CS196886B1 - Method of preparing alcoholic sugars by hydrogenation ofmonosaccharides - Google Patents
Method of preparing alcoholic sugars by hydrogenation ofmonosaccharides Download PDFInfo
- Publication number
- CS196886B1 CS196886B1 CS866877A CS866877A CS196886B1 CS 196886 B1 CS196886 B1 CS 196886B1 CS 866877 A CS866877 A CS 866877A CS 866877 A CS866877 A CS 866877A CS 196886 B1 CS196886 B1 CS 196886B1
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- CS
- Czechoslovakia
- Prior art keywords
- hydrogenation
- hydrogenated
- ostion
- yield
- calculated
- Prior art date
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 17
- 235000000346 sugar Nutrition 0.000 title claims description 10
- 150000008163 sugars Chemical class 0.000 title claims description 9
- 230000001476 alcoholic effect Effects 0.000 title claims description 8
- 238000000034 method Methods 0.000 title description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 150000002772 monosaccharides Chemical class 0.000 claims description 8
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 7
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 7
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 239000000811 xylitol Substances 0.000 claims description 5
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 5
- 235000010447 xylitol Nutrition 0.000 claims description 5
- 229960002675 xylitol Drugs 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 240000000731 Fagus sylvatica Species 0.000 claims description 2
- 235000010099 Fagus sylvatica Nutrition 0.000 claims description 2
- 239000007868 Raney catalyst Substances 0.000 claims description 2
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims 1
- 150000001479 arabinose derivatives Chemical class 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 229920001429 chelating resin Polymers 0.000 claims 1
- 239000012153 distilled water Substances 0.000 claims 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 150000003741 xylose derivatives Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001323 aldoses Chemical class 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- -1 alcohol sugars Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 235000020880 diabetic diet Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003215 pyranoses Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález popisuje přípravu alkoholických cukrov katalytickou hydrogenáciou monosacharidov vodíkom pod tlakom, pri upravenom pH hydrogenovaných roztokov, s nasledovnou ionomeničovou úpravou produktu hydrogenácie.The invention describes the preparation of alcoholic sugars by catalytic hydrogenation of monosaccharides with hydrogen under pressure, at adjusted pH of hydrogenated solutions, followed by ion exchange treatment of the hydrogenation product.
Alkoholické cukry, najma sorbitol a xylitol, sa používajú ako sladidlo pri diabetickej diéte, majú však aj širšie uplatnenie v kozmetike a ako nahrážka glycerínu v potravinárskom priemysle. Z alkoholických cukrov sa pripravujú oxyetyláciou povrchovo-aktívne látky. Dajú sa obecne použit v chemickej syntéze všade, kde sa ako jedna zložka uplatňujú polyoly.Alcoholic sugars, in particular sorbitol and xylitol, are used as a sweetener in the diabetic diet, but are also widely used in cosmetics and as a substitute for glycerin in the food industry. Alcoholic sugars are prepared by oxyethylation of surfactants. They can generally be used in chemical synthesis wherever polyols are used as one component.
Příprava alkoholických cukrov je dávno známa, a to klasickým postupom, redukciou aldóz a ketóz sodíkovou amalgámou.The preparation of alcoholic sugars has long been known by the classical method of reducing aldoses and ketoses with sodium amalgam.
Je ich tiež možné připravovat katalytickou hydrogenáciou za atmosferického tlaku vodíka, reakcia sa však uskutočňuje len velmi pomaly. S Raneyovým niklom ako katalyzátorom je možné hydrogenovať dxylózu ako 70 %-ný roztok v etanole. Je výhodné před hydrogenáciou roztoky čeřit napr. aktívnym uhlím. Daleko účinnejšia je katalytická hydrogenácia monosacharidov na alkoholické cukry za zvýšeného tlaku vodíka, 5 až 20 MPa. Ako katalyzátory sa používajú nikel na kremeline, Raneyov nikel, nikel průmotovaný chrómom, zmesný nikel-kobal — chrómový katalyzátor a katalyzátory na báze médi.They can also be prepared by catalytic hydrogenation under atmospheric hydrogen pressure, but the reaction is carried out only very slowly. With Raney nickel catalyst, it is possible to hydrogenate dxylose as a 70% solution in ethanol. It is preferred to clarify the solutions before hydrogenation e.g. activated carbon. Far more efficient is the catalytic hydrogenation of monosaccharides to sugar alcohols under elevated hydrogen pressure of 5 to 20 MPa. As catalysts, nickel for silica, Raney nickel, chromium-prized nickel, mixed nickel-cobal-chromium catalyst and medium-based catalysts are used.
Nevýhodou katalyzovanej hydrogenácie vodných roztokov monosacharidov je stúpanie ich kystlosti tvorbou oxykyselfn Cannizarovou reakciou. Kyseliny móžu vznikat aj z aldóz cez pyranózy, ich dehydrogenáciou a následnou hydratáciou. Kyseliny dezaktivujú hydrogenačně katalyzátory, v dosledku čoho sa znižuje rýchlost hydrogenácie a dosahuje sa nižšia konverzia monosacharidov na alkoholické cukry.A disadvantage of the catalysed hydrogenation of aqueous monosaccharide solutions is the increase in their cysticity by the formation of the oxykyselfn Cannizar reaction. Acids can also be formed from aldoses via pyranoses, their dehydrogenation and subsequent hydration. The acids deactivate the hydrogenation catalysts, as a result of which the rate of hydrogenation is reduced and the conversion of monosaccharides to alcohol sugars is lowered.
Zlepšenie přípravy alkoholických cukrov sa dosahuje postupom podlá vynálezu, ktorým sa dosahujú vysoké výtažky čistých finálnych produktov.Improvement of the preparation of alcoholic sugars is achieved by the process according to the invention, which achieves high yields of pure end products.
Spósob přípravy alkoholických cukrov hydrogenáciou monosacharidov, vykonává sa podl'a vynálezu pri tlaku vodíka alebo vodík obsahujúceho plynu 2 až 25 MPa, v přítomnosti hydrogenačných katalyzátorov, najvýhodnejšie niklových, násadovým alebo kontinuálnym sposobom tak, že u hydrogenovaného roztoku s obsahom 5 až 50 % monosacharidov s výhodou připravených hydrolýzou dřeva, upravuje sa prídavkom alkalicky reagujúcich látok pH na hodnotu 7 až 10 a produkt hydrogenácie sa upravuje na katiónaktívnych a aniónaktívnych ionomeničoch pri objemovej rýchlosti 0,5 až 5 1. h_1 na 1 1 ionomeničovej náplně.The process for preparing alcoholic sugars by hydrogenating monosaccharides according to the invention is carried out at a hydrogen or hydrogen pressure of 2 to 25 MPa in the presence of hydrogenation catalysts, most preferably nickel, batch or continuous process, such that in a hydrogenated solution containing 5 to 50% monosaccharides preferably by hydrolysis of the timber, provides for the addition of alkaline reactants to pH 7-10 and the product of the hydrogenation is adjusted to the cationic and anionic ion-exchange at a space velocity of 0.5 to 5 h _1 1 1 1 ion exchange cartridge.
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Postup podía vynálezu ukazujú ďalej uvedené příklady.The following examples show the process according to the invention.
Příklad 1Example 1
V rotačnom autokláve z nehrdzavejúcej ocele, o obsahu 0,5 1 urobila sa hydrogenácia 100 g 20 % vodného roztoku čistej xylózy, za přídavku 1,6 g katalyzátora, nlkel na kremeline, ktorý obsahoval 49,1 °/o niklu. Prídavkom pevného kysličníka vápenatého upravilo sa pH hydrogenovaného roztoku na 8,4.In a 0.5 L stainless steel rotary autoclave, 100 g of a 20% aqueous xylose aqueous solution was hydrogenated with 1.6 g of nlkel catalyst on silica gel containing 49.1% nickel. The pH of the hydrogenated solution was adjusted to 8.4 by addition of solid calcium oxide.
Hydrogenácia sa uskutočnila vo dvoch stupňoch. V 1. stupni pri 80 °C a v 2. stupni pri 110 °C. Tlak vodíka v autokláve sa udržiaval na 12,5 MPa. Po 90 minútach reakčného času sa dosiahla 98,3 °/o-ná konverzia xylózy.Hydrogenation was carried out in two stages. In the 1st stage at 80 ° C and in the 2nd stage at 110 ° C. The hydrogen pressure in the autoclave was maintained at 12.5 MPa. After a reaction time of 90 minutes, a 98.3% conversion of xylose was achieved.
Produkt hyrogenácie sa demineralizoval prietokom cez štipec katexu Wofatit KPS200, Wofatit SBW pri objemovej rýchlostiThe product of hydrogenation was demineralized by passing through a cation exchanger column of Wofatit KPS200, Wofatit SBW at volumetric rate
2,5 1. h_1 na 1 lit. ionomeničovej náplně. Získal sa číry produkt, z ktorého sa kryštalizáciou připravil xylitol s teplotou topenia 92,5 °C, vo výtažku 75,1 %.2,5 1 h _1 per 1 liter ion exchange filler. A clear product was obtained, from which xylitol with a melting point of 92.5 ° C was obtained by crystallization in a yield of 75.1%.
Příklad 2Example 2
Kontinuálna hydrogenácia hydrolyzátu z bukových pilin sa vykonala v reaktore z nehrdzavejúcej ocele, dlžky 4000 mm, o obsahu 2,8 1. Vodík a 1,129 kg.h-1 hydrolyzátu sa privádzali do reaktora protiprúdne. Ako katalyzátor sa používal kúskovitý Raneyov nlkel, zrnenia 6 až 8 mm, s obsahom 41,83 °/o Ni v neaktivovanej zliatine. Hydrolyzát obsahoval 49,4 % hmot. sušiny tohto zloženia: xylóza 75,58 % hmot., arabinóza 8,9 % hmot., glukóza 4,24 % hmot. a galaktóza 6,82 % hmot., zbytok minerálně a neidentifikované látky. Prídavkom vodného roztoku hydroxidu sódneho o koncentrácii 10 % upravilo sa pH hydrogenovaného roztoku na 8,7. KontinuálnaContinuous hydrogenation of the beech sawdust hydrolyzate was carried out in a stainless steel reactor, 4000 mm long, containing 2.8 L of hydrogen and 1.129 kg.h -1 of hydrolyzate were fed countercurrently into the reactor. The catalyst used was a piece of Raney nlkel, grain size 6 to 8 mm, containing 41.83% Ni in the non-activated alloy. The hydrolyzate contained 49.4 wt. dry matter of this composition: xylose 75.58% by weight, arabinose 8.9% by weight, glucose 4.24% by weight and galactose 6.82 wt%, the remainder of the mineral and unidentified substance. The pH of the hydrogenated solution was adjusted to 8.7 by the addition of 10% aqueous sodium hydroxide. continuous
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CS866877A CS196886B1 (en) | 1977-12-22 | 1977-12-22 | Method of preparing alcoholic sugars by hydrogenation ofmonosaccharides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CS866877A CS196886B1 (en) | 1977-12-22 | 1977-12-22 | Method of preparing alcoholic sugars by hydrogenation ofmonosaccharides |
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Publication Number | Publication Date |
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CS196886B1 true CS196886B1 (en) | 1980-04-30 |
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CS866877A CS196886B1 (en) | 1977-12-22 | 1977-12-22 | Method of preparing alcoholic sugars by hydrogenation ofmonosaccharides |
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1977
- 1977-12-22 CS CS866877A patent/CS196886B1/en unknown
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