CA1089199A - Catalytic hydrogenation reactor - Google Patents
Catalytic hydrogenation reactorInfo
- Publication number
- CA1089199A CA1089199A CA265,724A CA265724A CA1089199A CA 1089199 A CA1089199 A CA 1089199A CA 265724 A CA265724 A CA 265724A CA 1089199 A CA1089199 A CA 1089199A
- Authority
- CA
- Canada
- Prior art keywords
- shell
- reactor
- inlet
- liquid
- collector
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
- C10G49/12—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles suspended in the oil, e.g. slurries
Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to a catalytic hydro-genation reactor suitable for hydrogenating oil in an ebullated bed of catalyst particles, said reactor being a vertical cylindrical closed shell having an inlet for liquids at the lower end and an outlet for vapors at the upper end, and having internally disposed inside the upper end of the shell a truncated conical collector joined to the inside wall of the shell and connected at its upper end to a short cylindrical weir; the weir, which has an internal cross-sectional area approximately one-half of the internal cross-sectional area of the shell, serving to remove liquid product from the ebullating bed Also included in the reactor is a downcomer conduit located near the wall of the shell and joining the collector at one end means such as a pump for recirculating liquid; packing means internally disposed in the lower end of the shell for diverting and distributing liquid feed material introduced through the inlet of the shell; and means for introducing fresh catalyst into and removing spent catalyst from, the interior of said shell.
This invention relates to a catalytic hydro-genation reactor suitable for hydrogenating oil in an ebullated bed of catalyst particles, said reactor being a vertical cylindrical closed shell having an inlet for liquids at the lower end and an outlet for vapors at the upper end, and having internally disposed inside the upper end of the shell a truncated conical collector joined to the inside wall of the shell and connected at its upper end to a short cylindrical weir; the weir, which has an internal cross-sectional area approximately one-half of the internal cross-sectional area of the shell, serving to remove liquid product from the ebullating bed Also included in the reactor is a downcomer conduit located near the wall of the shell and joining the collector at one end means such as a pump for recirculating liquid; packing means internally disposed in the lower end of the shell for diverting and distributing liquid feed material introduced through the inlet of the shell; and means for introducing fresh catalyst into and removing spent catalyst from, the interior of said shell.
Description
1(~89199 This invention relates to a design of a catalytic reaction vessel, and more particularly, the design of a reactor for catalytically hydrogenating oil.
This invention deals with the catalytic hydrogenation of a liquid wherein the catalyst is in the form of small particles that are intimately distributed throughout the liquid in the reaction zone. In general, this type of process is described in the patent of Johanson, U.S. 2,987,~65, where it is described that the mixture of liquid and hydrogen is passed through a bed of the catalyst particles at such a rate that the particles are forced into a random motion as the liquid is pumped through the bed, and that motion is so ; ;~
controlled that the majority of the catalyst particles stay below a certain level in the reactor while the liquid being hydrogenated and any unused hydrogen gas passes beyond that level of catalyst particles and is removed from the reactor or recycled to the inlet at the bottom of the reactor. This type of reactor is frequently referred to as an "ebullated"
bed reactor. Such reactors have assumed several different `
designs, although the usual design has been to include a centrally located pipe which functions as a downcomer to recycle liquid from the top of the reactor where substantially no catalyst particles are present to the bottom of the reactor where it is again pumped along with fresh feed upwardly through the bed of catalyst particles. Hydrogenated liquid is removed from the upper portion of the reactor where the liquid is substantially free of catalyst particles and may be further treated for any of a variety of purposes. Unused hydrogen gas and other vapors are removed through a vapor q~tlet at the top of the reactor and after separation and purification the hydrogenation gases may be returned and recycled with the feed.
This invention deals with the catalytic hydrogenation of a liquid wherein the catalyst is in the form of small particles that are intimately distributed throughout the liquid in the reaction zone. In general, this type of process is described in the patent of Johanson, U.S. 2,987,~65, where it is described that the mixture of liquid and hydrogen is passed through a bed of the catalyst particles at such a rate that the particles are forced into a random motion as the liquid is pumped through the bed, and that motion is so ; ;~
controlled that the majority of the catalyst particles stay below a certain level in the reactor while the liquid being hydrogenated and any unused hydrogen gas passes beyond that level of catalyst particles and is removed from the reactor or recycled to the inlet at the bottom of the reactor. This type of reactor is frequently referred to as an "ebullated"
bed reactor. Such reactors have assumed several different `
designs, although the usual design has been to include a centrally located pipe which functions as a downcomer to recycle liquid from the top of the reactor where substantially no catalyst particles are present to the bottom of the reactor where it is again pumped along with fresh feed upwardly through the bed of catalyst particles. Hydrogenated liquid is removed from the upper portion of the reactor where the liquid is substantially free of catalyst particles and may be further treated for any of a variety of purposes. Unused hydrogen gas and other vapors are removed through a vapor q~tlet at the top of the reactor and after separation and purification the hydrogenation gases may be returned and recycled with the feed.
-2-.~ .. , - . . . .
~(~89199 The feed oil for the reactor of this invention may be an oil or residue from a petroleum distillation process, a dispersion of coal particles in a petroleum oil, or a low yrade hydrocar~on liquid from any of several sources. The feed hydrogen for this reactor is gaseous hydrogen or a hydrogen-rich gas or vapor. The products produced in this reactor from such feed materials include fuel oil, diesel oil, or other combustible hydrocarbons. General operating conditions for such a process are~about 700-1,000F and 1500-3500 psig.
It is an object of this invention to provide a small simplified reactor for the catalytic hydrogenation of ?
oil through a bed of catalyst particles.
It is another object of this invention to provide such a catalytic reactor which is preferably employed in small volume operations. Other objects will appear from the more detailed description of this invention which fQllows.
The present invention resides in a catalytic hydrogenation reactor suitable for processes employing an ;
ebullated bed of catalyst particles comprising a generally -cylindrical, vertical, closed shell having an inlet for liquids at the lower end, an outlet for vapors at the upper end, a truncated conical collector joining the inside of said shell with the bottom of a short cylindrical weir located inside the top portion of said shell, said weir having an internal cross-sectional area approximately one-half of the internal cross-~ sectional area of said shell, a downcomer pipe lying near the ; wall of said shell and joining said collector with a recirculating -,i?~ï, pump having its discharge connected to the inlet of the said`~- 30 shell, the lower end of said shell being filled with packing means for diverting and distributing a liquid feed material introduced through the inlet of said shell, and means for -
~(~89199 The feed oil for the reactor of this invention may be an oil or residue from a petroleum distillation process, a dispersion of coal particles in a petroleum oil, or a low yrade hydrocar~on liquid from any of several sources. The feed hydrogen for this reactor is gaseous hydrogen or a hydrogen-rich gas or vapor. The products produced in this reactor from such feed materials include fuel oil, diesel oil, or other combustible hydrocarbons. General operating conditions for such a process are~about 700-1,000F and 1500-3500 psig.
It is an object of this invention to provide a small simplified reactor for the catalytic hydrogenation of ?
oil through a bed of catalyst particles.
It is another object of this invention to provide such a catalytic reactor which is preferably employed in small volume operations. Other objects will appear from the more detailed description of this invention which fQllows.
The present invention resides in a catalytic hydrogenation reactor suitable for processes employing an ;
ebullated bed of catalyst particles comprising a generally -cylindrical, vertical, closed shell having an inlet for liquids at the lower end, an outlet for vapors at the upper end, a truncated conical collector joining the inside of said shell with the bottom of a short cylindrical weir located inside the top portion of said shell, said weir having an internal cross-sectional area approximately one-half of the internal cross-~ sectional area of said shell, a downcomer pipe lying near the ; wall of said shell and joining said collector with a recirculating -,i?~ï, pump having its discharge connected to the inlet of the said`~- 30 shell, the lower end of said shell being filled with packing means for diverting and distributing a liquid feed material introduced through the inlet of said shell, and means for -
-3- :
-::
1(~89199 introducing fresh catalyst into and removing spent catalyst from the interior of said shell.
In the attached drawings:
Figure 1 is a longitudinal cross-section of the reactor of this invention; and Figure 2 is a horizontal cross-section taken along AA of Figure 1.
With specific reference to the drawings, the reactor comprises shell 10 having an outlet 11 for vapor to be removed from the top of the reactor and an inlet 12 for liquid to be introduced into the bottom of the reactor. Internally near the top of the reactor is a truncated conical collector 13 which is welded or otherwise joined with a liquid tight seal around the base of the conical section to the inside surface of shell 10. The upper portion of conical collector 13 is joined to the bottom of a short cylindrical weir 14 which is concentrically located with respect to the wall of shell 10.
This cylindrical section is open at both ends so as to direct the flow of liquid from the interior of the reactor up and over weir 14 and thence into the annular space between conical collector 13 and the wall of shell 10. The annular space formed between cylinder 14, shell 10, and collector 13 permits -liquid to be withdrawn from such a space through downcomer pipe 18 through opening 15. Net liquid from the reactor is withdrawn through pipe 16 as liquid product 17 which may be treated -further to produce any of a variety o substances and to re-cover the heat energy in that liquid. Downcomer pipe 18 leads to pump 20 which discharges liquid to be joined with feed oil in line 24 and feed hydrogen in line 25 to be introduced through inlet 12 for recycling through the catalytic hydrogenation reaction. It will be seen that the downcomer 18 lies against the inside surface of shell 10 so as to cause as little
-::
1(~89199 introducing fresh catalyst into and removing spent catalyst from the interior of said shell.
In the attached drawings:
Figure 1 is a longitudinal cross-section of the reactor of this invention; and Figure 2 is a horizontal cross-section taken along AA of Figure 1.
With specific reference to the drawings, the reactor comprises shell 10 having an outlet 11 for vapor to be removed from the top of the reactor and an inlet 12 for liquid to be introduced into the bottom of the reactor. Internally near the top of the reactor is a truncated conical collector 13 which is welded or otherwise joined with a liquid tight seal around the base of the conical section to the inside surface of shell 10. The upper portion of conical collector 13 is joined to the bottom of a short cylindrical weir 14 which is concentrically located with respect to the wall of shell 10.
This cylindrical section is open at both ends so as to direct the flow of liquid from the interior of the reactor up and over weir 14 and thence into the annular space between conical collector 13 and the wall of shell 10. The annular space formed between cylinder 14, shell 10, and collector 13 permits -liquid to be withdrawn from such a space through downcomer pipe 18 through opening 15. Net liquid from the reactor is withdrawn through pipe 16 as liquid product 17 which may be treated -further to produce any of a variety o substances and to re-cover the heat energy in that liquid. Downcomer pipe 18 leads to pump 20 which discharges liquid to be joined with feed oil in line 24 and feed hydrogen in line 25 to be introduced through inlet 12 for recycling through the catalytic hydrogenation reaction. It will be seen that the downcomer 18 lies against the inside surface of shell 10 so as to cause as little
4-1~8~199 obstruction as possible to the random motion of the catalyst particles and the reactants inside the reactor. It is an alternative procedure to have the downcomer pipe outside shell 10 as shown at 19 conducting the liquid to pump 20 and thence for recycling as previously described. It will be understood that the exact configuration of reactor shell 10 to accommodate downcomer pipe 18 or 19 and pump 20 may be modified to include such pipes inside the shell and yet have the interior surface of the shell entirely smooth for the most efficient streamlined operation, or still other arrangements in accordance with good engineering practice can be employed.
It is of particular importance and advantage that this reactor employs a simplified distribution system at the inlet portion of reactor 10. It is common for reactors employing an ebullated bed to require a complicated distributor plate involving bubble caps, risers, etc., such as described in The Oil And Gas Journal, December 1, 1975, pages 127-128.
The distribution system in the present invention is nothing more than a short section of the reactor filled with a suitable ; 20 packing material. -~
The bottom of the reactor immediately above inlet 12, is the portion which is filled with that packing material. ;~
A suitable material for such purpose is a bed of spheres of metal, glass ceramic, or the like, although there are many ; `
other types of packing material which are available commercially to serve this same purpose. It is only important that the packing provide sufficient free space for the incoming feed -material to flow without an undue amount of friction loss. It is, of course, important that the materials from which the `-packing is made be entirely inert to the oil and the hydrogen in the feed. In general, the spheres or other shaped packing material may be or a size such that the diameter or maximum .
,~ - - - , . .. . . . .
~SI`89~99 dimension is from about 1/2 inch to about 2 inches. The packing material is indicated in Figure 1 by ~e~erence 28.
The packing material is maintained in place by a suitable grate 27 which covers the entire opening of inlet 12 and prevents the packing material from falling into that opening. The upper surface of the packing material is covered by a suitable screen 29 having the largest possible openings that will serve to maintain the packing material in place and yet provide the least possible obstruction to the flow of fluid. In Figure 2, screen 29 is shown as a large mesh rectangular-opening screen.
Catalyst particles must be replaced during the operation of the reaction as they become spent. Any suitable draw off line 22 may be located in the bottom of the reactor with an opening immediately above screen 29 for the removal of spent catalysts. The introduction of fresh catalysts can ~;
~,! be located at almost any position in the reactor although it is shown in Figure 1 as being near the top of the reaction zone at inlet 21. The means for introducing and removing the catalysts are not shown and inlet 21 and outlet 22 are merely set forth in a schematic fashion since this is not a critical feature of this invention but rather is only an operational feature shown for complete description of the invention. There " is also shown by dotted line 30 the general level above which `
catalyst particles are normally not found. The size of the catalyst particles and the energy imparted by pump 20 are so correlated that the large majority of catalyst particles remain ~ in random motion below line 30 while liquid above line 30 flows ; up and over the top of weir 14 and carries with it substantially no catalyst particles from the reactor. ;~
, Vapor produced in the process is removed through -outlet 11 at the top of the reactor and transported through line ~`
: ~ ' - ~ -6-.. . .
26 to further processing, e.g. to a vapor-liquid separator, to recover valuable gases and liquids therefrom. Some substantial portion of the gas is usually hydrogen which can be purified and recycled to inlet 12 of the reactor.
This reactor design is particularly preferred when the size of the operation is such that the diameter of shell 10 is not more than about 6-7 feet. Such a reactor for relatively small operations has the advantage of a simplified design, and uncomplicated flow pattern for the circulating oil and catalyst particles and a structural design which provides the necessary strength to withstand the internal pressures and temperatures.
Although the invention has been described in . . .
considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and ~
scope of the invention as described hereinabove and as defined `
: . .
in the appended claims.
'.'`.'.`: , '~
, "`
:
: . :
" ~
.,~ .
.~.. . . .
It is of particular importance and advantage that this reactor employs a simplified distribution system at the inlet portion of reactor 10. It is common for reactors employing an ebullated bed to require a complicated distributor plate involving bubble caps, risers, etc., such as described in The Oil And Gas Journal, December 1, 1975, pages 127-128.
The distribution system in the present invention is nothing more than a short section of the reactor filled with a suitable ; 20 packing material. -~
The bottom of the reactor immediately above inlet 12, is the portion which is filled with that packing material. ;~
A suitable material for such purpose is a bed of spheres of metal, glass ceramic, or the like, although there are many ; `
other types of packing material which are available commercially to serve this same purpose. It is only important that the packing provide sufficient free space for the incoming feed -material to flow without an undue amount of friction loss. It is, of course, important that the materials from which the `-packing is made be entirely inert to the oil and the hydrogen in the feed. In general, the spheres or other shaped packing material may be or a size such that the diameter or maximum .
,~ - - - , . .. . . . .
~SI`89~99 dimension is from about 1/2 inch to about 2 inches. The packing material is indicated in Figure 1 by ~e~erence 28.
The packing material is maintained in place by a suitable grate 27 which covers the entire opening of inlet 12 and prevents the packing material from falling into that opening. The upper surface of the packing material is covered by a suitable screen 29 having the largest possible openings that will serve to maintain the packing material in place and yet provide the least possible obstruction to the flow of fluid. In Figure 2, screen 29 is shown as a large mesh rectangular-opening screen.
Catalyst particles must be replaced during the operation of the reaction as they become spent. Any suitable draw off line 22 may be located in the bottom of the reactor with an opening immediately above screen 29 for the removal of spent catalysts. The introduction of fresh catalysts can ~;
~,! be located at almost any position in the reactor although it is shown in Figure 1 as being near the top of the reaction zone at inlet 21. The means for introducing and removing the catalysts are not shown and inlet 21 and outlet 22 are merely set forth in a schematic fashion since this is not a critical feature of this invention but rather is only an operational feature shown for complete description of the invention. There " is also shown by dotted line 30 the general level above which `
catalyst particles are normally not found. The size of the catalyst particles and the energy imparted by pump 20 are so correlated that the large majority of catalyst particles remain ~ in random motion below line 30 while liquid above line 30 flows ; up and over the top of weir 14 and carries with it substantially no catalyst particles from the reactor. ;~
, Vapor produced in the process is removed through -outlet 11 at the top of the reactor and transported through line ~`
: ~ ' - ~ -6-.. . .
26 to further processing, e.g. to a vapor-liquid separator, to recover valuable gases and liquids therefrom. Some substantial portion of the gas is usually hydrogen which can be purified and recycled to inlet 12 of the reactor.
This reactor design is particularly preferred when the size of the operation is such that the diameter of shell 10 is not more than about 6-7 feet. Such a reactor for relatively small operations has the advantage of a simplified design, and uncomplicated flow pattern for the circulating oil and catalyst particles and a structural design which provides the necessary strength to withstand the internal pressures and temperatures.
Although the invention has been described in . . .
considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and ~
scope of the invention as described hereinabove and as defined `
: . .
in the appended claims.
'.'`.'.`: , '~
, "`
:
: . :
" ~
.,~ .
.~.. . . .
Claims (5)
1. A catalytic hydrogenation reactor suitable for processes employing an ebullated bed of catalyst particles comprising a generally cylindrical, vertical, closed shell having an inlet for liquids at the lower end, an outlet for vapors at the upper end, a truncated conical collector joining the inside of said shell with the bottom of a short cylindrical weir located inside the top portion of said shell, said weir having an internal cross-sectional area approximately one-half of the internal cross-sectional area of said shell, a downcomer pipe lying near the wall of said shell and joining said collector with a recirculating pump having its discharge connected to the inlet of the said shell, the lower end of said shell being filled with packing means for diverting and distributing a liquid feed material introduced through the inlet of said shell, and means for introducing fresh catalyst into and removing spent catalyst from the interior of said shell.
2. The reactor of Claim 1 wherein said downcomer pipe is inside said shell.
3. The reactor of Claim 1 wherein said downcomer, pipe is outside said shell.
4. The reactor of Claim 1 wherein the net liquid and vapor exits at the top of the reactor are connected to further processing equipment, for recovering valuable liquid and gas products.
5. A liquid phase catalytic hydrogenation reactor for processes employing an ebullated bed of catalyst particles comprising:
(a) a generally cylindrical, vertical closed shell;
(b) a means for introducing gases and liquids at the lower end of said shell;
(c) a means for removing vapors and gases at the upper end of said shell;
(d) a truncated conical collector internally disposed inside the upper end of said shell, said collector being joined at its base to the inside wall of said shell;
(e) a short cylindrical weir which is connected at its base to the upper end of the collector, said weir having an internal cross-sectional weir area approximately one-half of the internal cross-section area of said shell;
(f) a downcomer conduit parallel to the wall of said shell and communicating with said collector at one end;
(g) a means for recirculating a substantially solids free liquid positioned between said conduit and inlet means;
(h) a means for diverting and distributing a liquid and gaseous feed material internally disposed in the lower end of said shell connected with the inlet of said shell;
(i) a means for introducing fresh catalyst into the reactor shell; and (j) a means for removing spent catalyst from the interior of said shell.
(a) a generally cylindrical, vertical closed shell;
(b) a means for introducing gases and liquids at the lower end of said shell;
(c) a means for removing vapors and gases at the upper end of said shell;
(d) a truncated conical collector internally disposed inside the upper end of said shell, said collector being joined at its base to the inside wall of said shell;
(e) a short cylindrical weir which is connected at its base to the upper end of the collector, said weir having an internal cross-sectional weir area approximately one-half of the internal cross-section area of said shell;
(f) a downcomer conduit parallel to the wall of said shell and communicating with said collector at one end;
(g) a means for recirculating a substantially solids free liquid positioned between said conduit and inlet means;
(h) a means for diverting and distributing a liquid and gaseous feed material internally disposed in the lower end of said shell connected with the inlet of said shell;
(i) a means for introducing fresh catalyst into the reactor shell; and (j) a means for removing spent catalyst from the interior of said shell.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US65373676A | 1976-01-30 | 1976-01-30 | |
| US653,736 | 1984-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089199A true CA1089199A (en) | 1980-11-11 |
Family
ID=24622117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA265,724A Expired CA1089199A (en) | 1976-01-30 | 1976-11-16 | Catalytic hydrogenation reactor |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS581719B2 (en) |
| CA (1) | CA1089199A (en) |
| DE (1) | DE2656979A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0326253Y2 (en) * | 1984-11-28 | 1991-06-06 | ||
| JPS62237024A (en) * | 1986-04-07 | 1987-10-17 | Mazda Motor Corp | Cooling water controller for engine |
-
1976
- 1976-11-16 CA CA265,724A patent/CA1089199A/en not_active Expired
- 1976-12-16 DE DE19762656979 patent/DE2656979A1/en not_active Ceased
-
1977
- 1977-01-26 JP JP821777A patent/JPS581719B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52145403A (en) | 1977-12-03 |
| DE2656979A1 (en) | 1977-08-04 |
| JPS581719B2 (en) | 1983-01-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |