[go: up one dir, main page]

WO1997023511A2 - Procede de preparation d'inuline purifiee - Google Patents

Procede de preparation d'inuline purifiee Download PDF

Info

Publication number
WO1997023511A2
WO1997023511A2 PCT/NL1996/000494 NL9600494W WO9723511A2 WO 1997023511 A2 WO1997023511 A2 WO 1997023511A2 NL 9600494 W NL9600494 W NL 9600494W WO 9723511 A2 WO9723511 A2 WO 9723511A2
Authority
WO
WIPO (PCT)
Prior art keywords
inulin
hydrolysis
process according
less
sucrose
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
Application number
PCT/NL1996/000494
Other languages
English (en)
Other versions
WO1997023511A3 (fr
Inventor
Marinella Bettine Van Leeuwen
Theodoor Maximiliaan Slaghek
Dirk De Wit
Hendrika Cornelia Kuzee
Henricus Wilhelmus Carolina Raaymakers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cooperatie Cosun UA
Original Assignee
Cooperatie Cosun UA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cooperatie Cosun UA filed Critical Cooperatie Cosun UA
Priority to AU11538/97A priority Critical patent/AU1153897A/en
Publication of WO1997023511A2 publication Critical patent/WO1997023511A2/fr
Publication of WO1997023511A3 publication Critical patent/WO1997023511A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0051—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Fructofuranans, e.g. beta-2,6-D-fructofuranan, i.e. levan; Derivatives thereof
    • C08B37/0054—Inulin, i.e. beta-2,1-D-fructofuranan; Derivatives thereof

Definitions

  • the invention relates to a process for the preparation of oligosaccharides, in particular inulin, which are virtually free from mono- and disaccharides.
  • the invention also relates to a purified oligosaccharide obtained in this way.
  • Inulin is a completely or predominantly linear poly saccharide which is made up of 2,1- ⁇ -linked anhydrofructose units (fructan), usually with a terminal glucose unit and an occasional ⁇ -2,6 side chain. It is obtained, for example, from Jerusalem artichokes, artichokes, chicory, dahlias and dandelions. Inulin and other fructans can also be obtained by enzymatic synthesis.
  • Inulin can be represented by the formula GF n _ j , where n is the degree of polymerisation (DP), G is glucose or an anhydroglucose unit in a polysaccharide and F is fructose or an anhydrofructose unit in a polysaccharide.
  • Inulin has a wide variety of applications, both in the food industry, for example as nutrient fibre, a fat substitute or a thickener.
  • Inulin is also being used to an ever increasing extent in other sectors, such as the detergents industry and the paper industry, for which purposes the inulin is then frequently modified, for example by oxidation.
  • the inulin is free from the mono- and disaccharides glucose, fructose and sucrose.
  • these small sugars which are derived from inulin, have properties which deviate substantially from those of the longer chain inulin analogues, such as digestibility with a high calorific value, sweetening power, low water-binding capacity and the like.
  • these mono- and disaccharides are inevitably present in naturally occurring inulin and the direct derivatives thereof and specifically are present in quantities of a few percent up to 20 %.
  • EP-A 440074 discloses a method for the preparation of inulin oligosaccharides which are low in glucose, fructose and sucrose. According to this known process, inulin is treated with an endo-inulinase at pH 5.4 and then with an ⁇ -glucosidase, after which glucose and fructose formed are removed by column chromatography. The disadvantage of this method is that extensiv e chain degradation of inulin takes place: more than 50
  • % of the product is made up of tri-, tetra- and pentasaccharides. Moreover, the product also contains 3-4 % of fructosylfructosc (FF) and up to 2 % of glucose and fructose.
  • FF fructosylfructosc
  • This method is therefore unsuitable for the preparation of inulin which has been selectively depleted in glucose, fructose and sucrose, and optionally kestose and nystose.
  • EP-A 627490 describes a similar process in which inulin is treated with an inulinase or other hydrolase and the large amounts of fructose and other hydrolysis products formed as a result of this treatment arc separated off chro atographically.
  • an inulin product which has an av erage chain length of 12 or more.
  • This method has the same fundamental drawback as the known method mentioned above, namely that the enzymatic hydrolysis makes no distinction in substrate: the long chains are broken down (not desirable) to the same extent as the short chains (desirable). The yield of long-chain inulin is therefore also low (less than 45 %).
  • Other disadvantages are that the reaction is slow (24 hours at 50-60 °C) and that during the chromatographic separation large quantities of di- and trisaccharides and the like have to be separated off - in addition to fructose and glucose.
  • WO 94/12541 describes a process for separating inulin by chromatography of a prctreatcd inulin solution of pH 5.4 hav ing a conductivity of 150 ⁇ S on a styrene- divinylbcnzene column in the potassium form.
  • the raffinate is obtained in a 75% dry matter yield.
  • mono- and disaccharides arc removed rather effectively, the separation of higher homologues is poor: for example kestose (GF 2 ) is reduced form 3.8 to 2.3 % only, and nystose is indifferent (from 4.6 to 4.8 %).
  • GF 2 kestose
  • nystose is indifferent (from 4.6 to 4.8 %).
  • a part of the valuable penta- and higher saccharides is lost during the separation.
  • the method according to US Patent 4,613,377 is aimed at producing fructo- oligosaccharides with fructosylfructosc (F 2 ) as major component by passing an acidic inulin solution through a strong acid cation exchange column (e.g. styrene-divinyl- benzene) followed by acid hydrolysis (pH 2-2.5) at 70-100°C, decolouring, anion exchange chromatography and further purification.
  • a strong acid cation exchange column e.g. styrene-divinyl- benzene
  • acid hydrolysis pH 2-2.5
  • the commonest method for the removal of monosaccharides, disaccharides and optionally higher oligomers from inulin is column chromatographic separation.
  • Glucose and fructose can be removed by this means without too many problems, but the separation of sucrose is at best incomplete or associated with a significant loss of valuable inulin components. Furthermore, the column chromatographic separation of sucrose is time-consuming and this method demands sizeable apparatus in comparison with the quantities processed. No methods whatsoever are known for separating off kestose and nystose.
  • the aim of the invention is, therefore, to provide a process with which oligo- saccharides, in particular inulin, can effectively be rendered free from glucose, fructose and sucrose, and, where appropriate, from kestose and nystose, within a short time and at acceptable costs.
  • oligosaccharides can be selectively hydrolysed by the use of heterogeneous catalysis, derivatives with short chains, including, in any event, disaccharides, but, depending on the heterogeneous system to be used, optionally also higher homologues, such as trisaccharides and tctrasaccharidcs, being selectively hydro ⁇ lysed to monosaccharides, and the higher oligomers, for example pentasaccharides (DP 5) and above, not being hydrolysed or hardly being hydrolysed.
  • heterogeneous catalysis derivatives with short chains, including, in any event, disaccharides, but, depending on the heterogeneous system to be used, optionally also higher homologues, such as trisaccharides and tctrasaccharidcs, being selectively hydro ⁇ lysed to monosaccharides, and the higher oligomers, for example pentasaccharides (DP 5) and above, not being hydrolysed or hardly being hydrolysed
  • an oligosaccharide is understood to be a mixture of saccharides consisting of repeating units with increasing chain length (degree of polymerisation), having an average chain length of 5 monosaccharide units or longer, in particular having an average chain length of 7-30.
  • the oligosaccharides may be straight or branched.
  • Preferred oligosaccharides arc fructans and modified fructans, such as partially, optionally enzymatically, pre-hydrolysed or partially reduced or oxidised fructans and enzymatically synthesised fructo-oligosaccharidcs.
  • Fructans comprise levan and in particular inulin. The invention is described in more detail below with inulin as the oligosaccharide, but other oligosaccharides can be treated in the same way.
  • Solid catalysts can be used for the hctcrogeneously catalysed hydrolysis.
  • Said solid catalysts are preferably insoluble in water.
  • Possible catalysts are both inorganic catalysts (zeolites, clay minerals and the like) and organic catalysts.
  • organic resins such as phenol derivatives cross-linked with formaldehyde and cross-linked polystyrenes or polystyrene copolymers, for example with acrylonitrile.
  • the solid catalysts have acid groups which effect the hydrolysis.
  • the resins are preferably of the strongly acid type. Sulphonated polystyrenes cross-linked with divinylbenzene, which are available commercially, are the most preferred.
  • the degree of cross-linking can be, for example, 2-14 %. said percentage being expressed as the percentage of divinylbenzene relative to polystyrene. It has been found that the best combination of selectivity and effectiveness is obtained with an acid resin which is 3-10 %, in particular 4-8 %, cross-linked.
  • the hcterogeneously catalysed hydrolysis can be carried out either batchwise or continuously.
  • Continuous hydrolysis can, for example, take place in a column which is filled with the acid resin and through which a solution of inulin in water is passed.
  • a continuous hydrolysis can also advantageously be coupled with a continuous removal of glucose and fructose by column chromatography, for example by connecting two or more columns in series.
  • the hydrolysis can be carried out at a temperature of 0-90 °C, preferably at an elevated temperature such as 30-60 °C, preferably at a neutral pH of between 5.5 and 8.0, more preferably 6-8.
  • the inulin is preferably dissolved or dispersed in water of low ionic strength, preferably having a conductivity of less than 60 ⁇ S, especially less than 40 ⁇ S.
  • inulin which contains less than 1 % by weight of the sum of glucose, fructose, fructosylfructose and sucrose, less than 1 % by weight of kestose (GF 2 ), at least 3 wt.% of the sum of pentasaccharide (GF 4 ) and hexasaccharidc (GF ) and at least 75 wt.% of higher homologues (GF ⁇ , n ⁇ 7).
  • the total amount of monosaccharides (G and F) is less than 0.1 %.
  • inulin which contains appreciably less glucose, fructose, fructosylfructose and sucrose, the sum of said four sugars being, for example, less than 0.5 % by weight, or even less than 0.1 % by weight. It is also possible substantially to remove trisaccharides (kestose, GF ⁇ and, where appropriate, tetrasaccharides (nystosc, GF 3 ).
  • the total amount of kestose and nystose is preferably less than 2 wt.%, the individual levels being for example less than 0.5 wt.% kestose and, where appropriate, less than 1 wt.% nystose.
  • an acid catalyst is preferably chosen which has a degree of cross-linking which is not too high, for example of 3-8 % or even 3-6 %. If it is desired to remove sucrose alone, with some of the kestose, a catalyst with a higher degree of cross-linking, for example of 6-10 %, will be used.
  • the sum of GF 4 and GF 5 is at least 4 wt.%, GF 4 especially accounting for at least 1.5 wt.% and GF 5 for at least 3 wt.%.
  • the higher homologues (GF n _-, , n ⁇ 7) preferably comprise at least 80 wt.% of the total amount of oligosaccharides.
  • the mixture may also contain oligosaccharides of the type F n , wherein n ⁇ 2, especially ⁇ 3, although they arc advantageously only a minor components (e.g. ⁇ 20%).
  • This chain length dispersion applies primarily to inulin fractions (GF n _ j ), but also to other oligosaccharides such as other fructans, glucans, glucomannans, galacto- mannans and the like.
  • inulin 100 g inulin (Frutafit®, average chain length DP 6-10, 2-3 % fructose, 1-2 % glucose, 5-7 % sucrose, 3-4 % kestose, 3-4 % nystosc) were dissolved in 400 ml water (pH 6-8), to which 1,200 ml acid catalyst (polystyrene-divinylbenzene, PSDVB) with a degree of cross-linking of 6 % (Bayer catalyst MDS 1368) had been added.
  • the heterogeneous mixture was stirred at 40 °C. Samples were taken at set times, which samples were filtered and examined by column chromatography with the aid of a Dionex HPLC system.
  • Example I was repeated, except that an 8 % cross-linked PSDVB resin (Bayer catalyst K 1431) was used. After 60 minutes the sucrose and kestose concentrations had decreased to 2-3 % and 1 %, respectively. After 120 minutes the signals for sucrose and kestose had virtually disappeared. The nystosc concentration had also decreased
  • Example II is repeated with the same resin, but at 50 and 60 °C instead of 40°C, the hydrolysis then proceeds approximately twice as fast in each case, but, incidentally, the composition found is virtually the same.
  • Example HI is repeated with the same resin, but at 50 and 60 °C instead of 40°C, the hydrolysis then proceeds approximately twice as fast in each case, but, incidentally, the composition found is virtually the same.
  • Example I was repeated, except that a 2 % cross-linked PSDVB resin (Bayer catalyst K 1131) and a 4 % cross-linked resin (Bayer catalyst K 1221) were used.
  • the weight ratio between DP 2 (sucrose), DP 5, DP 10 and DP 15 during the hydrolysis is shown in Figure la (K 1131) and in Figure lb (K 1221) and the weight ratio between DP 2 (sucrose), DP 3, DP 4 and DP 5 during the hydrolysis is shown in Figure 2a and Figure 2b, respectively.
  • the resin with 2 % cross-linking is found to be less selective.
  • Example IV 150 g inulin (Frutafit 1 ⁇ was added to a suspension of 2,500 ml acid Bayer catalyst K 1431 (degree of cross-linking 8 %) in 600 ml water, after which the suspension was stirred for 1 hour at 50 °C.
  • the fluid fraction was collected by means of filtration and neutralised with 5-10 ml 0.1 N NaOH or using a "mixed bed” column consisting of a weakly basic catalyst and a weakly acid catalyst.
  • the fluid fraction contained 15-17 % dry inulin. It can be deduced from the Dionex analysis that the quantities of sucrose and kestose have decreased appreciably (see Figure 3b) compared to the starting material ( Figure 3a). The quantity of nystose has also fallen.
  • the solution obtained from the hydrolysis was then passed through a Bayer column K 1221 in the sodium form, glucose and fructose being separated off virtually quantitatively (see Figure 3c).
  • the weight percentages (and mole percentages) of the lower components were found to be as follows: G and F together 0.01 (0.08), GF 0.1 (0.5), GF 2 0.1 (0.4), GF 3 0.7 (2.3), GF 4 1.8 (4.8), GF 5 3.0 (6.7), GF s6 (DP ⁇ 7) > 85 (> 75).
  • Comparative example Example IV was repeated with the same resin, except that it was in its Na + fa form.
  • the Dionex analysis shows that little, if any, hydrolysis has occurred (sec
  • Figure 1 shows the weight ratio between sucrose (S), DP 5, DP 10 and DP 15 of the hydrolysate of 2% (la), 4% (lb), 6% (lc) and 8% (Id), respectively, crosslinked resin in the H + form (Examples I-III).
  • Figure 2 shows the weight ratio between sucrose (S), DP 3, DP 4 and DP 5 of the hydrolysate of 2% (2a), 4% (2b), 6% (2c) and 8% (2d), respectively, crosslinked resin in the H + form (Examples I-III).
  • Figure 3 shows the Dionex chromatogram of an inulin solution before treatment
  • figure 3d shows the Dionex chromatogram of an inulin solution after treatment on a 8% crosslinked Na + resin (comparative example).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

La présente invention concerne un procédé de préparation d'oligosaccharides, en particulier l'inuline, qui sont pratiquement exempts de monosaccharides et disaccharides tels que le glucose, le fructose et le sucrose. L'oligosaccharide est soumis à une hydrolyse en présence d'un catalyseur acide solide, en particulier une résine de polystyrène réticulée et fortement acide, puis cet oligosaccharide est séparé des monosaccharides (glucose et fructose) par chromatographie sur colonne.
PCT/NL1996/000494 1995-12-21 1996-12-20 Procede de preparation d'inuline purifiee Ceased WO1997023511A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU11538/97A AU1153897A (en) 1995-12-21 1996-12-20 Process for the preparation of purified inulin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1001956 1995-12-21
NL1001956A NL1001956C2 (nl) 1995-12-21 1995-12-21 Werkwijze voor het bereiden van gezuiverd inuline.

Publications (2)

Publication Number Publication Date
WO1997023511A2 true WO1997023511A2 (fr) 1997-07-03
WO1997023511A3 WO1997023511A3 (fr) 1997-08-28

Family

ID=19762068

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1996/000494 Ceased WO1997023511A2 (fr) 1995-12-21 1996-12-20 Procede de preparation d'inuline purifiee

Country Status (3)

Country Link
AU (1) AU1153897A (fr)
NL (1) NL1001956C2 (fr)
WO (1) WO1997023511A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998005793A1 (fr) * 1996-08-01 1998-02-12 Raffinerie Tirlemontoise Procede de preparation d'une composition polydispersee de saccharides et composition polydispersee de saccharides obtenue
WO2013142864A1 (fr) * 2012-03-23 2013-09-26 Ciranda, Inc. Aliment à base d'agave modifiée et son procédé de fabrication
US11291222B2 (en) 2013-03-15 2022-04-05 Cargill, Incorporated Carbohydrate compositions

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1246556A (fr) * 1984-07-24 1988-12-13 Hiroshi Yamazaki Production du sirop de fructose
JP2822566B2 (ja) * 1990-03-30 1998-11-11 味の素株式会社 フラクタン組成物の製造法
BE1006377A3 (fr) * 1992-11-24 1994-08-09 Raffinerie Tirlemontoise Sa Procede de separation d'une composition polydispersee de saccharides, produits obtenus par ce procede et utilisation des produits obtenus dans des compositions alimentaires.
FR2727980A1 (fr) * 1994-12-07 1996-06-14 Agrichimie Sa Procede de fabrication d'une solution pure de sucres simples par hydrolyse d'au moins un sucre compose en presence d'un adsorbant selectif

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998005793A1 (fr) * 1996-08-01 1998-02-12 Raffinerie Tirlemontoise Procede de preparation d'une composition polydispersee de saccharides et composition polydispersee de saccharides obtenue
US7084131B2 (en) 1996-08-01 2006-08-01 Raffinerie Tirlemontoise S.A. Method for preparing a polydispersed saccharide composition and resulting polydispersed saccharide composition
WO2013142864A1 (fr) * 2012-03-23 2013-09-26 Ciranda, Inc. Aliment à base d'agave modifiée et son procédé de fabrication
US11291222B2 (en) 2013-03-15 2022-04-05 Cargill, Incorporated Carbohydrate compositions

Also Published As

Publication number Publication date
WO1997023511A3 (fr) 1997-08-28
AU1153897A (en) 1997-07-17
NL1001956C2 (nl) 1997-06-24

Similar Documents

Publication Publication Date Title
US5478732A (en) Process for the preparation of long-chain inulin with inulinase
Churms Recent progress in carbohydrate separation by high-performance liquid chromatography based on hydrophilic interaction
Verraest et al. Carboxymethylation of inulin
US4418144A (en) Process for producing gamma-cyclodextrins
FI113453B (fi) Kasvimateriaalin kromatografinen fraktiointi
PH27202A (en) Polydextrose compositions
JP4831420B2 (ja) 糖の分離
Kolender et al. Sulfated polysaccharides from the red seaweed Georgiella confluens
Knutsen et al. A rapid method for the separation and analysis of carrageenan oligosaccharides released by iota-and kappa-carrageenase
JPH0347832B2 (fr)
WO1997023511A2 (fr) Procede de preparation d'inuline purifiee
Pazur et al. Determination of the sugar-sequences and the glycosidic-bond arrangements of immunogenic heteroglycans
Ben-bassat et al. Review high performance liquid chromatography of mono-and oligosaccharides
Mendonça-Previato et al. Investigations on polysaccharide components of cells of Herpetomonas samuelpessoai grown on various media
JP4588205B2 (ja) キチンオリゴ糖製造方法
Hayashi Study on the Degradation of Glycosaminoglycans by Canine Liver Lysosomal Enzymes: I. The Mode of Contribution of Hyaluronidase, β-Glucuronidase, and β-N-Acetylhexosaminidase on Hyaluronic Acid
EP3615213B1 (fr) Traitement de solutions de sucres
Yamaguchi et al. Effects of hexametaphosphate on soybean pectic polysaccharide extraction
US5194094A (en) Fractionating starch hydrolysates
Osman et al. The structure of the acidic exopolysaccharide of Pseudomonas marginalis strains PF-05-2 and PM-LB-1
Churms High performance hydrophilic interaction chromatography of carbohydrates with polar sorbents
JPS60181102A (ja) 新規な合成のホモ及びヘテロポリサツカライド及びその製造法
Andersson et al. Structural studies of the extracellular polysaccharide produced by Butyrivibrio fibrisolvens strain H10b
Capek et al. An acidic heteropolysaccharide from the flowers of Malva mauritiana L.
Rozie et al. Crosslinked xylan as an affinity adsorbent for endo-xylanases

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI

AK Designated states

Kind code of ref document: A3

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97523526

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase