CA1174697A - Catalytic dehydrohalogenation process - Google Patents
Catalytic dehydrohalogenation processInfo
- Publication number
- CA1174697A CA1174697A CA000423149A CA423149A CA1174697A CA 1174697 A CA1174697 A CA 1174697A CA 000423149 A CA000423149 A CA 000423149A CA 423149 A CA423149 A CA 423149A CA 1174697 A CA1174697 A CA 1174697A
- Authority
- CA
- Canada
- Prior art keywords
- reactor
- zeolite
- catalyst
- cracking
- reaction
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
- C07C2529/035—Crystalline silica polymorphs, e.g. silicalites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
Abstract
ABSTRACT
Saturated C1-6 hydrochlorocarbons are dehy-drochlorinated by contacting with ZSM-5 or silicalite zeolites at 200°C-400°C.
Saturated C1-6 hydrochlorocarbons are dehy-drochlorinated by contacting with ZSM-5 or silicalite zeolites at 200°C-400°C.
Description
~74f~37 CATALYTIC DEHYDROHALOGENATION PROCESS
It is well-known that ethylenically unsatu-rated compounds can be produced from hydrochlorocarbons by means of a cracking or pyrolysis process by splitting off a molecule of hydrogen chloride. The cracking is accomplished in the absence of a catalyst by heating the hydrochlorocarbon in an inert atmosphere under high tem-perature and pressure. Usually a temperature in the range of 500C to 600C and a pressure of 100 to 600 psig is used. The generation of such energy, of course, is ~O
expensive.
In European patent 2,021, a catalyst system comprising a zeolite which has been treated or reacted with a volatile Lewis acid was disclosed for the dehydro-halogenation of ethylene dichloride. Suitable catalysts include faujasite Y zeolite reacted with TiC14.
Synthetic activated divalent cation exchanged sodium zeolite A was disclosed in USP 2,920,122 as suit-able in the dehydrochlorination of halo-substituted hydro-carbons. Specific examples included the conversion of tertiary butyl chloride to isobutene.
`~, ,; 30,037-F -1- ~
~.~
., . ~
1~ 74~ 7 In USP 3,927,131, at column 4, lines 28-50, Table I, the use of a synthetic zeolite, SK-120, contain-ing 10 percent rare earths of unspecified identity and 0.5 percent palladium in the dehydrohalogenation of ali-phatic hydrochlorocarbons was disclosed. Temperaturesemployed were from 400C-600C.
Prior art processes for dehydrochlorination of hydrochlorocarbons have required that the synthetic zeolite be modified by reaction with Lewis acids or by exchange of divalent cations or incorporation therein of rare earths or noble metals. It would be desirable to provide a synthetic zeolite catalyst for the dehydro-chlorination of hydrocarbons that does not require prep-aration or modification in the above ways.
Prior art processes have also obtained only limited conversions of hydrochlorocarbons thereby requir-ing long contact or reaction times or multiple passes of the hydrochlorocarbon over the catalyst bed.
It would be desirable to provide a catalyst system that allows the artisan to prepare dehydrochlori-nation products in relatively high conversions using reduced reaction or contact times without the formation of substantial quantities of by-products.
It would further be desirable to provide a catalyst system that will obtain the dehydrochlorination of hydrochlorocarbons at relatively mild reaction temper-atures, thereby resulting in reduced energy consumption.
30,037-F -2-~ ~46~7 It has now unexpectedly been found that improved conversion with less energy can be obtained by a process which comprises cracking or dehydrohalo-genating hydrochlorocarbons by employing, as catalyst, a synthetic siliceous zeolite selected from the group consisting of ZSM-5 and silicalite. The use of the above zeolite cracking catalysts enables operation at temperatures far below that normally required with prior processes. Using the catalysts of the instant invention, the cracking process can be operated at a temperature in the range of preferably 200C to 400C, more preferably from 250C-350C.
The hydrochlorocarbons which may be dehydro-chlorinated according to the present invention are C1 6 saturated halogenated compounds such as 1,1- and 1,2-di-chloroethane, 1,2- and 1,3-dichloropropane, 1,2,3-trichlo-ropropane, 1,1,2-trichloroethane, 1,2-dichlorobutane and the like. Preferred are 1,1- and 1,2-dichloroethane which are used to prepare vinyl chloride.
The synthetic siliceous zeolites employed in the present invention are well-known in the art. ZSM-5 has been described in USP 3,702,886. Silicalite is fur-ther described as crystalline silica which after calcina-tion in air at 600C for one hour produces a silica poly-morph having a mean refractive index of 1.39+0.01 and a specific gravity at 25C of 1.70+0.05 g/cc. Silicalite has been described in USP 4,061,724. D. H. Olson et al., writing in J. of Catalysis, 61, 390-396 (1980) clarified the various zeolite structures related to ZSM-5 and con-cluded that highly siliceous pentasil structures such as silicalite have properties in conformity with and directly 30,037-F -3-. , f 3'7 . ~
related to the level of aluminum content. Therefore, sili-calite may be considered as an end member of a substitu-tional series, e.g., a substantially aluminum-free form of ZSM-5. For the above teachings, these references are herein incorporated by reference in their entireties.
These synthetic zeolites are employed in the instant invented process in either an alkali metal or hydrogen ion form. No special processing or preparation of the catalyst is required other than normal procedures such as calcining in order to remove organic residues.
It is to be understood that the zeolite cata-lyst is placed in the cracking reactor in such fashion as to allow the rapid passage of vapor or gas therethrough.
The catalyst in the reactor may be either a fixed bed or a fluidized bed. The cracking step is done either neat or in an inert atmosphere, nitrogen being particularly good for this purpose. After the cracking reactor has been purged with nitrogen, the hydrochlorocarbon, pref-erably in gaseous form, is introduced into the reactor.
When the hydrochlorocarbon comes in contact with the catalyst, the dehydrochlorination reaction or cracking proceeds smoothly and rapidly, converting the hydrochloro-carbon to the corresponding ethylenically unsaturated derivative and by-product hydrogen chloride.
The temperature in the cracker is preferably maintained in the range of 200C to 400C. Temperatures lower than 200C may be employed or one may use tempera-tures higher than 400C. However, optimum results are obtained when operating within the temperature range given above.
30,037-F -4-1~74~i~37 , .
While the cracking reaction may be operated at atmospheric pressure, or slightly below, it is pre-ferred in the present invention to operate at superat-mospheric pressure. A pressure anywhere up to about 100 atmospheres is satisfactory. At higher pressures cracking of the hydrochlorocarbon into undesirable chlorohydrocar-bon by-products, such as CC14, etc., may occur. However, when using superatmospheric pressure, less coking or car-bon formation tends to occur. Periodically the reactor is shut down and the carbon or coke formation, if any, is removed, usually by burning off, that is, heating the reactor at a high temperature in the presence of oxygen or air. Usually a temperature in the range of 300C to 700C is sufficient to remove the coke formation.
The reaction or contact time of the hydro-chlorocarbon with the catalyst in the reactor can be varied. The contact time necessary between the hydro-chlorocarbon and catalyst to promote the desired dehy-drochlorination reaction is obtained by controlling the space velocity of the gaseous material passing through the reaction zone. The contact time is dependent upon several factors, namely, the scale of the operation, the quantity of catalyst in the reactor or cracker, and the type of reactor employed. For most reactors a contact time as high as about 25 seconds or more and as low as 0.5 second can be employed. If the contact time is too low the quantity of unreacted hydrochlorocarbon coming over is too high. On the other hand, if the contact time is too high, that is, much above 25 seconds, the impuri-ties increase which makes it more difficult to recoverthe desired compound in a pure form. One can readily adjust the gaseous feed rate to obtain the optimum reac-tion or contact time for any particular type reactor.
30,037-F -5-;
, .
1~ ~4~i~'7 The gaseous mixture that is withdrawn from the cracker or reaction zone can be passed directly to a condenser thus recovering the condensable materials and allowing the hydrogen chloride to pass overhead and recycling the same. Alternatively, the gases leaving the reaction zone can be cooled and subjected to fractional distillation under superatmospheric pressure, preferably at the same or lower pressure as that used for the crack-ing.
The following examples are given to more spe-cifically define the instant invention. It is understood that these examples are intended in an illustrative and not limitative sense.
Example 1 A sample of Linde molecular sieve zeolite, S115 silicalite (lot 8251-1-2) (5.2 g) was loaded into a glass reactor l~l' diameter x 41~11 length. The reactor was equipped with 2 thermocouples at approximately l/3 and 2/3 of the reactor length. The reactor was calcined by heating to 450C for approximately 16 hours while purg-ing with nitrogen.
After calcining, the reactor was cooled and liquid ethylene dichloride flow initiated at a rate of 1.3 cc/hr and a nitrogen flow of 25 cc/min at atmospheric pressure. The ethylene dichloride was vaporized by a pre-heater and mixed with the nitrogen stream in a 21-stage static mixer before passing into the catalyst bed main-tained at 325C. After attainment of steady-state condi-tions (about 1 hour), the mixture was sampled and analyzed -~ 30,037-F -6-~ ~46~3~
before and after passing through the reactor by flame ioni-zation gas chromatograph. The results indicated a 50 per-cent conversion of ethylene dichloride. The only products detected were vinyl chloride and ethylene (1-3 percent).
Exam~le 2 The reaction conditions of Example 1 were substantially repeated to obtain approximately 50 per-cent conversion of ethyl chloride to ethylene at 265C.
Example 3 The reaction conditions of Example 1 were substantially repeated to obtain approximately 50 per-cent conversion of 1,1,2-trichloroethane to 1,2-dichlo-roethylene at 225C.
Example 4 The reaction conditions of Example 1 were substantially repeated to obtain approximately 100 per-cent conversion of 1,1,2-trichloroethane to 1,2-dichlo-roethylene at 350C.
Exam~le 5 The reaction conditions of Example 4 were substantially repeated to obtain approximately 75 per-cent conversion of ethylene dichloride to vinyl chloride.
30,037-F -7-
It is well-known that ethylenically unsatu-rated compounds can be produced from hydrochlorocarbons by means of a cracking or pyrolysis process by splitting off a molecule of hydrogen chloride. The cracking is accomplished in the absence of a catalyst by heating the hydrochlorocarbon in an inert atmosphere under high tem-perature and pressure. Usually a temperature in the range of 500C to 600C and a pressure of 100 to 600 psig is used. The generation of such energy, of course, is ~O
expensive.
In European patent 2,021, a catalyst system comprising a zeolite which has been treated or reacted with a volatile Lewis acid was disclosed for the dehydro-halogenation of ethylene dichloride. Suitable catalysts include faujasite Y zeolite reacted with TiC14.
Synthetic activated divalent cation exchanged sodium zeolite A was disclosed in USP 2,920,122 as suit-able in the dehydrochlorination of halo-substituted hydro-carbons. Specific examples included the conversion of tertiary butyl chloride to isobutene.
`~, ,; 30,037-F -1- ~
~.~
., . ~
1~ 74~ 7 In USP 3,927,131, at column 4, lines 28-50, Table I, the use of a synthetic zeolite, SK-120, contain-ing 10 percent rare earths of unspecified identity and 0.5 percent palladium in the dehydrohalogenation of ali-phatic hydrochlorocarbons was disclosed. Temperaturesemployed were from 400C-600C.
Prior art processes for dehydrochlorination of hydrochlorocarbons have required that the synthetic zeolite be modified by reaction with Lewis acids or by exchange of divalent cations or incorporation therein of rare earths or noble metals. It would be desirable to provide a synthetic zeolite catalyst for the dehydro-chlorination of hydrocarbons that does not require prep-aration or modification in the above ways.
Prior art processes have also obtained only limited conversions of hydrochlorocarbons thereby requir-ing long contact or reaction times or multiple passes of the hydrochlorocarbon over the catalyst bed.
It would be desirable to provide a catalyst system that allows the artisan to prepare dehydrochlori-nation products in relatively high conversions using reduced reaction or contact times without the formation of substantial quantities of by-products.
It would further be desirable to provide a catalyst system that will obtain the dehydrochlorination of hydrochlorocarbons at relatively mild reaction temper-atures, thereby resulting in reduced energy consumption.
30,037-F -2-~ ~46~7 It has now unexpectedly been found that improved conversion with less energy can be obtained by a process which comprises cracking or dehydrohalo-genating hydrochlorocarbons by employing, as catalyst, a synthetic siliceous zeolite selected from the group consisting of ZSM-5 and silicalite. The use of the above zeolite cracking catalysts enables operation at temperatures far below that normally required with prior processes. Using the catalysts of the instant invention, the cracking process can be operated at a temperature in the range of preferably 200C to 400C, more preferably from 250C-350C.
The hydrochlorocarbons which may be dehydro-chlorinated according to the present invention are C1 6 saturated halogenated compounds such as 1,1- and 1,2-di-chloroethane, 1,2- and 1,3-dichloropropane, 1,2,3-trichlo-ropropane, 1,1,2-trichloroethane, 1,2-dichlorobutane and the like. Preferred are 1,1- and 1,2-dichloroethane which are used to prepare vinyl chloride.
The synthetic siliceous zeolites employed in the present invention are well-known in the art. ZSM-5 has been described in USP 3,702,886. Silicalite is fur-ther described as crystalline silica which after calcina-tion in air at 600C for one hour produces a silica poly-morph having a mean refractive index of 1.39+0.01 and a specific gravity at 25C of 1.70+0.05 g/cc. Silicalite has been described in USP 4,061,724. D. H. Olson et al., writing in J. of Catalysis, 61, 390-396 (1980) clarified the various zeolite structures related to ZSM-5 and con-cluded that highly siliceous pentasil structures such as silicalite have properties in conformity with and directly 30,037-F -3-. , f 3'7 . ~
related to the level of aluminum content. Therefore, sili-calite may be considered as an end member of a substitu-tional series, e.g., a substantially aluminum-free form of ZSM-5. For the above teachings, these references are herein incorporated by reference in their entireties.
These synthetic zeolites are employed in the instant invented process in either an alkali metal or hydrogen ion form. No special processing or preparation of the catalyst is required other than normal procedures such as calcining in order to remove organic residues.
It is to be understood that the zeolite cata-lyst is placed in the cracking reactor in such fashion as to allow the rapid passage of vapor or gas therethrough.
The catalyst in the reactor may be either a fixed bed or a fluidized bed. The cracking step is done either neat or in an inert atmosphere, nitrogen being particularly good for this purpose. After the cracking reactor has been purged with nitrogen, the hydrochlorocarbon, pref-erably in gaseous form, is introduced into the reactor.
When the hydrochlorocarbon comes in contact with the catalyst, the dehydrochlorination reaction or cracking proceeds smoothly and rapidly, converting the hydrochloro-carbon to the corresponding ethylenically unsaturated derivative and by-product hydrogen chloride.
The temperature in the cracker is preferably maintained in the range of 200C to 400C. Temperatures lower than 200C may be employed or one may use tempera-tures higher than 400C. However, optimum results are obtained when operating within the temperature range given above.
30,037-F -4-1~74~i~37 , .
While the cracking reaction may be operated at atmospheric pressure, or slightly below, it is pre-ferred in the present invention to operate at superat-mospheric pressure. A pressure anywhere up to about 100 atmospheres is satisfactory. At higher pressures cracking of the hydrochlorocarbon into undesirable chlorohydrocar-bon by-products, such as CC14, etc., may occur. However, when using superatmospheric pressure, less coking or car-bon formation tends to occur. Periodically the reactor is shut down and the carbon or coke formation, if any, is removed, usually by burning off, that is, heating the reactor at a high temperature in the presence of oxygen or air. Usually a temperature in the range of 300C to 700C is sufficient to remove the coke formation.
The reaction or contact time of the hydro-chlorocarbon with the catalyst in the reactor can be varied. The contact time necessary between the hydro-chlorocarbon and catalyst to promote the desired dehy-drochlorination reaction is obtained by controlling the space velocity of the gaseous material passing through the reaction zone. The contact time is dependent upon several factors, namely, the scale of the operation, the quantity of catalyst in the reactor or cracker, and the type of reactor employed. For most reactors a contact time as high as about 25 seconds or more and as low as 0.5 second can be employed. If the contact time is too low the quantity of unreacted hydrochlorocarbon coming over is too high. On the other hand, if the contact time is too high, that is, much above 25 seconds, the impuri-ties increase which makes it more difficult to recoverthe desired compound in a pure form. One can readily adjust the gaseous feed rate to obtain the optimum reac-tion or contact time for any particular type reactor.
30,037-F -5-;
, .
1~ ~4~i~'7 The gaseous mixture that is withdrawn from the cracker or reaction zone can be passed directly to a condenser thus recovering the condensable materials and allowing the hydrogen chloride to pass overhead and recycling the same. Alternatively, the gases leaving the reaction zone can be cooled and subjected to fractional distillation under superatmospheric pressure, preferably at the same or lower pressure as that used for the crack-ing.
The following examples are given to more spe-cifically define the instant invention. It is understood that these examples are intended in an illustrative and not limitative sense.
Example 1 A sample of Linde molecular sieve zeolite, S115 silicalite (lot 8251-1-2) (5.2 g) was loaded into a glass reactor l~l' diameter x 41~11 length. The reactor was equipped with 2 thermocouples at approximately l/3 and 2/3 of the reactor length. The reactor was calcined by heating to 450C for approximately 16 hours while purg-ing with nitrogen.
After calcining, the reactor was cooled and liquid ethylene dichloride flow initiated at a rate of 1.3 cc/hr and a nitrogen flow of 25 cc/min at atmospheric pressure. The ethylene dichloride was vaporized by a pre-heater and mixed with the nitrogen stream in a 21-stage static mixer before passing into the catalyst bed main-tained at 325C. After attainment of steady-state condi-tions (about 1 hour), the mixture was sampled and analyzed -~ 30,037-F -6-~ ~46~3~
before and after passing through the reactor by flame ioni-zation gas chromatograph. The results indicated a 50 per-cent conversion of ethylene dichloride. The only products detected were vinyl chloride and ethylene (1-3 percent).
Exam~le 2 The reaction conditions of Example 1 were substantially repeated to obtain approximately 50 per-cent conversion of ethyl chloride to ethylene at 265C.
Example 3 The reaction conditions of Example 1 were substantially repeated to obtain approximately 50 per-cent conversion of 1,1,2-trichloroethane to 1,2-dichlo-roethylene at 225C.
Example 4 The reaction conditions of Example 1 were substantially repeated to obtain approximately 100 per-cent conversion of 1,1,2-trichloroethane to 1,2-dichlo-roethylene at 350C.
Exam~le 5 The reaction conditions of Example 4 were substantially repeated to obtain approximately 75 per-cent conversion of ethylene dichloride to vinyl chloride.
30,037-F -7-
Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the dehydrochlorination of saturated C1-6 hydrochlorocarbons comprising contacting the hydrochlorocarbon in the gaseous phase with a synthetic zeolite comprising a siliceous zeolite which is ZSM-5 or silicalite.
2. The process of Claim 1 wherein the dehydro-chlorination is conducted at a temperature of 200°C to 400°C.
3. The process of Claim 1 wherein the saturated C1-6 hydrochlorocarbon comprises 1,1-dichloroethane, 1,2--dichloroethane or mixtures thereof.
30,037-F -8-
30,037-F -8-
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/357,508 US4384159A (en) | 1982-03-12 | 1982-03-12 | Catalytic dehydrohalogenation process |
US357,508 | 1982-03-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1174697A true CA1174697A (en) | 1984-09-18 |
Family
ID=23405924
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000423149A Expired CA1174697A (en) | 1982-03-12 | 1983-03-09 | Catalytic dehydrohalogenation process |
Country Status (9)
Country | Link |
---|---|
US (1) | US4384159A (en) |
EP (1) | EP0089579B1 (en) |
JP (1) | JPS58167526A (en) |
AU (1) | AU557361B2 (en) |
BR (1) | BR8301299A (en) |
CA (1) | CA1174697A (en) |
DE (1) | DE3360643D1 (en) |
ES (1) | ES520511A0 (en) |
NO (1) | NO157413C (en) |
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US5430215A (en) * | 1994-04-14 | 1995-07-04 | The Dow Chemical Company | Selective hydrodechlorination of 1,2,3-trichloropropane to produce propylene |
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US4061724A (en) * | 1975-09-22 | 1977-12-06 | Union Carbide Corporation | Crystalline silica |
AR219135A1 (en) * | 1977-11-18 | 1980-07-31 | Goodrich Co B F | PROCEDURE FOR PRODUCING VINYL CHLORIDE |
JPS55130923A (en) * | 1979-03-30 | 1980-10-11 | Mitsubishi Heavy Ind Ltd | Condensation of methyl chloride through dehydrochlorination |
-
1982
- 1982-03-12 US US06/357,508 patent/US4384159A/en not_active Expired - Lifetime
-
1983
- 1983-03-09 CA CA000423149A patent/CA1174697A/en not_active Expired
- 1983-03-10 AU AU12331/83A patent/AU557361B2/en not_active Ceased
- 1983-03-11 NO NO830860A patent/NO157413C/en unknown
- 1983-03-11 EP EP83102417A patent/EP0089579B1/en not_active Expired
- 1983-03-11 DE DE8383102417T patent/DE3360643D1/en not_active Expired
- 1983-03-11 BR BR8301299A patent/BR8301299A/en not_active IP Right Cessation
- 1983-03-11 ES ES520511A patent/ES520511A0/en active Granted
- 1983-03-11 JP JP58039331A patent/JPS58167526A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
NO830860L (en) | 1983-09-13 |
ES8500877A1 (en) | 1984-11-01 |
AU1233183A (en) | 1983-09-15 |
NO157413B (en) | 1987-12-07 |
BR8301299A (en) | 1983-11-22 |
AU557361B2 (en) | 1986-12-18 |
NO157413C (en) | 1988-03-16 |
US4384159A (en) | 1983-05-17 |
ES520511A0 (en) | 1984-11-01 |
EP0089579A1 (en) | 1983-09-28 |
JPS58167526A (en) | 1983-10-03 |
EP0089579B1 (en) | 1985-08-28 |
JPH0352451B2 (en) | 1991-08-12 |
DE3360643D1 (en) | 1985-10-03 |
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