EP0690900B1 - Thermal cracking of a hydrocarbon feed - Google Patents
Thermal cracking of a hydrocarbon feed Download PDFInfo
- Publication number
- EP0690900B1 EP0690900B1 EP94912498A EP94912498A EP0690900B1 EP 0690900 B1 EP0690900 B1 EP 0690900B1 EP 94912498 A EP94912498 A EP 94912498A EP 94912498 A EP94912498 A EP 94912498A EP 0690900 B1 EP0690900 B1 EP 0690900B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stream
- products stream
- distillation column
- heavy products
- vacuum distillation
- 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
Links
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 7
- 238000004227 thermal cracking Methods 0.000 title claims abstract description 6
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 32
- 239000012530 fluid Substances 0.000 claims abstract description 18
- 238000009834 vaporization Methods 0.000 claims abstract description 15
- 230000008016 vaporization Effects 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 description 30
- 239000007788 liquid Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/06—Vacuum distillation
Definitions
- the present invention relates to thermal cracking of a hydrocarbon feed as described in The Petroleum Handbook, 6th Edition, Elsevier, 1983, pages 279-281.
- Thermal cracking of a hydrocarbon feed comprises heating the feed at a pressure in the range of from 0.2 to 5 MPa and at a temperature in the range of from 390 to 530 °C; supplying the feed to a reaction chamber; separating the stream from the reaction chamber into a light products stream and into a heavy products stream; and supplying the heavy products stream to a vacuum distillation column to separate the heavy products stream into fractions at a pressure in the range of from 1 to 10 kPa and at a temperature in the range of from 320 to 400 °C.
- a conduit is used to pass the heavy products stream to the vacuum distillation column.
- the pressure drop along the conduit should equal the pressure difference between the pressure of the heavy products stream and the pressure in the vacuum distillation column.
- One way of obtaining this rather high pressure drop along the conduit is to provide the conduit with a restricted opening, for example in the form of a flow control valve.
- a flow control valve for example in the form of a flow control valve.
- the present invention provides a simple way to suppress vaporization over the restricted opening.
- the process of thermal cracking of a hydrocarbon feed comprises heating the feed at a pressure in the range of from 0.2 to 5 MPa and at a temperature in the range of from 390 to 530 °C; supplying the feed to a reaction chamber; separating the stream from the reaction chamber into a light products stream and into a heavy products stream; and supplying the heavy products stream to a vacuum distillation column to separate the heavy products stream into fractions at a pressure in the range of from 1 to 10 kPa and at a temperature in the range of from 320 to 400 °C, wherein supplying the heavy products stream to the vacuum distillation column comprises passing the heavy product stream through a restricted opening, passing the heavy products stream upwards through a stand-pipe having such a length that the fluid pressure at the end of the stand-pipe is such that vaporization at its bottom end is suppressed, and subsequently passing the heavy products stream through a transfer conduit debouching into the vacuum distillation column, the transfer conduit having such a configuration that the fluid pressure at its
- configuration of the transfer conduit' in the specification and in the claims is used to refer to the features of the transfer conduit that contribute to the pressure drop along the transfer conduit, such as the dimensions of the transfer conduit and other flow resistances such as bends or U-turns in the transfer conduit.
- the line-up for the process according to the present invention includes a furnace 1 provided with a burner 2 and a stack 3 and a heater tube 4 arranged in the furnace 1.
- the heater tube 4 is connected to an inlet conduit 7 and an outlet conduit 9.
- the outlet conduit 9 is connected to the inlet of a reaction chamber 15.
- the reaction chamber is more clearly described in European patent No. 7 656.
- the outlet of the reaction chamber 15 is connected by conduit 17 to a separation device in the form of cyclonic separator 20.
- the cyclonic separator 20 has two outlets, an outlet 21 for light products and an outlet 24 for heavy products.
- the outlet 21 for light products is connected by a conduit (not shown) to a device (not shown) for further treating the light products.
- the outlet 24 for heavy products is connected by means of a conduit system 26 to a vacuum distillation column 30.
- the vacuum distillation column 30 has an outlet conduit 31 which is connected to a vacuum pump (not shown), a residue outlet conduit 32 for heavy products and an outlet conduit 33 for an intermediate product fraction.
- a vacuum pump not shown
- a residue outlet conduit 32 for heavy products and an outlet conduit 33 for an intermediate product fraction.
- Devices for providing a suitable reflux stream to the top part of the vacuum distillation column 30 and stream of stripping medium to the bottom part of the vacuum distillation column 30 are not shown.
- the conduit system 26 includes a conduit section 35 in which a restricted opening in the form of flow control valve 36 is arranged, a stand-pipe 38 joined to the conduit section 35 and a transfer conduit 40 debouching into the vacuum distillation column 30.
- the length of the stand-pipe 38 is so determined that, during normal operation, the fluid pressure at the bottom end of the stand-pipe 38 is such that vaporization of the fluid at its bottom end is suppressed.
- the expression "suppressing the vaporization of the fluid” is used in the specification and in the claims to indicate that at most a small amount of liquid is vaporized (less than 5% by volume).
- the configuration of the transfer conduit 40 is so determined that, during normal operation, the fluid pressure in the transfer conduit 40 at its outlet end 41 matches the fluid pressure in the vacuum distillation column 30. This implies that the transfer conduit 40 is so designed that the friction experienced by the fluid flowing through the transfer conduit 40 equals the difference in pressure at the outlet of the stand-pipe 38 and in the vacuum distillation column 30.
- the transfer conduit 40 includes several straight lines 43 joined by means of curved connectors in the form of U-shaped connectors 44.
- the pressure drop over the flow control valve 36 is 150 kPa.
- the length of the stand-pipe 38 is 15 m, the presence of liquid in the stand-pipe 38 prevents vaporization of liquid at the downstream end of the flow control valve 36.
- the length of the transfer conduit 40 is 70 m, the average internal diameter of the transfer conduit 40 is 50 cm and the transfer conduit includes four U-shaped connectors 44.
- the fluid pressure at the inlet of the transfer conduit 40 is 60 kPa and the fluid pressure at the outlet of it matches the fluid pressure in the vacuum distillation column 30.
- the heavy products stream is then supplied through conduit system 26 to the vacuum distillation column 30.
- Curved connectors 44 may have a U-shape as shown in Figures 1 and 2, or the curved connectors may have an L-shape.
- the stand-pipe 38 as described with reference to Figures 1 and 2 is a vertical pipe, it will be understood that the stand-pipe can also be a slanted pipe provided that there is, during normal operation, sufficient liquid in the stand-pipe to prevent vaporization.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
- The present invention relates to thermal cracking of a hydrocarbon feed as described in The Petroleum Handbook, 6th Edition, Elsevier, 1983, pages 279-281.
- Thermal cracking of a hydrocarbon feed comprises heating the feed at a pressure in the range of from 0.2 to 5 MPa and at a temperature in the range of from 390 to 530 °C; supplying the feed to a reaction chamber; separating the stream from the reaction chamber into a light products stream and into a heavy products stream; and supplying the heavy products stream to a vacuum distillation column to separate the heavy products stream into fractions at a pressure in the range of from 1 to 10 kPa and at a temperature in the range of from 320 to 400 °C.
- In the known process a conduit is used to pass the heavy products stream to the vacuum distillation column. As the pressure of the heavy products stream is larger than the pressure in the vacuum distillation column, the pressure drop along the conduit should equal the pressure difference between the pressure of the heavy products stream and the pressure in the vacuum distillation column. One way of obtaining this rather high pressure drop along the conduit is to provide the conduit with a restricted opening, for example in the form of a flow control valve. However, when the heavy products stream is throttled over a flow control valve rapid vaporization occurs. This rapid vaporization is accompanied by the formation of very small liquid droplets which cannot easily be handled in the vacuum distillation column.
- The present invention provides a simple way to suppress vaporization over the restricted opening.
- To this end the process of thermal cracking of a hydrocarbon feed according to the present invention comprises heating the feed at a pressure in the range of from 0.2 to 5 MPa and at a temperature in the range of from 390 to 530 °C; supplying the feed to a reaction chamber; separating the stream from the reaction chamber into a light products stream and into a heavy products stream; and supplying the heavy products stream to a vacuum distillation column to separate the heavy products stream into fractions at a pressure in the range of from 1 to 10 kPa and at a temperature in the range of from 320 to 400 °C, wherein supplying the heavy products stream to the vacuum distillation column comprises passing the heavy product stream through a restricted opening, passing the heavy products stream upwards through a stand-pipe having such a length that the fluid pressure at the end of the stand-pipe is such that vaporization at its bottom end is suppressed, and subsequently passing the heavy products stream through a transfer conduit debouching into the vacuum distillation column, the transfer conduit having such a configuration that the fluid pressure at its outlet matches the fluid pressure in the vacuum distillation column.
- The expression "configuration of the transfer conduit' in the specification and in the claims is used to refer to the features of the transfer conduit that contribute to the pressure drop along the transfer conduit, such as the dimensions of the transfer conduit and other flow resistances such as bends or U-turns in the transfer conduit.
- The invention will now be described by way of example in more detail with reference to the accompanying drawings, wherein
- Figure 1 shows schematically a line-up for the process according to the present invention; and
- Figure 2 shows schematically an alternative line-up for the process according to the present invention.
- Reference is made to Figure 1. The line-up for the process according to the present invention includes a furnace 1 provided with a burner 2 and a stack 3 and a heater tube 4 arranged in the furnace 1. The heater tube 4 is connected to an inlet conduit 7 and an
outlet conduit 9. - The
outlet conduit 9 is connected to the inlet of areaction chamber 15. The reaction chamber is more clearly described in European patent No. 7 656. The outlet of thereaction chamber 15 is connected byconduit 17 to a separation device in the form ofcyclonic separator 20. - The
cyclonic separator 20 has two outlets, anoutlet 21 for light products and anoutlet 24 for heavy products. Theoutlet 21 for light products is connected by a conduit (not shown) to a device (not shown) for further treating the light products. Theoutlet 24 for heavy products is connected by means of aconduit system 26 to avacuum distillation column 30. - The
vacuum distillation column 30 has anoutlet conduit 31 which is connected to a vacuum pump (not shown), aresidue outlet conduit 32 for heavy products and anoutlet conduit 33 for an intermediate product fraction. Devices for providing a suitable reflux stream to the top part of thevacuum distillation column 30 and stream of stripping medium to the bottom part of thevacuum distillation column 30 are not shown. - The
conduit system 26 includes aconduit section 35 in which a restricted opening in the form offlow control valve 36 is arranged, a stand-pipe 38 joined to theconduit section 35 and atransfer conduit 40 debouching into thevacuum distillation column 30. - The length of the stand-
pipe 38 is so determined that, during normal operation, the fluid pressure at the bottom end of the stand-pipe 38 is such that vaporization of the fluid at its bottom end is suppressed. The expression "suppressing the vaporization of the fluid" is used in the specification and in the claims to indicate that at most a small amount of liquid is vaporized (less than 5% by volume). - The configuration of the
transfer conduit 40 is so determined that, during normal operation, the fluid pressure in thetransfer conduit 40 at itsoutlet end 41 matches the fluid pressure in thevacuum distillation column 30. This implies that thetransfer conduit 40 is so designed that the friction experienced by the fluid flowing through thetransfer conduit 40 equals the difference in pressure at the outlet of the stand-pipe 38 and in thevacuum distillation column 30. In this case thetransfer conduit 40 includes severalstraight lines 43 joined by means of curved connectors in the form ofU-shaped connectors 44. - During normal operation, 3 000 ton/day of a hydrocarbon feed is continuously supplied to the furnace 1 at a pressure of 3 MPa, the feed is heated at a temperature of 450 °C in the furnace 1. Then heated feed is supplied to the
reaction chamber 15 where the feed is allowed to crack. The stream of products from thereaction chamber 15 is separated incyclonic separator 20 into 900 ton/day of light products removed throughoutlet 21 and into 2 100 ton/day of heavy products removed throughoutlet 24. The heavy products are supplied through theconduit system 26 to thevacuum distillation column 30 which operates at a pressure of 5 kPa and at a temperature of 380 °C. In thevacuum distillation column 30 the heavy products stream is separated into 200 ton/day of a gaseous fraction removed throughoutlet conduit 31, 400 ton/day of intermediate fraction removed throughoutlet conduit 33, and 1 500 ton/day of a residue removed throughresidue outlet conduit 32. - The pressure drop over the
flow control valve 36 is 150 kPa. - The length of the stand-
pipe 38 is 15 m, the presence of liquid in the stand-pipe 38 prevents vaporization of liquid at the downstream end of theflow control valve 36. - The length of the
transfer conduit 40 is 70 m, the average internal diameter of thetransfer conduit 40 is 50 cm and the transfer conduit includes fourU-shaped connectors 44. The fluid pressure at the inlet of thetransfer conduit 40 is 60 kPa and the fluid pressure at the outlet of it matches the fluid pressure in thevacuum distillation column 30. - Omitting the stand-
pipe 38 would result in vaporization at or near theflow control valve 36, which vaporization is uncontrolled and is accompanied by the formation of extremely small liquid droplets. - Reference is now made to Figure 2 showing an alternative line-up for the process according to the present invention. Parts of the line-up which are similar to the line-up as described with reference to Figure 1 have got the same reference numeral.
- In the line-up of Figure 2 the stream from the
reaction chamber 15 is separated in adistillation column 50 into a light products stream removed throughoutlet 51 and into a heavy products stream removed throughoutlet 52. - The heavy products stream is then supplied through
conduit system 26 to thevacuum distillation column 30. - Devices for providing a suitable reflux stream to the top part of the
distillation column 50 and stream of stripping medium to the bottom part of thedistillation column 50 are not shown. -
Curved connectors 44 may have a U-shape as shown in Figures 1 and 2, or the curved connectors may have an L-shape. - The presence of liquid in the stand-pipe prevents vaporization of liquid at the downstream end of the restricted opening. Omitting the stand-pipe would result in vaporization at or near the restricted opening, which vaporization is uncontrolled and is accompanied by the formation of very small liquid droplets. In the vacuum distillation column these small fine liquid droplets cannot be separated from the gas stream so that the liquid droplets are entrained with the fraction leaving the vacuum distillation column through the outlet conduit for the intermediate fraction or with the gaseous stream leaving the top of the vacuum distillation column through outlet conduit. This entrainment adversely affects the separation efficiency of the vacuum distillation column.
- The stand-
pipe 38 as described with reference to Figures 1 and 2 is a vertical pipe, it will be understood that the stand-pipe can also be a slanted pipe provided that there is, during normal operation, sufficient liquid in the stand-pipe to prevent vaporization.
Claims (4)
- Process of thermal cracking of a hydrocarbon feed comprising heating the feed at a pressure in the range of from 0.2 to 5 MPa and at a temperature in the range of from 390 to 530 °C; supplying the feed to a reaction chamber; separating the stream from the reaction chamber into a light products stream and into a heavy products stream; and supplying the heavy products stream to a vacuum distillation column to separate the heavy products stream into fractions at a pressure in the range of from 1 to 10 kPa and at a temperature in the range of from 320 to 400 °C, wherein supplying the heavy products stream to the vacuum distillation column comprises passing the heavy product stream through a restricted opening, passing the heavy products stream upwards through a stand-pipe having such a length that the fluid pressure at the end of the stand-pipe is such that vaporization at its bottom end is suppressed, and subsequently passing the heavy products stream through a transfer conduit debouching into the vacuum distillation column, the transfer conduit having such a configuration that the fluid pressure at its outlet matches the fluid pressure in the vacuum distillation column.
- Process according to claim 1, wherein the transfer conduit includes a plurality of straight sections joined by curved connectors.
- Process according to claim 1 or 2, wherein the stream from the reaction chamber is separated in a cyclone separator in a light products stream and a heavy products stream.
- Process according to claim 1 or 2, wherein the stream from the reaction chamber is separated in a distillation column in a light products stream and a heavy products stream.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94912498A EP0690900B1 (en) | 1993-03-22 | 1994-03-18 | Thermal cracking of a hydrocarbon feed |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93200832 | 1993-03-22 | ||
EP93200832 | 1993-03-22 | ||
PCT/EP1994/000895 WO1994021749A1 (en) | 1993-03-22 | 1994-03-18 | Thermal cracking of a hydrocarbon feed |
EP94912498A EP0690900B1 (en) | 1993-03-22 | 1994-03-18 | Thermal cracking of a hydrocarbon feed |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0690900A1 EP0690900A1 (en) | 1996-01-10 |
EP0690900B1 true EP0690900B1 (en) | 1996-11-13 |
Family
ID=8213718
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94912498A Expired - Lifetime EP0690900B1 (en) | 1993-03-22 | 1994-03-18 | Thermal cracking of a hydrocarbon feed |
Country Status (17)
Country | Link |
---|---|
EP (1) | EP0690900B1 (en) |
JP (1) | JP3499873B2 (en) |
KR (1) | KR100295069B1 (en) |
CN (1) | CN1038043C (en) |
AU (1) | AU675530B2 (en) |
CA (1) | CA2158765C (en) |
CZ (1) | CZ283755B6 (en) |
DE (1) | DE69400917T2 (en) |
ES (1) | ES2096463T3 (en) |
FI (1) | FI119938B (en) |
HU (1) | HU216102B (en) |
MD (1) | MD1207C2 (en) |
NO (1) | NO309388B1 (en) |
RU (1) | RU2114894C1 (en) |
SA (1) | SA94140602B1 (en) |
WO (1) | WO1994021749A1 (en) |
ZA (1) | ZA941922B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR960031577A (en) * | 1995-02-03 | 1996-09-17 | 신호근 | High vacuum refinery and method |
BR9917568A (en) * | 1999-12-10 | 2002-08-06 | Jgc Corp | Oil processing method and equipment |
US9988584B2 (en) | 2013-02-15 | 2018-06-05 | Rival Technologies Inc. | Method of upgrading heavy crude oil |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3025232A (en) * | 1957-07-12 | 1962-03-13 | Texaco Inc | Automatic control of the viscosity of a fractionator product |
US3075578A (en) * | 1959-07-27 | 1963-01-29 | Sumiya Shinzo | Multiple vacuum effect evaporator |
FR2493171A1 (en) * | 1980-11-06 | 1982-05-07 | Bailet Victor | Vacuum distn. using thermal siphon to separate vessels - eliminates use of extn. pumps for removing product or bottoms |
US5110447A (en) * | 1988-09-12 | 1992-05-05 | Kasten, Eadie Technology Ltd. | Process and apparatus for partial upgrading of a heavy oil feedstock |
-
1994
- 1994-03-18 RU RU95121591A patent/RU2114894C1/en active
- 1994-03-18 WO PCT/EP1994/000895 patent/WO1994021749A1/en active IP Right Grant
- 1994-03-18 MD MD96-0308A patent/MD1207C2/en not_active IP Right Cessation
- 1994-03-18 ZA ZA941922A patent/ZA941922B/en unknown
- 1994-03-18 CA CA002158765A patent/CA2158765C/en not_active Expired - Fee Related
- 1994-03-18 CZ CZ952440A patent/CZ283755B6/en not_active IP Right Cessation
- 1994-03-18 JP JP52066494A patent/JP3499873B2/en not_active Expired - Fee Related
- 1994-03-18 KR KR1019950704030A patent/KR100295069B1/en not_active IP Right Cessation
- 1994-03-18 ES ES94912498T patent/ES2096463T3/en not_active Expired - Lifetime
- 1994-03-18 HU HUP9502609A patent/HU216102B/en not_active IP Right Cessation
- 1994-03-18 DE DE69400917T patent/DE69400917T2/en not_active Expired - Lifetime
- 1994-03-18 EP EP94912498A patent/EP0690900B1/en not_active Expired - Lifetime
- 1994-03-18 CN CN94191543A patent/CN1038043C/en not_active Expired - Fee Related
- 1994-03-18 AU AU65038/94A patent/AU675530B2/en not_active Ceased
- 1994-03-22 SA SA94140602A patent/SA94140602B1/en unknown
-
1995
- 1995-09-20 NO NO953715A patent/NO309388B1/en not_active IP Right Cessation
- 1995-09-20 FI FI954441A patent/FI119938B/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
FI954441A0 (en) | 1995-09-20 |
DE69400917T2 (en) | 1997-05-22 |
ES2096463T3 (en) | 1997-03-01 |
NO953715D0 (en) | 1995-09-20 |
JPH08511039A (en) | 1996-11-19 |
DE69400917D1 (en) | 1996-12-19 |
AU6503894A (en) | 1994-10-11 |
NO309388B1 (en) | 2001-01-22 |
NO953715L (en) | 1995-09-20 |
CN1119875A (en) | 1996-04-03 |
KR100295069B1 (en) | 2001-10-24 |
RU2114894C1 (en) | 1998-07-10 |
CZ244095A3 (en) | 1996-01-17 |
WO1994021749A1 (en) | 1994-09-29 |
SA94140602B1 (en) | 2005-07-31 |
FI954441A (en) | 1995-09-20 |
MD1207C2 (en) | 1999-11-30 |
HUT73408A (en) | 1996-07-29 |
CN1038043C (en) | 1998-04-15 |
HU216102B (en) | 1999-04-28 |
CA2158765A1 (en) | 1994-09-29 |
ZA941922B (en) | 1994-10-14 |
CZ283755B6 (en) | 1998-06-17 |
HU9502609D0 (en) | 1995-11-28 |
CA2158765C (en) | 2004-03-30 |
EP0690900A1 (en) | 1996-01-10 |
JP3499873B2 (en) | 2004-02-23 |
MD960308A (en) | 1997-10-31 |
FI119938B (en) | 2009-05-15 |
AU675530B2 (en) | 1997-02-06 |
KR960701171A (en) | 1996-02-24 |
MD1207B2 (en) | 1999-04-30 |
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