Process for the Simultaneous Production
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Europäisches Patentamt *EP000983374B1* (19) European Patent Office Office européen des brevets (11) EP 0 983 374 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: C12P 19/24, C12S 3/02, of the grant of the patent: C07H 3/04 23.11.2005 Bulletin 2005/47 // C12P19/12, A23L1/236 (21) Application number: 98922807.7 (86) International application number: PCT/FI1998/000421 (22) Date of filing: 19.05.1998 (87) International publication number: WO 1998/053089 (26.11.1998 Gazette 1998/47) (54) PROCESS FOR THE SIMULTANEOUS PRODUCTION OF ISOMALTULOSE (AND/OR TREHALULOSE) AND BETAINE VERFAHREN ZUR GLEICHZEITIGEN HERSTELLUNG VON ISOMALTULOSE (UND/ODER TREHALULOSE) UND BETAINE PRODEDE DE PRODUCTION SIMULTANEE D’ISOMALTULOSE (ET/OU DE TREHALULOSE) ET DE BETAINE (84) Designated Contracting States: • LINDROOS, Mirja AT BE CH DE DK ES FI FR GB GR IE IT LI NL PT FIN-02400 Kirkkonummi (FI) SE • OJALA, Päivi FIN-02460 Kantvik (FI) (30) Priority: 22.05.1997 FI 972186 • RAVANKO, Vili FIN-02150 Espoo (FI) (43) Date of publication of application: • TYLLI, Matti 08.03.2000 Bulletin 2000/10 FIN-02460 Kantvik (FI) (73) Proprietor: Danisco Sweeteners Oy (74) Representative: Hjelt, Pia Dorrit Helene et al 48210 Kotka (FI) Borenius & Co Oy Ab Tallberginkatu 2 A (72) Inventors: 00180 Helsinki (FI) • HEIKKILÄ, Heikki FIN-02320 Espoo (FI) (56) References cited: • SARKKI, Marja-Leena EP-A- 0 345 511 EP-A- 0 625 578 FIN-02460 Kantvik (FI) DE-A- 3 241 788 Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 0 983 374 B1 Printed by Jouve, 75001 PARIS (FR) EP 0 983 374 B1 Description [0001] The present invention relates to a process for the simultaneous obtaining of converted and non-converted sugar and/or non-sugar products. The invention relates especially to the simultaneous production of isomaltulose and/ 5 or trehalulose, and betaine. [0002] Isomaltulose (or palatinose) is a reducing disaccharide produced from sucrose. Isomaltulose has been pro- posed for use as a sweetener in the food industry and it is a raw material for the production of the sweetener isomalt (palatinit) by hydrogenation. Isomalt is a substantially equimolar mixture of α-D-glucopyranosyl-(1,6)-sorbitol and α-D- glucopyranosyl-(1,1)-mannitol. 10 [0003] Trehalulose is another reducing sugar which may be obtained from sucrose. Hydrogenation of trehalulose yields a mixture of α-D-glucopyranosyl-(1,1)-sorbitol and α-D-glucopyranosyl-(1,1)-mannitol also having a sweet taste. [0004] Various processes for the isomerization or transglucosylation of sucrose to isomaltulose and/or trehalulose have been reported. The isomerization is performed by a transglucosylase enzyme which has been found to exist in microorganisms such as Protaminobacter rubrum, Serratica plymuthica, Erwinia rhapontici, Pseudomonas mesoaci- 15 dophile, etc. The known isomerization techniques include isomerization with viable or dead microorganism cells or with the enzyme in extracted form. The enzyme has been used in both immobilized and free form. [0005] Prior art processes for the production of isomaltulose and/or trehalulose are described, for instance, in pub- lications such as EP 028 900, US 4,386,158, US 4,640,894, DE 1 049 800, EP 1 099, EP 77 971, EP 049 801, EP 200 069, EP 160 253, EP 483 755 and EP 625 578. A discussion on the transglucosylation of sucrose is disclosed in the 20 publication Munir, M. et al. Carbohydrate Res. 164 (1987) 477-485. + - [0006] Betaine is a quaternary ammonium compound having the formula (CH3)3N ·CH2-COO . It is known to accu- mulate in sugar beets and it is generally recovered from beet molasses or vinasse by various techniques such as ion exchange, crystallization, extraction or by chromatography. Betaine is used in animal fodder as well as in pharmaceu- tical and cosmetic applications. 25 [0007] Prior art processes for the recovery of betaine are disclosed, for instance in EP 54 544 and EP 345 511. [0008] Sugar cane juices do not contain betaine but they provide instead significant amounts of invert sugar, which is a mixture of glucose and fructose. The invert sugar may be used as a sweetener as such or, after purification, it may be separated further into glucose and fructose. [0009] Prior art processes for the obtaining of invert sugar from sugar cane are disclosed, for instance, in the publi- 30 cations Saska, M. et al., Int. Sugar Jnl, 1994, Vol. 96, No. 1150, p. 403-410, and Hongisto, H. et al., Desugarization of cane molasses by the Finnsugar chromatographic separation process, Finnish Sugar Co. Ltd., Kantvik, Finland, March 4, 1977, the disclosures of which are hereby incorporated by reference. Said prior art discusses batch or continuous chromatographic desugarisation of sugarcane molasses. The processes allow separate recovery of sucrose and invert sugar. 35 [0010] Further, US Patent 3,214,293 describes the separation of non-sugars from sugars in an aqueous sugar so- lution by a combination of ion exchange and ion exclusion. [0011] GB Patent 1 448 524 discloses a method for separating sugars from the non-sugars of beet or cane molasses by liquid distribution chromatography on cation exchangers. Fractions of sugars and non-sugars, including invert sugar and betaine may be recovered. 40 [0012] EP 625 578 discloses a process for the obtaining of a specific three-component product, i.e. the hydrogenation products of both isomaltulose and trehalulose. [0013] DE 3241788 relates to the production of trehalulose by conversion of thick juice into isomaltulose and treha- lulose. [0014] EP 345 511 discloses a method for the recovery of betaine and sucrose from beet molasses. 45 [0015] None of the prior art processes provide for the recovery of betaine in connection with the production of iso- maltulose. [0016] An object of the present invention is to provide a process for obtaining valuable sugar and non-sugar products from aqueous plant derived solutions. [0017] Another object of the invention is to provide a new process for producing sugar and non-sugar products from 50 molasses. [0018] A special object of the invention is to provide a process which makes it possible to recover betaine as well as isomaltulose and/or trehalulose from aqueous sugar-containing solutions, especially from molasses. [0019] A further object of the invention is to provide a process for obtaining the hydrogenation products of isomaltulose and/or trehalulose. 55 [0020] It has now been discovered that it is possible to convert the sucrose of aqueous sugar beet derived solutions into isomaltulose and/or trehalulose without materially affecting the betaine present in the solution and that the separate target products may be recovered from the resulting liquid in good yields. It has also been discovered that the sugar in molasses may readily be converted into isomaltulose and/or trehalulose and that the produced disaccharide may 2 EP 0 983 374 B1 be effectively recovered while allowing recovery of betaine from said converted molasses. [0021] The present invention is based on the above finding. Accordingly, the present invention provides a process for the simultaneous obtaining of isomaltulose and other sugar and/or non-sugar products, said process comprising the following steps in combination: 5 a) providing an aqueous sugar beet derived solution containing sucrose as well as betaine; b) subjecting said sucrose in said solution to transglucosylation; and c) recovering from said transglucosylated solution isomaltulose and/or trehalulose and non converted betaine by a process including 10 chromatographic recovery of the target products as separate fractions. [0022] When the sugar beet derived solution contains large amounts of sucrose, such as is the case for thin or thick juices the process according to the invention may include a step for crystallizing sucrose from the beet derived solution to provide molasses. Alternatively, all the sucrose in said beet derived solution may be used for conversion into iso- 15 maltulose and/or trehalulose. When the ratio of isomaltulose in said solution is large, it may be preferable to separate at least a portion of the isomaltulose by crystallization prior to the recovery of the other products. [0023] In case the plant derived solution is derived from sugar beets, isomaltulose, trehalulose and betaine are the main target products recovered in step c) of the process. [0024] In another embodiment according to the invention betaine is separated from the solution prior to the trans- 20 glucosylation of the sucrose. [0025] The conversion of sucrose into isomaltulose and/or trehalulose is preferably provided by a transglycosylating enzyme (sucrose-6 glucosyl mutase) found in micro organisms capable of converting sucrose into isomaltulose and/ or trehalulose. The preferred microorganism for the production of isomaltulose is Protaminobacter rubrum (CBS 574.77) but also other converting microorganisms may be used. It is also possible to use any of the prior art types of processes 25 with immobilized or free microbial cells or with the enzyme isolated from the cells. In fact, it is necessary only to have the converting activity of the enzyme, and the way in which this enzyme activity is provided is not critical for the per- formance of the present invention. For instance, enhanced activity may be provided by recombinant techniques. [0026] The sucrose-containing aqueous sugar beet derived solution which forms the raw material for the present process may be a plant juice such as thin or thick juice of a sugar beet mill.