EP0598022B1 - Procede pour l'impregnation de grains avec un liquide, ainsi que dispositif pour la realisation du procede et application du procede - Google Patents

Procede pour l'impregnation de grains avec un liquide, ainsi que dispositif pour la realisation du procede et application du procede Download PDF

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Publication number
EP0598022B1
EP0598022B1 EP92917686A EP92917686A EP0598022B1 EP 0598022 B1 EP0598022 B1 EP 0598022B1 EP 92917686 A EP92917686 A EP 92917686A EP 92917686 A EP92917686 A EP 92917686A EP 0598022 B1 EP0598022 B1 EP 0598022B1
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Prior art keywords
grains
liquid
process according
pipe
grain
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EP92917686A
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German (de)
English (en)
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EP0598022A1 (fr
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Dieter Otto Dipl.-Ing. Gräf
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02B—PREPARING GRAIN FOR MILLING; REFINING GRANULAR FRUIT TO COMMERCIAL PRODUCTS BY WORKING THE SURFACE
    • B02B1/00—Preparing grain for milling or like processes
    • B02B1/04—Wet treatment, e.g. washing, wetting, softening

Definitions

  • the invention relates to a method for wetting cereals, in particular cereal grains, with a liquid, hereinafter referred to simply as water, and a device for carrying out the method.
  • the flour body (endosperm) of a cereal grain must be separated from the husk (bran and germ).
  • the cereal grains are wetted with water, so that their husk softens and can then be better separated during the grinding process.
  • the cereal grains are mixed with water in a screw conveyor and mixed in the process.
  • FR-A 2 540 746 provides for the screw conveyor to be designed as a roller with protruding plates arranged helically on the roller.
  • the cereals are only slowly transported to the outlet opening, because some of the cereals can fall through between the plates and are not transported forward, so that the residence time of the cereal-liquid mixture in the mixing device is long-lasting.
  • Such wetting usually causes an even distribution of water on the surface of the grain. This uniform water distribution is not sufficient, as has been shown, for example, to separate the flour body from the shell in a subsequent grinding process.
  • the long standing time has a disadvantageous effect on the quality of the flour, since mold and yeast and / or bacteria (for example enterobacteria C) often form and multiply during the long storage period because of the moisture in the grain.
  • mold and yeast and / or bacteria for example enterobacteria C
  • enterobacteria C enterobacteria C
  • the snail which has a length of between three and eight meters, or is designed in accordance with FR-A 2 540 746 is a good source of germs for mold and / or bacteria, so that the snails have to be cleaned frequently, which leads to interruptions and greatly interferes with the continuous process.
  • the screw conveyor according to FR-A 2 540 746 is difficult to clean because of the protruding plates.
  • cereals are wetted with water for the production of a malt in the production of beer.
  • the whole of the grains i.e. the kernel and shell for the production of the malt, should absorb a very high water content so that the grains start to germinate.
  • the penetration of the water into the shell and from the shell into the core is promoted in that the Shell of each grain is in turn wetted as evenly as possible, so that the water can penetrate into the shell and the core from all sides.
  • the cereals are moved forward on a conveyor table by swinging the table and are sprayed with water with the aid of a plurality of nozzles arranged along the conveyor table, so that the cereals are mixed well with the water and, so to speak, a water film is placed around each grain.
  • a pressure of the wheat column on the vibrating sieve of at least 0.01 atm is required, which corresponds to a thickness of the wheat layer above the vibrating sieve of 0.5 to 0.6 meters.
  • This process of conditioning wheat kernels before grinding the varieties increases the Yield of flour of high quality grades by 5.0 to 5.5% achieved with a reduction in the ash content of the flour by 0.03 to 0.05%.
  • the grain is soaked several times over a long period in the course of conditioning.
  • a soaking time of 10 hours is provided in the course of the first treatment stage, a soaking time of 4 hours in the course of the second treatment stage and finally a soaking time of 10 to 20 minutes in the course of the third treatment stage.
  • cereals is to be understood to mean all fruits which have a core and a hard or soft skin or skin surrounding the core.
  • Water can be used as the liquid for the treatment.
  • corn should be used as an extruder Popcorn are processed, sugar will be added to the liquid (water), so use sugar water.
  • Molasses can be used as liquid for the treatment of cattle feed.
  • the object of the invention is to provide a wetting process for cereals, in which the cereals are wetted with liquid in such a way that the standing time is practically eliminated as a storage time, and in which the transportability of the cereals wetted with liquid is immediate, that is to say immediately or already after 10 to 30 minutes is given.
  • Transportability is understood to mean that the cereals, for example wetted with water, no longer have an outer water film which leads to sticking to the means of transport (belts, screws or the like).
  • This shaking process can be carried out gently, that is, in such a way that the husks of the cereals are not damaged, so that the liquid, evenly distributed, penetrates directly into the husk of each grain.
  • the shell of the grain is first penetrated with moisture relatively quickly, and the moisture then penetrates from the shell into the interior of the grain relatively uniformly from all sides.
  • the advantage of the method according to the invention is therefore to be seen in the fact that the grain can be transported to its processing site immediately or after a short residence time after wetting, in order to be ground there, for example, and that there is no intermediate storage of the grain.
  • the method according to the invention also has the advantage that, for example, a mesh screw for mixing the grain with the water is no longer necessary, since other simpler means are available, such as a simple agitator or a funnel arrangement according to subclaim 8. This results in greater cleanliness and thus achieved better hygiene.
  • an energy saving is achieved since the drive of the line screw or similar devices requires considerably more energy than the vibrating device according to the invention.
  • bacteria and fungi in particular have less opportunity to multiply due to the lack of storage time.
  • the device according to the invention expediently consists of a tube with a preferably vertically arranged axis, which is connected, for example, approximately in the middle to one or more vibrating motors.
  • the cereals, mixed with liquid, for example water, can be filled into the tube at the top, and they run out again below.
  • the flow rate can be regulated by measuring and control devices. In this way, the residence time of the cereal-liquid mixture in the tube can be regulated.
  • a discharge element can be provided at the lower end of the tube, which takes the cereals in the desired amount either continuously or discontinuously from the tube.
  • Such a discharge element can be formed, for example, by a cone which is introduced more or less into the pipe end and thus either completely interrupts the outflow of the cereals or optionally allows certain quantities of cereal / liquid mixture to escape.
  • a cone which is introduced more or less into the pipe end and thus either completely interrupts the outflow of the cereals or optionally allows certain quantities of cereal / liquid mixture to escape.
  • cellular wheel sluices, vibrating troughs, sliders of all kinds or screw conveyors can also be used.
  • the tube can also be arranged with a horizontal axis, so that the cereals are inserted from one side. This shaking may be appropriate when the grain-liquid mixture is to be shaken in batches.
  • the tube advantageously has smooth walls on the inside, so that, in particular, the shells of the cereals are not injured when shaken for the reasons mentioned at the outset, because, as already stated, if the shells are injured, the water penetrates the shell unevenly, namely first at the injury sites in order to penetrate further from here on the one hand into the shell and on the other hand into the core. As a result, the shell is moistened unevenly and therefore the desired exact separation of the shell and core is negatively influenced during the grinding process. Because at the points where the shell is not yet sufficiently moist, core pieces of the Grain still firmly on the bowl and stick to the bowl during the grinding process.
  • the tube can also have partition walls so that the maximum distance of each grain from one of the walls set in vibration remains small.
  • the cereal-liquid mixture does not hit the walls hard since the grains mixed with liquid are arranged relatively compactly in the tube or in the tube chambers, i.e. the energy transfer to the cereal-liquid mixture does not take place by hard impacts on it Mixture, but by contact of the grains and possibly the liquid droplets on the pipe wall or an intermediate wall.
  • the liquid tears into the finest droplets, which are deposited directly on the husks of the cereals and penetrate into the husks.
  • additives can be added to the liquid in a further embodiment of the invention.
  • Enzymes such as proteinases, proteases or the like, vitamins such as ascorbic acid, nitrates, salts and / or sugars can be provided as additives.
  • These additives dissolved in the liquid can change the properties of the cereals, such as raw fibers, starch, proteins, fats and / or mucilages, as well as the cell structures and thus, for example, the grindability of the grains.
  • the process according to the invention can, as already mentioned, also be used for the production of malt, as required by the brewer, by adding the cereals are expediently shaken several times with the addition of a liquid.
  • a liquid for example water
  • more liquid, for example water can be bound in the cereals in a short time, that is to say the percentage by weight of liquid in the grain can be increased far above the usual level, so that the cereal grains begin to germinate in a much shorter time.
  • cereal grains (100) are filled in the direction of arrow (101) in a funnel (102), in such a way that fewer cereal grains run out of the funnel opening (103) than are filled in above, so that the cereal grains are over the top edge (104) of the funnel swell and fall past it through the lower opening (105) of an outer funnel (106) surrounding the funnel (102). With the help of an inflow (107), water is supplied to the cereal grains in the area of the funnel (102).
  • a simple stirrer or other device can also be used to mix the cereals with the water.
  • the cereal grains thus mixed with water fall through an enlarged opening (110) of an approximately vertically arranged pipe (111).
  • the tube (111) is supported by means of rubber buffers (112) on a fixed frame (113) in such a way that it can move in the direction of the arrow (115) and its upper part (111a) and the lower part (111b) can swing transversely to the axis AA of the tube in the direction of arrow (115).
  • the tube (111) carries a sleeve (116) which is firmly connected to a vibrating motor (114).
  • a cellular wheel sluice known per se, a slide mechanism, a vibrating trough or the like can also be suitably connected to the tube.
  • the grain can also be passed through in batches.
  • the outlet opening (121) is closed and the tube is shaken for a predetermined time after filling in the cereal-liquid mixture. After opening the outlet, the wetted cereals flow out of the tube and the tube can be refilled.
  • a control device (130) is provided for the continuous passage of the cereals.
  • the control device (130) receives measured values from a sensor (131) which indicates the flow rate of the cereals into the tube (111).
  • the device (130) regulates the refilling of the funnel (102) with cereals and water.
  • a measuring device (132) measures the outflow quantity of the cereals from the tube (111).
  • the measuring device (130) controls this outflow quantity and thus the residence time of the cereals in the tube.
  • the cereal-liquid mixture lies compactly in the tube during the shaking process, so that it does not hit the tube wall too strongly when shaking, but rather is only exposed to high acceleration forces.
  • a tube filling usually requires 2 to about 15 seconds or more of shaking time, i.e. the cereals which have entered above should be shaken in the tube for about 2 to 15 seconds or more, regardless of whether they are filled and shaken in batches in the tube or run continuously through the pipe.
  • the length of the tube is dimensioned accordingly.
  • a tube of one meter length is usually sufficient.
  • the cereals emerging from the bottom of the tube (111) fall through a guide tube (140) onto a distribution plate (141) and from there into a collecting container (142).
  • the emerging cereals are immediately transportable, so that they can be transported with the aid of conveyor belts, snails and the like, without sticking to these parts due to adhesive forces, to a processing location without time-consuming intermediate storage.
  • the tube (111) can have a circular, elliptical or rectangular, also square, cross section. It is only intended to ensure that the cereals receive their acceleration energy from the inner wall of the tube to a sufficient extent during the shaking process.
  • the diameter of the tube (111) can be increased in order to allow larger quantities to pass through.
  • the vibrating effect is reduced towards the inside of the pipe, since the energy transfer of the cereal-liquid mixture from grain to grain to the center of the pipe is reduced.
  • longitudinal walls (150) are provided in a further exemplary embodiment in the interior of a tube (122), which further Form energy transfer walls for the grain-liquid mixture passing through.
  • FIG. 4 Another solution to this problem is shown in FIG. 4.
  • Three tubes (151, 152, 153) are provided here, which are firmly connected to one another and can be shaken together.
  • Fig. 5 shows the tube (123) with retracted partitions (124), so that rectangular spaces (125) are formed in the tube over the length of the tube, the transverse walls being at a relatively short distance from one another, so that the rectangular spaces become very narrow. If one shakes such a tube with a frequency of 75 to 80 Hz, the tube walls give the grain-liquid mixture an acceleration of five to fifteen times the acceleration due to gravity, whereby the liquid tears and the grains evenly wet, so that the liquid directly into the bowls that penetrates grains. This penetration is promoted by the acceleration forces exerted on the cereals and also the further penetration of the liquid into the core of the cereals.

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  • Cereal-Derived Products (AREA)
  • Storage Of Fruits Or Vegetables (AREA)
  • Processing Of Solid Wastes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Transmission And Conversion Of Sensor Element Output (AREA)
  • Formation And Processing Of Food Products (AREA)
  • Materials For Photolithography (AREA)
  • Apparatuses For Bulk Treatment Of Fruits And Vegetables And Apparatuses For Preparing Feeds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Grain Derivatives (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Adjustment And Processing Of Grains (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (33)

  1. Procédé pour l'imprégnation de graminés avec un liquide selon lequel les graminés, au cours d'un mouvement transporteur, sont mélangés avec un liquide et secoués dans un récipient (111) caractérisé en ce que les graminés après ou pendant du mélange avec le liquide traversent continuellement ou par lots le récipient du dispositif de vibrations, de sorte que les parois du récipient en forme de tube transfèrent leur énergie cinétique au mélange de graminés-liquide de telle sorte que les graminés et le liquide sont soumis à de grandes forces d'accélération.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on secoue le mélange de graminés-liquide avec une fréquence de 50 à 300 Hz, de préférence de 75 Hz.
  3. Procédé selon la revendication 1, caractérisé en ce que la durée de secousses est d'environ 2 à 20 secondes.
  4. Procédé selon la revendication 1, caractérisé en ce qu'on secoue le mélange de graminés-liquide à l'aide d'énergie mécanique, électrique et/ou magnétique et/ou à l'aide d'ultrasons.
  5. Procédé selon la revendication 1, caractérisé en ce que les graminés sont disposés de façon compacte dans le récipient ou qu'ils traversent celui-ci.
  6. Procédé selon la revendication 1, caractérisé en ce que les graminés et l'eau sont rassemblés dans un dispositif de mélange installé avant le dispositif de secousses et sont conduits de ce dispositif de mélange directement dans le dispositif de se secousses.
  7. Procédé selon la revendication 1, caractérisé en ce que les graminés sont amenés dans une trémie dans une telle quantité que, d'une part ils sortent par l'orifice inférieure de la trémie en ruisselant et d'autre part, ils tombent par-dessus le bord supérieur de la trémie, en ce que le liquide est conduit dans l'orifice de remplissage de la trémie et en ce que les graminés ainsi humidifiés sont conduits, respectivement tombent, dans l'installation à secousses.
  8. Dispositif pour la mise en oeuvre du procédé selon la revendication 1, un récipient (111) avec son axe longitudinal (A-A) étant disposé dans le sens du flux de produit et relié avec au moins un moteur (114) qui met le récipient en mouvement de secousses, caractérisé en ce que le récipient se compose d'au moins un tube (111) dont l'axe longitudinal (A-A) est disposé horizontalement ou verticalement, où le moteur (114) produisant les mouvements de secousses agit sur la partie sensiblement médiane d'au moins un tube, de sorte que celui est secoué dans le sens perpendiculaire à son axe longitudinal.
  9. Dispositif selon la revendication 8, caractérisé en ce que le tube est disposé avec un axe sensiblement vertical, en ce que dans la partie supérieure du tube (111) est prévu le dispositif de mélange (102, 107) pour les graminés avec le fluide et dans la partie inférieure du tube (111), un dispositif de réglage (120, 121) du débit et/ou de reprise des graminés.
  10. Dispositif selon la revendication 9, caractérisé en ce que le dispositif de réglage (120, 121) du vidange des graminés du tube (111) se compose, plus ou moins, d'un corps conique (120) que l'on peut introduire dans l'extrémité du tube (121), dont la pointe est orientée vers l'extrémité du tube.
  11. Dispositif selon la revendication 9, caractérisé en ce que l'installation (120, 121) comprend une écluse à roue cellulaire, une vis pivotante autour de son axe avec une vitesse réglable, une gouttière secouée, reliée à l'extrémité du tube, ou un dispositif de verrouillage.
  12. Installation selon la revendication 8, caractérisée par un dispositif (130, 131) de mesure et de contrôle de la quantité de graminés et de liquide amenée dans le récipient de dispositif à secousse.
  13. Installation selon la revendication 9, caractérisée par un dispositif (132,130) de mesure et de contrôle de la quantité déchargée de graminés.
  14. Installation selon les revendication 12 et 13, caractérisée par un dispositif de réglage (130) qui règle la durée de séjour du mélange des graminé et de liquide dans l'installation à secousse.
  15. Installation selon la revendication 9, caractérisée en ce qu'après le dispositif (120, 121) est connecté un plateau distributeur.
  16. Installation selon la revendication 8, caractérisé en ce que le tube (111) présente une coupe transversale circulaire ou elliptique.
  17. Installation selon la revendication 8, caractérisée en ce que le tube présente une coupe transversale rectangulaire ou quadratique.
  18. Installation selon la revendication 8, caractérisée en ce le tube (122) présente plusieurs parois séparatrices (124, 150) divisant l'espace intérieur dans le sens longitudinal.
  19. Installation selon la revendication 18, caractérisée en ce que les espaces (125) formés par les parois (124) présentent une coupe transversale rectangulaire sensiblement plate.
  20. Installation selon la revendication 8, caractérisée en ce plusieurs tubes (151, 152, 153) sont reliés entre eux.
  21. Installation selon la revendication 8, caractérisée en ce le diamètre des tubes (111, 151, 152, 153) est d'environ dix centimètres.
  22. Procédé selon la revendication 1, caractérisé en ce que la vitesse d'accélération que l'on applique au le mélange de graminés et de liquide est d'environ 10 à 15 g (g = un gravité de la pesanteur).
  23. Procédé selon la revendication 1, caractérisé en ce que par graminés on entend des fruits avec une enveloppe dure et souple, comme les grains de céréales, les légumineuses, le maïs, le riz, ainsi que le riz décortiqué et similaire, ainsi que les graines, tels que les grains de café, les fèves de cacao ou analogues, ainsi que des fruits qu'on peut extruder
  24. Procédé selon la revendication 1, caractérisé en ce qu'on utilise en tant que liquide l'eau, l'eau sucrée, la mélasse ou similaires.
  25. Procédé selon la revendication 1, caractérisé en ce qu'on ajoute au liquide au moins un additif soluble dans ce liquide, tels que l'enzyme, la vitamine, le nitrate, le sel et/ou le sucre, lequel additif modifie au moins une caractéristique des graminés, comme les fibres brutes, l'amidon, les protéines, les graisses, les substances muqueuses ou analogues, mais aussi les matières aromatiques, les colorantes et autres.
  26. Procédé selon la revendication 1, caractérisé en ce que les graminés mélangés avec le liquide sont secoués à plusieurs reprises à des intervalles de temps pour les séparer l'un de l'autre.
  27. Procédé selon la revendication 26, caractérisé en ce que l'intervalle de temps est d'environ 30 minutes à 5 heures.
  28. Utilisation du procédé selon la revendication 26 dans le domaine de la brasserie pour la préparation de maltes, tel que le malte de froment, le malte d'orge, le malte de millet, le malte de sorgho ou analogues, caractérisée en ce que les graminés sont secoués à des intervalles de temps pour les séparer l'un de l'autre en ajoutant chaque fois du liquide.
  29. Procédé selon la revendication 1, caractérisé en ce que les graminés sont secoués sans qu'ils soient endommagés sur leur surface.
  30. Dispositif selon la revendication 8, caractérisée en ce que le tube (111) présente à l'intérieur des parois séparatrices et/ou des parois lisses.
  31. Procédé selon la revendication 1, caractérisé en ce que les graminés sont traités de telle façon que l'on applique aux graminés une pression osmotique lors du passage à travers le tube.
  32. Procédé selon la revendication 1, caractérisé en ce que les graminés sont transformés après le procédé de secouage en farine.
  33. Procédé selon la revendication 1, caractérisé en qu'on utilise le mélange de graminés-liquide suite au procédé de secouage pour la préparation de produit d'extrusion.
EP92917686A 1991-08-17 1992-08-12 Procede pour l'impregnation de grains avec un liquide, ainsi que dispositif pour la realisation du procede et application du procede Expired - Lifetime EP0598022B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4127290 1991-08-17
DE4127290A DE4127290A1 (de) 1991-08-17 1991-08-17 Verfahren zum benetzen von koernerfruechten mit einer fluessigkeit sowie vorrichtung zur durchfuehrung des verfahrens
PCT/EP1992/001843 WO1993003843A1 (fr) 1991-08-17 1992-08-12 Procede pour l'impregnation de grains avec un liquide, ainsi que dispositif pour la realisation du procede et application du procede

Publications (2)

Publication Number Publication Date
EP0598022A1 EP0598022A1 (fr) 1994-05-25
EP0598022B1 true EP0598022B1 (fr) 1995-05-24

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EP92917686A Expired - Lifetime EP0598022B1 (fr) 1991-08-17 1992-08-12 Procede pour l'impregnation de grains avec un liquide, ainsi que dispositif pour la realisation du procede et application du procede

Country Status (13)

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US (2) US5512310A (fr)
EP (1) EP0598022B1 (fr)
JP (2) JPH0822386B2 (fr)
AT (1) ATE122933T1 (fr)
AU (1) AU2406492A (fr)
BR (1) BR9203191A (fr)
CA (1) CA2115832C (fr)
CZ (1) CZ284035B6 (fr)
DE (4) DE9110617U1 (fr)
ES (1) ES2072764T3 (fr)
HK (1) HK41397A (fr)
UY (1) UY23461A1 (fr)
WO (1) WO1993003843A1 (fr)

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EP0861600A1 (fr) * 1997-02-26 1998-09-02 Micronizing Company (UK) Limited Traitement des graines et semences

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RU2181308C2 (ru) 1997-07-09 2002-04-20 Машинен-унд Мюлленбау Виттенберг ГмбХ Способ помола зерна и устройство для его осуществления
US6000321A (en) * 1999-06-23 1999-12-14 Kabushiki Kaisha International Chemical Rice washing apparatus
JP4160710B2 (ja) * 2000-03-09 2008-10-08 鈴茂器工株式会社 洗米装置
KR100495010B1 (ko) * 2002-01-22 2005-06-13 정명구 정미기
ITMI20022066A1 (it) * 2002-09-30 2004-04-01 Barilla Alimentare Spa Procedimento per la produzione di sfarinati di grano.
CN100482142C (zh) * 2004-05-12 2009-04-29 皇家飞利浦电子股份有限公司 包括煮器和用于将煮器连接到设备的壳体的连接装置的热饮料制备设备
US20080075815A1 (en) * 2006-09-25 2008-03-27 Reynolds Rodney K Free low popcorn funnel apparatus
PL1978084T3 (pl) * 2007-03-30 2010-01-29 Krones Ag Sposób filtracji piwa
DE102010061318B3 (de) 2010-12-17 2012-04-05 Vibronet Gräf Gmbh & Co. Kg Vorrichtung zum Benetzen von Körnerfrüchten mit einer Flüssigkeit sowie Verfahren zum Benetzen von Körnerfrüchten mit einer Flüssigkeit
RU2566482C1 (ru) * 2014-07-24 2015-10-27 Общество с ограниченной ответственностью Инновационная научно-производственная компания "Хлеботехника" Способ непрерывного изготовления и порционного дозирования мучного клейстеризата на замес теста батоно-булочных изделий
CN104492521A (zh) * 2014-11-18 2015-04-08 陈江浩 一种谷物振动着水机
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DE102019205793A1 (de) 2019-04-23 2020-10-29 Elea Vertriebs- Und Vermarktungsgesellschaft Mbh Verfahren zum Konditionieren von Pflanzensamen für die Zerkleinerung, insbesondere zur Beeinflussung der Elastizität der Pflanzensamen, und Anlage zur Zerkleinerung von Pflanzensamen
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DE4127290A1 (de) 1993-02-18
BR9203191A (pt) 1993-04-06
JP2646171B2 (ja) 1997-08-25
DE59202365D1 (de) 1995-06-29
CA2115832C (fr) 1999-01-19
UY23461A1 (es) 1992-10-21
JPH06504722A (ja) 1994-06-02
DE4292660D2 (de) 1995-12-21
DE9110617U1 (de) 1991-11-07
US5512310A (en) 1996-04-30
WO1993003843A1 (fr) 1993-03-04
JPH06213678A (ja) 1994-08-05
ES2072764T3 (es) 1995-07-16
CZ32494A3 (en) 1994-10-19
CZ284035B6 (cs) 1998-07-15
DE4127290C2 (fr) 1993-07-08
CA2115832A1 (fr) 1993-03-04
AU2406492A (en) 1993-03-16
HK41397A (en) 1997-04-11
EP0598022A1 (fr) 1994-05-25
JPH0822386B2 (ja) 1996-03-06
ATE122933T1 (de) 1995-06-15
US5586492A (en) 1996-12-24

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