• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    sweeteners and process for their production. The present invention relates to a sweetener as well as a process for its production.
    公开号:BR112012015490B1
    申请号:R112012015490-7
    申请日:2010-12-15
    公开日:2019-09-24
    发明作者:Olivier Zehnacker；Thomas Tacke；Thomas Haas；Nicole Brausch；Marc Becker
    申请人:Evonik Degussa Gmbh；
    IPC主号:
    专利说明:

    Field of Invention [001] The object of the invention is a sweetener, as well as a process for its production.
    State of the Art [002] Isomalt (also isomaltite, isomaltitol, Palatinit®) is a sugar substitute, which is obtained from sucrose. Its production is carried out in a two-step process: initially sucrose is converted through rearrangement to isomaltulose (Q-D-glycopyranosyl-1,6fructose, also Palatinose®). The purified isomaltulose is then reacted by catalytic hydrogenation to isomalt.
    [003] Within the hydrogenation of isomaltulose, two isomers are formed, QD-glycopyranosyl-1,1-D-mannitol (hereinafter referred to as 1,1-GPM) and QD-glycopyranosyl-1,6-D- sorbitol (hereinafter referred to as 1,6-GPS), of which isomalt essentially consists.
    [004] The isomerization of sucrose in isomaltulose is usually carried out enzymatically with isomaltulose synthases (sucrose glycosylmutases, EC 5.4.99.11).
    [005] DE1049800, DE 2217628, EP 28900, EP 49472 and EP 91063 describe processes with immobilized bacterial cells for the enzymatic transformation of sucrose into isomaltulose. EP 0625578 employs strains of bacteria from the group Protaminobacter rubrum (CBS 574.77), Serratia plymuthica (ATCC 15928), Serratia marcescens (NCIB 8285), Leuconostoc mesenteroides (NRRL-B 512 F (ATCC 1083 a)) for this purpose and Erwinia rhapontici (NCPPB 1578). EP 0392556 and EP 1257638 describe the use of strains of bacteria from the group of Klebsiella terrigena JCM 1687, Klebsiella sp.
    Petition 870190007277, of 23/01/2019, p. 6/28
    2/15
    No. 88 (FERM BP-2838) and Klebsiella singaporensis LX3 and LX21.
    [006] These isomerization processes are carried out with either live or dead cells, with immobilized or free cells: thus, DE3133123 and EP0915986 describe, for example, processes of immobilization of enzyme catalysts with calcium alginate or ion exchangers, as well as EP0001099 a process with free, living cells, which can produce isomaltulose in the context of a fermentation.
    [007] It is common for all known processes for isomerization, that sucrose is never fully reacted, therefore, it always remains detectable in traces and for the other processing of isomaltulose into isomalt, it is necessary to separate the non-isomerized sucrose.
    [008] As a rule, isomaltulose is usually crystallized to separate non-isomerized sucrose. Such processes are described, for example, in EP0091063 and EP1550666.
    [009] EP0625578 describes a process, in which the removal of non-isomerized sucrose is obtained through an additional dissociation in the corresponding fructose and glucose monosaccharides and their separation.
    [0010] Hydrogenation of isomaltulose is generally known and, for example, in GB1429334, DE2520173 and EP0625578 processes are described, which use Raney nickel as catalysts with high pressures and temperatures.
    [0011] Furthermore, in EP152779 and DE-A 4416115 are known processes for the continuous hydrogenation of isomaltulose which employ moldings support elements free of the 8th subgroup of the periodic system or molded bodies subgroup elements of the support free iron eighth subgroup of the periodic system of the elements 6 with the subgroup as catalyst. EP0854148 des
    Petition 870190007277, of 23/01/2019, p. 7/28
    3/15 describes a process for hydrogenation of isomaltulose in a catalyst containing nickel, nickel oxide and wolframium oxide.
    [0012] EP0838468 describes a process for the hydrogenation of isomaltulose in free-supported molded bodies that serve as hydrogenation catalysts containing alloys of elements of the iron subgroup of the VIII subgroup of the periodic system with elements of the IV and / or V subgroup of the system periodical.
    [0013] DE19523008 describes a process for hydrogenation of isomaltulose, to obtain certain proportions from 1,1-GPM to 1,6-GPS using a ruthenium, nickel catalyst and mixtures in an inert support. DE19523008 describes a process for the hydrogenation of isomaltulose in a catalyst containing ruthenium and / or nickel in an inert support for the control of the proportion of isomers.
    [0014] Since in the enzymatic reaction of sucrose as a by-product, trehalulose (aD-glucopyranosyl-1,1fructose) is frequently formed, as well as fructose and glucose, which, depending on the purification carried out after the isomerization step, can lead to the hydrogenation reaction . Trehalulose is reacted there to a-D-glycopyranosyl-1,1-Dmanitol and a-D-glycopyranosyl-1,1-D-sorbitol (hereinafter referred to as 1,1-GPS), as well as fructose and glucose for sorbitol and mannitol. In this way, isomalt can sometimes contain, in addition to the essential components 1,1-GPM and 1,6-GPS, also 1,1-GPS, mannitol and sorbitol.
    [0015] Such isomalt and processes for its production are described, for example, in JP-A 751079 and EP0625578.
    [0016] One of the main disadvantages of all known processes for the production of dietary sweeteners based on sucrose, such as isomalt, is the need to separate residual sucrose with strong glycemic action after enzymatic isomerization of the
    Petition 870190007277, of 23/01/2019, p. 8/28
    4/15 starting sugar. EP0625578 describes that residual sucrose remaining, therefore, explicitly referring to it as non-hydrogenable.
    [0017] In the separation of residual sucrose by means of the processes described above, losses of isomaltulose or other valuable products must occur.
    [0018] The objective of the present invention is to provide a sucrose-based sweetener, the production of which separates the residual sucrose from the isomerization step and which has excellent properties for further processing, such as, for example, formulation capacity in sweeteners. Description of the Invention [0019] It was surprisingly found that the sweetener described in claim 1, as well as the process described below for its production, contributes to the resolution of the objective mentioned initially.
    [0020] Therefore, the object of the present invention is a sucrose-based sweetener as a starting substance. Another objective of the invention is a catalytic process, which allows the simultaneous hydrogenation of isomaltulose and optionally trehalulose in isomalt and sucrose in sorbitol and mannitol.
    [0021] An advantage of the sweetener according to the invention is that compared to conventional isomalt and in relation to 1,1-GPM, it is enriched with 1,6-GPS, which has an intense sweetening strength and good dissolving power in water; this is also the advantage of the process according to the invention, since it directly makes such a sweetener available as a product.
    [0022] An advantage of the process according to the invention is that, in addition, it can be carried out at relatively low temperatures and pressures and, thus, saves energy and resources.
    Petition 870190007277, of 23/01/2019, p. 9/28
    5/15 [0023] The term residual sucrose in the context of the present invention means sucrose content, which was not reacted in the reaction of sucrose initially used with sucrose mutase and is present as sucrose, in addition to isomerized sucrose, for example, for isomaltulose or trehalulose.
    [0024] By the term sweetener in the context with the present invention is meant a mixture of compounds, which can be present in liquid or solid, crystalline or dissolved form, optionally can contain water and have a sweet taste.
    [0025] By the term acid support in the context of the present invention, the person skilled in the art designates an ordinary vehicle as an acidic vehicle, such as, for example, metal oxides, such as Al2Ü3, SiO2, TeÜ2 or mixed oxides thereof, which due to its intrinsic properties it has an acidity, but also such a vehicle, which only through proper treatment has acidic functionalities on the surface; in this case, it may be, for example, carrier materials, which are treated with acids, such as, for example, phosphoric acid or vehicles, in which only through the application of the active component ruthenium, for example, as chloride ruthenium in acidic solution an acidic functionality is introduced; such an acid support is, for example, an activated carbon impregnated with ruthenium chloride in acidic solution.
    [0026] All percentages (%) indicated are, when not stated otherwise, percent by mass.
    [0027] A contribution to the resolution of the objectives mentioned above is provided by a sweetener containing, preferably consisting of 20% by weight, 75% by weight, preferably 40% by weight to 60% by weight, particularly preferably , 45% by weight to 57% by weight, of aD-glycopyranosyl-1,6-D-sorbitol, [0028] 20% by weight to 75% by weight, preferably 40%, in
    Petition 870190007277, of 23/01/2019, p. 10/28
    6/15 wt. To 60 wt.%, Particularly preferably 45 wt.% To 55 wt.% Of aD-glycopyranosyl-1,1-D-mannitol, [0029] 0.02%, by weight to 15% by weight, preferably 0.1% by weight to 10% by weight, particularly preferably 0.2% by weight to 5% by weight of aD-glycopyranosyl -1,1-D-sorbitol, [0030] 0.02% by weight to 15% by weight, preferably 0.1% by weight to 10% by weight, particularly preferably 0, 2%, by weight, to 2.9%, by weight, of mannitol, in each case in relation to the total amount of aD-glycopyranosyl-1,1-D-mannitol, aD-glycopyranosyl1,6-sorbitol, aD-glycopyranosyl -1,1-D-sorbitol, sorbitol and mannitol, [0031] with the proviso, that the weight ratio of a-Dglycopyranosyl-1,6-D-sorbitol to aD-glycopyranosyl-1,1-D-mannitol is greater than 1: 1, preferably greater than 53:47, especially greater than 55:45.
    [0032] If the sweetener according to the invention consists of the substances mentioned above, then the indicated weight% add up to 100.
    [0033] To determine the respective parts by weight, the processes described in the ISOMALT specifications, written within the scope of 69 to JECFA (2008), published in FAO JECFA Monographs 5 (2008), can be referred to.
    [0034] Preferably, the sum of% by weight, of aD-glycopyranosyl-1,6-D-sorbitol and aD-glycopyranosyl-1,1-D-mannitol is greater than 75, preferably greater than 80, particularly preferably , greater than 86, in relation to the total weight of the sweetener dry substance.
    [0035] Preferably, the sweetener according to the invention contains less than 2.5% by weight, especially less than 0.3% by weight, most preferably, no detectable amount of sucrose, relative to the total weight of the dry substance of the sweetener.
    Petition 870190007277, of 23/01/2019, p. 11/28
    7/15 [0036] Another contribution to the resolution of the objectives mentioned above is provided by a process for the production of a sweetener through the reaction of a carbohydrate mixture containing isomaltulose, sucrose and optionally trehalulose, fructose and glucose and / or others polysaccharides with hydrogen, characterized by the fact that the reaction is carried out in the presence of at least one catalyst, which is based on ruthenium (Ru) and / or at least one ruthenium oxide.
    [0037] In this process, preferably by means of hydrogen, both isomaltulose and optionally trehalulose is catalytically hydrogenated to 1,1-GPM and 1,6-GPS and optionally to 1,1-GPS, as well as sucrose is dissociated in fructose and glucose and this is hydrogenated to mannitol and sorbitol. The last two mentioned are also sugar substitutes and, therefore, are ideal by-products for the obtained 1.1-GPM, 1.6-GPS and 1.1-GPS. In this way, the reaction in the process according to the invention corresponds to a catalytic hydrogenation that occurs together with a dissociation of sucrose in fructose and glucose. Therefore, it is preferable that the dissociation of sucrose and the hydrogenation of other carbohydrates present are carried out simultaneously. In the processes according to the invention, catalysts are preferably used, in which ruthenium (Ru) and / or the compound containing ruthenium are present immobilized in a vehicle, especially in an acidic or carbon-containing vehicle.
    [0038] The reaction is preferably carried out in an aqueous solution, so that the carbohydrate mixture may contain water.
    [0039] Preferably, the carbohydrate mixture thus contains 20% by weight to 80% by weight, preferably 30% by weight to 70% by weight, particularly preferably 40% by weight. weight, 60%, by weight, of water, in relation to the whole mixture of carPetition 870190007277, of 23/01/2019, p. 12/28
    8/15 bohydrate.
    [0040] The pH of the aqueous solution is preferably in a neutral or acidic range corresponding to a pH value below 8.
    [0041] The carbohydrate mixture employed in the process according to the invention can preferably be obtained through the enzymatic reaction of aqueous solutions, containing sucrose, such as, for example, aqueous solutions of sugar beet or cane sugar, with isomaltulose synthases . Suitable isomaltulose synthases are, for example, those of Enterobacter sp. strain FMB1, Erwinia rhapontici, Klebsiella planticola strain UQ14S, Klebsiella pneumoniae NK33-98-8, Klebsiella sp. LX3, Pantoea dispersa UQ68J, Protaminobacter ruber Z12, Protaminobacter rubrum, Pseudomonas mesoacidophila MX-45, Serratia plymuthica. Especially carbohydrate mixtures that can be obtained through the enzymatic reaction of aqueous solutions containing sucrose with isomaltulose synthases of Protaminobacter rubrum, especially the Protaminobacter rubrum strain CBS 574.77, can be used advantageously in the process according to the invention.
    [0042] In the case of sucrose contained in the carbohydrate mixture, this is preferably residual sucrose. Preferably, the carbohydrate mixture employed in the process according to the invention, contains 0.01% by weight to 15% by weight, preferably 0.1% by weight to 5% by weight, and so particularly preferred, 0.2% by weight to 2% by weight of sucrose, based on the dry weight of the entire carbohydrate mixture.
    [0043] Preferably, the carbohydrate mixture used in the process according to the invention contains 0.02% by weight to 30% by weight, preferably 0.1% by weight to 20% by weight. particularly preferably 0.2% by weight to 10% by weight of trehalulose in relation to the dry weight of the whole carbohydrate mixture.
    Petition 870190007277, of 23/01/2019, p. 13/28
    9/15 [0044] The catalysts mentioned based on ruthenium (Ru) and / or ruthenium oxide, with respect to a total conversion of the educts employed and with respect to an extremely high selectivity in relation to the products mentioned above, have surprisingly proved to be significantly higher than other known hydrogenation catalysts.
    [0045] As a catalyst support are included all solids that seem to be suitable for the person skilled in the art. These are, for example, carbon in the form of, for example, activated carbon, as well as especially acidic supports, such as, for example, metal oxides, such as AbOa, SiO2, TeO2, mixed oxides thereof or also MgO-SiO2 , ZrO2-SiO2, as well as heteropoly acids. In addition, the following can be mentioned: mineral acids, such as, for example, HaPO4 or H2SO4, which are applied in solid vehicles, preferably porous, likewise, preferably inert, cation exchangers, mineral acid salts containing oxygen, preferably heavy metals (phosphates, sulphates, wolframates), trivalent metal halides (such as, for example, AlCla) in porous supports, zeolites (form H) or the so-called H2SO4 treated ZrO2 or TiO2 super acids.
    [0046] Furthermore, vehicles are suitable, which from their functionality are classified more as neutral, such as, for example, activated carbon or TiO2, which preferably through suitable impregnation processes and / or through the application of the metal catalyst obtains an acidic functionality themselves.
    [0047] In this context it is preferable, that these vehicles have adequate pore volumes, which are suitable for the good connection and absorption of the hydrogenation catalyst. In addition, total pore volumes according to DIN 66133 in a range of 0.01 to 3 ml / g are preferred and in a range of 0.2 to 1 ml / g are particu
    Petition 870190007277, of 23/01/2019, p. 14/28
    10/15 widely preferred. In addition, it is preferable that the solids suitable as vehicles have a surface in the range of 0.001 to 1500 m 2 / g, preferably in the range of 10 to 450 m 2 / g, moreover, preferably in the range of 10 to 270 m 2 / g according to the BET test according to DIN 66131. As vehicles for the hydrogenation catalyst, a bulk material can be used, which has an average particle diameter in a range of 0.1 to 40 mm, preferably in a range of 0.8 to 7 mm and, moreover, preferably in a range of 1.5 to 7 mm. In addition, the hydrogenation reactor wall can serve as an inert vehicle.
    [0048] As techniques for applying the hydrogenation catalyst, immersion or impregnation or incorporation in a vehicle matrix are mentioned.
    [0049] This corresponds to an embodiment according to the invention, that the acidic vehicle consists at least partially of an oxidic compound. Such oxidic compounds should have at least one of the elements selected from the group comprising Si, Ti, Te, Zr, Al, P or a combination of at least two of these elements.
    [0050] Preferred acidic vehicles are selected from the group comprising, preferably consisting of oxides of silicon, aluminum, tellurium and phosphorus, with AbÜ3, SiÜ2, TeÜ2 and mixed oxides thereof being particularly preferred and AbÜ3 is particularly preferred.
    [0051] In the process according to the invention, it is possible to use superacid vehicles as vehicles as well.
    [0052] These are known to the specialist as those vehicles, such as, for example, H-Y zeolites, preferably with a Si-Al ratio> 50, as well as acid ion exchangers
    Petition 870190007277, of 23/01/2019, p. 15/28
    11/15 with corresponding temperature resistance, such as, for example, those available under the trade name Amberlyst.
    [0053] In an alternative way of carrying out the process according to the invention, it is possible to use neutral vehicles as vehicles as well. These are selected especially from the list consisting of elemental carbon, especially activated carbon and TiO2, where activated carbon is particularly preferred.
    [0054] The process according to the invention is advantageously carried out at elevated temperatures. The preferred temperature range matter at 80 ° C to 150 ° C, whereas the temperature as process temperature, which is measured in the carbohydrate mixture, which optionally already contains sweetener according to the invention.
    [0055] An alternative way of carrying out the process according to the invention is characterized by the fact that the process up to a conversion of 50% to 95% in relation to the hydrogenation of the isomaltulose is carried out in a temperature range between 80 to 120 o C and the other conversion essentially at 100% in relation to the hydrogenation of isomaltulose, in a temperature range between 100 o C to 150 o C, preferably 121 o C to 150 o C.
    [0056] In this context, it is preferable according to the invention, that the two different temperature ranges are spatially separated from each other and in the two temperature ranges a catalyst is used, in which ruthenium (Ru) and / or the compound containing ruthenium are present immobilized in a vehicle containing oxide, the oxide being specially selected from ALO3 and TiO2.
    [0057] In an alternative form of execution, in this context it is preferable according to the invention, that the two different temperature ranges are separated from each other, in the temperature range, which imports from 80 o C to 120 o C, a catalyst, in which ruthenium (Ru) and / or the compound containing ruthenium are present immobilized
    Petition 870190007277, of 23/01/2019, p. 16/28
    12/15 in a support containing oxide, the oxide being specially selected from AbOa and TiÜ2 and in the temperature range, which imports from 100 o C to 150 o C, preferably 121 o C to 150 o C, a catalyst, in the which ruthenium (Ru) and / or the compound containing ruthenium are present immobilized in a vehicle containing carbon.
    [0058] A particular form of execution of the process according to the invention, is characterized by the fact that as a vehicle a super acid vehicle is used and the process temperature matters below 120 o C, especially 80 o C to 110 o C .
    [0059] With regard to the pressure set during the hydrogenation reaction, a pressure of at least 1.5 MPa (15 bar), preferably of at least 3 MPa (30 bar), has been proved to be particularly advantageous, particularly preferred , of at least 4 MPa (40 bar). Particularly preferred are values between 4 MPa (40 bar) and 15 MPa (150 bar), especially between 4 MPa (40 bar) and 9 MPa (90 bar), for example, in the range of about 5 to 6 MPa (50 to 60 bar).
    [0060] Preferably, the process is carried out for so long, until the sweetener obtained is no longer detectable any sucrose.
    [0061] To transform the sweetener obtained by the process according to the invention, which is preferably present as a mixture of carbohydrates in liquid form, for the dry form, the water present as a solvent can be removed using an evaporator or a dryer, for example , a falling film evaporator or a drum dryer or atomization dryer.
    [0062] It may be advantageous to treat the sweetener obtained later with other stages of purification or enrichment and / or depletion.
    [0063] In this way, it may be advantageous to reduce the mani content
    Petition 870190007277, of 23/01/2019, p. 17/28
    13/15 tol by another crystallization step, for example, to 0.02% by weight to 15% by weight, preferably to 0.1% by weight to 10% by weight, particularly preferred, to 0.2%, by weight, to 2.9%, by weight, in relation to the dry mass of the sweetener; this is quite possible due to the low water solubility of mannitol.
    [0064] In the examples listed below, the present invention is described by way of examples, without the invention, its range of applications resulting from the entire specification and claims, being restricted to the forms of execution mentioned in the examples.
    Examples:
    Example 1: Ru-catalyzed hydrogenation of an isomaltulose solution containing sucrose at 90 ° C [0065] An aqueous solution containing 40% by weight of isomaltulose and 3% by weight of sucrose is hydrogenated according to the invention in a Ru catalyst, 1.5%, by weight, in aluminum oxide, at 6 MPa (60 bar) of hydrogen and 90 o C through a solid bed reactor continuously operated, with an LHSV (Liquid Hourly Space Velocity) 0.47 h -1 . The equipment consisted of a tubular reactor with air heating or air cooling with an internal diameter of the tubular reactor of 11 mm. The tube was fed with 19 mL of Noblyst® 3001 catalyst, Evonik Degussa GmbH.
    [0066] The volume flow of hydrogen imported at 100 NmL / min.
    [0067] The product shows an isomeric ratio of 1.6-GPS to 1.1-GPM of 56:44 with a conversion of 80% in relation to the isomaltulose used and 24% in relation to sucrose. In this case, the reacted isomaltulose was hydrogenated with a selectivity of almost 100% for isomalt. Sucrose is hydrogenated in mannitol and sorbitol under the reaction conditions.
    Example 2: Ru-catalyzed hydrogenation of an isoPetition solution 870190007277, of 23/01/2019, p. 18/28
    14/15 maltulose containing sucrose at 120 ° C [0068] If the same solution used as in example 1 diverging from 120 o C is reacted in the same conditions, in addition, then the isomaltulose used is hydrogenated in 95%, the sucrose in 93%. Here too, the reacted isomaltulose was hydrogenated with a selectivity of almost 100% for isomalt. The isomeric ratio of 1.6GPS to 1.1-GPM also reaches 56:44. Sucrose is hydrogenated to mannitol and sorbitol under the reaction conditions.
    Example 3: Ru-catalyzed hydrogenation (Ru / C) of an isomaltulose solution containing sucrose at 90 o C [0069] An aqueous solution containing 40% by weight of isomaltulose and 3% by weight of sucrose is hydrogenated from according to the invention in a Ru catalyst, 2% by weight, on activated carbon, with 6 MPa (60 bar) of hydrogen and 90 o C through a solid bed reactor continuously activated, with an LHSV of 0.47 h -1 . The equipment consisted of a tubular reactor with air cooling with an internal diameter of the tubular reactor of 11 mm. The tube was fed with 19 mL of Noblyst® 3000 catalyst, Evonik Degussa GmbH.
    [0070] The flow of water volume imported at 100 NmL / min.
    [0071] The product shows an isomeric ratio of 1.6-GPS to 1.1-GPM of 56:44 with a conversion of 96% in relation to the isomaltulose used and 60% in relation to sucrose. In this case, the reacted isomaltulose was hydrogenated with a selectivity of almost 100% for isomalt. Sucrose is hydrogenated to mannitol and sorbitol under the reaction conditions.
    Example 4: Ru-catalyzed hydrogenation (Ru / C) of an isomaltulose solution containing sucrose at 90 o C [0072] If the same solution used as in example 3 diverging from 120 o C is reacted under the conditions, in addition, the same, then the isomaltulose used is hydrogenated by> 99%, sucrose in
    Petition 870190007277, of 23/01/2019, p. 19/28
    15/15
    98%. Here too, the reacted isomaltulose was hydrogenated with a selectivity of almost 100% for isomalt. The isomeric ratio of 1.6-GPS to 1.1-GPM also reaches 56:44. Sucrose is hydrogenated to mannitol and sorbitol under the reaction conditions.
    Example 5: Hydrogenation not according to the invention, catalyzed with Ni of an isomaltulose solution containing sucrose at 90 ° C [0073] An aqueous solution containing 40% by weight of isomaltulose and 3% by weight of sucrose is hydrogenated with 10.5 g of Raney nickel catalyst, B 113 W, Evonik Degussa GmbH, to 6 MPa (60 bar) of hydrogen and 90 o C in a stirring boiler reactor. The equipment consisted of a Parr RK2 stirring boiler reactor with gasification stirrer, a nominal volume of 1.8 liters and a reaction volume of 1.2 liters; hydrogenation was carried out isothermally without basket in the suspension.
    [0074] After 4 hours, a complete conversion of isomaltulose to 1,6-GPS and 1,1-GPM is obtained with an isomeric ratio of 53:47, it is not possible to recognize a conversion of sucrose during that time . In this case, the reacted isomaltulose is hydrogenated with an almost 100% selectivity for isomalt.
    权利要求:
    Claims (17)
    [1]
    1. Process for producing a sweetener through the reaction of a mixture of carbohydrates containing isomaltulose and sucrose, characterized by the fact that the reaction is carried out in the presence of at least one catalyst, based on ruthenium (Ru), and / or minus a ruthenium oxide, and the vehicle being a neutral vehicle.
    [2]
    2. Process according to claim 1, characterized by the fact that the carbohydrate mixture contains from 0.01% by weight to 15% by weight of sucrose in relation to the dry weight of the whole carbohydrate mixture .
    [3]
    3. Process according to claim 1, characterized by the fact that the carbohydrate mixture contains from 0.02% by weight to 30% by weight of trehalulose in relation to the dry weight of the entire carbohydrate mixture .
    [4]
    Process according to any one of claims 1 to 3, characterized in that the carbohydrate mixture contains from 20% by weight to 70% by weight of water in relation to the dry weight of the entire mixture of carbohydrate.
    [5]
    5. Process according to any one of claims 1 to 4, characterized by the fact that in the catalyst ruthenium (Ru) and / or the compound containing ruthenium are present immobilized in a vehicle.
    [6]
    6. Process, according to claim 5, characterized by the fact that the total pore volume of the support, according to DIN 66133, is in a range of 0.01 to 3 mL / g.
    [7]
    7. Process, according to claim 5 or 6, characterized by the fact that the support has a surface in a range from 0.001 to 1500 m 2 / g, according to the BET test according to
    Petition 870190007277, of 23/01/2019, p. 21/28
    2/3
    DIN 66131.
    [8]
    Process according to any one of claims 5 to 7, characterized in that said neutral vehicle is particularly TiÜ2 or activated carbon.
    [9]
    Process according to any one of claims 5 to 7, characterized in that the vehicle is selected from the group comprising acidic oxides and mixed oxides, natural and synthetic silicate substances.
    [10]
    Process according to any one of claims 5 to 7, characterized in that the vehicle consists, at least partially, of an oxidic compound of at least one of the elements selected from the group comprising Si, Ti, Te, Zr, Al, P or a combination of at least two of these elements, especially in AbÜ3.
    [11]
    11. Process according to any one of claims 1 to 7, characterized by the fact that the vehicle is a super-acid vehicle selected from H-Y type zeolites or acid ion exchangers.
    [12]
    12. Process according to any one of claims 1 to 11, characterized by the fact that it is conducted in a temperature range of 80 o C to 150 o C.
    [13]
    13. Process according to claim 11, characterized by the fact that it is conducted at a temperature below 120 o C.
    [14]
    Process according to any one of claims 1 to 12, characterized in that it is carried out until a conversion of 50% to 95%, in relation to the hydrogenation of the isomaltulose, in a temperature range of 80 ° C to 120 o C, and the other conversion essentially at 100% in relation to the hydrogenation of isomaltulose, in a temperature range of 100 o C
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    3/3 to 150 o C.
    [15]
    15. Process, according to claim 14, characterized by the fact that the two different temperature ranges are spatially separated from each other, and in the two temperature ranges a catalyst is used, in which ruthenium (Ru) and / or the ruthenium-containing compound is present immobilized in a vehicle containing oxide, the oxide being particularly selected from AbÜ3 and TiÜ2.
    [16]
    16. Process, according to claim 14, characterized by the fact that the two different temperature ranges are particularly separated from each other, in the temperature range of 80 o C to 150 o C, a catalyst is used, in which the ruthenium (Ru) and / or the compound containing ruthenium are present immobilized in a vehicle containing oxide, the oxide being specially selected from AbÜ3 and TiÜ2, and in the temperature range of 100 o C to 150 o C, a catalyst is employed in which ruthenium (Ru) and / or the compound containing ruthenium are present immobilized in the vehicle containing carbon.
    [17]
    17. Process according to any one of claims 1 to 16, characterized in that the pressure set during the process is at least 1.5 MPa (15 bar).
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    同族专利:
    公开号 | 公开日
    AU2010335313A1|2012-06-07|
    AU2010335313B2|2014-03-06|
    BR122019001300B1|2020-03-03|
    US20220002331A1|2022-01-06|
    US20180282360A1|2018-10-04|
    CN102656176A|2012-09-05|
    JP6091896B2|2017-03-08|
    AU2010335313C1|2015-07-02|
    EP2361255A1|2011-08-31|
    IL219694A|2017-09-28|
    US20120315366A1|2012-12-13|
    WO2011076625A1|2011-06-30|
    JP2013515467A|2013-05-09|
    TW201141876A|2011-12-01|
    CN107048328A|2017-08-18|
    IL219694D0|2012-07-31|
    BR112012015490A2|2015-09-22|
    TWI567086B|2017-01-21|
    CN107048328B|2021-07-09|
    EP2361255B1|2014-06-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2868847A|1956-10-05|1959-01-13|Engelhard Ind Inc|Hydrogenation of mono-and disaccharides to polyols|
    DE1049800B|1957-10-11|1959-01-29|Süddeutsche Zucker-Aktiengesellschaft, Mannheim|METHOD FOR MANUFACTURING PALATINOSE |
    DE2217628C2|1972-04-12|1974-06-06|Sueddeutsche Zucker Ag|Process for the production of alpha-D-glucopyranosido square bracket on 1-6 square bracket to sorbitol |
    US4072628A|1974-11-05|1978-02-07|Ici Americas Inc.|Regeneration of supported ruthenium catalyst|
    US3963788A|1974-08-20|1976-06-15|Kruse Walter M|Polyhydric alcohol production using ruthenium zeolite catalyst|
    DE2520173C3|1975-05-06|1989-08-10|Suedzucker Ag Mannheim/Ochsenfurt, 6800 Mannheim, De|
    EP0001099B1|1977-09-13|1980-08-20|Bayer Ag|Process for the continuous isomerisation if saccharose to isomaltulose by means of microorganisms|
    DE3066516D1|1979-11-07|1984-03-15|Tate & Lyle Plc|Production of isomaltulose|
    JPS5836959B2|1980-08-21|1983-08-12|Mitsui Sugar Co|
    JPS6232361B2|1980-10-02|1987-07-14|Matsushita Electric Ind Co Ltd|
    DE3213107A1|1982-04-07|1983-10-13|Süddeutsche Zucker AG, 6800 Mannheim|METHOD FOR PRODUCING ISOMALTULOSE -D-GLUCOPYRANOSIDO-D-FRUCTOSE) WITH THE AID OF IMMOBILIZED BACTERIA CELLS|
    DE3403973A1|1984-02-04|1985-08-14|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING A MIXTURE OF -D-GLUCOPYRANOSIDO-1,6-MANNITE AND -D-GLUCOPYRANOSIDO-1,6-SORBITE FROM -D-GLUCOPYRANOSIDO-1,6-FRUCTOSE|
    JPH02273192A|1989-04-13|1990-11-07|Meito Sangyo Kk|Production of isomaltulose|
    FR2650158B1|1989-07-31|1992-10-30|Searle France|NOVEL COMPOSITION ESPECIALLY USEFUL FOR THE PREPARATION OF A SUGAR PRODUCT INTENDED FOR FOOD CONSUMPTION; PROCESSES FOR THE PREPARATION OF THIS COMPOSITION AND THE SUGAR PRODUCT WHICH IT PROVIDES|
    IT1256801B|1992-01-31|1995-12-15|Novamont Spa|HYDROGENATION CATALYST, PROCEDURE FOR ITS PREPARATION AND USE, IN PARTICULAR FOR THE HYDROGENATION AND / OR HYDROGENOLYSIS OF CARBOHYDRATES AND POLYOLS.|
    ES2089691T5|1993-05-06|2004-12-01|Sudzucker Aktiengesellschaft Mannheim/Ochsenfurt|SWEETENER, PROCEDURE FOR ITS MANUFACTURE AND ITS USE.|
    DE9321600U1|1993-05-06|2000-04-06|Suedzucker Ag|Sweeteners|
    FR2708269B1|1993-07-26|1995-10-06|Roquette Freres|Viscous liquid xylitol compositions and process for their preparation.|
    DE4416115A1|1994-05-06|1995-11-09|Bayer Ag|Process for the preparation of alpha-D-glucopyranosido-1,6-mannitol and sorbitol from alpha-D-glucopyranosido-1,6-fructose|
    IL110126A|1994-06-26|2001-01-28|Gadot Biochemical Ind Ltd|Process for the manufacture of isomaltitol|
    JP3602903B2|1995-05-02|2004-12-15|東和化成工業株式会社|Crystal maltitol and method for producing nectar-containing crystals containing the same|
    DE19532396C2|1995-09-02|1997-08-21|Suedzucker Ag|Sugar-free products and process for their preparation|
    DE19549825B4|1995-09-02|2010-11-04|Südzucker AG Mannheim/Ochsenfurt|Sugar-free hard caramels|
    FI104563B|1996-05-17|2000-02-29|Xyrofin Oy|Method and carrier for the production of isomaltulose by immobilized microorganisms|
    DE19636625A1|1996-09-10|1998-03-12|Bayer Ag|Process for the preparation of alpha-D-glucopyranosido-1,6-mannitol and sorbitol from alpha-D-glucopyranosido-1,6-fructose|
    DE19701439C2|1997-01-17|2001-01-25|Suedzucker Ag|Process for the hydrogenation of sugars|
    DE19720496B4|1997-01-17|2004-10-21|Südzucker AG Mannheim/Ochsenfurt|Process for the hydrogenation of sugars or sugar mixtures to give sugar alcohols or sugar alcohol mixtures|
    FR2769023B1|1997-09-26|2000-08-25|Roquette Freres|PROCESS FOR THE MANUFACTURE OF A MALTOSE-RICH SYRUP|
    DE19911504B4|1999-03-16|2006-02-23|Südzucker AG Mannheim/Ochsenfurt|Process for the industrial oxidation of alcohols, aldehydes or polyhydroxy compounds|
    FI990924A|1999-04-23|2000-10-24|Xyrofin Oy|Crystallization of glucopyranocylalditols, crystalline glucopyranocyl alditol products and their use|
    DE19929368A1|1999-06-25|2000-12-28|Merck Patent Gmbh|Mannitol preparation, for use in tableting or as a sugar substitute, by continuous hydrogenation of fructose over Raney copper catalyst|
    AU2841600A|2000-02-15|2001-08-27|Inst Of Molecular Agrobiology|Bacterial isolates of the genus klebsiella, and an isomaltulose synthase gene isolated therefrom|
    ES2234806T3|2000-02-17|2005-07-01|Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyusho|SOLID COMPOSITION OF CRYSTAL MIXTURE AND CORRESPONDING PRODUCTION PROCEDURE.|
    EP1513942B1|2002-06-07|2006-09-13|Südzucker Aktiengesellschaft Mannheim/Ochsenfurt|Galactosyl isomalt, method for production and use thereof|
    DE10242062B4|2002-09-11|2007-02-15|Südzucker Aktiengesellschaft Mannheim/Ochsenfurt|Hydrogenated condensed Palatinose, process for their preparation and their use|
    EP1572607A1|2002-12-11|2005-09-14|Basf Aktiengesellschaft|Continuous method for the production of sugar alcohols|
    JP2004313056A|2003-04-15|2004-11-11|Ueno Seiyaku Oyo Kenkyusho:Kk|Foaming composition, whipped cream, and method for producing the cream|
    JP4482336B2|2004-01-05|2010-06-16|上野製薬株式会社|Method for producing isomaltulose crystals and reduced isomaltulose|
    DE102004058811A1|2004-12-07|2006-06-08|Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.|Process for the preparation of sugar alcohols|
    FR2879603B1|2004-12-21|2007-04-06|Roquette Freres|PROCESS FOR PRODUCING A POWDER CONTAINING CRYSTALLINE PARTICLES OF GLUCOPYRANOSYL-ALDITOLS|
    CN100396780C|2005-06-22|2008-06-25|万代生物技术（深圳）有限公司|Process for preparing isomaltitol|
    US7678950B2|2005-12-16|2010-03-16|Conocophillips Company|Process for converting carbohydrates to hydrocarbons|
    DK2104658T3|2006-12-22|2016-03-07|Cargill Inc|A PROCEDURE FOR HYDROGENATION OF A SUGAR OR SUGAR MIXTURE|DE102006025821A1|2006-06-02|2007-12-06|Degussa Gmbh|An enzyme for the production of Mehylmalonatsemialdehyd or Malonatsemialdehyd|
    DE102010015807A1|2010-04-20|2011-10-20|Evonik Degussa Gmbh|Biocatalytic oxidation process with alkL gene product|
    MX344165B|2011-02-16|2016-12-07|Evonik Degussa Gmbh|Liquid cation exchanger.|
    HUE032045T2|2011-07-20|2017-08-28|Evonik Degussa Gmbh|Oxidation and amination of secondary alcohols|
    EP2602328A1|2011-12-05|2013-06-12|Evonik Industries AG|Method of Oxidation of alkanes employing an AlkB alkane 1-monooxygenase|
    EP2607490A1|2011-12-22|2013-06-26|Evonik Industries AG|Method for improved separation of a hydrophobic organic solution from an aqueous culture medium|
    DE102012200907A1|2012-01-23|2013-07-25|Evonik Industries Ag|Method and absorption medium for absorbing CO2 from a gas mixture|
    EP2631298A1|2012-02-22|2013-08-28|Evonik Industries AG|Biotechnological method for producing butanol and butyric acid|
    EP2639308A1|2012-03-12|2013-09-18|Evonik Industries AG|Enzymatic omega-oxidation and -amination of fatty acids|
    DE102012207509A1|2012-05-07|2013-11-07|Evonik Degussa Gmbh|Method for absorbing CO2 from a gas mixture|
    EP2700448A1|2012-08-21|2014-02-26|Evonik Industries AG|Branched fatty acids as liquid cation exchangers|
    EP2730655A1|2012-11-12|2014-05-14|Evonik Industries AG|Process for converting a carboxylic acid ester employing BioH-deficient cells|
    EP2746397A1|2012-12-21|2014-06-25|Evonik Industries AG|Production of omega amino fatty acids|
    EP2746400A1|2012-12-21|2014-06-25|Evonik Industries AG|Preparation of amines and diamines from a carboxylic acid or dicarboxylic acid or a monoester thereof|
    CN103549364A|2013-11-01|2014-02-05|广西科学院生物研究所|Functional food sweetening agent and preparation method thereof|
    US9833015B2|2014-06-13|2017-12-05|NutraEx Food Inc.|Sweetener with imbedded high potency ingredients and process and apparatus for making the sweetener|
    DE102015212749A1|2015-07-08|2017-01-12|Evonik Degussa Gmbh|Method for dehumidifying moist gas mixtures|
    DE102016210478A1|2016-06-14|2017-12-14|Evonik Degussa Gmbh|Method for dehumidifying moist gas mixtures|
    DE102016210481B3|2016-06-14|2017-06-08|Evonik Degussa Gmbh|Process for purifying an ionic liquid|
    EP3257568B1|2016-06-14|2019-09-18|Evonik Degussa GmbH|Method for the removal of moisture from moist gas mixtures by use of ionic liquids|
    DE102016210483A1|2016-06-14|2017-12-14|Evonik Degussa Gmbh|Process and absorbent for dehumidifying moist gas mixtures|
    EP3257843A1|2016-06-14|2017-12-20|Evonik Degussa GmbH|Method of preparing a high purity imidazolium salt|
    DE102016210484A1|2016-06-14|2017-12-14|Evonik Degussa Gmbh|Method for dehumidifying moist gas mixtures|
    CN111107753A|2017-08-02|2020-05-05|赢创运营有限公司|Isomaltulose-based sweeteners|
    EP3849991A1|2018-09-11|2021-07-21|Südzucker AG|Method for improved production of isomalt|
    法律状态:
    2017-10-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-11-06| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-07-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-05-12| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102009055256.1|2009-12-23|
    DE102009055256|2009-12-23|
    PCT/EP2010/069726|WO2011076625A1|2009-12-23|2010-12-15|Sweetener and method for the production thereof|BR122019001300-4A| BR122019001300B1|2009-12-23|2010-12-15|PROCESS FOR THE PRODUCTION OF SWEETENERS|
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