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WO2001021633A1 - Cristaux de lactitol anhydre, produit les contenant, leur procede de preparation et leur utilisation - Google Patents

Cristaux de lactitol anhydre, produit les contenant, leur procede de preparation et leur utilisation Download PDF

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Publication number
WO2001021633A1
WO2001021633A1 PCT/FI2000/000791 FI0000791W WO0121633A1 WO 2001021633 A1 WO2001021633 A1 WO 2001021633A1 FI 0000791 W FI0000791 W FI 0000791W WO 0121633 A1 WO0121633 A1 WO 0121633A1
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WIPO (PCT)
Prior art keywords
lactitol
crystals
anhydrous
orthorhombic
solution
Prior art date
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PCT/FI2000/000791
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English (en)
Inventor
Craig Myers
Heikki Heikkilä
Hannele Nikander
Juha Nurmi
Johanna Nygren
Paula Perkkalainen
Tammy Pepper
Ilkka Pitkänen
Jussi Valkonen
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.)
Danisco Sweeteners Oy
Xyrofin Oy
Original Assignee
Danisco Sweeteners Oy
Xyrofin Oy
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Publication date
Application filed by Danisco Sweeteners Oy, Xyrofin Oy filed Critical Danisco Sweeteners Oy
Priority to AU72921/00A priority Critical patent/AU7292100A/en
Priority to EP00960720A priority patent/EP1214329A1/fr
Publication of WO2001021633A1 publication Critical patent/WO2001021633A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/30—Artificial sweetening agents
    • A23L27/33—Artificial sweetening agents containing sugars or derivatives
    • A23L27/34—Sugar alcohols
    • A—HUMAN NECESSITIES
    • A21—BAKING; EDIBLE DOUGHS
    • A21D—TREATMENT OF FLOUR OR DOUGH FOR BAKING, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS
    • A21D13/00—Finished or partly finished bakery products
    • A21D13/30—Filled, to be filled or stuffed products
    • A21D13/38—Filled, to be filled or stuffed products characterised by the filling composition
    • A—HUMAN NECESSITIES
    • A21—BAKING; EDIBLE DOUGHS
    • A21D—TREATMENT OF FLOUR OR DOUGH FOR BAKING, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS
    • A21D2/00—Treatment of flour or dough by adding materials thereto before or during baking
    • A21D2/08—Treatment of flour or dough by adding materials thereto before or during baking by adding organic substances
    • A21D2/14—Organic oxygen compounds
    • A21D2/18—Carbohydrates
    • A21D2/181—Sugars or sugar alcohols
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G1/00—Cocoa; Cocoa products, e.g. chocolate; Substitutes therefor
    • A23G1/30—Cocoa products, e.g. chocolate; Substitutes therefor
    • A23G1/32—Cocoa products, e.g. chocolate; Substitutes therefor characterised by the composition containing organic or inorganic compounds
    • A23G1/40—Cocoa products, e.g. chocolate; Substitutes therefor characterised by the composition containing organic or inorganic compounds characterised by the carbohydrates used, e.g. polysaccharides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • A23G3/346—Finished or semi-finished products in the form of powders, paste or liquids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents
    • A23G2200/06—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents containing beet sugar or cane sugar if specifically mentioned or containing other carbohydrates, e.g. starches, gums, alcohol sugar, polysaccharides, dextrin or containing high or low amount of carbohydrate
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • Anhydrous lactitol crystals a product containing the same and a process for the preparation thereof as well as use thereof
  • the present invention relates to novel anhydrous lactitol crystals, to crystalline lactitol products containing the same and to a process for the preparation thereof and to the use thereof.
  • Lactitol is a special sweetener replacing saccharose; however, its energy content is only half of that of saccharose, and it does not cause an elevated blood glucose content; furthermore, it is friendly to the teeth (cf. Developments in Sweeteners, Ed. Grenby, T.H. , Vol. 3, 1987, pp. 65-81).
  • lactitol from lactose has long been known.
  • Industrially lactitol is prepared analogously with the preparation of sorbitol, by hydrogenation in the presence of e.g. Raney nickel catalyst.
  • An aqueous solution of lactose typically having a concentration of 30% to 40% by weight on account of the low solubility of lactose, is hydrogenated at 70°C to 130°C at a pressure of 30 atm to 74 arm.
  • the preparation has been described by Wolfrom et al. , J. Am. Chem. Soc. 60 (1938), pp. 571-573.
  • lactitol anhydride could be crystallized by adding ethanol to a lactitol solution evaporated to a high concentration. After a crystallization time of one month (from anhydrous ethanol), the lactitol yield was 80% ; the product was recrystallized from a water-ethanol solution in an ice bath. The resultant "lactitol anhydride” was a highly hygroscopic substance. The crystal form was tetrahedric, the melting point was 144°C to 146°C and the specific rotation in water + 14° (4 g/100 ml, 23 °C).
  • Lactitol hydrate powders anhydrated to a water content below 3 % have been prepared by drying both a lactitol solution and crystalline hydrate. The hygroscopicity of these powders is made use of in the drying of moist mixtures (European Patent Application No . 0231643, 1986).
  • Japanese Patent Application No. 64-19452 (1989) discloses a solid lactitol product which is called "lactitol anhydride" and which is prepared by drying crystalline lactitol mono- hydrate.
  • the product is hygroscopic and has a melting point of 121 °C to 123 °C.
  • This product is instable and has been named A or Al anhydrous lactitol in the literature.
  • EP Patent 39981 describes the crystallization of lactitol to form a product melting at about 121-123 °C.
  • lactitol monohydrate it appears that this product is in reality a hydrate mixture containing a substantial portion of anhydrous lactitol.
  • a different anhydrous lactitol may be crystallized from an aqueous solution as described in WO 92/16542, incorporated herein by reference.
  • the process comprises cooling or evaporating a supersaturated lactitol solution at a temperature above 70 °C to provide anhydrous lactitol having a melting range of 149-152°C.
  • the anhydrous lactitol has a monoclinic crystal structure and a low hygroscopicity .
  • This anhydrous lactitol crystal form has also been called B or A2 anhydrous lactitol in the literature. It will herein be called lactitol, as it was the first known crystal structure of anhydrous lactitol.
  • lactitol has a melting enthalpy of about 149 J/g and it is considered to be a very stable anhydrous lactitol form.
  • lactitol In addition to the anhydrous form crystalline lactitol has been reported to occur in the form of monohydrate, dihydrate and trihydrate. Among these crystal forms of lactitol, lactitol monohydrate and anhydrous lactitol are of great commercial interest e.g. on account of their low hygroscopicity.
  • the present invention is based on the finding that lactitol is capable of crystallizing in a new anhydrous crystal structure which is distinct from the two earlier known anhydrous forms.
  • the crystal shape (morphology) is typically elongated. The crystal shape may be affected by the actual crystallization conditions and by other components in the feed liquid. The shape is often more or less needle-like. The crystals belong to the ortho- rhombic crystal system.
  • the Al form has been found to be difficult to crystallize in pure form from aqueous solutions although it seems to crystallize with the crystalline hydrate forms giving a distinct peak around 121-123 °C in the DSC curves of impure hydrate forms such as those produced according to the above mentioned EP Patent 39981.
  • the lactitol form is more stable than the Al form and is the crystal form so far predominantly crystallized from aqueous solutions above 70 °C. Its crystal form is monoclinic and the crystals are typically square-like in shape.
  • the novel anhydrous lactitol crystal is called ⁇ (or A3) throughout this description for ease of distinguishing it from the prior known anhydrous lactitol crystals, (AT) and Al .
  • a simulated projection formula of the molecule is shown in Fig 1 while Fig. 2 shows the projection formula of the prior known monoclinic anhydrous lactitol a.
  • the pure ⁇ crystal has a melting point of 151 °C (onset) to 152.5°C (peak) measured by DSC (Differential Scanning Calorimetry) at a heating rate of 2°C/min, it has a water content below 0.5 % and a lactitol content of more than 99% .
  • the cell units have been measured by single crystal x-ray measurement and by a powder diffraction measurement using a Pirum analysis.
  • the unit cell constants presented above should not be taken to be absolutely correct. Thus, as persons skilled in the art will understand, the unit cell dimensions of any crystal structure vary within certain accepted limits and the identical measurement is hardly ever obtained for two different single crystals or powder diffractograms. A normal variation in the cell unit dimensions is thus implied herein.
  • the volume of the unit cell of the ⁇ lactitol is about 1502 A 3 .
  • the orthorhombic anhydrous ⁇ lactitol crystals have been measured to show a very low hygroscopicity and it has been found that the anhydrous ⁇ crystals have a very low lactulitol content.
  • Lactulitol is a common impurity in hydrogenated lactitol syrups.
  • the amount of lactulitol found in the anhydrous ⁇ crystals is typically below 0.5 % and most often below 0.1 % on the dry substance, even when lactulitol is present in the feed liquid.
  • the novel ⁇ lactitol crystals have also been observed to have a low content of coloured impurities.
  • the ⁇ lactitol can provide a very pure product in industrial production. Because of its low water content and low hygroscopicity the ⁇ lactitol is easy to dry in industrial processes .
  • the orthorhombic anhydrous ⁇ lactitol may have as impurities monoclinic anhydrous lactitol and also a slight amount of lactitol monohydrate. It is also possible to produce a mixture of the anhydrous ⁇ and anhydrous and/or lactitol monohydrate. Such mixed products form part of the present invention.
  • Samples of the orthorhombic anhydrous ⁇ lactitol crystals of the present invention have been found to have a melting enthalpy of about 165-170 J/g, more typically 166-169 J/g.
  • the prior known crystalline monoclinic anhydrous lactitol form has a melting enthalpy of about 149 J/g.
  • the ⁇ crystals are stable and hard and are not appreciably affected by milling.
  • the melting enthalpy of a sample of ⁇ lactitol crystals was reduced to about 160-165 J/g, more typically to 161-163 J/g by milling, although the ⁇ form was not found to have changed into the form.
  • melting point and melting enthalpy for the novel anhydrous lactitol crystals should not be considered as limiting the invention since the melting point and melting enthalpy may vary somewhat depending on the structural and chemical purity level of the sample.
  • the novel orthorhombic anhydrous ⁇ lactitol there are various ways of producing the novel orthorhombic anhydrous ⁇ lactitol. Specifically the crystals can be produced by crystallization from aqueous solutions of lactitol either by boiling (evaporative) crystallization or by cooling crystallization or by a combination of the two.
  • the appended claims define the preferred ways of producing ⁇ lactitol by crystallization. The contents of said claims are included herein by reference.
  • the orthorhombic anhydrous ⁇ lactitol crystals may be produced by any boiling and/or cooling crystallization processes at a temperature between about 70 and 150°C which typically produce the form of anhydrous lactitol as a first crystal yield, provided that the first obtained crystal yield is conditioned in the solution at a temperature of about 70-100°C for a sufficient time to allow the first crystal yield to convert into a second crystal yield comprising orthorhombic anhydrous lactitol ⁇ crystals.
  • condition as used in this specification and the appended claims is intended to mean that the crystal yield is allowed a sufficient time under suitable conditions for the crystals to take the orthorhombic anhydrous shape of ⁇ .
  • the typical square shaped monoclinic anhydrous lactitol crystals will, when maintained in the solution at a temperature at or above about 70 to 80 °C, preferably closer to 70 °C, slowly change into the typical elongated orthorhombic anhydrous ⁇ lactitol crystals. This is so even though the solution may have been seeded with seed crystals of the form. Although applicants do not wish to be bound by any theory, this seems to indicate that the ⁇ crystals have the more stable crystal form of the two at the crystalliza- tion conditions.
  • the time required for the change from monoclinic anhydrous lactitol a to orthorhombic anhydrous lactitol ⁇ depends on many factors such as the temperature, the impurities in the solution, the supersaturation of the solution, etc. Normally the change begins within one or more days, while a total change may require up to two or three weeks to be complete. Mixing of the solution during crystallization also improves the yield of ⁇ lactitol.
  • the orthorhombic anhydrous lactitol ⁇ may also be crystallized directly from supersaturated aqueous solutions of lactitol either by boiling or cooling crystallization, provided that the crystallization is seeded with seed crystals of ⁇ .
  • the crystal form of the initial crystal yield will comprise orthorhombic anhydrous lactitol ⁇ and no conditioning is needed to obtain ⁇ crystals.
  • a combination of boiling and cooling crystallization is performed, wherein a boiling crystallization is first performed while using seeds of ⁇ crystals, and after the boiling crystallization a cooling crystallization is performed down to about 70 °C to optimize the crystal yield. It has been found that the end temperature of the crystallization may even drop slightly below 70°C, such as to about 68 °C without any undue amount of lactitol monohydrate being formed, especially if the cooling at the end is fairly rapid. However, no conditioning should be performed below 70°C, since in such a case contamination by lactitol monohydrate is very likely to happen.
  • the ⁇ seeds used for the seeding may comprise milled and/or sieved crystals or, in a preferred embodiment a so called crystal foot of ⁇ crystals is produced by providing a large amount of ⁇ crystals in a solution by a pre-crystallization step.
  • the crystal mass is preferably conditioned so as to make sure that the crystal form in the crystal foot is the desired ⁇ lactitol.
  • the novel orthorhombic anhydrous lactitol ⁇ of the present invention may also be crystallized directly from an aqueous solution by boiling and/or cooling crystallizations in which the crystallization is slow, i.e. a boiling crystallization wherein there is a low input of energy or a cooling crystallization wherein the cooling time is long compared to normal industrial crystallization times used in the production of anhydrous lactitol .
  • Such a crystallization may even take two days or more in order to provide a crystal yield which consists essentially of ⁇ crystals.
  • ⁇ crystals have also been observed under suitable conditions in much shorter crystallization times.
  • a shorter crystallization may require the use of accelerating means or the above mentioned conditioning time in order to provide a meaningful yield of ⁇ .
  • the aqueous lactitol solution may be seeded or allowed to seed spontaneously.
  • the lactitol solution is evaporated under stirring at a temperature of 80° C to 100° C to a suitable supersaturation, seed crystals are added if desired, and the evaporation is continued, advantageously with addition of solution, to increase the crystal concentration to a dry solids content of about 90% by weight. Thereafter the crystals can be conditioned if they are square shaped anhydrous crystals or just separated and dried if they are typical elongated anhydrous ⁇ crystals.
  • the crystallization yield is appropriate, typically 40% to 60% , whereupon the crystals are wet conditioned if needed, separated or, if necessary, washed and dried.
  • Dried crystals are typically obtained at a yield of 30% to 50% , and the purity of the crystals is typically more than 99% and the water content typically below 0.5 % .
  • Conventional evaporating and cooling crystallizers, centrifuges, and driers of the sugar industry may be used in the preparation.
  • the crystalline orthorhombic anhydrous lactitol ⁇ of the invention has been found to have a very low hygroscopicity both at 25 °C and 60 % relative humidity and at 40°C and 75 % relative humidity.
  • the water sorption of a sample of ⁇ crystals was less than about 0.3 % of water in 45 days even when the relative humidity of the ambient air was 75 % at 40 °C.
  • the novel crystalline orthorhombic anhydrous lactitol ⁇ is distinct from the prior known anhydrous crystalline lactitol forms Al and . It is also distinct from the other known crystalline lactitol forms. Table 1 below indicates the various known characteristic data of the crystalline lactitol forms. Table 1
  • the novel ⁇ lactitol crystals seem to be very stable and they have been found to be harder than the crystals. These two stable anhydrous lactitol crystal forms can easily be distinguished from each other by their different crystal structures as determined by x-ray powder diffraction. They can also be distinguished by their different melting enthalpies ( : 149 J/g; ⁇ : 166-169 J/g). However, their melting points are so close to each other that a melting point analysis alone cannot distinguish ⁇ from a.
  • the term crystalline signifies the fact that the product is crystalline in the technical sense (Integral crystal structure) and not powdery (microcrystal- line).
  • the mean crystal size of the industrially manufactured product is preferably between 0.2 mm and 0.6 mm depending on the application, and the desired size is obtained when the seeding technique of the invention is employed in the crystallization.
  • the crystal size is not limited to below 1 mm as crystals above 2 mm have also been obtained and the crystal size is only dependent on the crystallization conditions.
  • the new crystalline orthorhombic anhydrous lactitol ⁇ has a good flowability and storabili- ty. since it is stable at room temperatures, the relative humidity being below 60% .
  • the new crystalline orthorhombic anhydrous lactitol ⁇ is particularly suitable as a substitute for sugar in foodstuffs and sweets.
  • other sweeteners such as saccharine or xylitol or other lactitol forms such as lactitol monohydrate or anhydrous lactitol ⁇
  • a sweetener resembling sugar and yet having a considerably lower energy content.
  • Such a sweetener is friendly to the teeth. It can be used instead of sugar for instance in sweets, jams, bakery products, chocolate, juices, cream fillings and ice-creams, as well as in pharmaceutical and hygienic products, such as laxative and toothpaste.
  • the new anhydrous lactitol can also be used for tabletting purposes.
  • the new anhydrous lactitol ⁇ also is particularly suitable for the production of chocolate, to which it is considerably better suited than lactitol monohydrate and lactitol dihydrate and anhydrides prepared therefrom by drying.
  • the new anhydrous lactitol ⁇ can be milled for various applications wherein smaller particle sizes are required. Milling lowers the melting point of the product to about 145-149°C and the melting enthalpy to about 160-165 J/g, typically 161-163 J/g. While not wishing to be bound by any theories, the change in characteristics is believed to be due to a certain formation of amorphous components at milling.
  • the milling may produce particles having a mean particle size between about 5 and 300 ⁇ m, preferably between 50 and 200 ⁇ m.
  • the crystals were retained in the solution and the solution was kept at 76 °C for 44 hours. During this time the square shaped anhydrous crystals changed into typical needle-like anhydrous ⁇ crystals.
  • the needle-like crystals were separated from the mother liquor with a conventional centrifuge (diameter of basket 0.4 m); the centrifuging was carried out for three minutes at a speed of rotation of 1800 rpm.
  • the crystals were washed with 0.5 1 of warm water at a speed of rotation of about 1000 rpm. Finally, the crystals were dried with a conventional drum drier with hot air (90 °C).
  • a lactitol solution containing 99.5 % of lactitol on dry solids was evaporated to a super- saturation of about 1.15 and transferred into a cooling crystallizer.
  • the crystallizer was a conventional horizontal cylindrical batch-operated cooling crystallizer provided with a mixer and a recycling water jacket whose temperature was controlled by means of a microprocessor.
  • the cooling crystallization was performed in 10 hours from 82 °C to 70 °C with seeding with anhydrous crystals. At the end of the cooling the crystal yield was composed of square shaped anhydrous crystals. The crystals were retained in the solution at about 70 °C for 38 hours at the end of which the square shaped crystals had changed into typical needle-like crystals of anhydrous ⁇ .
  • the crystals were centrifuged off, washed rapidly with water, and dried with a fluidization drier with air having a temperature of about 65 °C. Dried anhydrous ⁇ crystals were obtained at a yield of about 30% ; the crystal size was about 0.45 mm, the melting point 151 °C to 152°C and the water content 0.2% .
  • the lactitol used was lactitol monohydrate produced by Xyrofin Oy, Kotka, Finland and the lactulitol was crystalline lactulitol with a purity of 91 % produced in the laboratory by Xyrofin Oy, Kantvik, Finland.
  • the evaporated solutions were each divided into two reaction vessels which were heated to 82 °C. The solutions were stirred for 10-20 minutes to reach the seeding temperature. Where appropriate the solutions were seeded with 1 g milled monoclinic anhydrous lactitol a (lot N050 32701 manufactured by Xyrofin Oy, Kotka). One lot was seeded with milled ⁇ crystals. Then the cooling programs were started: 80°C- > 70°C during 2 h and 80°C- > 70°C during 44 h, respectively.
  • a crystallization was performed in a pilot plant 400-1 crystallizer as boiling and cooling crystallization. Lactitol run-off from a previous lactitol crystallization (purity 94% on DS; 0.6% lactulitol) was used as free solution.
  • the lactitol run-off was filtered (1 ⁇ m GAF) and used as feed solution.
  • the solution was evaporated to RDS 86 - 87 % at a temperature of 67 - 74 °C during 3.5 hours.
  • the resulting crystals were seen to have the characteristic needle-like form of ⁇ .
  • the mass was then dropped into a 400 1 cooling crystallizer.
  • the resulting crystals were typical needlelike in shape indicating the production of anhydrous lactitol ⁇ .
  • Example 5 The crystals were analysed and were found to be ⁇ crystals. The crystals were milled, sieved and used in the application tests of Examples 5 to 7. Example 5
  • the crystallization was performed in a pilot plant 400-1 crystallizer as boiling and cooling crystallization. Lactitol run-off from a previous lactitol crystallization (purity 96 % on DS; 0.5 % lactulitol) was used as feed solution.
  • the lactitol run-off was filtered (1 ⁇ m GAF) and used as feed solution.
  • the mass was then dropped into a 400 1, cooling crystallizer.
  • the cooling program was (81 °C - > 70°C, 16 h, linear). After cooling the mass was left at constant temperature (about 70 °C) for 8 hours after which a crystal sample was taken for analysis. The crystals were found to be ⁇ crystals.
  • a crystallization was performed in a pilot plant 400 liter crystallizer as boiling and cooling crystallization. Lactitol run-off from a previous lactitol crystallization (purity 96 % on DS; 0.5 % lactulitol) was used as feed solution.
  • the lactitol run-off was filtered (5 ⁇ m GAF) and used as feed solution.
  • the mass was then dropped into a 400 liter cooling crystallizer.
  • the cooling program was (85 °C - > 70°C, 16 h, linear). After cooling the mass was left at constant temperature (about 70 °C) for 8 hours after which a crystal sample was taken for analysis. The crystals were found to be ⁇ crystals, a detectable amount of form crystals was present.
  • a crystallization was performed in a pilot plant 400 liter crystallizer as boiling and cooling crystallization. Lactitol run-off from a previous lactitol crystallization (purity 96% on DS;
  • the lactitol run-off was filtered (5 ⁇ m GAF) and used as feed solution.
  • the crystal foot was made as described in Example 6, except that seeding was made at 90°C and the cooling program was as follows: 90°C - > 80°C, 16 h, linear.
  • the mass was then dropped into a 400 1 cooling crystallizer.
  • the cooling program was (92°C - > 80°C, 16 h, linear). After cooling the resulting crystals were seen to have the characteristic needle-like form of ⁇ lactitol.
  • a crystallization was performed in a pilot plant 6 liter crystallizer as cooling crystallization. Lactitol run-off from a previous lactitol crystallization (purity 96% on DS; 0.5 % lactulitol) was used as feed solution.
  • the lactitol run-off was filtered (5 ⁇ m GAF) and used as feed solution.
  • the solution was evaporated to RDS 87-88 % at a temperature of about 80 °C during 3 hours. Thereafter seeding was made by ⁇ form crystal foot (about 2 % on DS) at a temperature of about 86°C.
  • the crystal foot was made as described in example 8.
  • the cooling program was (86°C - > 70°C, 16 h, linear). After cooling the resulting crystals were seen to have the characteristic needle-like form of ⁇ lactitol.
  • a crystallization was performed in a pilot plant boiling pan and a 2 liter reaction vessel. Lactitol run-off from a previous lactitol crystallization (purity 96 % on DS; 0.5 % lactulitol) was used as feed solution. The lactitol run-off was filtered (1 ⁇ g GAF) and used as feed solution. The solution was evaporated in a boiling pan to RDS about 88 % at a temperature of about 95 °C. Spontaneous square shaped form crystals were observed. The boiling was continued for about 40 minutes, after which part of the mass was transferred into 2-1 reaction vessel at a temperature of 95 °C.
  • the cooling program was (95 °C - > 85 °C, 16 h, linear). After cooling the mass was left at constant temperature (about 85 °C) and the conversion from form crystals to ⁇ form crystals was observed. After 10 days conditioning only a form crystals were seen. After 11 days conditioning also some ⁇ form crystals were seen and after 14 days the crystal yield was totally in the ⁇ lactitol form.
  • a crystallizations were performed in a pilot plant 400 liter, in a 10 liter and a 6 liter crystallizer as boiling and cooling crystallizations. Lactitol run-off from a previous lactitol crystallization (purity 96% on DS; 0.5% lactulitol) was used as feed solution.
  • the lactitol run-off was filtered. (1 ⁇ m GAF) and used as feed solution. The solution was evaporated to RDS 86-87 % at a temperature of 70-80 °C during 2 hours. Thereafter seeding (75 g; 0.025 % on DS) was made by milled and sieved anhydrous c. lactitol seed crystals (lot N050T9CI6 produced at Thomson, USA) at a temperature of 80°C. Boiling was continued for 3.5 hours (final Brix about 91). The crystals were seen to have the square shaped form of crystals.
  • the mass was then transferred into 400-1, 10-1 and 6-1 cooling crystallizers.
  • the cooling program in the 400-1 crystallizer was (84°C - > 70°C, 16 h, exp. 1). After cooling the mass was left at constant temperature (about 70 °C) and the conversion from form crystals to ⁇ form crystals was observed. After 3 days conditioning the crystals were still in the form. After 6 days conditioning the crystal mass was totally in ⁇ form.
  • the cooling program in the 6-1 crystallizer was (84°C - > 70°C, 16 h, exp. 1). After cooling the mass was left at constant temperature (about 70°C) and the conversion from a form crystals to ⁇ form crystals was observed. One day from the start of the cooling program the crystals were still form. Two days after the start of the cooling program also needle-like ⁇ form crystals were present in the mass and after three days the crystal mass was totally in ⁇ form.
  • the cooling program in the 10-1 crystallizer was (84°C - > 70°C, 75 h, exp. 3). After cooling the mass was left at constant temperature (about 70 °C) and the conversion from form crystals to ⁇ form crystals was observed. One day from the start of the cooling program the crystals were still form. Two days after the start of cooling program also needle-like ⁇ form crystals were present in the mass and after three days the crystal mass was totally in ⁇ lactitol form.
  • the milled lactitol particles were still in the anhydrous ⁇ form according to DSC measurements and X-ray powder diffractograms .
  • Lactitol product crystallization run-off (RDS 49.1 % , purity about 94%) was used as feed solution.
  • the solution was evaporated under reduced pressure to RDS 93.2% .
  • the syrup was further concentrated by boiling without vacuum until the temperature 133 °C was reached.
  • the syrup (2.9 kg, RDS 95 %) was moved to a reaction vessel.
  • Seeding was made by 1 g milled anhydrous lactitol (lot N050 32701 manufactured by Xyrofin Oy, Kotka) at 120°C. The mass was cooled from 120°C to 100°C linearly during 2 hours. The obtained crystals were typically needle-like in shape indicative of orthorhombic anhydrous ⁇ lactitol.
  • the mass was centrifuged using a laboratory centrifuge after 18 hours from seeding. Centrifugation parameters: 3500 rpm for 1 minute with hot 20 ml 85 °C water wash. The slightly yellowish crystals were dried over night at 80 °C oven.
  • Lactitol product crystallization run-off (RDS 49.1 % , purity about 94%) was used as feed solution. The solution was evaporated under reduced pressure to RDS 84.6% . The syrup was further concentrated by boiling without vacuum until the temperature 129 °C was reached. The syrup (RDS 91.6%) was moved to a reaction vessel. Seeding was made at 105 °C by 1 g milled anhydrous lactitol (lot N050 32701) manufactured by Xyrofin Oy, Kotka, Finland). The mass was cooled from 105°C to 85°C linearly during 2 hours. The crystals were seen to have the typical elongated shape indicative of anhydrous ⁇ lactitol.
  • the mass was centrifuged using a laboratory centrifuge after 18 hours from seeding. Centrifugation parameters: 3500 rpm for 1 minute with hot 20 ml 85 °C water wash. The white crystals were dried over night at 80 °C oven.
  • Orthorhombic anhydrous ⁇ lactitol was produced in accordance with Example 4 and dried. The crystals were milled to a mean particle size under 312 ⁇ . Milled lactitol CM50 (produced by Danisco Sweeteners), which has previously proven to give a biscuit with good eating qualities, was used as a control.
  • Orthorhombic anhydrous ⁇ lactitol was produced in accordance with Example 4 and dried.
  • the anhydrous ⁇ lactitol crystals had a particle size under 800 ⁇ .
  • As a control crystalline lactitol monohydrate (produced by Danisco Sweeteners) was used.
  • the lactitol grade used for this application was anhydrous ⁇ lactitol having a particle size under 250 ⁇ . As a control commercially available milled lactitol was used.
  • the sample was then stored molten at 50 °C for a period of 7 days.
  • the viscosity of the conched chocolate mass was measured (Haake RV 20 Viscometer) and the yield value was calculated. No thickening was observed. Performance was comparable to anhydrous lactitol and superior to lactitol monohydrate and lactitol dihydrate where thickening would be apparent.
  • the viscosity and yield values have been presented in Table 3 below.
  • chocolate mass manufactured using crystalline anhydrous ⁇ lactitol was easier to treat further into products than lactitol monohydrate or dihydrate masses.

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Abstract

L'invention concerne de nouveaux cristaux de lactitol (β) anhydre appartenant au système cristallin orthorhombique P212121 et ayant des constantes de cellules unitaires a = 9,6 Å, b = 11,1 Å, c = 14,0 Å. L'invention concerne également des produits au lactitol cristallin contenant le nouveau lactitol (β) anhydre ainsi qu'un procédé permettant de les préparer par cristallisation à partir d'une solution aqueuse de lactitol. Le nouveau lactitol (β) anhydre, stable et non-hygroscopique, peut être utilisé comme produit de substitution du sucre dans des aliments et sucreries, ainsi que dans des produits pharmaceutiques et hygiéniques.
PCT/FI2000/000791 1999-09-20 2000-09-19 Cristaux de lactitol anhydre, produit les contenant, leur procede de preparation et leur utilisation Ceased WO2001021633A1 (fr)

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AU72921/00A AU7292100A (en) 1999-09-20 2000-09-19 Anhydrous lactitol crystals, a product containing the same and a process for thepreparation thereof as well as use thereof
EP00960720A EP1214329A1 (fr) 1999-09-20 2000-09-19 Cristaux de lactitol anhydre, produit les contenant, leur procede de preparation et leur utilisation

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US60/154,853 1999-09-20

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02255694A (ja) * 1989-03-29 1990-10-16 Towa Kasei Kogyo Kk ラクチトール無水物結晶を含有する含密結晶の製造方法及び含密結晶組成物の製造方法
WO1992016542A1 (fr) * 1991-03-22 1992-10-01 Xyrofin Oy Lactitol anhydre cristallin, et procede de preparation et d'utilisation du lactitol
EP0832899A1 (fr) * 1996-09-27 1998-04-01 Roquette FrÀ¨res Composition de lactitol et son procédé de préparation
WO1998039350A1 (fr) * 1997-03-03 1998-09-11 Xyrofin Oy Procede de cristallisation du lactitol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02255694A (ja) * 1989-03-29 1990-10-16 Towa Kasei Kogyo Kk ラクチトール無水物結晶を含有する含密結晶の製造方法及び含密結晶組成物の製造方法
WO1992016542A1 (fr) * 1991-03-22 1992-10-01 Xyrofin Oy Lactitol anhydre cristallin, et procede de preparation et d'utilisation du lactitol
EP0832899A1 (fr) * 1996-09-27 1998-04-01 Roquette FrÀ¨res Composition de lactitol et son procédé de préparation
WO1998039350A1 (fr) * 1997-03-03 1998-09-11 Xyrofin Oy Procede de cristallisation du lactitol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199047, Derwent World Patents Index; AN 1990-352830, XP002908992 *

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