PT101590B - PROCESS OF EXTRACTION OF AROMAS OF WINE MUSTS USING SUPERCRITICAL FLUIDS - Google Patents
PROCESS OF EXTRACTION OF AROMAS OF WINE MUSTS USING SUPERCRITICAL FLUIDS Download PDFInfo
- Publication number
- PT101590B PT101590B PT10159094A PT10159094A PT101590B PT 101590 B PT101590 B PT 101590B PT 10159094 A PT10159094 A PT 10159094A PT 10159094 A PT10159094 A PT 10159094A PT 101590 B PT101590 B PT 101590B
- Authority
- PT
- Portugal
- Prior art keywords
- extraction
- musts
- aromas
- supercritical
- solvent
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000000605 extraction Methods 0.000 title claims abstract description 18
- 239000012530 fluid Substances 0.000 title claims abstract description 13
- 235000019568 aromas Nutrition 0.000 title claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000014101 wine Nutrition 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 239000000796 flavoring agent Substances 0.000 claims abstract description 10
- 235000019634 flavors Nutrition 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000006837 decompression Effects 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 238000005194 fractionation Methods 0.000 claims abstract description 3
- 238000000855 fermentation Methods 0.000 claims description 8
- 230000004151 fermentation Effects 0.000 claims description 8
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- -1 phenylethanol Chemical class 0.000 claims description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 238000005899 aromatization reaction Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000000284 extract Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 244000018436 Coriandrum sativum Species 0.000 description 1
- 235000002787 Coriandrum sativum Nutrition 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- QUMXDOLUJCHOAY-UHFFFAOYSA-N alpha-methylbenzyl acetate Natural products CC(=O)OC(C)C1=CC=CC=C1 QUMXDOLUJCHOAY-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Extraction Or Liquid Replacement (AREA)
Abstract
Description
Processo de extracçao de aromas de mostos de vinho utilizando fluidos super-críticos.Extraction process of wine musts using super-critical fluids.
Figura (para interpretação do resumo)Figure (for summary interpretation)
Resumo: (máx. 150 palavras) A presente invenção de mostos de vinhos dioxido de carbono, acima das suas de extracçao.Abstract: (max. 150 words) The present invention of carbon dioxide wine musts, above their extraction.
refere-se a um processo de extracçao de aromas utilizando fluidos super-críticos, em particular Neste processo um gás sob pressão, ligeiramente temperaturas e pressão criticas, e usado como solvente 0 dioxido de carbono e especialmente adequado para a presente aplicaçao, dado ser inócuo e um bom solvente das substâncias aromáticas a separar dos mostos. A extracçao pode ser seguida por um fraccionamento da mistura de aromas, obtido por um método de precipitação por descompressões sucessivas do solvente. Este processo permite a obtenção de extractos fortemente enriquecidos em substâncias aromaticas presentes em pequenas quantidades nos mostos, extractos estes adequados para a aromatizaçao de vinhos.refers to a process of extracting aromas using super-critical fluids, in particular In this process a gas under pressure, slightly critical temperatures and pressure, and used as a solvent 0 carbon dioxide is especially suitable for the present application, since it is harmless and a good solvent for the aromatic substances to be separated from the musts. The extraction can be followed by a fractionation of the flavor mixture, obtained by a precipitation method by successive decompression of the solvent. This process makes it possible to obtain extracts strongly enriched with aromatic substances present in small quantities in the musts, which are suitable for flavoring wines.
□SP<J. -worwç·»^.,·. ___________□ SP <J. -worwç · »^., ·. ___________
Memória descritiva deDescriptive memory of
Processo de extracção de aromas de mostos de vinhos por extracção com fluidos supercríticosExtraction process of wine mus aromas by extraction with supercritical fluids
A presente invenção refere-se a umprocesso de extracção d£ aromas; a partir de mostos de vinhos, que utiliza como solventes de extracção, gases sob pressão ligeiramente acima das suas temperatura e pressão críticas, designados por fluidos supercríticos.The present invention relates to a flavor extraction process; from wine musts, which use as extraction solvents, gases under pressure slightly above their critical temperature and pressure, called supercritical fluids.
A Extracção com Fluidos Supercríticos (ESC) é uma técnica de separação em que são usados gases perto do ponto crítico, em condições em que a sua densidade depende fortemente da pressão e temperatura. Estes fluidos supercríticos dispõem assim dum poder solvente facilmente ajustável. Esta propriedade pode ser utilizada para, por exemplo, fraccionar misturas complexas ou separar um produto duma reacção do solvente, por passos sucessivos de descompressão. Combinando algumas das vantagens da destilação e da extracção líquido-líquido com a possibilidade de ser utilizada a temperaturas muito perto da ambiente, a extracção com Fluidos Supercríticos pode substituir processos de separação clássicos, especialmente quando em operações com substâncias que venham a ser incluídas no ciclo biológico humano ou que sejam termicamente instáveis.Extraction with Supercritical Fluids (ESC) is a separation technique in which gases are used near the critical point, under conditions where their density depends heavily on pressure and temperature. These supercritical fluids therefore have an easily adjustable solvent power. This property can be used to, for example, fractionate complex mixtures or separate a product from a solvent reaction by successive decompression steps. Combining some of the advantages of distillation and liquid-liquid extraction with the possibility of being used at temperatures very close to the environment, extraction with Supercritical Fluids can replace classic separation processes, especially when in operations with substances that will be included in the cycle human biological or thermally unstable.
A aplicação destes processos na separação de aromas e sabores com dióxido de carbono supercrítico combina a vantagem do solvente utilizado ser uma substância inócua e largamente utilizada na indústria alimentar com a das baixas temperaturas de trabalho, que asseguram uma degradação química mínima dos produtos.The application of these processes in the separation of aromas and flavors with supercritical carbon dioxide combines the advantage of the solvent used being a harmless substance and widely used in the food industry with that of the low working temperatures, which ensure a minimum chemical degradation of the products.
Por outro lado, o mosto de vinho é um caldo de fermentação cujo conteúdo em aromas e sabores vai variando ao longo do processo fermentativo. Alguns dos componentes aromáticos libertam-se em quantidades apreciáveis e perdem-se na atmosfera, quer devido à sua volatilidade, quer por arrastamento pelo dióxido de carbono produzido durante a fermentação. É possível que a reinserção dalgumas destas substâncias no vinho produzido viesse melhorar as suas qualidades, tomando-o mais aceitável em alguns mercados.On the other hand, the wine must is a fermentation broth whose content in aromas and flavors varies throughout the fermentation process. Some of the aromatic components are released in appreciable quantities and are lost in the atmosphere, either due to their volatility or by entrainment by the carbon dioxide produced during fermentation. It is possible that the reinsertion of some of these substances in the wine produced would improve its qualities, making it more acceptable in some markets.
Foi sugerido por Muller et al.1 que a captura destes componentes fosse realizada por adsorção em carvão activado e posterior desorpção com freon-11.It was suggested by Muller et al. 1 that the capture of these components was carried out by adsorption on activated carbon and subsequent desorption with freon-11.
No entanto, os métodos baseados em adsorção correm sempre o risco do adsorvente libertar componentes próprios ou previamente adsorvidos, sendo os aromas obtidos normalmente pouco fiéis aos originais. A invenção aqui descrita refere-se à extracção destas substâncias aromáticas de mostos de vinhos, utilizando como solventes 'MULLER, C.J., WAHLSTROM, V.L.. FUGELSANG, K.C. Capture and Use of Volatile Flavor Constituents Emitted During Wine Fermentation in Beer and Winc Production, B.H. Gump and D.J. Pruett eds., ACS Symposium Series 536, American Chemical Society, Washington DC (1993) fluidos supercríticos e, em particular, dióxido de carbono supercrítico. Este método evita os riscos inerentes à utilização de adsorventes.However, the adsorption-based methods always run the risk of the adsorbent releasing its own or previously adsorbed components, and the obtained aromas are usually not very faithful to the originals. The invention described here relates to the extraction of these aromatic substances from wine musts, using as solvents' MULLER, C.J., WAHLSTROM, V.L .. FUGELSANG, K.C. Capture and Use of Volatile Flavor Constituents Emitted During Wine Fermentation in Beer and Winc Production, BH Gump and DJ Pruett eds., ACS Symposium Series 536, American Chemical Society, Washington DC (1993) supercritical fluids and, in particular, supercritical carbon dioxide . This method avoids the risks inherent in the use of adsorbents.
Até agora só uma referência pôde ser encontrada na literatura técnica sobre extracção de aromas de vinhos com dióxido de carbono. Trata-se do trabalho de Jolly2, que extraiu aromas de vinhos australianos com dióxido de carbono líquido.So far only one reference has been found in the technical literature on extracting wine aromas with carbon dioxide. This is the work of Jolly 2 , who extracted aromas from Australian wines with liquid carbon dioxide.
O processo aqui apresentado diferencia-se deste porque utiliza dióxido de carbono supercrítico e porque os aromas são retirados do mosto, e portanto ainda no decorrer do processo de fermentação. Trabalhos recentes3, em que se comparam osextractos de aromas de plantas com dióxido de carbono líquido e supercrítico, comprovam a existência de diferenças significativas na capacidade de dissolução dessa substância nos dois estados, sendo o extracto obtido por dióxido de carbono supercrítico muito mais fiel ao aroma original da planta. Os extractos obtidos podem ser posteriormente injectados em vinhos para melhorar as suas propriedades aromáticas.The process presented here differs from this because it uses supercritical carbon dioxide and because the aromas are removed from the wort, and therefore still during the fermentation process. Recent studies 3 , in which plant aroma extracts are compared with liquid and supercritical carbon dioxide, prove the existence of significant differences in the dissolution capacity of this substance in the two states, with the extract obtained by supercritical carbon dioxide being much more faithful to the original aroma of the plant. The extracts obtained can then be injected into wines to improve their aromatic properties.
Os mostos desaromatizados podem continuar o processo de fermentação, dando origem a vinhos menos aromáticos. O processo normalmente utilizado para obter a; J χ/χ?/ desaromatização é a adsorção em carvão activado, que provoca a inutilização dos k, L aromas extraídos, dada a dificuldade de desadsorção acima apontada. Os resíduos de í cuuxL’ '.nL j carvão representam por outro lado um problema ambiental significativo. O processo 1 aqui descrito de extracção supercrítica tem assim a vantagem de desaromatizar os mostos com aproveitamento das substâncias aromáticas e sem problemas de resíduos.Disarmatized musts can continue the fermentation process, giving rise to less aromatic wines. The process normally used to obtain the; J χ / χ? / Desaromatização is the adsorption on activated carbon, which causes the k, L aromas extracted to become unusable, given the difficulty of desorption mentioned above. Waste from coal, on the other hand, represents a significant environmental problem. The process 1 described here of supercritical extraction thus has the advantage of disarming the musts with the use of aromatic substances and without waste problems.
O exemplo seguintes ilustra o processo de extracção inventado:The following example illustrates the extraction process invented:
ExemploExample
Utilizou-se um aparelho constituído essencialmente por um extractor de alta pressão de capacidade 100 cm3, um compressor manual de líquidos e um dispositivo de precipitação do extracto. A tampa do extractor é perfurada por dois tubos, soldados a essa mesma tampa. Um destes é destinado à alimentação de fluido supercrítico, prolongando-se até ao fundo do recipiente, enquanto o outro se destina à saída de solvente e extracto.An apparatus consisting essentially of a 100 cm 3 high-pressure extractor, a manual liquid compressor and an extract precipitation device was used. The extractor cover is pierced by two tubes, welded to the same cover. One of these is intended for the supply of supercritical fluid, extending to the bottom of the container, while the other is intended for the outlet of solvent and extract.
No extractor de alta pressão colocaram-se 40 cm3 de mosto. A tampa do reactor foi ajustada e o conjunto colocado num banho termostático, à temperatura de compressor foi cheio com dióxido de carbono líquido, que foi comprimido feito passar pelo mosto no extractor, a um caudal de cerca de 1 g min*1,40 cm 3 of wort were placed in the high-pressure extractor. The reactor lid was adjusted and the set placed in a thermostatic bath, at the compressor temperature, was filled with liquid carbon dioxide, which was compressed through the wort in the extractor, at a flow rate of about 1 g min * 1 ,
-/ 2JOLLY, D.R. P. Process Biochemistry 1981, 16, 36 3A.S. REIS MACHADO, E. GOMES DE AZEVEDO, R.M. SARDINHA, M. NUNES DA PONTE High Pressure Carbon Dioxide Extraction from Coriander Plants J. Essent. Oil Res., 1993, 5, 645- / 2 JOLLY, DRP Process Biochemistry 1981, 16, 36 3 THE KINGS MACHADO, E. GOMES DE AZEVEDO, RM SARDINHA, M. NUNES DA PONTE High Pressure Carbon Dioxide Extraction from Coriander Plants J. Essent. Oil Res., 1993, 5, 645
A.S. REIS MACHADO, E. GOMES DE AZEVEDO, R.M. SARDINHA, M.NUNES DA PONTE High Pressure Carbon Dioxide Extraction from Geranium Plants J. Essent. Oil Res. 1993, 5, 185.A.S. REIS MACHADO, E. GOMES DE AZEVEDO, R.M.SARDINHA, M.NUNES DA PONTE High Pressure Carbon Dioxide Extraction from Geranium Plants J. Essent. Oil Res. 1993, 5, 185.
previamente aquecido a 40 °C (nestas condições, o dioxidc de carbono é um fluido supercrítico).previously heated to 40 ° C (under these conditions, carbon dioxidc is a supercritical fluid).
Obtiveram-se cromatogramas por técnica dc head-spuce do exíracto e do mosto inicial. Estes cromatogramas evidenciam um grande enriquecimento do extracto em relação ao mosto numa série de substâncias aromáticas, tendo sido identificadas, entre outras: acetato de etilo, isopropamol.,-isobutahQJL.3-metil-2-butaRQL álcool amflico,Chromatograms were obtained by the head-spuce technique of the exirate and the initial must. These chromatograms show a great enrichment of the extract in relation to the wort in a series of aromatic substances, having been identified, among others: ethyl acetate, isopropamol., - isobutahQJL.3-methyl-2-butaRQL alcohol,
1-hexanol, 'Ί-decanol, feniletánol, ' Iinalol, geraniol,' heptanal, octanal, acetato feniletílico, succinato dietílico.1-hexanol, 'Ί-decanol, phenylethanol,' Iinalol, geraniol, 'heptanal, octanal, phenylethyl acetate, diethyl succinate.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PT10159094A PT101590B (en) | 1994-10-14 | 1994-10-14 | PROCESS OF EXTRACTION OF AROMAS OF WINE MUSTS USING SUPERCRITICAL FLUIDS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PT10159094A PT101590B (en) | 1994-10-14 | 1994-10-14 | PROCESS OF EXTRACTION OF AROMAS OF WINE MUSTS USING SUPERCRITICAL FLUIDS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PT101590A PT101590A (en) | 1996-04-30 |
| PT101590B true PT101590B (en) | 1999-05-31 |
Family
ID=20085446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PT10159094A PT101590B (en) | 1994-10-14 | 1994-10-14 | PROCESS OF EXTRACTION OF AROMAS OF WINE MUSTS USING SUPERCRITICAL FLUIDS |
Country Status (1)
| Country | Link |
|---|---|
| PT (1) | PT101590B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004043168A1 (en) * | 2002-11-09 | 2004-05-27 | Degussa Ag | Method for the selective separation of volatile flavorings from monophase, (semi)liquid starting materials having a fat content and/or oil content of = 20 percent by weight |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2168955B1 (en) * | 2000-04-06 | 2003-11-01 | Univ Madrid Autonoma | CONTINUOUS PROCESS FOR OBTAINING AROMATIC EXTRACTS OF ALCOHOLIC BEVERAGES DISTILLED BY SUPERCRITICAL FLUIDS. |
-
1994
- 1994-10-14 PT PT10159094A patent/PT101590B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004043168A1 (en) * | 2002-11-09 | 2004-05-27 | Degussa Ag | Method for the selective separation of volatile flavorings from monophase, (semi)liquid starting materials having a fat content and/or oil content of = 20 percent by weight |
Also Published As
| Publication number | Publication date |
|---|---|
| PT101590A (en) | 1996-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4561452A (en) | Procedure for producing low nicotine tobacco by means of high pressure extraction | |
| US4104409A (en) | Production of hop extracts | |
| AU2003261187B2 (en) | Reduction of constituents in tobacco | |
| US4123559A (en) | Process for the production of spice extracts | |
| EP1359403A4 (en) | Apparatus and method of extracting volatile components | |
| JPH066028B2 (en) | Extraction method of flavor components | |
| PT101590B (en) | PROCESS OF EXTRACTION OF AROMAS OF WINE MUSTS USING SUPERCRITICAL FLUIDS | |
| US5079025A (en) | Process for the removal of ethanol from drinks produced utilizing extraction with compressed carbon dioxide and carbon dioxide regeneration | |
| Knez et al. | Product, Process and Plant Design Using Subcritical and Supercritical Fluids for Industrial Application | |
| KR900006421B1 (en) | Supercritical Extraction Method for Solid Samples | |
| CN115279198A (en) | Method for producing aromatic gas, aromatic gas and use of aromatic gas | |
| FR2695931A1 (en) | Process for obtaining sesquiterpene lactone parthenolide, and therapeutic preparation containing such a product for the treatment of migraine. | |
| Birtigh et al. | New method for supercritical fluid regeneration | |
| ATE340618T1 (en) | METHOD FOR PRODUCING AN OIL-LOADED ADSORPTION AGENT | |
| EP3577201B1 (en) | Method and test kit for recreation of an odor | |
| Catchpole et al. | Gas anti-solvent fractionation of natural products | |
| WO2004026430A3 (en) | Solvent extraction method and apparatus | |
| Eller et al. | Use of liquid carbon dioxide to remove hexane from soybean oil | |
| Sequeira et al. | Supercritical fluid extraction of wood pulps | |
| Kassim et al. | Direct extraction-separation of essential oils from citrus peels by supercritical carbon dioxide | |
| Ahmad et al. | Supercritical fluid extraction and capillary gas chromatography of the rhizomes of Z. Zerumbet | |
| JPS62148598A (en) | Extraction of volatile natural aroma | |
| WO2004023889A2 (en) | Full range nutritional supplements from plant materials and methods for their manufacture | |
| JPH0499776A (en) | Extraction of chlorophyll | |
| JPS60127397A (en) | Extraction separation of oil and fat from seed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| BB1A | Laying open of patent application |
Effective date: 19950203 |
|
| FG3A | Patent granted, date of granting |
Effective date: 19990224 |
|
| MM4A | Annulment/lapse due to non-payment of fees, searched and examined patent |
Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20080414 |