EP0629707B1 - Verfahren zur Enthartung von zuckerenthaltenden Säften wie Melasse und Verwendung desselben zu einem Verfahren zur Gewinnung der in dieser Melasse enthaltenden Zuckern - Google Patents
Verfahren zur Enthartung von zuckerenthaltenden Säften wie Melasse und Verwendung desselben zu einem Verfahren zur Gewinnung der in dieser Melasse enthaltenden Zuckern Download PDFInfo
- Publication number
- EP0629707B1 EP0629707B1 EP94401313A EP94401313A EP0629707B1 EP 0629707 B1 EP0629707 B1 EP 0629707B1 EP 94401313 A EP94401313 A EP 94401313A EP 94401313 A EP94401313 A EP 94401313A EP 0629707 B1 EP0629707 B1 EP 0629707B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- resin
- sugars
- liquid effluent
- sugar juice
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B35/00—Extraction of sucrose from molasses
- C13B35/02—Extraction of sucrose from molasses by chemical means
- C13B35/06—Extraction of sucrose from molasses by chemical means using ion exchange
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B20/00—Purification of sugar juices
- C13B20/14—Purification of sugar juices using ion-exchange materials
- C13B20/144—Purification of sugar juices using ion-exchange materials using only cationic ion-exchange material
Definitions
- the present invention relates to a process for softening a sweet juice such than a sugar molasses and its use in a sugar recovery process contained in this sweet juice.
- the sugar cane or sugar beet industry produces significant amounts of non-crystallizable sweet juice known as candy molasses. Since this molasses has a non-negligible sugar content, it is usual to subject it to an appropriate treatment in order to extract the major part of the sugars which it contains. This treatment notably consists in subjecting the molasses to an ion exclusion chromatography using a fixed support constituted by a strong cationic resin, in the Na + and / or K + form .
- the said resin since the sugar molasses contains non-negligible quantities of dissolved calcium and / or magnesium salts, the said resin becomes charged with Ca 2+ and / or Mg 2+ ions during the chromatography operation and sees therefore its separation power decreases relatively quickly. This requires the periodic interruption of the chromatography operation to regenerate the cationic resin, which implies the consumption of a regeneration reagent and a decrease in productivity.
- the regeneration step of the process according to the invention makes astute use of one of the liquid effluents available in a sugar refinery installation, namely the so-called raffinate fraction generated during the separation by chromatography of the sugars from a sweetened sweetened juice loaded with Na + and / or K + ions, a fraction which was usually purely and simply rejected out of this installation.
- raffinate fraction generated during the separation by chromatography of the sugars from a sweetened sweetened juice loaded with Na + and / or K + ions
- the liquid effluent (raffinate) used in step (b) is advantageously constituted by that produced during the separation by chromatography of the sugars from the juice sweetened sweetness obtained in step (a).
- the invention it is also advantageous to concentrate the liquid effluent (raffinate) before its implementation in step (b), since the degree of regeneration is all the higher as the concentration of Na ions + and / or K + of this effluent is higher. It is also advantageous according to the invention, that before bringing said resin into contact with said liquid effluent in step (b), Na + and / or K + ions are added to said effluent, which will further improve the regeneration.
- the cation exchange resin used in step (a) will preferably be a strong cationic resin in the Na + and / or K + form and that the chromatography producing the liquid effluent (raffinate) used in step (b) is preferably carried out on a strong cationic resin in the Na + and / or K + form with elution with water.
- a strong cationic resin it is possible to choose in particular any resin comprising a polymer matrix, for example of the polystyrene or polyacrylate type, crosslinked by a crosslinking agent such as divinylbenzene, matrix on which are grafted cation exchange groups, such as acid groups. strongly acid sulfonic. Particular preference is given to IR 200 resin (trademark of a resin sold by Rohm and Haas).
- said first liquid effluent (raffinate) is preferably concentrated before its implementation in step (iii), that Na + and / or K + ions may be added to said first liquid effluent before the implementation of the latter in step (iii), that the cation exchange resin used in step (i) is preferably a strong cationic resin in the Na + and / or K + form and that the chromatography used in step (ii) is preferably carried out on a strong cationic resin in the Na + and / or K + form with elution with water.
- a strong cationic resin use can be made of those already mentioned above in connection with the softening process.
- the installation shown by way of example in this figure comprises, in a manner known per se, two softening units 1,2 each consisting of a column filled with a strong cationic resin, in the form Na + and / or K + , for example the IR®200 resin sold by Rohm and Haas. These columns are each provided, at their upper part, with a conduit 3,4 for supplying candy molasses (aqueous sweet juice) previously clarified and diluted with deionized water.
- the clarification can be carried out by any known method, for example by implementing the clarification process described in US-A-5 110 363. As for dilution, it is carried out so that the dry matter content of the molasses after dilution or preferably of the order of 10 to 70% by weight.
- the molasses thus clarified and diluted essentially comprises sugars, mineral salts of sodium, potassium, calcium and optionally magnesium and colorings.
- Each softening column 1, 2 is further provided, at its lower part, with a conduit 5,6 for softened molasses outlet, the conduits 5,6 both leading to a three-way valve 7 from which a conduit 8, the free end of which opens out at the top of a chromatography column 9.
- a circulation pump 10, 11 can be provided on each conduit 5.6.
- Each column 1,2 is finally provided, at its upper part, with a conduit 12, 13 for supplying resin regeneration liquid and, at its lower part, with a conduit 12 a , 13 a for outlet from spent regeneration liquid carrying respectively a shut-off valve 12 b , 13 b .
- the chromatography column 9 is of the type comprising a fixed support constituted by a strong cationic resin, in the Na + and / or K + form , the elution liquid being water brought into the upper part of the column by a conduit 14.
- This same column 9 further comprises, at its lower part, a conduit 15 for extracting a liquid effluent (raffinate) rich in sugars and a conduit 16 for extracting a liquid effluent poor in sugars.
- the concentration unit can be constituted by an evaporator operating under reduced pressure. It may for example be a simple falling-stream evaporator or multiple effect, well known in the art considered. In this case, the output 22 ensures the evacuation of condensates formed during evaporation.
- valve 7 is positioned to communicate the conduit 8 with the conduits 5 and 6, the pumps 10, 11, 18 and 24 are in operation, the pump 27 is stopped and the valves 12 b , 13 b and 28 are closed.
- the clarified and diluted molasses (10 to 70% by weight of dry matter) is brought via conduits 3 and 4 into columns 1 and 2 where it undergoes a cation exchange, the Na + and / or K + ions of the resin arranged in these columns being progressively replaced by the Ca 2+ and / or Mg 2+ ions present in the molasses.
- molasses is enriched in Na + and / or K + ions and is depleted in Ca 2+ and / or Mg 2+ ions, while the resin is enriched in Ca 2+ and / or Mg ions 2+ and depletes in Na + and / or K + ions.
- the molasses from the columns 1,2 is then brought via the conduits 5,6, the pumps 10, 11, valve 7 and line 8 in the chromatography column 9.
- the molasses is subjected to a separation there under the effect of the resin and the water brought by the conduit 14 as eluent.
- the first eluted fractions (constituting the raffinate) poor in sugars and rich in sodium and / or potassium salts and dyes, are extracted via line 16 and poured into the tank 20.
- the following fractions, poor in sodium salts and / or potassium and high in sugars are extracted through line 15.
- the raffinate recovered in the tank 20 is brought via the conduit 19, the pump 18 and the piping 17 in the evaporation unit 21.
- the concentrated raffinate (preferably 10-70% by weight of dry matter) produced in this unit 21 is extracted from the latter by the conduit 23 and the pump 24 and discharged in tank 25.
- the ion-exchange resin of one of the columns 1 and 2 is regenerated, for example the resin of column 1.
- the supply of molasses to be softened is stopped, the pump 10 is stopped, valve 7 is positioned to communicate conduit 8 only with conduit 6, valve 12b is open, valve 28 is positioned to communicate conduit 26 only with conduit 29 and pump 27 is brought into operation.
- the concentrated raffinate from tank 25 is brought via conduits 26, 29 and 12 to column 1 where said concentrated raffinate, rich in Na + and / or K + ions, will pass through the resin contained in the column 1 and regenerate it, the Na + and / or K + ions of said concentrated raffinate progressively replacing the Ca 2+ and / or Mg 2+ ions of the resin.
- the concentrated raffinate which, during its passage through the resin, is enriched in Ca 2+ and / or Mg 2+ ions is then evacuated via line 12 a .
- the second and third cycles are then repeated at regular time intervals.
- the flow clarified and diluted molasses (10 to 70% by weight of dry matter) through each column 1.2 may be of the order of 0.1 to 5 times the volume of the resin bed / hour and that during the regeneration operation, the flow of regeneration liquid (raffinate concentrate present in tank 25 and containing 10 to 70% by weight of dry matter) through each column 1.2 may be of the order of 0.1 to 5 times the volume of the bed resin / hour.
- these flow rates will be chosen according to the dry matter content of the liquid used.
- the higher the dry matter content of molasses and the lower the molasses flow rate through the columns 1,2 will be low for the operation softening.
- the higher the dry matter content of the regeneration liquid (concentrated raffinate) is high and the more the flow of this liquid through the columns 1,2 will be weak.
- the temperature of the regeneration liquid to have a liquid having a viscosity suitable for regeneration operations; this one may be in the range of 20 to 70 ° C depending on the dry matter content.
- Na + and / or K + ions in the form of NaCl and / or KCl for example
- the concentrated raffinate for example at the level of tank 25.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Saccharide Compounds (AREA)
- Non-Alcoholic Beverages (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Claims (11)
- Verfahren zur Enthärtung eines wäßrigen zuckerhaltigen, die Zucker und Ca2+-Ionen und/oder Mg2+-Ionen enthaltenden Safts, etwa einer Melasse der Zuckerfabrik, mit Hilfe eines Kationenaustauscherharzes in Na+- und/oder K+-Form, und zur Regeneration des genannten Harzes, umfassend:(a) einen Schritt der Enthärtung, der darin besteht, den genannten zuckerhaltigen Saft mit dem genannten Kationenaustauscherharz in Na+- und/oder K+-Form in Kontakt zu bringen, um einerseits einen enthärteten, an Ca2+- und Mg2+-Ionen verarmten und mit Na+- und/oder K+-Ionen beladenen zuckerhaltigen Saft, andererseits ein mit Ca2+- und/oder Mg2+-Ionen beladenes Kationenaustauscherharz zu erhalten, und(b) einen Schritt der Regeneration dieses Harzes,
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das in Schritt (b) eingesetzte Abwasser dasjenige ist, das bei der chromatographischen Trennung der Zucker des in Schritt (a) erhaltenen enthärteten zuckerhaltigen Safts gebildet wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das flüssige Abwasser konzentriert wird, bevor es in Schritt (b) eingesetzt wird.
- Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß dem genannten Abwasser Na+- und/oder K+-Ionen zugesetzt werden, bevor man in Schritt (b) das genannte Harz mit dem genannten Abwasser in Kontakt bringt.
- Verfahren nach Anspruch 1, 2, 3 oder 4, dadurch gekennzeichnet, daß das in Schritt (a) eingesetzte Kationenaustauscherharz ein starkes kationisches Harz in Na+- und/oder K+-Form ist und daß die Chromatographie, die das in Schritt (b) eingesetzte Abwasser erzeugt, auf einem starken kationischen Harz in Na+- und/oder K+-Form mit einer Elution durch Wasser ausgeführt wird.
- Verfahren zur Gewinnung der Zucker, die in einem wäßrigen zuckerhaltigen, im wesentlichen die Zucker, Ca2+- und/oder Mg2+-Ionen und farbgebende Stoffe enthaltenden Saft, etwa einer Melasse der Zuckerfabrik, enthalten sind, umfassend:(i) einen Schritt der Enthärtung, der darin besteht, den genannten wäßrigen zuckerhaltigen Saft mit einem Kationenaustauscherharz in Na+- und/oder K+-Form in Kontakt zu bringen, um einerseits einen enthärteten, an Ca2+- und Mg2+-Ionen verarmten und mit Na+- und/oder K+-Ionen beladenen zuckerhaltigen Saft, andererseits ein mit Ca2+- und/oder Mg2+-Ionen beladenes Kationenaustauscherharz zu erhalten, und(ii) einen Schritt der Trennung der Zucker, der darin besteht, den in Schritt (i) gebildeten enthärteten zuckerhaltigen Saft einer chromatographischen Trennung zu unterziehen, um ein erstes, mit Na+- und/oder K+-Ionen angereichertes und an Zuckern verarmtes Abwasser und ein zweites, mit Zuckern angereichertes und an Na+- und/oder K+-Ionen verarmtes Abwasser zu erhalten,(iii) einen Schritt der Regeneration, der darin besteht, das in Schritt (i) erhaltene, mit Ca2+- und/oder Mg2+-Ionen beladene Kationenaustauscherharz in Kontakt mit dem genannten ersten, in Schritt (ii) gebildeten Abwasser in Kontakt zu bringen, um einerseits ein mit Ca2+- und/oder Mg2+-Ionen angereichertes Abwasser, andererseits ein regeneriertes Kationenaustauscherharz in Na+- und/oder K+-Form zu erhalten.
- Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das genannte erste Abwasser konzentriert wird, bevor es in Schritt (iii) eingesetzt wird.
- Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß Na+- und/oder K+-Ionen dem genannten ersten Abwasser zugesetzt werden, bevor dieses in Schritt (iii) eingesetzt wird.
- Verfahren nach Anspruch 6, 7 und 8, dadurch gekennzeichnet, daß das in Schritt (i) eingesetzte Kationenaustauscherharz ein starkes kationisches Harz in Na+- und/oder K+-Form ist und daß die in Schritt (ii) vorgenommene Chromatographie auf einem starken kationischen Harz in Na+- und/oder K+-Form mit einer Elution durch Wasser ausgeführt wird.
- Anlage zur Ausführung des Verfahrens nach einem der Ansprüche 7 bis 10, umfassend:mindestens eine Enthärtungseinheit (1, 2), die ein Kationenaustauscherharz in Na+- und/oder K+-Form enthält und Einrichtungen (3, 4) zur Zufuhr von zu enthärtendem wäßrigem zuckerhaltigem Saft, Einrichtungen (12, 13) zur Zufuhr von Regenerationsflüssigkeit, Einrichtungen (5, 6) zur Abtrennung von enthärtetem wäßrigem zuckerhaltigem Saft und Einrichtungen (12a, 12b) zur Abtrennung verbrauchter Regenerationsflüssigkeit umfaßt, undmindestens eine chromatographische Einheit (9), die Einrichtungen (14) zur Zufuhr von Elutionsmittel, Einrichtungen (8) zur Zufuhr von in der Enthärtungseinheit (1, 2) produziertem enthärtetem wäßrigem zuckerhaltigem Saft und Einrichtungen (16) zur Abtrennung eines mit Na+-und/oder K+-Ionen angereicherten und an Zuckern verarmten Abwassers umfaßt,
- Anlage nach Anspruch 10, dadurch gekennzeichnet, daß die genannten Verbindungseinrichtungen eine Einheit zur Konzentration (21) umfassen.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08075634 US5443650B2 (en) | 1993-06-11 | 1993-06-11 | Process for softening a sugar-containing aqueous solution such as sugar juice or molasses |
US75634 | 1993-06-11 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0629707A2 EP0629707A2 (de) | 1994-12-21 |
EP0629707A3 EP0629707A3 (de) | 1995-02-15 |
EP0629707B1 true EP0629707B1 (de) | 1999-03-24 |
Family
ID=22127050
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94401313A Expired - Lifetime EP0629707B1 (de) | 1993-06-11 | 1994-06-10 | Verfahren zur Enthartung von zuckerenthaltenden Säften wie Melasse und Verwendung desselben zu einem Verfahren zur Gewinnung der in dieser Melasse enthaltenden Zuckern |
Country Status (18)
Country | Link |
---|---|
US (1) | US5443650B2 (de) |
EP (1) | EP0629707B1 (de) |
CN (1) | CN1043903C (de) |
AT (1) | ATE178099T1 (de) |
AU (1) | AU668305B2 (de) |
CA (1) | CA2125749A1 (de) |
CZ (1) | CZ289046B6 (de) |
DE (1) | DE69417292T2 (de) |
DK (1) | DK0629707T3 (de) |
ES (1) | ES2130375T3 (de) |
GR (1) | GR3030118T3 (de) |
MA (1) | MA23222A1 (de) |
PH (1) | PH31548A (de) |
PL (1) | PL303771A1 (de) |
RU (1) | RU2122031C1 (de) |
SK (1) | SK280574B6 (de) |
UA (1) | UA27814C2 (de) |
ZA (1) | ZA944017B (de) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5554227A (en) * | 1993-11-12 | 1996-09-10 | Societe Nouvelle De Recherches Et D'applications Industrielles D'echangeurs D'ions Applexion | Process of manufacturing crystal sugar from an aqueous sugar juice such as cane juice or sugar beet juice |
IT1275974B1 (it) * | 1995-03-27 | 1997-10-24 | Resindion S R L | Procedimento di trattamento con una resina scambiatrice di ioni di una soluzione zuccherina derivata da barbabietola |
FR2753456B1 (fr) * | 1996-09-18 | 1998-12-31 | Generale Sucriere Sa | Procede de regeneration de resines echangeuses d'ions dans le processus de decalcification des jus de sucrerie |
AU726559C (en) * | 1997-07-24 | 2001-08-30 | Commonwealth Scientific And Industrial Research Organisation | Process for the purification of nutrients from food process streams |
AUPO821397A0 (en) * | 1997-07-24 | 1997-08-14 | Commonwealth Scientific And Industrial Research Organisation | Process for the purification of nutrients from food process streams |
JP5073884B2 (ja) * | 1998-10-09 | 2012-11-14 | 三井製糖株式会社 | 感染予防治療剤、抗エンドトキシン剤、ワクチンアジュバント剤および成長促進剤 |
WO2000060128A1 (en) * | 1999-04-07 | 2000-10-12 | Aeci Limited | Treatment of sugar juice |
IL147529A0 (en) * | 2002-01-09 | 2002-08-14 | Oladur Ltd | A method for the production of soybean sugars and the product produced thereof |
FR2844151B1 (fr) * | 2002-09-06 | 2006-05-26 | Applexion Ste Nouvelle De Rech | Procede de decalcification d'une solution aqueuse et utilisation de ce procede pour la decalcification de lactoserum ou d'un permeat d'ultrafiltration de lactoserum |
FR2844209B1 (fr) * | 2002-09-06 | 2007-10-19 | Applexion Ste Nouvelle De Rech | Procede de purification par nanofiltration d'une solution aqueuse sucree contenant des anions et cations monovalents et polyvalents |
US6790245B2 (en) * | 2002-10-07 | 2004-09-14 | Benetech, Inc. | Control of dust |
FR2907687B1 (fr) * | 2006-10-30 | 2008-12-26 | Applexion | Procede de purification de sialyllactose par chromatographie |
CA2697087C (en) * | 2007-08-30 | 2015-12-29 | Iogen Energy Corporation | Process of removing calcium and obtaining sulfate salts from an aqueous sugar solution |
CN101403017B (zh) * | 2008-10-31 | 2011-06-08 | 华南理工大学 | 一种二混蜜脱钾钠树脂的再生方法 |
US9572852B2 (en) | 2011-02-08 | 2017-02-21 | The Product Makers (Australia) Pty Ltd | Sugar extracts |
US9017767B2 (en) | 2012-06-13 | 2015-04-28 | Benetech, Inc. | Method of suppressing dust in piles and railcars using plasticized cellulose ethers |
US9267063B2 (en) | 2012-11-19 | 2016-02-23 | Benetech, Inc. | Dust suppression formulas using plasticized cellulose ethers |
RU2621995C1 (ru) * | 2016-09-21 | 2017-06-08 | Федеральное государственное бюджетное научное учреждение "Краснодарский научно-исследовательский институт хранения и переработки сельскохозяйственной продукции" (ФГБНУ КНИИХП) | Способ очистки диффузионного сока |
CN112795710A (zh) * | 2020-12-08 | 2021-05-14 | 武汉美味源生物工程有限公司 | 制糖过程中离子交换树脂的再生方法 |
CN112593017A (zh) * | 2020-12-15 | 2021-04-02 | 新疆冠农果茸股份有限公司 | 一种用于甜菜制糖糖分高效分离方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1404591A (fr) * | 1964-05-21 | 1965-07-02 | Magyar Cukoripar Ki | Procédé pour régénérer les échangeurs d'ions et pour réduire la teneur en ions alcalins des jus de sortie des sucreries, en vue de leur utilisation pour l'adoucissement des jus dilués, au moyen d'un échange d'ions |
DE2362211C3 (de) * | 1973-12-14 | 1978-05-11 | Sueddeutsche Zucker Ag, 6800 Mannheim | Verfahren zur Aufarbeitung von Melassen |
DE2511904C3 (de) * | 1975-03-19 | 1980-05-22 | Sueddeutsche Zucker-Ag, 6800 Mannheim | Verfahren zur Aufarbeitung von Melassen |
US4140541A (en) * | 1977-03-25 | 1979-02-20 | Karel Popper | Treatment of crude sugar juices by ion exchange |
US4519845A (en) * | 1984-02-09 | 1985-05-28 | Uop Inc. | Separation of sucrose from molasses |
US5110369A (en) * | 1990-10-24 | 1992-05-05 | Mobil Solar Energy Corporation | Cable interconnections for solar cell modules |
-
1993
- 1993-06-11 US US08075634 patent/US5443650B2/en not_active Expired - Lifetime
-
1994
- 1994-06-07 CZ CZ19941393A patent/CZ289046B6/cs not_active IP Right Cessation
- 1994-06-08 SK SK705-94A patent/SK280574B6/sk not_active IP Right Cessation
- 1994-06-08 ZA ZA944017A patent/ZA944017B/xx unknown
- 1994-06-09 MA MA23535A patent/MA23222A1/fr unknown
- 1994-06-09 PH PH48411A patent/PH31548A/en unknown
- 1994-06-10 EP EP94401313A patent/EP0629707B1/de not_active Expired - Lifetime
- 1994-06-10 DE DE69417292T patent/DE69417292T2/de not_active Expired - Fee Related
- 1994-06-10 UA UA94005250A patent/UA27814C2/uk unknown
- 1994-06-10 CN CN94106564A patent/CN1043903C/zh not_active Expired - Fee Related
- 1994-06-10 AT AT94401313T patent/ATE178099T1/de not_active IP Right Cessation
- 1994-06-10 DK DK94401313T patent/DK0629707T3/da active
- 1994-06-10 ES ES94401313T patent/ES2130375T3/es not_active Expired - Lifetime
- 1994-06-10 AU AU64676/94A patent/AU668305B2/en not_active Ceased
- 1994-06-10 PL PL94303771A patent/PL303771A1/xx unknown
- 1994-06-10 RU RU94020736A patent/RU2122031C1/ru not_active IP Right Cessation
- 1994-06-13 CA CA002125749A patent/CA2125749A1/fr not_active Abandoned
-
1999
- 1999-04-30 GR GR990401200T patent/GR3030118T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
CA2125749A1 (fr) | 1994-12-12 |
US5443650B2 (en) | 2000-05-30 |
DE69417292T2 (de) | 1999-09-02 |
AU668305B2 (en) | 1996-04-26 |
EP0629707A3 (de) | 1995-02-15 |
PL303771A1 (en) | 1995-01-09 |
GR3030118T3 (en) | 1999-07-30 |
CZ289046B6 (cs) | 2001-10-17 |
SK70594A3 (en) | 1995-03-08 |
EP0629707A2 (de) | 1994-12-21 |
US5443650A (en) | 1995-08-22 |
AU6467694A (en) | 1994-12-15 |
CN1043903C (zh) | 1999-06-30 |
DK0629707T3 (da) | 1999-10-11 |
ATE178099T1 (de) | 1999-04-15 |
ZA944017B (en) | 1995-02-09 |
SK280574B6 (sk) | 2000-04-10 |
UA27814C2 (uk) | 2000-10-16 |
MA23222A1 (fr) | 1994-12-31 |
PH31548A (en) | 1998-11-03 |
US5443650B1 (en) | 1998-05-26 |
CZ139394A3 (en) | 1995-02-15 |
CN1111678A (zh) | 1995-11-15 |
ES2130375T3 (es) | 1999-07-01 |
RU2122031C1 (ru) | 1998-11-20 |
DE69417292D1 (de) | 1999-04-29 |
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