that of an acid converted syrup, are commercialised. These syrups are obtained by blending acid or enzymatically converted syrups with high maltose and/or 95DE glucose syrup.
  • DE 41 25 969 discloses a process in which a mixture of certain enzymes is used to convert native starch directly into a sirup with high glucose content (DE>80). This type of syrup is very different from the so called acid converted glycose syrups for which the present invention aims at providing a countertype product.
  • DE 30 12 143 discloses a continuous process for the conversion of starch into a glucos syrup by means of a mixture alpha-amylase and amyloglycosydase, also yielding sugar syrups with a DE value above 80.
  • the glucose syrups according to the invention which are obtainable by the process according to the invention, consist of a starch based, enzymatically converted glucose syrups, having a DE value (Dextrose Equivalent) between 30 and 50 and a sugar spectrum in which
  • DE value Dextrose Equivalent
  • the process according to the invention comprises treating a liquified starch substrate by means of an enzyme mixture in a single enzymatic conversion step, whereas said enzyme mixture comprises together a bacterial alpha amylase, a maltogenic amylase and a glucoamylase.
  • the starting substrate for the process according to the invention is a liquified starch, as may for instance be obtained by liquifaction of native starch with a thermostable alpha amylase to a DE of 10-12, deactivation of the thermostable alpha amylase, and cooling of the liquified starch to a temperature of about 60°C.
  • the enzymes used in the enzyme mixture according to the invention are widely available on the market.
  • the preferred glucoamylase, exo-1,4-aplha-D-glucosidase, can in particular be obtained from a selected strain of Aspergillus niger by submerged fermentation.
  • the bacterial alpha amylase is preferably an endo-amylase which hydrolyses 1,4-alpha-glucosidic bonds in gelatinised starch.
  • the alpha amylase can be produced by fermentation of a selected strain of Bacillus subtilis.
  • the preferred maltogenic amylase (EC3.2.1.133) hydrolyses 1,4-alpha-glucosidic linkages in starch, partially hydrolysed starch and low-molecular weight oligosaccharides, including maltotriose. Maltose units are removed in a stepwise manner from the non-reducing chain ends.
  • the enzyme which can come from Bacillus stearothermophilus, can be expressed in and produced by a genetically modified strain of Bacillus subtilis. For industrial applications the recommended operating conditions are 60°C and pH 5,0-5,5.
  • the single enzymatic conversion step - i.e. a saccharification step - applied to the starting substrate in accordance with the invention is preferably performed at a temperature in the range from 55 to 65° C for a period of 10 to 48 hours, at a pH between 4,9 and 5,1; most preferably at a temperature in the range from 60 to 62° C for a period of 18 to 24 hours, at a pH between 4,9 and 5,1.
  • the dry substance content of reaction mixture is preferably between 30 and 40% , more preferably between 32 and 37% , and most preferably between 33 and 35%.
  • the process according to the invention is particularly suitable for preparing the new glucose syrups according to the invention as defined above.
  • the enzyme concentrations and the enzyme ratios during the enzymatic conversion step according to the invention entirely depend on the process conditions applied and on the specific properties of the glucose one wishes to obtain. These concentrations will readily be determined by the skilled art worker on the basis of the data provided by the supplier of the commercial enzymes used in the process and/or by using mathematical calculations on the basis of empirical models, as is already known in the art ("Development and field confirmation of a mathematival model for amyloglucosidase/pullulanase saccharification" by T.R. Swanson et al. - Starch/Staerke (1986), 38 (11), 382-387).
  • An empirical model can be construed based on information obtained from a design set-up of experiments of saccharification tests. By selecting an appropriate model, equations are obtained by which the amount (%w/w) of the different DP fractions in function of the concentrations of the different enzymes and the time can be calculated. The empirical equations are then used to calculate those combinations of enzyme concentrations and reaction time which fit at best the sugar spectrum of the acid converted glucose syrup which has to be countertyped.
  • Native starch was suspended in water at a concentration of 33-35% d.s. and at a slightly acidic pH (3,5-4,0). This slurry was then gelatinised at 160°C. After cooling to 95°C, pH was adjusted to 5,7-5,9 and thermostable alpha amylase was added (0,5-0,6ml comm./kg d.s.). This slurry was then further liquified during 2-3 hours at 90-95°C until a DE of 10-12 was reached. Then the alpha amylase was inactivated by adjusting the pH to 4 while heating the liquefied starch for an additional 5 minutes at 95°C. This substrate was then cooled to 60°C and pH was adjusted to 5,0. To this liquified starch a mixture of enzymes was added composed of a glucoamylase, a maltogenic amylase and a bacterial alpha amylase. The following enzyme quantities were used :
  • Native starch was suspended in water at a concentration of 33-35% d.s. and at a slightly acidic pH (3,5-4,0). This slurry was then gelatinised at 160°C. After cooling to 95°C, pH was adjusted to 5,7-5,9 and thermostable alpha amylase was added (0,5-0,6ml comm/kg d.s.). This slurry was then further liquified during 2-3 hours at 90-95°C until a DE of 10-12 is reached. Then the alpha amylase was inactivated by adjusting the pH to 4 while heating the liquified starch for an additional 5 minutes at 95°C. This substrate was then cooled to 60°C and pH is adjusted to 5,0. To this liquefied starch a mixture of enzymes was added composed of a glucoamylase, a maltogenic amylase and a bacterial alpha amylase. The following enzyme quantities were added :

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Jellies, Jams, And Syrups (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Saccharide Compounds (AREA)

Claims (14)

  1. Enzymatisch umgesetzter Glucosesirup aus Stärke, gekennzeichnet durch einen DE-Wert (Dextrose Equivalent) zwischen 30 und 50 und durch ein Zucker- "Polymerisierungsgrad" (DP)-Spektrum wobei:
    die Fraktion von DP1 - DP3 zwischen 30 und 60% liegt,
    die Fraktion von DP4 - DP6 zwischen 25 und 16% liegt,
    die Fraktion von DP7 - DP9 zwischen 14 und 4% liegt und
    die Fraktion über DP9 zwischen 38 und 18% liegt, auf trockene Substanz bezogen, mit Hilfe des erfindungsgemäßen Verfahrens in Anspruch 4 erhältlich.
  2. Glucosesirup nach Anspruch 1, gekennzeichnet durch einen DE-Wert zwischen 36 und 45 und durch ein Zuckerspektrum in dem:
    die Fraktion von DP1 - DP3 zwischen 38 und 55% liegt,
    die Fraktion von DP4 - DP6 zwischen 24 und 17% liegt,
    die Fraktion von DP7 - DP9 zwischen 13 und 4,5% liegt,
    die Fraktion über DP9 zwischen 32 und 21% liegt auf trockene Substanz bezogen.
  3. Glucosesirup nach Anspruch 1, gekennzeichnet durch einen DE-Wert zwischen 38 und 42 und durch ein Zuckerspektrum in dem:
    die Fraktion von DP1 - DP3 zwischen 40 und 52% liegt,
    die Fraktion von DP4 - DP6 zwischen 24 und 18% liegt,
    die Fraktion von DP7 - DP9 zwischen 13 und 5% liegt,
    die Fraktion über DP9 liegt zwischen 30 und 22% auf trockener Substanz bezogen.
  4. Verfahren zur Herstellung von Glucosesirup durch Behandlung von Stärke mit Enzymen, dadurch gekennzeichnet, dass besagtes Verfahren die Behandlung eines verflüssigten Stärkesubstrats mittels eines Enzymgemisches in einer einzigen enzymatischen Umsetzungsphase umfasst, wobei besagtes Enzymgemisch eine bakterielle Alpha-Amylase, eine maltogene Amylase und eine Glucoamylase zusammen enthält.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass die enzymatische Umsetzungsphase ausgeführt wird bei einer Temperatur im Bereich von 55 bis 65°C, während einer Periode von 10 bis 48 Stunden, bei einem pH-Wert zwischen 4,9 und 5,1.
  6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass die enzymatische Umsetzungsphase ausgeführt wird bei einer Temperatur im Bereich von 60 bis 62°C liegt, während einer Periode von 18 bis 24 Stunden, bei einem pH-Wert zwischen 4,9 und 5,1.
  7. Verfahren nach den Ansprüchen 4 bis 6, dadurch gekennzeichnet, dass während der enzymatischen Umsetzungsphase, der Gehalt der trockenen Substanz des Reaktionsgemisches zwischen 30 und 40%, auf trockene Substanz bezogen, liegt.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass während der enzymatischen Umsetzungsphase, der Gehalt der trockenen Substanz des Reaktionsgemisches zwischen 32 und 37%, auf trockene Substanz bezogen, liegt.
  9. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass während der enzymatischen Umsetzungsphase, der Gehalt der trockenen Substanz des Reaktionsgemisches zwischen 33 und 35%, auf trockene Substanz bezogen, liegt.
  10. Verfahren nach den Ansprüchen 4 bis 9, dadurch gekennzeichnet, dass das verflüssigte Stärkesubstrat einen DE-Wert von 10 - 12 hat.
  11. Verfahren nach den Ansprüchen 4 bis 10 dadurch gekennzeichnet, dass das verflüssigte Stärkesubstrat von einer Vorbehandlung der Naturstärke mit wärmebeständiger Alpha-Amylase, von einer Inaktivierung der wärmebeständigen Alpha-Amylase gefolgt, herrührt.
  12. Verfahren nach den Ansprüchen 4 bis 11 zur Herstellung eines Glucosesirups, gekennzeichnet durch einen DE-Wert zwischen 30 und 50 und ein Zuckerspektrum in dem:
    die Fraktion von DP1 - DP3 zwischen 30 und 60% liegt,
    die Fraktion von DP4 - DP6 zwischen 25 und 16% liegt,
    die Fraktion von DP7 - DP9 zwischen 14 und 4% liegt und
    die Fraktion über DP9 zwischen 38 und 18% liegt, auf trockene Substanz bezogen.
  13. Verfahren nach den Ansprüchen 4 bis 12 zur Herstellung eines Glucosesirups, gekennzeichnet durch einen DE-Wert zwischen 36 und 45 und durch ein Zuckerspektrum in dem:
    die Fraktion von DP1 - DP3 zwischen 38 und 55% liegt,
    die Fraktion von DP4 - DP6 zwischen 24 und 17% liegt,
    die Fraktion von DP7 - DP9 zwischen 13 und 4,5% liegt,
    die Fraktion über DP9 zwischen 32 und 21% liegt auf trockene Substanz bezogen,
  14. Verfahren nach den Ansprüchen 4 bis 13 zur Herstellung eines Glucosesirups, gekennzeichnet durch einen DE-Wert zwischen 38 und 42 und durch ein Zuckerspektrum in dem:
    die Fraktion von DP1 - DP3 zwischen 40 und 52% liegt,
    die Fraktion von DP4 - DP6 zwischen 24 und 18% liegt,
    die Fraktion von DP7 - DP9 zwischen 13 und 5% liegt,
    die Fraktion über DP9 liegt zwischen 30 und 22% auf trockene Substanz bezogen.
EP96931816A 1996-09-17 1996-09-17 Glucosesirup mit speziellen eigenschaften und verfahren zu seiner herstellung Expired - Lifetime EP0929690B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP1996/004088 WO1998012342A1 (en) 1996-09-17 1996-09-17 Glucose syrup having specific properties and process for obtaining the same

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EP0929690A1 EP0929690A1 (de) 1999-07-21
EP0929690B1 true EP0929690B1 (de) 2001-12-12

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EP (1) EP0929690B1 (de)
AT (1) ATE210730T1 (de)
AU (1) AU7085796A (de)
BG (1) BG64008B1 (de)
DE (1) DE69618025T2 (de)
ES (1) ES2169263T3 (de)
WO (1) WO1998012342A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021257921A1 (en) * 2020-06-18 2021-12-23 Archer Daniels Midland Company Maltodextrin syrup having a de less than 20 while having properties like a corn syrup of de 30-45

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010041617A (ko) * 1998-03-09 2001-05-25 피아 스타르 전분으로부터 글루코스 시럽의 효소성 제조
CA2906984A1 (en) 2013-03-15 2014-09-18 Cargill, Incorporated Carbohydrate compositions
US11064716B2 (en) 2015-04-17 2021-07-20 Societe Des Produits Nestie S.A. Composition for coating frozen confectionery and a process for manufacturing same
CN117660704A (zh) * 2023-11-10 2024-03-08 肇庆焕发生物科技有限公司 一种可食用玩具专用的葡萄糖浆及其制备方法

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ZA801803B (en) * 1979-04-02 1981-03-25 Apv Co Ltd Starch hydrolysis
DE4125969A1 (de) * 1991-08-06 1993-02-11 Ceresan Gmbh Markranstaedt Verfahren zur herstellung eines glucosereichen staerkehydrolysates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WEBB E.C.: "Enzyme nomenclature, p. 346 and 365", 1992, ACADEMIC PRESS INC., SAN DIEGO, CALIFORNIA/USA *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021257921A1 (en) * 2020-06-18 2021-12-23 Archer Daniels Midland Company Maltodextrin syrup having a de less than 20 while having properties like a corn syrup of de 30-45

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BG64008B1 (bg) 2003-09-30
ES2169263T3 (es) 2002-07-01
AU7085796A (en) 1998-05-11
EP0929690A1 (de) 1999-07-21
DE69618025D1 (de) 2002-01-24
BG103254A (en) 2000-05-31
WO1998012342A1 (en) 1998-03-26
ATE210730T1 (de) 2001-12-15
DE69618025T2 (de) 2002-06-20

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