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Starch Technology International Starch Institute SORBITOL TM39-2e Starch Technology TMTM398-12-1ee 2 2 INTRODUCTION HSH Sorbitol is a sugar alcohol, C6H14O6 Hydrogenated starch hydrolysates found in nature as the sweet constituent (HSH), - polyglycitol syrups - are found in of many berries and fruits – best known a variety of foods. They serve as bulk from Sorbus aucuparia (Rowan or sweeteners, viscosity or bodying agents, European Rowan) from which it was moisture retaining ingredients, crystalliza- isolated for the first time in 1872. tion modifiers etc. – just like sorbitol. Mid 1950’s, sorbitol large scale HSH and sorbitol are made the same manufacture began due to new way, but from starch hydrolysates of applications, such as humectant in different Dextrose Equivalent (DE) and cosmetology and sugar substitute in non different composition. cariogenic confectionery. Sorbitol is the result of hydrogenation of Sorbitol is today commercially produced dextrose or starch syrup with a high DE from starch by enzymatic hydrolysis and equivalent to pure dextrose, while a catalytic hydrogenation. It has wide appli- hydrogenation of low DE hydrolysate will cations as a sweetener and humectant. lead to a mixture of sorbitol, maltitol, and longer chain hydrogenated saccharides (maltitritol a.o.) With no single dominant polyol the generic name “Hydrogenated Starch Hydrolysate” is used. If 50% or Sorbitol more of the polyols are of one type, it can C6H14O6 182.17 g mol−1 be labelled as "Sorbitol syrup", or "Maltitol syrup", etc. A special variety is manufactured by hydrogenation of the mother liqueur (hydrol) after first dextrose CRYSTALLINE PROPERTIES monohydrate crystallization. Hydrogenated starch hydrolysates are 20% Sorbitol has four crystal structures - four to 50% as sweet as sugar depending on its anhydrous crystalline phases plus the particular composition. hydrate. It may be crystallized from an aqueous solution or low moisture melt or The HSH family of polyols is an approved even spray dried / spray crystallized. food ingredient in most countries. U.S. Gamma polymorph is the most stable of food manufacturers may use HSH while the anhydrous crystalline forms FDA reviews the petition seeking confirmed by its high melting point and approval for its use in foods. low hygroscopicity and is the only form of significance for the confectionery and SYNONYMS pharmaceutical industries. • Sorbitol Density 1.489 g/cm³ • Glucitol Melting point 95 °C • D-glucitol Boiling point 296 °C • D-Sorbitol • Sorbite • Hydrogenated Starch Hydrolysate (HSH) Copyright © 2009 International Starch Institute, Science Park Aarhus, Denmark. Copyright © 2009 International Starch Institute,Rowan Science Tree, Park Aarhus, Sorbus Denmark. aucuparia Sorbitol is the sweet constituent of the berries. TM39-2e 4 RAW MATERIALS PROCESS Starch crops – grain or roots – are the The front end design depends on the basic raw materials. selected agro commodity. The attached diagram shows briefly the process route. Also purified starch of any origin – corn, The various designs are described in wheat, potato or cassava – can be used. greater detail in respective Technical Memorand a. The hydrogenation can of course begin with dextrose – liquid or dry – but in real The basic raw materials are cleaned and life the process begins with basic raw the starch is extracted in a wet milling materials like cassava, corn or wheat. process and then concentrated and purified. So far the process is identical to the one used for the manufacturing of native starch as the end product. Multi stage starch extractors. Being a tropical crop cassava can be Instead of drying the starch, the grown and harvested round the year, concentrated pure starch milk is liquefied which is a great advantage. This makes by cooking with acid or alpha-amylase. cassava a cheap carbohydrate source for The cooking is carried out continuously in the manufacture of starch sugar and a converter by injecting steam. downstream products like starch sugar alcohols. A rather low DE hydrolysate is the resulting intermediate of this conversion. The hydrolysate is then hydrolyzed to the very end as the monosaccharide dextrose and purified. The purified fully saccharified starch solution is concentrated and is now identical to standard high DE dextrose syrup. Hydrogenation in progress Copyright © 2009 International Starch Institute, Science Park Aarhus, Denmark. TM39-2e 5 The clear high purity dextrose solution is hydrogenated in the presence of a Process Route catalyst in vigorously stirred reactors at specified pressure and temperature. It is Reception of (1) Starch ► necessary to safe-guard the process crop grain or roots carefully, because of the hydrogen ▼ Cleaning of grain Water ► ► Waste applied. Head space of the autoclave is or roots initially flushed with nitrogen to remove ▼ Disintegrating and air and its oxygen completely. Hydrogen is made on site. The hydrogenation is wet milling carried out intermittently in few hours’ ▼ Starch ► Byproducts cycles. The hydrogenated solution is Extraction decanted and subsequently subjected to ▼ Starch carbon treatment and ion exchange. The catalyst is recycled and reused. Concentration ▼ Starch Refining ▼ Starch (2) Native ► starch Liquefaction ▼ Hydrolysate Saccharification ▼ Dextrose Purification ▼ Dextrose Concentration ▼ Dextrose (3) Glu- ► cose syrup preparation ▼ Hydrogen ► Dextrose Catalyst ► Hydrogenation ▼ Sorbitol Purification ▼ Sorbitol Sorbitol ► Syrup condenser Concentration 70% ▼ Sorbitol Sorbitol ► Solidification powder The purified solution is evaporated to 70% dry matter - the most usual Input to the process may be either concentration of Liquid Sorbitol. The (1) a starchy crop like cassava, corn and wheat, syrup may be spray dried or crystallized (2) a native starch of any origin or to obtain a powder. (3) pure dextrose monohydrate or glucose syrup of a suitable DE dependent on sorbitol specifications. Copyright © 2009 International Starch Institute, Science Park Aarhus, Denmark. Danish factory for the manufacture of D-sorbitol and L-ascorbic acid. D-sorbitol is obtained by catalytic reduction of D-glucose. By means of gluconobacter oxydans D-sorbitol is oxidized to L-sorbose, which is a necessary intermediate in the process for L-ascorbic acid (Vitamin C). Copyright © 2009 International Starch Institute, Science Park Aarhus, Denmark. TM39-2e 8 SUGAR ALCOHOL MARKET Sorbitol has a smooth mouth feel with a Once upon a time glycerol was the sole sweet, cool and pleasant taste. Sorbitol ruler on the sugar alcohol market. This acts as a crystallization modifier or position was challenged, when sorbitol inhibitor; it can prevent syrups from half a century ago was introduced on a forming crystals of sugar. It is used to larger scale. This market has since add body and viscosity to mixtures, and undergone a major expansion in terms of can protect against damage from freezing quantity and uses. This expansion is due (cryoprotectant) and drying. to new sugar alcohols with new and different properties and consequently Liquid sorbitol itself has a tendency to more uses. crystallize at room temperature. A product of choice for most applications is One important use is replacement of non-crystallizing sorbitol (NCS) - a 70% traditional table sugar (sucrose). Sugar solution with approximately 50% sorbitol alcohols (polyols) are all low-caloric, and smaller amounts of other polyols sugar-free, alternative sweeteners. They (maltitol a.o.) are replacement for sucrose and starch syrup in low-sugar and sugar-free It shares many applications with formulations. They are qualified for propylene glycol and glycerine and product labelling as "Sugar Free", glycerine provides hard competition in the market for humectants. A new fuel – bio- "Reduced Sugar" and "No Sugar Added". They provide exceptional bulk and body diesel - has glycerine as by-product and and are lower in calories than sucrose. will increase the output of glycerine in the future and put some polyol based glycerine replacements under pressure. Polyols are non-cariogenic. They can be used alone or in combination with other polyols and/or sweeteners. Even mixtures Global production of sorbitol has reached with glycerine are available as perfect approximately 800.000 MT per year. glycerine substitutes. Sorbitol being the most commonly used The common sugar alcohols – sorbitol, polyol (it is the least costly) held the mannitol, maltitol, erythritol, and biggest market share among similar polyols. hydrogenated starch hydrolysates – are manufactured from starch. • Sorbitol 800,000 MT SORBITOL • Xylitol 200,000 MT • Mannitol 180,000 MT • Maltitol 160,000 MT Roquette Frères is the world's biggest sorbitol producer. Together with Cargill and Corn Products Specialty Ingredients they hold a market share of over 70%. Roquette has set up several production bases worldwide and is also constructing a large sorbitol plant in the east of China. Copyright © 2009 International Starch Institute, Science Park Aarhus, Denmark. TM39-2e 9 POLYOLS LACTITOL XYLITOL Polyols are made for the Lactitol is a non-starch Xylitol is a non-starch industrial market and hard to sweetener produced from sweetener found in straw- find in a supermarket. whey. The lactose is isolated berries, raspberries a.o. It is and hydrogenated. Largest made by hydrogenation of In the European Union (EU) manufacturer is the Danish xylose. This in turn is derived polyols are considered as food company Danisco. from xylan extracted from birch additives and are given the trees or corn cobs.
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