EP0081895A1 - Method and apparatus for the thermal treatment of heavy fuel oil - Google Patents
Method and apparatus for the thermal treatment of heavy fuel oil Download PDFInfo
- Publication number
- EP0081895A1 EP0081895A1 EP82302978A EP82302978A EP0081895A1 EP 0081895 A1 EP0081895 A1 EP 0081895A1 EP 82302978 A EP82302978 A EP 82302978A EP 82302978 A EP82302978 A EP 82302978A EP 0081895 A1 EP0081895 A1 EP 0081895A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stream
- distillation unit
- gas oil
- vacuum
- heat
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000010763 heavy fuel oil Substances 0.000 title claims abstract description 11
- 238000007669 thermal treatment Methods 0.000 title claims abstract description 7
- 239000003921 oil Substances 0.000 claims abstract description 40
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 239000001993 wax Substances 0.000 claims abstract description 9
- 238000004227 thermal cracking Methods 0.000 claims abstract description 8
- 230000005611 electricity Effects 0.000 claims abstract description 6
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims 1
- 239000012141 concentrate Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- 239000000446 fuel Substances 0.000 description 7
- 239000012530 fluid Substances 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 4
- 230000003134 recirculating effect Effects 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000012432 intermediate storage Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/06—Vacuum distillation
Definitions
- the present invention relates to a method and apparatus for the thermal treatment of heavy fuel oil, for example a method and apparatus to recover lighter products and to utilise the heavier products, and such a method comprises supplying the heavy fuel oil to a vacuum distillation unit operating at a sub-atmospheric pressure, withdrawing a heavy gas oil and any other contained lighter fractions as a top product, and withdrawing a vacuum residue as a bottom product.
- vacuum unit In modern oil refineries the reduced crude from a crude oil topping still is commonly passed to a unit referred to as a vacuum unit, where, under sub-atmospheric pressure, heavy gas oil is flashed out and separated from the heaviest petroleum fraction, commonly called vacuum residue. When cooled to atmospheric temperatures this residue is a very viscous fluid.
- the heavy gas oil is usually recovered for subsequent use as feedstock in cracking processes and is generally accepted as being more valuable than reduced crude.
- a method for the thermal treatment of heavy fuel oil characterised by supplying the hot vacuum residue directly to a burner and burning the vacuum residue to release heat energy.
- the heat energy may be used to generate electricity.
- the method may be particularly suitable in situations where a power station receives fuel oil, delivered by water or served by a conncecting pipeline from an oil refinery.
- the method according to the invention is preferably carried out on or close to the power station premises and preferably as close to the boilers as is practically possible.
- the techniques may be allied to other large consumers of heavy oil fuels such as cement manufacturers.
- reduced crude or heavy fuel oil to typical power station specifications may be recieved at the power station and supplied to a vacuum still to separate out those petroleum fractions lighter than vacuum residue.
- the vacuum residue may then be at a sufficiently high temperature, e.g. between 200 and 375 0 C such that it readily flows through pipework and can be effectively burnt in the power station boilers.
- the separated heavy gas oil and lighter fractions which are recovered may be returned to the originating oil refinery or may be marketed as a more valuable product than the fuel oil feedstock recieved at the power station.
- any subsequent pipework, intermediate storage and burner systems should preferably be provided with appropriate insulation and heat tracing to keep the fuel hot.
- a considerable benefit of the method of the invention is that it is possible to save that energy which would otherwise be consumed in visbreaking the vacuum residue or alternatively to conserve more valuable lower boiling petroleum fractions so that they may be put to more useful applications.
- the method includes the steps of withdrawing one or more fractions from the column and heat- exchanging these streams against the feedstock inlet stream to the column.
- a characteristic of many crude oils is that wax components tendto concentrate in the heavier gas oil fractions recovered in a vacuum unit. This impairs the fluid flow characteristics of the recovered heavy gas oil, especially at ambient temperature. A method of measuring this characteristic is a well known test to determine the pour point of the fluid. Pour points greater than 25°C are generally unacceptable. It is quite common for recovered heavy gas oil to have a pour point value greater that 25°C.
- the heat supplied to the system to enable the vacuum column to operate is also used to subject a portion of the fuel oil, namely the heavier gas oil fraction, to mild thermal cracking conditions.
- This is preferably carried out by withdrawing a stream of heavy gas oil from near the base of the vacuum column and passing this stream through a heater. This heated stream may then be mixed with the feedstock inlet stream to the column. No additional heat may be required to be introduced into the system.
- the vacuum distillation unit operates at a temperature of between about 150 and 375°C e.g. about 345°C and at a pressure of between 0.03 and 0.3 atmospheres e.g. about 0.065 atmospheres.
- apparatus for the thermal treatment of heavy fuel oil comprising a vacuum distillation unit, a heater arranged to supply heat to the distillation unit, a burner arranged to receive directly the hot bottom product from the distillation unit and an electrical generator arranged to convert the heat produced by the burner into electricity.
- the distillation unit includes two or more sections of gas/liquid contact medium and a liquid catch tray beneath each section.
- Reduced crude feedstock enters the process at 11 at ambient temperature and is heat exchanged in heat exchangers 12, 13 against recirculating heavy gas oil in two recycle streams 14, 15 respectively.
- the feedstock is then passed via a transfer line 16 to the flash zone 17 of a vacuum column 18 which operates between 0.03 and 0.3 atmospheres pressure and at about 345°C.
- the heavier gas oil fractions are withdrawn as a liquid stream 20 by means of a catch tray 21 located immediately above the flash zone 17 having been condensed by a cooled recirculating gas oil stream 22, . in a packing section 23.
- the heavier fractions are fed to a heater 24 where the temperature is raised to about 480°C to induce mild thermal cracking. This tends to crack and hence reduce the wax components in the gas oil.
- the heated stream is then mixed with the feedstock in line 16 and thus recycled.
- a portion of the withdrawn heavy gas oil 20 is heat exchanged with feedstock as recycle stream 15 in heat exchanger 13, cooled to about 260°C and returned as stream 22 to the column 18 at the top of section 23.
- Excess gas oil in this recirculating circuit comprises an overflow line 25 which joins recycle stream 14.
- This stream comprises recirculating gas oil from a catch tray 26 located beneath a second packing section 27 and is heat exchanged against the feedstock in heat exchanger 12. The stream is then reintroduced to the column 18 above the packing section 27 where gas oil and lighter fractions in the column are condensed.
- Excess gas oil and lighter fractions in the recycle stream 14 comprise overflow stream 28 which is passed to a top-packing section 29.
- This stream 28 is cooled against cooling water or air in a heat exchanger 31 to a temperature between about 40 and 60°C.
- the final product is withdrawn in stream 32 from a catch tray 33 beneath the packing section 29 at about 75°C and some of this stream is mixed with. stream 28 via line 34 prior to its being cooled.
- the lightest fractions resulting from mild thermal cracking of the heavier gas oil fraction tend to dissolve into the final withdrawn product stream 32 together with any light fractions contained in the feedstock. This also reduces the load on the vacuum inducing'equipment.
- the vacuum in the system may be induced by any suitable means such as vacuum pumps or steam ejectors (not shown) via a top outlet 35.
- the vacuum residue in line 19. is removed from the process at the temperature of the flash zone 17 and either passed directly to burners 36 in a power station boilers 37 or to intermediate hot storage Cnot shown) without heat exchanging against any other stream.
- the boilers generate steam which is transferred via steam line 38 to electricity generators 39.
- the vacuum residue in line 19 may be heat exchanged and cooled to the practical temperature limit set by the fluid flow properties of the fuel which will be above 150°C.
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
- The present invention relates to a method and apparatus for the thermal treatment of heavy fuel oil, for example a method and apparatus to recover lighter products and to utilise the heavier products, and such a method comprises supplying the heavy fuel oil to a vacuum distillation unit operating at a sub-atmospheric pressure, withdrawing a heavy gas oil and any other contained lighter fractions as a top product, and withdrawing a vacuum residue as a bottom product.
- In modern oil refineries the reduced crude from a crude oil topping still is commonly passed to a unit referred to as a vacuum unit, where, under sub-atmospheric pressure, heavy gas oil is flashed out and separated from the heaviest petroleum fraction, commonly called vacuum residue. When cooled to atmospheric temperatures this residue is a very viscous fluid.
- The heavy gas oil is usually recovered for subsequent use as feedstock in cracking processes and is generally accepted as being more valuable than reduced crude.
- When it is required to market vacuum residue as a fuel, it is either necessary to blend in lighter more valuable fractions, such as cracked recycle oil or to process it in a process unit such as a visbreaker, or a combination of both so that it may be readily pumped through pipework at ambient tempeature. All these solutions result in further expense.
- It is an object of the present invention to utilise the vacuum residue as a fuel without the expense and waste of incorporating lighter fractions and/or visbreaking the vacuum residue.
- According to the invention, there is provided a method for the thermal treatment of heavy fuel oil characterised by supplying the hot vacuum residue directly to a burner and burning the vacuum residue to release heat energy. The heat energy may be used to generate electricity.
- The method may be particularly suitable in situations where a power station receives fuel oil, delivered by water or served by a conncecting pipeline from an oil refinery. In such cases, the method according to the invention is preferably carried out on or close to the power station premises and preferably as close to the boilers as is practically possible. The techniques may be allied to other large consumers of heavy oil fuels such as cement manufacturers.
- Thus, reduced crude or heavy fuel oil to typical power station specifications may be recieved at the power station and supplied to a vacuum still to separate out those petroleum fractions lighter than vacuum residue. The vacuum residue may then be at a sufficiently high temperature, e.g. between 200 and 3750C such that it readily flows through pipework and can be effectively burnt in the power station boilers.
- The separated heavy gas oil and lighter fractions which are recovered may be returned to the originating oil refinery or may be marketed as a more valuable product than the fuel oil feedstock recieved at the power station.
- Transportation economies. could also be realised since a ship bringing the fuel to the power station could return with the recovered gas oils as ballast.
- Once the vacuum residue has been separated, any subsequent pipework, intermediate storage and burner systems should preferably be provided with appropriate insulation and heat tracing to keep the fuel hot.
- Thus, a considerable benefit of the method of the invention is that it is possible to save that energy which would otherwise be consumed in visbreaking the vacuum residue or alternatively to conserve more valuable lower boiling petroleum fractions so that they may be put to more useful applications.
- Preferably the method includes the steps of withdrawing one or more fractions from the column and heat- exchanging these streams against the feedstock inlet stream to the column.
- A characteristic of many crude oils is that wax components tendto concentrate in the heavier gas oil fractions recovered in a vacuum unit. This impairs the fluid flow characteristics of the recovered heavy gas oil, especially at ambient temperature. A method of measuring this characteristic is a well known test to determine the pour point of the fluid. Pour points greater than 25°C are generally unacceptable. It is quite common for recovered heavy gas oil to have a pour point value greater that 25°C.
- It is well known that wax tends to accumulate in the heavier gas oils recovered in vacuum stills and invariably results in pour points greater than 25 C. Clearly, this will be unacceptable when that fraction has to be-shipped or transported at ambient temperature.
- There are several well established processes for removing-..these waxes. One example is solvent extraction though this can be quite expensive. Another process entails subjecting the heavy gas oil to mild thermal cracking conditions which may break down a substantial proportion of the wax.
- It is therefore a further object of the present invention to improve the fluid flow characteristics of recovered heavy gas oil and vacuum residue by reducing the wax content.
- Preferably, therefore, the heat supplied to the system to enable the vacuum column to operate is also used to subject a portion of the fuel oil, namely the heavier gas oil fraction, to mild thermal cracking conditions. This is preferably carried out by withdrawing a stream of heavy gas oil from near the base of the vacuum column and passing this stream through a heater. This heated stream may then be mixed with the feedstock inlet stream to the column. No additional heat may be required to be introduced into the system.
- Thus, there may be provided a process which separates out heavy gas oil and lighter fractions from a reduced crude or heavy fuel feedstock and simultaneously subjects the heavier recovered gas oils to mild thermal cracking conditions to reduce the wax content and as a result reduce the pour point of both the separated gas oil and vacuum residue. This can also result in the formation of some lighter, more valuable distillate products.
- Preferably, the vacuum distillation unit operates at a temperature of between about 150 and 375°C e.g. about 345°C and at a pressure of between 0.03 and 0.3 atmospheres e.g. about 0.065 atmospheres.
- According to another aspect of the invention there. is provided apparatus for the thermal treatment of heavy fuel oil comprising a vacuum distillation unit, a heater arranged to supply heat to the distillation unit, a burner arranged to receive directly the hot bottom product from the distillation unit and an electrical generator arranged to convert the heat produced by the burner into electricity.
- Preferably the distillation unit includes two or more sections of gas/liquid contact medium and a liquid catch tray beneath each section.
- The invention may be carried into practice in various ways and one embodiment will now be described by way of example with reference to the accompanying drawings in which the single figure is a schematic diagram of apparatus for thermally treating heavy fuel oil in accordance with the invention.
- Reduced crude feedstock enters the process at 11 at ambient temperature and is heat exchanged in
heat exchangers recycle streams transfer line 16 to theflash zone 17 of avacuum column 18 which operates between 0.03 and 0.3 atmospheres pressure and at about 345°C. - In the
flash zone 17 heavy gas oil and lighter fractions are flashed out of the feedstock as a vapour and pass up thecolumn 18, whilst the vacuum residue also at about 345°C is removed from the bottom of the column vialine 19. - The heavier gas oil fractions are withdrawn as a
liquid stream 20 by means of acatch tray 21 located immediately above theflash zone 17 having been condensed by a cooled recirculatinggas oil stream 22, . in apacking section 23. The heavier fractions are fed to aheater 24 where the temperature is raised to about 480°C to induce mild thermal cracking. This tends to crack and hence reduce the wax components in the gas oil. The heated stream is then mixed with the feedstock inline 16 and thus recycled. - A portion of the withdrawn
heavy gas oil 20 is heat exchanged with feedstock asrecycle stream 15 inheat exchanger 13, cooled to about 260°C and returned asstream 22 to thecolumn 18 at the top ofsection 23. - Excess gas oil in this recirculating circuit comprises an
overflow line 25 which joinsrecycle stream 14. This stream comprises recirculating gas oil from acatch tray 26 located beneath asecond packing section 27 and is heat exchanged against the feedstock inheat exchanger 12. The stream is then reintroduced to thecolumn 18 above thepacking section 27 where gas oil and lighter fractions in the column are condensed. - Excess gas oil and lighter fractions in the
recycle stream 14 compriseoverflow stream 28 which is passed to a top-packing section 29. Thisstream 28 is cooled against cooling water or air in aheat exchanger 31 to a temperature between about 40 and 60°C. The final product is withdrawn instream 32 from acatch tray 33 beneath thepacking section 29 at about 75°C and some of this stream is mixed with.stream 28 vialine 34 prior to its being cooled. - In the process described, the lightest fractions resulting from mild thermal cracking of the heavier gas oil fraction tend to dissolve into the final withdrawn
product stream 32 together with any light fractions contained in the feedstock. This also reduces the load on the vacuum inducing'equipment. - As an alternative to overflowing excess gas oil from one circuit to the next a portion or all of the excess gas oil in a circuit may be withdrawn as a separate product.
- The vacuum in the system may be induced by any suitable means such as vacuum pumps or steam ejectors (not shown) via a
top outlet 35. - The vacuum residue in
line 19. is removed from the process at the temperature of theflash zone 17 and either passed directly toburners 36 in apower station boilers 37 or to intermediate hot storage Cnot shown) without heat exchanging against any other stream. The boilers generate steam which is transferred viasteam line 38 toelectricity generators 39. - Should the intermediate storage or transfer equipment have a temperature restriction then the vacuum residue in
line 19 may be heat exchanged and cooled to the practical temperature limit set by the fluid flow properties of the fuel which will be above 150°C.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT82302978T ATE18252T1 (en) | 1981-12-09 | 1982-06-09 | METHOD AND DEVICE FOR THERMAL TREATMENT OF HEAVY FUEL OIL. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8137083 | 1981-12-09 | ||
GB8137083 | 1981-12-09 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0081895A1 true EP0081895A1 (en) | 1983-06-22 |
EP0081895B1 EP0081895B1 (en) | 1986-02-26 |
Family
ID=10526470
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82302978A Expired EP0081895B1 (en) | 1981-12-09 | 1982-06-09 | Method and apparatus for the thermal treatment of heavy fuel oil |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0081895B1 (en) |
JP (1) | JPS58122983A (en) |
AT (1) | ATE18252T1 (en) |
CA (1) | CA1181710A (en) |
DE (1) | DE3269344D1 (en) |
DK (1) | DK547082A (en) |
GB (1) | GB2111074B (en) |
GR (1) | GR77105B (en) |
NO (1) | NO824128L (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2134920A (en) * | 1983-02-09 | 1984-08-22 | Intevep Sa | Upgrading heavy hydrocarbons employing a diluant |
US5052175A (en) * | 1988-04-27 | 1991-10-01 | Siemens Aktiengesellschaft | Steam power plant |
ES2170660A1 (en) * | 2000-05-04 | 2002-08-01 | Sinae En Y Medio Ambiente S A | Conversion of waste oils into diesel oil comprises purification, visbreaking, flash separation and fractionation, for additional production of e.g. fuel oil |
US6855248B1 (en) * | 1998-08-21 | 2005-02-15 | Sulzer Chemtech Limited | Process for distilling fischer-tropsch derived paraffinic hydrocarbons |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1219236A (en) * | 1985-03-01 | 1987-03-17 | David W. Mcdougall | Diluent distallation process and apparatus |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB389203A (en) * | 1931-12-12 | 1933-03-16 | Auguste Haeck | Improvements in or relating to process and apparatus for the manufacture of mixturessuitable for carburation or combustion, from oils wholly or partly unfit for such uses |
US1945600A (en) * | 1929-11-16 | 1934-02-06 | Lummus Co | Contact apparatus |
DE1034299B (en) * | 1956-02-23 | 1958-07-17 | Josef Raky | Method and device for the energy utilization of the crude gasoline produced during the distillation of crude oil to drive gas turbines |
GB829966A (en) * | 1957-09-17 | 1960-03-09 | Exxon Research Engineering Co | Power generation |
US3207675A (en) * | 1961-11-24 | 1965-09-21 | James Morris Gladieux | Apparatus for recovering waste gases in a refinery |
-
1982
- 1982-06-09 AT AT82302978T patent/ATE18252T1/en not_active IP Right Cessation
- 1982-06-09 DE DE8282302978T patent/DE3269344D1/en not_active Expired
- 1982-06-09 EP EP82302978A patent/EP0081895B1/en not_active Expired
- 1982-06-22 CA CA000405703A patent/CA1181710A/en not_active Expired
- 1982-12-08 NO NO824128A patent/NO824128L/en unknown
- 1982-12-08 JP JP57214066A patent/JPS58122983A/en active Pending
- 1982-12-09 GB GB08235152A patent/GB2111074B/en not_active Expired
- 1982-12-09 DK DK547082A patent/DK547082A/en not_active Application Discontinuation
- 1982-12-09 GR GR70031A patent/GR77105B/el unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1945600A (en) * | 1929-11-16 | 1934-02-06 | Lummus Co | Contact apparatus |
GB389203A (en) * | 1931-12-12 | 1933-03-16 | Auguste Haeck | Improvements in or relating to process and apparatus for the manufacture of mixturessuitable for carburation or combustion, from oils wholly or partly unfit for such uses |
DE1034299B (en) * | 1956-02-23 | 1958-07-17 | Josef Raky | Method and device for the energy utilization of the crude gasoline produced during the distillation of crude oil to drive gas turbines |
GB829966A (en) * | 1957-09-17 | 1960-03-09 | Exxon Research Engineering Co | Power generation |
US3207675A (en) * | 1961-11-24 | 1965-09-21 | James Morris Gladieux | Apparatus for recovering waste gases in a refinery |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2134920A (en) * | 1983-02-09 | 1984-08-22 | Intevep Sa | Upgrading heavy hydrocarbons employing a diluant |
US5052175A (en) * | 1988-04-27 | 1991-10-01 | Siemens Aktiengesellschaft | Steam power plant |
US6855248B1 (en) * | 1998-08-21 | 2005-02-15 | Sulzer Chemtech Limited | Process for distilling fischer-tropsch derived paraffinic hydrocarbons |
ES2170660A1 (en) * | 2000-05-04 | 2002-08-01 | Sinae En Y Medio Ambiente S A | Conversion of waste oils into diesel oil comprises purification, visbreaking, flash separation and fractionation, for additional production of e.g. fuel oil |
Also Published As
Publication number | Publication date |
---|---|
JPS58122983A (en) | 1983-07-21 |
DK547082A (en) | 1983-06-10 |
GB2111074A (en) | 1983-06-29 |
GR77105B (en) | 1984-09-06 |
NO824128L (en) | 1983-06-10 |
GB2111074B (en) | 1984-10-10 |
DE3269344D1 (en) | 1986-04-03 |
EP0081895B1 (en) | 1986-02-26 |
ATE18252T1 (en) | 1986-03-15 |
CA1181710A (en) | 1985-01-29 |
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